DIRECT CURRENT (DC) RETICULATED POWER CABLE AND PROCESS FOR THE SAME PRODUCTION

专利摘要:
polymer composition that can be cross-linked and cable with advantageous electrical properties. the invention relates to a composition of polymers with improved electrical properties of cd and cable surrounded by at least one layer comprising the composition of polymers.
公开号:BR112012011131B1
申请号:R112012011131-0
申请日:2010-11-03
公开日:2021-03-30
发明作者:Birgitta Kãllstrand；Ulf Nilsson；Gustavo Dominguez；Liu Rongsheng；Annika Smedberg；Per-Ola Hagstrand；Villgot Englund；Carl-Olof Olsson；Marc Jeroense
申请人:Borealis Ag；
IPC主号:

专利说明:

Field of the Invention
[0001] The invention relates to a polymer composition comprising a polyolefin, a method for reducing the electrical conductivity of a polymer composition that can be cross-linked, a process for producing an article that can be cross-linked and cross-linked , a power cable that can be cross-linked and cross-linked, more preferably a direct-current power cable (CD) that can be cross-linked and cross-linked, which comprises the composition of polymers, as well as the use of the composition of polyolefin in a layer of power cable. Background Technology
[0002] Polyolefins produced in a high pressure process (HP) are widely used in polymer applications on demand where polymers have to satisfy high mechanical and / or electrical requirements. For example, in power cable applications, particularly in medium voltage (MV) and especially in high voltage (HV) and extra high voltage (EHV) cable applications, the electrical properties of the polymer composition are of significant importance. In addition, electrical properties of importance may differ in different cable applications, as is the case between alternating current (AC) and direct current (CD) cable applications. Cable reticulation
[0003] A typical power cable comprises a conductor surrounded at least by an internal semiconductor layer, an insulation layer and an external semiconductor layer, in that order. Cables are commonly produced by extruding the layers over a conductor. The polymeric material in one or more of said layers is then normally cross-linked to improve, for example, heat and deformation resistance, deformation properties, mechanical resistance, chemical resistance and abrasion resistance of the polymer in the layer (s) the cable. In the crosslinking reaction of a polymer, interpolymer cross bonds (bridges) are primarily formed. Cross-linking can be carried out using, for example, a compound that generates free radicals, such as a peroxide. An agent that generates free radicals is typically incorporated into the material layer prior to extruding the layer (s) over a conductor. After the formation of the layered cable, the cable is then subjected to a crosslinking step to initiate radical formation and thus the crosslinking reaction.
[0004] Peroxides are compounds that generate very common free radicals used i.a. in the polymer industry for said polymer modifications. Decomposition products resulting from peroxides can include volatile by-products that are unwanted, as they can be dangerous and can have a negative influence on the electrical properties of the cable. Therefore, volatile decomposition products such as methane, for example, in which dicumylperoxide is used, are conventionally reduced to a minimum or removed after cross-linking and the cooling step. Such a removal step is generally known as a degassing step. The degassing step is time consuming and requires energy and is therefore an expensive operation in a cable production process.
[0005] Also, the cable production line and the desired production speed used can bring limitations to the cable materials, especially when larger power cables are produced. In addition, the crosslinking rate and degree of crosslinking of the polymer in the cable layer should be sufficient in order to minimize or avoid any undesirable bending problems that occur during cable production, particularly when the cable is produced, for example. example, in a continuous catenary vulcanization line (CCV) (especially for thicker constructions), which is a type of vulcanization line well known in the field and described in the literature. Electric conductivity
[0006] The electrical conductivity on CD is an important material property, for example, for the insulation of materials for high voltage direct current (HV DC) cables. First, the temperature and the strong electric field dependence of this property will influence the electric field. The second issue is the fact that the heat will be generated within the insulation by the electrical dispersion current that runs between the inner and outer semiconductor layers. This dispersion current depends on the electric field and the electrical conductivity of the insulation. The high conductivity of the insulation material can also lead to the escape of heat under high voltage / high temperature conditions. The conductivity must therefore be low enough to prevent the escape of heat.
[0007] Consequently, in HV DC cables, the insulation is heated by the dispersion current. For specific cable planning, heating is proportional to the conductivity of the insulation x (electric field) 2. Thus, if the voltage is increased, much more heat will be generated.
[0008] There are high demands to increase the voltage of a power cable, preferably a direct current DC power cable and thus a continuous need to find alternative polymer compositions with reduced conductivity. Such polymer compositions should preferably also have the good mechanical properties necessary for the power cable modalities in demand. Objectives of the invention
[0009] One of the aims of the present invention is to provide an alternative cross-linked polymer composition which comprises a polyolefin and which has surprisingly advantageous properties suitable for a CD power cable.
[00010] An additional object of the invention is to provide a method for the reduction of electrical conductivity, that is, for the supply of low electrical conductivity, of a polymer composition that can be cross-linked, preferably of a cross-linked polymer composition present in at least least one layer of insulation from a cross-linked power cable, preferably from a cross-linked direct current (CD) cable.
[00011] Another objective of the invention is to provide a crosslinked power cable, preferably a direct current (CD) power cable, in which at least one layer comprises a crosslinkable polymer composition that has surprisingly advantageous properties.
[00012] The invention and additional objectives and benefits of it are described and defined in detail below. Figures
[00013] Figure 1 illustrates the geometry of the samples used in the stress test. Description of the invention
[00014] The present invention provides a crosslinkable polymer composition comprising a polyolefin and a peroxide, wherein the amount of the peroxide is less than 35 mmols -O-O- / kg of the polymer composition.
[00015] "That can be cross-linked" means that the cable layer can be cross-linked before use in its final application. The crosslinkable polymer compositions comprise polyolefin and peroxide in an amount that is defined above, below or in the claims. In addition, the cross-linked polymer composition, or, respectively, the cross-linked polyolefin, is cross-linked through the reaction of radicals using the claimed amount of peroxide present in the polymer composition prior to cross-linking. The cross-linked polymer composition has a typical network, i.e., interpolymer cross-links (bridges), which are well known in the field. As is apparent to one skilled in the art, the crosslinked polymer can be and is defined here with characteristics that are present in the polymer or polyolefin composition before or after crosslinking, as cited or evident from the context. For example, the presence and amount of peroxide in the polymer composition or the type and property of composition, such as MFR, density and / or degree of unsaturation, of the polyolefin component are defined, unless stated otherwise. , before crosslinking and characteristics after crosslinking are, for example, electrical conductivity, degree of crosslinking or mechanical properties measured from the crosslinked polymer composition.
[00016] The present invention further provides a crosslinkable polymer composition comprising a crosslinked polyolefin, wherein the polymer composition comprises before crosslinking (i.e., before being crosslinked) a polyolefin and a peroxide, wherein the amount of peroxide is less than 35 mmols -O- O- / kg of the polymer composition.
[00017] Consequently, the present cross-linked polymer composition is preferred and can be obtained by cross-linking with an amount of peroxide that is defined before or after.
[00018] The present invention further provides a crosslinkable polymer composition comprising a polyolefin which is crosslinked with peroxide used in an amount less than 35 mmols -O-O- / kg of the polymer composition.
[00019] The terms "can be obtained through crosslinking", "crosslinked with" and "crosslinked polymer composition" are used interchangeably here and mean the category "product by process", that is, that the product has a characteristic technique that is due to the cross-linking step as explained below.
[00020] The unit "mmol -O-O- / kg of the polymer composition" here means the content (mmol) of functional peroxide groups per kg of the polymer composition, when measured from the polymer composition before crosslinking. For example, the 35 mmols -O-O- / kg of the polymer composition corresponds to 0.95% by weight of the well-known dicumyl peroxide based on the total amount (100% by weight) of the polymer composition.
[00021] The "crosslinked polymer composition" is referred to here below also abbreviated as "Polymeric composition" or "polymeric composition". Still "polymer compositions which can be cross-linked" are referred to hereinafter also abbreviated as "Polymeric composition" or "polymeric composition". The meaning is evident from the context.
[00022] Unexpectedly, the electrical conductivity of a polymer composition is reduced, that is, lower, when cross-linked using a peroxide (for example, a well-known dicumyl peroxide) in a low amount that is defined before or after, compared with the electrical conductivity obtained after crosslinking the same polymeric material using the same peroxide, but in typical amounts of 37 to 55 mmols -OO- / kg of the polymer composition, which correspond to 1.0 to 2.5% by weight of dicumil peroxide, conventionally used for crosslinking power cables.
[00023] The polymer composition of the invention has electrical properties expressed as reduced electrical conductivity, that is, low, in which the formation of unwanted heat, for example, in the insulation layer of a power cable, preferably of a power cable. CD strength, can be minimized. The invention is particularly advantageous for CD power cables.
[00024] Electrical conductivity is measured here according to the CD conductivity method which is described in "Determination Methods". "Low" or "low" electrical conductivity as used interchangeably here means that the value obtained from the conductivity method CD is low, that is, reduced.
[00025] The low electrical conductivity of the polymer composition is very advantageous in a power cable, preferably in an AC or CD power cable, preferably in direct current (DC) power cables, more preferably in power cables. Low voltage (LV), medium voltage (MV), high voltage (HV) or extra high voltage (EHV) CD, most preferably on CD power cables that operate at any voltage, preferably at greater than 36 kV, such as HV DC cables.
[00026] Furthermore, the electrical conductivity of the polymer composition is surprisingly low even without the removal of volatile by-products after crosslinking, that is, without degassing, compared to the electrical conductivity of a non-degassed crosslinked polymer composition with conventional amounts of peroxide. Therefore, if desired, the degassing step of the crosslinked cable containing the polymer composition can be considerably shortened and / or performed under conditions of lesser demands during the cable production process which naturally increases the production efficiency. Consequently, if desired, the degassing step during cable production can be shortened.
[00027] The invention is further directed to a method for the reduction of, that is, for providing low electrical conductivity of a crosslinkable polymer composition comprising a peroxide crosslinked polyolefin, wherein the method comprises a step of production of the crosslinked polyolefin by crosslinking the polyolefin with an amount of peroxide less than 35 mmols -OO- / kg of the polymer composition.
[00028] More preferably the invention is directed to a method for reducing the electrical conductivity of a polymer composition that can be cross-linked from a cross-linked power cable, preferably from a cross-linked direct current (CD) power cable, more preferably of a crosslinked HV or EHV CD power cable, which comprises a conductor which is surrounded by at least one insulation layer, preferably by at least one internal semiconductor layer, one insulation layer and one external semiconductor layer, in this order, wherein at least the insulation layer comprises a polymer composition comprising a peroxide crosslinked polyolefin, wherein the method comprises a step of producing the crosslinked polyolefin by crosslinking the polyolefin with an amount of peroxide less than 35 mmols -OO- / kg of the polymer composition. In this method, it is preferred to use the polymer composition that is defined earlier or later.
