cable and its production process

专利摘要:
CABLE AND PRODUCTION PROCESS OF THE SAME. The present invention relates to a cable comprising a semiconductive layer and an insulation layer with enhanced DC electrical properties.
公开号:BR112012011265B1
申请号:R112012011265-1
申请日:2010-11-03
公开日:2020-12-01
发明作者:Ulf Nilsson；Annika Smedberg；Alfred Campus
申请人:Borealis Ag；
IPC主号:

专利说明:

Field of the Invention
[0001] The present invention relates to a cable comprising at least one semiconductive layer and at least one insulation layer suitable for a power cable, preferably for a direct current (DC) power cable, applications and a cable production process. Background Technique
[0002] Polyolefins produced in a high pressure process (High Pressure - HP) are widely used in applications that require polymer, in which polymers must meet high mechanical and / or electrical requirements. For example, in power cable applications, particularly in medium voltage (Medium Voltage - MV) and especially high voltage (High Voltage - HV) and extra high voltage (Extra High Voltage - EHV) applications, the properties polymeric composition are of significant importance. In addition, the requirement for electrical properties may differ in different cable applications, as is the case between alternating current (alternating current - CA) and direct current (direct current - DC) cable applications.
[0003] A typical power cable comprises a conductor surrounded at least by an internal semiconductive layer, an insulation layer and an external semiconductive layer, in that order. Space Load
[0004] There is a fundamental difference between AC and DC regarding the distribution of electric field in the cable. The electric field in the AC cable is easily calculated, since it depends on the material property only, that is, the relative permissibility (the dielectric constant) with a known temperature dependence. The dielectric 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 condition, containment and accumulation of electrical charges, the so-called space charges, within the insulation. Spatial charges within the insulation will distort the electric field and can lead to very high voltage points, possibly so high that a dielectric failure will follow.
[0005] Preferably, there will be no spatial charges present, as this will make it possible to easily design the cable, since the electric field distribution in the insulation will be known.
[0006] Usually, space charges are located near the electrodes; charges of the same polarity as the nearest electrode are called homocharges, charges of opposite polarity are called heterocharges. Heterocharges will increase the electric field at that electrode, homocharges will reduce the electric field. Electric conductivity
[0007] DC electrical conductivity is an important material property, for example, for insulation materials for DC HV cables. First, the strong dependence on the electric field and temperature of this property will influence the electric field distribution via the accumulation of space charge, as described above. The second problem is the fact that heat will be generated within the insulation by the electrical leakage current that flows between the inner and outer semiconductive layers. This leakage current depends on the electric field and the electrical conductivity of the insulation. High conductivity of the insulation material can even lead to thermal instability under high voltage / high temperature conditions. The conductivity, therefore, must be kept low enough to avoid thermal instability. Compressor Lubricants
[0008] The HP process is typically operated at high pressures up to 400 MPa (4000 bar). In known reactor systems, the initial monomer (s) must be compressed (pressurized) before being introduced into the actual high pressure polymerization reactor. Compressor lubricants are conventionally used in hypercompressor (s) for cylinder lubrication to allow the mechanical compression step of the initial monomer (s). It is not known that small amounts of the lubricant normally leak through the seals in the reactor and mix with the monomer (s). As a result, the reaction mixture contains traces (up to hundreds of ppm) of the compressor lubricant during the actual polymerization step of the monomer (s). These traces of compressor lubricants can have an effect on the electrical properties of the final polymer.
[0009] As examples of commercial compressor lubricants, for example, polyalkylene glycol (PAG): R - [Cx RyHz-O] n - H, where R can be H or straight or branched hydrocarbyl ex, y, n they are, independently, whole numbers that can vary in a known way and lubricants based on a mineral oil (by-product in the distillation of petroleum) can be mentioned. Compressor lubricants which are based on mineral oil which meet the requirements for white mineral oil in European Directive 2002/72 / EC, Annex V, for plastics used in contact with food are used, for example, for polymerization of polymers, especially for the food and pharmaceutical industry. Such mineral oil based lubricants usually contain lubricity additive (s) and may also contain other type (s) of additive (s), such as antioxidants.
[00010] Dow document WO2009012041 discloses that, in high pressure polymerization processes, in which compressors are used to pressurize reagents, that is, one or more monomers, the compressor lubricant can have an effect on the polymer properties polymerized. The document describes the use of a polyether polyol which comprises one or no hydroxyl functionality as a compressor lubricant to prevent premature crosslinking, particularly of HP silane-modified polyolefins. WO2009012092 from Dow discloses a composition which comprises (i) an HP polyolefin without 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 single hydroxyl functionality . Component (ii) appears to originate from a compressor lubricant. The composition is, inter alia, for W&C applications and is said to reduce dielectric losses in MV and HV power cables, see page 2, paragraph 006. In both orders, it is stated that hydrophilic groups (eg hydroxyl groups) present in compressor lubricant may result in increased water uptake by the polymer which, in turn, can increase dielectric losses or, respectively, premature surface burn when the polymer is used as a cable layer material. The problems are solved by a specific PAG type lubricant with reduced amount of hydroxyl functionality.
[00011] There is a continuing need in the field of polymers to discover polymers which are suitable for applications that require polymer, such as wire and cable applications, with high requirements and strict regulations. Objectives of the Invention
[00012] One of the objectives of the present invention is to provide an alternative cable, particularly a power cable with highly advantageous properties useful for alternating current (alternating current - CA) or direct current (direct current - CC) cable applications.
[00013] In addition, the invention provides the use of an alternative polymeric composition in an insulating layer in contact with a semiconductive layer comprising a carbon black, whereby highly advantageous properties for use in alternating current cable applications (Alternating Current) - AC) or direct current (DC), preferably in DC cable applications, are provided.
[00014] The invention and other objectives of it are described and defined in detail below. Figures
[00015] Figure 1 describes the model cable with three layers used with an insulation thickness of 1.5 mm used in the Conductivity Determination Method CC 4. Description of the Invention
[00016] As the first invention, the present invention provides a cable comprising a conductor surrounded by at least one semiconductive layer and an insulation layer, in any order, in which: - the semiconductive layer comprises a semiconductive composition comprising carbon black and - the insulation layer comprises a polymeric composition comprising a polyolefin, characterized by the fact that: (i) the polymeric composition of the insulation layer has an electrical conductivity of 150 fS / m or less, when measured at 70 ° C and a field average electrical power of 30 kV / mm from a sample of non-degassed plate with a thickness of 1 mm consisting of a crosslinked polymer composition according to the CC conductivity method (1), as determined under "Determination Methods".
[00017] The advantageous electrical conductivity of the polymeric composition of the insulation layer, which contributes to the advantageous electrical properties of the cable of the invention, is characterized and expressed here using the CC conductivity method (1) as defined in claim 1 and described under "Methods for Determining CC Conductivity" in the "Determination Methods" section below. Preferred embodiments of the invention are defined with other definitions of conductivity according to CC conductivity methods (2) to (4) as described under "Methods for Determining CC Conductivity" in the "Determination Methods" section below. The DC conductivity method (1) (definition (i)) above and method (2) below describe the electrical conductivity of the polymeric composition of the insulation layer measured with a cross-linked plate sample. The DC conductivity method (3) (definition (ii)) and the DC conductivity method (4) below characterize the electrical conductivity property of the cross-linked polymeric composition of the cable insulation layer measured from a model cable in the presence of a semiconductive layer of the cable. Methods (3) and (4) indicate the leakage property of electrical current from the insulation layer in a cable.
[00018] The polymeric composition of the insulation layer of the invention is also referred to herein as "Polymeric Composition" or "polymeric composition". The polyolefin of the polymeric composition of the insulation layer is also referred to herein as "polyolefin". The cable of the invention is also referred to here for short as "Cable". The semiconductive composition of the cable's semiconductive layer is also referred to here as "Semiconductive Composition".
[00019] The term "conductor" means, here above and below, that the conductor comprises one or more wires. In addition, the cable may comprise one or more of such conductors. The conductor is an electrical conductor.
[00020] The unexpectedly low electrical conductivity contributed by the polymeric composition for the cable is very advantageous for power cables, preferably for direct current (DC) power cables. The invention is particularly advantageous for DC power cables.
[00021] The polymeric composition is preferably produced in a high pressure process (High Pressure - HP). As is well known, the high pressure reactor system typically comprises a compression zone for a) compression of one or more initiation monomers into one or more compressors, which are also known as hypercompressor (s), a zone of polymerization for b) polymerization of the monomer (s) in one or more polymerization reactors and a recovery zone for c) separating the unreacted products in one or more separators and for recovering 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), for recovering the separated polymer in the form of pellets. The process is described in more detail below.
[00022] Surprisingly, it has now been found that, when in an HP reactor system for compressing the initiation monomer (s), a compressor lubricant comprising a mineral oil is used in compressors for cylinder lubrication, so the resulting polyolefin has highly advantageous electrical properties, such as reduced electrical conductivity, which contributes to the cable's excellent electrical properties. This is unexpected, since mineral oils are conventionally used for the production of polymers for the medical and food industry, in which health aspects are considered, not the reduced conductivity as required for W&C applications.
[00023] Compressor lubricant means, here, a lubricant used in compressor (s), that is, in hypercompressor (s), for cylinder lubrication.
[00024] Consequently, in a second invention, a cable is independently provided, which comprises a conductor surrounded by at least one semiconductive layer and an insulating layer, in any order, in which: - the semiconductive layer comprises a semiconductive composition comprising carbon black and - the insulation layer comprises a polymeric composition comprising a polyolefin, in which the polyolefin of the polymeric Composition is obtainable through a high pressure process comprising: (a) compression of one or more monomers under pressure in a compressor, using a compressor lubricant for lubrication, (b) optionally polymerizing a monomer together with one or more comonomers in a polymerization zone, (c) separating the polyolefin obtained from unreacted products and recovering the separate polyolefin in a recovery zone, wherein, in step a), the compressor lubricant comprises a mineral oil.
[00025] The terms "obtainable through the process" or "produced through the process" are used interchangeably here and mean the category "product by process", that is, that the product has a technical characteristic which is due to the process of preparation.
[00026] The unifying technical characteristic in common with the cables of the first and second inventions is the reduced electrical conductivity of the Polymeric Composition, a characteristic which can be expressed through electrical conductivity or, alternatively, through product-by-product. process.
[00027] "Low" or "low" electrical conductivity, as used interchangeably here, means that the value obtained from the DC conductivity method is low, that is, reduced.
[00028] More preferably, the cable of the invention has the properties of the first and second inventions, that is, it comprises a conductor surrounded by at least one semiconductive layer and an insulation layer, in any order, in which: - the semiconductive layer comprises a semiconductive composition comprising carbon black and - the insulation layer comprises a polymeric composition comprising a polyolefin, in which (i) the polymeric composition of the insulation layer has an electrical conductivity of 150 fS / m or less when measured at 70 ° C and an average electric field of 30 kV / mm from a sample of non-degassed plate with a thickness of 1 mm consisting of a cross-linked polymeric composition according to the CC conductivity method (1) as described under “Determination Methods” ; and wherein the polyolefin of the polymeric composition is obtainable through a high pressure process comprising (a) compression of one or more monomer (s) under pressure in a compressor, using a compressor lubricant for lubrication, (b) polymerization of a monomer optionally together with one or more comonomer (s) in a polymerization zone, (c) separation of the polyolefin obtained from unreacted products and recovery of the separate polyolefin in a recovery zone, where, in step a), the lubricant for compressor comprises a mineral oil.
[00029] The cable of the first and second inventions are commonly referred to here as the cable.
[00030] Electric power cables, especially medium voltage, high voltage and extra-high voltage cables, typically and preferably comprise two semiconductive layers and an insulation layer.
[00031] Said cable preferably comprises a conductor surrounded by at least one semiconductive layer and an insulating layer, in that order. More preferably, the Cable comprises a conductor surrounded by an internal semiconductive layer, an insulation layer and optionally and preferably an external semiconductive layer, in that order, as defined above. More preferably, at least the inner semiconductive layer comprises the semiconductive composition. Also preferably, the outer semiconductive layer comprises the semiconductive composition.
[00032] It is evident to those skilled in the field that the Cape may optionally comprise one or more of another layer (s) comprising one or more canvas (s), (one) shirt layer (s) or other (s) ) protective layer (s), layer (s) which (s) are conventionally used in the W&C field.
[00033] The semiconductive composition preferably comprises a polyolefin (2) and said carbon black.
[00034] The cable insulation layer is preferably crosslinkable. In addition, at least the inner semiconductive layer of the Cable is optionally and, preferably, crosslinkable. The cable's preferred external semiconductive layer can be crosslinkable or non-crosslinkable, depending on the final application. In addition, the outer semiconductive layer of the Cable, if present, can be connected or removable, terms which have a well-known meaning in the field. Preferably, the optional and preferable outer semiconductive layer is bonded and crosslinkable.
[00035] The Polymeric and / or semiconductive Composition of the Cable may comprise other component (s), such as other polymeric component (s) and / or one or more additives. In addition, the polymeric composition with the electrical conductivity as defined above or below or the semiconductive composition or both, can be cross-linked.
[00036] Accordingly, the cable according to the present invention comprises layers made of a semiconductive composition and a polymeric composition. Such compositions are preferably crosslinkable. “Crosslinkable” means that the cable layer can be crosslinked prior to use in its final application. In the crosslinking reaction of a polymer, interpolymer bonds (bridges) are primarily formed. Crosslinking can be carried out by free radical reaction using irradiation or, preferably, using a crosslinking agent which is typically a free radical generating agent or by incorporating crosslinkable groups into polymeric component (s) ), as known in the art. In addition, the crosslinking step of one or both of the polymeric composition and the semiconductive composition is typically carried out after the formation of the cable. It is preferred that at least the polymeric composition of the insulation layer is cross-linked before the final use of the cable.
The free radical generation crosslinking agent can be a radical forming crosslinking agent which contains at least one -O-O- bond or at least one -N = N- bond. More preferably, the crosslinking agent is a peroxide, whereby crosslinking is preferably carried out using a well-known peroxide crosslinking technology that is based on free radical crosslinking and is well described in the field. The peroxide can be any suitable peroxide, for example, as conventionally used in the field.
[00038] As mentioned above, crosslinking can also be achieved by incorporating crosslinkable groups, preferably hydrolyzable silane groups, into the polymeric component (s) of any of the semiconductive and / or polymeric Composition. Hydrolyzable silane groups can be introduced into the polymer through copolymerization, for example, ethylene monomers with comonomers containing silane group or by grafting with compounds containing silane groups, that is, by means of chemical modification of the polymer through the addition of groups silane mainly in a radical reaction. Such silane groups containing comonomers and compounds are well known in the field and, for example, are commercially available. Hydrolyzable silane groups are then typically cross-linked through hydrolysis and subsequent condensation in the presence of a silanol and H2 O condensation catalyst in a manner known in the art. Also, the silane crosslinking technique is well known in the art. If silane crosslinking groups are used, then these are typically used in a semiconductive composition.
[00039] Preferably, the crosslinkable polymeric composition of the insulation layer comprises crosslinking agent (s), preferably free radical generating agent (s), more preferably peroxide. Therefore, the crosslinking of at least the insulation layer and optionally and preferably of at least one semiconductive layer is preferably carried out by free radical reaction using one or more free radical generation agents, preferably , peroxide (s).
[00040] When the preferred peroxide is used as a crosslinking agent, then the crosslinking agent is preferably used in an amount of less than 10% by weight, more preferably in an amount of between 0.2 to 8 % by weight, even more preferably in an amount of 0.2 to 3% by weight and, more preferably, in an amount of 0.3 to 2.5% by weight with respect to the total weight of the composition to be cross-linked.
[00041] The preferred crosslinking agent is peroxide. Non-limiting examples are organic peroxides, such as di-tert-amyl peroxide, 2,5-di (tert-butylperoxy) -2,5-dimethyl-3-hexino, 2,5-di (tert-butylperoxy) -2 , 5-dimethylhexane, tert-butylcumyl peroxide, di- (tert-butyl) peroxide, dicumyl peroxide, butyl-4,4-bis (tert-butylperoxy) - valerate, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, tert-butylperoxybenzoate, dibenzoyl peroxide, bis (tert-butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 1,1-di (tert-butylperoxy ) cyclohexane, 1,1-di (tert-amylperoxy) cyclohexane or any mixtures thereof. Preferably, the peroxide is selected from 2,5-di (tert-butylperoxy) -2,5-dimethylhexane, di (tert-butylperoxyisopropyl) benzene, dicumyl peroxide, tert-butylcumyl peroxide, di- (tert- butyl) or mixtures thereof. More preferably, the peroxide is dicumyl peroxide.
[00042] Preferably, the Cable is characterized by the fact that the polymeric composition has (i) an electrical conductivity of 140 fS / m or less, preferably 130 fS / m or less, preferably 120 fS / m or less, preferably 100 fS / m or less, preferably 0.01 to 90 fS / m, more preferably 0.05 to 90 fS / m, more preferably 0.1 to 80 fS / m, more preferably 0.5 to 75 fS / m, when measured at 70 ° C and an average electric field of 30 kV / mm from a sample of non-degassed plate with a thickness of 1 mm consisting of a cross-linked polymeric composition according to CC conductivity method (1) as described under “Determination Methods”. In this embodiment, the polymeric composition also preferably has (ia) an electrical conductivity of 140 fS / m or less, preferably 130 fS / m or less, preferably 60 fS / m or less, preferably 0 , 01 to 50 fS / m, more preferably from 0.05 to 40 fS / m, more preferably from 0.1 to 30 fS / m, when measured at 70 ° C and an average electric field of 30 kV / mm from of a 1 mm thick degassed plate sample consisting of a cross-linked polymeric composition according to the CC conductivity method (1), as described under “Determination Methods”.
[00043] In the preferred reticulated modalities, the electrical conductivity contributed by the insulation layer is surprisingly low, even without removing the volatile by-products after cross-linking, that is, without degassing. Therefore, if desired, the degassing step during cable production can be reduced.
[00044] In a preferred embodiment of the invention, the polymeric composition of the insulation layer is characterized by (ii) an electrical conductivity of 1300 fS / m or less, when determined from a sample of the model cable of the polymeric composition as a layer of insulation with a thickness of 5.5 mm and the semiconductive composition as a semiconductive layer and measured at 70 ° C and an average electric field of 27 kV / mm according to the conductivity method CC (3) as described under “Methods of Determination ”. More preferably, the polymeric composition of the insulation layer is characterized by (ii) an electrical conductivity of 1000 fS / m or less, preferably 700 fS / m or less, preferably 500 fS / m or less, more preferably of 0.01 to 400 fS / m, when determined from a sample cable model of the polymeric composition as an insulation layer with a thickness of 5.5 mm and the semiconductive composition as a semiconductive layer and measured at 70 ° C and an average electric field of 27 kV / mm according to the DC conductivity method (3) as described under “Determination Methods”.
[00045] More preferably, the polymeric composition has an electrical conductivity of 0.27 fS / m or less, preferably 0.25 f / Sm or less, more preferably of 0.001 to 0.23 fS / m, when measuring the 20 ° C and an average electric field of 40 kV / mm from a 0.5 mm thick degassed plate sample consisting of a crosslinked polymeric composition according to the CC conductivity method (2) as described under “Methods of Determination ”.
[00046] More preferably, the polymeric composition of the Cable is characterized by an electrical conductivity of 0.15 fS / m or less, preferably 0.14 fS / m or less, preferably 0.001 to 0.13 fS / m or less, when determined from a sample cable model of the polymeric composition as an insulation layer with a thickness of 1.5 mm and the semiconductive composition as a semiconductive layer, when measured at 20 ° C and an average electric field of 40 kV / mm according to the DC conductivity method (4) as described under “Determination Methods”.
[00047] Therefore, the electrical properties defined using methods (1) to (4) above are measured using a sample of the polymeric composition of the insulation layer after crosslinking with a crosslinking agent. The amount of the crosslinking agent can vary. Preferably, in these test methods, peroxide is used and the amount of peroxide can vary between 0.3 to 2.5% by weight with respect to the total weight of the composition to be cross-linked. The respective sample preparation of the cross-linked polymeric composition is described below under "Determination Methods". It is evident that the non-crosslinked polymeric composition of the insulation layer also has the advantages of low electrical conductivity, the Determination Methods provided being used only as a means to characterize and define the electrical conductivity property of the polymeric composition and thus the Cable .
[00048] In addition to the crosslinking agent (s), as optional additives, the semiconductive and / or polymeric composition may contain other additive (s), such as antioxidant (s), stabilizer (s), additive water retardant (s), processing aid (s), firing retardant (s), metal deactivator (s), crosslinking agent (s), flame retardant (s), acid remover (s) or ions, inorganic filler (s), strain stabilizer (s) or any mixtures thereof. As non-limiting examples of antioxidants, for example, sterically hindered or semi-hindered phenols, aromatic amines, sterically hindered aliphatic amines, organic phosphites or phosphonites, thio compounds and mixtures thereof can be mentioned.
[00049] In a more preferable modality of the Cable, the polymeric composition of the insulation layer comprises free radical generation agent (s) and one or more antioxidants as defined above so that, as non-limiting examples of thio compounds, for example: 1. sulfur-containing phenolic antioxidant (s), preferably selected from thiobisphenol (s), the most preferred being 4,4'-thiobis (2-tert-butyl-5-methylphenol) (CAS number: 96- 69-5), 2,2'-thiobis (6-t-butyl-4-methylphenol), 4,4'-thiobis (2-methyl-6-t-butylphenol), bis [3- (3,5- di-tert-butyl-4-hydroxyphenyl) thiodiethylene propionate or 4,6-bis (octylmethyl) -o-cresol (CAS: 110553-27-0) or derivatives thereof; or any mixtures thereof, 2. other thio compounds, such as distearyl-thio-dipropionate or similar compounds with various lengths on the carbon chains or mixtures thereof, 3. or any mixtures of 1) and 2), may be mentioned .
[00050] Group 1) above is the preferred antioxidant (s) for the polymeric composition of the insulation layer.
[00051] In this preferred embodiment of the Cabo, the amount of an antioxidant is preferably from 0.005 to 2.5% by weight based on the weight of the polymeric composition. The antioxidant (s) are preferably added in an amount of 0.005 to 2% by weight, more preferably 0.01 to 1.5% by weight, more preferably 0.03 to 0.8 % by weight, even more preferably 0.04 to 1.2% by weight, based on the weight of the polymeric composition.
[00052] In another preferred embodiment of the cable, the polymeric composition of the insulation layer comprises free radical generation agent (s), one or more antioxidant (s) and one or more burning retardant (s).
[00053] Firing retardant (SR) is a type of additive well known in the field and can, inter alia, prevent premature crosslinking. As is also known, SRs can also contribute to the level of unsaturation of the polymeric composition. As examples of firing retardants, allyl compounds, such as aromatic alpha-methyl alkenyl monomer dimers, preferably 2,4-diphenyl-4-methyl-1-pentene, substituted or unsubstituted diphenylethylenes, derived from quinone, hydroquinone derivatives, monofunctional vinyl-containing esters and ethers, monocyclic hydrocarbons having at least two or more double bonds or mixtures thereof, may be mentioned. Preferably, the amount of a firing retardant is within the range of 0.005 to 2.0% by weight, more preferably within the range of 0.005 to 1.5% by weight, based on the weight of the polymeric composition. Other preferred ranges are, for example, 0.01 to 0.8% by weight, 0.03 to 0.75% by weight, 0.03 to 0.70% by weight or 0.04 to 0.60% by weight, based on the weight of the polymeric composition. The preferred SR of the polymeric composition is 2,4-Diphenyl-4-methyl-1-pentene (CAS Number 6362-80-7).
[00054] The preferred cable is preferably an AC or DC power cable, preferably a DC power cable, more preferably a medium voltage DC power cable (Medium Voltage - MV), high voltage (High Voltage - HV) or extra high voltage (Extra High Voltage - EHV), more preferably an HV or EHV DC power cable.
[00055] It is evident that the most preferable modalities to follow, subgroups and other properties of the polymeric compositions and components thereof and the layers of the Cape are generalizable and independent definitions can be used in any combination to further define the Cape. Polyolefin of the Polymeric Composition of the Insulation Layer
[00056] The term polyolefin means an olefin homopolymer and an olefin copolymer with one or more comonomers. As is well known, “comonomer” refers to copolymerizable comonomer units.
[00057] The polyolefin can be any polyolefin, such as a conventional polyolefin, which is suitable as a polymer in at least one insulation layer of an electrical cable, preferably of a power cable.
[00058] The polyolefin can be, for example, a commercially available polymer or can be prepared according to or analogously to a known polymerization process described in the chemical literature.
[00059] More preferably, the polyolefin is a polyethylene produced in a high pressure process, more preferably a low density LDPE polyethylene produced in a high pressure process. The meaning of LDPE polymer is well known and documented in the literature. Although the term LDPE is an abbreviation for low density polyethylene, the term should be understood as not limiting the density range, but it covers LPDE-like HP polyethylenes with low, medium and higher densities. The term LDPE describes and distinguishes only the nature of polyethylene HP with typical characteristics, such as a different branching architecture, compared to the PE produced in the presence of an olefin polymerization catalyst.
[00060] LDPE as said polyolefin means a low density ethylene homopolymer (referred to herein as LDPE homopolymer) or a low density ethylene copolymer with one or more comonomers (referred to here as an LDPE copolymer). The one or more LDPE copolymer comonomers are preferably selected from the polar comonomer (s), non-polar comonomer (s) or a mixture of the polar comonomer (s) ( (s) and non-polar comonomer (s) as defined above or below. In addition, said LDPE homopolymer or LDPE copolymer, such as said polyolefin, can be optionally unsaturated.
[00061] As a polar comonomer for the LDPE copolymer like said polyolefin, comonomer (s) containing hydroxyl group (s), alkoxy group (s), carbonyl group (s), carboxy group (s), ether group (s) or ester group (s) or a mixture thereof, may be used. More preferably, comonomer (s) containing carboxyl group (s) and / or ester are used as said polar comonomer. Even more preferably, the polar LDPE copolymer comonomer (s) is (are) selected from the groups of acrylate, methacrylate (s) or acetate (s) or any mixtures thereof. If present in said LDPE copolymer, the polar comonomer (s) is (are) preferably (are) selected from the group of alkyl acrylates, alkyl methacrylates or vinyl acetate or a mixture thereof. More preferably, said polar comonomers are selected from C1- to C6-alkyl acrylates, C1- to C6-alkyl methacrylates or vinyl acetate. Even more preferably, said polar LDPE copolymer is an ethylene copolymer with C1- to C4-alkyl acrylate, such as methyl, ethyl, propyl or butyl acrylate or vinyl acetate or any mixture thereof.
[00062] As the non-polar comonomer (s) for the LDPE copolymer such as said polyolefin, other comonomer (s) other than the polar comonomers defined above can be used . Preferably, non-polar comonomers are other than non-comonomer (s) containing hydroxyl group (s), alkoxy group (s), carbonyl group (s), carboxyl group (s), ether group (s) or group (s) ester. A preferred non-polar comonomer (s) group preferably comprises 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); (a) comonomer (s) containing silane group; or any mixtures thereof. The polyunsaturated comonomer (s) is (are) further described below in relation to unsaturated LDPE copolymers.
[00063] If the LDPE polymer is a copolymer, it preferably comprises 0.001 to 50% by weight, more preferably 0.05 to 40% by weight, even more preferably less than 35% by weight, even more preferably less than 30 % by weight, more preferably less than 25% by weight, of one or more comonomers.
