POWER CABLE AND PROCESS FOR THE PREPARATION OF THE SAME

专利摘要:
polymer composition for electrical devices. the present invention relates to a polymer composition, the use of the composition for the production of an electrical device, as well as a cable surrounded by at least one layer comprising the polymer composition.
公开号:BR112013028128B1
申请号:R112013028128-6
申请日:2012-05-03
公开日:2021-06-01
发明作者:Johan Andersson；Villgot Englund；Per-Ola Hagstrand；Ulf Nilsson；Annika Smedberg；Thomas Steffl；Johannes Wolfschwenger
申请人:Borealis Ag；
IPC主号:

专利说明:

Field of Invention
[0001] The present invention relates to a polymer composition for the production of an electrical or communication device, preferably a layer of a cable, preferably a power cable, more preferably, of a direct current (DC) power cable, for a cable, preferably a power cable, more preferably a direct current (DC) cable, which comprises the crosslinkable polymer composition and is optionally and subsequently crosslinked, as well as a cable preparation process. Background of the technique
[0002] Polyolefins are widely used in demanding polymer applications where polymers must meet high mechanical and/or electrical requirements. For example, in power cable applications, particularly in medium voltage (MV) and especially in high voltage (HV) and very high voltage (EHV) cable applications the electrical properties of the polymer composition are of significant importance. Furthermore, the electrical properties of importance may differ in different cable applications, as is the case, for example, between alternating current (AC) and direct current (DC) cable applications.
[0003] A typical power cable is composed by means of a conductor surrounded at least by means of an inner semiconductor layer, an insulating layer and an outer semiconductor layer, in that order. Cables are typically produced by extruding the layers onto a conductor. The crosslinking of cables
[0004] The polymer material in one or more of said layers is often cross-linked for example, in order to improve heat and creep resistance, creep properties, mechanical strength, chemical resistance and abrasion resistance of the polymer in the (s) layer(s) of the cable. In the interpolymer crosslinking reaction of a polymer crosslinks (bridges) are first formed. Crosslinking can be carried out using, for example, a free radical generating compound. The free radical generating agent is typically incorporated into the layer material prior to extrusion of the layer(s) onto a conductor. After the formation of the layered cable, the cable is then subjected to a crosslinking step to initiate the formation of radicals and therefore the crosslinking reaction.
[0005] Peroxides are widely used as compounds that generate free radicals. The resulting decomposition products of peroxides can include volatile by-products, which are often undesirable, for example, can have a negative influence on the electrical properties of the cable. In this way, volatile decomposition products, such as methane, are conventionally reduced to a minimum or removed after the crosslinking and cooling step. Such a removal step, commonly known as a degassing step, is time consuming and causing extra costs to consume energy. Electric conductivity
[0006] The DC electrical conductivity is an important property material, for example for the insulating materials for high voltage direct current (DC HV) cables. First of all, the temperature and the strong electric field dependence of this property will influence the electric field. The second problem is the fact that heat is generated inside the insulation through the leakage of electrical current that passes between the inner and outer semi-conductive layers. This leakage current depends on the electrical field and the electrical conductivity of the insulation. The high conductivity of the insulation material can even lead to thermal runaway under high voltage / high temperature conditions. Conductivity must be low enough to prevent thermal runaway.
[0007] Therefore, in DC HV cables, the insulation is heated by means of leakage current. For a specific design, the heating cable is proportional to the insulation conductivity x (electric field) 2. In this way, if the voltage is increased, much more heat will be generated.
[0008] JP2018811A describes an insulation layer for a DC cable, which contains a mixture of 2 to 20% by weight of a high density polyethylene with a low density polyethylene. The mixture is said to provide greater DC breakage and a boost property. The mixture is mixed with 2 to 3% by weight of a crosslinking agent. The structure of cable type and layer is not specified.
[0009] There are high demands to increase the voltage of a power cable, preferably of the DC current power cable, and therefore a continual need to find alternative polymer compositions with reduced conductivity. Such polymer compositions should preferably also have good mechanical properties required for demanding power cable embodiments.
[00010] Figure 1 is a schematic partial section of two lamellae and an intermediate layer between the illustration of a general form of the lamellar structure of an anion exchange additive preferable as the ion exchange (b). Stable layers of lamellae are shown as continuous layers and round-shaped species illustrate the exchangeable interlayer anions. Description of the invention
[00011] The present invention provides a polymer composition that is a highly suitable polymer material for a layer, preferably an insulating layer of a cable, preferably of a power cable, more preferably of a cable of direct current (DC) feed, and comprising (a) a polyolefin which is different than low density polyethylene (LDPE), (b) a second polyolefin which is different from polyolefin (a); (c) an ion exchange additive.
[00012] The polymer composition of the present invention is hereinafter also referred to briefly as "polymer composition" or "polymer composition". Its components, as defined above, are also little referred to in the present invention as "polyolefin (a)", "second polyolefin (b)", and, respectively, "ion exchange additive (c)".
[00013] "Low Density Polyethylene", LDPE, is a polyethylene produced in a high pressure polymerization (HP) process. Typically, the polymerization of ethylene and optional additional comonomer(s) in the high pressure process is carried out in the presence of an initiator(s). The meaning of LDPE polymer is well known and documented in the literature. Although the term LDPE is an abbreviation for low density polyethylene, the term is not intended to limit the density range, but encompasses HP type LDPE polyethylenes with low, medium and high densities. The term LDPE only describes and distinguishes the nature of HP polyethylene with typical characteristics such as different branching architecture compared to PE produced in the presence of an olefin polymerization catalyst. "Polyolefin produced in the presence of an olefin polymerization catalyst", in turn, is also often called "low pressure polyolefin" to clearly distinguish it from LDPE. Both expressions are well known in the polyolefin field.
[00014] Unexpectedly, when a polyolefin (a) except LDPE is blended with a second polyolefin (b) the resulting polymer composition shows improved electrical properties. Furthermore, when said mixture is further mixed together with an ion exchange additive (c) the resulting polymer composition further exhibits the improved electrical properties compared to the electrical properties of the reference polymer comprising a single polymer component or the same polymer blend, but without ion exchange additive (c) or with the conventional small molecule acid scavengers that are typically used with polyolefins produced in the presence of an olefin polymerization catalyst. Namely, the polymer composition of the present invention surprisingly has a reduced, i.e., low DC electrical conductivity. "Reduced" or "low" electrical conductivity, as used in the present invention, means that alternately the value obtained from measuring the DC conductivity, as defined below under "Methods of determination" is low, i.e., reduced.
[00015] Without being bound by any theory, it is believed that the ion exchange additive (c) captures ion species that worsen (increase) DC electrical conductivity, for example, harmful ion species such as chlorine, which may be present in polymer (A).
[00016] Therefore, the polymer composition is very desirable for electrical and communication applications, preferably for wire and cable applications, especially for layers of power cables. On the other hand, low DC electrical conductivity is beneficial in minimizing unwanted heat build-up, for example, in an insulation layer of a cable, preferably a power cable, more preferably a power cable of direct current.
[00017] Furthermore, for example, polyolefins produced in the presence of an olefin polymerization catalyst usually contain catalyst residues such as ion species, typically halogens, often chlorine. Therefore acid scavengers have been added to polyolefin produced for example to protect processing equipment against corrosion caused by unwanted waste such as hydrochloric acid formed from chlorine-based waste. In the prior art, conventionally used acid sequestrants have been found to increase the DC electrical conductivity of the polymer which is highly undesirable for the power cable layer material and limits the use of polyolefins produced by means of an olefin polymerization catalyst in power cables operating at MV and particularly at HV levels, more particularly in direct current (DC) EHV and HV cable applications. The ion exchange additive (c) of the polymer composition of the present invention effectively captures unwanted ion catalyst residues and significantly reduces the DC electrical conductivity of a polyolefin produced by means of an olefin polymerization catalyst . As a result, the use of conventional acid scavengers with undesirable effect on DC electrical conductivity can be avoided.
[00018] The present invention is thus very advantageous for polymer compositions comprising blends of either LDPEs or a polyolefin produced by means of an olefin catalyst, or for both.
[00019] Thus, polymer composition is very desirable, particularly for power cable applications. A power cable is defined as a power transfer cable operating at any voltage level. Furthermore, the material composition of the polymer layer is very advantageous for a DC power cable, which can be, for example, a low voltage DC cable (LV), a medium voltage (MV), high voltage (HV) or a extra high voltage (MAT), whose well-known terms indicate the operating voltage level. The polymer composition is even more preferable layer material for an HV power cable operating at any voltages, preferably by means of a DC HV power cable operating at voltages greater than 36 kV. For DC HV cables the operating voltage is defined in the present invention as the electrical voltage between the ground and the conductor of the high voltage cable. The preferred cable is a DC HV power cable.
[00020] Therefore, the present invention is further directed to a use of a polymer composition, comprising (a) a polyolefin that is different than low density polyethylene (LDPE), (b) a second polyolefin that is other than polyolefin (a); (c) an ion exchange additive, as defined above, below, or in the claims, for the production of an electrical or communication device comprising said polymer composition, preferably for the production of an insulation of an electrical apparatus or communication. Such devices are, for example, cables, joints including termination joints in cable applications, capacitor films, etc. The most preferred use of the present invention is the use of said polymer composition for producing a layer of a cable.
[00021] More preferably, the present invention is directed to the use of a polymer composition for the production of at least one layer, preferably at least one insulating layer, of a cable, preferably more than a power cable, more preferably a direct current (DC) power cable, comprising a conductor surrounded by at least an inner semiconductor layer, an insulating layer and an outer semiconductor layer, in that order, in that the polymer composition comprises (a) a polyolefin which is different than low density polyethylene (LDPE), (b) a second polyolefin which is different from polyolefin (a); (c) an ion exchange additive as defined above, below, or in the claims.
[00022] The present invention also provides a cable, preferably a power cable, preferably a direct current (DC) power cable, comprising a conductor that is surrounded by at least one layer, preferably at least , by an insulating layer, preferably a direct current (DC) power cable, comprising a conductor that is surrounded by at least an inner semiconductor layer, an insulating layer and an outer semiconductor layer, in that order, where said at least one layer, preferably at least the insulating layer, comprises a polymer composition comprising (a) a polyolefin which is different than low density polyethylene (LDPE), (b) a second polyolefin which is different from polyolefin (a); (c) an ion exchange additive as defined above, below, or in the claims.
[00023] Preferably, the polymer composition is used in a layer of a high voltage power cable operating at voltages of 40 kV or higher, even at voltages of 50 kV or higher. Most preferably, the polymer composition is used in a layer of a high voltage power cable operating at voltages of 60 kV or greater. The present invention is also highly feasible in many demanding cable applications and can be used with a layer of a high voltage power cable operating at voltages in excess of 70 kV. The upper limit is not limited. The practical upper limit can be up to 900 kV. The present invention is advantageous for use in high voltage power cable applications operating at 75 to 400 kV, preferably at 75 to 350 kV. The present invention is also considered advantageous even in high voltage power cable applications running extra 400 to 850 kV. The preferred HV or extra high voltage power cable in any of the voltage ranges above is a DC HV power cable or an extra DC HV power cable.
[00024] The high voltage DC power cable, as used below, or in the claims means in the present invention a high voltage DC power cable, preferably operating at voltages as defined above, or a high power cable extra high voltage DC, preferably with operation with voltages as defined above. In this way, the term independently covers the operating areas for both HV DC power cables as well as for EHV DC cable applications.
[00025] The polymer composition preferably has an electrical conductivity of 100 fs / m or less, preferably 90 fs / m or less, more preferably < 0.01 (smaller values not detectable through of DC conductivity measurement) for 80 fs / m, more preferably < 0.01 to 70 fs / m, more preferably < 0.01 to 60 fs / m, more preferably, from < 0.01 to 10 fs / m, more preferably from < 0.01 to 8.00 fs / m, more than preferably from < 0.01 to 6.00 fs / m, more than one preferably from < 0.01 to 5.00 fs / m, more than preferably from < 0.01 to 4.00 fs / m, more preferably between 0.01 and 3.5 fs / m, more than preferably from 0.02 to 3.0 fs/m, when measured according to the DC conductivity method as described in "Methods of determination".
[00026] Therefore, the present invention is also directed to a method for the reduction, that is, to provide a low electrical conductivity of a polymer composition of a power cable, preferably a DC power cable, through of producing at least one layer, preferably an insulating layer, using the polymer composition comprising (a) a polyolefin which is different than low density polyethylene (LDPE), (b) a second polyolefin which is different from polyolefin (a); (c) an ion exchange additive as defined above, below, or in the claims.
[00027] Preferably, the polymer composition comprises the polyolefin (a) in an amount of 0.1 to 99.9% by weight, preferably equal to or greater than 0.5% by weight, preferably 0.5 to 80% by weight, more preferably from 1.0 to 70% by weight, more preferably from 1.0 to 50% by weight, most preferably from 1.0 to 40% by weight , more preferably from 1.0 to 30% by weight, more preferably from 1.0 to 25% by weight, even more preferably from 1.0 to 20% by weight, even more preferably from 1.0 to 17% by weight, based on the combined weight of the polyolefin (a) and the second polyolefin (b).
[00028] Polyolefin (a) is preferably a polyethylene produced in the presence of an olefin polymerization catalyst and selected from an ethylene homopolymer or an ethylene copolymer with one or more comonomer(s), or a homo- or C3 -20 - alpha olefin copolymer produced in the presence of an olefin polymerization catalyst, which is preferably selected from a homopolymer of propylene, a random copolymer of propylene with one or more comonomer(s) or heterophasic copolymer of propylene with one or more comonomer(s), or from homo or copolymers of butene
[00029] According to a preferred embodiment, polyolefin (a) is a polyethylene produced in the presence of an olefin polymerization catalyst selected from very low density polyethylene (VLDPE), linear low density polyethylene copolymers (LLDPE) ), copolymers of medium density polyethylene (MDPE) copolymers or homopolymers of high density polyethylene (HDPE). Low pressure polyethylene can be unimodal or multimodal with respect to molecular weight distribution.
[00030] The preferred polyolefin (a) is a polyethylene produced in the presence of an olefin polymerization catalyst and selected from an ethylene homopolymer or an ethylene copolymer with one or more comonomer(s) as defined above or below. Even more preferably the polyolefin (a) is an MDPE polymer or an HDPE polymer, even more preferably an HDPE polymer as defined above or below, more preferably an HDPE polymer that is unimodal or multimodal with respect to the molecular weight distribution as defined above or below.
[00031] Still preferably, the polymer composition comprises the polyolefin (b) in an amount from 0.1 to 99.9% by weight, preferably from 99.5% by weight or less, preferably from 20 to 99 .5% by weight, more preferably from 30 to 99.0% by weight, more preferably from 50 to 99.0% by weight, more preferably from 60 to 99.0% by weight , more preferably from 70 to 99.0% by weight, more preferably from 75 to 99.0% by weight, even more preferably from 80 to 99.0% by weight, still in a manner more preferably from 83 to 99.0% by weight, based on the combined weight of the polyolefin (a) and the second polyolefin (b).
[00032] Preferably, the second polyolefin (b) is a polyolefin, as defined by polyolefin (a), above or higher hereinafter in the text and is different from polyolefin (a), or is a low density polyethylene (LDPE) of polymer selected from an optionally unsaturated LDPE homopolymer or an optionally unsaturated LDPE copolymer of ethylene with one or more comonomer(s). In the most preferred embodiment of the present invention, the polyolefin (b) is an LDPE selected from an optionally unsaturated LDPE homopolymer or an optionally unsaturated LDPE copolymer of ethylene with one or more comonomer(s). ).
[00033] Polyolefin (a) and the second polyolefin (b), and the other properties and preferred embodiments thereof, are described later in the text.
[00034] As an additive for the ion exchange (c) of the polymer composition:
[00035] The ion exchange additive (c) of the polymer composition of the present invention can be added to the polymer composition as such, that is, pure, or as an additive composition as provided by additive producers, which they may contain, for example a support material, for example a carrier polymer, and optionally other additives. Furthermore, such an ion exchange additive (c), or the same additive composition may be added to the polymer composition, such as, for example, as supplied by the additive producer, or on another support material, for example , on a polymer support, for example, in a so-called master batch (MB). The amount of the ion exchange additive (c), as presented below and in the claims, is the weight (amount) of said ion exchange additive (c), as such, i.e., pure, based on the total weight of (amount) (100% by weight) of the polymer composition.
[00036] The ion exchange additive (c) of the polymer composition of the present invention is preferably an inorganic ion exchange additive, more preferably an inorganic ion exchange additive. Furthermore, preferably an ion exchange additive (c) can exchange anions for halogens (eg scavenging halogens), preferably at least the chlorine-based species. More than preferably the ion exchange additive (c) has a lamellar structure.
[00037] The preferred modality of the ion exchange additive (c) is a lamellar anion exchange, preferably a lamellar anion exchange comprising ion interlayers. The lamellar ion exchange additive preferably (c) comprises lamellar layers which form the stable host network and the ion interlayers are interchangeable between said lamellars. Ion interlayers in the present invention means that the interlayers comprise the anions which are loosely bound to the lamellar layers and interchangeable with the ion species present in polymer (a) of the polymer composition. Figure 1 illustrates the general lamellar structure (a schematic partial section, showing two lamellae and an intermediate layer between them) of an ion exchange additive as a preferable ion exchange additive (c). In this preferred embodiment, the lamellar anion exchange interlayers (c) preferably comprise CO32 anions that are interchangeable with the ion species present in the polymer composition, such as in any or both of the polyolefin components (a) and (b) of the polymer composition. Furthermore, in this preferred embodiment, the stable lamellae preferably comprise, for example, cation species selected from any Mg-Al-Fe-Cr-, Cu, Ni or Mn- cation, or any mixtures thereof. , more preferably from at least Mg2 + - cations, and more preferably from Mg2 + and Al3 + - cations, on a species basis.
