alternating current (ac) electric cable and its production process

专利摘要:
POLYMERIC COMPOSITION AND AN ELECTRICAL CABLE UNDERSTANDING THE POLYMERIC COMPOSITION. The present invention relates to the use of a polymeric composition for producing an insulating layer of an alternating current (AC) electric cable and an AC cable surrounded by at least one insulating layer comprising said polymeric composition.
公开号:BR112013011084B1
申请号:R112013011084-8
申请日:2011-11-01
公开日:2020-12-22
发明作者:Ulf Nilsson；Annika Smedberg；Alfred Campus
申请人:Borealis Ag；
IPC主号:

专利说明:

Field of invention
[001] The invention relates to a polymeric composition suitable for a layer of an electrical cable, the use of the polymeric composition in a layer of an electrical cable, an electrical cable comprising the polymeric composition and a process for producing the cable. Fundamentals of Technique
[002] Polyolefins produced in a high pressure process (HP) are widely used in demanding polymeric applications where polymers must meet high mechanical and / or electrical requirements. For example, in electrical cable applications, particularly medium voltage (MV) and especially high voltage (HV) and extra high voltage (EHV) cable applications, the electrical properties of the polymeric composition are of significant importance. In addition, requirements for electrical properties may differ for different cable applications, such as alternating current (AC) and direct current (DC) cable applications.
[003] A typical electrical cable comprises a conductor surrounded by at least one inner semiconductor layer, one insulation layer and one outer semiconductor layer, in that order. Space load
[004] There is a fundamental difference between AC and DC in relation to the distribution of electric field in the cable. The electric field in an AC cable is easily calculated, as it depends on only one property of the material, namely, the relative permittivity (dielectric constant) with known temperature dependence. The electric field will not influence the dielectric constant. On the other hand, the electric field in a DC cable is much more complex and depends on the conduction, trapping and build-up of electrical charges, called space charges, within the insulation. Spatial loads within the insulation will distort the electric field and can cause very high voltage points, possibly so high that it will cause a failure of the dielectric.
[005] Usually space charges are located in the vicinity of the electrodes; charges of the same polarity as the neighboring electrode are called homocharges, opposite polarity charges are called heterocharges. Heterocharges will increase the electric field at this electrode, homocharges will instead reduce the electric field. Tan δ (dielectric losses)
[006] Tan δ and thus dielectric losses (which are linearly proportional to tan δ) will be as low as possible for both technical and economic reasons: • Low losses mean that a low amount of transmitted electrical energy is lost as thermal energy within cable insulation. These losses will mean economic losses for the power line operator. • Low losses will reduce the risk of thermal runaway, i.e., an unstable situation in which the insulation temperature will increase due to tan δ. When the temperature is increased, tan δ will also normally rise. This will further increase the dielectric losses, and thus the temperature. The result will be a dielectric failure of the cable that needs to be replaced. Compressor lubricants
[007] The HP process is typically operated at high pressures of up to 4000 bar. In known HP reactor systems, the starting monomer (s) must be compressed (pressurized) before being introduced into the high pressure polymerization reactor. Compressor lubricants are conventionally used in hypercompressor (s) for lubricating cylinders, in order to allow the mechanically demanding step of compression of the starting monomer (s). It is well known that small amounts of lubricant that normally leak through the seals in the reactor mix with the monomer (s). As a consequence, the reaction mixture comprises traces (up to hundreds of ppm) of the compressor lubricant during the polymerization step of the monomer (s). These traces of compressor lubricants can have an effect on the electrical properties of the final polymer.
[008] Examples of commercial compressor lubricants can be mentioned, for example, polyalkylene glycol (PAG): R [Cx RyHz-O] n H, where R can be H or straight or branched hydrocarbyl ex, y, x, n are independent integers that can vary in a known way, and lubricants based on mineral oil (by-product of petroleum distillation). Compressor lubricants that are based on mineral oil that meets the requirements established for white mineral oil in the European Directive (European Directive) 2002/72 / EC, Annex V, for plastics used in contact with food, are used eg to polymerize polymers especially for the food and pharmaceutical industry. Such mineral oil based lubricants usually contain lubricity additive (s) and may also contain other types of additive (s), such as antioxidants.
[009] WO2009012041 from Dow discloses that in a high pressure polymerization process, in which compressors are used to pressurize the reagents, ie one or more monomer (s), the compressor lubricant can have an effect on the properties of the polymer polymerized. The document describes the use of a polyether polyol that comprises one or no hydroxyl functionality, such as a compressor lubricant, to prevent premature crosslinking, particularly of silane modified HP polyolefins. WO2009012092 from Dow discloses a composition comprising (i) an HP polyolefin free of silane functionality and (ii) a hydrophobic polyether polyol of the PAG type in which at least 50% of its molecules comprise no more than a hydroxyl functionality. Component (ii) appears to originate from a compressor lubricant. The composition is, among others (ia), for W&C applications and is presented as a dielectric loss reducer in MV and HV electrical cables, see page 2, paragraph 0006. In both applications, hydrophilic groups (for example, groups hydroxyl) present in the compressor lubricant can result in increased uptake of water by the polymer, which in turn can increase electrical losses or, respectively, premature pre-vulcanization (scorch), when the polymer is used as a cable layer. The problems are solved by a specific lubricant type PAG with reduced amount of hydroxyl functionalities.
[0010] There is a continuing need, in the field of polymers, to find polymers that are suitable for demanding polymeric applications such as applications in wires and cables with high demands and severe regulations. Objectives of the invention
[0011] One of the objectives of the present invention is to provide a polymeric composition for use in an insulating layer of an alternating electrical cable (AC) with improved properties, as well as an alternating electrical cable (AC) with improved properties.
[0012] The invention and additional objectives of it are described and defined in detail below. Description of the invention
[0013] The invention relates to the use of a polymeric composition comprising a polyolefin and a crosslinking agent in which the polymeric composition has a dielectric loss expressed as tan δ (50 Hz) of 12.0 x 10-4 or less, when measured at 25 kV / mm and 130 ° C according to "Test for measuring tan δ on 10 kV cables" as described in the descriptive part under Determination methods, to produce an insulation layer for an MV, HV or EHV AC, preferably from an HV or EHV AC electrical cable, comprising a first semiconductor composition, an insulation layer comprising a polymeric composition, an outer semiconductor layer comprising a second semiconductor composition and optionally a jacketing layer comprising a composition coverage, in that order.
[0014] Furthermore, the invention relates to an alternating current (AC) electric cable, comprising a conductor surrounded by at least one inner semiconductor layer comprising a first semiconductor composition, an insulation layer comprising a polymeric composition, a outer semiconductor layer comprising a second semiconductor composition and optionally a cover layer comprising a cover composition, in that order, wherein the polymeric composition of the insulation layer comprises a polyolefin and a crosslinking agent, and wherein the polymeric composition of the coating layer insulation has a dielectric loss expressed as tan δ (50 Hz) of 12.0 x 10-4 or less, when measured at 25 kV / mm and 130 ° C according to "Test for measuring tan δ on 10 kV cables" as described in the descriptive part under "Determination methods".
[0015] The cable of the invention is also referred to here for short as "cable". The polymeric composition of the cable insulation layer is also referred to hereinafter as "Polymeric composition" or "polymeric composition". The term "tan δ" or "tan delta", as used herein, means tangent delta which is a well-known measure of dielectric loss. As mentioned, the method for determining tan delta is described below in "Determination methods".
[0016] The term "conductor" here and above means that the conductor consists of one or more wires. In addition, the cable may contain one or more of such conductors. Preferably, the conductor is an electrical conductor and comprises one or more metallic wires.
[0017] The polymeric composition of the insulation layer has surprisingly reduced dielectric losses expressed as tan delta at high temperature and high voltage. Dielectric losses are due both to the oscillation of dipoles (such as carbonyls) and to the conduction of free charge carriers (electrons, ions). The relative importance of these mechanisms depends on parameters such as temperature, electric field and frequency during measurement. At room temperature and 50 Hz, the main contribution clearly falls to the dipoles. However, at temperatures above the melting point, especially with a high electric field, the contribution of free charge carriers increased significantly.
[0018] The polymeric composition with unexpectedly low dielectric losses at high voltage and high temperatures thus has advantageously low conductivity and is a layer material highly suitable for insulating layers of electrical cables, preferably alternating current electrical cables ( B.C). In addition, unexpectedly low dielectric losses are maintained even when the polymeric composition is surrounded by semiconductor layers.
[0019] The cable preferably comprises a cover layer. When the semiconductor layers and the insulation layer are combined with the optional cover layer, and preferable, then a superior AC power cable is obtained, which is particularly suitable for use as a cable medium voltage (MV), high voltage (HV) or extra high voltage (EHV) electric AC, more preferably as an AC electric cable operating at any voltages, preferably greater than 36 kV, most preferably as an AC HV or EHV.
[0020] The polyolefin of the polymeric composition is preferably produced with a high pressure process (HP). As well known, the high pressure reactor system typically includes a compression zone to a) compress one or more starting monomer (s) into one or more compressor (s) also known as hypercompressor (s), a polymerization zone to b) polymerize the monomer (s) in one or more polymerization reactor (s) and a recovery zone to c) separate unreacted products in one or more separators and to recover the separated polymer. In addition, the recovery zone of the HP reactor system typically comprises a mixing and pelletizing section, such as a pelletizing extruder, after the separator (s), to recover the separated polymer in pellet form. The process is described in more detail below.
[0021] Surprisingly, when a mineral oil is used in compressors for cylinder lubrication in an HP reactor system to compress the starting monomer (s), the resulting polyolefin has dielectric losses at high voltage and surprisingly low high temperatures that contribute to excellent electrical properties of the polymeric composition in a cable insulation layer, as mentioned above or below.
[0022] Compressor lubricant here means a lubricant used in compressor (s), i.e. in hypercompressor (s), for cylinder lubrication.
[0023] More preferably the polymeric composition of the insulation layer comprises a polyolefin and a crosslinking agent, and the polyolefin can be obtained by a high pressure (HP) process comprising (a) compressing one or more monomer (s) under pressure in a compressor, using a compressor lubricant for lubrication, (b) polymerize a monomer, optionally together with one or more comonomer (s) in a polymerization zone, (c) separate the obtained polyolefin from unreacted products and recover the polyolefin separated into a recovery zone,
[0024] in which in step a) the compressor lubricant comprises mineral oil.
[0025] The resulting polymeric composition has the advantageous reduced dielectric losses at the above mentioned high temperatures and high voltages.
[0026] The terms "obtainable by the process" or "produced by the process" are used interchangeably here and mean the category "product of the process", i.e. that the product has a technical characteristic that is due to the preparation process.
[0027] Therefore, it is more preferable that the cable insulation layer contains a polymer composition with dielectric loss expressed as tan δ (50 Hz) of 12.0 x 10-4 or less, when measured at 25 kV / mm and 130 ° C according to "Test for measuring tan δ on 10 kV cables" as described below in "Determination methods"; and
[0028] wherein the polyolefin of the polymeric composition is obtainable by a high pressure process comprising (a) compressing one or more monomer (s) under pressure in a compressor, using a compressor lubricant for lubrication, (b) polymerizing a monomer, optionally together with one or more comonomer (s), in a polymerization zone, (c) separating the obtained polyolefin from unreacted products and recovering the separated polyolefin in a recovery zone,
