EP2498263B1 - low and middle voltage electric cable - Google Patents

low and middle voltage electric cable Download PDF

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Publication number
EP2498263B1
EP2498263B1 EP20120158603 EP12158603A EP2498263B1 EP 2498263 B1 EP2498263 B1 EP 2498263B1 EP 20120158603 EP20120158603 EP 20120158603 EP 12158603 A EP12158603 A EP 12158603A EP 2498263 B1 EP2498263 B1 EP 2498263B1
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EP
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Prior art keywords
cross
polyolefin
layer
cable according
aliphatic
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German (de)
French (fr)
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EP2498263A1 (en
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Jérôme Alric
Jean-Michel Marty
Yannick Goutille
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Nexans SA
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Nexans SA
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes

Definitions

  • the present invention relates to an electric cable. It applies typically, but not exclusively, to the fields of medium-voltage (in particular 6 to 45-60 kV) or high-voltage (in particular greater than 60 kV, and up to 800 kV) energy cables. , whether DC or AC.
  • the medium or high voltage energy cables typically comprise a central electrical conductor and, successively and coaxially around this electrical conductor, a semiconducting inner layer, an electrically insulating intermediate layer, a semiconducting outer layer, these three layers being crosslinked by techniques well known to those skilled in the art.
  • these three crosslinked layers are obtained from a composition based on a polyethylene polymer matrix associated with an organic peroxide of the dicumyl peroxide or tert-butyl peroxide cumyl (i.e. cumyl peroxide) type.
  • this type of peroxide decomposes and forms cross-linking by-products such as in particular methane, acetophenone, cumyl alcohol, acetone, tertiobutanol, alpha Styrene methyl and / or water.
  • cross-linking by-products such as in particular methane, acetophenone, cumyl alcohol, acetone, tertiobutanol, alpha Styrene methyl and / or water.
  • the object of the present invention is to overcome the drawbacks of the techniques of the prior art by proposing a medium or high voltage electrical cable, comprising a crosslinked layer whose manufacture significantly limits the presence of cross-linking by-products, such as for example methane and / or water, while ensuring optimum thermomechanical properties, such as hot creep, characteristics of the good crosslinking of said layer.
  • a medium or high voltage electrical cable comprising a crosslinked layer whose manufacture significantly limits the presence of cross-linking by-products, such as for example methane and / or water, while ensuring optimum thermomechanical properties, such as hot creep, characteristics of the good crosslinking of said layer.
  • the present invention firstly relates to an electrical cable comprising an electrical conductor, a first semiconductor layer surrounding the electrical conductor, a second electrically insulating layer surrounding the first layer, and a third semiconductor layer. surrounding the second layer, characterized in that at least one of these three layers is a crosslinked layer obtained from a crosslinkable composition comprising at least one polyolefin, and an aliphatic peroxide as crosslinking agent, characterized in that that the crosslinkable composition further comprises an aromatic compound comprising at least one aromatic ring and a single reactive function capable of grafting to the polyolefin.
  • the crosslinkable composition according to the first subject of the invention may further comprise at least one crosslinking agent comprising at least two identical or different reactive functional groups, which are able on the one hand to be grafted to the polyolefin, and on the other hand to participate in the crosslinking of the polyolefin.
  • the second subject of the present invention is an electrical cable comprising an electrical conductor, a first semiconductor layer surrounding the electrical conductor, a second electrically insulating layer surrounding the first layer, and a third semiconductor layer surrounding the second layer, on the other side.
  • the crosslinkable composition according to the second subject of the invention may further comprise an aromatic compound comprising at least one aromatic nucleus and a single reactive functional group capable of grafting to the polyolefin.
  • the crosslinking agent of the invention has the advantage of not forming cumyl alcohol as a by-product of crosslinking during the crosslinking the crosslinkable composition, and thus significantly reduces the presence of water within the crosslinked layer, while maintaining very good thermomechanical properties.
  • the thermomechanical properties for the crosslinked layer according to the invention can advantageously result in a maximum stress elongation under the standard NF EN 60811-2-1 of at most 100%, preferably at most 80%, and in a particularly preferred manner ranging from 60 to 80%.
  • the amount of methane formed is less than that formed during the decomposition of the cumyl peroxide: the presence of methane in the crosslinking by-products is therefore advantageously reduced.
  • the amount of aliphatic peroxide required is less than the amount of cumyl peroxide.
  • tertiary dialkyl aliphatic peroxides it will be preferred to use tertiary dialkyl aliphatic peroxides. This type of peroxide has a very good compromise between speed of crosslinking and the risk of roasting or pre-crosslinking during the implementation of the composition.
  • the peroxidic crosslinking of the crosslinkable composition according to the invention can be carried out under the action of heat and pressure, for example by means of a vulcanization tube under a nitrogen atmosphere, this crosslinking technique being well known to those skilled in the art.
  • the crosslinkable composition of the invention may comprise at most 3.00 parts by weight of aliphatic peroxide per 100 parts by weight of polymer (s) in the composition; preferably 1.50 parts by weight of aliphatic peroxide per 100 parts by weight of polymer (s) in the composition; preferably 1.25 parts by weight of aliphatic peroxide per 100 parts by weight of polymer (s) in the composition; and particularly preferably 1.10 parts by weight of aliphatic peroxide per 100 parts by weight of polymer (s) in the composition.
  • the crosslinkable composition does not comprise any aromatic peroxide, such as in particular dicumyl peroxides or their derivatives.
  • polyolefin as such generally means homopolymer or copolymer of olefin. It may in particular designate a thermoplastic polymer or an elastomer.
  • the olefin polymer is an ethylene homopolymer or an ethylene copolymer.
  • LLDPE linear low density polyethylene
  • LDPE low density polyethylene
  • MDPE medium density polyethylene
  • HDPE high density polyethylene
  • EVA copolymers of d ethylene and vinyl acetate
  • EBA methyl acrylate
  • EMA 2-hexylethyl acrylate
  • EPR copolymers of ethylene and alpha-olefins
  • PEO polyethylene-octene
  • PEB polyethylene-butene
  • EPR ethylene and propylene
  • EPDM terpolymers of ethylene propylene diene
  • LDPE low density polyethylene
  • low density a density that can range from 0.910 to 0.940 g / cm 3 , and preferably ranging from 0.910 to 0.930 g / cm 3 according to ISO 1183 (at a temperature of 23 ° C).
  • low density polyethylene can be obtained by a polymerization process in a high pressure tubular reactor, or in an autoclave reactor.
  • the crosslinkable composition may comprise more than 50.0 parts by weight of polyolefin per 100 parts by weight of polymer (s) (ie polymer matrix) in the composition, preferably at least 70 parts by weight of polyolefin per 100 parts by weight of polymer (s) in said composition, and particularly preferably at least 90 parts by weight of polyolefin per 100 parts by weight of polymer (s) in said composition.
  • the crosslinkable composition comprises a polymer matrix which is composed solely of a polyolefin or a mixture of polyolefins.
  • this crosslinking agent may comprise at least two reactive functions, identical or different, which are able on the one hand to be grafted to the polyolefin and, secondly, to participate in the crosslinking of the polyolefin (ie in the formation of the three-dimensional network of the crosslinked polyolefin), in the presence of the aliphatic peroxide of the invention.
  • said at least two reactive functions of the crosslinking agent are unsaturated functions.
  • the crosslinking coagent notably makes it possible to significantly reduce the proportion of peroxide to be used in the crosslinkable composition, while maintaining good thermomechanical properties such as hot creep, as well as a satisfactory crosslinking rate.
  • a coagent whose boiling temperature is sufficiently high so that it does not volatilize during the stage of implementation of the crosslinkable composition, in particular by extrusion, will be used.
  • the crosslinking agent may be chosen from 1,3-hexadiene; 1,4-hexadiene; 1,5-hexadiene; 2,3-dimethyl-1,3-butadiene; 2,4-hexadiene; 2-methyl-1,4-pentadiene; 3-methyl-1,3-pentadiene; 3-methyl-1,3-pentadiene; 1,6-heptadiene; 2,4-dimethyl-1,3-pentadiene; 2-methyl-1,5-hexadiene; 4-vinyl-1-cyclohexene; 1,7-octadiene; 2,5-dimethyl-1,5-hexadiene; 2,5-dimethyl-2,4-hexadiene; 5-ethylidene-2-norbornene; Vinyl-2 norbornene; 1,8-nonadiene; 7-methyl-1,6-octadiene; 1,5,9-decatriene; 2,6-Dimethyl-2,4,
  • the concentration of the coagent is preferably limited so as not to disturb the extrusion process of the crosslinkable composition of the invention.
  • the crosslinkable composition may comprise at most 3 parts by weight of crosslinking agent per 100 parts of polymer (s) in the crosslinkable composition. It will be preferred to use from 0.5 to 2 parts coagent weight per 100 parts by weight of polymer (s) in the crosslinkable composition.
  • the crosslinkable composition of the invention further comprises an aromatic compound comprising at least one aromatic ring, and a single reactive function capable of grafting to the polyolefin
  • said reactive function of the aromatic compound may be a vinyl function.
  • the crosslinked layer obtained from this crosslinkable composition has enhanced and durable properties in the field of electric cables, offering better resistance to water trees. More particularly, this relates to the resistance to electrical breakdown, and in particular the ability to dissipate the space charges that accumulate especially in high voltage cables under direct current.
  • the aromatic compound may be selected from styrene, styrene derivatives, and their isomers.
  • styrene derivatives By way of example of styrene derivatives, mention may be made of the compounds of the following general formula: wherein X is hydrogen, an alkyl group or an aryl group; and R is either a hydrogen, an alkyl group or an aryl group. More particularly, mention may be made of 4-methyl-2,4-diphenyl pentene and triphenyl ethylene.
  • styrene derivatives of the polycyclic aromatic hydrocarbon (PAH) type More particularly, mention may be made of vinyl naphthalene, for example 2-vinyl naphthalene; vinyl anthracene such as 9-vinyl anthracene or 2-vinyl anthracene; and vinyl phenanthrene such as 9-vinyl phenanthrene.
  • PAH polycyclic aromatic hydrocarbon
  • grafting of these aromatic compounds onto the polymer chain of the polyolefin is typically carried out during the crosslinking phase of the polyolefin, according to a radical addition mechanism well known to those skilled in the art, in the presence of tertiary alkylperoxide. aliphatic of the invention.
  • the crosslinkable composition according to the invention may further comprise at least one protective agent such as an antioxidant.
  • a protective agent such as an antioxidant.
  • Antioxidants help to protect the composition of thermal stresses generated during the cable manufacturing or cable operation steps.