[00064] The polymeric composition, preferably a polyolefin component thereof, more preferably the LDPE polymer, can be optionally unsaturated, i.e. the polymeric composition, preferably the polyolefin, preferably the LDPE polymer, can comprise double bonds carbon-carbon. "Unsaturated" here means that the polymeric composition, preferably polyolefin, contains carbon-carbon double bonds / 1000 carbon atoms in a total amount of at least 0.4 / 1000 carbon atoms.
[00065] As is well known, unsaturation can be imparted to the polymeric composition, inter alia, by means of polyolefin, (a) low molecular weight (Mw) compound (s), such as crosslink reinforcement or burning retardant additive (s) or any combinations thereof. The total number of double bonds here means double bonds determined from sources that are known and deliberately added to contribute to unsaturation. If two or more sources of double bonds above are chosen to be used to provide unsaturation, then the total amount of double bonds in the polymeric composition means the sum of the double bonds present in the double bond sources. It is evident that a characteristic model compound for calibration is used for each source chosen to allow quantitative infrared (FTIR) determination.
[00066] Any double bond measurements are taken before crosslinking.
[00067] If the polymeric composition is unsaturated before crosslinking, then it is preferred that the unsaturation originates from at least one unsaturated polyolefin component. More preferably, the unsaturated polyolefin is an unsaturated polyethylene, more preferably an unsaturated LDPE polymer, even more preferably an unsaturated LDPE homopolymer or an unsaturated LDPE copolymer. When polyunsaturated comonomer (s) is (are) present in the LDPE polymer as said unsaturated polyolefin, then the LDPE polymer is an unsaturated LDPE copolymer.
[00068] In a preferred embodiment, the term "a total amount of carbon-carbon double bonds" is defined from the unsaturated polyolefin and refers, if not otherwise specified, to the combined amount of double bonds which originate of vinyl groups, vinylidene groups and trans-vinylene groups, if present. Of course, polyolefin does not necessarily contain all of the above three types of double bonds. However, any of the three types, when present, are calculated for the "total amount of carbon-carbon double bonds." The amount of each type of double bond is measured as indicated under "Determination Methods".
[00069] If an LDPE homopolymer is unsaturated, unsaturation can be provided, for example, by a Chain Transfer Agent (CTA), such as propylene and / or by the polymerization conditions. If an LDPE copolymer is unsaturated, then unsaturation can be provided by one or more of the following means: by a Chain Transfer Agent (CTA), by one or more polyunsaturated comonomers or by conditions of polymerization. It is well known that selected polymerization conditions, such as peak temperatures and pressure, can have an influence on the level of unsaturation. In the case of an unsaturated LDPE copolymer, it is preferably an unsaturated ethylene LDPE copolymer with at least one poly-unsaturated comonomer and optionally with other comonomer (s), such as polar comonomer (s) which one (s) is (are) preferably selected from the acrylate or acetate comonomer (s). More preferably, an unsaturated LDPE copolymer is an unsaturated ethylene LDPE copolymer with at least one polyunsaturated comonomer.
[00070] Polyunsaturated comonomers suitable for unsaturated polyolefin preferably consist of a straight carbon chain with at least 8 carbon atoms and at least 4 carbons between the unconjugated double bonds, of which at least one is terminal . More preferably, said polyunsaturated comonomer is a diene, preferably a diene which comprises at least eight carbon atoms, the first carbon-carbon double bond being terminal and the second carbon-carbon double bond being unconjugated to the first . Preferred dienes are selected from C8 to C14 unconjugated dienes or mixtures thereof, most preferably selected from 1,7-octadiene, 1,9-decadiene, 1,11-dodecadiene, 1,13-tetradecadiene, 7-methyl-1, 6- octadiene, 9-methyl-1,8-decadiene or mixtures thereof. Even more preferably, the diene is selected from 1,7-octadiene, 1,9-decadiene, 1,11-dodecadiene, 1,13-tetradecadiene or any mixture thereof, however, without limitation to the above dienes.
[00071] It is well known that, for example, propylene can be used as a comonomer or as a Chain Transfer Agent (CTA) or both, so it can contribute to the total amount of CC double bonds, preferably for the total amount of vinyl groups. Here, when a compound which can also act as a comonomer, such as propylene, is used as CTA to provide double bonds, then said copolymerizable comonomer is not calculated for the comonomer content.
[00072] If the polyolefin, more preferably the LDPE polymer, is unsaturated, then it preferably has the total amount of carbon-carbon double bonds, which originate from vinyl groups, vinylidene groups and trans-vinylene groups, if present, more than 0.5 / 1000 carbon atoms. The maximum limit on the amount of carbon-carbon double bonds present in the polyolefin is not limited and may preferably be less than 5.0 / 1000 carbon atoms, preferably less than 3.0 / 1000 carbon atoms.
[00073] In some embodiments where, for example, a higher level of crosslinking of the final crosslinked insulation layer is desired, the total amount of carbon-carbon double bonds, which originate from vinyl groups, vinylidene groups and groups and trans - vinylene, if present, in the unsaturated LDPE is preferably greater than 0.50 / 1000 carbon atoms, preferably greater than 0.60 / 1000 carbon atoms.
[00074] If desired, the higher content of double bonds, combined with the preferable presence of a crosslinking agent, preferably peroxide, gives the Cable an advantageous balance between electrical and mechanical properties, preferably combined with good heat resistance and deformation.
[00075] Therefore, the polyolefin is preferably unsaturated and contains at least vinyl groups and the total amount of vinyl groups is preferably greater than 0.05 / 1000 carbon atoms, even more preferably greater than 0.08 / 1000 carbon atoms and, more preferably, greater than 0.11 / 1000 carbon atoms. Preferably, the total amount of vinyl groups is less than 4.0 / 1000 carbon atoms. More preferably, the polyolefin, before crosslinking, contains vinyl groups in a total amount of more than 0.20 / 1000 carbon atoms, even more preferably more than 0.30 / 1000 carbon atoms and, more preferably, more 0.40 / 1000 carbon atoms. In some embodiments, preferably in power cables, more preferably in DC power cables, at least one layer, preferably the insulation layer, comprises LDPE polymer, preferably LDPE copolymer, which contains vinyl groups in one total amount of more than 0.50 / 1000 carbon atoms.
[00076] The preferred polyolefin for use in the polymeric composition is a saturated LDPE homopolymer or an ethylene LDPE copolymer saturated with one or more comonomers; or an unsaturated LDPE polymer, which is selected from an unsaturated LDPE homopolymer or an LDPE ethylene copolymer with one or more comonomers, even more preferably an unsaturated LDPE homopolymer or an unsaturated LDPE copolymer with one or more comonomers which are, preferably at least one polyunsaturated comonomer, preferably a diene as defined above and optionally with other comonomer (s) and has the total amount of carbon-carbon double bonds, which originate from vinyl groups, vinylidene groups and trans-vinylene groups, if present, as defined above, preferably have the total amount of vinyl groups as defined above. Said unsaturated LDPE polymer is highly usable for an insulation layer of a power cable, preferably a DC power cable, of the invention.
[00077] 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 greater than 960 kg / m3 and, preferably, 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 / 10 min, more preferably from 0.1 to 20 g / 10 min and more preferably, it is 0.2 to 10 g / 10 min. Compressor lubricant
[00078] The compressor lubricant used in the polymerization process for the production of the preferred polyolefin of the polymeric composition comprises mineral oil, which is a known petroleum product.
[00079] Mineral oils have a well-known meaning and are used, inter alia, for lubrication in commercial lubricants. "Compressor lubricant comprising mineral oil" and "mineral oil based compressor lubricants" are used interchangeably here.
[00080] Mineral oil can be a synthetic mineral oil, which is produced synthetically or a mineral oil obtainable from crude oil refinery processes.
[00081] Typically, mineral oil, also known as liquid petroleum, is a by-product in the distillation of petroleum to produce gasoline and other petroleum-based products from crude oil.
[00082] The mineral oil of the compressor lubricant of the invention is preferably a paraffinic oil. Such paraffinic oil is derived from petroleum-based hydrocarbon feed stocks.
[00083] Mineral oil is preferably the base oil of the compressor lubricant. The compressor lubricant may comprise other components, such as lubricity additive (s), viscosity-increasing agents, antioxidants, other additive (s) or any mixtures thereof, as is well known in the art.
[00084] More preferably, the compressor lubricant comprises a mineral oil which is conventionally used as compressor lubricants for the production of plastics, for example, LDPE, for the medical or food industry, more preferably the compressor lubricant comprises an oil mineral which is a white oil. Even more preferably, the compressor lubricant comprises white oil like mineral oil and is suitable for the production of polymers for the medical or food industry. White oil has a well-known meaning. In addition, such 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.
[00085] As is known, mineral oil, preferably white mineral oil from the preferred compressor lubricant contains paraffinic hydrocarbons.
[00086] 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, contains 5% by weight (% by weight) or less of hydrocarbons with less than 25 carbon atoms; - in a third preferable embodiment, the hydrocarbons in the mineral oil, preferably the white mineral oil of the compressor lubricant, have an average molecular weight (Mw) of 480 or more.
[00087] The "amount of hydrocarbons", "viscosity" and "Mw" above are preferably in accordance with European Directive 2002/72 / EC of 6 August 2002 above.
[00088] It is preferred that the compressor lubricant complies with each of the three modalities 1-3 above.
[00089] The most preferred compressor lubricant of the invention meets the requirements provided for white mineral oil in European Directive 2002/72 / EC of 6 August 2002, Annex V, for plastics used in contact with food. The Directive is published, for example, in L 220/18 EN Official Journal of the European Communities, 15/08/2002. Therefore, mineral oil is, more preferably, a white mineral oil which complies with the aforementioned European Directive 2002/72 / EC of 6 August 2002, Annex V. In addition, it is preferred that the compressor lubricant be European Directive 2002/72 / EC of 6 August 2002.
[00090] 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 applications or food. Non-exhaustive examples of preferred commercially available compressor lubricants are, for example, Exxcolub R Series compressor lubricants for the production of used polyethylene in contact with food and supplied, inter alia, by ExxonMobil, Shell Corena for the production of polyethylene for use pharmacist and supplied by Shell or CL-1000-SONO-EU, supplied by Sonneborn.
[00091] The compressor lubricant preferably does not contain components based on polyalkylene glycol.
[00092] It is preferred 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 preferred that no mineral oil is added to the polymeric composition or to the polyolefin after polymerization thereof.
[00093] Traces of the mineral oil from the compressor lubricant and present, if any, in the produced polyolefin typically add up to a maximum amount of up to 0.4% by weight, based on the amount of the polyolefin. The limit provided is the absolute maximum based on the calculation of the worst case scenario where all the lost compressor lubricant (medium leakage) will have gone into the final polyolefin. Such a scenario is unlikely and the resulting polyolefin usually contains an evidently lower level of mineral oil.
[00094] The compressor lubricant of the invention is used in a conventional manner and is well known to those skilled in the field for lubricating the compressor (s) in the compression step (a) of the invention. Process
[00095] The high pressure (HP) process is the preferred process for the production of a polyolefin of the polymeric composition, preferably a low density polyethylene (LDPE) polymer selected from LDPE homopolymer or ethylene LDPE copolymer with one or more comonomers.
[00096] The invention also provides a process for the polymerization of a polyolefin in a high pressure process, which comprises the steps of: (a) compressing one or more monomers under pressure in a compressor, in which a compressor lubricant is used for lubrication, (b) polymerization of a monomer, optionally together with one or more comonomers in a polymerization zone, (c) separation of the polyolefin obtained from unreacted products and recovery of the separate polyolefin in a recovery zone, where, in step a), a compressor lubricant comprises a mineral oil, including its preferred embodiments.
[00097] Accordingly, the polyolefin of the invention is preferably produced under high pressure through free radical initiated polymerization (referred to as high pressure radical polymerization). The preferred polyolefin is an LDPE homopolymer or LDPE ethylene copolymer with one or more comonomers, as defined above. The LDPE polymer obtainable by means of the process of the invention preferably confers the advantageous electrical properties, as defined above or below. High pressure polymerization (HP) and adjustment of process conditions to further configure 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 those skilled in the art.
[00098] Compression step a) of the invention process:
[00099] Monomer, preferably ethylene, with one or more optional comonomer (s), is fed to one or more compressor in the compression zone to compress the monomer (s) to the desired polymerization pressure and allow handling of high amounts of monomer (s) at a controlled temperature. Typical compressors, ie hypercompressors, for the process can be piston compressors or diaphragm compressors. The compression zone usually comprises several compressors that can operate in series or in parallel. The compressor lubricant of the invention is used for cylinder lubrication in at least one, preferably in all hypercompressors present in the compression zone. The compression step a) usually comprises 2-7 compression steps, often with intermediate cooling zones. The 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.
[000100] Polymerization step b) of the process:
[000101] Preferred high pressure polymerization is carried out in a polymerization zone which comprises one or more polymerization reactors, preferably at least one tubular reactor or an autoclave reactor, preferably a tubular reactor. The polymerization reactor (s), preferably a tubular reactor, can comprise one or more reactor zones, in which different polymerization conditions can occur and / or be adjusted as is well known in the HP field. One or more reaction zones are provided in a known manner with means for feeding the monomer and optional comonomer (s), as well as means for adding initiator (s) and / or other components, such as CTA (s) ). In addition, the polymerization zone can comprise a preheating section which precedes or is integrated with the polymerization reactor. In a preferred HP process, the monomer, preferably ethylene, optionally together with one or more comonomers is polymerized in a preferable tubular reactor, preferably in the presence of chain transfer agent (s). Tubular Reactor:
[000102] 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, are divided into two or more currents and the divided feed (s) is (are) introduced into the tubular reactor in the 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 further divided and each division is injected at different locations along the reactor. Also, the starter (s) feed can be divided into two or more currents. In addition, in a multi-feed system, the split chains of monomer (/ comonomer) and / or other optional component (s), such as CTA and, respectively, the split chains of initiator (s) they may have the same or different component (s) or concentrations of components or both.
[000103] The single feeding system for the optional monomer and comonomer (s) is preferred in the tubular reactor for the production of the invented polyolefin.
[000104] The first part of the tubular reactor is to adjust the temperature of the monomer feed, preferably ethylene and optional comonomer (s); the usual temperature is below 200 ° C, such as 100-200 ° C. Then, the radical initiator is added. As the radical initiator, any compound or mixture thereof that decomposes to radicals at an elevated temperature can be used. 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), is added at the front and optionally the monomer feed (s) can be divided to the addition of the optional monomer and / or comonomer (s) at any time in the process, in any zone of the tubular reactor and from one or more injection point (s), for example, 1-5 point (s) ), with or without separate compressors.
[000105] 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.
[000106] Non-polar CTA, if present, is preferably selected from: i) one or more compounds which do not contain a polar group selected from 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 cyclic or branched or straight chain hydrocarbons optionally containing a heteroatom, such as O, N, S, Si or P. More preferably, the CTA (s) ) non-polar (s) is (are) selected from one or more cyclic alpha-olefins of 5 to 12 carbon atoms or one or more straight- or branched-chain alpha-olefins from 3 to 12 carbon atoms , more preferably one or more straight or branched chain alpha-olefins of 3 to 6 carbon atoms. The preferred non-polar CTA is propylene.
[000107] Polar CTA, if present, is preferably selected from: i) one or more compounds comprising one or more polar groups selected from nitrile (CN), sulfide, hydroxyl, alkoxy, aldehyde (HC = O), carbonyl, carboxyl, ether or ester or mixtures thereof; ii) one or more aromatic organic compounds or iii) any mixture thereof.
[000108] Preferably, any such polar CTA (s) has up to 12 carbon atoms, for example, up to 10 carbon atoms, preferably up to 8 carbon atoms. A preferred option includes (a) straight or branched chain alkane (s) having up to 12 carbon atoms (e.g., up to 8 carbon atoms) and having at least one nitrile (CN), sulfide, hydroxyl, alkoxy group , aldehyde (HC = O), carbonyl, carboxyl or ester.
[000109] More preferably, the polar CTA (s), if present, is (are) selected from (i) one or more compound (s) containing one or more hydroxyl groups, alkoxy, HC = O, carbonyl, carboxyl and ester or a mixture thereof, more preferably one or more compounds of alcohol, aldehyde and / or ketone. The preferred polar CTA (s), if present, is (a) straight or branched chain alcohol (s), aldehyde (s) or ketone (s) having up to 12 atoms of carbon, preferably up to 8 carbon atoms, especially up to 6 carbon atoms, more preferably isopropanol (IPA), methyl ethyl ketone (MEK) and / or propionaldehyde (PA).
[000110] The quantity of the preferred CTA (s) is not limited and can be configured by those skilled in the field, depending on the desired final properties of the final polymer. Therefore, the preferred chain transfer agent (s) can be added at any injection point of the reactor to the polymeric invention. The addition of one or more CTA (s) can be carried out from one or more injection points at any time during polymerization.
[000111] In the case where the polyolefin polymerization is carried out in the presence of a CTA mixture comprising one or more polar CTA (s) as defined above and one or more non-polar CTA (s) as defined above, then the proportion of feed, by weight%, from 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 CTA feed polar and non-polar CTA in the reactor.
[000112] The addition of monomer, comonomer (s) and optional CTA (s) can include, and typically includes, fresh and recycled feed (s).
[000113] The reactor is continuously cooled, for example, by water or steam. The highest temperature is called the peak temperature and the initial reaction temperature is called the initial temperature.
[000114] Suitable temperatures range up to 400 ° C, preferably from 80 to 350 ° C and the pressure from 70 MPa (700 bar), preferably 100 to 400 MPa (1000 to 4000 bar), more preferably from 100 to 350 MPa (1000 to 3500 bar). The pressure can be measured at least after the compression stage and / or after the tubular reactor. The temperature can be measured at several points during all stages. High temperature and high pressure generally increase productivity. Use of various temperature profiles selected by those versed in the field will allow control of the polymer chain structure, that is, long chain branch and / or short chain branch, density, branch factor, comonomer distribution, MFR, viscosity, distribution molecular weight, etc.
[000115] The reactor conventionally ends with a valve, the so-called production control valve. The valve regulates the pressure in the reactor and depressurizes the reaction mixture from the reaction pressure to the separation pressure.
[000116] Step c) of recovery of the process: Separation
[000117] The pressure is typically reduced to approximately 10 to 45 MPa (100 to 450 bar) and the reaction mixture is fed to a separating vessel, where most unreacted, often gaseous products are removed from the flow stream. polymer. Unreacted products comprise, for example, monomer or optional comonomer (s) and most of the unreacted components are recovered. The polymer stream is optionally further separated at a lower pressure, typically less than 0.1 MPa (1 bar), in a second separating vessel where more of the unreacted products are recovered. Normally, low molecular weight compounds, that is, wax, are removed from the gas. The gas is usually cooled and cleaned before recycling. Separate polymer recovery
[000118] After separation, the polymer obtained is typically in the form of a molten polymer which is normally mixed and pelletized in a pelletizing section, such as a pelletizing extruder, arranged in connection with the HP reactor system. Optionally, additive (s), such as antioxidant (s), can be added to that mixer in a manner known to result in the polymeric composition.
[000119] Further details of the production of ethylene (co) polymers through high pressure radical polymerization can be found, inter alia, in Encyclopedia of Polymer Science and Engineering, Vol. 6 (1986), pages 383-410 and Encyclopedia of Materials: Science and Technology, 2001 Elsevier Science Ltda .: "Polyethylene: High-pressure", R. Klimesch, D. Littmann and F.-O. Mahling, pages 7181-7184.
[000120] 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, a chain transfer agent during polymerization or by adjusting the reaction temperature or pressure (which also have, to some extent, an influence on the level of unsaturation).
[000121] When an unsaturated ethylene 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 comonomers, agent (s) chain transfer, process conditions or any combinations thereof, for example, using the desired feed ratio monomer, preferably ethylene and polyunsaturated comonomer and / or chain transfer agent, depending on the nature and amount of CC double bonds desired for the unsaturated LDPE copolymer. Inter alia, WO 9308222 describes the high pressure radical polymerization of ethylene with polyunsaturated monomers, such as α, w-alkadienes, to increase the unsaturation of an ethylene copolymer. The unreacted double bond (s) thus provides, inter alia, vinyl groups pendent to the polymer chain formed at the site where the polyunsaturated comonomer has been incorporated through polymerization. As a result, unsaturation can be uniformly distributed along the polymer chain in a manner by random copolymerization. Also, for example, WO 9635732 describes radical polymerization at high pressure of ethylene and a certain type of polyunsaturated α, w-divinyl siloxanes. Furthermore, as is known, for example, propylene can be used as a chain transfer agent to provide said double bonds. Polymeric composition of the insulation layer
[000122] 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 100% by weight and, more preferably, 85 to 100% by weight of polyolefin, based on the total weight of the polymeric component (s) present in the polymeric composition. The preferred polymeric composition consists of polyolefin as the only polymeric component. The expression means that the polymeric composition does not contain other polymeric components, but polyolefin as the only polymeric component. However, it should be understood here that the polymeric composition can comprise component (s) other than polymeric components, such as additive (s) which (s) can, optionally, be added ) in a mixture with a carrier polymer, that is, in the so-called master batch.
[000123] The polymeric composition of the advantageous reduced electrical conductivity insulation layer may comprise another component (s), preferably additive (s) conventionally used for W&C applications, such as crosslinking agent (s) , preferably in the presence of at least one peroxide and / or antioxidant (s). The amounts of additives used are conventional and well known to those skilled in the field, for example, as already described above under "Description of the invention".
[000124] The polymeric composition preferably comprises peroxide (s) and the optional antioxidant (s) and optionally burning retardant (s). Preferable examples of peroxide (s), optional antioxidant (s) and optional burning retardant (s) are listed above under "Description of the invention".
[000125] The polymeric composition preferably consists of the polyolefin which is preferably polyethylene, more preferably homo or LDPE copolymer which can, optionally, be unsaturated, of the invention as the only polymeric component. The most preferred polyolefin of the polymeric composition is an unsaturated LDPE homo or copolymer. Semiconductive composition of the semiconductive layer
[000126] Accordingly, the semiconductive composition used for the production of the semiconductive layer comprises carbon black and preferably a polyolefin (2).
[000127] The polyolefin (2) can be any polyolefin suitable for a semiconductive layer. Preferably, the polyolefin (2) is an olefin homopolymer or copolymer, which contains one or more comonomers, more preferably a polyethylene, which can be made in a low pressure process or a high pressure process.
[000128] When polyolefin (2), preferably polyethylene, is produced in a low pressure process, then it is typically produced using a coordination catalyst, preferably selected from a Ziegler Natta catalyst, a single site catalyst, which comprises a metallocene and non-metallocene catalyst and a Cr catalyst or any mixture thereof. Polyethylene produced at a low pressure can have any density, for example, a very low density linear polyethylene (VLDPE), a low density linear polyethylene (LLDPE) copolymer with one or more comonomers, medium density polyethylene (MDPE) or high density polyethylene (HDPE). Low pressure polyethylene can be unimodal or multimodal with respect to one or more of the molecular weight distribution, comonomer distribution or density distribution. When low pressure PE is multimodal with respect to molecular weight distribution, then it has at least two polymeric components which are different, preferably one of lower average gravimetric molecular weight (LMW) and one of gravimetric molecular weight major medium (HMW). A low pressure unimodal PE is typically prepared using a single stage polymerization, for example, solution, paste or gas phase polymerization, in a manner well known in the art. A low pressure multimodal PE (for example, bimodal) can be produced by mechanically mixing two or more separate polymer components or by in situ mixing in a multi-stage polymerization process during the process of preparing the polymer components . Mechanical and in situ mixing is well known in the field.
[000129] When polyolefin (2), preferably polyethylene, is produced in a high pressure process, then the preferred polyolefin is an LDPE homopolymer or an ethylene LDPE copolymer with one or more comonomers. In some embodiments, the LDPE homopolymer and copolymer may be unsaturated. Examples of suitable 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 being limited to any specific lubricant in the compressor (s) during the compression step (a ) of the process. For the production of ethylene (co) polymers through high pressure radical polymerization, reference can be made to the Encyclopedia of Polymer Science and Engineering, Vol. 6 (1986), pages 383-410 and Encyclopedia of Materials: Science and Technology , 2001 Elsevier Science Ltda .: "Polyethylene: High-pressure", R. Klimesch, D. Littmann and F.-O. Mahling, pages 7181-7184.
[000130] The semiconductive properties result from the carbon black added to the polyolefin (2). Thus, the amount of carbon black is at least such that a semiconductive 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.
[000131] Preferably, the polymeric composition comprises 10 to 50% by weight of carbon black, based on the weight of the semiconductive composition.
[000132] In other embodiments, the minimum amount of carbon black is 10% by weight, preferably 20% by weight, more preferably 25% by weight, based on the weight of the semiconductive composition. The maximum amount of carbon black is preferably 50% by weight, preferably 45% by weight, more preferably 41% by weight, based on the weight of the semiconductive composition.
[000133] Any carbon black which is electrically conductive can be used. Preferably, carbon black can have a nitrogen surface area (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. More preferably, 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 average numerical particle diameter according to ASTM D3849-95a, procedure D , ii) iodine Absorption Number (IAN) of at least 10 mg / 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) Absorption number of DBP (dibutyl phthalate) (= oil number) of at least 30 cm3 / 100 g, preferably 60 to 300 cm3 / 100 g, preferably 70 to 250 cm3 / 100 g, more preferably from 80 to 200, preferably from 90 to 180 cm3 / 100 g, when measured according to ASTM D 2414-06a.
[000134] More preferably, carbon black has one or more of the following properties: a) a primary particle size of at least 5 nm, which is defined as the numerical mean particle diameter according to ASTM D3849-95a , b) iodine number of at least 30 mg / g, according to ASTM D1510, c) oil absorption number of at least 30 ml / 100 g, which is measured according to ASTM D2414. Non-limiting examples of preferable carbon blacks include oven blacks and acetylene blacks.
[000135] A group of preferred oven blacks has a primary particle size of 28 nm or less. The primary mean particle size is defined as the numerical mean particle diameter, measured according to ASTM D3849-95a. Particularly suitable oven blacks in this category preferably have an iodine number between 60 and 300 mg / g, according to ASTM D1510. It is also preferred that the oil absorption number (of that category) is between 50 and 225 ml / 100g, preferably between 50 and 200 ml / 100 g and this is measured according to ASTM D2414.
[000136] Another group of equally preferred kiln blacks has a primary particle size of more than 28 nm. The primary mean particle size is defined as the numerical mean particle diameter, according to ASTM D3849-95a. Particularly suitable oven blacks in this category preferably have an iodine number between 30 and 200 mg / g, according to ASTM D1510. It is preferred that the oil absorption number (of this category) is between 80 and 300 ml / 100 g, measured according to ASTM D2414.
[000137] Other suitable carbon blacks can be made using any other process or can be additionally treated. Carbon blacks suitable for semiconductive cable layers are preferably characterized by their cleanliness. Therefore, preferred carbon blacks have an ash content of less than 0.2% by weight, measured according to ASTM D1506, a 325 mesh sieve residue of less than 30 ppm according to ASTM D1514 and have less of 1% by weight in total sulfur according to ASTM D1619.
[000138] Furnace carbon black is a commonly known term for a well-known type of carbon black that is produced in an oven-type reactor. As examples of carbon blacks, the process of preparing them and the reactors, reference can be made, inter alia, to Cabot EP629222, documents US 4,391,789, US 3,922,335 and US 3,401,020. As an example of commercial grades of oven carbon black described in ASTM D 1765-98b, inter alia, N351, N293 and N550 can be mentioned.