[0029] in which in step a) the compressor lubricant comprises mineral oil.
[0030] Even more preferably, the polymeric composition of the insulation layer has the dielectric loss expressed as tan δ (50 Hz) of 12.0 x 10-4 or less, preferably 11.0 x 10-4 or less, preferably 0.01 10.0 x 10—4, more preferably 0.1 9.0 x 10—4, more preferably 0.3 8.0 x 10—4, more preferably 0.5 7.0 x 10-4, when measured at 25 kV / mm and 130 ° C according to "Test for measuring tan δ in 10 kV cables", as described below in "Determination methods".
[0031] In a most preferred embodiment of the cable, at least the polymeric composition of the insulation layer is crosslinkable and is crosslinked in the presence of the crosslinking agent, before the cable end use application.
[0032] "Crosslinkable" means that the polymeric composition can be crosslinked using crosslinking agent (s), prior to use in its final application. Crosslinkable polymeric composition comprises the polyolefin and the crosslinking agent. It is preferred that the polyolefin of the polymeric composition is cross-linked. The crosslinking of the polymeric composition is carried out at least with the crosslinking agent of the polymeric composition of the invention. In addition, the crosslinked polymeric composition or, respectively, the crosslinked polyolefin, is most preferably crosslinked via radical reaction with a free radical generating agent. The cross-linked polymeric composition has a typical network, among others, interpolymeric cross-links (bridges), as is well known in the field. As is evident to a skilled person, the crosslinked polymer can be and is defined herein with characteristics that are present in the polymeric composition or polyolefin before or after crosslinking, as mentioned or evident in the context. For example, the presence of the crosslinking agent in the polymeric composition or the type and compositional property, such as flow rate (MFR), density and / or degree of unsaturation, of the polyolefin component are defined, unless otherwise specified, before crosslinking, and characteristics after crosslinking are, for example, electrical property or degree of crosslinking measured in the crosslinked polymeric composition.
[0033] The preferred crosslinking agent of the polymeric composition is (are) (a) free radical-generating agent (s), more preferably peroxide (s).
[0034] Thus, the present preferred cross-linked polymeric composition is obtainable by cross-linking with peroxide as defined above or below. The terms "crosslinkable", "crosslinked with" and "crosslinked polymeric composition" are used here and mean that the crosslinking step provides an additional technical feature for the polymeric composition as will be explained below.
[0035] It is evident to a specialized person that the cable may optionally contain one or more other layers comprising one or more shield (s) (screen (s)), (one) cover layer (s) or other protective layers , which are conventionally used in the field of wires and cables (W&C).
[0036] The preferred subgroups, properties and modalities of the polymeric composition, first semiconductor composition, second semiconductor composition and cover composition before or after any optional crosslinking apply equally and independently to the compositions and layers as such, as well as to the crosslinkable cable and to the crosslinked cable as defined above or below.
[0037] Preferably, the polymeric composition comprises the crosslinking agent, preferably peroxide, in an amount of less than 10% by weight, less than 6% by weight, more preferably less than 5% by weight, less than 3.5 % by weight, even more preferably from 0.1% by weight to 3% by weight, and most preferably from 0.2% by weight to 2.6% by weight, based on the total weight of the polymeric composition.
[0038] Peroxide is the preferred crosslinking agent. Non-limiting examples are organic peroxides, such as di-t-amylperoxide, 2,5-di (tbutylperoxy) -2,5-dimethyl-3-hexino, 2,5-di (t-butylperoxy) -2,5-dimethyl- hexane, t-butylcumilpe-oxide, di (t-butyl) peroxide, dicumylperoxide, butyl4,4-di (t-butylperoxy) -valerate, 1,1-di (t-butylperoxy) -3,3,5-trimethylcyclo- hexane, t-butylperoxybenzoate, dibenzoylperoxide, di (t-butylperoxy-isopropyl) benzene, 2,5-dimethyl-2,5-di (benzoylpe-roxy) hexane, 1,1-di (tbutylperoxy) cyclohexane, 1,1- di (tamylperoxy) cyclohexane, or any mixtures thereof. Preferably, the peroxide is selected from 2,5-di (t-butylperoxy) -2,5-dimethylhexane, di (t-butylperoxy-isopropyl) benzene, dicumylperoxide, t-butylcumilpe-oxide, di (tbutil) peroxide, or mixtures thereof. Most preferably, the peroxide is dicumylperoxide.
[0039] In addition to the crosslinking agent (s), the polymeric composition with the advantageous electrical properties may contain other component (s), such as other polymeric component (s) and / or one or more additive (s). As optional additives, the polymeric composition may contain antioxidant (s), stabilizer (s), water tree retardant additive (s) (water tree), processing aid (s), pre- vulcanization, metal deactivator (s), crosslinking reinforcer (s), flame retardant additive (s), acid or ion scavengers, inorganic charge (s), water stabilizer (s) tension or any mixtures thereof.
[0040] In a most preferred embodiment, the polymeric composition comprises one or more antioxidant (s) and optionally one or more pre-vulcanization retarder (s) (scorch retarders (SR)).
[0041] As non-limiting examples of antioxidants can be mentioned. sterically hindered or semi-hindered phenols, aromatic amines, sterically hindered aliphatic amines, organic phosphites or phosphonites, thiocompounds, and mixtures thereof. Non-limiting examples of thiocompounds are, for example, 1. sulfur-containing phenolic antioxidant (s), preferably selected from thiobisphenols, the most preferred being 4,4'-thiobis (2-t-butyl-5-methylphenol) (CAS number: 96-69-5), 2,2'-thiobis (6-tbutyl-4-methylphenol), 4,4'-thiobis (2-methyl-6-t-butylphenol), thiodethylene bis [3 ( 3,5-di-t-butyl-4-hydroxyphenyl) propionate, or 4,6-bis (octylmethyl) -ocresol (CAS: 110553-27-0) or derivatives thereof; or any mixtures thereof, 2. Other thiocompounds such as di-stearyl-thio-dipropionate or similar compounds with varying lengths of carbon chains; or mixtures thereof, 3. or any mixtures of 1) and 2). Group 1) above is the preferred antioxidant (s).
[0042] In this preferred embodiment the amount of antioxidant is preferably from 0.005 to 2.5% by weight, based on the weight of the polymeric composition. The antioxidant (s) is (are) preferably added in an amount of 0.005 to 2.0% by weight, more preferably 0.01 to 1.5% by weight, even more preferably 0.03 to 0.8% by weight, even more preferably 0.04 to 0.8% by weight, based on the weight of the polymeric composition.
[0043] In another preferred embodiment, the polymeric composition comprises at least one or more antioxidants and one or more pre-vulcanization retarders.
[0044] The pre-vulcanization retardant (SR) is a type of additive well known in the field and can, among others, prevent premature crosslinking. As is also known, SRs can also contribute to the level of unsaturation of the polymeric composition. As examples of pre-vulcanization retarders, allyl compounds, such as dimers of aromatic alpamethyl alkenyl monomers, preferably 2,4-di-phenyl-4-methyl-1-pentene, substituted or unsubstituted diphenylethylenes, quinone derivatives, may be mentioned. hydroquinone derivatives, esters and ethers containing monofunctional vinyl, monocyclic hydrocarbons having at least two or more double bonds, or mixtures thereof. Preferably, the pre-vulcanization retardant amount is in the range of 0.005 to 2.0% by weight, more preferably in the range of 0.005 to 1.5% by weight, based on the weight of the polymeric composition. Other preferred ranges are, for example, from 0.01 to 0.8% by weight, from 0.02 to 0.75% by weight, from 0.02 to 0.7% by weight, or from 0.03 to 0.60% by weight, based on the weight of the polymer composition. The preferred SR of the polymeric composition is 2,4-diphenyl-4-methyl-1-pentene (CAS number 6362-80-7).
[0045] The polymeric 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 80 to 80% by weight. 100% by weight and more preferably 85 to 100% by weight of polyolefin, based on the total weight of the polymer component (s) present in the polymeric composition. The preferred polymeric composition consists of polyolefin as the sole polymer component. The expression means that the polymeric composition does not contain other polymers as components, with polyolefin being the only polymer component. However, it should be understood that the polymeric composition may contain component (s) other than polymer component (s), as an additive (s) that can optionally be added in admixture with a carrier polymer, ie in a so-called "master batch".
[0046] In an even more preferable embodiment of the cable, at least the first semiconductor composition of the inner semiconductor layer and a polymeric composition of the insulation layer are cross-linked before the final application on the cable. The cover composition of the optional and preferred cover layer can also be cross-linked.
[0047] In addition, each of the first and second semiconductor compositions and the optional, and preferred, cover composition, when crosslinked, can contain any crosslinking agent and is preferably crosslinked in a conventional manner using conventional amounts of the crosslinking agent used. For example, any of the semiconductor compositions or the optional, and preferred, topping composition can be crosslinkable by a peroxide or via crosslinkable groups, such as via hydrolyzable silane groups. Peroxide is preferably used in the amounts indicated above. Hydrolyzable silane groups can be introduced into the polymer of the composition by copolymerization of olefin monomer (s), preferably ethylene, with comonomers containing silane group or by grafting the polymer with compounds containing silane groups, ie by chemical modification of the polymer by adding silane groups mainly in a radical reaction. Such comonomers and compounds containing silane groups are well known in the field and, for example, commercially available. The hydrolyzable silane groups are then typically crosslinked by hydrolysis and subsequent condensation in the presence of a silanol and H2 O condensation catalyst in a manner known in the art. The silane crosslinking technique is also well known in the art.
[0048] The invention also relates to a process for producing a crosslinkable and crosslinked alternating current (AC) electric cable, as defined above or below, using the polymeric composition of the invention. Polyolefin component of the polymeric composition of the cable insulation layer
[0049] The following preferable modalities, properties and subgroups of the polyolefin component suitable for the polymeric composition are generalizable so that they can be used in any order or combination to define the preferred modalities of the polymeric composition. In addition, it is evident that the description given applies to the polyolefin before being cross-linked.
[0050] The term polyolefin means both an olefin homopolymer and an olefin copolymer with one or more comonomer (s). As well-known "comonomer" refers to copolymerizable comonomer units.
[0051] The polyolefin can be any polyolefin, such as a conventional polyolefin, which is suitable as a polymer in an insulating layer of the AC power cable.
[0052] The polyolefin can be, for example, a commercially available polymer or it can be prepared according to or analogously to a known polymerization process described in the chemical literature.
[0053] More preferably, the polyolefin is a polyethylene produced in a high pressure process, more preferably a low density polyethylene LDPE 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 covering HP polyethylenes similar to LDPE with low, medium and higher densities; The term LDPE describes and distinguishes only the nature of polyethylene with typical characteristics, as different branching architecture, when compared to the PE produced in the presence of an olefin polymerization catalyst.
[0054] LDPE as a polyolefin means a low density ethylene homopolymer (hereinafter referred to as LDPE homopolymer) or a low density ethylene copolymer with one or more comonomer (s) (hereinafter referred to as LDPE copolymer). The one or more LDPE copolymer comonomers are preferably selected from polar comonomer (s), non-polar comonomer (s) or a mixture of polar comonomer (s) and non-polar comonomer (s) as defined above or below. In addition, said LDPE homopolymer or LDPE copolymer such as said polyolefin can optionally be unsaturated.
[0055] As a polar comonomer for the LDPE copolymer as said polyolefin, comonomer (s) containing hydroxyl group (s), alkoxy group (s), carbonyl group (s), carboxyl group (s) or ether group (s) 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 polar LDPE copolymer comonomer (s) is (are) selected from the groups of acrylate (s), methacrylate (s) or acetate (s), or any mixtures of the themselves. If present in said LDPE copolymer, the polar comonomer (s) is (are) preferably selected (s) from the group of alkyl acrylates, alkyl methacrylates or vinyl acetate, or a mixture thereof. More preferably, said polar comonomers are selected from C1a C6-alkyl acrylates, C1a C6-alkyl methacrylates or vinyl acetate. Even more preferably, said polar LDPE copolymer is an ethylene copolymer with C1a C4-alkyl acrylate, such as methyl, ethyl, propyl or butyl acrylate, or vinyl acetate, or any mixture thereof.
[0056] As the non-polar comonomer (s) for the LDPE copolymer as said polyolefin, comonomer (s) other than the above-defined polar comonomers can be used. Preferably, the non-polar comonomers are different from the comonomer (s) containing hydroxyl group (s), alkoxy group (s), carbonyl group (s), carboxyl group (s), ether group (s) ) ester. A preferred non-polar comonomer group (s) includes, preferably consists of, monounsaturated comonomer (s) (= a double bond), preferably olefins, preferably alpha-olefin (s), more preferably C3 to C10 alpha-olefin (s), 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 a silane group; or any mixtures thereof. The polyunsaturated comonomer (s) is (are) further described below with respect to unsaturated LDPE copolymers.