  • the type of stabilizer and its level in the crosslinkable composition are conventionally chosen according to the maximum temperature experienced by the polymers during the production of the mixture and during the implementation by extrusion on the cable as well as according to the maximum duration of exposure to this temperature.
  • the crosslinkable composition may typically comprise from 0.1% to 2% by weight of antioxidant (s). Preferably, it may comprise at most 0.7% by weight of antioxidant (s), especially when the antioxidant is TMQ.
  • additives and / or other fillers well known to those skilled in the art may also be added to the crosslinkable composition of the invention such as scorch retarders; agents promoting implementation such as lubricants or waxes; compatibilizing agents; coupling agents; UV stabilizers; non-conductive charges; conductive charges; and / or semiconductor charges.
  • the crosslinked layer of the invention is the electrically insulating layer (ie second layer).
  • the crosslinkable composition may not comprise an (electrically) conductive filler and / or may not comprise a semiconductor filler.
  • At least two of the three layers of the cable are crosslinked layers, and preferably the three layers of the cable are crosslinked layers.
  • the crosslinkable composition When the crosslinkable composition is used for the manufacture of the semiconductor layers (first layer and / or third layer), the crosslinkable composition further comprises at least one (electrically) conductive filler or a semiconductor filler, in an amount sufficient to to make the composition crosslinkable semiconductor.
  • a layer is semiconductive when its electrical conductivity is at least 0.001 Sm -1 (Siemens per meter).
  • the crosslinkable composition used to obtain a semiconductor layer may comprise from 0.1 to 40% by weight of (electrically) conductive filler, preferably at least 15% by weight of conductive filler, and even more preferably at least 25% by weight. conductive charge weight.
  • the semiconductor filler may advantageously be chosen from carbon blacks, carbon nanotubes, and graphites, or a mixture thereof.
  • At least one of these three layers is an extruded layer, preferably two of these three layers are extruded layers, and more preferably, these three layers are extruded layers.
  • the first semiconductor layer, the second electrically insulating layer and the third semiconductor layer constitute a three-layer insulation.
  • the second electrically insulating layer is directly in physical contact with the first semiconductor layer
  • the third semiconductor layer is directly in physical contact with the second electrically insulating layer.
  • the electrical cable of the invention may further comprise a metal screen surrounding the third semiconductor layer.
  • This metal screen may be a "wired” screen, consisting of a set of copper or aluminum conductors arranged around and along the third semiconductor layer, a so-called “ribbon” screen composed of one or more ribbons conductive metal laid helically around the third semiconductor layer, or a so-called “sealed” type metal screen surrounding the third semiconductor layer.
  • This last type of screen makes it possible in particular to provide a moisture barrier that tends to penetrate the electrical cable radially.
  • All types of metal screens can act as grounding of the electric cable and can carry fault currents, for example in the event of a short circuit in the network concerned.
  • the electrical cable of the invention may comprise an outer protective sheath surrounding the third semiconductor layer, or more particularly surrounding said metal screen when it exists.
  • This outer protective sheath can be made conventionally from suitable thermoplastic materials such as HDPE, MDPE or LLDPE; or materials retarding the propagation of the flame or resisting the spread of fire. In particular, if the latter materials do not contain halogen, it is called cladding type HFFR (for the Anglicism " Halogen Free Flame Retardant").
  • the electrical conductor of the cable of the invention may also comprise swelling materials in the presence of moisture to obtain a "sealed core".
  • Medium or high voltage power cable 1 shown in FIG. figure 1 comprises an elongate central conductive element 2, in particular made of copper or aluminum. Successively and coaxially around this conductive element 2, the energy cable 1 further comprises a first semiconductor layer 3 called “internal semiconductor layer”, a second electrically insulating layer 4, a third so-called semiconductor layer 5 "External semiconductor layer”, a metal screen 6 for grounding and / or protection, and an outer protective sheath 7, the layers 3, 4 and 5 being obtainable from a composition according to invention. Layers 3, 4 and 5 are extruded and crosslinked layers.
  • compositions C1 and C3 refer to comparative examples, while compositions C2 and C4 refer to compositions according to the invention.
  • compositions C1 to C4, detailed in Table 1 are expressed in parts by weight (phr) per 100 parts by weight of polymer in the crosslinkable composition.
  • Compositions C1 to C4 are prepared by mixing the polyethylene granules and additives such as peroxide, antioxidants, and optionally the coagent, in a closed jar placed on a roller mixer for 3 hours to thoroughly impregnate the granules. polyethylene.
  • the polyethylene granules were preheated to 60 ° C before impregnation.
  • the MDR rheometer (Moving Die Rheometer, Alpha Technologies) makes it possible to follow the crosslinking / vulcanization of a material by measuring the evolution of its viscosity (DIN 53529 (1983)).
  • the chamber containing the sample consists of two heating trays.
  • the lower plate applies a constant oscillation frequency (100 cycles / min, 1.67Hz) and amplitude ⁇ 0.5 ° arc; the upper plate measures the response of the material, ie its resistance to the stress applied.
  • the unit of measure is that of a pair, expressed in dN.m.
  • the sample is prepared from the impregnated polyethylene granules, molded in a hydraulic press into a plate 3 mm thick at a temperature of 120 ° C., following a cycle of 2 minutes without pressure followed by 3 minutes under a pressure of 100 bars. before being cooled.
  • Two washers 35 mm in diameter to completely fill the chamber are cut in the plate with a punch, then placed between two sheets of terphane polyester ® , to be positioned in the rheometer chamber.
  • the measurement is made at a temperature of 190 ° C., representative of the tube vulcanization conditions. After an initial torque drop due to the prior melting of the material, the viscosity of the material and the resulting torque increase, sign that the crosslinking takes place.
  • a parameter of interest is the MH which corresponds to the maximum measured torque. This is a plateau value, obtained when the entire system has reacted and the maximum accessible crosslinking level is reached. For a given material, there is a good correlation between MH and crosslinking density that govern the thermomechanical properties after the crosslinking step.
  • the Mooney viscometer (Monsanto MV2000) is used to measure the viscosity of a material, or in the case of crosslinkable materials, to monitor its evolution over time (ASTM D1646 (2005)).
  • the chamber consists of two jaws forming a cylindrical cavity in which is placed the sample to be tested.
  • the chamber has in its center a metal disk which is rotated at a constant speed of 2 rpm. In our case, of the two standard rotors available, the "big" is used.
  • the jaws and the chamber are maintained under pressure and at a temperature of 130 ° C.
  • the sample is prepared from the impregnated polyethylene granules, molded in a hydraulic press into a plate 3 mm thick at a temperature of 120 ° C., following a cycle of 2 minutes without pressure followed by 3 minutes under a pressure of 100 bars. before being cooled.
  • the measure is expressed in arbitrary unit, the Mooney (MU).
  • the parameters of interest are: ML, minimum viscosity value, measured at time t0 (min). ML + 1, viscosity value corresponding to ML increased by one Mooney unit. This is measured at time t1 (min). ML + 2, viscosity value corresponding to ML increased by two Mooney units. This is measured at time t2 (min).
  • the determination of the amount of volatiles produced during the crosslinking phase of the polyethylene, then desorbed, is made by the Sievert method, using the PCT Pro 2000 (HY-ENERGY, SETARAM).
  • the sample is prepared from the impregnated polyethylene granules, molded in a hydraulic press into a plate 1 mm thick at a temperature of 120 ° C., following a cycle of 2 minutes without pressure followed by 3 minutes under a pressure of 100 bars. before being cooled.
  • the sample is placed in the chamber of the apparatus, pressurized (helium).
  • This chamber is connected by means of a valve, to a tank of 5ml also under pressure.
  • the pressures in the chamber and in the tank are identical.
  • the valve opens and closes intermittently, allowing a new equilibrium to be established when it is open, then measuring the new pressure in the tank when it is closed.
  • the evolution of the pressure comes partly from the release of the methane, and partly from the dimensional variation of the chamber with the temperature. A real-time reading of the amount of methane released therefore requires a prior calibration by subjecting the chamber to the temperature cycle envisaged.
  • the equipment allows controlled temperature ramps of 1 ° C / s, simulating the crosslinking conditions of the different layers of polyethylene vulcanization tube.
  • the cycle provides heating from room temperature up to 250 ° C.
  • the difference between the final and initial pressure measurements, at the same temperature, makes it possible to access the level of methane released.
  • the amount of volatiles i.e. methane is expressed in ⁇ mol / g of cross-linked polyethylene.
  • 1mm thick plates are molded from the impregnated polyethylene granules.
  • the molding is done in a press at 120 ° C, following a cycle of 2 minutes without pressure and then 3 minutes under 100 bars.
  • the plates are then cooled under a pressure of 100 bar.
  • the crosslinking step is carried out in a press at a temperature of 190 ° C. under 100 bar pressure and lasts 10 minutes.
  • the molds are preheated to 190 ° C.
  • the cooling step is carried out under pressure maintained at 100 bars.
  • the measurement of the hot creep of a material under mechanical stress is determined according to the standard NF EN 60811-2-1.
  • This test is commonly referred to as the Anglemia Hot Set Test (HST) and consists of ballasting one end of a dumbbell type H2 specimen with a mass corresponding to the application of a stress equivalent to 0.2MPa, and to place the whole in an oven heated to 200 +/- 1 ° C for a period of 15 minutes.
  • HST Anglicism Hot Set Test
  • the suspended mass is then removed, and the test piece is kept in the oven for another 5 minutes.
  • the remaining permanent elongation also called remanence (or remanent elongation) is then measured before being expressed in%.
  • test result would then logically be considered a failure.
  • an elongation value will be considered as meeting the requirements if it does not exceed 100%. Beyond this value, in the same way as a break, the test will be considered as non-compliant.
  • the quantity of aliphatic peroxide used in the crosslinkable composition C2 of the invention is much smaller than that used in the crosslinkable composition C1 (1.25 for C2 against 1.42 for C1).
  • the amount of methane released during the crosslinking increases from 113 to 104 ⁇ mol / g of XLPE.
  • tertiobutanol in the composition C2, during the crosslinking.
  • Tertiobutanol like any tertiary alcohol, can of course dehydrate to form isobutene and water.
  • isobutene being significantly less stabilized than the alpha-methyl styrene formed in the context of the dehydration reaction of cumyl alcohol, this reaction is markedly disadvantaged, and the formation of water slowed down.