[00038] In this preferred embodiment, the most preferred ion exchange additive (c) is a lamellar anion exchange additive of the hydrotalcite type, preferably a lamellar anion exchange additive of a synthetic hydrotalcite type comprising the ion interlayers which comprise exchangeable anions CO32 -, yet more preferably a lamellar anion exchange additive of the synthetic hydrotalcite type having a general formula Ry MgX (3 +) (OH) z (CO3) k * nH2O, where R ( 3+) = Al, Cr or Fe, preferably Al. In said general formula, it is preferably between 4-6 x, y is 2, z is between 6-18, k is 1 and n is between 3- 4. Of course the proportions can vary depending on for example the amount of water in the crystal etc. As a non-limiting example just a general formula Mg6R2(3+)(OH)16CO3*4H2O, where R(3+) = Al , Cr or Fe, preferably Al, may be mentioned.
[00039] Furthermore, in this preferred embodiment, the ion exchange additive (c), preferably hydrotalcite as specified above, below and in the claims, can be modified, e.g. surface treated, as well known in the art.
[00040] The ion exchange additives (c) which are suitable for the present invention are, for example, commercially available. Among the preferred ion exchange additives (c), a commercially available synthetic hydrotalcite (IUPAC name: Dialuminum carbonate hexadecahydroxide, CAS 11097-59-9), may be mentioned, as supplied by Kisuma Chemicals under the trade name of DHT 4V.
[00041] The amount of the ion exchange additive (C), preferably hydrotalcite as defined above, below, or in the claims, naturally depends on the desired end application (for example, the desired level of conductivity) and the values of the components of the polymer (a) and (b) and can be adapted by a person skilled in the art. Preferably, the polymer composition comprises the ion exchange additive (c), preferably hydrotalcite, as defined above, below, or in the claims, as such, i.e., pure, in an amount of less than 1% by weight , preferably less than 0.8% by weight, preferably from 0.000001 to 0.7% by weight, preferably from 0.000005 to 0.6% by weight, more preferably from 0.000005 to 0.5 % by weight, more preferably from 0.00001 to 0.1 % by weight, more preferably from 0.00001 to 0.08% by weight, most preferably from 0.00005 to 0.0 07% by weight, more preferably from 0.0001 to 0.065% by weight, more preferably from 0.0001 to 0.06% by weight, more preferably from 0.0001 to 0.05 % by weight, based on the total weight of the polymer composition.
[00042] Furthermore, in the case where the polymer composition comprises polyolefin (a) in amounts less than 50% by weight, based on the combined weight of the polyolefin (a) and the second polyolefin (b), then the additive of ion exchange (c), preferably hydrotalcite as defined above, below, or in the claims, is in an amount of 0.0001 to 0.06% by weight, more preferably of 0.0001 to 0.05% by weight, more preferably from 0.0001 to 0.045% by weight, more preferably from 00015 to 0.035% by weight, more preferably from 0.0002 to 0.025% by weight, more than preferably from 0.0003 to 0.015% by weight, more preferably from 0.0005 to 0.01% by weight, more preferably from 0.0008 to 0.005% by weight, most preferably from 0.001 to 0.004% by weight, more preferably from 0.0015 to 0.0035% by weight, based on the total weight of the polymer composition.
[00043] In a most preferred embodiment, the polymer composition comprises the polyolefin (a) in an amount of 1.0 to 50% by weight, preferably 1.0 to 40% by weight, more preferably of 1.0 to 30% by weight, more preferably 1.0 to 25% by weight, even more preferably 1.0 to 20% by weight, even more preferably 1.0 to 17% by weight, based on the combined weight of the polyolefin (a) and the second polyolefin (b), and the polymer composition comprises the polyolefin (b) in an amount of from 50 to 99.0% by weight, preferably from 60 to 99.0% by weight, more preferably from 70 to 99.0% by weight, more preferably from 75 to 99.0% by weight, even more preferably from 80 to 99.0% by weight, still of more preferably from 83 to 99.0% by weight, based on the combined weight of polyolefin (a) and the second polyolefin (b), and additionally the ion exchange additive (c), preferably hydrotalcite as defined above , below, or in the claims, in an amount of 0.0001 to 0.06% by weight, more preferably 0.0001-0.05% by weight, more preferably 0.0001-0.045% by weight, more preferably, from 00015 to 0.035% preferred from 0.0002 to 0.025% preferred from 0.0003 to 0.015% preferred from 0.0005 to 0.01% preferred from 0.0008 to 0.005 % preferred from 0.001 at 0.004%, preferably from 0.0015 to 0.0035% of the polymer composition. by weight, more than one way by weight, more than one way by weight, more than one way by weight, more than one way by weight, more than one way by weight, based on total weight
[00044] The polymer composition of the present invention can be cross-linked or non-cross-linked.
[00045] Surprisingly, the polymer composition has a beneficial low DC electrical conductivity also when crosslinked. Therefore, the polymer composition of the present invention is preferably cross-linkable. Crosslinking preferably also contributes to the mechanical and heat properties and deformation resistance of the polymer composition.
[00046] "Cross-linkable" means that the polymer composition can be cross-linked with a cross-linking agent(s) prior to use in the final application thereof. The crosslinkable polymer composition of the present invention further comprises a crosslinking agent. It is preferred that the polymer composition comprising the polyolefin (a), the second polyolefin (b) and the ion exchange additive (c), the polymer composition is cross-linked. Furthermore, the cross-linked polymer composition, or, respectively, one or both polymer components with cross-links of the polyolefin (a) and the second polyolefin (b) is/are preferably radical with cross-links through reaction with a generating agent. free radicals. The crosslinked polymer composition has a typical network, i.e. the interpolymer crosslinks (bridges), as is well known in the field. As is evident to a person skilled in the art, the crosslinked polymer composition can be and is defined in the present invention, with characteristics that are present in the polyolefin polymer composition (a) or the second polyolefin (b) before or after of the halftone, as indicated or evident from the context. For example, the amount of crosslinking agent in the polymer composition or composition of a property, such as MFR, density and/or degree of unsaturation, of the polyolefin (a) or the second polyolefin (b) is defined, unless otherwise indicated, before crosslinking. "Cross-linked" means that the cross-linking step provides another technical feature to the cross-linked polymer composition (process by-product), which makes an additional difference over the prior art.
[00047] In embodiments, in which the polymer composition comprises any crosslinking agent, the DC electrical conductivity as described in the "method of determination" is measured from a sample of said polymer composition that is non-crosslinked (i.e. is, does not contain a cross-linking agent and has not been cross-linked with a cross-linking agent). In embodiments where the polymer composition is cross-linkable and comprises a cross-linking agent, then DC electrical conductivity is measured from a sample of the cross-linked polymer composition (i.e., a sample of polymer composition is cross-linked by the first time during sample preparation using the crosslinking agent that is initially present in the polymer composition and then the electrical conductivity is measured from the crosslinked sample obtained). The measurement of DC conductivity from a sample of an uncrosslinked or crosslinked polymer composition is described in "Methods of Determination". The amount of crosslinking agent, when present, may preferably vary within the ranges indicated below.
[00048] The expression "no cross-linking agent" in the present invention means above and below that the polymer composition does not comprise any cross-linking agent that has been added to the polymer composition for the purpose of the cross-linking polymer composition.
[00049] In the preferred embodiment of the present invention, the polymer composition comprises (a) a polyolefin which is different than the low density polyethylene (LDPE), (b) a second polyolefin which is different from the polyolefin (A), (c) an ion exchange additive, and a crosslinking agent as defined above, below, or in the claims.
[00050] Still preferably, the polymer composition comprises crosslinking agent, which is preferably a peroxide. The polymer composition preferably comprises the peroxide in an amount of up to 110 mmols -OO- / kg of the polymer composition, preferably up to 90 mmols -OO- / kg of the polymer composition, more preferably from 0 to 75 mmols -OO- / kg of polymer composition, preferably less than 50mmols -OO- / kg of polymer composition, preferably less than 40 mmols -OO- / kg of polymer composition.
[00051] In a preferred embodiment the polymer composition comprises peroxide in an amount less than 37 mmols polymer composition -OO- / kg mmols, preferably less than 35 mmols -OO- / kg polymer composition, preferably between 0, 1 and 34 mmols -OO- / kg of polymer composition, preferably between 0.5 and 33 mmols -OO- / kg of polymer composition, more preferably 5.0 to 30 mmols -OO- / kg of composition of polymer, more preferably from 7.0 to 30 mmols -OO- / kg of the polymer composition, more preferably from 10.0 to 30 mmols -OO- / kg of the polymer composition.
[00052] The unit "mmols -OO- / kg of polymer composition" in the present invention means the content (mmols) of peroxide functional groups per kg of polymer composition, when measured from the polymer composition before crosslinking . For example, 35 mmols -O-O-/kg of the polymer composition corresponds to 0.95% by weight of well-known dicumyl peroxide based on the total amount (100% by weight) of the polymer composition.
[00053] Low DC electrical conductivity with low peroxide contents can advantageously be achieved and the drawbacks of the prior art relating to the use of a crosslinking agent in a cable layer can be minimized. Furthermore, the lower content of peroxide used can shorten the step of the crosslinking cable produced and desired degassing, if desired. This is unexpected and not predictable from the prior art.
[00054] This polymer composition may comprise one type of peroxide, or two or more different types of peroxide, in which case the amount (in mmols) of the polymer composition -OO- / kg, as defined above, below, or in claims, is the sum of the amount of polymer composition -OO- / kg of each type of peroxide. As non-limiting examples of suitable organic peroxides, di-tert-amylperoxide, 2,5-di(tert-butylperoxy)-2,5-dimethyl-3-hexine, 2,5-di(tert-butyl-peroxy)-2 , 5-dimethyl-hexane, tert-butylcumylperoxide, di(tert-butyl)peroxide, dicumylperoxide, butyl-4,4-bis(tert-butylperoxy)-valerate, 1,1-bis(tert-butylperoxy)-3.3 ,5- trimethylcyclo, tert-butylperoxybenzoate, dibenzoylperoxide, bis(tert-butylperoxysopropyl)benzene, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, 1,1-di(tert-butylperoxy)cyclohexane, 1 , 1-di(tert-amylperoxy)cyclohexane, or any mixtures thereof, may be mentioned. Preferably, the peroxides selected from 2,5-di(tert-butylperoxy)-2,5-dimethyl-hexane, benzene di(tert-butylperoxysopropyl), dicumylperoxide, tert-butylcumylperoxide, di(tert-butyl)peroxide, or as mixtures thereof. Most preferably, the peroxide is dicumyl peroxide.
[00055] In addition, the polymer composition of the present invention may contain, in addition to the polyolefin (a), the second polyolefin (b), the ion exchange additive (c) and the optional peroxide, other (s) component(s), such as the polymer component(s) and/or additive(s), preferably additive(s), such as any of the antioxidant(s), burns the retardant(s) ( SR), crosslinking booster(s), stabilizer(s), processing aid(s), flame retardant(s), water tree additive(s), water retardant(s), acid additional or ion sequestrant(s), inorganic filler(s) and strain stabilizer(s), as is known in the field of polymers. The polymer composition comprises additive(s) preferably conventionally used for W&C applications, such as one or more antioxidant(s) and optionally one or more of the burn retardant(s) or crosslinking enhancer(s), from preferably at least one or more antioxidant(s). The amounts of additives used are conventional and well known to a person skilled in the art.
[00056] As non-limiting examples of antioxidants, for example, sterically hindered or semi-hindered phenols, aromatic amines, sterically hindered amine aliphatics, organic phosphites or phosphonites, thio compounds, and mixtures thereof, may be mentioned.
[00057] The combined amount of polyolefin (a) and the second polyolefin (b) in the polymer composition of the present invention is typically at least 50% by weight, preferably at least 60% by weight, more preferably by less 70% by weight, more preferably at least 75% by weight, more preferably from 80 to 100% by weight and more preferably from 85 to 100% by weight, of the total weight of the (s). ) polymer component(s) present in the polymer composition. The preferred polymer composition consists of polyolefin (a) and the second polyolefin (b) as the only polymer components. The expression means that the polymer composition does not contain other polymer components, but polyolefin (a) and the second polyolefin (b) as the sole polymer component(s). However, it is to be understood in the present invention that the polymer composition may comprise more than others of the polyolefin (a), the second polyolefin (b), the ion exchange additive (c) and the optional crosslinking agent preferable and components such as additives may optionally be added, such as the ion exchange additive (c), in a mixture with a carrier polymer, i.e., in the so-called master batch.
[00058] The polymer composition, preferably one or both of the polyolefin (a) and the second polyolefin (b), preferably the second polyolefin (b), may optionally be unsaturated (contain carbon-carbon double bonds), prior to optional crosslinking, as described further below, to the second polyolefin (b).
[00059] The present invention also independently provides a preferred subgroup of the polymer composition comprising (a) a polyolefin which is different than low density polyethylene (LDPE), and which is selected from a polyethylene produced in the presence of an olefin polymerization catalyst or a polypropylene produced in the presence of an olefin polymerization catalyst, preferably a polyethylene produced in the presence of an olefin polymerization catalyst, more preferably an MDPE polymer or an HDPE polymer, further more preferably an HDPE polymer, (b) a second polyolefin which is different from the polyolefin (a), preferably an LDPE polymer, more preferably an unsaturated LDPE homopolymer or an unsaturated LDPE copolymer optionally saturated ethylene with one or more comonomer(s), (c) an ion exchange additive, preferably a hydrotalcite, as defined above , below, or in the claims, and a peroxide in an amount of less than 37 mmols -OO- / kg of the polymer composition, preferably less than 35 mmols -OO- / kg of the polymer composition, preferably between 0.1 and 34 mmols -OO- / kg of polymer composition, preferably from 0.5 to 33 mmols -OO- / kg of polymer composition, more preferably from 5.0 to 30 mmols -OO- / kg of polymer composition of more preferably 7.0 to 30 mmols -OO- / kg mmols of the polymer composition, more preferably 10.0 to 30 mmols -OO- / kg of the polymer composition. This crosslinkable subgroup and is preferably, when crosslinked, provides highly reduced electrical conductivity c. The polymer composition subgroup is new and most preferred.
[00060] In this subgroup of the polymer composition, the amount of polyolefin (a) is preferably equal to or less than 50% by weight, more preferably from 1.0 to 40% by weight, most preferably from 1 0.0 to 30% by weight, more preferably 1.0 to 25% by weight, even more preferably 1.0 to 20% by weight, based on the combined weight of polyolefin (a) and a second polyolefin (b). Also preferably, in this subgroup, the amount of the second polyolefin (b) is 50% by weight or more, more preferably 60 to 99.0% by weight, more preferably 70 to 99.0% by weight, more preferably from 75 to 99.0% by weight, even more preferably from 80 to 99.0% by weight, based on the combined weight of the polyolefin (a) and the second polyolefin (b).
[00061] This independent subgroup of the polymer composition of the present invention is also the most preferred subgroup of the polymer composition of the present invention present in at least one layer, preferably at least in the insulating layer, of the cable of the present invention, as defined above, below or in the claims.
[00062] In general, it is preferable that the polymer composition of the present invention and its subgroup as defined above, below, or in the claims are used for the production of an insulating layer.
[00063] Still preferably, the composition of the polymer is to be avoided, that is, it does not comprise a carbon black. Also preferably, the polymer composition is to avoid, does not comprise, the flame retardant additive(s) in amounts conventionally used for the quality of "flame retardants", for example a hydroxide of metal containing additives in flame retardant amounts.
[00064] The following preferred embodiments, the properties and subgroups of the polyolefin (a) and second polyolefin (b) components, as well as the preferred embodiments, the above properties and the appropriate ion exchange additive (c) subgroups for polymer composition are independently generalizable so that they can be used in any order or combination to further define preferred embodiments of polymer composition and cable produced using the polymer composition. Furthermore, it is evident that the polyolefin descriptions (a) and (b) given apply to the optional cross-linking of polyolefins. Polyolefins (a)
[00065] Preferably, the polyolefin (a) is a low pressure polyethylene, that is, a polyethylene produced (= polymerized) in the presence of an olefin polymerization catalyst, or a homo - or copolymer of C3 -20 alpha - polymerized olefin, in the presence of an olefin polymerization catalyst, which is then preferably a homo- or copolymers of polypropylene, or a homo- or copolymers of butane. The most preferred polyolefin (a) is a polyethylene produced in the presence of an olefin polymerization catalyst or polypropylene produced in the presence of an olefin polymerization catalyst and even more preferably a polyethylene produced in the presence of an olefin polymerization catalyst. olefin polymerization.
[00066] The "Olefin polymerization catalyst" in the present invention means a conventional coordination catalyst. It is preferably selected from a Ziegler-Natta catalyst, single site catalyst comprising a metallocene term and a non-metallocene catalyst, or a chromium catalyst, or any mixtures thereof.
[00067] The term "polyethylene" (PE) means homopolymer of ethylene or a copolymer of ethylene with one or more comonomer(s). "Polypropylene" (PP) means homopolymer of propylene, a random copolymer of propylene with one or more comonomer(s) or a heterophasic copolymer of propylene with one or more comonomer(s).
[00068] Low pressure PE or PP can be unimodal or multimodal with respect to molecular weight distribution (MWD = MW / Mn). In general, a polymer comprising at least two polymer fractions, which have been produced under different polymerization conditions, resulting in different (weight average) molecular weights and molecular weight distributions for the fractions, is referred to as "multimodal". The prefix "multi" refers to the number of different polymer fractions present in the polymer. Thus, for example, multimodal polymer polymer includes so-called "bimodal", which consist of two fractions. The shape of the molecular weight distribution curve, i.e. the appearance of the graph of polymer weight fraction as a function of its molecular weight, of a multimodal polymer will show two or more maximum values or is typically distinctly broadened compared to curves for individual fractions. For example, if a polymer is produced in a sequential multi-step process using the reactors coupled in series and using different conditions in each reactor, the polymer fractions produced in the different reactors will each have their own molecular weight distribution and of average molecular weight. When the molecular weight distribution curve of such a polymer is plotted, the individual curves of these fractions together typically form an extended molecular weight distribution curve for the resulting total polymer product.
[00069] The term "multimodal" in the present invention means, unless otherwise indicated, multimodality, at least with respect to the molecular weight distribution (MWD = MW / Mn) and also includes bimodal polymers.
[00070] A low pressure multimodal PE or PP usable in the present invention comprises a lower weight medium molecular weight (LMW) component (A) and a high molecular weight medium weight (HMW) component (B). Said LMW component has a lower molecular weight than the HMW component.