[0057] 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. weight, more preferably less than 25% by weight, of one or more comonomer (s).
The polymeric composition, preferably the polyolefin component thereof, more preferably the LDPE polymer, may optionally be unsaturated, i.e. the polymeric composition, preferably the polyolefin, preferably the LDPE polymer, may contain vinyl groups. The "unsaturated" here means that the polymeric composition, preferably polyolefin, contains vinyl groups / 1000 carbon atoms in a total amount of at least 0.04 / 1000 carbon atoms. In general, "vinyl group" here means portion CH2 = CH.
[0059] As it is well known unsaturation can be passed to the polymeric composition, among others, by means of polyolefin, compound (s) of low molecular weight (Mw), as reinforcing additive (s) of reticulation or retarder pre-vulcanization (s), or any combinations thereof. If two or more sources of vinyl groups are chosen to be used to provide unsaturation, then the total amount of vinyl groups in the polymeric composition means the sum of the vinyl groups present in the vinyl group sources. The content of vinyl groups is determined according to the descriptive part of the "Method for determining the amount of double bonds in the polymeric composition or in a polymer" under "Determination methods" which refers to the measurement of the content of vinyl groups.
[0060] Any vinyl group measurements are taken before crosslinking.
[0061] If the polymeric composition is unsaturated before crosslinking, then it is preferable 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 polyunsaturated comonomer (s) are present in the LDPE polymer as said unsaturated polyolefin, then the LDPE polymer is an unsaturated LDPE copolymer.
[0062] If an LDPE homopolymer is unsaturated, then unsaturation can be provided, for example, by a chain transfer agent (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 comonomer (s) or by conditions of polymerization. It is well known that selected polymerization conditions, such as peak temperatures and pressure, can influence 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) which are preferably selected from acrylate or acetate comonomer (s).
[0063] The polyunsaturated comonomer (s) suitable for the unsaturated polyolefin preferably consists of a linear carbon chain with at least 8 carbon atoms and at least 4 carbons between 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 carbonocarbon double bond being terminal and the second double bond carbon-carbon being not conjugated to the first. Preferred dienes are selected from C8 to C14 unconjugated dienes or mixtures thereof, more preferably selected from 1,7-octadiene, 1,9-decadiene, 1,11-dodecadiene, 1,13-tetradecadiene, 7-methyl-1, 6-octadiene, 9-methyl1,8-decadiene, or mixtures thereof. Even more preferably, the diene is selected from 1,7-octadiene, 1,9-decadiene, 1,11dodecadiene, 1,13-tetradecadiene, or any mixture thereof, however, without limiting the above dienes.
[0064] It is well known that, for example, .propylene can be used as a comonomer or as a chain transfer agent (CTA), or both, and can thus contribute to the total amount of CC double bonds, preferably to the amount total vinyl groups. In this context, when a compound that can also act as a comonomer, such as propylene, is used as CTA to provide double bonds, then said copolymerizable comonomer is not calculated on the comonomer content.
[0065] If the polyolefin, more preferably the LDPE polymer, is unsaturated, then 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, even more preferably greater than 0.11 / 1000 carbon atoms and most preferably greater than 0.15 / 1000 carbon atoms. Preferably, the total amount of vinyl groups is less than 4.0 / 1000 carbon atoms. In some modalities, even greater unsaturation is desired; then the polyolefin, before crosslinking, preferably comprises vinyl groups in a total amount of more than 0.20 / 1000 carbon atoms, more preferably more than 0.25 / 1000 carbon atoms, even more preferably more than 0.30 / 1000 carbon atoms. Larger amounts of vinyl group are preferably provided by an LDPE copolymer of unsaturated ethylene with at least one polyunsaturated comonomer.
[0066] The preferred polyolefin for use in the polymeric composition is a saturated LDPE homopolymer or an ethylene saturated LDPE copolymer with one or more comonomer (s) or an unsaturated LDPE polymer, which is selected from an unsaturated LDPE homopolymer or an unsaturated LDPE copolymer ethylene with one or more comonomer (s), preferably with at least one polyunsaturated comonomer.
[0067] Typically, and preferably in 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 more than 960 kg / m3, and preferably is 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 from 0.1 to 20 g / 10min, and most preferably 0 , 2 to 10 g / 10min. Compressor lubricant
[0068] The compressor lubricant used in the polymerization process to produce the preferred polyolefin of the polymeric composition comprises mineral oil which is a known petroleum product.
[0069] Mineral oils have a well-known meaning and are used, among others, for lubrication in commercial lubricants. "Compressor lubricant comprising a mineral oil" and "compressor lubricants based on mineral oil" are used interchangeably in this context.
[0070] Mineral oil can be a synthetic mineral oil that is produced synthetically or a mineral oil obtainable from crude oil refining processes.
[0071] Typically, mineral oil, also known as liquid petroleum, is a by-product of petroleum distillation to produce gasoline and other petroleum-based products from crude oil.
[0072] The mineral oil of the compressor lubricant of the invention is preferably a paraffinic oil. This paraffinic oil is derived from petroleum-based hydrocarbon feeds.
[0073] Mineral oil is preferably the base oil of the compressor lubricant. The compressor lubricant may contain other components, such as lubricity additive (s), viscosity builders, antioxidants, other additive (s) or any mixtures thereof, as is well known in the art.
[0074] More preferably, the compressor lubricant comprises a mineral oil that is conventionally used as compressor lubricants for plastics production, for example, LDPE, for the food industry or medical industry, more preferably the compressor lubricant comprises an oil mineral that is a white oil. Even more preferably, the compressor lubricant comprises white oil as mineral oil and is suitable for the production of polymers for the food or medical industry. White oil has a well-known meaning. In addition, these white oil-based compressor lubricants are well known and commercially available. Even more preferably, white oil meets the requirements for a white food or medical oil.
[0075] As is known, mineral oil, preferably white mineral oil from the preferred compressor lubricant contains paraffinic hydrocarbons.
[0076] Even more preferably, the compressor lubricant meets one or more of the modalities below: -In a preferred embodiment, the mineral oil, preferably the white mineral oil, of the compressor lubricant has a viscosity of at least 8.5 x 10 -6 m2 / s at 100 ° C; In a second preferred embodiment, the mineral oil, preferably the white mineral oil, of the compressor lubricant comprises 5% by weight (p%) or less of hydrocarbons with less than 25 carbon atoms;
[0077] In a third preferred embodiment, the hydrocarbons in the mineral oil, preferably in the white mineral oil, of the compressor lubricant have an average molecular weight (Mw) of 480 or more.
[0078] The "hydrocarbon amount", "viscosity" and "Mw" above are preferably in accordance with the European Directive 2002/72 / EC of 6 August 2002 above.
[0079] It is preferable that the compressor lubricant complies with each of the three modalities 1-3 above.
[0080] The most preferred compressor lubricant of the invention meets the requirements provided for white mineral oil in the European Directive 2002/72 / EC of August 6, 2002, Annex V, for plastics used in contact with food. Directive is published, for example, in L 220/18 EN Official Journal of the European Communities 15.8.2002. Thus, mineral oil is most preferably a white mineral oil that meets the aforementioned European Directive 2002/72 / EC of August 6, 2002, Annex V. In addition, it is preferable that the compressor lubricant complies with said European Directive 2002/72 / EC of 6 August 2002.
The compressor lubricant of the invention can be a commercially available compressor lubricant or can be produced by conventional means, and is preferably a commercial lubricant used in high pressure polymerization processes for the production of plastics for medical or food applications. Non-exhaustive examples of preferable commercially available lubricants are, for example, Exxcolub R Series compressor lubricant for the production of polyethylene used in contact with food and supplied, among others, by ExxonMobil, Shell Corena for the production of polyethylene for pharmaceutical use and supplied by Shell, or CL-1000SONO-EU, supplied by Sonneborn.
[0082] The compressor lubricant preferably does not contain components based on polyalkylene glycol.
[0083] It is preferable that any mineral oil present in the polymeric composition of the invention originates from the compressor lubricant used in the process equipment during the polyolefin polymerization process. Therefore, it is preferable that no mineral oil is added to the polymeric composition or to the polyolefin after polymerization thereof.
[0084] Traces of the mineral oil that originates from the compressor lubricant and present, if any, in the polyolefin produced would typically amount to a maximum of 0.4% by weight, based on the amount of polyolefin. The limit given is the absolute maximum based on the calculation of the worst case scenario where all the lost compressor lubricant (medium leakage) would go to the final polyolefin. This worst case scenario is unlikely and usually the resulting polyolefin clearly contains a lower level of mineral oil.
[0085] The compressor lubricant of the invention is used in a conventional and well known manner to a specialized person, for the lubrication of the compressor (s) in the compression stage (a) of the invention. Process
The high pressure process (HP) is the preferred process for producing a polyolefin of the polymeric composition, preferably a low density polyethylene (LDPE) polymer selected from LDPE homopolymer or LDPE ethylene copolymer with one or more comonomers.
[0087] The invention further provides a process for polymerizing a polyolefin in a high pressure process comprising the steps of: (a) compressing one or more monomer (s) under pressure in a compressor, in which a compressor lubricant is used for lubrication, (b) optionally polymerize a monomer together with one or more comonomer (s) in (a) polymerization zone (s), (c) separate the obtained polyolefin from unreacted products and recover the separated polyolefin in a zone of recovery,
[0088] wherein in step a) a compressor lubricant comprises a mineral oil including the preferred modalities thereof.
[0089] Thus, the polyolefin of the invention is preferably produced at high pressure by free radical initiated polymerization (referred to as high pressure radical polymerization). The preferred polyolefin is LDPE homopolymer or LDPE ethylene copolymer with one or more comonomer (s), as defined above. The LDPE polymer obtainable by the process of the invention preferably provides the advantageous electrical properties defined above or below. High pressure polymerization (HP) and adjustment of process conditions for further adaptation of the other properties of the polyolefin depending on the desired final application are well known and described in the literature, and can be readily used by a specialist. Compression stage a) of the invention process:
[0090] Monomer, preferably ethylene, with one or more optional comonomer (s), is fed to one or more compressors in the compressor zone to compress the monomer (s) to the desired polymerization pressure and to allow handling high amounts of monomer (s) at controlled temperature. Typical compressors, i.e. hypercompressors, for the process can be piston compressors or diaphragm compressors. The compressor zone usually comprises one or more compressor (s), i.e. hypercompressor (s), which can work in series or in parallel. The compressor lubricant of the invention is used for cylinder lubrication in at least one, preferably in all hyper-compressors (s), present in the compressor zone. The compression stage a) usually comprises 2-7 compression stages, often with intermediate cooling zones. Temperature is typically low, usually in the range of less than 200 ° C, preferably less than 100 ° C. Any recycled monomer, preferably ethylene, and optional comonomer (s) can be added at viable points depending on the pressure. Polymerization step b) of the process:
[0091] Preferred high pressure polymerization is carried out in a polymerization zone comprising one or more polymerization reactor (s), preferably at least one tubular reactor or an autoclave reactor, preferably a tubular reactor. The polymerization reactor (s), preferably a tubular reactor, can contain one or more reactor zones, in which different polymerization conditions can occur and / or be adjusted, as is well known in the field of HP. One or more reactor zone (s) are provided in a known manner with means for feeding the optional monomer and comonomer (s), as well as means for adding initiator (s) and / or other components, such as CTA (s). In addition, the polymerization zone can contain a preheating section that is preceded or integrated with the polymerization reactor. In a preferred HP process, the monomer, preferably ethylene, optionally together with one or more comonomer (s) is polymerized in a preferably tubular reactor, preferably in the presence of chain transfer agent (s). Tubular reactor:
[0092] The reaction mixture is fed to the tubular reactor. The tubular reactor can be operated as a single feed system (also known as front feed), in which the total flow of monomer from the compressor zone is fed to the entrance of the first reaction zone of the reactor. Alternatively, the tubular reactor can be a multi-feed system, in which, for example, the monomer (s), optional comonomer (s) or other component (s) (such as CTA (S) ) coming from the compression zone, separately or in any combination, is / are divided into two or more currents and the divided supply (s) is (are) introduced to the tubular reactor in different reaction zones along the reactor. For example 10-90% of the total amount of monomer is fed to the first reaction zone and the other 90-10% of the remaining amount of monomer is optionally divided further and each divided portion is injected at different locations along the reactor. Also, the initiator (s) feed can be divided into two or more currents. In addition, in a multi-feed system, the divided currents of monomer (/ comonomer) and / or other component (s) option (l) ( is, such as CTA, and, respectively, the initiator (s) split streams can have the same or different component (s) or concentrations of the components, or both.
[0093] The single feed system for the optional monomer and comonomer (s) is preferred in the tubular reactor for producing the invented polyolefin.
[0094] The first part of the reactor is to adjust the temperature of the monomer feed, preferably ethylene, and the optional comonomer (s); usual temperature is below 200 ° C, like 100200 ° C. Then the radical initiator is added. As a radical initiator, any compound or a mixture thereof that decomposes into radicals at elevated temperature can be used (a). Usable radical initiators such as peroxides are commercially available. The polymerization reaction is exothermic. There may be several injection points of radical initiator, for example, 1-5 points, along the reactor, usually supplied with separate injection pumps. As already mentioned, also the monomer, preferably ethylene, and optional comonomer (s), are added at the front and optionally the monomer feed (s) can be divided for the addition of the monomer and / or optional comonomer (s), at any time of the process, in any zone of the tubular reactor and one or more injection point (s), for example, 1-5 point (s), with or without separate compressors.
[0095] In addition, one or more CTA (s) are preferably used in the polyolefin polymerization process. Preferred CTA (s) can be selected from one or more non-polar CTA (s) and one or more polar CTA (s), or any mixtures thereof.
[0096] Non-polar CTA, if present, is preferably selected from i) one or more compound (s) that do not contain a polar group selected from group (s) nitrile (CN), sulfide, hydroxyl, alkoxy, aldehyde (HC = O), carbonyl, carboxyl, ether or ester, or mixtures thereof. Non-polar CTA is preferably selected from one or more non-aromatic hydrocarbyl (s), linear, branched or cyclic, optionally containing a hetero atom such as O, N, S, Si or P. More preferably the CTA (s) non-polar CTA (s) is (are) selected from one or more cyclic alpha-olefin (s) of 5 to 12 carbons or one or more 3-linear or branched chain alpha-olefin (s) to 12 carbon atoms, more preferably one or more straight or branched chain alphaolefin (s) of 3 to 6 carbon atoms. The preferred non-polar CTA is propylene.
[0097] Polar CTA, if present, is preferably selected from i) one or more compound (s) comprising one or more polar group (s) selected from nitrile (CN), sulfide group (s) , hydroxyl, alkoxy, aldehyde (HC = O), carbonyl, carboxyl, ether or ester, or mixtures thereof; ii) one or more aromatic organic compound (s), or iii) any mixture thereof.
[0098] Preferably any of these polar CTA (s) have up to 12 carbon atoms, for example up to 10 carbon atoms, preferably up to 8 carbon atoms. A preferred option includes straight chain or branched chain alkane (s) having up to 12 carbon atoms (for example, up to 8 carbon atoms) and having at least one nitrile (CN), sulfide, hydroxyl, alkoxy, aldehyde (HC) group = O), carbonyl, carboxyl or ester.
[0099] More preferably the polar CTA (s), if present, is (are) selected from (i) one or more compound (s) containing one or more group (s) hydroxyl, alkoxy, HC = O, carbonyl, carboxyl and ester, or a mixture thereof, more preferably one or more alcohol, aldehyde and / or ketone compound (s). The preferred polar CTA (s), if present, is (are) alcohol (1), aldehyde (s) or straight chain or branched chain ketone (s) having up to 12 carbon atoms, preferably up to 8 carbon atoms, especially up to 6 carbon atoms, most preferably, isopropanol (IPA), methyl ethyl ketone (MEK) and / or propionaldehyde (PA).
[00100] The amount of the preferred CTA (s) is not limited and can be adjusted by a specialist within the limits of the invention depending on the desired final properties of the final polymer. In this way, the preferred chain transfer agent (s) can be added at any injection point of the reactor to the polymeric mixture. The addition of one or more CTA (s) can be done at one or more injection point (s) at any time during polymerization.
[00101] In case the polyolefin polymerization is carried out in the presence of a mixture of CTAs comprising one or more polar CTA (s) as defined above and one or more non-polar CTA (s) as defined above, then the feed ratio in weight% of polar CTA to non-polar CTA is preferably 1 to 99% by weight of polar CTA and 1 to 99% by weight of non-polar CTA, based on the combined amount of the feed of polar CTA and Non-polar CTA in the reactor.
[00102] The addition of monomer, comonomer (s) and CTA (s) options (l) (s) can include and typically include fresh and recycled food (s).
[00103] The reactor is continuously cooled, for example, by water or steam. The highest temperature is called the peak temperature and the reaction start temperature is called the initiation temperature.
[00104] Suitable temperatures are in the range of up to 400 ° C, preferably from 80 to 350 ° C and pressure from 700 bar, preferably 1000 to 4000 bar, more preferably from 1000 to 3500 bar. Pressure can be measured at least after the compression stage and / or after the tubular reactor. Temperature can be measured at several points during all stages. High temperature and high pressure generally increase production. Using various temperature profiles selected by a person skilled in the art will allow control of the polymer chain structure, ie long chain branch and / or short chain branch, density, branch factor, comonomer distribution, MFR, viscosity, weight distribution molecular, etc.
[00105] The reactor conventionally ends with a valve called the production control valve. The valve regulates the reactor pressure and depressurizes the reaction mixture from the reaction pressure to the separation pressure. Recovery step c) of the process: Separation:
[00106] The pressure is typically reduced to approximately 100 to 450 bar and the reaction mixture is fed to a separating vessel where most unreacted products, often gaseous, are removed from the polymer stream. Unreacted products include, for example ,. monomer or comonomer (s) are available, and most of the unreacted components are recovered. The polymer stream is optionally additionally separated at a lower pressure, typically less than 1 bar, in a second separator vessel where more unreacted products are recovered. Normally low molecular weight compounds, i.e. wax, are removed from the gas. The gas is usually cooled and cleaned before recycling. Separated polymer recovery:
[00107] After separation, the polymer obtained is typically in the form of a molten polymer which is normally mixed and pelletized in a pelletizing section, as a pelletizing extruder, arranged in connection with the HP reactor system. Optionally, additive (s), such as antioxidant (s), can be added to this mixer, in a known manner, to result in the polymeric composition.
[00108] Further details of the production of ethylene (co) polymers by high pressure radical polymerization can be found, among others, in the Encyclopedia of Polymer Science and Engineering, Encyclopedia of Polymer Science and Engineering, Vol. 6 (1986 ), pp 383-410 and Encyclopedia of Materials: Science and Technology (2001 Encyclopedia of Materials: Science and Technology), 2001 Elsevier Science Ltd .: "Polyethylene: High-pressure", R. Klimesch, D. Littmann and F.-O. Mahling pp. 7181-7184.
[00109] As for the properties of the polymer, for example, MFR, of the polymerized polymer, preferably LDPE polymer, the properties can be adjusted using, for example ,. chain transfer agent during polymerization, or by adjusting the reaction temperature or pressure (which also have some influence on the level of unsaturation).
[00110] When an ethylene unsaturated LDPE copolymer is prepared, then, as is well known, the CC double bond content can be adjusted by polymerization of ethylene, for example, in the presence of one or more polyunsaturated comonomer (s) , chain transfer agent (s), 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 the nature and amount of desired CC double bonds for the unsaturated LDPE copolymer. Among others, WO 9308222 describes a high pressure radical polymerization of ethylene with polyunsaturated monomers, such as α, walcadienes, to increase the unsaturation of an ethylene copolymer. The unreacted double bond (s) thus provides, among others, vinyl groups hanging from the polymer chain formed at the site, where the polyunsaturated comonomer was incorporated by polymerization. As a result, unsaturation can be uniformly distributed along the polymer chain in a random copolymerization manner. Also, for example ,. WO 9635732 describes high pressure radical polymerization of ethylene and a certain type of unsaturated α, w-divinylsiloxanes. Furthermore, as is known, for example, propylene can be used as a chain transfer agent to provide said double bonds. First and second semiconductor cable compositions
[00111] The first and second semiconductor compositions can be different or the same and the following preferred embodiments of the semiconductor composition apply independently to each of them.
[00112] The semiconductor composition preferably comprises a polyolefin (S) and a conductive charge.
[00113] A suitable polyolefin (S) can be any polyolefin, like any conventional polyolefin, which can be used to produce a semiconductor layer of a cable of the present invention. For example, such suitable conventional polyolefins are in themselves well known and can, for example, be commercially available or can be prepared according to or analogously to known polymerization processes described in the chemical literature.
[00114] The polyolefin (S) for the polymeric composition is preferably selected from a polypropylene (PP) or polyethylene (PE), preferably from a polyethylene. For polyethylene, ethylene will form the highest monomer content present in any polyethylene polymer.
[00115] The preferred polyolefin (S) is a polyethylene produced in the presence of an olefin polymerization catalyst or a polyethylene produced in a high pressure process.
[00116] In the event that a polyolefin (S) is an ethylene copolymer with at least one comonomer, then that comonomer (s) is (are) selected from non-polar comonomer (s) or polar comonomer (s), or any mixtures thereof. Preferable non-polar comonomer (s) and optional polar comonomer (s) are described below in relation to polyethylene produced in a high pressure process. These comonomers can be used in any polyolefin (S) of the invention.
[00117] "Olefin polymerization catalyst" in this context preferably means a conventional coordinating catalyst. This is preferably selected from the Ziegler-Natta catalyst, single-site catalyst, the term of which includes a metallocene catalyst and a non-metallocene catalyst, or a chromium catalyst, or any mixture thereof. The terms have a well-known meaning.
[00118] Polyethylene polymerized in the presence of an olefin polymerization catalyst is also often called a "low pressure polyethylene" to clearly distinguish it from high pressure polyethylene. Both expressions are well known in the field of polyolefins. Low-pressure polyethylene can be produced in the polymerization process by operating, among others, under mass, mud, solution or gaseous conditions or in any combination thereof. The olefin polymerization catalyst is typically a coordination catalyst as defined above.
[00119] More preferably, the polyolefin (S) is selected from a homopolymer or an ethylene copolymer produced in the presence of a coordinating catalyst or produced in a high pressure polymerization process.
[00120] When polyolefin (S) is a low pressure polyethylene (PE), then that low pressure PE is preferably selected from a very low density ethylene copolymer (VLDPE), a linear low density ethylene copolymer ( LLDPE), a medium density ethylene copolymer (MDPE) or a high density ethylene homopolymer or copolymer (HDPE). These well-known types are named according to their density area. The term VLDPE here includes polyethylenes which are also known as plastomers and elastomers and covers the density range of 850 to 909 kg / m3. The LLDPE has a density of 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 931 to 945 kg / m3. HDPE has a density of more than 945 kg / m3, preferably more than 946 kg / m3, preferably 946 to 977 kg / m3, more preferably 946 to 965 kg / m3.
[00121] More preferably, that low pressure ethylene copolymer for polyolefin (S) is copolymerized with at least one comonomer selected from C3-20 alpha olefin, more preferably from C4-12 alpha-olefin, more preferably from C4-8 alpha-olefin, for example, with 1-butene, 1-hexene or 1-octene, or a mixture thereof. The amount of comonomer (s) present in a PE copolymer is 0.1 to 15 mol%, typically 0.25 to 10 mol-%.