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Description

La présente invention se rapporte à un câble électrique. Elle s'applique typiquement, mais non exclusivement, aux domaines des câbles d'énergie à moyenne tension (notamment de 6 à 45-60 kV) ou à haute tension (notamment supérieur à 60 kV, et pouvant aller jusqu'à 800 kV), qu'ils soient à courant continu ou alternatif.The present invention relates to an electric cable. It applies typically, but not exclusively, to the fields of medium-voltage (in particular 6 to 45-60 kV) or high-voltage (in particular greater than 60 kV, and up to 800 kV) energy cables. , whether DC or AC.

Les câbles d'énergie à moyenne ou haute tension comprennent typiquement un conducteur électrique central et, successivement et coaxialement autour de ce conducteur électrique, une couche interne semi-conductrice, une couche intermédiaire électriquement isolante, une couche externe semi-conductrice, ces trois couches étant réticulées par des techniques bien connues de l'homme du métier.The medium or high voltage energy cables typically comprise a central electrical conductor and, successively and coaxially around this electrical conductor, a semiconducting inner layer, an electrically insulating intermediate layer, a semiconducting outer layer, these three layers being crosslinked by techniques well known to those skilled in the art.

Classiquement, ces trois couches réticulées sont obtenues à partir d'une composition à base d'une matrice polymère de polyéthylène associée à un peroxyde organique du type peroxyde de dicumyle ou peroxyde de tert-butyle cumyle (i.e. peroxyde cumylique). Lors de la réticulation desdites compositions, ce type de peroxyde se décompose et forme des sous-produits de réticulation tels que notamment du méthane, de l'acétophénone, de l'alcool cumylique, de l'acétone, du tertiobutanol, de l'alpha-méthyle styrène et/ou de l'eau. Ces deux derniers sous-produits se forment par la réaction de déshydratation de l'alcool cumylique.Conventionally, these three crosslinked layers are obtained from a composition based on a polyethylene polymer matrix associated with an organic peroxide of the dicumyl peroxide or tert-butyl peroxide cumyl (i.e. cumyl peroxide) type. During the crosslinking of said compositions, this type of peroxide decomposes and forms cross-linking by-products such as in particular methane, acetophenone, cumyl alcohol, acetone, tertiobutanol, alpha Styrene methyl and / or water. These latter two by-products are formed by the dehydration reaction of cumyl alcohol.

La formation d'eau à partir d'alcool cumylique est relativement lente et peut se produire après plusieurs mois, voire quelques années une fois que le câble est en configuration opérationnelle. Le risque de claquage des couches réticulées est ainsi augmenté de façon significative.The formation of water from cumyl alcohol is relatively slow and can occur after several months or even years once the cable is in operational configuration. The risk of breakdown of the crosslinked layers is thus significantly increased.

En outre, si le méthane formé au cours de l'étape de réticulation n'est pas évacué des couches réticulées, des risques liés à l'explosivité du méthane et sa capacité à s'enflammer ne doivent pas être ignorés. Ce gaz peut également occasionner des dégâts une fois le câble mis en service. Lorsque la couche externe semi-conductrice est entourée par un écran métallique, ce qui est généralement le cas dans la structure des câbles moyenne et haute tension, celui-ci ne peut se diffuser que longitudinalement le long du câble jusqu'aux jonctions et aux terminaisons de l'installation électrique (i.e. accessoires d'énergie). Le méthane peut donc s'accumuler et exercer une pression sur les accessoires d'énergie, ce qui peut provoquer un claquage électrique. Même si des solutions existent pour limiter la présence de méthane au sein du câble, telles que par exemple traiter le câble thermiquement afin d'accélérer la diffusion de méthane en dehors du câble, elles deviennent longues et coûteuses lorsque l'épaisseur des couches réticulées est importante.In addition, if the methane formed during the crosslinking step is not removed from the crosslinked layers, risks related to the explosiveness of methane and its ability to ignite should not be ignored. This gas can also cause damage once the cable is put into service. When the semiconductor outer layer is surrounded by a metal screen, which is generally the case in the medium and high voltage cable structure, it can only diffuse longitudinally along the cable to the junctions and terminations of the electrical installation (ie energy accessories). As a result, methane can accumulate and exert pressure on the energy accessories, which can lead to electrical breakdown. Even if solutions exist to limit the presence of methane within the cable, such as for example to treat the cable thermally to accelerate the diffusion of methane outside the cable, they become long and expensive when the thickness of the crosslinked layers is important.

Le document US 5 252 676 présente une solution pour limiter les sous-produits de réticulation provenant des agents de réticulation, dans les câbles électriques d'énergie. Pour ce faire, il préconise la diminution de la quantité d'agent de réticulation afin que la quantité de gaz et d'eau libérée pendant la décomposition de l'agent de réticulation ne soit trop importante, tout en continuant à utiliser du peroxyde de tert-butyle cumyle (IPC) com me agent de réticulation dans la fabrication des trois couches réticulées. Néanmoins, la quantité d'eau reste sensiblement importante, et une diminution trop importante de la quantité de peroxyde tend à dégrader les propriétés thermomécaniques des couches réticulées.The document US 5,252,676 presents a solution for limiting the cross-linking by-products from crosslinking agents in electrical energy cables. To do this, he recommends reducing the amount of crosslinking agent so that the amount of gas and water released during the decomposition of the crosslinking agent is too great, while continuing to use tert-peroxide. butyl cumyl (IPC) as crosslinking agent in the manufacture of three crosslinked layers. Nevertheless, the amount of water remains substantially significant, and a too large decrease in the amount of peroxide tends to degrade the thermomechanical properties of the crosslinked layers.

On peut également citer le document US 6 586 509 proposant une solution pour limiter les sous-produits de réticulation en mélangeant à une polyoléfine et son agent de réticulation du type peroxyde de dicumyle, un antioxydant à base de thioéther.We can also mention the document US 6,586,509 proposing a solution for limiting the cross-linking by-products by mixing with a polyolefin and its dicumyl peroxide crosslinking agent, a thioether-based antioxidant.

Le but de la présente invention est de pallier les inconvénients des techniques de l'art antérieur en proposant un câble électrique à moyenne ou haute tension, comprenant une couche réticulée dont la fabrication limite de façon significative la présence de sous-produits de réticulation, comme par exemple le méthane et/ou l'eau, tout en garantissant des propriétés thermomécaniques optimales, telles que le fluage à chaud, caractéristiques de la bonne réticulation de ladite couche.The object of the present invention is to overcome the drawbacks of the techniques of the prior art by proposing a medium or high voltage electrical cable, comprising a crosslinked layer whose manufacture significantly limits the presence of cross-linking by-products, such as for example methane and / or water, while ensuring optimum thermomechanical properties, such as hot creep, characteristics of the good crosslinking of said layer.

La présente invention a pour premier objet un câble électrique comprenant un conducteur électrique, une première couche semi-conductrice entourant le conducteur électrique, une deuxième couche électriquement isolante, entourant la première couche, et une troisième couche semi-conductrice entourant la deuxième couche, caractérisé en ce qu'au moins une de ces trois couches est une couche réticulée obtenue à partir d'une composition réticulable comprenant au moins une polyoléfine, et un peroxyde aliphatique en tant qu'agent de réticulation, caractérisé en ce que la composition réticulable comprend en outre un composé aromatique comprenant au moins un noyau aromatique et une unique fonction réactive apte à se greffer à la polyoléfine.The present invention firstly relates to an electrical cable comprising an electrical conductor, a first semiconductor layer surrounding the electrical conductor, a second electrically insulating layer surrounding the first layer, and a third semiconductor layer. surrounding the second layer, characterized in that at least one of these three layers is a crosslinked layer obtained from a crosslinkable composition comprising at least one polyolefin, and an aliphatic peroxide as crosslinking agent, characterized in that that the crosslinkable composition further comprises an aromatic compound comprising at least one aromatic ring and a single reactive function capable of grafting to the polyolefin.

De préférence, la composition réticulable selon le premier objet de l'invention peut comprendre en outre au moins un coagent de réticulation comportant au moins deux fonctions réactives, identiques ou différentes, qui sont aptes d'une part à se greffer à la polyoléfine, et d'autre part à participer à la réticulation de la polyoléfine. De façon particulièrement préférée, l'une de ces deux fonctions réactives peut être une fonction vinylique du type CH2= CH-.Preferably, the crosslinkable composition according to the first subject of the invention may further comprise at least one crosslinking agent comprising at least two identical or different reactive functional groups, which are able on the one hand to be grafted to the polyolefin, and on the other hand to participate in the crosslinking of the polyolefin. In a particularly preferred manner, one of these two reactive functions may be a vinyl function of the CH 2 = CH- type.