[00071] Naturally, the low pressure multimodal of PE or PP can, in addition or in an alternative way, with respect to the multimodality of MWD being multimodal with respect to density and comonomer content. That is, the LMW and HMW components can have different comonomer content, or density, or both.
[00072] Preferably, the low pressure PE and PP independently have a MWD of at least 2.0, preferably of at least 2.5, preferably of at least 2.9, preferably of 3 to 30, more preferably 3.3 to 25, more preferably 3.5 to 20, preferably 3.5 to 15. A unimodal PE or PP normally has a MWD of 3.0 to 10.0.
[00073] The low pressure of PE or PP can be a copolymer of ethylene or, respectively, of propylene (random or heterophasic), with one or more comonomer(s). Comonomer as used in the present invention means that it is not the monomer units of ethylene or propylene, respectively, which are copolymerizable with ethylene, or, respectively, with propylene.
[00074] The low pressure PE copolymer is preferably an ethylene copolymer with one or more olefin comonomers(s), preferably with at least C3 -20 -olefin, more preferably with at least less one C4 -12 alpha olefin, more preferably with at least one C4 -8 alpha olefin, for example with 1-butene, 1-hexene or 1-octene. The amount of comonomer(s) present in a PE copolymer is 0.1 to 15 mol%, typically 0.25 and 10 mol%.
[00075] In the PP copolymer is preferably a copolymer of propylene with one or more olefin comonomers(s), preferably with at least one of ethylene, or C4-20 α-olefin, more preferably with at least one less one of ethylene, or C4-12 alpha-olefin, more preferably with at least one of ethylene, or C4-8 alpha-olefin, for example, with ethylene, 1-butene, 1-hexene or 1-octene.
[00076] Preferably, the low pressure PE or PP copolymer can be a binary copolymer, that is, the polymer contains ethylene and a comonomer or a terpolymer, that is, the ethylene polymer and contains two or three comonomers.
[00077] In the most preferred polymer composition of the present invention, polyolefin (a) is a low pressure PE selected from a very low density ethylene copolymer (VLDPE), a linear low density ethylene copolymer (LDPEL). ), a medium density ethylene copolymer (MDPE) or a high density homopolymer or ethylene copolymer (HDPE). These known types are named according to their areal density. The term VLDPE includes in the present invention PES which are also known as plastomers and elastomers and covers the density range of 850 to 909 kg/m3. LLDPE has a density from 909 to 930 kg/m3, preferably from 910 to 929 kg/m3, more preferably from 915 to 929 kg/m3. MDPE has a density of 930 to 945 kg / m3, preferably of 931 to 945 kg / m3 The HDPE has a density of more than 945 kg / m3, preferably of more than 946 kg / m3, preferably of 946 to 977 kg / m3, more preferably 946 to 965 kg / m3.
[00078] A more preferable unimodal or multimodal MDPE or a unimodal or multimodal HDPE are the low pressure PE types for use as the polyolefin (A) of the present invention. More preferably polyolefin (a) is a unimodal or multimodal HDPE homopolymer or copolymer, preferably a unimodal or multimodal HDPE homopolymer.
[00079] The low pressure of PE preferably has an MFR2 of up to 1200 g / 10 min, such as up to 1000 g / 10 min, preferably up to 500 g / 10 min, preferably up to 400 g / 10 min, preferably up to 300 g / 10 min, preferably up to 200 g / 10 min, preferably up to 150 g / 10 min, preferably from 0.01 to 100, preferably from 0.01 to 50 g / 10 min, preferably from 0 .01 to 40.0 g / 10 min, preferably from 0.05 to 30.0 g / 10 min, preferably from 0.1 to 20.0 g / 10 min, more preferably from 0.2 at 15.0 g / 10 min.
[00080] As mentioned, the preferred polyolefin (A) is a polyethylene produced in the presence of an olefin polymerization catalyst and selected from an ethylene homopolymer or an ethylene copolymer with one or more comonomer(s) as defined above or below, including preferred above and below subgroups thereof.
[00081] Appropriate low pressure PE and PP, preferably PE, such as polyolefin (A) are as such well known and can for example be commercially available or alternatively can be produced in accordance with or analogously to conventional polymerization processes, which are well documented in the literature.
[00082] The olefin polymerization catalyst can be selected from well-known coordination catalysts, preferably Ziegler Natta, single-site, which comprises well-known term metallocene and non-metallocene catalyst, or chromium catalyst, or any of their mixtures. It is evident to a person skilled in the art that the catalyst system comprises a co-catalyst. Ziegler Natta catalysts suitable for low pressure are described, for example PE in EP0810235 or EP0688794, which are all incorporated in the present invention by way of reference. Suitable Ziegler Natta catalysts for PP are described for example in WO03000754 or EP 1 484 345, which are all incorporated in the present invention by way of reference. As known PP catalysts they can typically contain internal or external donors. As is well known the catalytically active catalyst component(s), such as the catalytically active component of Ziegler Natta catalyst, is normally combined with an activator. In addition, the catalyst system may be unsupported or supported on a vehicle, such as an external vehicle, such as a silica-based or Mg-based vehicle.
[00083] Unimodal low pressure PE and PP, preferably PE, can be produced by means of single-phase polymerization of a single reactor in a well-known and documented manner. Low pressure PE or multimodal PP (eg bimodal), preferably PE, can be produced for example by mechanically mixing together two or more separate polymer components or preferably by mixing in situ during the polymerization process of the components. Both mechanical and in situ blending are well known in the field. Therefore, by preferable in situ mixing is meant the polymerization of the polymer components, under different polymerization conditions, for example, in several stages, i.e. two or more stages, of polymerization or through the use of two or more catalysts. different types of polymerization, including multi-site or dual catalysts, a phased polymerization, or through the use of a combination of multi-stage polymerization and two or more different polymerization catalysts. In the multistage polymerization process, the polymer is polymerized in a process comprising at least two stages of polymerization. Each polymerization step can be carried out in at least two distinct polymerization zones in one reactor or in at least two separate reactors. Preferably, the polymerization process is carried out in several stages, with at least two cascade polymerization zones. The polymerization zones can be connected in parallel, or, preferably, the polymerization zones operate in a cascade mode. The polymerization zones can operate in bulk, suspension, solution, or under gas phase conditions or in any combinations thereof. In the preferred multicellular process a first polymerization step is carried out in at least one suspension of, for example, loop reactor and the second polymerization step in one or more gas phase reactors. A preferable multi-stage process is described in EP517868. For polypropylenes suitable as said polyolefin (a) the preparation of these processes, reference is also made to, for example Nello Pasquini (Ed.) Polypropylene Handbook, Hanser, Munich, 2005, pages 15 to 141.
[00084] In general, the temperature at low pressure PE and PP, preferably PE, polymerization is typically from 50 to 115 °C, preferably from 60 to 10 °C. The pressure is from 1 to 150 bar , preferably from 10 to 100 bar. Precise control of polymerization conditions can be accomplished using different catalyst types and using different comonomer and/or hydrogen feeds.
[00085] Pre-polymerization can precede the actual polymerization step(s), as is well known in the field.
[00086] In the case of heterophasic propylene copolymer the propylene homopolymer matrix or a random copolymer can be produced, for example, in a single phase or in several phases of a process described above and the elastomeric part (rubber) of the propylene copolymer it can be produced as an in situ polymerization, eg in a separate reactor, eg the gas phase reactor, in the presence of the matrix polymer produced in the preceding step. Alternatively, the elastomeric one-part copolymer of propylene can be mechanically combined with the phase matrix material, well known in the art.
[00087] At low pressure PE or PP obtained, preferably PE, the polymerization product can be combined in a known manner and optionally with additive(s) and pelletized for further use. Second polyolefin (b)
[00088] The second polyolefin (b) can be any polyolefin as defined for polyolefin (a) or a polymer of low density polyethylene (LDPE).
[00089] A polyolefin suitable as the second polyolefin (b) can be any polyolefin, such as any conventional polyolefin, which can be used in a cable layer, preferably in an insulating layer of a cable, preferably of a power cable.
[00090] Polyolefins suitable as the second polyolefin (b) are, for example as such, well known and can be for example commercially available or can be prepared according to or analogously to the known polymerization processes described in the chemical literature.
[00091] The second preferred polyolefin (b) is an LDPE polymer, which can be a low density ethylene homopolymer (hereinafter referred to as LDPE homopolymer) or a low density ethylene copolymer with one or more comonomer(s). ) (referred to in the present invention as LDPE copolymer). The one or more LDPE copolymer comonomers are preferably selected from the polar comonomer(s), non-polar comonomer(s) or from a mixture of the polar comonomer(s) (es) and non-polar comonomer(s), as defined above or below. Furthermore, said LDPE homopolymer or LDPE copolymer as said second polyolefin (b) may optionally be unsaturated.
[00092] As is well known "comonomer" refers to copolymerizable comonomer units.
[00093] As polar comonomer for LDPE copolymer as said second polyolefin (b), comonomer(s) containing hydroxyl group(s), alkoxy group(s), carbonyl group(s), carboxyl group(s), group Ether(s) or ester group(s), or a mixture thereof, may be used. More preferably, comonomer(s) containing carboxyl and/or ester group(s) are used as said polar comonomer. Even more preferably, the polar comonomer(s) of the LDPE copolymer is(are) selected from the group(s) of acrylate, methacrylate(s) or acetate of(s), or any mixtures thereof. If present in said LDPE copolymer, the polar comonomer(s) is (are) preferably selected from the group of alkyl acrylates, alkyl methacrylates or vinyl acetate, or a mixture of the same. More preferably, said polar comonomers are selected from C1-C6-alkyl acrylates, C1-C6-alkyl methacrylates or vinyl acetate. Even more preferably, said polar LDPE copolymer is a copolymer of ethylene with C1- to C4-alkyl acrylate, such as methyl, ethyl, propyl or butyl, or vinyl acetate, or any of the mixtures thereof. .
[00094] As the non-polar comonomer(s) for the LDPE copolymer as said second polyolefin(b), comonomer(s) except the polar comonomers defined above may be used. Preferably, non-polar comonomers are different from comonomer(s) containing hydroxyl group(s), alkoxy group(s), carbonyl group(s), carboxyl group(s), ether group(s) or a group ester(s). A preferable group of non-polar comonomer(s) comprise, preferably consist of, mono unsaturated comonomer(s) (= a double bond), preferably of olefins, preferably alpha-olefins, more than one preferentially C3 to C10 alpha-olefins, such as propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, styrene, 1-octene, 1-nonene; poly unsaturated comonomer(s) (= more than one double bond) and a silane group containing comonomer(s), or any of the mixtures thereof. The poly unsaturated comonomer(s) is(are) further described below in relation to the unsaturated LDPE copolymers.
[00095] If the polymer is an LDPE copolymer, it preferably comprises 0.001 to 50% by weight, More preferably 0.05 to 40% by weight, Even more preferably less than 35% by weight, Even more preferably less than 30% by weight, more preferably less than 25% by weight, of one or more comonomer(s).
[00096] The polymer composition, preferably at least the second polyolefin (b) the component thereof, more preferably the LDPE polymer, may optionally be unsaturated, that is, the polymer composition, preferably at least the second polyolefin (b), preferably the LDPE polymer, may comprise carbon-carbon double bonds (-C = C -). The "unsaturated" used in the present invention means that the polymer composition, preferably the second polyolefin (b), contains the carbon-carbon double bonds / 1000 carbon atoms in a total amount of at least 0.4 / 1000 atoms of carbon.
[00097] As is well known, unsaturation can be provided to the polymer composition, that is, through the polyolefin component(s), low molecular weight (Mw) compound(s), such as crosslinks of flame retardant enhancer(s) or additive(s), or any combinations thereof. The total amount of double bonds in the present invention means the double bonds determined from the source(s) which are known and deliberately added to contribute to unsaturation. If two or more double bond sources are chosen to be used to provide unsaturation, then the total amount of double bonds in the polymer composition means the sum of the double bonds present in the double bond sources. It is evident that a model compound for the calibration characteristic is used for each chosen source to allow quantitative infrared (FTIR) determination.
[00098] Double bond measurements are performed before optional crosslinking.
[00099] If the polymer composition is unsaturated (prior to optional crosslinking), then it is preferable that the unsaturation originates at least from the second unsaturated polyolefin component (b). More preferably, the second unsaturated polyolefin (b) is an unsaturated polyethylene, more preferably an unsaturated LDPE polymer, even more preferably an unsaturated LDPE homopolymer or an unsaturated LDPE copolymer . When the polyunsaturated comonomer(s) are present in the LDPE polymer as said unsaturated polyolefin, then the LDPE polymer is an unsaturated LDPE copolymer.
[000100] In a preferred embodiment, the term "total amount of carbon-carbon double bonds" is defined from the second unsaturated polyolefin (b), and refers, if not otherwise specified, to the combination of the amount from double bonds that originate from vinyl groups, vinylidene groups and trans-vinylene groups, if any. Of course, the second polyolefin (b) does not necessarily contain all three of the above types of double bonds. However, none of the three types, when present, is calculated the "total amount of carbon-carbon double bonds". The amount of each type of double bond is measured as indicated in "Methods of determination".
[000101] If an LDPE homopolymer is unsaturated, then unsaturation can be provided for example by means of a chain transfer agent (CTA) such as propylene, and/or through polymerization conditions. If an LDPE copolymer is unsaturated, then unsaturation can be provided by one or more of the following means: by a chain transfer agent (CTA), by one or more polyunsaturated comonomer(s) (s) or by polymerization conditions. It is well known that the selection of polymerization conditions, such as peak temperatures and pressures, can have an influence on the level of unsaturation. In the case of an unsaturated LDPE copolymer, this is preferably an ethylene unsaturated LDPE copolymer with at least one polyunsaturated comonomer and optionally with other comonomer(s) such as comonomer polar(s) which is then preferably selected from ethyl acrylate or comonomer(s). More preferably an unsaturated LDPE copolymer is an unsaturated ethylene LDPE copolymer with at least polyunsaturated comonomer(s).
[000102] Poly-unsaturated comonomers suitable for the second unsaturated polyolefin (b) preferably consists of a linear carbon chain, with at least 8 carbon atoms and at least four carbons between the unconjugated double bonds, of the which at least one is terminal, more preferably, said polyunsaturated comonomer is a diene, preferably a diene, comprising at least eight carbon atoms, the first carbon-carbon double bond being the terminals and the second carbon-carbon double bond being unconjugated to the first. Preferred dienes are selected from C8 to C14 non-conjugated dienes or mixtures thereof, more preferably selected from 1,7-octadiene, 1,9-decadiene, 1.11, 1.13, dodecadiene - tetradecadiene, 7-methyl-1,6-octadiene, 9-methyl -1,8-decadiene, or mixtures thereof. Even more preferably, the diene is selected from 1,7-octadiene, 1,9-decadiene, 1,11-dodecadiene, 1,13 tetradecadiene-, or any of their mixtures, however, without limit to the dienes above.
[000103] It is well known that, for example, propylene can be used as a comonomer or as a chain transfer agent (CTA), or both, whereby it can contribute to the total amount of carbon-double bonds. carbon, preferably with the total amount of vinyl groups. In the present invention, when a compound that can also act as a comonomer, such as propylene, is used as the CTA to provide the double bonds, then said copolymerizable comonomer is not calculated for the comonomer content.
[000104] If the second polyolefin (b), more preferably the LDPE polymer, is unsaturated, then it preferably has a total amount of carbon-carbon double bonds, which originate from vinyl groups, groups of vinylidene, and trans-vinylene groups, if present, more than 0.4 / 1000 carbon atoms, preferably more than 0.5 / 1000 carbon atoms. The upper limit on the amount of carbon-carbon double bonds present in the polyolefin is not limited and may preferably be less than 5.0/1000 carbon atoms, preferably less than 3.0/1000 carbon atoms.
[000105] In some embodiments, for example, where the highest level of crosslinking of low peroxide content is desired, the total amount of carbon-carbon double bonds, which originate from vinyl groups, vinylidene groups , and the trans-vinylene groups, if present, in unsaturated LDPE, is preferably greater than 0.40 / 1000 carbon atoms, preferably greater than 0.50 / 1000 carbon atoms, preferably greater than 0.60 / 1000 carbon atoms.
[000106] In a most preferred embodiment the second polyolefin (b) is unsaturated LDPE polymer as defined above and the polymer composition contains the preferable "accessible" peroxide content of the present invention as defined above or in the claims . The higher double bond content combined with the preferable "low" peroxide content further contributes to the low electrical conductivity. The embodiment is also preferable, for example, if high cable production speed or increased extrusion time, or both, is desired. The embodiment also contributes to the desirable mechanical and/or heat resistance properties being required for the layer, preferably layer, insulating material.
[000107] More preferably, the second polyolefin (b) is unsaturated LDPE as defined above and contains at least vinyl groups and the total amount of vinyl groups is preferably greater than 0.05 / 1000 carbon atoms , even more preferably greater than 0.08/1000 carbon atoms, and more preferably greater than 0.11/1000 carbon atoms. Preferably, the total amount of vinyl groups is up to 4.0 / 1000 carbon atoms. More preferably, the second polyolefin (b), before crosslinking, contains vinyl groups in the total amount of more than 0.20 / 1000 carbon atoms, even more preferably of more than 0.30 / 1000 atoms of carbon.
[000108] The second preferred polyolefin (b) for use in the polymer composition is an ethylene unsaturated LDPE copolymer with at least one polyunsaturated comonomer, preferably a diene as defined above, and optionally with another (s) comonomer(s). More preferably, such unsaturated ethylene LDPE copolymer with at least one polyunsaturated comonomer, preferably a diene as defined above, and optionally with another comonomer(s), contain vinyl groups . In this embodiment the total amount of vinyl groups is preferably as defined above, below, or in the claims. Said unsaturated LDPE copolymer is highly useful for the present invention, for use as the second polyolefin (b) of a polymer composition, preferably in an insulating layer of a power cable, preferably a power cable. DC power supply.
[000109] Typically, and preferably in wire and cable applications (W & C), the density of the second polyolefin (b), preferably the LDPE polymer, is greater than 860 kg / m3. Preferably, the density of the second polyolefin (b), preferably of the LDPE homopolymer or copolymer, is not more than 960 kg/m3, and preferably it is 900 to 945 kg/m3. The MFR2 (2.16 kg, 190°C) of the second polyolefin (b), preferably the LDPE polymer, is preferably 0.01 to 50 g / 10 min, more preferably 0.01 at 40.0 g / 10, more preferably it is 0.1 to 20 g / 10 min, and more preferably it is 0.2 to 10 g / 10 min.
[000110] Thus, the second polyolefin (b) of the present invention is an LDPE polymer, as defined above or in the claims, which is preferably produced at high pressure through free radical initiated polymerization (referred to as polymerization radical at high pressure (HP)). The reactor can be, for example HP a well known autoclave or tubular reactor, or a mixture thereof, preferably a tubular reactor. High pressure (HP), polymerization and the adaptation of process conditions for further adaptation of the other properties of the polyolefin depending on the desired end application are well known and described in the literature, and can be easily used by a person skilled in the art. Suitable polymerization temperatures range up to 400°C, preferably 80 to 350°C and at a pressure of 70 MPa, preferably 100 to 400 MPa, more preferably 100 to 350 MPa. Pressure can be measured at least after the compression phase and/or after the tubular reactor. Temperature can be measured at various points during all steps.