[00122] Furthermore, when the polyolefin (S) is a low pressure PE polymer, then that PE can be unimodal or multimodal in relation to the molecular weight distribution (MWD = Mw / Mn). Generally, a polymer comprising at least two polymer fractions, which were produced under different polymerization conditions (including, but not limited to, any of the process parameters, feeds of starting materials, feeds of process control agents and feeds of systems catalyst) resulting in different molecular weight (s) (weight average) and molecular weight distributions for the fractions, is designated as "multimodal". The prefix "multi" refers to the number of different polymer fractions present in the polymer. Thus, for example, multimodal polymer includes the so-called "bimodal" polymer consisting of two fractions. The shape of the molecular weight distribution curve, i.e. the appearance of the polymer's fraction by weight graph as a function of its molecular weight, of a multimodal polymer will show two or more maximums or is typically widened compared to the curves of the individual fractions.
[00123] Low pressure unimodal PE can be produced, for example, by a single polymerization stage in a single reactor in a well-known and documented manner. Low pressure multimodal PE (e.g., bimodal) can be produced, for example, by mechanically mixing two or more separate polymer components or, preferably, by in-situ mixing during the polymerization process of the components. Both mechanical and in situ mixing are well known in the field. In-situ mixing means the polymerization of polymer components under different polymerization conditions, for example in a multistage polymerization process, ie two or more stages, or with the use of two or more different polymerization catalysts, in one process single-stage polymerization, or using a combination of multistage polymerization process and two or more polymerization catalysts. The polymerization zones can operate in conditions of mass, mud, solution, or gas phase or in any combination thereof, as is known in the field.
[00124] According to a second modality, polyolefin (S) is a polyethylene produced in a high pressure polymerization process, preferably by radical polymerization in the presence of (one) initiator (s). Most preferably the polyolefin (S) is a low density polyethylene (LDPE). When polyolefin (S), preferably polyethylene, is produced in a high pressure process, then the preferred polyolefin is an LDPE homopolymer or an LDPE ethylene copolymer with one or more comonomers. In some embodiments, the LDPE homopolymer and copolymer may be unsaturated. Examples of LDPE polymers and general principles for their polymerization are described above in relation to the polyolefin of the polymeric composition of the insulation layer, however, without limitations regarding any specific lubricant in the compressor (s) during the compression stage (a) of the process. For the production of ethylene (co) polymers by high pressure radical polymerization, reference can be made to 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-presure, R. Klimesch, D.Littmann and F.-O. Mahling pp. 7181-7184.
[00125] The conductive charge of the semiconductor composition is preferably carbon black. Any electrically conductive carbon black can be used and provide the necessary semiconductor property for the semiconductor layer.
[00126] Preferably, carbon black may have a surface area of nitrogen (BET) of 5 to 400 m2 / g, preferably 10 to 300 m2 / g, more preferably 30 to 200 m2 / g, when determined accordingly with ASTM D3037-93. It is further preferable that the carbon black has one or more of the following properties: i) a primary particle size of at least 5 nm which is defined as the numerical average particle diameter according to ASTM D384995a procedure D, ii) iodine absorption number (iAN) of at least 10mg / g, preferably from 10 to 300 mg / g, more preferably from 30 to 200 mg / g, when determined according to ASTM D-1510-07 ; and / or iii) DBP (dibutyl phthalate) absorption number from 60 to 300 cm3 / 100g, preferably from 70 to 250 cm3 / 100g, more preferably from 80 to 200, preferably from 90 to 180 cm3 / 100g, when measured from according to ASTM D 2414-06a. More preferably, carbon black has a nitrogen surface area (BET) and properties (i), (ii) and (iii) as defined above. Non-limiting examples of preferred carbon blacks include oven carbon blacks and acetylene blacks.
[00127] The amount of carbon black is at least that in which a semiconductor composition is obtained. Depending on the desired use, the conductivity of the carbon black and the conductivity of the composition, the amount of carbon black may vary.
[00128] Furnace carbon black is a commonly recognized term for the well-known type of carbon black that is produced in an oven-type reactor. As examples of carbon blacks, their preparation process and reactors, reference can be made, for example, to Cabot EP629222, US 4 391 789, US 3 922 335 and US 3 401 020. Oven carbon black it is distinguished here from acetylene carbon black which is produced by reacting acetylene and unsaturated hydrocarbons, for example, as described in US 4,340,577.
[00129] Acetylene carbon black is a commonly recognized term, being well known and, for example, produced by Denka. They are produced in an acetylene black process.
[00130] Preferably, the semiconductor composition of the cable has a volumetric resistivity, measured at 90 ° C according to ISO 3915 (1981), of less than 500,000 Ohm cm, more preferably less than 100,000 Ohm cm, even more preferably less than 50,000 Ohm cm. Volumetric resistivity is a reciprocal relationship to electrical conductivity, i.e. the lower the resistivity, the greater the conductivity.
[00131] The semiconductor composition of the present invention comprises, depending on the carbon black used, preferably 9.5 to 49.5% by weight, more preferably 9 to 49% by weight, more preferably 5 to 45% by weight of black. based on the weight of the polymeric composition.
[00132] The crosslinking option and usable crosslinking agents are described above in relation to description n of the polymeric composition of the insulation layer.
[00133] The semiconductor composition of the cable may naturally contain other components, such as other polymeric component (s), such as miscible thermoplastic (s); or other additive (s), such as antioxidant (s), pre-vulcanization retarder (s); additive (s), such as any antioxidant (s), pre-vulcanization (SR) retarder (s), water-tree retardant additives, cross-linking reinforcer (s), stabilizer (s), as tension stabilizer (s) , flame retardant additive (s), ion and acid eliminators, other filler (s), processing aid (s), such as lubricant (s), foaming agent (s) or coloring (s), as it is known in the field of polymers. Additives depend on the type of layer, for example, whether semiconductor or insulation layer, and can be selected by a specialist. The total amount of other additive (s), if present, is generally 0.01 to 10% by weight, preferably 0.05 to 7% by weight, more preferably 0.2 to 5 % by weight, based on the total amount of the polymeric composition.
[00134] The semiconductor composition of the cable of the invention typically comprises at least 50% by weight, preferably at least 60% by weight, more preferably at least 70% by weight to 100% by weight, of the polyolefin based on the total weight of the (s) ) polymeric component (s) present in the semiconductor composition. However, it should be understood here that the semiconductor composition may contain other component (s) other than the polymeric components, as an additive (s) that can optionally be added in admixture with a carrier polymer, ie in so called master batch. Cover composition of the cable cover layer
[00135] The coating composition preferably comprises a polyolefin (j) which is preferably selected from a polypropylene (PP), polyethylene (PE), or any mixtures thereof. More preferably, the polyolefin (j) of the cover composition is selected independently of the polyolefin (S) described for the first and second semiconductor composition.
[00136] The crosslinking option and usable crosslinking agents are described above in relation to the description of the polymeric composition of the insulation layer.
[00137] The coating composition may contain other components such as other polymeric component (s), another additive (s), such as antioxidant (s), stabilizer (s), fillers, pigments or any mixtures thereof. The cover layer preferably comprises a pigment or carbon black, or both, in amounts conventionally used.
The cable cover composition of the invention typically comprises at least 50% by weight, preferably at least 60% by weight, more preferably at least 70% by weight to 100% by weight, of the weight based cover polyolefin. total of the polymeric component (s) present in the cover composition. However, it should be understood here that the coating composition may contain another component (s) other than the polymeric components, as an additive (s) that can optionally be added in a mixture with a carrier polymer, ie in the so-called batch. Invention AC electrical cable
[00139] An alternating current (AC) electrical cable of the invention is very suitable for AC electrical cables, especially for electrical cables operating at voltages between 6 kV and 36 kV (medium voltage (MV) cables) and at voltages greater than 36 kV, known as high voltage cables (HV) and extra high voltage cables (EHV), EHV cables operating, as is well known, at very high voltages. The terms have well-known meanings and indicate the level of operation of these cables. The most preferred AC power cable is a
[00140] Thus, the polymeric composition with advantageous low dielectric loss properties is highly suitable for AC HV or EHV electrical cables, operating at voltages greater than 36 kV, preferably at voltages of 40 kV or more, even at voltages of 50 kV or more. AC EHV electrical cables operate in very high voltage ranges, for example, as high as up to 800 kV, however without being limited to these.
[00141] The invention also provides a process for producing an alternating current (AC) electric cable, preferably an AC HV or EHV electric cable, as defined above or in the claims, wherein the process includes the steps of applying a layer on a conductor semiconductor inner layer comprising a first semiconductor composition, an insulation layer comprising a polymeric composition, an outer semiconductor layer comprising a second semiconductor composition, and optionally, and preferably, a cover layer comprising a cover composition, optionally, and preferably, crosslinked by minus the polyolefin of the polymeric composition of the insulation layer, optionally, and preferably, the first semiconductor composition of the inner semiconductor layer, optionally the second semiconductor composition of the outer semiconductor layer and optionally the cover composition of the optional cover layer, in the presence of a agent of cross-linking and under cross-linking conditions.
[00142] In the preferred embodiment of the AC HV or EHV electric cable production process of the invention, the process comprises the steps of (a) providing and mixing, preferably mixing melting (meltmixing) in an extruder, an optionally crosslinkable first semiconductor composition comprising a polyolefin, a conductive filler, preferably carbon black, and optionally other component (s) for the inner semiconductor layer, providing and mixing, preferably mixing by melting in an extruder, a crosslinkable polymeric composition of the invention for the insulation layer , providing and mixing, preferably mixing by melting in an extruder, a second optionally cross-linkable semiconductor composition comprising a polyolefin, a conductive charge, preferably carbon black, and optionally other component (s) for the outer semiconductor layer, providing and mix, preferably mix by melting in an extruder, a cover composition optionally crosslinkable material comprising a polyolefin and optionally other component (s) for the outer semiconductor layer, (b) applying a melt mixture of the first semiconductor composition obtained from step (a) to a conductor, preferably by coextrusion. forming the inner semiconductor layer, a molten mixture of the polymeric composition of the invention obtained from step (a) to form the insulation layer, a molten mixture of the second semiconductor composition obtained from step (a) to form the outer semiconductor layer, a molten mixture of the coating composition obtained in step (a) to form the shield jacketing layer, and (c) optionally crosslinking under crosslinking conditions one or more between polymeric composition of the insulation layer, semiconductor composition of the internal semiconductor layer , semiconductor composition of the outer semiconductor layer, and cover composition of the cover layer of the obtained cable, preferably by the less the polymeric composition of the insulation layer, more preferably the polymeric composition of the insulation layer, at least the semiconductor composition of the inner semiconductor layer, optionally the semiconductor composition of the outer semiconductor layer and optionally the covering composition of the covering layer.
[00143] Mixing by melting means mixing above the melting point of at least the largest polymeric component (s) of the mixture obtained and is typically carried out at a temperature of at least 10-15 ° C above melting point or softening of the polymeric component (s).
[00144] 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 well known in the art. The term "(co) extrusion" here means that all or part of the layer (s) are formed simultaneously using one or more extrusion heads. For example, triple extrusion can be used to form three layers of cable.