La présente invention a pour second objet un câble électrique comprenant un conducteur électrique, une première couche semi-conductrice entourant le conducteur électrique, une deuxième couche électriquement isolante, entourant la première couche, et une troisième couche semi-conductrice entourant la deuxième couche, au moins une de ces trois couches est une couche réticulée obtenue à partir d'une composition réticulable comprenant au moins une polyoléfine, et un peroxyde aliphatique en tant qu'agent de réticulation caractérisé en ce que la composition réticulable comprend en outre au moins un coagent de réticulation comportant au moins deux fonctions réactives, identiques ou différentes, qui sont aptes d'une part à se greffer à la polyoléfine, et d'autre part à participer à la réticulation de la polyoléfine, l'une de ces deux fonctions réactives étant une fonction vinylique du type CH2= CH-.The second subject of the present invention is an electrical cable comprising an electrical conductor, a first semiconductor layer surrounding the electrical conductor, a second electrically insulating layer surrounding the first layer, and a third semiconductor layer surrounding the second layer, on the other side. at least one of these three layers is a crosslinked layer obtained from a crosslinkable composition comprising at least one polyolefin, and an aliphatic peroxide as crosslinking agent, characterized in that the crosslinkable composition further comprises at least one coagent of crosslinking comprising at least two reactive functions, identical or different, which are able on the one hand to graft to the polyolefin, and on the other hand to participate in the crosslinking of the polyolefin, one of these two reactive functions being a vinyl function of the type CH 2 = CH-.

De préférence, la composition réticulable selon le second objet de l'invention peut comprendre en outre un composé aromatique comprenant au moins un noyau aromatique et une unique fonction réactive apte à se greffer à la polyoléfine.Preferably, the crosslinkable composition according to the second subject of the invention may further comprise an aromatic compound comprising at least one aromatic nucleus and a single reactive functional group capable of grafting to the polyolefin.

L'agent de réticulation de l'invention a pour avantage de ne pas former d'alcool cumylique en tant que sous-produit de réticulation lors de la réticulation de la composition réticulable, et ainsi permet de limiter significativement la présence d'eau au sein de la couche réticulée, tout en gardant de très bonnes propriétés thermomécaniques. Les propriétés thermomécaniques pour la couche réticulée selon l'invention peuvent avantageusement se traduire par un allongement maximal à chaud sous contrainte selon la norme NF EN 60811-2-1 d'au plus 100%, de préférence d'au plus 80%, et de façon particulièrement préférée allant de 60 à 80%.The crosslinking agent of the invention has the advantage of not forming cumyl alcohol as a by-product of crosslinking during the crosslinking the crosslinkable composition, and thus significantly reduces the presence of water within the crosslinked layer, while maintaining very good thermomechanical properties. The thermomechanical properties for the crosslinked layer according to the invention can advantageously result in a maximum stress elongation under the standard NF EN 60811-2-1 of at most 100%, preferably at most 80%, and in a particularly preferred manner ranging from 60 to 80%.

En outre, lors de la décomposition du peroxyde aliphatique, la quantité de méthane formée est moins importante que celle formée lors de la décomposition du peroxyde cumylique : la présence de méthane dans les sous-produits de réticulation s'en trouve donc avantageusement diminuée. A propriétés thermomécaniques sensiblement identiques, la quantité de peroxyde aliphatique nécessaire est moins importante que la quantité de peroxyde cumylique.In addition, during the decomposition of the aliphatic peroxide, the amount of methane formed is less than that formed during the decomposition of the cumyl peroxide: the presence of methane in the crosslinking by-products is therefore advantageously reduced. With substantially identical thermomechanical properties, the amount of aliphatic peroxide required is less than the amount of cumyl peroxide.

Le peroxyde aliphatique de l'invention est un peroxyde ne comprenant pas de groupement aromatique. Le peroxyde aliphatique peut être notamment un peroxyde aliphatique comprenant au moins un groupement alkyle tertiaire. Parmi les peroxydes aliphatiques de l'invention, on peut citer :

  • les peroxycarbonates aliphatiques tels que par exemple le tert-amylperoxy 2-ethylhexyl carbonate, le tert-amylperoxy 2-ethylhexyl carbonate, le tert-butylperoxy isopropyl carbonate ;
  • les peroxydes aliphatiques de dialkyle tertiaire tels que par exemple le 1,1-di(tert-butylperoxy)cyclohexane, 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne, 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexane, le di-tert-amyl peroxyde, le di-tert-butyl peroxyde, les peroxydes cycliques tels que le 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxonane ;
  • les peroxyacetals aliphatiques tels que par exemple le butyl 4,4-di(tert-butylperoxy)valerate ; et
  • les peroxyesters aliphatiques tels que par exemple le tert-butyl peroxyacétate, le tert-amyl peroxyacétate.
The aliphatic peroxide of the invention is a peroxide not comprising an aromatic group. The aliphatic peroxide may in particular be an aliphatic peroxide comprising at least one tertiary alkyl group. Among the aliphatic peroxides of the invention, mention may be made of:
  • aliphatic peroxycarbonates such as for example tert-amylperoxy 2-ethylhexyl carbonate, tert-amylperoxy 2-ethylhexyl carbonate, tert-butylperoxy isopropyl carbonate;
  • tertiary dialkyl aliphatic peroxides such as, for example, 1,1-di (tert-butylperoxy) cyclohexane, 2,5-dimethyl-2,5-di (tert-butylperoxy) -3-hexyne, 2,5-dimethyl- 2,5-di (tert-butylperoxy) -3-hexane, di-tert-amyl peroxide, di-tert-butyl peroxide, cyclic peroxides such as 3,6,9-triethyl-3,6,9 trimethyl-1,4,7-triperoxonane;
  • aliphatic peroxyacetals such as butyl 4,4-di (tert-butylperoxy) valerate; and
  • aliphatic peroxyesters such as for example tert-butyl peroxyacetate, tert-amyl peroxyacetate.

Parmi les peroxydes cités, on préférera utiliser les peroxydes aliphatiques de dialkyle tertiaire. Ce type de peroxyde présente un très bon compromis entre vitesse de réticulation et risque de grillage ou de pré-réticulation lors de la mise en oeuvre de la composition.Among the peroxides mentioned, it will be preferred to use tertiary dialkyl aliphatic peroxides. This type of peroxide has a very good compromise between speed of crosslinking and the risk of roasting or pre-crosslinking during the implementation of the composition.

La réticulation par voie peroxyde de la composition réticulable selon l'invention peut être réalisée sous l'action de la chaleur et de pression, par exemple à l'aide d'un tube de vulcanisation sous atmosphère d'azote, cette technique de réticulation étant bien connue de l'homme du métier.The peroxidic crosslinking of the crosslinkable composition according to the invention can be carried out under the action of heat and pressure, for example by means of a vulcanization tube under a nitrogen atmosphere, this crosslinking technique being well known to those skilled in the art.

La composition réticulable de l'invention peut comprendre au plus 3,00 parties en poids de peroxyde aliphatique pour 100 parties en poids de polymère(s) dans la composition ; de préférence 1,50 parties en poids de peroxyde aliphatique pour 100 parties en poids de polymère(s) dans la composition ; de préférence 1,25 parties en poids de peroxyde aliphatique pour 100 parties en poids de polymère(s) dans la composition ; et de façon particulièrement préférée 1,10 parties en poids de peroxyde aliphatique pour 100 parties en poids de polymère(s) dans la composition.The crosslinkable composition of the invention may comprise at most 3.00 parts by weight of aliphatic peroxide per 100 parts by weight of polymer (s) in the composition; preferably 1.50 parts by weight of aliphatic peroxide per 100 parts by weight of polymer (s) in the composition; preferably 1.25 parts by weight of aliphatic peroxide per 100 parts by weight of polymer (s) in the composition; and particularly preferably 1.10 parts by weight of aliphatic peroxide per 100 parts by weight of polymer (s) in the composition.

De préférence, la composition réticulable ne comprend aucun peroxyde aromatique, tel que notamment des peroxydes de dicumyl ou leurs dérivés.Preferably, the crosslinkable composition does not comprise any aromatic peroxide, such as in particular dicumyl peroxides or their derivatives.

Le terme « polyoléfine » en tant que tel signifie de façon générale homopolymère ou copolymère d'oléfine. Il peut notamment désigner un polymère thermoplastique ou un élastomère.The term "polyolefin" as such generally means homopolymer or copolymer of olefin. It may in particular designate a thermoplastic polymer or an elastomer.

De préférence, le polymère d'oléfine est un homopolymère d'éthylène ou un copolymère d'éthylène.Preferably, the olefin polymer is an ethylene homopolymer or an ethylene copolymer.

A titre d'exemple de polymères d'éthylène, on peut citer le polyéthylène linéaire basse densité (LLDPE), le polyéthylène basse densité (LDPE), le polyéthylène moyenne densité (MDPE), le polyéthylène haute densité (HDPE), les copolymères d'éthylène et d'acétate de vinyle (EVA), les copolymères d'éthylène et d'acrylate de butyle (EBA), d'acrylate de méthyle (EMA), de 2-hexyléthyl acrylate (2HEA), les copolymères d'éthylène et d'alpha-oléfines tels que par exemple les polyéthylène-octène (PEO), les polyéthylène-butène (PEB), les copolymères d'éthylène et de propylène (EPR) tels que par exemple les terpolymères d'éthylène propylène diène (EPDM), et leurs mélanges.By way of example of ethylene polymers, mention may be made of linear low density polyethylene (LLDPE), low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), copolymers of d ethylene and vinyl acetate (EVA), copolymers of ethylene and butyl acrylate (EBA), methyl acrylate (EMA), 2-hexylethyl acrylate (2HEA), copolymers of ethylene and alpha-olefins such as for example polyethylene-octene (PEO), polyethylene-butene (PEB), copolymers of ethylene and propylene (EPR) such as for example terpolymers of ethylene propylene diene (EPDM), and mixtures thereof.