[000111] After the separation of LDPE is typically obtained in the form of a polymer melt, which is usually mixed and pelletized in a pelletizing section, such as the extruder pellet, arranged in connection with the reactor system of HP. Optionally, the additive(s), such as antioxidant(s), can be added to this mixer in a known manner.
[000112] More details on the production of ethylene (co)polymers by high pressure radical polymerization can be found in the Encyclopedia of Polymer Science and Engineering, vol. 6 (1986), pp 383 to 410 and 2001 Elsevier Science Ltd. Encyclopedia of Materials: Science and Technology: "Polyethylene: High-Pressure, R.Klimesch, D.Littmann and F.-O. Mahling pp. 7181 to 7184 .
[000113] When an ethylene unsaturated LDPE copolymer is prepared and then, as is well known, the carbon-carbon double bond content can be adjusted through the polymerization of ethylene, for example in the presence of one or more comonomer (s) polyunsaturated(s), chain transfer agent(s), or both, using the desired ratio of feed monomer, preferably ethylene, and polyunsaturated comonomer and/or agent of chain transfer, depending on the nature and amount of DC double bonds desired for the unsaturated LDPE copolymer. A.I. WO 9308222 describes a high pressure radical polymerization of ethylene with poly unsaturated monomers. As a result, unsaturation can be evenly distributed along the polymer chain in the form of random copolymerization. Furthermore, for example, WO 9635732 describes the high pressure radical polymerization of ethylene and a certain type of α w - polyunsaturated divinylsilaxanes. End uses and applications of the polymer composition of the present invention
[000114] The polymer composition of the present invention is most preferably used to produce a layer of a cable, preferably a power cable, more preferably a direct current (DC) power cable, including the preferred subgroups of they may be combined in any order, with the preferred subgroups and composition properties of the polymer and its components as defined above, below, or in the claims.
[000115] The present invention further provides a cable, preferably a power cable, more preferably a direct current (DC) power cable, comprising a conductor that is surrounded by at least one layer, which is preferably a insulating layer, wherein said at least one layer comprises, preferably consists of a polymer composition as defined above, below, or in the claims comprising (a) a polyolefin which is different than polyethylene from low density polyethylene (LDPE), (a) a polyolefin that is different than low density polyethylene (LDPE), (b) a second polyolefin that is different from polyolefin (a); (c) an ion exchange additive as defined above, below, or in the claims.
[000116] The preferred cable of the present invention is a power cable, preferably a direct current (DC) power cable, comprising a conductor that is surrounded by at least an inner semiconductor layer, an insulation layer and a layer semiconductor exterior, in this order, wherein at least one layer, preferably at least the insulating layer comprises, preferably consists of, a polymer composition as defined above, below, or in the claims comprising (a) a polyolefin which is different than low density polyethylene (LDPE), (b) a second polyolefin which is different from polyolefin (a); (c) an ion exchange additive as defined above, below, or in the claims.
[000117] Therefore, the inner semiconductor layer of the power cable preferably comprises a first semiconductor composition, the insulating layer preferably comprises an insulating composition and the outer semiconductor layer comprises of preferably, it consists of a second semiconductor composition. Thus, one of the compositions, preferably at least the insulating composition, more preferably comprises the polymer composition of the present invention.
[000118] The term "conductor" in the present invention means above and below that the conductor comprises one or more wires. Furthermore, the cable may comprise one or more such conductors. Preferably, the conductor is an electrical conductor and comprises one or more metal strands.
[000119] The first and second semiconductor compositions can be identical or different and comprise a polymer(s), which is preferably a polyolefin or a mixture of polyolefins and a conductive filler material, preferably carbon black. The (5) suitable polyolefin(s) is (are) for example polyethylene produced in a low pressure process or a polyethylene produced in an HP process (LDPE). The general description of polymer as indicated above in relation to polyolefin (a) and, respectively, in relation to the optional second polyolefin (b) applies also for suitable polymers for the semiconductor layers. Carbon black can be any conventional carbon black used in the semiconductor layers of a power cable, preferably in the semiconductor layer of a DC power cable. Preferably, carbon black has one or more of the following properties: a) primary particle size of at least 5 nm, which is defined as the number average particle diameter according to ASTM D3849 -95A, procedure of dispersion D; b) The iodine number of at least 30 mg / g according to ASTM D1510, c) the oil absorption number of at least 30 ml / 100 g, which is measured according to ASTM D2414 . Non-limiting examples of carbon blacks are, for example, acetylene carbon black, furnace carbon black and Ketjen carbon black, preferably furnace carbon black and acetylene carbon black. Preferably, the first and second semiconductor polymer compositions comprise 10 to 50% by weight of carbon black, based on the weight of the semiconductor composition.
[000120] The power cable, preferably the DC power cable, of the present invention is preferably crosslinkable, wherein at least one layer, preferably at least the insulating layer preferably comprises the polymer composition as defined above, below, or in the claims comprising (a) a polyolefin which is different than low density polyethylene (LDPE), (b) a second polyolefin which is different from polyolefin (a); (c) an ion exchange additive as defined above or in the claims, and a crosslinking agent, preferably a peroxide, in an amount of up to 110 mmols -OO- / kg of the polymer composition, preferably up to 90 mmols -OO- / kg of polymer composition, more preferably 1.0 to 75 mmols -O- O- / kg of polymer composition, preferably less than 50 mmols -OO- / kg of polymer composition polymer, preferably less than 40 mmols -OO- / kg of polymer composition, preferably less than 37 mmols -OO- / kg of polymer composition, preferably less than 35 mmols -OO- / kg of polymer composition preferably between 0.1 and 34 mmols -OO- / kg of polymer composition, preferably between 0.5 and 33 mmols -O- O- / kg of polymer composition, more preferably from 5.0 to 30 mmols -OO- / kg of the polymer composition, more preferably 7.0 to 30 mmols -OO- / kg of the polymer composition, c most preferably from 10.0 to 30 mmols -O-O-/kg of the polymer composition.
[000121] Of course, the most preferred subgroups of the above properties, the other properties, the variants and modalities as defined above or below for the polymer composition or for the polyolefin (a), the second polyolefin (b) or the additive of ion exchange (c) and the preferred crosslinking agent components thereof similarly apply to the power cable, preferably for the DC power cable, of the present invention.
[000122] As is well known, the cable may optionally comprise other layers, for example layers around the insulating layer or, if present, the outer semiconductor layers such as the screen(s), layer(s) coating, other protective layer(s) or any combination thereof.
[000123] The present invention also provides a process for producing a cable, preferably a power cable, more preferably a DC power cable, as defined above or in the claims, which is of preferably crosslinkable, wherein the process comprises the steps of - Applying onto a conductor, preferably by (co)extrusion, at least one semiconductive inner layer, preferably a layer comprising a first semiconductive composition, an insulating layer comprising a insulating composition and an outer semiconductor layer comprising a second semiconductor composition, in that order, wherein the composition of at least one layer, preferably the insulating layer preferably comprises, consists of the polymer composition comprising (a) a polyolefin which is different than low density polyethylene (LDPE), (b) a second polyolefin which is different from polyolefin (a); (c) an ion exchange additive as defined above or in the claims, and
[000124] Optionally, and preferably, a crosslinking agent, which is preferably a peroxide, in an amount of up to 110 mmols -OO- / kg of the polymer composition, preferably up to 90 mmols -OO- / kg of the composition of polymer, more preferably from 0 to 75 mmols -OO- / kg of the polymer composition, preferably less than 50 mmols -OO- / kg of the polymer composition, preferably less than 40 mmols -OO- / kg of polymer composition, preferably less than 37 mmols -O-O- / kg polymer composition, preferably less than 35 mmols -OO- / kg polymer composition, preferably between 0.1 and 34 mmols -OO- / kg of the polymer composition, preferably between 0.5 and 33 mmols -OO- / kg of the polymer composition, more preferably from 5.0 to 30 mmols -OO- / kg of the polymer composition, more than one preferably from 7.0 to 30 mmols -OO- / kg of the polymer composition, more preferably from 10.0 to 30 m mols -O-O- / kg of polymer composition. Preferably, the polymer composition comprises the cross-linking agent and the process comprises an additional step of cross-linking at least one polymer composition of said thermal insulation layer, in the presence of the cross-linking agent, preferably in an amount such as defined above under crosslinking conditions, and optionally and preferably crosslinking at least one, preferably both, of the first semiconductor composition of the inner semiconductor layer and the second semiconductor composition of the outer semiconductor layer, in the presence of a crosslinking agent under crosslinking conditions.
[000125] More preferably, a crosslinkable power cable, more preferably a crosslinkable DC power cable, more preferably a crosslinkable DC high voltage power cable, is produced, wherein the process comprises the steps of (a) - Providing and mixing, preferably a melt mixture in an extruder, optionally one and preferably the first crosslinkable semiconductor composition comprising a polymer, a carbon black and optionally another component(s) ( s) for an inner semiconductor layer, - Providing and mixing, preferably a melt mixture in an extruder, a crosslinkable polymer composition of the present invention comprising, preferably consisting of, (a) a polyolefin which is different than polyethylene from low density (LDPE), (b) a second polyolefin that is different from polyolefin (a); (c) an ion exchange additive as defined above or in the claims, and
[000126] Optionally, and preferably, a crosslinking agent, which is preferably a peroxide, in an amount of up to 110 mmols -OO- / kg of the polymer composition, preferably up to 90 mmols -OO- / kg of the composition of polymer, more preferably from 0 to 75 mmols -OO- / kg of the polymer composition, preferably less than 50 mmols -OO- / kg of the polymer composition, preferably less than 40 mmols -OO- / kg of polymer composition, preferably less than 37 mmols -O-O- / kg of polymer composition, preferably less than 35 mmols -OO- / kg of polymer composition, preferably between 0.1 and 34 mmols -OO- / kg of polymer composition, preferably between 0.5 and 33 mmols -OO- / kg of polymer composition, more preferably from 5.0 to 30 mmols -OO- / kg of polymer composition, more than preferably from 7.0 to 30 mmols -OO- / kg of the polymer composition, more preferably from 10.0 to 3 0 mmols -OO- / kg of polymer composition, by an insulating layer, - Supplying and mixing, preferably a melt mixture in an extruder, optionally, and preferably, the second crosslinkable semiconductor composition comprising a polymer, a carbon black and optionally other component(s) for an outer semiconductor layer, (b) apply on a conductor, preferably by co-extrusion, - A melt mixture of the first semiconductor composition obtained from step (a) for the purpose of forming the semiconductor inner layer, - A melt mixture of the polymer composition of the present invention obtained from step (a) for the purpose of forming the insulating layer, and - A melt mixture of the second semiconductor composition obtained from step (a) for the purpose of forming the outer semiconductor layer, and (c) optionally crosslinking, in the presence of a crosslinking and crosslinking agent in the conditions of one or more of the polymer composition of the insulating layer, the first semiconductor composition of the inner semiconductor layer and the second semiconductor composition of the outer semiconductor layer, the obtained cable, preferably at least the polymer composition of the insulating layer, of preferably the polymer composition of the insulating layer, the first semiconductor composition of the inner semiconductor layer and the second semiconductor composition of the outer semiconductor layer.
[000127] Mixing by means of melting means mixing above the point of at least the main polymer component(s) of the mixture obtained from melting and is carried out, for example, without limiting to, at a temperature at least 15 °C above the melting or softening point of the polymer component(s).
[000128] The term "(co)extrusion" means in the present invention that in the 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 into one same extrusion step, well known in the art. The term "(co)extrusion" in the present invention also means that all or part of the layer(s) are formed simultaneously using one or more extrusion heads.
[000129] As is well known, the polymer composition of the present invention and the optional and preferred first and second semiconductor compositions can be produced before or during the cable production process. Furthermore, the polymer composition of the present invention and the optional and preferred first and second semiconductor compositions each independently comprise part or all of the component(s) of the final composition, prior to introducing the (melting) phase a) of the cable production process.
[000130] Preferably, the polymer composition of the present invention and optionally the first and second optional semiconductor compositions are provided for the cable production process in powder, grain or pellet form. Pellets generally in the present invention mean any polymer product that is formed from reactors made of polymers (obtained directly from the reactor), by means of a post-reactor modification of particles of a solid polymer. A known post-reactor modification is a pelletizing of the melt mixture of a polymer product and optional additive(s) in a pelletizing equipment for solid pellets. Pellets can be of any shape and size. Furthermore, the polyolefin components (a) and (b) can be combined into the same powder, grains or granulated products, which therefore contain a mixture of solid polyolefin polymer (a) and the second polyolefin (b). Alternatively and preferably, the polyolefin (a) and the second polyolefin (b) are supplied separately, for example as two separate pellet products for the cable production process.
[000131] The ion exchange additive(s) may be present in pellets comprising the two polyolefin components (a) and (b), or, in the case of the individual pellets of each polyolefin component, then , in any of the separate pellets. Alternatively the ion exchange additive (c) can be added to the polymer components during the cable production process.
[000132] All or part of the optional additives may be present in any such powders, grains or pellets or added separately.
[000133] In this way, the polyolefin (a) and the second polyolefin (b) of the polymer composition can be pre-mixed, for example, melt blended together and pelletized, before feeding to the blending step (a). Alternatively and preferably, these components can be supplied, for example, in separate pellets to the mixing (melting) step (a), where the pellets are mixed together. As stated above, the ion exchange additive (c) can be present in either of the separate pellets or added during the mixing (melting) step (a). Preferably, the ion exchange additive (c) is present in at least the polyolefin (a) of the component, which is preferably a polyethylene produced in the presence of an olefin polymerization catalyst as defined above or in the claims .
[000134] The step of mixing (melting) (a) the polymer composition provided of the present invention and the first and second preferred semiconductor compositions is preferably carried out in a cable extruder. Step a) of the cable production process may optionally comprise a separate mixing step, for example in a mixer arranged in connection with and before the cable extruder of the cable production line. Mixing in a preceding separate mixer can be carried out by mixing, with or without external heating (heating with an external source) of the component(s). In the case of a polyolefin (a), the second polyolefin (b) and the ion exchange additive (c), or the optional and preferred peroxide(s) and a part or all of the optional additional component(s), such as a major additive(s), the polymer composition of the present invention and, respectively, a part or all of the component(s) s) of the first or second semiconductor compositions, are added to the polyolefin during the cable production process, after the addition(s) can take place at any stage during the mixing step (a), by example, in the separate optional mixer preceding the cable extruder or at any point(s) on the cable extruder. The addition of the optional and preferred peroxide(s) may be done simultaneously or separately, such as, preferably in liquid form, or in a well-known master batch, and at any stage during the mixing step (a).
[000135] The polymer composition preferably comprises a crosslinking agent, which is preferably peroxide. The cross-linking agent can be added before the cable production process or during the mixing (melting) step (a). For example, and preferably, the cross-linking agent, and also the optional additional component(s), such as additive(s), may already be present in at least one of the polyolefins. ) or the second polyolefin (b) before use in the production line of the cable production process. The crosslinking agent can be, for example, mixed by melting together with the polyolefin (A) or the second polyolefin (b), or both, or a mixture thereof, and other optional component(s) , and then the mixture by means of melting is pelletized. Alternatively and preferably, the crosslinking agent is added, preferably impregnated with the solid polymer particles, preferably pellets, the polyolefin component(s) or polymer composition.
[000136] It is preferable that the melt blending of the polymer composition obtained from the melt blending of step (a) comprises the polyolefin (a) and the second polyolefin (b) of the present invention, such as the individual polymer components. The ion exchange additive (c) and the optional and preferred additive(s) may be added to the polymer composition as such or as a mixture with a carrier polymer, i.e., in a form of master batch call.
[000137] In a preferred embodiment of the cable production process, the crosslinkable power cable, preferably a crosslinkable DC power cable, more preferably a crosslinkable high voltage DC power cable, is produced, wherein the insulating layer comprises, preferably consists of, a crosslinking polymer composition of the present invention, which further comprises a peroxide in an amount as indicated above or below, and wherein the second polyolefin (b) is optionally, and of preferably, an unsaturated LDPE homo or copolymer, and wherein at least the insulating layer of the obtained crosslinkable cable is crosslinked in step c) under crosslinking conditions.
[000138] Therefore, the present invention further provides a crosslinking electrical cable, preferably a DC power crosslinking cable, more preferably a crosslinking DC high voltage power cable, wherein at least the layer comprising the polymer composition of the present invention, as defined above or in the claims, is cross-linked.
[000139] The crosslinking of the polymer composition of the insulating layer is preferably carried out in the presence of a peroxide, in an amount as defined above or below the claims, and the optional and preferable crosslinking of the first semiconductor composition of the interior semiconductor is The presence of a crosslinking agent(s) is carried out, preferably in the presence of a free radical generating agent(s), which is preferably a peroxide(s).
[000140] The crosslinking agent(s) may (m) already be present in the first and second optional semiconductor composition before introducing step c) crosslinks or introduced during the crosslinking step. Peroxide is the preferred crosslinking agent for said optional first and second semiconductor compositions and is preferably included for the semiconductor composition pellets before the composition is used in the cable production process as described above.
[000141] Crosslinking can be carried out at an increase in temperature, which is chosen, as well known, depending on the type of crosslinking agent. For example, temperatures above 150°C, such as 160 to 350°C, are typical, but not limited to them.