[00029] Consequently, the invention further provides a crosslinkable power cable, preferably a direct current crosslinking (DC) power cable, comprising a conductor surrounded by one or more layers, in which at least one of said layer (s) comprises a polymer composition comprising a crosslinkable polyolefin and a peroxide in an amount less than 35 mmoles -OO- / kg of the polymer composition. More preferably, the invention is directed to a crosslinkable power cable, preferably a direct current crosslinked (DC) power cable, more preferably an HV or EHV crosslinked power cable. , which comprises a conductor surrounded by at least one inner semiconductor layer, an insulation layer and an external semiconductor layer, in that order, wherein at least one layer, preferably the insulation layer, comprises a polymer composition that can be cross-linked of the invention comprising a polyolefin and a peroxide in an amount less than 35 mmoles -OO- / kg of the polymer composition.
[00030] The invention is additionally directed to a reticulated power cable, preferably to a reticulated direct current (DC) power cable, which comprises a conductor surrounded by one or more layers, in which at least one of said (s) layer (s) comprises a crosslinkable polymer composition comprising a peroxide crosslinked polyolefin in an amount less than 35 mmoles -OO- / kg of the polymer composition. More preferably, the invention is directed to a crosslinked power cable, preferably to a crosslinked direct current (CD) power cable, more preferably to a crosslinked HV or EHV CD power cable, which comprises a conductor surrounded by at least one inner semiconductor layer, one insulation layer and one outer semiconductor layer, in that order, wherein at least one layer, preferably the insulation layer, comprises a crosslinkable polymer composition comprising a peroxide crosslinked polyolefin in an amount less than 35 mmols -OO- / kg of the polymer composition. The expression on the crosslinked cable "peroxide crosslinked polyolefin in an amount less than 35 mmols -OO- / kg of the polymer composition" means that the polymer composition before crosslinking contains a polyolefin and peroxide in an amount less than 35 mmols -OO- / kg of the polymer composition.
[00031] The preferred subgroups, properties and modalities below of the polymer composition apply equally and independently to the polymer composition as such, as well as to the polymer composition of the invention in the method for reducing electrical conductivity, in the cable that can be cross-linked and in the cross-linked cable, as defined previously or below.
[00032] More preferably, the cross-linked polymer composition of the invention, before cross-linking, comprises said peroxide in the amount of 34 mmols -OO- / kg of the polymer composition or less, preferably 33 mmols -OO- / kg of the composition of polymers or less, more preferably from 5.0 to 30 mmols -OO- / kg of the polymer composition, 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, even more preferably from 15 to 30 mmols -OO- / kg of the polymer composition. The peroxide content depends on the level of crosslinking desired and in one embodiment it is desired that the peroxide content before crosslinking is preferably equal to 17 to 29 mmols -O-O- / kg of the polymer composition. In addition, the polyolefin can be unsaturated, where the peroxide content may depend on the degree of unsaturation.
[00033] In case the cable is produced in a cable line with continuous catenary vulcanization, then before crosslinking, the polymer composition preferably comprises peroxide in an amount of 7 mmols -OO- / kg of the polymer composition or more, preferably from 15 to 30.0 mmols -OO- / kg of the polymer composition.
[00034] More preferably, the crosslinked polymer composition of the invention has an electrical conductivity of 45 fS / m or less after crosslinking, when measured according to the CD conductivity method which is described in "Determination Methods". The crosslinked polymer composition of the invention preferably has an electrical conductivity of 40 fS / m or less, more preferably from 0.01 to 38 fS / m, even more preferably from 0.5 to 35 fS / m, when measured according to the conductivity method CD which is described in "Determination Methods".
[00035] In a preferred embodiment the polymer composition of the invention preferably comprises a crosslinked low density polyethylene (LDPE) polymer which is defined below below including the subgroups and preferable modalities thereof and has an electrical conductivity from 1 to 45 fS / m, preferably from 1 to 40 fS / m, preferably from 1 to 38 fS / m, more preferably from 1 to 38 fS / m, when measured according to the conductivity method CD which is described in "Determination Methods" .
[00036] Still unexpectedly, the peroxide content can be reduced without sacrificing the mechanical properties of the obtained cross-linked polymer composition that are important for the power cable layers. So unexpectedly, in addition to the reduced electrical conductivity of the polymer composition, also one or more, more preferably all of the mechanical properties selected from PENT (Pennsylvania Notch Test) and the stress properties expressed in the form of Stress at Break and / or Stress at Breakage, they remain at a possible level or at least similar to the mechanical properties of the cross-linked polymer compositions of the prior art used in the cable layers. The reason for the advantageous balance between improved electrical conductivity and good mechanical properties is not fully understood. Without being bound by any theory one of the reasons may be that an unexpectedly high degree of crystallinity (%) of the crosslinked polymer is maintained compared to the degree of crystallinity obtained with conventional concentrations of peroxide. Consequently and still preferably the polymer composition of the invention has an unexpected balance between electrical and mechanical properties, which is very advantageous, for example, for CD power cables and, surprisingly, also for HV or CD power cables. EHV.
Accordingly, the crosslinked polymer composition of the invention preferably still has a PENT life span of 200 hours or more, preferably 400 hours or more, preferably 500 hours or more, more preferably 800 hours or more, most preferably 1000 hours or more, when measured according to the PENT test under load at 2 MPa and at an aging temperature of 70 ° C which as described in "Determination Methods". PENT indicates the resistance to the slow propagation of cracks and the higher the value the better the said resistance.
[00038] Even more preferably, the cross-linked polymer composition of the invention has advantageous stress properties which are expressed here as Stress at Break or Stress at Break, each of which is defined at two temperatures.
[00039] Preferably the cross-linked polymer composition of the invention has Breakdown Stress at 70 ° C of 7.0 MPa or more, preferably of 10.0 MPa or more, more preferably of 12.0 MPa or more or at - 10 ° C of 25.0 MPa or more, preferably of 26.0 MPa or more, preferably of 30.0 MPa or more. More preferably, the crosslinked polymer composition has a Break Stress at 70 ° C as defined above and a Break Stress at - 10 ° C as defined above, when measured according to the Stress test method that is described in "Determination Methods". The upper limit of Stress at Break is not limited and can be, for example, 25.0 MPa at 70 ° C and, for example, 50.0 MPa at - 10 ° C.
[00040] Still preferably, the crosslinked polymer composition of the invention has a Breakdown Voltage (%) at 70 ° C of 350% or more, preferably 400% or more, preferably 450% or more or at -10 ° C 400% or more. More preferably, the cross-linked polymer composition has a Break Tension (%) at 70 ° C which is defined previously and a Break Tension (%) at - 10 ° C which is defined previously, when measured according to the test method. of Stress which is described in "Determination Methods". The upper limit of Break Voltage is not limited and can be, for example, 1000% at 70 ° C and, for example, 800% at - 10 ° C.
[00041] Even more preferably, the polymer composition has both Stress at Break at 70 ° C and -10 ° C as well as Stress at Break at 70 ° C and -10 ° C as defined above.
[00042] The crosslinked polymer composition of the invention preferably has a gel content of at least 10% by weight (% by weight), preferably at least 28% by weight, preferably at least 35% by weight, preferably at least less than 40% by weight, more preferably at least 45% by weight, more preferably at least 50% by weight, more preferably at least 55% by weight, as measured according to ASTM D 2765-01, Method A, using decalin extraction as described in "Determination Methods".
[00043] In a preferred embodiment the polymer composition is cross-linked using peroxide in an amount of 7.0 mmols -OO- / kg of the polymer composition or more (0.2% by weight) and has a hair gel content at least 10% by weight, preferably 15 mmols -OO- / kg of the polymer composition or more (0.4% by weight) and has a gel content of at least 30% by weight, preferably in an amount from 19 to 30 mmols -OO- / kg of the polymer composition (0.5-0.8% by weight) and has a gel content of at least 30% by weight, preferably at least 50% by weight, when measured accordingly with ASTM D 2765-01, Method A, using extraction with decaline.
[00044] Consequently, the cross-linked polymer composition of the invention is used for determining the above electrical, mechanical and degree of cross-linking properties. The respective preparation of samples of the cross-linked polymer composition is described below under the "Determination Methods".
[00045] The invention is also directed to a process for the production of a power cable that can be cross-linked and cross-linked, preferably a direct current power cable (CD) that can be cross-linked and cross-linked, which is defined previously or a follow.
[00046] The additional preferable subgroups of the previous properties, the properties, variants and additional modalities that are defined previously or below for the composition of polymers or for their components apply similarly to the method for reducing electrical conductivity, to the power cable, preferably to the CD power cable, of the invention. Polyolefin Component
[00047] The preferred modalities, properties and subgroups of the appropriate polyolefin component to follow for the polymer composition can be generalized so that they can be used in any order or combination to further define the preferred polymer composition modalities. In addition, it is evident that the description provided applies to the polyolefin before being cross-linked.
[00048] The term polyolefin means both an olefin homopolymer and an olefin copolymer with one or more comonomer (s). "Comonomer" as it is well known refers to comonomer units that can be copolymerized.
[00049] The polyolefin can be any polyolefin, such as any conventional polyolefin, which is suitable as a polymer in a layer, preferably an insulating layer, of an electrical cable, preferably of a power cable.
[00050] The polyolefin can be, for example, a commercially available polymer or it can be prepared according to or in a manner analogous to the known polymerization process described in the chemical literature.
[00051] Most preferably the polyolefin is a polyethylene produced in a high pressure process, more preferably a low density LDPE polyethylene produced in a high pressure process. 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 understood as not limiting the density range, but it covers LDPE-like HP polyethylenes with low, medium and higher densities. The term LDPE describes and distinguishes only the nature of HP polyethylene with typical characteristics, such as different branching architecture, compared to the PE produced in the presence of an olefin polymerization catalyst.
[00052] LDPE as said polyolefin can be a low density ethylene homopolymer (referred to here as LDPE homopolymer) or a low density ethylene copolymer with one or more comonomer (s) (referred to here as LDPE copolymer) . The one or more LDPE copolymer comonomers are preferably selected from the polar comonomer (s), non-polar comonomer (s) or a mixture of the polar comonomer (s) and non-polar comonomer (s), as defined above or below. Furthermore, said LDPE homopolymer or said LDPE copolymer such as said polyolefin can be optionally unsaturated.
[00053] As a polar comonomer for the LDPE copolymer such as said polyolefin, comonomer (s) containing hydroxyl group (s), alkoxy group (s), carbonyl group (s), carboxyl group (s), group (s) ether or ester group (s) or a mixture thereof, may be used. More preferably, comonomer (s) containing carboxyl group (s) and / or ester are used as said polar comonomer. Even more preferably, the LDPE copolymer polar comonomer (s) is (are) selected from the groups of acrylate, methacrylate (s) or acetate (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 themselves. Preferably still, said polar comonomers are selected from C1- to C6-alkyl acrylates, C1- to C6-alkyl methacrylates or vinyl acetate. Even more preferably, said polar LDPE copolymer is an ethylene copolymer with C1- to C4-alkyl acrylate, such as methyl, ethyl, propyl or butyl acrylate or vinyl acetate or any mixture thereof.