[000139] Oven carbon blacks are conventionally distinguished from acetylene carbon blacks, which are another preferable type of carbon black for the semiconductive composition. Acetylene carbon blacks are produced in an acetylene black process by reacting acetylene and unsaturated hydrocarbons, for example, as described in US 4,340,577. Particularly preferable acetylene blacks can have a particle size of more than 20 nm, more preferably 20 to 80 nm. The primary mean particle size is defined as the numerical mean particle diameter, according to ASTM D3849- 95a. Particularly preferred acetylene blacks of this category have an iodine number between 30 to 300 mg / g, more preferably 30 to 150 mg / g, according to ASTM D1510. It is further preferred that the oil absorption number (of that category) is between 80 to 300 ml / 100 g, more preferably 100 to 280 ml / 100 g and this is measured according to ASTM D2414. Acetylene black is a commonly known and very well-known term and, for example, provided by Denka.
[000140] The semiconductive composition may contain other component (s), such as conventional additive (s) in conventional amounts, as used in W&C applications. Typical examples of additives are described above under "Description of the invention".
[000141] Preferably, the semiconductive composition has a volumetric resistivity according to ISO3915, measured at 90 ° C, 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 in a reciprocal relationship with electrical conductivity, that is, the lower the resistivity, the greater the conductivity. Final Uses and Final Applications of the Invention
[000142] As mentioned above, the new Polymeric Composition of the Cable insulation layer is highly useful in a wide variety of W&C applications, more preferably in one or more layers of a power cable.
[000143] A power cable is defined as a power transfer cable that operates at any voltage, typically operating at voltages greater than 1 kV. The voltage applied to the power cable can be alternating (AC), direct (DC) or transient (impulse). The polymeric composition of the invention is very suitable for power cables, especially for power cables that operate at voltages greater than 6 kV to 36 kV (medium voltage cables (MV)) and at voltages greater than 36 kV, known as high voltage cables (HV) and extra high voltage cables (EHV), EHV cables which operate, as is well known, at very high voltages. The terms have well-known meanings and indicate the level of operation of such cables. For DC HV and EHV cables, the operating voltage is defined here as the electrical voltage between the ground and the high voltage cable conductor. DC HV power cable and DC EHV power cable can operate, for example, at voltages of 40 kV or greater, even at voltages of 50 kV or greater. DC EHV power cables operate in very high voltage ranges, for example, as high as 800 kV, however, without being limited to them.
[000144] The polymeric composition with advantageous DC conductivity properties is also highly suitable for direct current (DC) power cables that operate at any voltage, preferably over 36 kV, such as HV or EHV DC power cables, as defined above.
[000145] In addition to reduced electrical conductivity, the polymeric composition preferably also has very good spatial charge properties, which are advantageous for power cables, particularly for DC power cables.
[000146] The invention further provides for the use of the inventive polyolefin, which is obtainable through the high pressure process (HP) of the invention, for the production of an insulating layer of a power cable, preferably of a power cable. DC power.
[000147] According to a preferred embodiment, the Cable is a power cable, preferably a DC power cable, comprising at least one semiconductive layer as defined above comprising, preferably consisting of, a semiconductive composition containing a CB which it is preferably selected from an oven black or an acetylene black and an insulation layer comprising, preferably consisting of, a polymeric composition as defined above. More preferably, the Cable, preferably the power cable, more preferably the DC power cable, comprises said at least one semiconductive layer as defined above as an internal semiconductive layer and said insulation layer as defined above and additionally a layer external semiconductive, in that order, optionally surrounded by one or more other layer (s), such as canvas (s), shirt layer (s) or other protective layer (s), as well known in the field. In this embodiment, the outer semiconductive layer preferably comprises a semiconductive composition as defined above. The semiconductive composition of the outer semiconductive layer can be identical or different from the semiconductive composition of the inner semiconductive layer.
[000148] Preferably, at least the polymeric composition of the insulation layer is crosslinkable. More preferably, also at least the semiconductive composition of the semiconductive layer is crosslinkable.
[000149] The invention also provides a process for the production of a cable, preferably a crosslinkable power cable, more preferably a crosslinkable DC power cable, as defined above or in the claims, comprising the application steps, on a conductor, preferably by means of coextrusion, at least one semiconductive layer comprising the semiconductive composition and an insulation layer comprising the polymeric composition, in any order.
[000150] A production process for the cable of the invention is preferably carried out by: (a) providing a semiconductive composition of the invention as defined above or below in the claims and mixing, preferably mixing by melting in an extruder, of the semiconductive composition optionally together with other component (s), such as other polymeric component (s) and / or additive (s), (b) providing a polymeric composition of the invention as defined above or below in the claims and preferably mixing by melting in an extruder, the polymeric composition optionally together with other component (s), such as other polymeric component (s) and / or additive (s), (c) application on a conductor, preferably by means of co-extrusion, - a molten mixture of the semiconductive composition obtained from step (a) to form a semiconductive layer, preferably at least the internal semiconductive layer , - a molten mixture of the composition p olimeric obtained from step (b) to form the insulation layer; and (d) optionally, crosslinking at least one layer of the obtained cable.
[000151] A more preferable embodiment of the invention provides a process for producing the power cable of the invention, preferably a DC power cable, comprising a conductor surrounded by an internal semiconductive layer, an insulation layer and an external semiconductive layer, in that order, wherein the process comprises the steps of (a) providing a semiconductive composition of the invention as defined above or below in the claims and mixing by melting the semiconductive composition, preferably in the presence of selected additive (s) from at least one or more cross-linking agents and optionally one or more antioxidants, (b) providing a polymeric composition and mixing by melting the polymeric composition, preferably in the presence of selected additive (s) of at least one or more cross-linking agents and, preferably, one or more antioxidants, (c) application on a conductor, preferably by means of co-extrusion, - a deep mixture flow of the Semiconductive Composition obtained from step (a) to form at least the inner semiconductive layer and, preferably, the outer semiconductive layer, - a molten mixture of the Polymeric Composition obtained from step (b) to form the insulation layer e (d ) optionally, crosslinking of at least one layer of the cable obtained under crosslinking conditions.
[000152] Mixture by melting means mixing above the melting point of at least the main polymeric component (s) of the mixture obtained and is typically carried out at a temperature of at least 10-15 ° C above the melting or softening point of the polymeric component (s).
[000153] The term "(co) extrusion" here means that, in the case of two or more layers, said layers can be extruded in different steps or at least two or all of said layers can be co-extruded in the same step of extrusion, as is well known in the art. The term "(co) extrusion" here also means that all or part of the layer (s) is (are) formed simultaneously using one or more extrusion heads. For example, triple extrusion can be used to form cables with three layers.
[000154] Preferably, said part or all of the polymeric composition, preferably at least the polyolefin, is in the form of a powder, grain or pellets, when supplied to the production process of the Cable. Pellets can be of any size and shape and can be produced by any conventional pelletizing device, such as a pelletizing extruder.
[000155] As is well known, the semiconductive composition and / or the polymeric composition can be produced before or during the production process of the Cable. In addition, the semiconductive composition and the polymeric composition can each independently comprise part or all of their component (s) prior to introduction into the mixing (melting) steps a) and b) of the cable production.
[000156] According to one embodiment, the polymeric composition comprises said (s) other optional component (s). In this modality, part or all of the aforementioned other component (s) can, for example, be added: 1) by means of melt mixing with polyolefin, which may be in a form as obtained from a polymerization process and, then, the melt mixture obtained is pelletized and / or 2) by mixing the polyolefin pellets, pellets which may already contain part of the aforementioned (s) other component (s). In this option 2), part or all (s) of the other component (s) can be mixed with the pellets and then the melt obtained is pelleted ; and / or part or all other components can be impregnated in the solid pellets.
[000157] In a second alternative embodiment, the polymeric composition can be prepared together with the production line of the Cape, for example, by supplying the polyolefin, preferably in the form of pellets which can optionally comprise part of the (s) ) other component (s) and combined with all or the rest of the other component (s) in the mixing step b) to provide a mixture (melted) to process step c) 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.
[000158] The other component (s) is preferably selected from at least one or more additive (s), preferably at least from free radical generating agent (s), more preferably peroxide (s), optionally, preferably antioxidant (s) and optionally burning retardant (s), as mentioned above.
[000159] In the preferred embodiment, the polymeric composition of the invention is supplied to the production process of the cable in the form of prefabricated pellets.
[000160] Similarly, the semiconductive composition is preferably supplied to step a) in the form of pellets comprising at least the polyolefin (2), preferably also carbon black and optionally part or all (s) of the ) other component (s), if present. Said pellets can be produced as described above in the first alternative embodiment for preparing the polymeric composition. As an equally alternative modality, the semiconductive composition can be prepared during the production process of the Cable in the mixing step a) by supplying the polyolefin (2) and any or all of the carbon black and other component (s) ) optional (s) in the mixing step a) to provide a (melted) mixture for step c) of the process of the invention. In this embodiment, the semiconductive layer preferably comprises polyolefin (2), carbon black and said other component (s), whereby polyolefin (2) is supplied to step a ) in the form of pellets which additionally contain at least carbon black and optionally part of the other component (s). Then, the reaction or all (s) of the other component (s) is (are) added in step a) and mixed (fused) with said pellets. In the event that the polyolefin pellets (2) contain the carbon black and / or other component (s), then the pellets can be prepared as described in the first embodiment above for preparing the polymeric composition. The other optional component (s) of the semiconductive composition is (are) preferably selected at least from free radical generating agent (s), more preferably from peroxide (s) ) and optionally, preferably, antioxidant (s).
[000161] The mixing step (a) and / or (b) of the supplied Polymeric Composition and Semiconductive Composition is preferably carried out in the Cable extruder. Step a) and / or b) can optionally comprise a separate mixing step, for example, in a mixer, before the cable extruder. Mixing in the preceding separate mixer can be carried out by mixing with or without external heating (heating with an external source) of the component (s). Any other component (s) of the polymeric composition and / or semiconductive composition, if present and added during the production process of the Cable, can be added in any stage and any (any) point (s) in the Cable extruder or optional separate mixer that precedes the Cable extruder. The addition of the additive (s) can be done simultaneously or separately as, preferably, in liquid form or in a well-known master batch and at any stage during the mixing step (a) and / or (b) .
[000162] It is preferred that the mixture (melted) of the polymeric composition obtained from the mixture (melted) in step b) consists of the polyolefin of the invention as the only polymeric component. The optional and preferable additive (s) can be added to the Polymeric Composition as such or as a mixture with a carrier polymer, that is, in the form of the so-called master batch .
[000163] More preferably, the mixture of the semiconductive composition of the invention obtained from step (a) and the mixture of the polymeric composition of the invention obtained from step (b) is a molten mixture produced at least in an extruder.
[000164] In a preferred embodiment of the cable production process, a crosslinked cable as defined above is produced, in which at least the polymeric composition of the insulation layer is crosslinkable and is crosslinked in step d) under crosslinking conditions. In a more preferred embodiment, a cross-linked power cable, preferably a cross-linked DC power cable, is produced comprising a conductor surrounded by an internal semiconductive layer comprising, preferably consisting of the semiconductive composition, an insulation layer comprising, preferably consisting of the polymeric composition and optionally, preferably, an outer semiconductive layer comprising, preferably consisting, of the semiconductive composition, wherein (d) one or more of the polymeric composition of the insulation layer, the semiconductive composition of the inner semiconductive layer and the semiconductive composition of the outer semiconductive layer, of the obtained cable, preferably at least the polymeric composition of the insulation layer, more preferably the polymeric composition of the insulation layer and at least one, preferably both, of the semiconductive composition of the internal semiconductive layer and the semiconductive composition of layer s external emiconductive, is crosslinked under crosslinking conditions. The crosslinking step (d) is carried out in the presence of a crosslinking agent (s), preferably free radical generation agent (s), more preferably peroxide (s) and under crosslinking conditions.
[000165] The crosslinking conditions in step (d) of the production process of the cable preferably mean an elevated temperature. Cross-linking can be carried out at an increased temperature, which is chosen, as is well known, depending on the type of cross-linking agent. For example, temperatures above 150 ° C, such as from 160 to 350 ° C, are typical, however, without being limited to them.
[000166] The invention further provides a cross-linked cable, preferably a cross-linked power cable, more preferably a cross-linked DC power cable, as defined above, including preferred embodiments, produced through the cable production process comprising step a) , step b) and step c), as defined above.
[000167] The thickness of the insulation layer of the power cable, preferably the DC cable, more preferably the DC power cable HV or EHV DC is typically 2 mm or more, preferably at least 3 mm, preferably at least 5 to 100 mm, when measured from a cross section of the Cable insulation layer.
[000168] The invention further provides the use of the Cable of the invention for reducing DC conductivity in final applications of DC power cable, preferably in final applications of DC power cable HV or EHV. Determination Methods
[000169] Unless otherwise stated in the description or experimental part, the following methods have been used for property determinations. Wt%:% by weight Melt Flow Rate
[000170] The melt flow rate (Melt Flow Rate - MFR) is determined according to ISO 1133 and is indicated in g / 10 min. MFR is an indication of the fluidity and, consequently, the processability of the polymer. The higher the melt flow rate, the lower the viscosity of the polymer. The MFR is determined at 190 ° C for polyethylenes and can be determined in different loads, such as 2.16 kg (MFR2) or 21.6 kg (MFR21). Density
[000171] 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
[000172] Mz, Mw, Mn and MWD are measured by Gel Permeation Chromatography (GPC) for low molecular weight polymers, as known in the field. Comonomer contents a) Quantification of alpha-olefin content in linear low-density polyethylenes and low-density polyethylenes through NMR spectroscopy:
[000173] The comonomer content was determined using 13C quantitative nuclear magnetic resonance (NMR) spectroscopy after basic assignment (J. Randall JMS - Rev. Macromol. Chem. Phys., C29 (2 & 3), 201-317 (1989 )). Experimental parameters were adjusted to ensure measurement of the quantitative spectra for this specific task.
[000174] Specifically, solution-state NMR spectroscopy was employed using a Bruker AvanceIII 400 spectrometer. Homogeneous samples were prepared by dissolving approximately 0.200 g of polymer in 2.5 ml of deuterated tetrachloroethene in 10 mm sample tubes using a thermal block and oven with a rotating tube at 140 ° C. Single-pulse NMR spectra of 13C protons decoupled with NOE (energy activated) were recorded using the following acquisition parameters: a 90-degree tilt angle, 4-simulation scans, 4096 transients, an acquisition time of 1.6s , a spectral width of 20 kHz, a temperature of 125 ° C, a bi-level WALTZ proton decoupling scheme and a 3.0 s relaxation delay. The resulting FID was processed using the following process parameters: zero-filling for 32 k data points and apodization using a Gaussian window function; automatic zero and first magnitude phase correction and automatic baseline correction using a fifth magnitude polynomial restricted to the region of interest.
[000175] Quantities were calculated using simple corrected proportions of the sign integrals of representative locations based on methods well known in the art. b) Comonomer content of polar comonomers in low density polyethylene (1) Polymers containing> 6% by weight of polar comonomer units
[000176] The comonomer content (% by weight) was determined in a known manner, based on determination by Fourier Transform Infrared Spectroscopy (FTIR) calibrated with quantitative nuclear magnetic resonance spectroscopy (Nuclear Magnetic Resonance - NMR). The determination of the polar comonomer content of ethylene ethyl acrylate, ethylene butyl acrylate and ethylene methyl acrylate is exemplified below. Polymer film samples were prepared for FTIR measurement: thicknesses of 0.5-0.7 mm were used for ethylene butyl acrylate and ethylene ethyl acrylate and film thicknesses of 0.10 mm for ethylene methyl acrylate in one amount> 6% by weight. The films were compressed using a Specac film press at 150 ° C, approximately 5 tonnes, 1-2 minutes and then cooled with ice water in an uncontrolled manner. The precise thickness of the film samples obtained was measured.
[000177] After FTIR analysis, baselines in the absorbance mode were extracted 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 the polyethylene at 2020 cm-1). The calibration procedure by NMR spectroscopy was carried out in the conventional manner, which is well documented in the literature, explained below.
[000178] For the determination of the methyl acrylate content, a sample of 0.10 mm thick film was prepared. After the analysis, the maximum absorbance for the peak of methyl acrylate at 3455 cm-1 was subtracted from the absorbance value for the baseline at 2475 cm-1 (Ametii acriiato - A2475). Then, the maximum absorbance peak for the polyethylene peak at 2660 cm-1 was subtracted from the absorbance value for the base line at 2475 cm-1 (A2660 -A2475). The ratio between (Ametii acriiato- A2475) and (A2660-A2475) was then caicuizado in the conventional way, which is well documented in the literature.
[000179]% by weight can be converted into% grind by means of kaolin. This is well documented in the literature. Quantification of copolymer content in polymers by NMR spectroscopy
[000180] The comonomer content was determined by quantitative nuclear resonance spectroscopy (NMR) after basic assignment (eg, “NMR Spectra of Polymers and Polymer Additives”, AJ Brandolini and DD Hills, 2000, Marcel Dekker, Inc. New York). Experimental parameters were adjusted to ensure measurement of quantitative spectra for that 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 proportions corrected for the sign integrals of representative locations in a manner known in the art. (2) Polymers containing 6% by weight or less of polar comonomer units
[000181] The comonomer content (% by weight) was determined in a known way, based on determination by Fourier Transform Infrared Spectroscopy (FTIR) calibrated with quantitative nuclear magnetic resonance spectroscopy (Nuclear Magnetic Resonance - NMR). The determination of the polar comonomer content of ethylene butyl acrylate and ethylene methyl acrylate is exemplified below. For the measurement of FT-IV, film samples with thicknesses from 0.05 to 0.12 mm were prepared, as described above under method 1). The precise thickness of the film samples obtained was measured.
[000182] After FT-IV analysis, baselines in the absorbance mode were extracted for the peaks to be analyzed. The maximum absorbance for the peak for the comonomer (for example, for methyl acrylate at 1164 cm-1 and butyl acrylate at 1165 cm-1) was subtracted from the absorbance value for the baseline at 1850 cm-1 (Polar Acomonomer - A1850). Then, the maximum absorbance peak for polyethylene 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 (A2660-A1850) 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).
[000183] The% by weight can be converted to molar% by means of calculation. This is well documented in the literature. CC Conductivity Determination Methods
[000184] Conductivity method DC 1: Electrical conductivity measured at 70 ° C and an average electric field of 30 kV / mm from a sample of non-degassed or degassed 1 mm plate consisting of a cross-linked polymeric composition.
[000185] The plates are molded by compression from pellets of the polymeric test composition. The end plates have a thickness of 1 mm and a diameter of 330 mm.
[000186] The plates are molded by compression at 130 ° C for 12 min, while the pressure is gradually increased from 2 to 20 MPa. Thereafter, the temperature is increased and reaches 180 ° C after 5 min. The temperature is then kept constant at 180 ° C for 15 min, during which time the plate becomes fully cross-linked by means of the peroxide present in the polymeric test composition. Finally, the temperature is lowered using the cooling rate of 15 ° C / min, until the ambient temperature is reached, when the pressure is released. The plates are immediately, after releasing the pressure, wrapped in a metal sheet in order to prevent loss of volatile substances (using the determination without degassing).
[000187] If the plate has to be degassed, it is placed in a vacuum oven at a pressure of less than 10 Pa and degassed for 24 h at 70 ° C. After that, the plate is rewound in a metal sheet in order to prevent further exchange of volatile substances between the plate and the environment.
[000188] A high voltage source is connected to the upper electrode to apply voltage to the test sample. The resulting current through the sample is measured by an electrometer. The measuring cell is a system with three electrodes, with bronze electrodes. The bronze electrodes are equipped with heating pipes connected to a heating circulator, to facilitate measurements at elevated temperature and to ensure uniform temperature of the test sample. The diameter of the measuring electrode is 100 mm. Silicone rubber protectors are placed between the edges of the bronze electrode and the test sample to prevent electrical discharges from the round edges of the electrodes.
[000189] The applied voltage was 30 kV DC, meaning an average electric field of 30 kV / mm. The temperature was 70 ° C. The current across the plate was calculated throughout the experiment, lasting 24 hours. The current after 24 hours was used to calculate the conductivity of the insulation.
[000190] This method and a schematic representation of the measurement configuration for conductivity measurements are fully described in a publication presented at Nordic Insulation Symposium 2009 (Nord-IS 09), Gothenburg, Sweden, 15-17 June 2009, pages 55-58: Olsson et al., “Experimental determination of DC conductivity for XLPE insulation”.
[000191] Conductivity method DC 2: Electrical conductivity at 20 ° C and an average electric field of 40 kV / mm from a plate sample consisting of a cross-linked polymeric composition
[000192] Plate sample preparation:
[000193] Pellets of the test polymeric composition were molded by compression using the following conditions: first, the pellets were melted at 120 ° C for 1 min at 2 MPa (20 bar). Then, the temperature was increased to 180 ° C while the pressure was increased to 20 MPa (200 bar). The plates then became fully cross-linked by means of the peroxide present in the polymeric composition. The total cross-linking time was 12 min, including the time to increase the temperature, from 120 to 180 ° C. After complete cross-linking, the plates were cooled to room temperature, with a cooling rate of 15 ° C / min, still under pressure. After removing the press, the cooled plates were degassed in an oven at 70 ° C for 72 h at 1 atm. The final thickness of the plates was 0.5 mm.
[000194] Conduction current measurement:
[000195] Conduction current measurement is performed by a cell with three terminals, in nitrogen at a pressure of 0.3 MPa (3 bar) and temperature at 20oC. Specimens are tested with gold-coated electrodes obtained by cold spray deposition. The low voltage electrode has a diameter of 25 mm (the measurement area is therefore 490 mm2). A protective electrode is located around, but separate from, the low voltage electrode. The high voltage electrode has a diameter of 50 mm, the same dimension as the outer diameter of the protective electrode.
[000196] A DC voltage (U) equal to the target average electrical voltage (E) x measured insulation thickness (d) is applied over the high voltage electrode. The average target electrical voltage E is, in this case, 40 kV / mm. The current through the tape between the high voltage electrode and the low voltage electrode is measured with an electrometer. Measurements are terminated when the current reaches a steady state level, usually after 24-48 hours. The reported α conductivity is calculated from the current in constant state (I) using the equation: α = I * d / (A * U) where A is the measurement area, in this case 490 mm2.
[000197] DC conductivity method 3: Electrical conductivity of a 5.5 mm model cable sample of the test cross-linked polymeric composition as an insulation layer and the test cross-linked semiconductive composition as a semiconductive layer and measured at 70 ° C and an average electric field of 27 kV / mm.
[000198] Model cable preparation:
[000199] A three-layer cable core was produced using a 1 + 2 construction on a pilot scale CCV line. The conductor was made of aluminum and had an area of 50 mm2. The inner and outer semiconductive layers consisted of the same test semiconductive composition comprising a crosslinking agent which, in the experimental part below, was peroxide. The inner semiconductive layer was 1.0 mm thick, the insulation layer 5.5 mm thick and the outer semiconductive layer 0.8 mm thick. The line speed used to manufacture the cable cores was 2 m / min. This CCV line has two heating zones for dry curing (crosslinking under nitrogen), each of 3 m and the temperatures used over these two zones were 450 and 400 ° C, respectively. The cooling section was 12.8 m long and the cable was cooled with water, maintaining a temperature around 25-30 ° C. Immediately after production, the cable core was tightly wrapped with aluminum foil (0.15 mm thick) to keep the peroxide by-products inside the cable core.
[000200] Cable samples were stored at room temperature for eight weeks, until they were heat treated in an oven for 72 hours at 70 ° C. The cable cores were covered with Al foil at all times, also during heat treatment and during electrical measurements.
[000201] Conduction current measurement:
[000202] The measurements were then made in an oven at 70 ° C using a cell with three terminals, where a voltage of 150 kV DC was applied over the conductor and the aluminum foil was connected to the low electrode voltage. This corresponds to an average electric field of 27 kV / mm (the ratio of the applied voltage to the insulation thickness). The test circuit consisted of a high voltage generator, a voltage divider isolated from the air, the test cable and its terminals and a current meter and its amplifier. Also, protection devices are included in case of failures in the test circuit. The current meter is connected to the Cable's external screen at each end of the cable and grounded. Protection electrodes were used in order to avoid leakage currents on the terminals so as not to alter the measurements. The distance between the electrodes of the cable (the measurement zone) was 53 m and this section of the cable was placed inside the oven, so the ends of the cable were located outside the oven.
[000203] The electrical conductivity is calculated from the conduction current (leakage current) after applying voltage for 24 hours using equations 1 and 2.
[000204] The conductivity α (S / m) was calculated using the formula:
Equation 1 R = U / I = Applied voltage (V) / leakage current (A) Equation 2 L: Extension of the measuring zone (53 m) U: Applied voltage (150 kV) D ed: Insulation external and internal diameters
[000205] DC conductivity method 4: Electrical conductivity of a 1.5 mm model cable sample of the test cross-linked polymeric composition as an insulation layer and the test cross-linked semiconductive composition as a semiconductive layer and measured at 20 ° C and an average electric field of 40 kV / mm
[000206] Model cable preparation:
[000207] Three-core cable cores were produced using a 1 + 2 construction on a pilot scale CCV line. The conductor was made of copper and had an area of 1.5 mm2. The inner and outer semiconductive layers consisted of the same test semiconductive composition comprising a crosslinking agent which, in the experimental part below, was peroxide. The inner semiconductive layer was 0.7 mm thick, the insulation layer 1.5 mm thick and the outer semiconductive layer 0.15 mm thick. The Cabo cores were produced in two stages. In step 1, the cable cores were extruded using a line speed of 8 m / min without passing through a vulcanization tube. In step 2, the cable cores were passed only through the vulcanization tube with a line speed of 5 m / min. The tube has two heating zones for dry curing (crosslinking under nitrogen), each of 3 m and the temperatures used in these two zones were 400 and 380 ° C, respectively. This resulted in fully cross-linked cables due to the peroxide in the insulating and semiconductive materials. The cooling section was 12.8 m long and the cable was cooled with water, maintaining a temperature around 25-30 ° C.
[000208] The cables were degassed at 80 ° C in a ventilated oven at atmospheric pressure for eight days. The cables were then cut into samples of 1 meter in length, with an active length of 10 cm (measurement zone) in the middle, where the outer semiconductive layer is present. The outer semiconductive layer in the final 45 cm of the sample was removed by a peeling tool.
[000209] The schematic view of the model cables with three layers with an insulation thickness of 1.5 mm used in method 4 is illustrated in figure 1.
[000210] Conduction current measurements:
[000211] Conduction current measurements are performed by a cell with three terminals, where the conductor acts as the high voltage electrode. The low voltage electrode is an aluminum foil that covers the external semicon on the active part. Protective electrodes are introduced by the aluminum foil covering the insulation on both sides of the measurement zone. The spans between the low voltage electrode and the protective electrodes are 5 cm.
[000212] The applied voltage is 60 kV DC and the temperature 20 ° C. Measurements are terminated when the current has reached a steady state level, usually after 24 hours. Constant current (leakage current) is used in the calculations.
[000213] Conductivity (S / m) was calculated using the formula:
and R = U / I = Applied voltage (V) / leakage current (A) Table. Data used to calculate the conductivity of model cable specimens Parameter Value