[000142] Processing temperatures and devices are well known in the art, for example mixers and extruders such as conventional single or twin screw extruders are suitable for the process of the present invention.
[000143] The present invention further provides a crosslinked power cable, preferably a direct current (DC) power cable, preferably a crosslinked DC high voltage power cable, wherein the inner semiconductor layer preferably comprises , consists of an optionally crosslinked first semiconductor composition, the polymer composition of the insulating layer comprises, preferably consists of, a crosslinked polymer composition of the present invention as defined above or in the claims, and the outer semiconductor layer comprises, preferably consists of a second optionally crosslinked semiconductor composition, more preferably wherein the inner semiconductor layer comprises, preferably consists of a first crosslinked semiconductor composition, the polymer composition of the insulating layer comprises of preferably, it consists of a cross-linked polymer composition according to with any of the preceding claims, and the outer semiconductive layer preferably comprises, optionally, a crosslink, preferably a second crosslinked semiconductor composition.
[000144] The preferred DC power cable of the present invention is a high voltage DC power cable. Preferably, the high voltage DC power cable operates with voltages as defined above for the high voltage DC cable or the extra high voltage DC cable, depending on the desired final cable application.
[000145] Furthermore, the power cable, preferably the DC power cable, more preferably the high voltage DC power cable, of the present invention is crosslinked as described above.
[000146] The thickness of the insulation layer of the DC power cable, preferably more of the high voltage DC power cable, is generally 2 mm or more, preferably at least 3 mm, preferably at least 5 at 100 mm, more preferably 5 to 50 mm and conventionally between 5 and 40 mm, for example 5 to 35 mm when measured from a cross section of the cable insulation layer. The thickness of the inner and outer conductive layers is generally less than that of the insulation layer, and high voltage DC power cables can be, for example more than 0.1 mM, such as from 0.3 to 20 mm, 0.3 to 10 semiconductor and the inner semiconductor outer layer. The thickness of the semiconductor inner layer is preferably from 0.3 to 5.0 mm, preferably from 0.5 to 3.0 mm, preferably from 0.8 to 2.0 mm. The thickness of the outer semiconductor layer is preferably 0.3 to 10 mm, such as 0.3 to 5 mm, preferably 0.5 to 3.0 mm, preferably 0.83.0 mm. It is evident within the abilities of a person skilled in the art that the thickness of the layers of the current cable depends on the voltage level of the cable that is intended for the final application and can be chosen accordingly. Determination Methods
[000147] Unless otherwise stated, in the description or experimental part the following methods were used for property determinations. Wt %: % by weight Melt Flow Index
[000148] The melt flux index (MFR) is determined in accordance with ISO 1133 and is stated in g / 10 min. The MFR is an indication of the fluidity and therefore the processability of the polymer. The higher the melt flow index, the lower the polymer viscosity. The MFR is determined at 190 °C for polyethylene and at 230 °C for polypropylene. MFR can be determined at different loads such as 2.16 kg (MFR2) or 21.6 kg (MFR21). Molecular weight
[000149] Mz, Mw, Mn, and MWD are measured by Gel Permeation Chromatography (GPC), according to the following method:
[000150] The weight average molecular weight Mw and the molecular weight distribution (MWD = MW / Mn where Mn is the number average molecular weight and Mw is the weight average molecular weight; Mz is the z average molecular weight ) is measured in accordance with ISO 16014 - 4: 2003 and ASTM D 6474 - 99. A Waters GPCV2000 instrument, equipped with a refractive index detector and in-line viscometer was used with the 2 x GMHXL -HT and 1x G7000HXL columns -HT TSK- gel from Tosoh Bioscience and 1,2,4 - trichlorobenzene (TCB, stabilized with 250 mg/L 2,6- Di - tert -butyl-4-methyl-phenol) as solvent at 140 °C and at a constant flow rate of 1 mL/min. 209.5 mL of sample solution was injected through the analysis. The column assembly has been calibrated using Universal Calibration (according to ISO 16014-2: 2003) with at least 15 MWD Narrow Polystyrene (PS) standards in the range of 1 kg/mol to 12 000 kg/mol. Mark Houwink constants were used as given in ASTM D 6474-99. All samples were prepared by dissolving 0.5 to 4.0 mg of polymer in 4 ml (at 140 °C) of stabilized TCB (same as mobile phase) and holding for approximately 3 hours at one temperature maximum 160°C with continuous gentle agitation prior sampling in the GPC apparatus. Comonomer contents a) the comonomer content in polypropylene random copolymer:
[000151] Quantitative Fourier Transformed Infrared Spectroscopy (FTIR) was used to quantify the amount of comonomer. Calibration was performed by correlation of comonomer content determined by quantitative nuclear magnetic resonance (NMR) spectroscopy.
[000152] The calibration procedure based on the results obtained from quantitative 13C-NMR spectroscopy was carried out in the conventional way well documented in the literature.
[000153] The amount of comonomer (N) was determined as percentage by weight (% by weight) by:
where A is the maximum defined absorbance of the comonomer band, where R is the maximum absorbance defined as the height of the reference peak and with linear constants k1 and k2 obtained through calibration. The band used for quantifying the ethylene content is selected depending on whether the ethylene content is random (730 cm -1) or block type (as in PP heterophasic copolymer) (720 cm-1). Absorption at 4324 cm - 1 was used as a reference band. b) The quantification of alpha-olefin content in linear low density polyethylenes and low density polyethylenes, by means of NMR spectroscopy:
[000154] The comonomer content was determined by means of resonance spectroscopy (NMR), quantitative 13C nuclear magnetic spectroscopy after base assignment (J. Randall JMS - Rev. Macromol Chem Phys, C29 (2 & 3), 201a 317 (1989) Experimental parameters were adjusted to ensure quantitative measurement of spectra for this specific task.
[000155] Specifically, solution-state NMR spectroscopy was employed using a Bruker AvanceIII 400 spectrometer. Homogeneous samples were prepared by dissolving about 0.200 g of polymer in 2.5 ml of deuterated tetrachloroethane in tubes. 10mm sample, using a heating block and rotating furnace tube at 140 C. The proton uncoupled single 13C NMR pulse spectrum with NOE (one for) were recorded using the following acquisition parameters: a thrown angle of 90 degrees , 4 false scans, 4096 transients at an acquisition time of 1.6s, a spectral width of 20 kHz, a temperature of 125 C, a WALTZ proton dissociation scheme and a relaxation delay of 3.0 s. The resulting FID was processed using the following processing parameters: zero padding to 32k data points and apodization, using a Gauss window function; first-order and automatic zero-order phase correction and and automatic baseline correction using a fifth-order polynomial restricted to the region of interest.
[000156] Amounts were calculated using the simple corrected proportions of the sign integral numbers of representative locations based on methods well known in the art. c) the comonomer content of polar comonomer in low density polyethylene (1) polymers containing > 6 wt% units of polar comonomer.
[000157] The comonomer content (% by weight) was determined in a known way based on Fourier Transformed Infrared Spectroscopy (FTIR), calibrated with quantitative nuclear magnetic resonance (NMR) determination. Below is exemplified the determination of polar comonomer content of ethyl ethylene acrylate, butyl ethylene acrylate and methyl ethylene acrylate. Polymer film samples were prepared for FTIR measurement: 0.5 to 0.7 mm thick was used for butyl ethylene acrylate and ethyl ethylene acrylate and 0.10 mm thick ethylene acrylate film in amount of > 6% by weight. Films were pressed using a Specac film press at 150 °C, at approximately 5 tons, 1 to 2 minutes, and then cooled with cold water in an uncontrolled manner. The exact thickness of the film samples was obtained.
[000158] After analysis with FTIR, baselines in absorbance mode were drawn for the peaks to be analyzed. The absorbance peak for the comonomer was normalized with the polyethylene absorbance peak (eg, the peak height of butyl acrylate or ethyl acrylate at 3450 cm-1 was divided with the peak height of polyethylene at 2.020 cm -1). The NMR spectroscopy calibration procedure was carried out in the conventional manner, which is well documented in the literature, explained below.
[000159] For the determination of the methyl acrylate content, a 0.10 mm thick film sample was prepared. After analyzing the maximum absorbance for the peak for methyl acrylate at 3455 cm -1 it was subtracted with the absorption value for the baseline at 2475 cm -1 (Amethylacrylate - A2475). Then, the maximum peak absorbance of the polyethylene peak of 2660 centimeters -1 was subtracted with the absorbance value for the baseline of 2.475 centimeters -1 (A2660, A2475). The ratio between (Amethylacrylate - A2475) and (A2660 - A2475) was then calculated in the conventional manner, which is well documented in the literature.
[000160] Weight % can be converted to mol % by calculation. It is well documented in the literature.
[000161] The quantification of copolymer content in polymers by NMR spectroscopy
[000162] The comonomer content was determined by means of resonance spectroscopy (NMR), quantitative nuclear magnetic spectroscopy after base assignment (eg, "NMR spectra of Polymers and Polymer Additives", AJ Brandolini and DD Hills, 2000, Marcel Dekker, Inc., New York). Experimental parameters were adjusted to ensure quantitative spectra measurement for this specific task (eg, "200 and more NMR Experiments: A Practical Course", S. Berger and S. Braun, 2004, Wiley-VCH, Weinheim). Amounts were calculated using the simple corrected proportions of the signal integrals from representative sites in a manner known in the art. (2) Polymers containing 6% by weight or less polar Comonomer Units
[000163] The comonomer content (% by weight) was determined in a known way based on Fourier transform infrared spectroscopy (FTIR), calibrated with quantitative nuclear magnetic resonance (NMR) determination. Below is exemplified the determination of the polar comonomer content of ethylene butyl acrylate and ethylene methyl acrylate. For FT-IR measurement of 0.05-0.12 mm thick film samples were prepared as described above in method 1). The exact thickness of the obtained film samples was measured.
[000164] After analyzing FT-IR baselines in absorbance mode were drawn for the peaks to be analyzed. The maximum absorbance for the peak for the comonomer (eg, methyl acrylate at 1.164 cm -1 and 1.165 cm for butylacrylate -1) was subtracted with the absorption value for the baseline at 1850 cm-1 (Apolar comonomer - A1850). Then, the maximum absorption peak for the polyethylene peak at 2660 cm -1 was subtracted with the absorbance value for the baseline of 1850 cm -1 (A2660 - A1850). The ratio between (Acomonomer - A1850) and (A2660 - A1850) was then calculated. The NMR spectroscopy calibration procedure was performed in the conventional manner, which is well documented in the literature, as described above under method 1).
[000165] Weight % can be converted to mole % by calculation. It is well documented in the literature.
[000166] Below is exemplified how the polar comonomer content, obtained from the preceding method (1) or (2), depending on the amount thereof, can be converted to micromol or mmols per g of polar comonomer as used in the definitions in the text and in the claims:
[000167] The millimols (mmols) and micromol calculations have been made as described below.
[000168] For example if 1 g of polymer poly(ethylene-co-butyl acrylate) which contains 20% by weight of butyl acrylate then this material contains 0.20 / Mbutylacrylate (128 g / mol) = 1.56 x 10-3 mol. (=1.563 micromol).
[000169] The content of polar comonomer units in the polar copolymer of the CCOpolar monomer is expressed in mmols / g (copolymer). For example, a polar poly(ethylene-co-butyl acrylate) polymer, which contains 20% by weight of butyl acrylate comonomer units has a polar CCO monomer of 1.56 mmols/g.
[000170] The molecular weights used are: Mbutylacrylate = 128 g / mol, Methylacrylate = 100 g / mol, Mmethylacrylate = 86 g / mol). Density
[000171] Low Density Polyethylene (LDPE): Density was measured in accordance with ISO 1183-2. Sample preparation was performed in accordance with ISO 1872-2 Table 3 Q (compression molding).
[000172] Low pressure polyethylene process: polymer density was measured according to ISO 1183 / 1872-2B. Method for determining the amount of double bonds in the polymer composition or polymer A) Quantification of the amount of carbon-carbon double bonds by IR spectroscopy
[000173] Quantitative Infrared Spectroscopy (IR) was used to quantify the amount of carbon-carbon double bonds (C = C). Calibration was performed by prior determination of the C = C molar extinction coefficient of functional groups present in representative low molecular weight compounds of the known structure model.
[000174] The quantity of each of these groups (N) was determined as the number of carbon-carbon double bonds per thousand total carbon atoms (C = C / 1000C) by means of:
was that A is the maximum absorbance defined as the height of the peak, and the molar extinction coefficient of the group in question (L mol -1 • • mm -1), L the thickness (mm) and D the density of the material (g • cm-1).
[000175] The total amount of C = C bonds per thousand total carbon atoms can be calculated by summing N for the individual C = C containing components.
[000176] For polyethylene samples of solid-state infrared spectra were recorded using an FTIR spectrometer (Perkin Elmer 2000) molded by compression into thin (0.5-1.0 mm) films at a resolution of 4 cm-1 and analyzed in absorption mode. 1) Polymer compositions comprising polyethylene homopolymers and copolymers, with the exception of polyethylene copolymers with >0.4% by weight of polar comonomer
[000177] For polyethylenes three types of C = C containing functional groups were quantified, each with a characteristic absorption and each calibrated for a different model compound, resulting in individual extinction coefficients: • vinyl (R-CH = CH2 ), through 910 centimeters -1 based on 1 -decene [ dec-1 -ene ] giving E = 13.13 l • mol -1 • mm -1 • vinylidene (RR'C = CH2) via 888 centimeters -1 based on 2-methyl -1-heptene [2-methylhept -1 -ene ] giving E = 18.24 l • mol - 1 • mm -1 • trans-vinylene (R-CH = CH -R'), through 965 centimeters -1 based on trans-4-decene [(E)-dec-4-ene ] giving E = 15.14 l • mol -1 • mm -1
[000178] For polyethylene homopolymers or copolymers with <0.4% by weight polar comonomer linear baseline correction was applied between about 980 and 840 cm-1. 2) Polymer compositions comprising polyethylene copolymers with >0.4% by weight of polar comonomer
[000179] For polyethylene copolymers with >0.4% by weight of polar comonomer two types of C = C that contain the functional groups were quantified, each with a characteristic absorption and each calibrated for a different model compound, resulting at individual extinction coefficients: • vinyl (R-CH = CH2), through 910 centimeters -1 based on 1 -decene [dec-1 -ene] giving E = 13.13 l • mol -1 • mm -1 • vinylidene (RR'C = CH2) via 888 cm -1 based on 2-methyl -1- heptene [2- methyl- hept -1 -ene ] giving E = 18.24 l • mol -1 • mm -1 EBA:
[000180] For poly(ethylene-co-butyl acrylate) (EBA), linear baseline correction systems were applied between about 920 and 870 cm- 1. EMA:
[000181] For poly(ethylene-co-methyl acrylate) (EMA) linear baseline correction of systems was applied between about 930 and 870 cm-1. 3) Polymer compositions comprising the low weight molecules molecular unsaturated
[000182] For systems containing low molecular weight C = C that contain species direct calibration using the molar extinction coefficient of C = C absorption in the low molecular weight species itself was performed. B) Quantification of molar extinction coefficients by IR spectroscopy
[000183] The molar extinction coefficients were determined according to the procedure indicated in ASTM D3124 -98 and ASTM D6248 -98. Solution-state infrared spectra were recorded using an FTIR spectrometer (Perkin Elmer 2000) equipped with a 0.1 mm net cell length path at a resolution of 4 cm-1.
[000184] The molar extinction coefficient (E) was determined as 1 • mol -1 • mm-1 through:
where A is the maximum absorbance defined as the peak height, C the concentration (mol • L-1) and L the cell thickness (mm).
[000185] At least three 0.18 mol • L-1 solutions in carbon disulfide (CS2) were used and the mean value of the molar extinction coefficient determined. DC conductivity method
[000186] Plates are compression molded from pellets of the test polymer composition. The final plates consist of test polymer composition and have a thickness of 1 mm and a diameter of 330 mm.
[000187] Conductivity measurement can be performed using a test polymer composition that does not comprise or comprises the optional crosslinking agent. In the case of no crosslinking agent the conductivity is measured from an uncrosslinked plate sample using the procedure described below. If the test polymer composition comprises the crosslinking agent, crosslinking then occurs during the preparation of the slab samples, wherein the conductivity is then measured according to the procedure described below from the resulting crosslinked slab sample . The crosslinking agent, if present in the polymer composition prior to crosslinking, is preferably a peroxide, as herein.
[000188] The plates are press molded at 130 °C for 12 min, while the pressure is gradually increased from 2 to 20 MPa. Then the temperature is increased and reaches 180 °C after 5 min. The temperature is then kept constant at 180°C for 15 min during which the board becomes completely cross-linked by means of peroxide, if present in the test polymer composition. Finally, the temperature is lowered, using a cooling rate of 15°C/min, until the ambient temperature is reached when the pressure is released. The plates are wrapped in a sheet of metal immediately after releasing pressure in order to prevent the loss of volatile substances.
[000189] The high voltage source is connected to the top electrode to apply voltage across the test sample. The resulting current through the sample is measured with an electrometer. The measuring cell is a three-electrode system with bronze electrodes. Metal electrodes are equipped with heating tubes connected to a heating circulator to facilitate measurements at elevated temperature and provide uniform temperature of the test sample. The diameter of the measuring electrode is 100 mm. Silicone rubber skirts are placed between the edges of the copper electrode and the test sample to prevent Flashovers from the rounded edges of the electrodes.
[000190] The applied voltage was 30 kV DC meaning an average electric field of 30 kV / mm. The temperature was 70°C. The current across the plate was recorded over the entire 24-hour experiments. The current after 24 hours was used to calculate the insulation conductivity.
[000191] This method and a schematic picture of the measurement setup for conductivity measurements have been exhaustively described in a publication presented at the Nordic Isolation Symposium 2009 (Nord -IS 09), Gothenburg, Sweden, June 15-17, 2009, page 55 to 58 : Olsson et al, "Experimental determination of DC conductivity for XLPE insulation". experimental part The preparation of the components of the polymer compositions of the present invention and the reference composition
[000192] LDPE1 (polyolefin (b)) : The polyolefin was low density polyethylene produced in a high pressure reactor. The production of polymers of the present invention and reference is described below. As with CTA feeds, for example, the PA content can be given as liter/hour or kg/hr, and converted to units using either a PA density of 0.807 kg/liter for the new calculation.
[000193] Recycled CTA ethylene was compressed in a 5-stage pre-compressor and a two-stage hyper-compressor with intermediate cooling to reach an initial reaction pressure of about 2628 bar. The total efficiency of the compressor was ca 30 tons/hour. In the compressor area approximately 4.9 liters/hour of propionic aldehyde (PA, CAS Number: 123-38-6) was added together with approximately 81 kg of propylene/hour as chain transfer agents to maintain an MFR of 1.89 g / 10 min. In the present invention also 1,7-octadiene was added to the reactor in an amount of 27 kg/h. The tablet mixture was heated to 157°C in a pre-heat section of a two-zone forward feed of the tubular reactor. A commercially available mixture of peroxide radical initiators dissolved in isododecane was injected just after the preheater, in an amount sufficient for the exothermic polymerization reaction to reach peak temperatures of ca 275°C, after which it was cooled to about 200 °C. The subsequent reaction temperature of the second peak was 264 °C. The reaction mixture was depressurized by means of a backflow valve, cooled and the polymer was separated from the unreacted gas. Table 1: LDPE1 Polymer Properties