[00054] As the non-polar comonomer (s) for the LDPE copolymer such as said polyolefin, comonomer (s) other than the polar comonomers defined above can be used. Preferably, non-polar comonomers are other than comonomer (s) containing hydroxyl group (s), alkoxy group (s), carbonyl group (s), carboxyl group (s), ether group (s) or ester group (s) . A preferable non-polar comonomer group (s) comprise, preferably consist of, monounsaturated comonomer (s) (= a double bond), preferably olefins, preferably alpha-olefins, more preferably C3 to C10 alpha-olefins, such as propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, styrene, 1-octene, 1-nonene; polyunsaturated comonomer (s) (= more than one double bond); comonomer (s) containing silane group; or any mixtures thereof. The polyunsaturated comonomer (s) is (are) further described below in relation to unsaturated LDPE copolymers.
[00055] If the LDPE polymer is a 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 comonomers.
[00056] The polymer composition, preferably a polyolefin component thereof, more preferably the LDPE polymer, can optionally be unsaturated, that is, the polymer composition, preferably the polyolefin, preferably the LDPE polymer, can comprise double bonds carbon-carbon. "Unsaturated" means that the polymer composition, preferably polyolefin, contains carbon-carbon double bonds / 1000 carbon atoms in a total amount of at least 0.4 / 1000 carbon atoms.
[00057] As is well known, unsaturation can be supplied to the ia polymer composition by means of polyolefin, a compound of low molecular hair (Pm), such as crosslinking enhancing agent (s) or additive (s) firing retardant (s) or any combination thereof. The total number of double bonds here means double bonds determined from the source (s) that are known and deliberately added to contribute to unsaturation. If two or more sources of previous double bonds 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 characteristic model compound for calibration is used for each source chosen to enable quantitative infrared (FTIR) determination.
[00058] Any measurements of the double bond are carried out before crosslinking.
[00059] If the polymer composition is unsaturated before crosslinking, then it is preferred that the unsaturation originates from at least one unsaturated polyolefin component. More preferably, the unsaturated polyolefin 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) is (are) present in the LDPE polymer as said unsaturated polyolefin, then the LDPE polymer is an unsaturated LDPE copolymer.
[00060] In a preferred embodiment the term "total amount of carbon-carbon double bonds" is defined starting from the unsaturated polyolefin and refers, if not specified otherwise, to the combined amount of double bonds originating from the vinyl groups, vinylidene groups and trans-vinylene groups, if present. Naturally, polyolefin does not necessarily contain all three types of anterior double bonds. However, any of the three types, when present, are calculated for the "total amount of carbon-carbon double bonds". The amount of each type of double bond is measured as indicated in "Determination Methods".
[00061] If an LDPE homopolymer is unsaturated, then unsaturation can be provided, for example, by a chain transfer agent (CTA), such as propylene and / or by 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 comonomers or by polymerization conditions. It is well known that selected polymerization conditions, such as maximum temperatures and pressure, can have an influence on the level of unsaturation. In the case of an unsaturated LDPE copolymer, it is preferably an ethylene unsaturated LDPE copolymer with at least one polyunsaturated comonomer and optionally with other comonomer (s), such as polar comonomer (s) that it is (are) preferably selected from the acrylate or acetate comonomer (s). Most preferably an unsaturated LDPE copolymer is an ethylene unsaturated LDPE copolymer with at least polyunsaturated comonomer (s).
[00062] Polyunsaturated comonomers suitable for unsaturated polyolefin preferably consist of a straight carbon chain with at least 8 carbon atoms and at least 4 carbons between the unconjugated double bonds, of 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 terminal and the second carbon-carbon double bond being not conjugated to the first. Preferred dienes are selected from C8 to C14 unconjugated dienes or mixtures thereof, most preferably selected from 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. Even more preferably, the diene is selected from 1,7-octadiene, 1,9-decadiene, 1,11-dodecadiene, 1,13-tetradecadiene or any mixture thereof, however, without limitation to the previous dienes.
[00063] It is well known that, for example, propylene can be used as a comonomer or as a chain transfer agent (CTA) or both, in which it can contribute to the total amount of CC double bonds, preferably to the amount total vinyl groups. Here, when a compound that can also act as a comonomer, such as propylene, is used as CTA for the provision of double bonds, then said comonomer that can be copolymerized is not calculated for the comonomer content.
[00064] If the polyolefin, more preferably the LDPE polymer, is unsaturated, then it preferably has the total amount of carbon-carbon double bonds, which originate from vinyl groups, vinylidene groups and trans-vinylene groups, if present, from more than 0.5 / 1000 carbon atoms. The upper limit of the amount of carbon-carbon double bonds present in the polyolefin is not limited and may be preferably less than 5.0 / 1000 carbon atoms, preferably less than 3.0 / 1000 carbon atoms.
[00065] In some embodiments, for example, where a higher level of crosslinking with low peroxide content is desired, the total amount of carbon-carbon double bonds, which originate from vinyl groups, vinylidene groups and trans-groups vinylene, if present, in the unsaturated LDPE, is preferably greater than 0.50 / 1000 carbon atoms, preferably greater than 0.60 / 1000 carbon atoms. Such a higher number of double connections is preferable, for example, if a high cable production speed is desired and / or it would be desirable to minimize or avoid bending problems that may occur for example, depending on the desired end application and / or the process cable production. The higher content of double bonds combined with the "low" peroxide content of the invention is also preferred in cable modalities, such as in CD power cables, where highly demanding mechanical and / or thermal resistance properties are required for the layer, preferably for the insulation layer material.
[00066] Most preferably the polyolefin is unsaturated 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 less than 4.0 / 1000 carbon atoms. More preferably, the polyolefin, 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 carbon atoms and more preferably of more than 0, 40/1000 carbon atoms. In some demanding modalities, preferably on power cables, more preferably on CD power cables, at least one layer, preferably the insulation layer, comprises LDPE polymer, preferably LDPE copolymer, which contains vinyl groups in the total amount of more than 0.50 / 1000 carbon atoms.
[00067] Unexpectedly unsaturation also contributes to the said desirable balance of low conductivity and mechanical properties. In the preferred embodiment the polyolefin of the polymer composition is an ethylene unsaturated LDPE copolymer with at least one polyunsaturated comonomer, preferably a diene that is defined previously and optionally with other comonomer (s) and has the total amount of carbon-carbon double bonds, which originate from vinyl groups, vinylidene groups and trans-vinylene groups, if present, which are defined previously, preferably have the total amount of vinyl groups that is defined previously. Said unsaturated LDPE copolymer is highly useful for the method of further reducing the electrical conductivity of a polymer composition that can be cross-linked, preferably of an insulation layer of a power cable, preferably of a CD power cable.
[00068] Typically and preferably in wire and cable (W&C) applications, the density of the polyolefin, preferably of the LDPE polymer, is greater than 860 kg / m3. Preferably the density of the polyolefin, preferably of the LDPE polymer, of the ethylene homo- or copolymer is not greater than 960 kg / m3 and preferably is from 900 to 945 kg / m3. The MFR2 (2.16 kg, 190 ° C) of the polyolefin, preferably of the LDPE polymer, is preferably from 0.01 to 50 g / 10min, more preferably it is from 0.1 to 20 g / 10min and most preferably it is from 0.2 to 10 g / 10min.
[00069] Consequently, the polyolefin of the invention is preferably produced at high pressure through polymerization initiated by free radicals (referred to as polymerization of high pressure radicals (HP)). The HP reactor can be, for example, a well-known tubular or autoclave reactor or a mixture thereof, preferably a tubular reactor. The preferred polyolefin is optionally and preferably LDPE homopolymer or ethylene LDPE copolymer unsaturated with one or more comonomers, as defined above. The LDPE polymer that can be obtained through the process of the invention preferably provides the advantageous electrical properties as defined above or below. High pressure polymerization (HP) and the adjustment of process conditions to further produce the other properties of the polyolefin depending on the desired final application are well known and described in the literature and can easily be used by one skilled in the art. Suitable polymerization temperatures range up to 400 ° C, preferably from 80 to 350 ° C and the pressure from 70 MPa, preferably 100 to 400 MPa, more preferably from 100 to 350 MPa. The pressure can be measured at least after the compression stage and / or after the tubular reactor. The temperature can be measured at several points during all stages.
[00070] After separation the polymer obtained is typically in the form of a molten polymer which is normally mixed and pelletized in a pelletizing section, such as a pelletizing extruder, arranged in association with the HP reactor system. Optionally, additive (s), such as antioxidant (s), can be added to this mixer in a manner known to result in the composition of polymers.
[00071] Additional details on the production of ethylene (co) polymers through the polymerization of high pressure radicals can be found in the Encyclopedia of Polymer Science and Engineering, Vol. 6 (1986), pp 383-410 and Encyclopedia of Materials: Science and Technology, 2001 Elsevier Science Ltd .: "Polyethylene: High-pressure, R. Klimesch, D.Littmann and F.-O. Mahling pp. 7181-7184.
[00072] When an ethylene unsaturated LDPE copolymer is prepared, then, as is well known, the content of CC double bonds can be adjusted through the polymerization of ethylene, for example, in the presence of one or more polyunsaturated comonomers, chain transfer agents, process conditions or any combinations thereof, for example, using the desired feed ratio between monomer, preferably ethylene and polyunsaturated comonomer and / or chain transfer agent, depending on the nature and amount of CC double bonds desired for the unsaturated LDPE copolymer. I.a. WO 9308222 describes a polymerization of radicals under high pressure of ethylene with polyunsaturated monomers. As a result, unsaturation can be uniformly distributed along the polymer chain in a copolymerization at random. Still, for example, WO 9635732 describes the polymerization of radicals under high pressure of ethylene and a certain type of polyunsaturated a, ®-divinylsiloxanes. Polymers composition
[00073] Before crosslinking the polymer composition comprises at least one peroxide which contains at least one -O-O- bond. Naturally, in the case where two or more different peroxide products are used in the polymer composition, then the amount (in mmol) of -OO- / kg of the polymer composition as defined above, below or in the claims is the sum of amount of -OO- / kg of the polymer composition of each peroxide product. 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-butylperoxy) -2,5 -dimethylhexane, tert-butylcumylperoxide, di (tert-butyl) peroxide, dicumylperoxide, butyl-4,4-bis (tert-butylperoxy) -valerate, 1,1-bis (tert-butylperoxy) -3,3,5 - trimethylcyclohexane, tert-butylperoxybenzoate, dibenzoylperoxide, bis (tert butylperoxyisopropyl) 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 peroxide is selected from 2,5-di (tert-butylperoxy) - 2,5-dimethylhexane, di (tert-butylperoxyisopropyl) benzene, di-cumylperoxide, tert-butylcumylperoxide, di (tert-butyl) peroxide or mixtures of themselves. Most preferably, the peroxide is dicumylperoxide.