[000214] Conductivity method DC 5: Electrical conductivity of a 1.5 mm model cable sample of the test cross-linked polymeric composition as an insulation layer and the test cross-linked semiconductive composition as a semiconductive layer and measured at 70 ° C and an average electric field of 30 kV / mm
[000215] Model cable preparation:
[000216] Three-core cable cores were produced using a 1 + 2 construction on a pilot scale CCV line. The conductor was made of copper and had an area of 1.5 mm2. The inner and outer semiconductive layers consisted of the same test semiconductive composition comprising a crosslinking agent which, in the experimental part below, was peroxide. The inner semiconductive layer was 0.7 mm thick, the insulation layer 1.5 mm thick and the outer semiconductive layer 0.15 mm thick. The Cabo cores were produced in two stages. In step 1, the cable cores were extruded using a line speed of 8 m / min without passing through a vulcanization tube. In step 2, the cable cores were passed only through the vulcanization tube with a line speed of 5 m / min. The tube has two heating zones for dry curing (crosslinking under nitrogen), each of 3 m and the temperatures used in these two zones were 400 and 380 ° C, respectively. This resulted in fully cross-linked cables due to the peroxide in the insulating and semiconductive materials. The cooling section was 12.8 m long and the cable was cooled with water, maintaining a temperature around 25-30 ° C.
[000217] The cables were not degassed before conducting current measurements. To prevent unwanted degassing from occurring, the cables were covered with aluminum foil until measurement was conducted. The cables were then cut into samples of 3 meters in length, with an active length of 100 cm (measurement zone) in the middle, where the outer semiconductive layer is present. The outer semiconductive layer in the final 100 cm of the sample was removed by a peeling tool. The schematic view of the three-layer model cables with an insulation thickness of 1.5 mm used in method 5 is illustrated in figure 1.
[000218] Conduction current measurements:
[000219] Conduction current measurements are performed by a cell with three terminals, where the conductor acts as the high voltage electrode. The low voltage electrode is an aluminum foil that covers the external semicon on the active part. Protective electrodes are introduced by the aluminum foil covering the insulation on both sides of the measurement zone. The spans between the low voltage electrode and the protective electrodes are 5 cm.
[000220] The applied voltage is 45 kV DC (average electric field of 30 kV / mm) and the temperature is 70 ° C. The measurements are finished after 24 h and the conductivity is measured as the average between 23-24 h. Constant current (leakage current) is used in the calculations.
[000221] The conductivity s (S / m) was calculated using the formula:
and R = U / I = Applied voltage (V) / leakage current (A) Table. Data used to calculate the conductivity of cable specimens Model. Parameter Value