[000194] HDPE (polyolefin (a)) : A conventional unimodal high density polyethylene (0.8 mol% of the content of butene-1 as the comonomer) which is produced in a gas phase reactor. HDPE has an MFR2 of 12g / 10min (190 °C / 2.16 kg) and a density of 962 kg / m3. The same base resin, except that, combined with an additive system other than that specified in table 2, is used in a commercially available grade Bormed HE9621 -PH (Borealis company).
[000195] Ion exchange additive (c): Synthetic hydrotalcite (IUPAC name: Hexadecahydroxide Hexamagnesium Dialuminum Carbonate, CAS 11097-59-9), supplied by Kisuma Chemicals under the trade name DHT-4V.
[000196] Cross-linking agent : Peroxide : dicumylperoxide, DCP (CAS 80-43-3), Commercially available.
[000197] Antioxidant (AO): 4,4'-thiobis (2-tert-butyl-5-methylphenol) (CAS # 96-69-5.), Commercially available.
[000198] Flame Retardant (SR) : 2,4-Diphenyl-4-methyl-1-pentene (CAS 6362-80-7.), Commercially available.
[000199] Acid Sequestrant (Cast) : Commercial Calcium Stearate CAS no. 1592-23-0, commercially available.
[000200] Acid sequestrant (ZnSt) : Commercial Zinc Stearate CAS no. 557-05-1, commercially available.
[000201] Composition of polymer compositions : Each polymer component of polymer test compositions were added as separate pellets to a pilate scale extruder (Prism TSE 24TC), together with additives, if not present in the pellets, except of the crosslinking agent and SR. The obtained mixture was melt blended under conditions given in the table below and extruded into pellets in a conventional manner.