[00074] In addition, before crosslinking the polymer composition of the invention may contain, in addition to the polyolefin and peroxide, additional component (s) such as polymer component (s) and / or additive (s), preferably additive (s), such as antioxidant (s), burning retardant (SR) agent (s), crosslinking enhancing agent (s), stabilizer (s), processing, flame retardant additive (s), free water retardant additive (s), acid or ion removal agent (s), inorganic filling (s) and voltage stabilizer (s) , which are known in the field of polymers. The polymer composition preferably comprises conventionally the additive (s) used for W&C applications, such as one or more antioxidants and optionally one or more flame retardant agents, preferably at least one or more antioxidants . The amounts of additives used are conventional and well known to one skilled in the art, for example, as already described above in "Description of the invention".
[00075] The polymer composition of the invention typically comprises at least 50% by weight, preferably at least 60% by weight, more preferably at least 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 polyolefin based on the total weight of the polymer component (s) present in the polymer composition. The preferred polymer composition consists of polyolefin as the sole polymer component. The term means that the polymer composition does not contain additional polymer components, but polyolefin as the sole polymer component. However, it is to be understood here that the polymer composition can comprise additional components other than the polymer components, such as additives that can optionally be added in a mixture with a carrier polymer, i.e., in the so-called master batch.
[00076] The polymer composition preferably consists of polyolefin, preferably polyethylene, more preferably LDPE homo or copolymer, which can optionally and preferably be unsaturated before cross-linking, as the only polyolefin component. End uses and end applications of the invention
[00077] The new polymer composition of the invention is highly useful in a wide variety of final polymer applications. The preferred use of the polymer composition is in W&C applications, more preferably in one or more layers of a power cable.
[00078] A power cable is defined as a cable that transfers energy operating at any voltage, typically operating at voltages greater than 1 kV. The voltage applied to the power cable can be alternating (AC), direct (CD) or transient (impulse). The polymer composition of the invention is very suitable for power cables operating at voltages greater than 36 kV, such cables cover high voltage (HV) and extra high voltage (EHV) power cables whose EHV cables operate at even more voltages tall, which are well known in the field. The foregoing terms have well-known meanings and thus indicate the operational level of such cables. For HV and EHV CD power cables, the operating voltage is defined here as the electrical voltage between the ground and the conductor of a high voltage cable. Typically an HV CD power cable and an EHV CD power cable operated at voltages of 40 kV or greater, even at voltages of 50 kV or greater. A power cable operating at very high voltages is known in the art as an EHV CD power cable which in practice can be as high as, but not limited to, 900 kV.
[00079] The polymer composition is highly suitable for use as a layer material for an AC or CD power cable, preferably for a direct current (CD) power cable, more preferably for a CD power cable operating at voltages greater than 36 kV, such as the well-known HV or EHV CD power cable, as defined above.
[00080] A crosslinkable power cable, preferably a crosslinkable CD power cable, is provided comprising a conductor surrounded by one or more layers, preferably at least one insulation layer, more preferably at least one layer internal semiconductor, an insulation layer and an external semiconductor layer, in that order, wherein at least one (or more) of said layer (s), preferably the insulation layer, comprises a polymer composition comprising a crosslinkable polyolefin and a peroxide in an amount less than 35 mmols -OO- / kg of the polymer composition, preferably 34 mmols -OO- / kg of the polymer composition or less, preferably 33 mmols -OO - / kg of the polymer composition or less, more preferably from 5.0 to 30 mmols -OO- / kg of the polymer composition, more preferably from 7.0 to 30 mmols -OO- / kg of the polymer composition, more prefer initially from 10.0 to 30 mmols -O-O- / kg of the polymer composition, even more preferably from 15 to 30 mmols -O-O- / kg of the polymer composition. Depending on the desired level of crosslinking and degree of unsaturation of the polymer composition, preferably of the polyolefin, the peroxide content of the polymer composition in some cases may be even more preferably from 17 to 29 mmols -OO- / kg of the polymer composition . The insulation layer of the power cable, preferably the CD power cable, preferably comprises said unsaturated LDPE copolymer which can be cross-linked as defined above.
[00081] The term "conductor" means here before and after that the conductor comprises one or more wires. In addition, the cable may comprise one or more such conductors. Preferably the conductor is an electrical conductor and comprises one or more metallic wires.
[00082] As the cable is well known, it can optionally comprise additional layers, for example, layers surrounding the insulation layer or, if present, the external semiconductor layers, such as canvas (s), a coating layer, other protective layer (s) or any combination thereof.
[00083] The invention further provides a process for the production of a power cable, preferably a crosslinkable power cable, more preferably a crosslinkable CD power cable, more preferably an HV or EHV that can be cross-linked, as defined above or in the claims comprising a conductor surrounded by one or more layers, preferably at least one insulation layer, more preferably at least one inner semiconductor layer, an insulation layer and a semiconductor layer external, in this order, in which the process comprises the steps of applying one or more layers on a conductor in which at least one layer, preferably the insulating layer, comprises a crosslinkable polymer composition of the invention comprising a polyolefin and a peroxide in an amount less than 35 mmols -OO- / kg of the polymer composition, preferably 34 mmols -OO- / k g of polymer composition or less, preferably 33 mmols -OO- / kg of polymer composition or less, preferably 30 mmols - OO- / kg of polymer composition or less, more preferably from 5.0 to 30 mmols - OO- / kg of the polymer composition, 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.
[00084] In the preferred embodiment of the invention's power cable production process, a power cable that can be cross-linked is produced by (a) supplying and mixing, preferably fusion mixture in an extruder, of said polymer compositions that can be cross-linked to the invention as defined previously or below in the claims, (b) applying at least one melt mixture of the polymer composition obtained starting from step (a), preferably by (co) extrusion, on a conductor to form one or more more layers, preferably at least one insulation layer and (c) optional crosslinking of at least the polymer composition of the invention in said at least one layer, preferably in the insulation layer.
[00085] More preferably in this embodiment a crosslinkable CD power cable, preferably a crosslinkable HV CD power cable, of the invention comprising a conductor surrounded by an internal semiconductor layer, an insulation layer and an external semiconductor layer, in this order, is produced, in which the process comprises the steps of (a) - supply and mixing, preferably fusion mixture in an extruder, of a first cross-linked semiconductor composition comprising a polymer, a carbon black and optionally additional component (s) for the internal semiconductor layer, - supplying and mixing, preferably melting mixture in an extruder, of a polymer composition that can be cross-linked of the invention to the insulation layer, - supply and mixing, preferably fusion mixing in an extruder, of a second semiconductor composition which is preferably crosslinkable and purchased addresses a polymer, carbon black and optionally additional component (s) for the outer semiconductor layer, (b) application over a conductor, preferably by coextrusion of, - a fusion mixture of the first semiconductor composition obtained starting from the step (a) to form the internal semiconductor layer, - a polymer composition melt mixture of the invention obtained from step (a) to form the insulation layer, and - a melt mixture of the second semiconductor composition obtained starting from step (a ) to form the outer semiconductor layer and (c) optional crosslinking under crosslinking conditions of one or more of the polymer compositions of the insulation layer, the semiconductor composition of the inner semiconductor layer and the semiconductor composition of the outer semiconductor layer, of the obtained cable , preferably at least the polymer composition of the insulation layer, more preferably the polymer composition of the insulation layer, the co semiconductor composition of the inner semiconductor layer and the semiconductor composition of the outer semiconductor layer.
[00086] The polymer of the first and second semiconductor compositions is preferably a polyolefin which is described in relation to the polymer composition of the invention. The carbon black can be any conventional carbon black used in the semiconductor layers of a power cable, preferably in the semiconductor layer of a CD power cable. Non-limiting examples of carbon black are any conventional conductive carbon black, such as furnace carbon black and acetylene carbon black. In addition, the first and second semiconductor compositions are preferably identical.
[00087] Melting mixture means mixing above the melting point of at least the major polymer component (s) of the mixture obtained and is typically carried out at a temperature of at least 10-15 ° C above melting or softening point of polymer component (s).
[00088] The term "(co) extrusion" here means 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 in the same extrusion step, as it is well known in the art. The term "(co) extrusion" here also means all or part of the layer (s) is formed simultaneously using one or more extruder ends. For example, a triple extrusion can be used to form three layers. In case a layer is formed using more than one extruder end, then for example, the layers can be extruded using two extruder ends, the first to form the inner semiconductor layer and the inner part of the insulation layer and the second end to form the outer insulation layer and the outer semiconductor layer.
[00089] As is well known, the polymer composition of the invention and the first and second optional and preferred semiconductor compositions can be produced before or during the cable making process. In addition, the polymer composition of the invention and the first and second optional and preferred semiconductor compositions can each independently comprise part or all components thereof prior to introduction into the mixing (fusion) step a) of the cable production process .
[00090] The mixing step (a) of the polymer composition provided of the invention and the first and second preferred semiconductor compositions is preferably carried out in a cable extruder. Step a) of the cable production process can optionally comprise a separate mixing step, for example, in a mixer arranged in association and preceding the cable extruder of the cable production line. Mixing in the preceding separate mixer can be carried out by mixing with or without external heating (heating with an external source) of the component (s). In the case of peroxide (s) and part or all (s) of the optional additional component (s), such as an additional additive (s), of the composition of polymers of the invention and the first and second optional and preferred semiconductor compositions, are (are) added to the polyolefin during the cable making process, so the addition (s) can (s) occur at any stage during the mixing step (a), for example, in the optional separate mixer that precedes the cable extruder or at any point (s) of the cable extruder. The addition of peroxide and optional additive (s) can be done simultaneously or separately as such, preferably in liquid form or in a well-known master batch and at any stage during the mixing step (a).
[00091] It is more preferred that peroxide and preferably also the optional additional component (s), such as an additive, are already present at least in the polymer composition, before of this to be used in the cable production process and in the cable production line. Peroxide can be supplied to the pellets of the polyolefin or polymer composition before the pellets are supplied to step (a) of the process. The peroxide can be, for example, mixed in melting together with the polyolefin and optional additional component (s) and then the melting mixture is pelleted or, preferably, can be added, preferably impregnated, to the solid pellets polyolefin or polymer composition. The peroxide is preferably added in a liquid state, that is, it can be in liquid form at room temperature or it is preheated before the melting point or glass transition point of the same or dissolved in a carrier medium, which is well known to an expert . The addition of the optional additive (s) in this modality can be done as previously described for the peroxide.