On préférera utiliser un polyéthylène basse densité (LDPE) puisqu'il présente de bonnes propriétés rhéologiques pour sa mise en oeuvre, notamment par extrusion, et de très bonnes propriétés thermomécaniques et électriques.It will be preferred to use a low density polyethylene (LDPE) since it has good rheological properties for its implementation, in particular by extrusion, and very good thermomechanical and electrical properties.

On entend par « basse densité » une densité pouvant aller notamment de 0,910 à 0,940 g/cm3, et de préférence pouvant aller de 0,910 à 0,930 g/cm3 selon la norme ISO 1183 (à une température de 23°C).The term "low density" a density that can range from 0.910 to 0.940 g / cm 3 , and preferably ranging from 0.910 to 0.930 g / cm 3 according to ISO 1183 (at a temperature of 23 ° C).

Typiquement, le polyéthylène basse densité (LDPE) peut être obtenu par un procédé de polymérisation dans un réacteur tubulaire à haute pression, ou dans un réacteur autoclave.Typically, low density polyethylene (LDPE) can be obtained by a polymerization process in a high pressure tubular reactor, or in an autoclave reactor.

La composition réticulable peut comprendre plus de 50,0 parties en poids de polyoléfine pour 100 parties en poids de polymère(s) (i.e. matrice polymère) dans la composition, de préférence au moins 70 parties en poids de polyoléfine pour 100 parties en poids de polymère(s) dans ladite composition, et de façon particulièrement préférée au moins 90 parties en poids de polyoléfine pour 100 parties en poids de polymère(s) dans ladite composition.The crosslinkable composition may comprise more than 50.0 parts by weight of polyolefin per 100 parts by weight of polymer (s) (ie polymer matrix) in the composition, preferably at least 70 parts by weight of polyolefin per 100 parts by weight of polymer (s) in said composition, and particularly preferably at least 90 parts by weight of polyolefin per 100 parts by weight of polymer (s) in said composition.

De façon particulièrement avantageuse, la composition réticulable comprend une matrice polymère qui n'est composé uniquement que d'une polyoléfine ou d'un mélange de polyoléfines.Particularly advantageously, the crosslinkable composition comprises a polymer matrix which is composed solely of a polyolefin or a mixture of polyolefins.

Lorsque la composition réticulable de l'invention comprend en outre au moins un coagent de réticulation de type mutifonctionnel, ce coagent de réticulation peut comprendre au moins deux fonctions réactives, identiques ou différentes, qui sont aptes d'une part à se greffer à la polyoléfine, et d'autre part à participer à la réticulation de la polyoléfine (i.e. à la formation du réseau tridimensionnel de la polyoléfine réticulée), en présence du peroxyde aliphatique de l'invention.When the crosslinkable composition of the invention further comprises at least one crosslinking coagent of mutifunctional type, this crosslinking agent may comprise at least two reactive functions, identical or different, which are able on the one hand to be grafted to the polyolefin and, secondly, to participate in the crosslinking of the polyolefin (ie in the formation of the three-dimensional network of the crosslinked polyolefin), in the presence of the aliphatic peroxide of the invention.

De préférence, lesdites au moins deux fonctions réactives du coagent de réticulation sont des fonctions insaturées.Preferably, said at least two reactive functions of the crosslinking agent are unsaturated functions.

De façon particulièrement préférée, l'une au moins desdites fonctions réactives est une fonction vinylique, notamment une fonction éthylénique du type CH2=CH-.In a particularly preferred manner, at least one of said reactive functional groups is a vinyl function, in particular an ethylenic function of the CH 2 = CH- type.

De façon encore plus préférée, lesdites deux fonctions réactives sont des fonctions vinyliques, notamment des fonctions éthyléniques du type CH2=CH-.Even more preferably, said two reactive functions are vinyl functional groups, in particular ethylenic functions of the CH 2 = CH- type.

Le coagent de réticulation permet notamment de réduire de manière significative la proportion de peroxyde à utiliser dans la composition réticulable, tout en maintenant de bonnes propriétés thermomécaniques telles que le fluage à chaud, ainsi qu'une vitesse de réticulation satisfaisante.The crosslinking coagent notably makes it possible to significantly reduce the proportion of peroxide to be used in the crosslinkable composition, while maintaining good thermomechanical properties such as hot creep, as well as a satisfactory crosslinking rate.

De préférence, on utilisera un coagent dont la température d'ébullition est suffisamment élevée de sorte qu'il ne se volatilise pas lors de l'étape de mise en oeuvre de la composition réticulable, notamment par extrusion.Preferably, a coagent whose boiling temperature is sufficiently high so that it does not volatilize during the stage of implementation of the crosslinkable composition, in particular by extrusion, will be used.

A titre d'exemple, le coagent de réticulation peut être choisi parmi le 1,3-hexadiene ; 1,4-hexadiene ; 1,5-hexadiene ; 2,3-dimethyl-1,3-butadiene ; 2,4-hexadiene ; 2-methyl-1,4-pentadiene ; 3-methyl-1,3-pentadiene ; 3-methyl-1,3-pentadiene ; 1,6-heptadiene ; 2,4-dimethyl-1,3-pentadiene ; 2-methyl-1,5-hexadiene ; 4-vinyl-1-cyclohexene ; 1,7-octadiene ; 2,5-dimethyl-1,5-hexadiene ; 2,5-dimethyl-2,4-hexadiene ; 5-ethylidene-2-norbornene ; 5 vinyl-2 norbornene ; 1,8-nonadiene ; 7-methyl-1,6-octadiene ; 1,5,9-decatriene ; 2,6-Dimethyl-2,4,6-octatriene ; Dipentene ; 7-Methyl-3-methylene-1,6-octadiene ; 1,9-Decadiene ; 3,9-Divinyl-2,4,8,10-tetraoxaspiro[5.5]undecane ; 1,2,4-Trivinylcyclohexane ; 1,13-Tetradecadiene ; 2,3-Diphenyl-1,3-butadiene ; trans,trans-1,4-Diphenyl-1,3-butadiene ; 1,15-Hexadecadiene ; 1,6-Diphenyl-1,3,5-hexatriene ; 2,3-Dibenzyl-1,3-butadiene ; et polybutadiène ; ou un de leurs mélanges.By way of example, the crosslinking agent may be chosen from 1,3-hexadiene; 1,4-hexadiene; 1,5-hexadiene; 2,3-dimethyl-1,3-butadiene; 2,4-hexadiene; 2-methyl-1,4-pentadiene; 3-methyl-1,3-pentadiene; 3-methyl-1,3-pentadiene; 1,6-heptadiene; 2,4-dimethyl-1,3-pentadiene; 2-methyl-1,5-hexadiene; 4-vinyl-1-cyclohexene; 1,7-octadiene; 2,5-dimethyl-1,5-hexadiene; 2,5-dimethyl-2,4-hexadiene; 5-ethylidene-2-norbornene; Vinyl-2 norbornene; 1,8-nonadiene; 7-methyl-1,6-octadiene; 1,5,9-decatriene; 2,6-Dimethyl-2,4,6-octatriene; Dipentene; 7-Methyl-3-methylene-1,6-octadiene; 1,9-Decadiene; 3,9-Divinyl-2,4,8,10-tetraoxaspiro [5.5] undecane; 1,2,4-Trivinylcyclohexane; 1,13-Tetradecadiene; 2,3-Diphenyl-1,3-butadiene; trans, trans-1,4-diphenyl-1,3-butadiene; 1,15-Hexadecadiene; 1,6-diphenyl-1,3,5-hexatriene; 2,3-Dibenzyl-1,3-butadiene; and polybutadiene; or a mixture thereof.

La concentration du coagent est de préférence limitée de telle façon à ne pas perturber le processus d'extrusion de la composition réticulable de l'invention. Par exemple, la composition réticulable pourra comprendre au plus 3 parties en poids de coagent de réticulation pour 100 parties de polymère(s) dans la composition réticulable. On préférera utiliser de 0,5 à 2 parties en poids de coagent pour 100 parties en poids de polymère(s) dans la composition réticulable.The concentration of the coagent is preferably limited so as not to disturb the extrusion process of the crosslinkable composition of the invention. For example, the crosslinkable composition may comprise at most 3 parts by weight of crosslinking agent per 100 parts of polymer (s) in the crosslinkable composition. It will be preferred to use from 0.5 to 2 parts coagent weight per 100 parts by weight of polymer (s) in the crosslinkable composition.

Lorsque la composition réticulable de l'invention comprend en outre un composé aromatique comprenant au moins un noyau aromatique, et une unique fonction réactive apte à se greffer à la polyoléfine, ladite fonction réactive du composé aromatique peut être une fonction vinylique. De ce fait, ce composé aromatique ne participe pas à la réticulation de la polyoléfine, contrairement au coagent de réticulation, lorsqu'il est présent dans la composition réticulable.When the crosslinkable composition of the invention further comprises an aromatic compound comprising at least one aromatic ring, and a single reactive function capable of grafting to the polyolefin, said reactive function of the aromatic compound may be a vinyl function. As a result, this aromatic compound does not participate in the crosslinking of the polyolefin, unlike the crosslinking coagent, when it is present in the crosslinkable composition.

La couche réticulée obtenue à partir de cette composition réticulable présente des propriétés renforcées et durables dans le domaine des câbles électriques, en offrant une meilleure résistance aux arborescences d'eau. Plus particulièrement, cela concerne la tenue au claquage électrique, et notamment la capacité à dissiper les charges d'espace qui s'accumulent notamment dans les câbles hautes tension sous courant continu.The crosslinked layer obtained from this crosslinkable composition has enhanced and durable properties in the field of electric cables, offering better resistance to water trees. More particularly, this relates to the resistance to electrical breakdown, and in particular the ability to dissipate the space charges that accumulate especially in high voltage cables under direct current.