[000222] Conductivity method DC 6: Electrical conductivity measured at 70 ° C and an average electric field of 30 kV / mm from a sample of non-degassed or degassed 1 mm plate consisting of a cross-linked polymeric composition.
[000223] The plates are molded by compression from pellets of the polymeric test composition. The end plates have a thickness of 1 ± 10% mm and 195 x 195 mm2. The thickness is measured at 5 different locations on the plates.
[000224] The plates are compression molded at 130 ° C for 600 s at 2 MPa (20 Bar). Thereafter, the temperature is increased and reaches 180 ° C after 170 s and the pressure is then increased to 20 MPa (200 Bar). The temperature is then kept constant at 180 ° C for 1000 s, during which time the plate becomes fully cross-linked by means of the peroxide present in the polymeric test composition. Finally, the temperature is lowered using the cooling rate of 15 ° C / min, until the ambient temperature is reached, when the pressure is released. The thickness of the plate is determined immediately after compression molding and, after that, placed in the test cell described below for conductivity measurement.
[000225] A high voltage source is connected to the upper electrode to apply voltage to the test sample. The resulting current through the sample is measured with an electrometer. The measuring cell is a system with three electrodes with bronze electrodes. The cell is installed in a heating oven to facilitate measurements at elevated temperature and to provide a uniform temperature of the test sample. The diameter of the measuring electrode is 100 mm. Silicone rubber protectors are placed between the edges of the bronze electrode and the test sample to prevent electrical discharges from the round edges of the electrodes.
[000226] The applied HVDC voltage was regulated according to the measured thickness of the plate to reach an average electric field of 30 kV / mm. The temperature was 70 ° C. The current across the plate was calculated for all experiments, lasting 24 hours. The current after 24 hours was used to calculate the conductivity of the insulation. Method for determining the amount of double bonds in the polymeric composition or in the polymer A) Quantification of the amount of carbon-carbon double bonds through IR spectroscopy
[000227] Quantitative infrared (IV) spectroscopy was used to quantify the amount of carbon-carbon double bonds (C = C). Calibration was obtained before determining the molar extinction coefficient of the functional groups C = C in representative low molecular weight model compounds of known structure.
[000228] 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) where A is the maximum absorbance defined as peak height, E the molar extinction coefficient of the group in question (l-mol ^ -mm'1), L the film thickness (mm) and D the density of the material (gW).
[000229] The total amount of C = C bonds per thousand carbon atoms in total can be calculated by adding N for the components containing individual C = C.
[000230] For polyethylene samples, infrared spectra in solid state were recorded using an FTIR spectrometer (Perkin Elmer 2000) on thin compression-molded films (0.51.0 mm) 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
[000231] For polyethylenes, three types of functional groups containing C = C were quantified, each with a characteristic absorption and each balanced for a different model compound, resulting in individual extinction coefficients: • vinyl (R-CH = CH2) via 910 cm-1 based on 1-decene [dec-1-ene], providing E = 13.13 l-moN-mm'1 • vinylidene (RR'C = CH2) via 888 cm-1 based on 2-methyl -1- heptene [2-metihept-1-ene], providing E = 18.24 l • mol "1 • mm" 1 • trans-vinylene (R-CH = CH-R ') via 965 cm-1 based on trans-4-decene [(E) -dec-4-ene], providing E = 15.14 l • mol "1 • mm" 1 For polyethylene homopolymers or copolymers with <0.4% by weight of polar comonomer, linear 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
[000232] For polyethylene copolymers with> 0.4% by weight of polar comonomer, two types of functional groups containing C = C were quantified, each with a characteristic absorption and each balanced for a different model compound, resulting in coefficients individual extinguishing media: • vinyl (R-CH = CH2) via 910 cm-1 based on 1-decene [dec-1-ene], providing E = 13.13 l • mol "1 • mm" 1 • vinylidene (RR 'C = CH2) via 888 cm-1 based on 2-methyl-1-heptene [2-metihept-1-ene], providing E = 18.24 l • mol "1 • mm" 1 EBA:
[000233] For (poly) ethylene-butyl coacrylate (EBA) systems, linear baseline correction was applied between approximately 920 and 870 cm-1. EMA:
[000234] For (poly) ethylene-coacrylate methyl (EMA) systems, linear baseline correction was applied between approximately 930 and 870 cm-1. 3) Polymeric compositions comprising low molecular weight unsaturated molecules
[000235] For systems containing species containing low molecular weight C = C, direct calibration using the molar extinction coefficient of the absorption of C = C in the low molecular weight species itself was performed. B) Quantification of molar extinction coefficients through IR spectroscopy
[000236] The molar extinction coefficients were determined according to the procedure provided in ASTM D3124-98 and ASTM D6248-98. Infrared spectra of the state in solution were recorded using an FTIR spectrophotometer (Perkin Elmer 2000) equipped with a liquid cell with 0.1 mm path length at a resolution of 4 cm-1.
[000237] The molar extinction coefficient (E) was determined as l-mol ^ -mm'1 via: E = A / (C x L) where A is the maximum absorbance defined as peak height, C the concentration (mold -1) and L the cell thickness (mm).
[000238] At least three solutions at 0.18 molT1 in carbon disulfide (CS2) were used and the mean value of the molar extinction coefficient determined. Experimental part Preparation of polyolefins from the examples of polymeric compositions of the insulation layer of the present invention and from the reference examples
[000239] Polyolefins were low density polyethylene produced in a high pressure reactor. The production of polymers of the invention and reference is described below. As CTA feeds, for example, the PA content can be supplied as liters / hour or kg / h and converted to units using a PA density of 0.807 kg / liter for recalculation. Example of invention 1:
[000240] 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 approximately 257.6 MPa (2576 bar). The total productivity of the compressor was approximately 30 tons / hour. In the compressor area, approximately 4.9 liters / hour of propionaldehyde (PA, CAS number: 123-38-6) was added, along with approximately 119 kg propylene / hour as a chain transfer agent to maintain an MFR of 2, 1 g / 10 min. The compressed mixture was heated to 166 ° C in a preheating section of a tubular reactor with three frontal feed zones with an internal diameter of approximately 40 mm and a total length of 1200 meters. A 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 approximately 276 ° C, after which it was cooled to approximately 221 ° C. The subsequent 2nd and 3rd peak reaction temperatures were 271 ° C and 261 ° C, respectively, with cooling to 225 ° C. The reaction mixture was depressurized by a displacement valve, cooled and the polymer was separated from the unreacted gas. Example of invention 2:
[000241] 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 approximately 252.3 MPa (2523 bar). The total productivity of the compressor was approximately 30 tons / hour. In the compressor area, approximately 4.5 liters / hour of propionaldehyde was added, along with approximately 118 kg propylene / hour as a chain transfer agent to maintain a 2.0 g / 10 min MFR. Here, too, 1,7-octadiene was added to the reactor in an amount of 23 kg / h. The compressed mixture was heated to 160 ° C in a preheating section of a tubular reactor with three frontal feed zones with an internal diameter of approximately 40 mm and a total length of 1200 meters. A mixture of commercially available peroxide radical initiators dissolved in isododecane was injected exactly after the preheater in an amount sufficient for the exothermic polymerization reaction to reach peak temperatures of approximately 272 ° C, after which it was cooled to approximately 205 ° C. The subsequent 2nd and 3rd peak reaction temperatures were 270 ° C and 253 ° C, respectively, with cooling to 218 ° C. The reaction mixture was depressurized by a displacement valve, cooled and the polymer was separated from the unreacted gas. Example of invention 3:
[000242] 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 approximately 259.2 MPa (2592 bar). The total productivity of the compressor was approximately 30 tons / hour. In the compressor area, approximately 4.9 liters / hour of propionaldehyde was added, along with approximately 77 kg propylene / hour as a chain transfer agent to maintain an MFR of 1.9 g / 10 min. The compressed mixture was heated to 163 ° C in a preheating section of a tubular reactor with three frontal feed zones with an internal diameter of approximately 40 mm and a total length of 1200 meters. A 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 approximately 281 ° C, after which it was cooled to approximately 208 ° C. The subsequent 2nd and 3rd peak reaction temperatures were 282 ° C and 262 ° C, respectively, with a cooling to 217 ° C. The reaction mixture was depressurized by a displacement valve, cooled and the polymer was separated from the unreacted gas. Example of invention 4:
[000243] 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 approximately 277.1 MPa (2771 bar). The total productivity of the compressor was approximately 30 tons / hour. In the compressor area, approximately 5.3 liters / hour of propionaldehyde was added, along with approximately 86 kg propylene / hour as a chain transfer agent to maintain an MFR of 0.7 g / 10 min. The compressed mixture was heated to 171 ° C in a preheating section of a tubular reactor with three frontal feed zones with an internal diameter of approximately 40 mm and a total length of 1200 meters. A 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 approximately 281 ° C, after which it was cooled to approximately 203 ° C. The subsequent 2nd and 3rd peak reaction temperatures were 273 ° C and 265 ° C, respectively, with cooling to 226 ° C. The reaction mixture was depressurized by a displacement valve, cooled and the polymer was separated from the unreacted gas. Reference example 1:
[000244] Purified ethylene was liquefied through compression and cooling to a pressure of 9 MPa (90 bar) and a temperature of -30 ° C and divided into up to two equal currents of approximately 14 tons / 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 24 kg / h. The two mixtures were separately pumped through a series of 4 intensifiers to reach pressures of 220-230 MPa (2200-2300 bar) and outlet temperatures around 40 ° C. These two currents were, respectively, fed at the front (zone 1) (50%) and side (zone 2) (50%) of a tubular reactor with two divided feed zones. The internal diameters and lengths of the two zones in the reactor were 32 mm and 200 m for zone 1 and 38 mm and 400 m for zone 2. MEK was added in quantities of 205 kg / h to the front chain to maintain an MFR2 around 2 g / 10 min. The front feed stream was passed through a heating section to reach a temperature sufficient for the exothermic polymerization reaction to begin. The reaction reached peak temperatures of 253 ° C and 290 ° C in the first and second zones, respectively. The side feed stream cooled the reaction down to the initial temperature in the second zone of 168 ° C. Air and peroxide solution were added to the two streams in sufficient quantities to reach the target peak temperatures. The reaction mixture was depressurized through the product valve, cooled and the polymer was separated from the unreacted gas. Reference example 2:
[000245] Purified ethylene was liquefied through compression and cooling to a pressure of 9 MPa (90 bar) and a temperature of -30 ° C and divided into up to two equal currents of approximately 14 tons / 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 separately pumped through a series of 4 intensifiers to achieve pressures of 210-230 MPa (2100-2300 bar) and outlet temperatures around 40 ° C. These two currents were, respectively, fed at the front (zone 1) (50%) and side (zone 2) (50%) of a tubular reactor with two divided feed zones. The internal diameters and lengths of the two zones in the reactor were 32 mm and 200 m for zone 1 and 38 mm and 400 m for zone 2. MEK was added in quantities around 216 kg / h to the front chain to maintain an MFR2 around 2 g / 10 min. The front feed stream was passed through a heating section to reach a temperature sufficient for the exothermic polymerization reaction to begin. The reaction reached peak temperatures around 250 ° C and 318 ° C in the first and second zones, respectively. The side feed stream cooled the reaction to the initial temperature of the second zone of 165-170 ° C. Air and peroxide solution were added to the two streams in sufficient quantities to reach the target peak temperatures. The reaction mixture was depressurized through the product valve, cooled and the polymer was separated from the unreacted gas. Reference example 3:
[000246] Purified ethylene was liquefied through compression and cooling to a pressure of 9 MPa (90 bar) and a temperature of -30 ° C and divided into up to two equal currents of approximately 14 tons / 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 separately pumped through a series of 4 intensifiers to achieve pressures of 210-230 MPa (2100-2300 bar) and outlet temperatures around 40 ° C. These two currents were, respectively, fed at the front (zone 1) (50%) and side (zone 2) (50%) of a tubular reactor with two divided feed zones. The internal diameters and lengths of the two zones in the reactor were 32 mm and 200 m for zone 1 and 38 mm and 400 m for zone 2. MEK was added in quantities around 201 kg / h to the front chain to maintain an MFR2 around 0.75 g / 10 min. The front feed stream was passed through a heating section to reach a temperature sufficient for the exothermic polymerization reaction to begin. The reaction reached peak temperatures around 251 ° C and 316 ° C in the first and second zones, respectively. The side feed stream cooled the reaction down to the initial temperature of the second zone to around 185190 ° C. Air and peroxide solution were added to the two streams in sufficient quantities to reach the target peak temperatures. The reaction mixture was depressurized through the product valve, cooled and the polymer was separated from the unreacted gas.
[000247] Semiconductive compositions for semiconductive layers of model cable samples
[000248] Semicon 1: LE0500, commercial grade from Borealis with acetylene carbon black, density of 1120 kg / cm3, volumetric DC resistivity at 23 ° C of less than 100 Qcm and at 90 ° C of less than 1000 Qcm (ISO3915 ), Hot Curing Test (200 ° C, 0.20 MPa, IEC 60811-2-1): Elongation under load 25%, Permanent Deformation 0%.
[000249] Semicon 2: LE0550, commercial grade from Borealis with acetylene carbon black, density of 1100 kg / cm3, DC volumetric resistivity at 23 ° C of less than 100 Qcm and at 90 ° C of less than 1000 Qcm (ISO3915 ), Hot Curing Test (200 ° C, 0.20 MPa, IEC 60811-2-1): Elongation under load 25%, Permanent Deformation: 0%. Göttfert elastographer: 1.2 Nm.
[000250] Semicon 3: LE0592, commercial grade from Borealis with oven carbon black, density of 1135 kg / cm3, DC volumetric resistivity at 23 ° C of less than 100 Qcm and at 90 ° C of less than 1000 Qcm (ISO3915 ). Hot Curing Test (200 ° C, 0.20 MPa, IEC 60811-2-1): Elongation under load 25%, Permanent Deformation: 0%. Göttfert elastographer: 1.14 - 1.38 Nm. Experimental Results: Mineral oil = Examples of the invention 1-3: lubricant based on mineral oil, Shell Corena E150, supplier Shell; Example of invention 4: lubricant based on mineral oil, M- RARUS PE KPL 201, supplier ExxonMobil PAG = References: lubricant based on polyalkylene glycol, Syntheso D201N, supplier Klueber. MEK = methyl ethyl ketone PA = propionaldehyde (CAS number: 123-38-6) Table 1. Summary and components of the polymeric compositions of the insulation layer
AO: 4,4'-thiobis (2-tert-butyl-5-methylphenol) (CAS No. 96-69-5) Peroxide: Dicumyl peroxide (CAS No. 80-43-3) ADD (Additive): 2 , 4-Diphenyl-4-methyl-1-pentene (CAS 6362-80-7) Table 2. Properties of the polyolefin components of the polymeric composition
Table 3. Conductivity (fS / m) of reticulated plates molded by compression of 1 mm Polymeric composition of the insulation measured at 70 ° C and an average electric field of 30 kV / mm (Conductivity method DC 1)
Table 4. Conductivity of compression-molded plates of 0.5 mm of cross-linked polymeric insulation composition measured at 20 ° C and 40 kV / mm. (Conductivity method CC 2)
Table 5. Cable compositions and test results for the 5.5 mm model cables measured at 70 ° C and an average electric field of 27 kV / mm. (Conductivity method CC 3)
Table 6. Cable compositions and test results for 1.5 mm model cables measured at 20 ° C and an average electric field of 40 kV / mm. (Conductivity method DC 4)
Table 7. Cable compositions and test results for 1.5 mm model cables measured at 70 ° C and one
Table 8. Conductivity (fS / m) of cross-linked plates molded by 1 mm compression