[00092] Preferably, said polymer composition and the first and second optional semiconductor compositions are used in the form of powder, grain or pellets when supplied to the cable production process. The pellets can be of any size and shape.
[00093] It is preferred that the melt blend of the polymer composition obtained starting from the melt blend step consists of the polyolefin of the invention as the sole polymer component. The optional and preferable additive (s) can be added in the polymer composition as such or as a mixture with a carrier polymer, that is, in a form so-called batch master.
[00094] In a preferred embodiment of the cable production process, a crosslinkable power cable, preferably a crosslinkable CD power cable, more preferably a crosslinkable HV CD power cable, is produced, wherein the insulation layer comprises the polymer composition of the invention which comprises a polyolefin which can optionally and preferably be cross-linked an unsaturated LDPE homo or copolymer and a peroxide in an amount which is provided before or after and then the polyolefin that can be cross-linked in the insulation layer of the obtained cable is cross-linked in step c) under cross-linking conditions. More preferably in this embodiment, a crosslinked power cable, preferably a crosslinked CD power cable, more preferably a crosslinked HV CD power cable, is produced, comprising a conductor surrounded by an inner semiconductor layer which preferably comprises in, a first semiconductor composition, an insulation layer comprising, preferably consisting of, a polymer composition of the invention as defined above and optionally and preferably, an outer semiconductor layer comprising, preferably consisting of, a second semiconductor composition , in which at least the polymer composition of the insulation layer, optionally and preferably at least one, preferably both, the first and the second internal semiconductor compositions and, respectively, the external semiconductor layer, are cross-linked under cross-linking conditions in step ( ç). The crosslinking of the polymer composition of the insulation layer is carried out in the presence of a peroxide in an amount that is defined previously or in the following claims and the optional and preferable crosslinking of the first semiconductor composition of the internal semiconductor layer is carried out in the presence of an agent (s) of crosslinking, preferably in the presence of an agent that generates free radical (s), which is preferably a peroxide (s).
[00095] The crosslinking of the polymer composition of the insulation layer of the invention is thus carried out in the presence of the "low amount" of the peroxide invention as defined above, below or in the claims.
[00096] The crosslinking agent (s) may already be present in the first and second optional semiconductor compositions prior to introduction in the crosslinking step c) or introduced (s) during the crosslinking step. Peroxide is the preferred crosslinking agent for said first and second optional semiconductor compositions and is preferably included in the semiconductor composition pellets before the composition is used in the cable making process that is described above.
[00097] Crosslinking can be carried out at the increased temperature that is chosen, as is well known, depending on the type of crosslinking agent. For example, temperatures above 150 ° C, such as from 160 to 350 ° C, are typical, however without being limited to these.
[00098] Temperatures and processing devices are well known in the art, for example, conventional mixers and extruders, such as single-screw or double-screw extruders, are suitable for the process of the invention.
[00099] The invention further provides a crosslinked power cable, preferably a crosslinked CD power cable, preferably a crosslinked HV or EHV CD power cable, which comprises a conductor surrounded by one or more layers, preferably at least at least one insulation layer, more preferably at least one internal semiconductor layer, one insulation layer and one external semiconductor layer, in that order, wherein at least the insulation layer comprises the cross-linked polymer composition or any of the subgroups or preferred embodiments thereof as defined above or in the claims. Optionally and preferably still one or both, preferably both the internal semiconductor composition and the optional and preferred external semiconductor composition are cross-linked.
[000100] Naturally, the polymer composition of the invention used in at least one layer of cable, preferably in an insulating layer, of the cable of the invention has, when cross-linked, the advantageous electrical properties and preferably any or all of the mechanical properties such as previously defined or in the claims.
[000101] The invention further provides the use of the polymer composition or any of the preferred subgroups or modalities thereof, as defined above or in the claims, in at least one layer, preferably in at least one insulation layer, of a cable crosslinked power cable, preferably a crosslinked power cable (CD), preferably a crosslinked HV or EHV CD power cable, comprising a conductor surrounded by at least one layer, preferably at least one internal semiconductor layer, one insulation layer and an external semiconductor layer, in that order. The invention further provides the use of the polymer composition or any of the preferred subgroups or modalities thereof, as defined above or in the claims, for the production of at least one layer, preferably at least one insulation layer, of a cable. crosslinked strength, preferably from a crosslinked power cable (CD), preferably from a crosslinked HV or EHV CD power cable, comprising a conductor surrounded by at least one layer, preferably at least one inner semiconductor layer, one layer insulation and an external semiconductor layer, in that order.
[000102] The thickness of the insulation layer of the power cable, preferably the DC cable, more preferably the HV or EHV CD power cable, is typically 2 mm or more, preferably at least 3 mm, preferably of at least 5 to 100 mm, more preferably from 5 to 50 mm, when measured starting from a cross section of the cable insulation layer. Determination Methods
[000103] Unless otherwise stated in the description or in the experimental part, the following methods were used to determine the properties. Wt%:% by weight Fusion Flow
[000104] The melt flow rate (MFR) is determined according to ISO 1133 and is indicated in g / 10 min. The MFR is an indication of the flow capacity and thus the processing capacity of the polymer. The higher the melt flow rate, the lower the viscosity of the polymer. MFR is determined at 190 ° C for polyethylenes and can be determined at different loads such as 2.16 kg (MFR2) or 21.6 kg (MFR21). Density
[000105] The density was measured according to ISO 1183-2. Sample preparation was performed according to ISO 1872-2 Table 3 Q (compression modeling). Comonomer content a) Quantification of alpha-olefin content in linear low density polyethylene and low density polyethylene by NMR spectroscopy:
[000106] The comonomer content was determined by quantitative 13C nuclear magnetic resonance (NMR) spectroscopy after basic assignment (J. Randall JMS - Rev. Macromol. Chem. Phys., C29 (2 & 3), 201-317 (1989) ). The experimental parameters were adjusted to guarantee the measurement of the quantitative spectra for this specific task.
[000107] Specifically solution state NMR spectroscopy was employed using a Bruker AvanceIII 400 spectrometer. Homogeneous samples were prepared by dissolving approximately 0.200 g of polymer in 2.5 ml of deuterated tetrachloroethane in 10 mm sample tubes using a heating block and a rotary tube oven at 140 ° C. The 13C isolated NMR spectra of proton decoupled with NOE (powergated) were recorded using the following acquisition parameters: a 90 degree tilt angle, 4 dummy scans, 4096 temporary an acquisition time of 1, 6 s, a 20kHz spectrum extension, a temperature of 125 ° C, a bilevel WALTZ proton decoupling scheme and a 3.0 s relaxation delay. The resulting FID was processed using the following processing parameters: zero-padding for 32k data points and apodization using a Gaussian window function; automatic zero and first order phase correction and automatic baseline correction using a fifth order polynomial restricted to the region of interest.
[000108] Quantities were calculated using simple corrected proportions of the sign integrals of representative sites based on methods well known in the art. b) Comonomer content of polar comonomers in low density polyethylene (1) Polymers containing> 6% by weight of polar comonomer units
[000109] The content of comonomers (% by weight) was determined in a known manner based on the determination by Fourier transform infrared spectroscopy (FTIR) calibrated with quantitative nuclear magnetic resonance (NMR) spectroscopy. Below is shown the determination of the content of polar comonomers of ethylene ethyl acrylate, ethylene butyl acrylate and ethylene methyl acrylate. Film samples of the polymers were prepared for measurement by FTIR: 0.5-0.7 mm thick was used for ethylene butyl acrylate and ethylene ethyl acrylate and 0.10 mm film thickness for ethylene methyl acrylate in amount of> 6% by weight. The films were pressed using a Specac film press at 150 ° C, approximately 5 tones, 1-2 minutes and then cooled with ice water in an uncontrolled manner. The accurate thickness of the obtained film samples was measured.
[000110] After the analysis with FTIR, the baselines in the absorbance mode were drawn for the peaks that would be analyzed. The absorbance peak for the comonomer was normalized to the polyethylene absorbance peak (for example, the peak height for butyl acrylate or ethyl acrylate at 3450 cm-1 was divided with the height of the polyethylene peak at 2020 cm- 1). The calibration procedure for NMR spectroscopy was carried out in the conventional manner which is well documented in the literature, explained below.
[000111] For the determination of methyl acrylate content a sample of 0.10 mm thick film was prepared. After the analysis, the maximum absorbance for the peak for methylacrylate at 3455 cm-1 was subtracted with the absorbance value for the baseline at 2475 cm-1 (Amethylacrylate - A2475). Then the maximum absorbance peak for the polyethylene peak at 2660 cm-1 was subtracted from the absorbance value for the baseline at 2475 cm-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.
[000112] The% by weight can be converted to mol-% by calculation. It is well documented in the literature. Quantification of copolymer content in polymers by NMR spectroscopy
[000113] Comonomer content was determined by quantitative nuclear magnetic resonance (NMR) spectroscopy after basic assignment (for example, "NMR Spectra of Polymers and Polymer Additives", AJ Brandolini and DD Hills, 2000, Marcel Dekker, Inc. New York). The experimental parameters were adjusted to ensure the measurement of quantitative spectra for this specific task (for example, "200 and More NMR Experiments: A Practical Course", S. Berger and S. Braun, 2004, Wiley-VCH, Weinheim). Quantities were calculated using simple corrected proportions of the signal integrals of representative sites in a manner known in the art. (2) Polymers containing 6% by weight or less units of polar comonomers
[000114] The comonomer content (% by weight) was determined in a known manner based on the determination by Fourier transform infrared spectroscopy (FTIR) calibrated with quantitative nuclear magnetic resonance (NMR) spectroscopy. Below, the determination of the content of polar comonomers of ethylene butyl acrylate and ethylene methyl acrylate is exemplified. For FT-IR measurement, film samples from 0.05 to 0.12 mm thick were prepared as described previously in method 1). The accurate thickness of the obtained film samples was measured.
[000115] After the FT-IR analysis, the baselines in the absorbance mode were drawn for the peaks that would be analyzed. The maximum absorbance for the peak for the comonomer (for example, for methylacrylate at 1164 cm-1 and butylacrylate at 1165 cm-1) was subtracted with the absorbance value for the baseline at 1850 cm-1 (Polar Acomonomer - A1850 ). Then the maximum absorbance peak for the polyethylene peak at 2660 cm-1 was subtracted with the absorbance value for the baseline at 1850 cm-1 (A2660 - A1850). The ratio between (Acomonomer-A1850) and (A2660-A1850) was then calculated. The calibration procedure for NMR spectroscopy was carried out in the conventional manner which is well documented in the literature, which is described previously in method 1).
[000116] The% by weight can be converted to mol-% by calculation. It is well documented in the literature.
[000117] PENT (Pennsylvania Notch Test) Resistance to slow crack growth has been assessed using the Pennsylvania Notch Test (PENT) according to ISO 16241: 2005 with some modifications.