[000202] The crosslinking agent, the peroxide in the present invention, and SR, if present, were added in liquid form, in which the pellets and the resulting pellets were used for the experimental part. Table 2: Polymer compositions of the present invention and reference compositions and electrical conductivity results:
* The weight % amounts of polymer components in the table are based on the combined amount of polymer components used. The amount of 100% by weight of the polymer component in table 1 means that the polymer is the only component of the polymer. ** Amounts of wt% ion exchange additive (c), acid scavenger, peroxide (wt%), AO and SR are based on final composition.
[000203] Cable preparation: The polymer composition of the present invention was used for the purpose of producing an insulating layer of a power cable.
[000204] Extrusion power cable. A three-layer cable was made using a commercial composite as an inner and outer semiconductor layer. The middle insulating layer was formed from the polymer composition of the present invention. The cable construction was 50mm2 of standard Al conductors and 5.5mm of insulation thickness. The inner and outer semiconductor layers were 1 mm and 1 mm thick, respectively. The cable line was a Nokia Maillefer +2 catenary system, so an extrusion head for the inner conduction layer and one for the insulation + outer semiconductor layer.
[000205] The uncrosslinked cable has been cooled in water.
[000206] If the cable was crosslinked, then crosslinking was performed in vulcanizing tube under nitrogen and then cooled in water.
[000207] The obtained cable has a low conductivity and shows the applicability of the polymer composition of the present invention as a cable layer, preferably as an insulating layer, the power cable, for example, an application of a cable HV DC power supply.