[00145] As is well known, the polymeric composition of the invention and the first and second semiconductor compositions and the preferred, optional coating composition can be produced before or during the cable production process. In addition, the polymeric composition of the insulation layer, the first and second semiconductor compositions and the preferred, optional coating composition can each independently contain part or all of their component (s) prior to introduction to the mixing step merging a) the cable production process.
[00146] Preferably, said part or all of the polymeric composition, preferably at least the polyolefin, is in the form of powder, grain or pellets, when supplied to the cable production process. Pellets can be of any size and shape and can be produced by any conventional pelletizing device, such as a pelletizing extruder.
[00147] According to one embodiment, at least the polymeric composition comprises the said other component (s). In this modality, part or all (s) of said other component (s) can, for example, be added 1) by melting mixture to the polyolefin, which can be in a form obtained from polymerization process, the molten mixture obtained being then pelleted, and / or 2) by mixing with the polyolefin pellets, which pellets may already contain part of the said other component (s). In this option 2) part or all (s) of the other component (s) can be mixed in melting together with the pellets and then the melt obtained be pelleted; and / or part or all (s) of the other component (s) can be impregnated with the solid pellets.
[00148] In a second alternative embodiment, the polymeric composition can be prepared in connection with the cable production line, for example, providing the polyolefin, preferably in the form of pellets, which may optionally contain part of the other (s) component (s), and combine with all or the rest of the other component (s) in the mixing step a) to provide a melt mixture for step b) of the process of the invention. In the event that the polyolefin pellets contain part of the other component (s), then the pellets can be prepared as described in the first embodiment above.
[00149] The other component (s) is (are) preferably selected (s) at least from one or more additive (s), preferably at least among free radical-generating agent (s) , more preferably between peroxide (s), optionally, and preferably, between antioxidant (s) and optionally between pre-vulcanization retardants as mentioned above.
[00150] The mixing step a) of the polymer composition provided, of the first and second semiconductor compositions and of the optional and preferable cover composition is preferably carried out in the cable extruder. Step a) can optionally contain a separate mixing step, for example in a mixer, preceding the cable extruder. Mixing in the separate preceding mixer can be carried out with mixing with or without external heating (heating with an external source) of the component (s). Any other component (s) of the polymeric composition or of the first and second semiconductor compositions and the optional and preferable coating composition, if present and added during the cable production process, can be added at any stage and at any point (s) ) in the cable extruder, or in the separate optional mixer that precedes the cable extruder. The addition of additives 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).
[00151] It is preferable that the melt mixture of the polymeric composition obtained from the melt mixing process of step (a) consists of the polyolefin of the invention as the single polymeric component. The additive (s) option (s), and preferably, can be added to the polymeric composition as such or as a mixture with a carrier polymer, ie in form of a so-called master batch.
[00152] Most preferably the mixture of the polymeric composition of the insulation layer with the mixture of each of the first and second semiconductor compositions and the optional and preferred coating composition obtained from step (a) is a molten mixture produced at least in an extruder.
[00153] In the preferred embodiment at least the polymeric composition of the insulation layer of the invention is provided to the cable production process in the form of prefabricated pellets.
[00154] In a preferred embodiment of the cable production process, an MV, HV or EHV crosslinked alternating current (AC) electric cable is produced, more preferably an HV or EHV AC alternating current (AC) cable, comprising a conductor surrounded by an inner semiconductor layer comprising, preferably consisting of, a first semiconductor composition, an insulation layer comprising, preferably consisting of, a crosslinkable polymeric composition of the invention comprising a polyolefin and a crosslinking agent, preferably peroxide, as defined above , an outer semiconductor layer comprising, preferably consisting of, a second semiconductor composition, and the optional cover layer, and preferably, comprising, preferably consisting of, cover composition, wherein at least the polymeric composition of the insulation layer is cross-linked in the presence of said cross-linking agent, more preferably, wherein at least the first semiconductor composition of the inner semiconductor layer and the polymeric composition of the insulation layer are cross-linked.
[00155] If crosslinked, then the crosslinking agent (s) may already be present in the first and second semiconductor compositions prior to introduction into the crosslinking step (c) or be introduced ( s) during the crosslinking step (c). Peroxide is the preferred crosslinking agent for said first and second semiconductor compositions and for the optional, and preferred, cover composition in case any of said layers are crosslinked, and is then preferably included in the pellets of the semiconductor compositions and in the pellets of the cover composition before the composition is used in the cable production process as described above.
[00156] Crosslinking can be carried out at an increased temperature, which is chosen, as is well known, depending on the type of crosslinking agent. For example, temperatures above 150 ° C are typical, however they are not limited to this condition.
[00157] Insulating layers for MV, HV or EHV alternating current (AC) electric cables, preferably for HV or EHV, generally have a thickness of at least 2 mm, typically at least 2.3 mm, when measured from a straight section of the cable insulation layer, and the thickness increases with the increase in tension for which the cable is designed. Determination methods
[00158] Unless otherwise specified in the description or experimental part the following methods have been used for the determination of properties.% By weight:% by weight Fluidity Index
[00159] The melt flow rate (MFR) is determined according to ISSO 1133 and is indicated in g / 10 min. The MFR is an indication of the flowability, and therefore processability, of the polymer. The higher the flow rate, the lower the viscosity of the polymer. The MFR is determined at 190 C for polyethylene and can be determined at different loads such as 2.16 kg (MFR2) or 21.6 kg (MFR21). Density
[00160] The density was measured according to ISO 1183-2. Sample preparation was performed according to ISO 1872-2 Table 3 Q (compression molding). Molecular weight
[00161] Mz, Mw, Mn, and MWD are measured by Gel Permeation Chromatography (GPC) for low molecular weight polymers, as is known in the field. Comonomer contents a) Quantification of alpha-olefin content in linear low density polyethylenes and low density polyethylenes by NMR spectroscopy:
[00162] The comonomer content was determined by quantitative 13C nuclear magnetic resonance (NMR) spectroscopy after base assignment (J. Randall JMS Rev. Macromol. Chem. Phys., C29 (2 & 3), 201- 317 (1989)). Experimental parameters were adjusted to ensure measurement of quantitative spectra for this specific task.
[00163] Specifically solution state NMR spectroscopy was employed using a Bruker Avance III 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 block heat and a rotary tube oven at 140 ° C. Single-pulse 13C NMR spectra with proton decoupling with NOE (with electrical switching (powergated)) were recorded using the following acquisition parameters: a 90-degree flip-angle, 4 preparatory scans (dummy scans) , 4096 transients, an acquisition time of 1.6 s, a spectral width of 20kHz, a temperature of 125 ° C, bilevel proton decoupling scheme WALTZ and a relaxation time (relaxation delay) of 3.0 s. The resulting FID was processed using the following process parameters: zeroing (zerofilling) at 32k points and apodization using a Gaussian window function; automatic correction of the zero order and first order phases and automatic correction of the baseline using a fifth order polynomial equation restricted to the region of interest.
[00164] Quantities were calculated using simple ratios corrected for 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 comprising> 6.% by weight of polar comonomer units
[00165] Comonomer content (% by weight) was determined in a known manner based on the determination of Fourier transform infrared spectroscopy (FTIR) spectroscopy calibrated with quantitative nuclear magnetic resonance (NMR) spectroscopy. Below, the determination of the polar comonomer content of ethylene ethyl acrylate, ethylene butyl acrylate and ethylene methyl acrylate is exemplified. Polymer film samples were prepared for FTIR measurement: 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 an amount of > 6% by weight. Films were pressed using a Specac film press at 150 ° C, approximately 5 tones, 1-2 minutes, and then referenced with cold water in an uncontrolled manner. The accurate thickness of the obtained film samples was measured.
[00166] After analysis with FTIR, baselines in the absorbance mode were drawn for the peaks to be analyzed. The peak absorbance for the comonomer was normalized to the peak absorbance of polyethylene (for example, the peak height for butyl acrylate or ethyl acrylate at 3450 cm-1 was divided by the peak height of polyethylene at 2020 cm-1). The calibration procedure with NMR spectroscopy was performed in a conventional manner, which is well documented in the literature, explained below.
[00167] To determine the methylacrylate content, a 0.10 mm thick film sample was prepared. After the analysis, the maximum absorbance for the methylacrylate peak at 3455 cm-1 was subtracted from the baseline absorbance value at 2475 cm-1 (Amθtiiacriiato 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 (A2660A2475) was then calculated in the conventional manner, which is well documented in the literature.
[00168] The% by weight can be converted to molar% by calculation, which is well documented in the literature.
[00169] Quantification of copolymer content in polymers by NMR spectroscopy
[00170] The comonomer content was determined by quantitative nuclear magnetic resonance (NMR) spectroscopy after base assignment (for example, "NMR Spectra of Polymers and Polymer Additives", AJ Brandolini and Polymer Additives) DD Hills, 2000, Marcel Dekker, Inc. New York). Experimental parameters have been adjusted to ensure 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 ratios corrected for the sign integrals of representative sites in a manner known in the art. (2) Polymers containing 6.% by weight or less of polar comonomer units.
[00171] Comonomer content (% by weight) was determined in a known manner based on the determination of Fourier transform infrared spectroscopy (FTIR) calibrated with quantitative nuclear magnetic resonance (NMR) spectroscopy. Below, the determination of the polar comonomer content of ethylene butyl acrylate and ethylene methyl acrylate is exemplified. For the measurement of FT-IR film samples from 0.05 to 0.12 mm thick were prepared as described above under method 1 The accurate thickness of the obtained film samples was measured.
[00172] After the analysis with FT-IR, baselines in the ab-sorbance mode were drawn for the peaks to 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 from the absorbance value for the baseline at 1850 cm-1 (The polar comonomer A1850) . Then, the maximum absorbance peak for polyethylene peak at 2660 cm-1 was subtracted from the absorbance value for the baseline at 1850 cm-1 (A2660 A1850). The ratio between (Acomonomer-A1850) and (A2660A1850) was then calculated. The calibration procedure by NMR spectroscopy was carried out in a conventional manner, which is well documented in the literature, as described above under method 1).
[00173] The% by weight can be converted to molar% by calculation, which is well documented in the literature. Test for measurement of tan δ in 10 kV cables Cable production
[00174] Polymer pellets of the polymeric composition under test were used to produce the insulation layer of the 10 kV cables under test in a CCV type Maillefer pilot line. The cables have a nominal insulation thickness of 3.4 mm (the inner semiconductor layer is 0.9 mm thick and the outer semiconductor layer is 1 mm thick). The conductor's cross section was 50 mm2, in braided aluminum. The cable was produced as a 1 + 2 construction (for example, first the inner semiconductor layer was applied over the conductor and then the remaining two layers were applied through the same extrusion head to the conductor with the inner semiconductor layer already applied). The semiconductor material used as the internal and external semiconductor material was LE0592 (a commercial semiconductor material supplied by Borealis). The cable cores were produced with a linear speed of 1.6 m / min. Cable Length: Cable sample preparation:
[00175] 12.5 m of each cable were available for testing, the active test length in the loss factor tests was approximately 11 m. The length is chosen according to IEC 60502-2; i.e.> 10 m active test length between the guard rings of the object under test. Conditioning:
[00176] The cables are thermally treated in a ventilated oven at 70 ° C for 72 hours before measurements. The samples are then kept in sealed aluminum bags until tan δ measurements are made. Test method:
[00177] Both ends of the loss factor cables were equipped with electric field leveling fabrics. Each termination was 0.7 m long. The ends were placed in plastic bags that were filled with SF6 gas and sealed with tapes. SF6 gas was used to increase the corona inception voltage above the maximum test voltage of ~ 55 kV.
[00178] 20 cm from the tension cones, guard rings were introduced. A 2 mm opening was opened in the insulation screen. A 5 cm long thick-walled thermocouple (Raychem) was used over the guard rings to avoid any influence of partial discharges and / or leakage currents from the high voltage terminations during measurements.
[00179] The active test length was wrapped in aluminum foil 0.45 m wide and 0.2 mm thick (6-7 layers). Then, it was covered with a heat-shrink tube of continuous insulation.
[00180] All tan δ measurements were carried out with the cable wound inside a large ventilated oven. The terminations were assembled and connected to the high voltage transformer outside the ventilated oven. Guard rings were also located outside the oven.
[00181] To achieve isothermal conditions in the entire cable, a period of 2 hours between measurements at each temperature level was necessary. The cable is thus heated by this oven, not by heating the conductor.
[00182] The test voltages at 50 Hz corresponding to 5, 10, 15, 20 and 25 kV / mm of conductor voltage were determined after the cable dimensions were determined by measurement.
[00183] The tan δ measurement bridge was of the Schering Tettex 2801 H1-64 type. The system was checked before measurements using tan δ standards. Method for determining the amount of double bonds in the polymeric composition or polymer
[00184] The method generally describes the determination of different types of double bonds, using the part of the description that describes the determination of the vinyl group content. A) Quantification of the amount of carbonocarbon double bonds by IR spectroscopy
[00185] Quantitative infrared (IR) spectroscopy was used to quantify the amount of carbon doubles (C = C). Calibration was obtained by prior determination of the molar extinction coefficient of the functional groups C = C in model low molecular weight compounds representative of known structure.
[00186] 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) via: N = (A x 14) / (E x L x D)
[00187] where A is the maximum absorbance defined as peak height, E the molar extinction coefficient of the group in question (l ^ molW), L the film thickness (mm) and D the material density (g-cm- 1).
[00188] The total amount of C = C bonds per thousand total carbon atoms can be calculated by adding N for the components comprising individual C = C.
[00189] For solid-state polyethylene samples, infrared spectra were recorded using an FTIR spectrometer (Perkin Elmer 2000) on thin films (0.5-1.0 mm) compression molded at a resolution of 4 cm-1 and analyzed in absorption mode. 1) Polymeric compositions comprising polyethylene homopolymers and copolymers, except polyethylene copolymers with> 0.4% by weight of polar comonomer
[00190] For polyethylenes three types of functional groups comprising C = C were quantified, each with a characteristic absorption and each calibrated according to 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-moM-mm'1 • vinylidene (RR'C = CH2) via 888 cm-1 based on 2- methyl1-heptene [2-methyl-hept-1-ene] providing E = 18.24 l • mol "1 • mm" 1 • trans-vinylene (R-CH = CH-R ') via 965 cm-1 based in trans-4-decene [(E) -dec-4-ene] providing E = 15.14 l-moM-mm'1
[00191] For polyethylene homopolymers or copolymers with <0.4% by weight of linear polar comonomer, baseline correction was applied between approximately 980 and 840 cm-1. 2) Polymeric compositions comprising polyethylene copolymers with> 0.4% by weight of polar comonomer
[00192] For polyethylene copolymers with> 0.4% by weight of polar comonomer two types of functional groups comprising C = C were quantified, each with a characteristic absorption and each calibrated according to a different model compound resulting in coefficients different extinguishing media: • 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-methyl-hept-1-ene] providing E = 18.24 l-moM-mm'1 EBA:
[00193] For poly (ethylene-co-butylacrylate) (EBA) linear baseline correction was applied between approximately 920 and 870 cm-1.EMA:
[00194] For poly (ethylene-co-methylacrylate) (EMA) linear baseline correction was applied between approximately 930 and 870 cm-1. 3) Polymeric compositions comprising low molecular weight unsaturated molecules
[00195] For systems including species comprising low molecular weight C = C, direct calibration was performed using the molar extinction coefficient of C = C absorption in low molecular weight species. B) Quantification of molar extinction coefficients by IR spectroscopy
[00196] The molar extinction coefficients were determined according to the procedure provided in ASTM D3124-98 and ASTM D6248-98. Infrared spectra in solution state were recorded using an FTIR spectrometer (Perkin Elmer 2000) equipped with a cell for liquid with an optical path length of 0.1 mm at a resolution of 4 cm-1.
[00197] The extinction coefficient (E) was determined as Lmol "1-mm'1 by means of: E = A / (C x L)
[00198] where A is the maximum absorbance defined as the peak height, C the concentration (molT1) and L the cell thickness (mm).
[00199] At least three 0.18 molT1 solutions in carbon disulfide (CS2) were used and the mean value of the molar extinction coefficient determined. Experimental Part Preparation of polyolefins of the examples of the present invention and reference examples
[00200] The polyolefins were low density polyethylene produced in a high pressure reactor. The production of polymers of the invention and reference is described below. As for CTA feeds, for example, the PA content can be supplied as liter / hour or kg / h and converted to the two units using a PA density of 0.807 kg / liter for recalculation. Comparative example 1: polyethylene polymer produced in a high pressure reactor
[00201] Purified ethylene was liquefied by compression and cooling to a pressure of 90 bars and a temperature of -30 ° C and divided into two equal currents of approximately 14 tones / hour each. CTA (methyl ethyl ketone (MEK)), air and a commercial peroxide radical initiator dissolved in a solvent were added to the two liquid ethylene streams in individual amounts. The two mixtures were pumped separately through an arrangement of 4 intensifiers to achieve pressures of 2100-2300 bars and outlet temperatures of around 40 ° C. These two currents were respectively fed to the front (zone 1) (50%) and side (zone 2) (50%) of a two-zone tubular reactor with split power. The internal diameters and lengths of the two reactor zones were 32 mm and 200 m for zone 1 and 38 mm and 400 m for zone 2. MEK was added in amounts of about 216 kg / h for the front chain to maintain an MFR2 of about 2 g / 10 min. The front feed current was passed through a heating section to reach a temperature sufficient for the exothermic polymerization reaction to begin. The peak temperatures reached by the reaction were about 250 ° C and about 318 ° C in the first and second zones, respectively. The side feed stream cooled the reaction to an initiation temperature of the second zone of 165-170 ° C. Air and peroxide solution were added to the two streams in amounts sufficient to reach the target peak temperature. The reaction mixture was depressurized by the product valve, cooled, and the polymer was separated from unreacted gas. Comparative example 2: polyethylene polymer produced in a high pressure reactor
[00202] Purified ethylene was liquefied by compression and cooling to a pressure of 90 bars and a temperature of -30 ° C and divided into two equal currents of approximately 14 tones / hour each. CTA (methyl ethyl ketone (MEK)), air and a commercial peroxide radical initiator dissolved in a solvent were added to the two liquid ethylene streams in individual amounts. Here too 1,7-octadiene was added to the reactor in an amount of about 24 kg / h. The two mixtures were pumped separately through an arrangement of 4 intensifiers to achieve pressures of 2200-2300 bars and outlet temperatures of around 40 ° C. These two currents were respectively fed to the front (zone 1) (50%) and side (zone 2) (50%) of a two-zone tubular reactor with split power. The internal diameters and lengths of the two reactor zones were 32 mm and 200 m for zone 1 and 38 mm and 400 m for zone 2. MEK was added in amounts of about 205 kg / h for the front chain to maintain an MFR2 of about 2 g / 10 min. The front feed current was passed through a heating section to reach a temperature sufficient for the exothermic polymerization reaction to begin. The peak temperatures reached by the reaction were about 253 ° C and about 290 ° C in the first and second zones, respectively. The side feed stream cooled the reaction to a second zone initiation temperature of about 168 ° C. Air and peroxide solution were added to the two streams in amounts sufficient to reach the target peak temperature. The reaction mixture was depressurized by the product valve, cooled, and the polymer was separated from unreacted gas. Example of invention 1: polyethylene polymer produced in a high pressure reactor
[00203] Ethylene with recycled CTA was compressed in a 5-stage pre-compressor and a 2-stage hyper-compressor with intermediate cooling to reach an initial reaction pressure of about 2700 bar. The total production of the compressor was about 30 tons / hour. In the compressor area, approximately 5.6 kg / hour of propionaldehyde was added together with approximately 89 kg of propylene / hour as chain transfer agents to maintain an MFR of 1.9 g / 10 min. The compressed mixture was heated to 163 ° C in a pre-heating section of a three-zone front feed tubular reactor with an internal diameter of about 40 mm and a total length of 1200 meters. The mixture of commercially available 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 around 286 ° C, after which it was cooled to approximately 215 ° C. The subsequent 2nd and 3rd peak reaction temperatures were 285 ° C and 268 ° C respectively with a cooling between them at 230 ° C. The reaction mixture was depressurized by a kick valve, cooled and polymer was separated from unreacted gas. Example of invention 2: Polyethylene polymer produced in a high pressure reactor
[00204] Ethylene with recycled CTA was compressed in a 5-stage pre-compressor and a 2-stage hyper-compressor with intermediate cooling to reach an initial reaction pressure of about 2580 bar. The total production of the compressor was about 30 tons / hour. In the compressor area, approximately 14.4 kg / hour of propionaldehyde was added to maintain an MFR of about 2.0 g / 10 min. The compressed mixture was heated to 164 ° C in a preheating section of a three-zone front feed tubular reactor with an internal diameter of about 40 mm and a total length of 1200 meters. The mixture of commercially available 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 about 305 ° C, after which it was cooled to approximately 208 ° C. The subsequent 2nd and 3rd peak reaction temperatures were 286 ° C and 278 ° C respectively with a cooling between them to 237 ° C. The reaction mixture was depressurized by a kick valve, cooled and the polymer was separated from unreacted gas. Example of invention 3: Polyethylene polymer produced in a high pressure reactor
[00205] Ethylene with recycled CTA was compressed in a 5-stage pre-compressor and a 2-stage hyper-compressor with intermediate cooling to reach an initial reaction pressure of about 2800 bar. The total production of the compressor was about 30 tons / hour. In the compressor area approximately 3.6 kg / hour of propionaldehyde was added together with 138 kg / h of propylene as chain transfer agents to maintain an MFR of about 2.1 g / 10 min. Here too, 1,7-octadiene was added to the reactor in an amount of 30.7 kg / h. The compressed mixture was heated to 167 ° C in a preheating section of a three-zone front feed tubular reactor with an internal diameter of about 40 mm and a total length of 1200 meters. The mixture of commercially available 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 about 271 ° C, after which it was cooled to approximately 195 ° C. The subsequent 2nd and 3rd peak reaction temperatures were 269 ° C and 247 ° C respectively with a cooling between them at 216 ° C. The reaction mixture was depressurized by a kick valve, cooled and the polymer was separated from unreacted gas. Example of invention 4: Polyethylene polymer produced in a high pressure reactor
[00206] Ethylene with recycled CTA was compressed in a 5-stage pre-compressor and a 2-stage hyper-compressor with intermediate cooling to reach an initial reaction pressure of about 2745 bar. The total production of the compressor was about 30 tons / hour. In the compressor area, approximately 2.8 kg / hour of propionaldehyde was added together with 77 kg / h of propylene as chain transfer agents to maintain a 1.8 g / 10 min MFR. Here too, 1,7-octadiene was added to the reactor in an amount of 28.7 kg / h and butyl acrylate in an amount of about 26 kg / hour. The compressed mixture was heated to 161 ° C in a pre-heating section of a three-zone front feed tubular reactor with an internal diameter of about 40 mm and a total length of 1200 meters. The mixture of commercially available 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 around 286 ° C, after which it was cooled to approximately 233 ° C. The subsequent 2nd and 3rd peak reaction temperatures were 280 ° C and 266 ° C respectively with a cooling between them to 237 ° C. The reaction mixture was depressurized by a kick valve, cooled and the polymer was separated from unreacted gas. Experimental Results: Mineral oil = lubricant based on mineral oil, MRARUS PE KPL 201, supplier ExxonMobil PAG = lubricant based on polyalkylene glycol, Syntheso D201N from Klueber. PA = propionaldehyde (CAS number: 123-38-6) MEK = methyl ethyl ketone.