权利要求:
Claims (18)
[0001]
1. A power cable comprising a conductor surrounded by at least one semiconductive layer and an insulation layer, in any order, in which: the semiconductive layer comprises a semiconductive composition comprising carbon black; and the insulation layer comprises a polymeric composition comprising a low density polyethylene (LDPE) ethylene copolymer with one or more non-polar comonomer (s) selected from a mixture of C3 to C10 alpha-olefin (s), comonomer (s) ) polyunsaturated (s), comonomer (s) containing silane group, or any mixtures thereof, in which the LDPE ethylene copolymer can be unsaturated ;, characterized by the fact that: (i) the polymeric composition of the insulation layer has an electrical conductivity of 150 fS / m or less when measured at 70 ° C and an average electric field of 30 kV / mm from a sample of non-degassed plate with a thickness of 1 mm consisting of a cross-linked polymeric composition as CC conductivity method (1) as described under “Determination Methods”; and wherein the LPDE of the polymeric composition of the insulation layer is produced in a high pressure process comprising: (a) compression of one or more monomers under pressure in a compressor, in which a compressor lubricant is used for lubrication, (b ) polymerization of a monomer, (c) separating the LPDE obtained from unreacted products and recovering the separated polyolefin in a recovery zone, in which, in step a), the compressor lubricant comprises a mineral oil, and the polymeric composition comprises up to 0.4% by weight of mineral oil, based on the amount of LPDE.
[0002]
2. Cable according to claim 1, characterized by the fact that the polymeric composition of the insulation layer has (i) an electrical conductivity of 140 fS / m or less, when measured at 70 ° C and an average electric field of 30 kV / mm from a sample of non-degassed plate with a thickness of 1 mm consisting of a cross-linked polymeric composition according to the CC conductivity method (1) as described under “Determination Methods”.
[0003]
Cable according to claim 1 or 2, characterized by the fact that at least the polymeric composition of the insulation layer is crosslinkable and contains a crosslinking agent.
[0004]
Cable according to any one of the preceding claims, characterized in that the polymeric composition of the insulation layer is cross-linked in the presence of a cross-linking agent.
[0005]
Cable according to any one of the preceding claims, characterized in that the polymeric composition of the insulation layer contains other additive (s) comprising at least one of: one or more antioxidants, and one or more retardants of burning or any mixtures thereof.
[0006]
6. Cable according to any of the preceding claims, characterized by the fact that the antioxidant (s) is (are) selected from sterically hindered or semi-hindered phenols, aromatic amines, sterically hindered aliphatic amines, organic phosphites or phosphonites, thio compounds and mixtures thereof; and where: the optional burning retardant (s) is (are) selected from allyl compounds, such as aromatic alpha-methyl alkenyl monomers dimers, substituted or unsubstituted diphenylethylenes, derivatives quinone, hydroquinone derivatives, monofunctional vinyl-containing esters and ethers, monocyclic hydrocarbons having at least two or more double bonds or mixtures thereof.
[0007]
Cable according to any one of the preceding claims, characterized in that the carbon black of the semiconductive layer is selected from a conductive carbon black.
[0008]
Cable according to any one of the preceding claims, characterized in that the carbon black of the semiconductive layer is selected from a conductive carbon black containing at least one of the following properties: i) a primary particle size of at least minus 5 nm, which is defined as the numerical mean particle diameter according to ASTM D3849-95a, procedure D, ii) iodine absorption number (IAN) of at least 10 mg / g, when determined in accordance with ASTM D-1510-07; iii) absorption number of DBP (dibutyl phthalate) (= oil number) of at least 30 cm3 / 100 g, when measured according to ASTM D 2414-06a.
[0009]
9. Cable according to any of the preceding claims, characterized by the fact that mineral oil is a white mineral oil which meets the requirements provided for white mineral oil in European Directive 2002/72 / EC of 6 August 2002, Annex V, for plastics used in contact with food.
[0010]
Cable according to any one of the preceding claims, characterized in that the low density polyethylene (LDPE) is selected from an LDPE homopolymer or LDPE ethylene copolymer with one or more comonomers, LDPE homopolymer or LDPE ethylene copolymer o which can be unsaturated.
[0011]
11. Cable according to any one of the preceding claims, characterized in that the unsaturated low density polyethylene (LDPE) is selected from an unsaturated LDPE homopolymer or an ethylene unsaturated LDPE copolymer with one or more comonomers.
[0012]
Cable according to any one of the preceding claims, characterized in that it is a power cable, comprising another semiconductive layer which comprises a semiconductive composition with carbon black, that is, a cable comprising a conductor surrounded by at least minus an internal semiconductive layer, an insulation layer and an external semiconductive layer, in that order.
[0013]
13. Process for the production of a power cable, as defined in any one of claims 1 to 12, characterized by the fact that it comprises the steps of application, on a conductor, of at least one semiconductive layer comprising said semiconductive composition and an insulation layer comprising said polymeric composition, in any order.
[0014]
Process according to claim 13, for the production of a power cable as defined in any one of claims 1 to 12, characterized in that it comprises the steps of: (a) supplying said semiconductive composition and mixture, (b) providing said polymeric composition of the invention and mixing, (c) applying to a conductor: a molten mixture of the semiconductive composition obtained from step (a) to form a semiconductive layer, and a molten mixture of the polymeric composition obtained from step (b) to form the insulation layer.
[0015]
Process according to claim 14, characterized in that it also comprises the crosslinking of at least one layer of the obtained cable.
[0016]
Process according to any one of claims 13 to 15, for the production of a power cable comprising a conductor surrounded by an internal semiconductive layer, an insulation layer and an external semiconductive layer, in that order, in which the process comprises the steps of: (a) providing said semiconductive composition and mixing by melting the semiconductive composition, (b) providing said polymer composition and mixing by melting the polymeric composition,, (c) application on a conductor, by means of coextrusion, from: a molten mixture of the Semiconductive Composition obtained from step (a) to form at least the internal semiconductive layer, a molten mixture of the Polymeric Composition obtained from step (b) to form the insulation layer.
[0017]
17. Process according to claim 16, characterized by the fact that it also comprises the crosslinking of at least one layer of the cable obtained under crosslinking conditions.
[0018]
18. Process according to any one of claims 13 to 17, characterized in that the process comprises the step of (d) crosslinking at least the insulating layer.