Le composé aromatique peut être choisi parmi le styrène, les dérivés du styrène, et leurs isomères.The aromatic compound may be selected from styrene, styrene derivatives, and their isomers.

A titre d'exemple de dérivés du styrène, on peut citer les composés de formule générale suivante :

Figure imgb0001
dans laquelle X est un hydrogène, un groupement alkyle ou un groupement aryle ; et R est soit un hydrogène, un groupement alkyle ou un groupement aryle. Plus particulièrement, on peut citer le 4-methyl-2,4-diphenyl pentene, et le triphenyl éthylène.By way of example of styrene derivatives, mention may be made of the compounds of the following general formula:
Figure imgb0001
 wherein X is hydrogen, an alkyl group or an aryl group; and R is either a hydrogen, an alkyl group or an aryl group. More particularly, mention may be made of 4-methyl-2,4-diphenyl pentene and triphenyl ethylene.

Dans le cadre de la présente invention, on peut également considérer les dérivés du styrène du type hydrocarbure aromatique polycyclique (HAP). Plus particulièrement, on peut citer les vinyl naphthalene comme par exemple le 2-vinyl naphtalene ; les vinyl anthracene comme par exemple le 9-vinyl anthracene ou le 2- vinyl anthracene ; et les vinyl phenanthrene comme par exemple le 9-vinyl phenanthrene.In the context of the present invention, it is also possible to consider the styrene derivatives of the polycyclic aromatic hydrocarbon (PAH) type. More particularly, mention may be made of vinyl naphthalene, for example 2-vinyl naphthalene; vinyl anthracene such as 9-vinyl anthracene or 2-vinyl anthracene; and vinyl phenanthrene such as 9-vinyl phenanthrene.

Le greffage de ces composés aromatiques sur la chaine polymère de la polyoléfine est typiquement réalisé lors de la phase de réticulation de la polyoléfine, selon un mécanisme d'addition radicalaire bien connu de l'homme du métier, en présence du peroxyde d'alkyle tertiaire aliphatique de l'invention.The grafting of these aromatic compounds onto the polymer chain of the polyolefin is typically carried out during the crosslinking phase of the polyolefin, according to a radical addition mechanism well known to those skilled in the art, in the presence of tertiary alkylperoxide. aliphatic of the invention.

La composition réticulable selon l'invention peut comprendre en outre au moins un agent de protection tel qu'un antioxydant. Les antioxydants permettent de protéger la composition des contraintes thermiques engendrées lors des étapes de fabrication du câble ou de fonctionnement du câble.The crosslinkable composition according to the invention may further comprise at least one protective agent such as an antioxidant. Antioxidants help to protect the composition of thermal stresses generated during the cable manufacturing or cable operation steps.

Les antioxydants sont choisis de préférence parmi :

  • les antioxydants phénoliques à encombrement stérique tels que le tetrakismethylene(3,5-di-t-butyl-4-hydroxy-hydrocinnamate) méthane, le octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, le 2,2'-thiodiethylene bis[3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate], le 2,2'-Thiobis(6-t-butyl-4-methylphenol), le 2,2'-methylenebis(6-t-butyl-4-methylphenol), le 1,2-Bis(3,5-di-t-butyl-4-hydroxyhydrocinnamoyl)hydrazine, le [2,2'-oxamido-bis(ethyl 3(3,5-di-t-butyl-4-hydroxyphenyl)propionate), et le 2,2'-oxamido-bis[ethyl 3-(t-butyl-4-hydroxyphenyl)propionate] ;
  • les thioethers tels que le 4,6-bis(octylthiomethyl)-o-cresol, le Bis[2-methyl-4-{3-n-alkyl (C12 ou C14)thiopropionyloxy}-5-t-butylphenyl]sulfide et le Thiobis-[2-t-butyl-5-methyl-4,1-phenylene] bis [3-(dodecyltio)propionate] ;
  • les antioxydants à base de soufre tels que le Dioctadecyl-3,3'-thiodipropionate ou le Didodecyl-3,3'-thiodipropionate ;
  • les antioxydants à base de phosphore tels que les phosphites ou phosphonates comme par exemple le Tris(2,4-di-t-butyl-phenyl)phosphite ou le Bis(2,4-di-t-butylphenyl) pentaerythritol diphosphite ; et
  • les antioxydants de type amine tels que le 2,2,4-trimethyl-1,2 dihydroquinoline polymérisé (TMQ), ce dernier type d'antioxydant étant particulièrement préféré dans la composition de l'invention.
The antioxidants are preferably chosen from:
  • hindered phenolic antioxidants such as tetrakismethylene (3,5-di- t- butyl-4-hydroxy-hydrocinnamate) methane, octadecyl 3- (3,5-di- t- butyl-4-hydroxyphenyl) propionate, 2,2'-thiodiethylene bis [3- (3,5-di- t- butyl-4-hydroxyphenyl) propionate], 2,2'-thiobis (6- t -butyl-4-methylphenol), 2 2'-methylenebis (6-t-butyl-4-methylphenol), 1,2-bis (3,5-di-t-butyl-4-hydroxyhydrocinnamoyl) hydrazine, [2,2'-oxamido-bis] (ethyl 3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate), and 2,2'-oxamido-bis [ethyl 3- (t-butyl-4-hydroxyphenyl) propionate];
  • thioethers such as 4,6-bis (octylthiomethyl) -o-cresol, bis [2-methyl-4- {3-n-alkyl (C 12 or C 14) thiopropionyloxy} -5- t- butylphenyl] sulfide and the Thiobis- [2- t -butyl-5-methyl-4,1-phenylene] bis [3- (dodecylthio) propionate];
  • sulfur-based antioxidants such as Dioctadecyl-3,3'-thiodipropionate or Didodecyl-3,3'-thiodipropionate;
  • phosphorus-based antioxidants such as phosphites or phosphonates such as, for example, Tris (2,4-di- t- butyl-phenyl) phosphite or bis (2,4-di- t- butylphenyl) pentaerythritol diphosphite; and
  • amine antioxidants such as polymerized 2,2,4-trimethyl-1,2 dihydroquinoline (TMQ), the latter type of antioxidant being particularly preferred in the composition of the invention.

Les TMQ peuvent avoir différents grades, à savoir :

  • un grade dit « standard » avec un faible degré de polymérisation, c'est-à-dire avec un taux de monomère résiduel supérieur à 1% en poids et ayant une teneur en NaCl résiduelle pouvant aller de 100 ppm à plus de 800 ppm (parties par million massiques) ;
  • un grade dit « à haut degré de polymérisation » avec un haut degré de polymérisation, c'est-à-dire avec un taux de monomère résiduel inférieur à 1% en poids et ayant une teneur en NaCl résiduelle pouvant aller de 100 ppm à plus de 800 ppm ;
  • un grade dit « à faible teneur en sel résiduel » avec une teneur en NaCl résiduelle inférieure à 100 ppm.
TMQs can have different grades, namely:
  • a so-called "standard" grade with a low degree of polymerization, that is to say with a residual monomer level greater than 1% by weight and having a residual NaCl content ranging from 100 ppm to more than 800 ppm ( parts per million mass);
  • a so-called "high degree of polymerization" grade with a high degree of polymerization, that is to say with a residual monomer content of less than 1% by weight and having a residual NaCl content ranging from 100 ppm to more 800 ppm;
  • a so-called "low residual salt" grade with a residual NaCl content of less than 100 ppm.

Le type de stabilisant et son taux dans la composition réticulable sont classiquement choisis en fonction de la température maximale subie par les polymères pendant la production du mélange et pendant la mise en oeuvre par extrusion sur le câble ainsi que selon la durée maximale d'exposition à cette température.The type of stabilizer and its level in the crosslinkable composition are conventionally chosen according to the maximum temperature experienced by the polymers during the production of the mixture and during the implementation by extrusion on the cable as well as according to the maximum duration of exposure to this temperature.

La composition réticulable peut typiquement comprendre de 0,1% à 2% en poids d'antioxydant(s). De préférence, elle peut comprendre au plus 0,7% en poids d'antioxydant(s) notamment lorsque l'antioxydant est le TMQ.The crosslinkable composition may typically comprise from 0.1% to 2% by weight of antioxidant (s). Preferably, it may comprise at most 0.7% by weight of antioxidant (s), especially when the antioxidant is TMQ.

D'autres additifs et/ou d'autres charges bien connus de l'homme du métier peuvent également être ajoutés à la composition réticulable de l'invention tels que des retardateurs de grillage ; des agents favorisants la mise en oeuvre tels que des lubrifiants ou des cires ; des agents compatibilisants ; des agents de couplage ; des stabilisants UV ; des charges non-conductrices ; des charges conductrices ; et/ou des charges semi-conductrices.Other additives and / or other fillers well known to those skilled in the art may also be added to the crosslinkable composition of the invention such as scorch retarders; agents promoting implementation such as lubricants or waxes; compatibilizing agents; coupling agents; UV stabilizers; non-conductive charges; conductive charges; and / or semiconductor charges.

Selon un mode de réalisation préféré, la couche réticulée de l'invention est la couche électriquement isolante (i.e. deuxième couche). Dans le cas de la couche électriquement isolante, la composition réticulable peut ne pas comprendre de charge (électriquement) conductrice et/ou peut ne pas comprendre de charge semi-conductrice.According to a preferred embodiment, the crosslinked layer of the invention is the electrically insulating layer (ie second layer). In the case of the electrically insulating layer, the crosslinkable composition may not comprise an (electrically) conductive filler and / or may not comprise a semiconductor filler.

Plus particulièrement, au moins deux des trois couches du câble sont des couches réticulées, et de préférence les trois couches du câble sont des couches réticulées.More particularly, at least two of the three layers of the cable are crosslinked layers, and preferably the three layers of the cable are crosslinked layers.