[000118] A compression-molded plate of each material was produced according to the following procedure. The granules were heated in a closed mold at 180 ° C for 15 minutes without pressure. The heat was turned off and a nominal pressure of 1.7 MPa was applied for 12.5 hours while the sample and mold were allowed to cool naturally. • Test piece dimensions: 60 mm x 25 mm x 10 mm • Main slot: 3.5 mm deep • Side slots: 0.7 mm deep • Test temperature of test pieces: 70 ° C • Stress of test (calculated over the cross-sectional area without crack): 2.0 MPa • 2 test pieces per material • The time until failure was recorded and the average of 2 test pieces calculated.
[000119] The stress test was performed according to ISO 5272: 1993 using sample geometry 5A and 250 mm / min of pulling speed using an Alwetron TCT10, Lorentzen & WettreAB tension tester. The measurement entities are: stress in the break and tension in the break.
[000120] Figure 1 illustrates the geometry of the samples used in the stress test. Figure 1. Sample geometry: 1: 50 ± 2 (mm) L0: 20 ± 0.5 (mm) 11: 25 ± 1 (mm) 12: = 75 (mm) b1: 4 ± 0.1 (mm) b2: 12.5 ± 1 (mm)
[000121] The samples for use in the stress test were molded according to this schedule: 60 s at 120 ° C and 20 bar after which the pressure was instantly increased to 200 bar and maintained throughout the rest of the modeling. The temperature was then raised to 180 ° C over 180 s and held there for 360 s after which the sample was cooled to 35 ° C over 600 s (15 ° C / min). The test sample was then punctured starting from the molded plate. This is based on ISO 1872-2 and ISO 293, however, without method B of preconditioning and cooling.
[000122] Crystallinity and melting temperature were measured with DSC using a TA Instruments Q2000. The temperature program used was starting at 30 ° C, heating to 180 ° C, an isotherm to 180 ° C for 2 min and then cooling to -15 ° C, an isotherm to -15 ° C for 2 min and then heating to 180 ° C. Heating and cooling rates are 10 ° C / min.
[000123] The samples that are cross-linked were all cross-linked at 180 ° C for 10 min and then degassed under vacuum at 70 ° C overnight to remove all peroxide by-products before crystallinity and melting temperature were measured.
[000124] The melting temperature, Tm, is the temperature at which the heat flowing to the sample is at its maximum.
[000125] The degree of crystallinity,% Crystallinity, = 100 x ΔHf / ΔH 100% where ΔH100% (J / g) is 290.0 for PE (L. Mandelkem, Macromolecular Physics, Vol. 1-3, Academic Press, New York 1973,1976 & 1980) The crystallinity assessment was carried out starting at 20 ° C. CD conductivity method
[000126] The plates are molded by compression starting from the pellets of the test polymer composition. The end plates consist of the composition of test polymers and have a thickness of 1 mm and a diameter of 330 mm.
[000127] The plates are press-molded at 130 ° C for 12 min while the pressure is gradually increased from 2 to 20 MPa. Thereafter 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 time the plate becomes completely cross-linked with that of the peroxide present in the test polymer composition. Finally, the temperature is lowered using the cooling rate of 15 ° C / min until the ambient temperature is reached when the pressure is released. The plates are immediately after the release of pressure packed in laminated paper to prevent the loss of volatile substances.
[000128] A high voltage source is connected to the upper electrode, to apply the voltage across the test sample. The resulting current through the sample is measured with an electrometer. The measurement cell is a three-electrode system with bronze electrodes. The bronze electrodes are equipped with heating tubes connected to a heating circulator, to facilitate measurements at elevated temperature and provide uniform temperature for the test sample. The diameter of the measuring electrode is 100 mm. Silicone rubber skirts are placed between the edges of the bronze electrode and the test sample, to avoid sparks from the rounded edges of the electrodes.
[000129] 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 course of the experiments lasting 24 hours. The current after 24 hours was used to calculate the conductivity of the insulation.
[000130] This method and a schematic figure of the measurement fit for conductivity measurements have been fully described in a publication presented at Nordic Insulation Symposium 2009 (Nord-IS 09), Gothenburg, Sweden, 15-17 June 2009, page 5558: Olsson et al., "Experimental determination of DC conductivity for XLPE insulation". Method for determining the amount of double bonds in the polymer composition or in the polymer A) Quantification of the amount of carbon-carbon double bonds by IR spectroscopy
[000131] Quantitative infrared (IR) spectroscopy was used to quantify the amount of carbon-carbon pairs (C = C). The calibration was achieved by previously determining the molar extinction coefficient of the functional groups C = C in the low molecular weight model compounds representative of known structure.
[000132] The amount of each of these groups (N) was determined as the number of carbon-carbon double bonds per thousand total carbon atoms (C = C / 1000C) using: N = (A x 14) / (E x L x D) where A is the maximum absorbance defined as the height of the peak, E the molar extinction coefficient of the group in question (Lmol-mm'1), L the thickness of the film (mm) and D the density of the material (gxm-1).
[000133] The total amount of C = C bonds per thousand total carbon atoms can be calculated by adding N to the components that contain individual C = C.
[000134] For polyethylene samples, solid state infrared spectra were recorded using an FTIR spectrometer (Perkin Elmer 2000) on thin compression-molded films (0.5-1.0 mm) at a resolution of 4 cm- 1 and analyzed in the absorption mode. 1) Compositions of polymers comprising homopolymers and copolymers of polyethylene, except copolymers of polyethylene with> 0.4% by weight of polar comonomer
[000135] For polyethylenes, three types of functional groups containing C = C were quantified, each with a characteristic absorption and each calibrated for a different model compound resulting in individual extinction coefficients: • vinyl (R-CH = CH2) via 910 cm-1 based on 1-decene [dec-1-ene] providing E = 13.13 l • mol-1 • mm-1 • vinylidene (RR'C = CH2) via 888 cm-1 based on 2-methyl-1-heptene [2-methylhept-1-ene] providing E = 18.24 l • mol-1 • mm-1 • trans-vinylene (R-CH = CH-R ') via 965 cm-1 based on trans-4-decene [(E) -dec-4-ene] providing E = 15.14 l-moH-mm'1
[000136] For homopolymers or copolymers of polyethylene with <0.4% by weight of polar comonomer the linear baseline correction was applied between approximately 980 and 840 cm-1. 2) Polymer compositions comprising polyethylene copolymers with> 0.4% by weight of polar comonomer
[000137] For polyethylene copolymers with> 0.4% by weight of polar comonomer two types of functional groups containing C = C were quantified, each with a characteristic absorption and each calibrated for a different model compound resulting in coefficients individual extinguishing media: • vinyl (R-CH = CH2) via 910 cm-1 based on 1-decene [dec-1-ene] providing E = 13.13 l-moH-mm'1 • vinylidene (RR'C = CH2) via 888 cm-1 based on 2-methyl-1-heptene [2-methylhept-1-ene] providing E = 18.24 l-moH-mm'1 EBA:
[000138] For poly (ethylene-co-butylacrylate) (EBA) systems the linear baseline correction was applied between approximately 920 and 870 cm-1. EMA:
[000139] For poly (ethylene-co-methylacrylate) (EMA) systems the linear baseline correction was applied between approximately 930 and 870 cm-1. 3) Compositions of polymers that comprise unsaturated low molecular weight molecules
[000140] For systems containing species that contain low molecular weight C = C, direct calibration was performed using the molar extinction coefficient of the absorption of C = C in the low molecular weight species themselves. B) Quantification of molar extinction coefficients by IR spectroscopy
[000141] The molar extinction coefficients were determined according to the procedure provided in ASTM D3124-98 and ASTM D6248-98. Infrared spectra in the solution state were recorded using an FTIR spectrometer (Perkin Elmer 2000) equipped with a 0.1 mm liquid path length cell at a resolution of 4 cm-1.
[000142] The molar extinction coefficient (E) was determined as l-moN-mm-1 via: E = A / (C x L) where A is the maximum absorbance defined as the peak height, C the concentration ( mol ^ l-1) and L the cell thickness (mm).
[000143] At least three solutions at 0.18 molT1 in carbonodisulfide (CS2) were used and the mean value of the molar extinction coefficient determined. Gel content
[000144] The gel content is measured according to ASTM D 276501, Method A, using decalin extraction. The samples for method A were prepared by modeling starting from the composition of test polymers that comprise peroxide in a certain amount. The modeling procedure was as follows: The test sample composition was pressed 60 s at 120 ° C and 20 bar after which the pressure was instantly increased to 200 bar and maintained throughout the rest of the modeling. The temperature was then raised to 180 ° C over 180 s and held there for 360 s after which the sample was cooled to 35 ° C over 600 s (15 ° C / min). The crosslinking occurred during the modeling step.
[000145] The reticulated plates obtained were then cut into pieces of 20mm x 20mm x 2mm and cut with microtome in strips of 200μm x 2mm. The 0.3 ± 0.015 g of the strips was then used in the procedure that is described in ASTM D 2765-01, Method A, with the following two variations starting from this standard: 1) An additional extraction for 1 hour with fresh decaline was performed for the purpose of ensuring that all solubles have been extracted. 2) Only 0.05% of antioxidant (Irganox 1076) was added to the decal instead of 1% as specified in the standard.
[000146] The gel content was then calculated according to said ASTM D 2765-01. Experimental part Preparation of polymers from the examples of the present invention and the comparative example
[000147] All polymers were low density polyethylene produced in a high pressure reactor. As for CTA feeds, for example, the PA content can be supplied in the form of liter / hour or kg / h and converted into any units using the PA density of 0.807 kg / liter for recalculation. LDPE1:
[000148] Ethylene with recycled CTA was compressed in a 5-stage pre-compressor and a 2-stage hyper-compressor with intermediate cooling to reach the initial reaction pressure of ca 2628 bar. The total performance of the compressor was ca 30 tons / hour. In the compressor area, approximately 4.9 liters / hour of propion 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. Here, 1,7-octadiene was added to the reactor in the amount of 27 kg / h. The compressed mixture was heated to 157 ° C in a preheating section of a two-zone tubular reactor with front feed with an internal diameter of ca 40 mm and a total length of 1200 meters. A mixture of commercially available peroxide radical initiators dissolved in isododecane was injected shortly after preheating in an amount sufficient for the exothermic polymerization reaction to reach maximum temperatures of ca 275 ° C after which it was cooled to approximately 200 ° Ç. The reaction temperature of the second subsequent peak was 264 ° C. The reaction mixture was depressurized by an expulsion valve, cooled and the polymer was separated from the unreacted gas. LDPE2:
[000149] Ethylene with recycled CTA was compressed in a 5-stage pre-compressor and a 2-stage hyper-compressor with intermediate cooling to reach the initial reaction pressure of ca 2904 bar. The total performance of the compressor was ca 30 tons / hour. In the compressor area, approximately 105 kg of propylene / hour were added as chain transfer agents to maintain an MFR of 1.89 g / 10 min. Here, 1,7-octadiene was added to the reactor in the amount of 62 kg / h. The compressed mixture was heated to 159 ° C in a preheating section of a three-zone tubular reactor with front feed with an internal diameter of ca 40 mm and a total length of 1200 meters. A mixture of commercially available peroxide radical initiators dissolved in isododecane was injected shortly after preheating in an amount sufficient for the exothermic polymerization reaction to reach maximum temperatures of ca 289 ° C after which it was cooled to approximately 210 ° Ç. The reaction temperatures of the 2nd and 3rd subsequent peaks were 283 ° C and 262 ° C respectively with a cooling between them to 225 ° C. The reaction mixture was depressurized by an expulsion valve, cooled and the polymer was separated from the unreacted gas.
[000150] The components of the polymer compositions of the examples of the invention 1 to 4, reference example 1 (non-crosslinked polyolefin) and reference example 2 (represents the cross-linked polymer composition of the prior art with a conventional amount of peroxide) and the properties and experimental results of the compositions are given in table 1. The additives used are commercially available: Peroxide: DCP = dicumil peroxide (CAS No. 80-43-3) Antioxidants: 4,4'-thiobis (2-tertbutil-5 -methylphenol) (CAS number: 96-69-5). Additive: 2,4-Diphenyl-4-methyl-1-pentene (CAS-No. 6362-80-7).
[000151] The amount of DCP is given in mmol of the -OO- functional group content per kg of the polymer composition. Quantities are also provided in parentheses as% by weight (% by weight). Table 1: The properties of the compositions of the examples of the invention and reference:



[000152] Weight% values provided at the bottom of the table in the total amount of the polymer composition. Table 2: Properties of the polyolefin components

[000153] Table 1 shows that the electrical conductivity of the polymer compositions of the invention is remarkably reduced compared to that of the reference polymer composition 2, while the mechanical properties expressed in the form of stress and PENT properties remain at the level comparable to or even improved over ref. 2. In addition, the gel content results show that the polymer compositions of the invention have a degree of crosslinking that is possible for the power cable including DC power cable applications.

权利要求:
Claims (6)
[0001]
1. Direct current reticulated power cable (CD), comprising a conductor which is surrounded by at least one internal semiconductor layer comprising a first semiconductor composition, an insulation layer comprising a polymer composition and an external semiconductor layer comprising a second semiconductor composition, in such order, in which the polymer composition of the insulation layer comprises an antioxidant and a crosslinked polyolefin, characterized in that the polyolefin is an ethylene unsaturated LDPE copolymer with 1,7-octadiene, 1,9 -decadiene, 1,11- dodecadiene, 1,13-tetradecadiene, or mixtures thereof, wherein the polymeric composition comprises before crosslinking a peroxide that is in an amount of less than 35 mmol of -OO- / kg of the polymeric composition , and in which the crosslinked polymer composition has an electrical conductivity of 45 fS / m or less, when measured according to the CD conductivity process that is described item in "Determination Methods"; where the polyolefin contains before crosslinking a total amount of more than 0.30 / 1000 carbon atoms, and a total amount of carbon-carbon double bonds, which originate from vinyl groups, vinylidene groups and trans-vinylidene groups, if present, of more than 0.5 / 1000 carbon atoms, and wherein said composition consists of said unsaturated LDPE polymer as the only polyolefin component.
[0002]
2. Direct current crosslinked power cable (CD) according to claim 1, characterized by the fact that the crosslinked polymer composition has an electrical conductivity of 40 fS / m or less, more preferably from 0.01 to 38 fS / m or less, even more preferably from 0.5 to 35 fS / m, which is measured according to the CD conductivity process which is described in "Determination Methods".
[0003]
3. Direct current crosslinked power cable (CD) according to claim 1 or 2, characterized by the fact that the crosslinked polymer composition has a PENT (Pennsylvania Notch Test) lifetime of 200 hours or more, preferably 400 hours or more, preferably 500 hours or more, more preferably 800 hours or more, which is measured according to the PENT test with a load at 2 MPa and at an aging temperature of 70 ° C which is described in "Methods of Determination".
[0004]
4. Direct current crosslinked power cable (CD) according to any one of claims 1 to 3, characterized by the fact that the crosslinked polymer composition has a 70 ° C Break Stress of 7.0 MPa or more, preferably 10.0 MPa or more, more preferably 12.0 MPa or more or at - 10 ° C of 25.0 MPa or more, preferably 26.0 MPa or more, preferably 30.0 MPa or more, which is measured according to the Stress test method which is described in "Determination Methods".
[0005]
Direct current reticulated power cable (CD) according to any one of claims 1 to 4, characterized by the fact that the crosslinked polymer composition has a (%) breakage voltage at 70 ° C of 350% or more, preferably 400% or more, preferably 450% or more or at -10 ° C of 400% or more, which is measured according to the Stress test method which is described in "Determination Methods".
[0006]
6. Process for the production of a direct current reticulated power cable (CD), as defined in any one of claims 1 to 5, in which the process comprises the steps of - application, preferably through (co) extrusion, a layer internal semiconductor comprising a first semiconductor composition, an insulation layer comprising a polymer composition and an external semiconductor layer comprising a second semiconductor composition, in such an order, characterized by the fact that the polymer composition of the insulation layer comprises a antioxidant and a polymer composition, comprising an ethylene LDPE unsaturated copolymer with 1,7-octadiene, 1,9-decadiene, 1,11-dodecadiene, 1,13-tetradecadiene, and a peroxide in an amount less than 35 mmols of -OO- / kg of the polymer composition, preferably 34 mmols of -OO- / kg of the polymer composition or less, preferably of 33 mmols of -OO- / kg of the polymer composition or less, preferably of 30 mmols of -OO- / kg of the polymer composition or less, more preferably of 5.0 to 30 mmols of -OO- / kg of the polymer composition, more preferably of 7.0 to 30 mmols of - OO- / kg of the polymer composition, more preferably from 10.0 to 30 mmols of -OO- / kg of the polymer composition, and where the polyolefin contains, before cross-linking, the cross-linked vinyl groups in a total amount of more than 0 , 30/1000 carbon atoms, and a total amount of carbon-carbon double bonds, which originate from vinyl groups, vinylidene groups and trans-vinylidene groups, if present, of more than 0.5 / 1000 carbon atoms, and wherein said composition consists of said unsaturated LDPE polymer as the only polyolefin component; and - cross-linking at least the polymer composition of the insulation layer under cross-linking conditions.