类似技术:

---

公开号 | 公开日 | 专利标题

---

BR112012011265B1|2020-12-01|cable and its production process

---

US10950366B2|2021-03-16|Polymer composition and a power cable comprising the polymer composition

---

ES2534468T3|2015-04-23|A polymer composition and an electric cable comprising the polymer composition

---

BR112012011131B1|2021-03-30|DIRECT CURRENT | RETICULATED POWER CABLE AND PROCESS FOR THE SAME PRODUCTION

---

EP3569648B1|2020-09-30|Power cable

---

EP3083797B1|2019-06-26|A new low mfr polymer composition, power cable insulation and power cable

---

EP3183278B1|2020-08-12|A new crosslinked polymer composition, structured layer and cable

同族专利:

---

公开号 | 公开日

---

AU2010318178B2|2013-10-24|

---

EP3190152B1|2019-10-09|

---

EG27174A|2015-08-31|

---

EP3190152A1|2017-07-12|

---

AU2010318178A1|2012-05-17|

---

CN102597093A|2012-07-18|

---

EA201290299A1|2012-12-28|

---

JP5739442B2|2015-06-24|

---

EA021355B1|2015-05-29|

---

KR101805215B1|2017-12-05|

---

MX2012005197A|2012-06-19|

---

BR112012011265A2|2016-04-12|

---

US20120273253A1|2012-11-01|

---

IN2012DN03436A|2015-10-23|

---

US9365708B2|2016-06-14|

---

KR20120104229A|2012-09-20|

---

WO2011057925A1|2011-05-19|

---

EP2499197B1|2017-03-01|

---

EP2499197A1|2012-09-19|

---

MX346513B|2017-03-23|

---

CN102597093B|2015-01-07|

---

ES2758129T3|2020-05-04|

---

JP2013511119A|2013-03-28|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

US3098893A|1961-03-30|1963-07-23|Gen Electric|Low electrical resistance composition and cable made therefrom|

---

US3401020A|1964-11-25|1968-09-10|Phillips Petroleum Co|Process and apparatus for the production of carbon black|

---

DE1769723A1|1968-07-03|1972-02-10|Ver Draht & Kabelwerke Ag|Process to improve the flexibility of crosslinked polyolefins|

---

US3717720A|1971-03-22|1973-02-20|Norfin|Electrical transmission cable system|

---

US3922335A|1974-02-25|1975-11-25|Cabot Corp|Process for producing carbon black|

---

DE2420784C3|1974-04-29|1979-02-15|Siemens Ag, 1000 Berlin Und 8000 Muenchen|Process for the production of molded articles made of polyolefins which are crosslinked by high-energy radiation|

---

JPS5938993B2|1980-03-11|1984-09-20|Denki Kagaku Kogyo Kk|

---

US4391789A|1982-04-15|1983-07-05|Columbian Chemicals Company|Carbon black process|

---

GB8333845D0|1983-12-20|1984-02-01|British Ropes Ltd|Flexible tension members|

---

JPS60133042A|1983-12-20|1985-07-16|Nippon Petrochem Co Ltd|Resin composition for electrically insulating use|

---

JPH0326688B2|1984-11-27|1991-04-11|Sumitomo Chemical Co|

---

JPH0218811A|1988-07-05|1990-01-23|Fujikura Ltd|Dc power cable|

---

JPH02272031A|1989-04-13|1990-11-06|Hitachi Cable Ltd|Produciton of polyolefin crosslinked molded article|

---

JPH0439815A|1990-06-04|1992-02-10|Nippon Petrochem Co Ltd|Ethylene polymer or ethylene polymer composition excellent in insulating characteristic and power cable using the same|

---

FI86867C|1990-12-28|1992-10-26|Neste Oy|FLERSTEGSPROCESS FOR FRAMSTAELLNING AV POLYETEN|

---

JP2538724B2|1991-06-14|1996-10-02|日立電線株式会社|Filler for DC power cable insulation|

---

US5246783A|1991-08-15|1993-09-21|Exxon Chemical Patents Inc.|Electrical devices comprising polymeric insulating or semiconducting members|

---

JPH0562529A|1991-08-29|1993-03-12|Fujikura Ltd|Power cable|

---

SE9103077D0|1991-10-22|1991-10-22|Neste Oy|UNSATURED FOOD COPY POLYMER AND SET FOR PREPARATION THEREOF|

---

BR9306018A|1992-03-05|1997-11-18|Cabot Corp|Process for the production of carbon black products of carbon black and composition|

---

JPH05279578A|1992-03-31|1993-10-26|Furukawa Electric Co Ltd:The|Intimate rubber-plastic mixture|

---

JP3327341B2|1992-04-20|2002-09-24|新日本石油化学株式会社|High insulator made of ethylene copolymer or its composition and power cable using the same|

---

JPH05302282A|1992-04-24|1993-11-16|Bridgestone Corp|Steel cord for reinforcing rubber article and pneumatic radial tire for heavy load|

---

US5243137A|1992-06-25|1993-09-07|Southwire Company|Overhead transmission conductor|

---

CA2109904C|1992-12-18|2004-09-14|Pol Bruyneel|Multi-strand steel cord|

---

JPH06251625A|1993-02-26|1994-09-09|Fujikura Ltd|Insulation composition and power cable|