Lorsque la composition réticulable est utilisée pour la fabrication des couches semi-conductrices (première couche et/ou troisième couche), la composition réticulable comprend en outre au moins une charge (électriquement) conductrice ou une charge semi-conductrice, en une quantité suffisante pour rendre la composition réticulable semi-conductrice.When the crosslinkable composition is used for the manufacture of the semiconductor layers (first layer and / or third layer), the crosslinkable composition further comprises at least one (electrically) conductive filler or a semiconductor filler, in an amount sufficient to to make the composition crosslinkable semiconductor.

On considère plus particulièrement qu'une couche est semi-conductrice lorsque sa conductivité électrique est d'au moins 0,001 S.m-1 (siemens par mètre).It is more particularly considered that a layer is semiconductive when its electrical conductivity is at least 0.001 Sm -1 (Siemens per meter).

La composition réticulable utilisée pour obtenir une couche semi-conductrice peut comprendre de 0,1 à 40% en poids de charge (électriquement) conductrice, de préférence au moins 15% en poids de charge conductrice, et encore plus préférentiellement au moins 25% en poids de charge conductrice.The crosslinkable composition used to obtain a semiconductor layer may comprise from 0.1 to 40% by weight of (electrically) conductive filler, preferably at least 15% by weight of conductive filler, and even more preferably at least 25% by weight. conductive charge weight.

La charge semi-conductrice peut être choisie avantageusement parmi les noirs de carbone, les nanotubes de carbone, et les graphites, ou un de leurs mélanges.The semiconductor filler may advantageously be chosen from carbon blacks, carbon nanotubes, and graphites, or a mixture thereof.

Que ce soient la première couche semi-conductrice, la deuxième couche électriquement isolante et/ou la troisième couche semi-conductrice, au moins une de ces trois couches est une couche extrudée, de préférence deux de ces trois couches sont des couches extrudées, et encore plus préférentiellement ces trois couches sont des couches extrudées.Whether it is the first semiconductor layer, the second electrically insulating layer and / or the third semiconductor layer, at least one of these three layers is an extruded layer, preferably two of these three layers are extruded layers, and more preferably, these three layers are extruded layers.

Dans un mode de réalisation particulier, généralement conforme au câble électrique bien connu dans le domaine d'application de l'invention, la première couche semi-conductrice, la deuxième couche électriquement isolante et la troisième couche semi-conductrice constituent une isolation tricouche. En d'autres termes, la deuxième couche électriquement isolante est directement en contact physique avec la première couche semi-conductrice, et la troisième couche semi-conductrice est directement en contact physique avec la deuxième couche électriquement isolante.In a particular embodiment, generally in accordance with the electrical cable well known in the field of application of the invention, the first semiconductor layer, the second electrically insulating layer and the third semiconductor layer constitute a three-layer insulation. In other words, the second electrically insulating layer is directly in physical contact with the first semiconductor layer, and the third semiconductor layer is directly in physical contact with the second electrically insulating layer.

Le câble électrique de l'invention peut comprendre en outre un écran métallique entourant la troisième couche semi-conductrice.The electrical cable of the invention may further comprise a metal screen surrounding the third semiconductor layer.

Cet écran métallique peut être un écran dit « filaire », composé d'un ensemble de conducteurs en cuivre ou aluminium arrangé autour et le long de la troisième couche semi-conductrice, un écran dit « rubané » composé d'un ou de plusieurs rubans métalliques conducteurs posé(s) en hélice autour de la troisième couche semi-conductrice, ou d'un écran dit « étanche » de type tube métallique entourant la troisième couche semi-conductrice. Ce dernier type d'écran permet notamment de faire barrière à l'humidité ayant tendance à pénétrer le câble électrique en direction radiale.This metal screen may be a "wired" screen, consisting of a set of copper or aluminum conductors arranged around and along the third semiconductor layer, a so-called "ribbon" screen composed of one or more ribbons conductive metal laid helically around the third semiconductor layer, or a so-called "sealed" type metal screen surrounding the third semiconductor layer. This last type of screen makes it possible in particular to provide a moisture barrier that tends to penetrate the electrical cable radially.

Tous les types d'écran métalliques peuvent jouer le rôle de mise à la terre du câble électrique et peuvent ainsi transporter des courants de défaut, par exemple en cas de court-circuit dans le réseau concerné.All types of metal screens can act as grounding of the electric cable and can carry fault currents, for example in the event of a short circuit in the network concerned.

En outre, le câble électrique de l'invention peut comprendre une gaine extérieure de protection entourant la troisième couche semi-conductrice, ou bien entourant plus particulièrement ledit écran métallique lorsqu'il existe. Cette gaine extérieure de protection peut être réalisée classiquement à partir de matériaux thermoplastiques appropriées tels que des HDPE, des MDPE ou des LLDPE ; ou encore des matériaux retardant la propagation de la flamme ou résistant à la propagation de l'incendie. Notamment, si ces derniers matériaux ne contiennent pas d'halogène, on parle de gainage de type HFFR (pour l'anglicisme « Halogen Free Flame Retardant »). In addition, the electrical cable of the invention may comprise an outer protective sheath surrounding the third semiconductor layer, or more particularly surrounding said metal screen when it exists. This outer protective sheath can be made conventionally from suitable thermoplastic materials such as HDPE, MDPE or LLDPE; or materials retarding the propagation of the flame or resisting the spread of fire. In particular, if the latter materials do not contain halogen, it is called cladding type HFFR (for the Anglicism " Halogen Free Flame Retardant").

D'autres couches, telles que des couches gonflantes en présence d'humidité, peuvent être ajoutées entre la troisième couche semi-conductrice et l'écran métallique lorsqu'il existe, et/ou entre l'écran métallique et la gaine extérieure lorsqu'ils existent, ces couches permettant d'assurer l'étanchéité longitudinale et/ou transversale du câble électrique à l'eau. Le conducteur électrique du câble de l'invention peut également comprendre des matières gonflantes en présence d'humidité pour obtenir une « âme étanche ».Other layers, such as swelling layers in the presence of moisture, may be added between the third semiconductor layer and the metal screen when it exists, and / or between the metal screen and the outer sheath when they exist, these layers making it possible to ensure the longitudinal and / or transverse sealing of the electric cable with water. The electrical conductor of the cable of the invention may also comprise swelling materials in the presence of moisture to obtain a "sealed core".

D'autres caractéristiques et avantages de la présente invention apparaîtront à la lumière de la description d'un exemple non limitatif d'un câble électrique selon l'invention fait en référence à la figure 1 représentant une vue schématique en perspective et en coupe d'un câble électrique selon un mode de réalisation préféré conforme à l'invention.Other characteristics and advantages of the present invention will appear in the light of the description of a non-limiting example of an electric cable according to the invention made with reference to the figure 1 representative a schematic view in perspective and in section of an electric cable according to a preferred embodiment according to the invention.

Pour des raisons de clarté, seuls les éléments essentiels pour la compréhension de l'invention ont été représentés de manière schématique, et ceci sans respect de l'échelle.For the sake of clarity, only the essential elements for understanding the invention have been shown schematically, and this without respect of the scale.

Le câble d'énergie 1 à moyenne ou haute tension, illustré dans la figure 1, comprend un élément conducteur 2 central allongé, notamment en cuivre ou en aluminium. Successivement et coaxialement autour de cet élément conducteur 2, le câble d'énergie 1 comprend en outre une première couche 3 semi-conductrice dite « couche semi-conductrice interne », une deuxième couche 4 électriquement isolante, une troisième couche 5 semi-conductrice dite « couche semi-conductrice externe », un écran métallique 6 de mise à la terre et/ou de protection, et une gaine extérieure de protection 7, les couches 3, 4 et 5 pouvant être obtenues à partir d'une composition selon l'invention. Les couches 3, 4 et 5 sont des couches extrudées et réticulées.Medium or high voltage power cable 1, shown in FIG. figure 1 comprises an elongate central conductive element 2, in particular made of copper or aluminum. Successively and coaxially around this conductive element 2, the energy cable 1 further comprises a first semiconductor layer 3 called "internal semiconductor layer", a second electrically insulating layer 4, a third so-called semiconductor layer 5 "External semiconductor layer", a metal screen 6 for grounding and / or protection, and an outer protective sheath 7, the layers 3, 4 and 5 being obtainable from a composition according to invention. Layers 3, 4 and 5 are extruded and crosslinked layers.

La présence de l'écran métallique 6 et de la gaine extérieure de protection 7 est préférentielle, mais non essentielle, cette structure de câble étant en tant que telle bien connue de l'homme du métier.The presence of the metal screen 6 and the outer protective sheath 7 is preferred, but not essential, this cable structure being as such well known to those skilled in the art.

ExemplesExamples Préparation de compositions réticulablesPreparation of crosslinkable compositions

Tableau 1Table 1 Composition réticulableCrosslinkable composition C1C1 C2C2 C3C3 C4C4 Polyoléfinepolyolefin 100100 100100 100100 100100 BCPBCP 1,421.42 -- 1,271.27 -- DTBHDTBH -- 1,251.25 -- 1,051.05 Antioxydantsantioxidants 0,180.18 0,180.18 0,180.18 0,180.18 TVCHTVCH -- -- 1,001.00 1,001.00

Dans le tableau 1, les compositions C1 et C3 font références à des exemples comparatifs, tandis que les compositions C2 et C4 font références à des compositions selon l'invention.In Table 1, compositions C1 and C3 refer to comparative examples, while compositions C2 and C4 refer to compositions according to the invention.

Les quantités des constituants des compositions C1 à C4, détaillées dans le tableau 1, sont exprimées en parties en poids (pcr) pour 100 parties en poids de polymère dans la composition réticulable.The amounts of the components of the compositions C1 to C4, detailed in Table 1, are expressed in parts by weight (phr) per 100 parts by weight of polymer in the crosslinkable composition.