[00207] The results of the tables below show that the polymeric compositions of the invention produced in HP process using mineral oil as the compressor lubricant reduced the losses in high stress (high stress) and high temperature expressed as tan delta measured at 50 Hz. 1. Tan delta (50Hz) at 25 kV / mm and 130 ° C of 10 kV crosslinked cables.
Table 2. Tan delta (50Hz) at 25 kV / mm and 130 ° C of 10 kV crosslinked cables.

[00208] The covering layer is coextruded in a cable extruder in a conventional manner as the shielding layer (external) of the final cable of the invention. The preferable cover layer of the cable further contributes to the improved electrical properties of AC through the provision of a layer mechanically.

权利要求:
Claims (18)
[0001]
1. Alternating current (AC) electric cable, characterized by the fact that it comprises a conductor surrounded by at least one inner semiconductor layer comprising of a first semiconductor composition, an insulation layer comprising of a polymeric composition and an external semiconductor layer comprising of a second semiconductor composition in that order, the polymeric composition of the insulation layer comprising a polyolefin and a crosslinking agent, the polyolefin being an unsaturated LDPE polymer, which is selected from the group consisting of unsaturated LDPE homopolymer and an LDPE copolymer ethylene unsaturated with one or more comonomer (s), with the polymeric composition of the insulation layer showing a dielectric loss expressed as tan δ (50 Hz) of 12.0 x 10-4 or less, when measured at 25 kV / mm and 130 ° C according to "Test for measuring tan δ in 10 kV cables", and the polyolefin is obtainable by a high pressure process which consists of: (a) compressing one or more monomer (s) under pressure in a compressor, using a compressor lubricant for lubrication, (b) optionally polymerizing a monomer together with one or more comonomer (s) in a zone polymerization, (c) separating the obtained polyolefin from unreacted products and recovering the separated polyolefin in a recovery zone, the compressor lubricant including a mineral oil.
[0002]
2. Cable according to claim 1, characterized by the fact that the polymeric composition of the insulation layer has a dielectric loss expressed as tan δ (50 Hz) of 11.0 x 10-4or less, when measured at 25 kV / mm and 130 ° C according to "Test for measuring tan δ on 10 kV cables".
[0003]
3. Cable, according to claim 1, characterized by the fact that the polymeric composition of the insulation layer presents a dielectric loss expressed as tan δ (50 Hz) of 0.01 10.0 x 10-4, when measured in 25 kV / mm and 130 ° C according to "Test for measuring tan δ on 10 kV cables".
[0004]
4. Cable according to claim 1, characterized by the fact that the lubricant that comprises a white oil such as mineral oil and is suitable for the production of polymers for the food or medical industry.
[0005]
5. Cable, according to claim 1, characterized by the fact that the crosslinking agent is peroxide.
[0006]
6. Cable according to claim 1, characterized by the fact that the polyolefin is an unsaturated LDPE copolymer of ethylene with one or more comonomer (s).
[0007]
7. Cable according to claim 1, characterized by the fact that the polyolefin is an unsaturated LDPE homopolymer or an ethylene unsaturated LDPE copolymer with at least one polyunsaturated comonomer.
[0008]
8. Cable according to claim 1, characterized by the fact that the polyolefin is an ethylene unsaturated LDPE copolymer with at least one polyunsaturated comonomer and optionally one or more comonomer (s).
[0009]
9. Cable according to claim 1, characterized by the fact that each of the internal and external semiconductor compositions independently comprises a conductive charge.
[0010]
10. Cable according to claim 1, characterized in that the cable includes a covering layer comprising a covering composition surrounded by an outer semiconductor layer.
[0011]
11. Cable according to claim 1, characterized by the fact that at least the polymeric composition of the insulation layer is cross-linked in the presence of said cross-linking agent.
[0012]
12. Cable according to claim 1, characterized by the fact that at least the first semiconductor composition of the inner semiconductor layer and the polymeric composition of the insulation layer are cross-linked.
[0013]
13. Cable according to claim 1, characterized by the fact that it is an MV, HV or EHV alternating current (AC) electric cable.
[0014]
14. Cable, according to claim 4, characterized by the fact that mineral oil is a by-product of petroleum distillation to produce gasoline and other petroleum-based products from crude oil.
[0015]
15. Cable according to claim 4, characterized by the fact that white oil comprises paraffinic hydrocarbons.
[0016]
16. Cable according to claim 4, characterized by the fact that the oil meets at least one of the following requirements: (a) the white oil has a viscosity of at least 8.5 x 10-6 m2 / s at 100 ° C ; (b) white oil contains 5% by weight or less of hydrocarbons having less than 25 carbon atoms; and white mineral oil contains hydrocarbons that have an average molecular weight of 480 or more.
[0017]
17. Process for producing an alternating current (AC) electric cable, as defined in any one of claims 1 to 16, characterized by the fact that it includes the steps of: applying a semiconductor inner layer comprising a first semiconductor composition to a conductor , an insulation layer comprising a polymeric composition, an outer semiconductor layer comprising a second semiconductor composition.
[0018]
18. Process according to claim 17, characterized by the fact that it further comprises: applying a covering layer that comprises a covering composition on the conductor.

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CN109320944A|2018-09-18|2019-02-12|国网江西省电力有限公司电力科学研究院|High dielectric constant screened film and preparation method thereof under a kind of power frequency|

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WO2020157301A1|2019-01-31|2020-08-06|Borealis Ag|Polyolefin composition comprising carbonaceous structures with reduced dielectric loss|

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WO2020157275A1|2019-01-31|2020-08-06|Borealis Ag|Polyolefin composition comprising carbonaceous structures with reduced dielectric loss|

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CN111584157B|2020-06-09|2021-11-09|湖南科技大学|Special electromagnetic wire and preparation method thereof|

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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2019-05-28| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|

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2019-12-17| B07A| Technical examination (opinion): publication of technical examination (opinion) [chapter 7.1 patent gazette]|

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2020-04-28| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application [chapter 6.1 patent gazette]|

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2020-10-06| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-12-22| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 01/11/2011, 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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EP10189853.4A|EP2450910B1|2010-11-03|2010-11-03|A polymer composition and a power cable comprising the polymer composition|

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EP10189853.4|2010-11-03|

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PCT/EP2011/069182|WO2012059483A1|2010-11-03|2011-11-01|A polymer composition and a power cable comprising the polymer composition|

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