---

JPH06251624A|1993-02-26|1994-09-09|Fujikura Ltd|Insulation composition and power cable|

---

US5556697A|1994-03-24|1996-09-17|Bicc Cables Corporation|Semiconductive power cable shield|

---

FI942949A0|1994-06-20|1994-06-20|Borealis Polymers Oy|Prokatalysator Foer production av etenpolymerer och foerfarande Foer framstaellning daerav|

---

JPH0859720A|1994-08-26|1996-03-05|Showa Denko Kk|Polymerizing catalyst for olefin, its production and production of ethylenic polymer|

---

US5718947A|1995-03-14|1998-02-17|The Dow Chemicalcompany|Processes for forming thin, durable coatings of cation-containing polymers on selected substrates|

---

BR9508009A|1995-04-27|1997-08-05|Polyplastics Co|Thermoplastic resin compositions and production process|

---

SE504364C2|1995-05-12|1997-01-20|Borealis Holding As|Silicon-containing ethylene polymer based on alpha, omega-divnyl silo production thereof and its use in electrical cable compositions|

---

US5806296A|1995-05-26|1998-09-15|Bridgestone Metalpha Corporation|Corrosion resistant spiral steel filament and steel cord made therefrom|

---

US6863177B2|1996-05-13|2005-03-08|Matsushita Electric Industrial Co., Ltd.|Electrically conductive propylene resin composition and part-housing container|

---

JPH09306265A|1996-05-16|1997-11-28|Nippon Unicar Co Ltd|Power cable and manufacture thereof|

---

US5767034A|1996-05-31|1998-06-16|Intevep, S.A.|Olefin polymerization catalyst with additive comprising aluminum-silicon composition, calixarene derivatives or cyclodextrin derivatives|

---

US5731082A|1996-06-24|1998-03-24|Union Carbide Chemicals & Plastics Technology Corporation|Tree resistant cable|

---

FR2753986B1|1996-09-30|1998-10-30|Elf Antar France|LUBRICANT FOR HYPERCOMPRESSOR AND PROCESS FOR OBTAINING SAME|

---

SE9603595D0|1996-10-02|1996-10-02|Borealis As|Semiconducting polymer composition and cable sheath including this|

---

DE19781602T1|1996-12-20|1999-03-11|Sumitomo Chemical Co|Olefin polymer and its sheet or plate and method of making the olefin polymer|

---

JP3470578B2|1997-01-14|2003-11-25|住友化学工業株式会社|Method for producing olefin polymer|

---

JPH10283851A|1997-04-04|1998-10-23|Furukawa Electric Co Ltd:The|Direct current power cable and its connection part|

---

US6140589A|1997-04-04|2000-10-31|Nextrom, Ltd.|Multi-wire SZ and helical stranded conductor and method of forming same|

---

US5989208A|1997-05-16|1999-11-23|Nita; Henry|Therapeutic ultrasound system|

---

SE9703798D0|1997-10-20|1997-10-20|Borealis As|Electric cable and a method of composition for the production thereof|

---

JP3682947B2|1998-08-12|2005-08-17|古河電気工業株式会社|Electrical insulating resin composition and electric wire / cable using the same|

---

SE515111C2|1998-10-23|2001-06-11|Borealis As|Electronic cable and methods for making them|

---

JP4428748B2|1999-03-05|2010-03-10|株式会社ブリヂストン|Pneumatic tire|

---

US6231978B1|1999-03-31|2001-05-15|Union Carbide Chemicals & Plastics Technology Corporation|Crosslinkable polyethylene composition|

---

JP2001004148A|1999-06-18|2001-01-12|Hitachi Hometec Ltd|Heating cooker|

---

US6086792A|1999-06-30|2000-07-11|Union Carbide Chemicals & Plastics Technology Corporation|Cable semiconducting shields|

---

ES2215778T3|1999-11-17|2004-10-16|PIRELLI &amp; C. S.P.A.|CABLE WITH RECYCLABLE COVER.|

---

RU2227187C2|1999-12-30|2004-04-20|Сосьете Де Текнолоджи Мишлен|Multilayer steel cord cable for pneumatic carcass of articles|

---

DK1124235T3|2000-02-08|2009-02-16|Gift Technologies Llc|Composite reinforced electric transmission conductor|

---

FR2805656B1|2000-02-24|2002-05-03|Cit Alcatel|HIGH AND VERY HIGH VOLTAGE DIRECT CURRENT ENERGY CABLE|

---

TWI315591B|2000-06-14|2009-10-01|Sumitomo Chemical Co|Porous film and separator for battery using the same|

---

US6559385B1|2000-07-14|2003-05-06|3M Innovative Properties Company|Stranded cable and method of making|

---

US6632848B2|2000-07-24|2003-10-14|Asahi Glass Company, Limited|Heterogeneous anion exchanger|

---

EP1211289A1|2000-11-29|2002-06-05|Borealis GmbH|Polyolefin compositions with improved properties|

---

US6824815B2|2000-12-27|2004-11-30|Pirelli Cavi E Sistemi S.P.A.|Process for producing an electrical cable, particularly for high voltage direct current transmission or distribution|

---

US6761905B2|2001-05-01|2004-07-13|Wei Ming Pharmaceutical Mfg. Co., Ltd.|Process for the preparation of direct tabletting formulations and aids|

---

AT328912T|2001-06-20|2006-06-15|Borealis Tech Oy|Preparation of a catalyst component for olefin polymerisation|

---

US20060249705A1|2003-04-08|2006-11-09|Xingwu Wang|Novel composition|

---

US7138448B2|2002-11-04|2006-11-21|Ciba Specialty Chemicals Corporation|Flame retardant compositions|

---

US20060151758A1|2002-11-13|2006-07-13|Jose Reyes|Fire resistant intumescent thermoplastic or thermoset compositions|

---

US20060116279A1|2003-01-09|2006-06-01|Hisao Kogoi|Composite particles and method for production thereof and use thereof|

---

EP1484345A1|2003-06-06|2004-12-08|Borealis Technology Oy|Process for the production of polypropylene using a Ziegler-Natta catalyst|

---

CN100572655C|2003-07-17|2009-12-23|贝卡尔特股份有限公司|Open layered steel cord with high breaking load|

---

JP4734593B2|2004-06-08|2011-07-27|タイコエレクトロニクスジャパン合同会社|Polymer PTC element|

---

US7093416B2|2004-06-17|2006-08-22|3M Innovative Properties Company|Cable and method of making the same|

---

US20050279526A1|2004-06-17|2005-12-22|Johnson Douglas E|Cable and method of making the same|

---

BRPI0512191B1|2004-06-18|2017-04-04|Aker Kvaerner Subsea As|umbilical|

---

EP1669403A1|2004-12-07|2006-06-14|Borealis Technology OY|Novel propylene polymer blends|

---

US7579397B2|2005-01-27|2009-08-25|Rensselaer Polytechnic Institute|Nanostructured dielectric composite materials|

---

AT456607T|2005-02-28|2010-02-15|Borealis Tech Oy|PROCESS FOR PRODUCING CROSS-LINKED POLYMERS|

---

ES2311181T3|2005-02-28|2009-02-01|Borealis Technology Oy|COMPOSITION POLYMERICA RETARDANTE OF THE COMBUSTION.|

---

JP2006291022A|2005-04-11|2006-10-26|J-Power Systems Corp|Insulating composition, wire/cable, and method for producing insulating composition|

---

EP1731563B1|2005-06-08|2016-04-13|Borealis Technology Oy|Polymer composition having improved wet ageing properties|

---

DK1731564T3|2005-06-08|2010-06-14|Borealis Tech Oy|Composition for water tree inhibition|

---

US7462781B2|2005-06-30|2008-12-09|Schlumberger Technology Corporation|Electrical cables with stranded wire strength members|

---

TW200713336A|2005-08-05|2007-04-01|Dow Global Technologies Inc|Polypropylene-based wire and cable insulation or jacket|

---

NO323516B1|2005-08-25|2007-06-04|Nexans|Underwater power cable and heating system|

---

US20070048472A1|2005-08-30|2007-03-01|Krishnaswamy Rajendra K|Polymeric pipe and method of making a polymeric pipe|

---

CA2841207C|2005-10-25|2016-04-19|General Cable Technologies Corporation|Improved lead-free insulation compositions containing metallocene polymers|

---

RU2008145492A|2006-04-18|2010-05-27|СОЛВЕЙ ЭДВАНСТ ПОЛИМЕРС, Эл.Эл.Си. |MULTILAYER POLYMERIC STRUCTURE|

---

JP2007299907A|2006-04-28|2007-11-15|Nitto Denko Corp|Structure having property of conducting or absorbing electromagnetic wave|

---

WO2008070022A1|2006-12-04|2008-06-12|Ingenia Polymers Inc.|Cross-linked polyolefin foam|

---

JP4475472B2|2007-06-12|2010-06-09|住友ゴム工業株式会社|Method for producing conductive thermoplastic elastomer composition, and conductive roller using the composition|

---

CN101743275A|2007-06-21|2010-06-16|埃克森美孚化学专利公司|Crosslinked polyethylene goods and preparation method thereof|

---

WO2009000326A1|2007-06-28|2008-12-31|Prysmian S.P.A.|Energy cable|

---

EP2015315B1|2007-07-12|2012-12-12|Borealis Technology Oy|Process for preparing and crosslinking a cable comprising a polymer composition and a crosslinked cable|

---

EP2015314B1|2007-07-12|2012-04-04|Borealis Technology Oy|Process for preparing and crosslinking a cable comprising a polymer composition and a crosslinked cable|

---

EP2014707B1|2007-07-12|2014-04-23|Borealis Technology Oy|Modified polymer compositions, modification process and free radical generating agents for i.a. wire and cable applications|

---

WO2009012041A1|2007-07-13|2009-01-22|Dow Global Technologies Inc.|Hypercompressor lubricants for high pressure polyolefin production|

---

CN104151666B|2007-07-13|2019-07-12|陶氏环球技术有限责任公司|The low dielectric absorption power cable sheath of high pressure polyolefin comprising not silane functionality|

---

WO2009056409A1|2007-10-31|2009-05-07|Borealis Technology Oy|Silane-functionalised polyolefin compositions, products thereof and preparation processes thereof for wire and cable applications|

---

JP4340314B2|2007-11-27|2009-10-07|住友ゴム工業株式会社|Pneumatic tire|

---

US8703288B2|2008-03-21|2014-04-22|General Cable Technologies Corporation|Low smoke, fire and water resistant cable coating|

---

CN102119313A|2008-06-09|2011-07-06|明选国际汽配有限责任公司|Lubricants for air donditioning systems|

---

ES2527655T3|2008-07-10|2015-01-28|Borealis Ag|Process to produce a polymer and a polymer for cable and wire applications|

---

US8525033B2|2008-08-15|2013-09-03|3M Innovative Properties Company|Stranded composite cable and method of making and using|

---

US20100059249A1|2008-09-09|2010-03-11|Powers Wilber F|Enhanced Strength Conductor|

---

CN102483973B|2009-07-16|2013-11-06|3M创新有限公司|Submersible composite cable and methods|

---

IN2012DN03434A|2009-11-11|2015-10-23|Borealis Ag|

---

BR112012011085A2|2009-11-11|2016-07-05|Borealis Ag|polymer composition and power cable comprising the polymer composition|

---

US20120298403A1|2010-02-01|2012-11-29|Johnson Douglas E|Stranded thermoplastic polymer composite cable, method of making and using same|

---

US20120170900A1|2011-01-05|2012-07-05|Alcan Products Corporation|Aluminum Alloy Conductor Composite Reinforced for High Voltage Overhead Power Lines|IN2012DN03434A|2009-11-11|2015-10-23|Borealis Ag|

---

BR112012011085A2|2009-11-11|2016-07-05|Borealis Ag|polymer composition and power cable comprising the polymer composition|

---

EP3591670A1|2010-11-03|2020-01-08|Borealis AG|A polymer composition and a power cable comprising the polymer composition|

---

MX340104B|2011-06-23|2016-06-27|Dow Global Technologies Llc|Low density polyethylene with low dissipation factor and process for producing same.|

---

EP2636691A1|2012-03-07|2013-09-11|Borealis AG|Process and plant for manufacturing polyethylene-diene-copolymers|

---

EP2636690A1|2012-03-07|2013-09-11|Borealis AG|Process and plant for manufacturing polyethylene-silane-copolymers|

---

JP2014072133A|2012-10-01|2014-04-21|Viscas Corp|Dc power cable|

---

US9115274B2|2012-12-13|2015-08-25|General Cable Technologies Corporation|Fire and water resistant cable cover|

---

EP2957602A4|2013-02-15|2016-09-28|Mitsubishi Gas Chemical Co|Resin composition for high dielectric constant materials, molded article containing same, and master batch for coloring|

---

US9728300B2|2013-03-12|2017-08-08|Dow Global Technologies Llc|Power cable with a thick insulation layer and a method for its manufacture|

---

CN105493202B|2013-09-20|2018-10-12|陶氏环球技术有限责任公司|The degassing method of cross-linked power cable|

---

WO2015089179A1|2013-12-10|2015-06-18|General Cable Technologies Corporation|Thermally conductive compositions and cables thereof|

---

FR3019368B1|2014-03-31|2017-10-06|Nexans|ELECTRICAL DEVICE WITH MEDIUM OR HIGH VOLTAGE|

---

EA034758B1|2014-08-19|2020-03-17|Бореалис Аг|New crosslinked polymer composition, structured layer and cable|

---

WO2016066619A1|2014-10-27|2016-05-06|Borealis Ag|Polymer composition for cable applications with advantageous electrical properties|

---

CN107001729A|2014-10-27|2017-08-01|北欧化工股份公司|Polymer composition and cable with superior electrical property|

---

EP3035344A1|2014-12-15|2016-06-22|Borealis AG|High pressure radical polymerisation process for a copolymer of ethylene with silane groups containing comonomer|

---

KR102249186B1|2014-12-17|2021-05-07|엘에스전선 주식회사|System for measuring volume electricla resistivity of DC cable|

---

CN107112071A|2014-12-19|2017-08-29|博里利斯股份公司|Power cable polymer composition comprising thermoplastic and with favorable property|

---

WO2016097250A1|2014-12-19|2016-06-23|Borealis Ag|Polymer composition for w&c application with advantageous electrical properties|

---

KR101717646B1|2015-02-12|2017-03-17|인테크놀로지|Environmental friendly non-toxic flame retardant high density polyethylene compound for extrusion sheath of ultra high-voltage cable and a method of manufacturing|

---

CN105115428B|2015-04-24|2018-02-02|上海工程技术大学|Towards the parallel image measuring method of spoke balanced cable section thickness of insulating layer|

---

US10851258B2|2015-12-09|2020-12-01|Dow Global Technologies Llc|Stabilized moisture-curable polymeric compositions|

---

JP6610411B2|2016-04-25|2019-11-27|住友電装株式会社|Conductive member|

---

EP3261096A1|2016-06-21|2017-12-27|Borealis AG|Cable and composition|

---

EP3261093A1|2016-06-21|2017-12-27|Borealis AG|Cable with advantageous electrical properties|

---

CN108003651B|2017-12-28|2021-01-22|深圳市沃尔核材股份有限公司|Prefabricated cable accessory and preparation method thereof|

---

US11031153B2|2018-11-05|2021-06-08|General Cable Technologies Corporation|Water tree resistant cables|

法律状态:
2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|

---

2019-03-19| B06T| Formal requirements before examination|

---

2019-07-30| B07A| Technical examination (opinion): publication of technical examination (opinion)|

---

2020-02-18| B07A| Technical examination (opinion): publication of technical examination (opinion)|

---

2020-07-28| B09A| Decision: intention to grant|

---

2020-12-01| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 10 (DEZ) ANOS CONTADOS A PARTIR DE 01/12/2020, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

---

申请号 | 申请日 | 专利标题

---

EP09175692|2009-11-11|

---

EP09175692.4|2009-11-11|

---

PCT/EP2010/066709|WO2011057925A1|2009-11-11|2010-11-03|A cable and production process thereof|

---