权利要求:
Claims (18)
[0001]
1. Cable, characterized in that it comprises a conductor surrounded by at least one layer, wherein the at least one layer comprises a polymer composition comprising (a) polyethylene produced in the presence of an olefin polymerization catalyst and selected from very low density polyethylene (VLDPE), linear low density polyethylene copolymers (LLDPE), medium density polyethylene copolymers (MDPE) or high density polyethylene homopolymers or copolymers (HDPE); and (b) an optionally unsaturated low density polyethylene (LDPE) homopolymer or an optionally unsaturated low density polyethylene copolymer with one or more comonomer(s), and (c) an ion exchange additive.
[0002]
2. Cable according to claim 1, characterized in that it is a power cable.
[0003]
3. Cable according to claim 2, characterized in that it is a DC power cable.
[0004]
4. Cable according to any one of claims 1 to 3, characterized in that the polymer (a) is a unimodal or multimodal HDPE or MDPE.
[0005]
5. Cable according to any one of claims 1 to 4, characterized in that the second polyolefin (b) is an unsaturated LPDE polymer, which is selected from an unsaturated LDPE homopolymer or an LDPE copolymer unsaturated ethylene with one or more comonomer(s).
[0006]
6. Cable according to any one of claims 1 to 5, characterized in that the polyolefin (b) is an ethylene unsaturated LDPE copolymer with at least one polyunsaturated comonomer and optionally with one or more other comonomer(s), in which the polyunsaturated comonomer is constituted by a straight carbon chain with at least 8 carbon atoms and at least 4 carbons between unconjugated double bonds, of which at least one is terminal.
[0007]
7. Cable according to claim 6, characterized in that the poly-unsaturated comonomer is 1,7-octadiene, 1,9-decadiene, 1,11-dodecadiene, 1,13 - tetradecadiene, 7-methyl - 1,6-octadiene, 9-methyl-1,8-decadiene, or mixtures thereof.
[0008]
8. Cable according to any one of claims 1 to 7, characterized in that the polyolefin (b) contains vinyl groups in the total amount of more than 0.20/1000 carbon atoms.
[0009]
9. Cable according to any one of claims 1 to 8, characterized in that the ion exchange additive (c) is a non-organic ion exchange additive.
[0010]
10. Cable according to any one of claims 1 to 9, characterized in that the ion exchange additive (c) is an anion exchange additive of the hydrotalcite type.
[0011]
11. Cable according to any one of claims 1 to 10, characterized in that the polymer composition comprises the ion exchange additive (c), as such, that is, pure, in an amount of less than 1% by weight .
[0012]
12. Cable according to any one of claims 1 to 11, characterized in that the amount of polyolefin (a) is from 0.5 to 80% by weight, based on the combined weight of the polyolefin (a) and the second polyolefin (b).
[0013]
13. Cable according to any one of claims 1 to 12, characterized in that the amount of the second polyolefin (b) is 20 to 99.5% by weight, based on the combined weight of the polyolefin (a) and the second polyolefin (b).
[0014]
14. Cable according to any one of claims 1 to 13, characterized in that the polymer composition further comprises a crosslinking agent.
[0015]
15. Cable according to any one of claims 1 to 14, characterized in that it comprises a conductor surrounded by at least one inner semiconductor layer, an insulating layer and an outer semiconductor layer, in that order, in which the insulating layer comprises said polymer composition.
[0016]
16. Power cable according to any one of claims 1 to 15, characterized in that it is a direct current (DC) crosslinkable power cable, wherein said polymer composition of the layer as defined in claim 1 or the insulating layer as defined in claim 15 further comprises a cross-linking agent.
[0017]
17. Power cable according to any one of claims 1 to 16, characterized in that it is a direct current (DC) crosslinkable power cable, in which the inner semiconductor layer comprises a first optionally crosslinked semiconductor composition, the polymer composition of the insulating layer comprises a polymer composition as defined in any one of claims 1 to 16 which is crosslinked in the presence of said crosslinking agent and the outer semi-inductive layer comprises an optionally crosslinked second semiconductor composition.
[0018]
18. Process for the production of a power cable, as defined in any one of claims 1 to 17, characterized in that the process comprises the following steps: - Application on a conductor at least one layer comprising a composition of polymer, wherein the polymer composition of at least one layer comprises a polymer composition as defined in any one of claims 1 to 17 and optionally further comprises a crosslinking agent.

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同族专利:

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公开号 | 公开日

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KR20140031928A|2014-03-13|

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EP2705087B1|2017-03-01|

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US9978478B2|2018-05-22|

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RU2614767C2|2017-03-29|

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EP2705087A1|2014-03-12|

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KR102024393B1|2019-09-23|

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BR112013028128A2|2017-09-19|

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CN103608394A|2014-02-26|

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WO2012150285A1|2012-11-08|

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CN103608394B|2016-08-17|

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JP2014518907A|2014-08-07|

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JP6255337B2|2017-12-27|

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US20140093732A1|2014-04-03|

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法律状态:
2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2020-03-31| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-08-04| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2020-11-24| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2021-03-23| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-06-01| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 03/05/2012, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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EP11164779|2011-05-04|

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EP11164779.8|2011-05-04|

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PCT/EP2012/058078|WO2012150285A1|2011-05-04|2012-05-03|Polymer composition for electrical devices|

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