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EP2499172B2|2019-11-06|

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IN2012DN03433A|2015-10-23|

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CN102666602B|2015-11-25|

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US20200115477A1|2020-04-16|

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CN102666602A|2012-09-12|

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KR101962839B1|2019-03-27|

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AU2010318182A1|2012-05-17|

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EP3098244B1|2019-01-02|

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US20130000947A1|2013-01-03|

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KR102080451B1|2020-02-21|

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EA201290300A1|2012-12-28|

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EP3098244A1|2016-11-30|

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AU2010318182B2|2014-07-24|

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BR112020011846A2|2017-12-18|2020-11-24|Borealis Ag|polymer composition comprising a polyethylene|

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JP2022516118A|2018-12-28|2022-02-24|ダウ グローバル テクノロジーズ エルエルシー|Curable composition containing unsaturated polyolefin|

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EP3739597A1|2019-05-16|2020-11-18|Borealis AG|Composition|

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KR20220010605A|2019-05-16|2022-01-25|보레알리스 아게|Composition comprising LDPE, polypropylene and functionalized polyolefin|

法律状态:
2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-03-19| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|

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2019-07-23| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|

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2019-12-31| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2020-06-16| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2020-10-13| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2021-02-02| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-03-30| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 10 (DEZ) ANOS CONTADOS A PARTIR DE 30/03/2021, 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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EP09175688.2|2009-11-11|

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EP09175688|2009-11-11|

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PCT/EP2010/066712|WO2011057928A1|2009-11-11|2010-11-03|Crosslinkable polymer composition and cable with advantageous electrical properties|

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