L'origine des différents constituants des compositions C1 à C4 du tableau 1 est détaillées come suit :

  • « Polyoléfine » est un polyéthylène basse densité commercialisé par la société Inéos sous la référence BPD 2000 ;
  • « BCP » est le peroxyde de tert-butyl cumyl, commercialisé par la société Arkema sous la référence Luperox 801 ;
  • « DTBH » est le 1,1-di(tert-butylperoxy) cyclohexane (peroxyde aliphatique de dialkyle tertiaire), commercialisé par la société Arkema sous la référence Luperox 101 ; et
  • « TVCH » est le coagent de réticulation 1,2,4-trivinylcylclohexane, commercialisé par la société BASF sous la référence TVCH.
The origin of the various constituents of compositions C1 to C4 of Table 1 is detailed as follows:
  • "Polyolefin" is a low density polyethylene sold by Inéos under the reference BPD 2000;
  • "BCP" is tert-butyl cumyl peroxide, sold by Arkema under the reference Luperox 801;
  • "DTBH" is 1,1-di (tert-butylperoxy) cyclohexane (tertiary dialkyl aliphatic peroxide), sold by Arkema under the reference Luperox 101; and
  • "TVCH" is 1,2,4-trivinylcyclohexane crosslinking coagent, marketed by BASF under the reference TVCH.

Les compositions C1 à C4 sont préparées en mélangeant les granulés de polyéthylène et les additifs tels que le peroxyde, les antioxydants, et optionnellement le coagent, dans un bocal fermé placé sur un mélangeur à rouleau pendant 3 heures, afin de bien imprégner les granulés de polyéthylène. Les granulés de polyéthylène ont été préchauffés à 60°C avant imprégnation.Compositions C1 to C4 are prepared by mixing the polyethylene granules and additives such as peroxide, antioxidants, and optionally the coagent, in a closed jar placed on a roller mixer for 3 hours to thoroughly impregnate the granules. polyethylene. The polyethylene granules were preheated to 60 ° C before impregnation.

Ensuite, le mélange a été placé à 40°C pendant 16 heures, avant d'être stockés hermétiquement.Then, the mixture was placed at 40 ° C for 16 hours, before being stored tightly.

Caractérisations des compositionsCharacterizations of the compositions Caractérisations sur plaque non réticuléeCharacterizations on non-crosslinked plate ● Cinétique et niveau de réticulation ● Kinetics and crosslinking level

Le rhéomètre MDR (Moving Die Rheometer, Alpha Technologies) permet de suivre la réticulation/vulcanisation d'un matériau par mesure de l'évolution de sa viscosité (DIN 53529 (1983)).The MDR rheometer (Moving Die Rheometer, Alpha Technologies) makes it possible to follow the crosslinking / vulcanization of a material by measuring the evolution of its viscosity (DIN 53529 (1983)).

La chambre qui renferme l'échantillon est constituée de deux plateaux chauffants. Le plateau inférieur applique une oscillation de fréquence constante (100 cycles/mn, soit 1,67Hz) et d'amplitude ± 0,5° d'arc ; le plateau supérieur mesure la réponse du matériau, c'est à dire sa résistance à la contrainte appliquée. L'unité de mesure est celle d'un couple, exprimée en dN.m.The chamber containing the sample consists of two heating trays. The lower plate applies a constant oscillation frequency (100 cycles / min, 1.67Hz) and amplitude ± 0.5 ° arc; the upper plate measures the response of the material, ie its resistance to the stress applied. The unit of measure is that of a pair, expressed in dN.m.

L'échantillon est préparé à partir des granulés de polyéthylène imprégnés, moulés sous presse hydraulique en une plaque de 3mm d'épaisseur à la température de 120°C, suivant un cycle de 2mn sans pression suivit de 3mn sous une pression de 100 bars, avant d'être refroidit.The sample is prepared from the impregnated polyethylene granules, molded in a hydraulic press into a plate 3 mm thick at a temperature of 120 ° C., following a cycle of 2 minutes without pressure followed by 3 minutes under a pressure of 100 bars. before being cooled.

Deux rondelles de 35 mm de diamètre permettant de garnir complètement la chambre, sont découpées dans la plaque à l'aide d'un emporte-pièce, puis placées entre deux feuilles de polyester terphane®, pour être positionnées dans la chambre du rhéomètre.Two washers 35 mm in diameter to completely fill the chamber, are cut in the plate with a punch, then placed between two sheets of terphane polyester ® , to be positioned in the rheometer chamber.

La mesure est faite à la température de 190°C, représentative des conditions de vulcanisation en tube. Après une chute initiale du couple due à la fusion préalable du matériau, la viscosité du matériau et le couple qui en résulte augmentent, signe que la réticulation a lieu.The measurement is made at a temperature of 190 ° C., representative of the tube vulcanization conditions. After an initial torque drop due to the prior melting of the material, the viscosity of the material and the resulting torque increase, sign that the crosslinking takes place.

Un paramètre d'intérêt est le MH qui correspond au couple maximum mesuré. Celui-ci est une valeur de plateau, obtenu lorsque la totalité du système a réagit et que le niveau de réticulation maximum accessible est atteint. Pour un matériau donné, on note une bonne corrélation entre MH et densité de réticulation qui gouvernent les propriétés thermomécaniques après l'étape de réticulation.A parameter of interest is the MH which corresponds to the maximum measured torque. This is a plateau value, obtained when the entire system has reacted and the maximum accessible crosslinking level is reached. For a given material, there is a good correlation between MH and crosslinking density that govern the thermomechanical properties after the crosslinking step.

● Temps de grillage ● Toasting time

Le viscosimètre Mooney (Monsanto MV2000) permet de mesurer la viscosité d'un matériau, ou dans le cas de matériaux réticulables, d'en suivre l'évolution dans le temps (norme ASTM D1646 (2005)).The Mooney viscometer (Monsanto MV2000) is used to measure the viscosity of a material, or in the case of crosslinkable materials, to monitor its evolution over time (ASTM D1646 (2005)).

Il se compose de deux mâchoires formant une cavité cylindrique dans laquelle est placé l'échantillon à tester. La chambre présente en son centre un disque métallique qui est mis en rotation à la vitesse constante de 2 tr/mn. Dans notre cas, des deux rotors normalisés disponibles, c'est le « grand » qui est utilisé.It consists of two jaws forming a cylindrical cavity in which is placed the sample to be tested. The chamber has in its center a metal disk which is rotated at a constant speed of 2 rpm. In our case, of the two standard rotors available, the "big" is used.

Pendant la mesure, les mâchoires et la chambre sont maintenues sous pression et à la température de 130°C.During the measurement, the jaws and the chamber are maintained under pressure and at a temperature of 130 ° C.

L'échantillon est préparé à partir des granulés de polyéthylène imprégnés, moulés sous presse hydraulique en une plaque de 3mm d'épaisseur à la température de 120°C, suivant un cycle de 2mn sans pression suivit de 3mn sous une pression de 100 bars, avant d'être refroidit.The sample is prepared from the impregnated polyethylene granules, molded in a hydraulic press into a plate 3 mm thick at a temperature of 120 ° C., following a cycle of 2 minutes without pressure followed by 3 minutes under a pressure of 100 bars. before being cooled.

Quatre rondelles de 50 mm de diamètre sont découpées dans la plaque à l'aide d'un emporte-pièce. Deux d'entre-elles sont percées en leur centre d'un trou de 12mm de diamètre permettant de les enfiler dans la tige du rotor, sous celui-ci ; les deux autres sont conservées intactes et seront placées au dessus du rotor. Le tout est alors placé entre deux feuilles de polyester terphane®, pour être positionné dans la chambre du viscosimètre.Four washers 50 mm in diameter are cut from the plate with a punch. Two of them are drilled in their center with a hole of 12mm in diameter to put them in the rotor shaft, under it; the other two are kept intact and will be placed above the rotor. The whole is then placed between two sheets of terphane ® polyester, to be positioned in the chamber of the viscometer.

C'est la résistance du matériau à la rotation du rotor qui est mesurée. La mesure est exprimée en unité arbitraire, le Mooney (MU). Les paramètres d'intérêt sont : Le ML, valeur minimale de viscosité, mesurée au temps t0 (min). Le ML+1, valeur de viscosité correspondant au ML augmenté d'une unité Mooney. Celle-ci est mesurée au temps t1 (min). Le ML+2, valeur de viscosité correspondant au ML augmenté de deux unités Mooney. Celle-ci est mesurée au temps t2 (min).It is the resistance of the material to the rotation of the rotor which is measured. The measure is expressed in arbitrary unit, the Mooney (MU). The parameters of interest are: ML, minimum viscosity value, measured at time t0 (min). ML + 1, viscosity value corresponding to ML increased by one Mooney unit. This is measured at time t1 (min). ML + 2, viscosity value corresponding to ML increased by two Mooney units. This is measured at time t2 (min).

● Mesure des volatils (cf. méthane) par technologie Sievert ● Measurement of volatiles (see methane) by Sievert technology

La détermination de la quantité de volatils produits pendant la phase de réticulation du polyéthylène, puis désorbés, est faite par la méthode Sievert, à l'aide du PCT Pro 2000 (HY-ENERGY, SETARAM).The determination of the amount of volatiles produced during the crosslinking phase of the polyethylene, then desorbed, is made by the Sievert method, using the PCT Pro 2000 (HY-ENERGY, SETARAM).

L'échantillon est préparé à partir des granulés de polyéthylène imprégnés, moulés sous presse hydraulique en une plaque de 1mm d'épaisseur à la température de 120°C, suivant un cycle de 2mn sans pression suivit de 3mn sous une pression de 100 bars, avant d'être refroidit.The sample is prepared from the impregnated polyethylene granules, molded in a hydraulic press into a plate 1 mm thick at a temperature of 120 ° C., following a cycle of 2 minutes without pressure followed by 3 minutes under a pressure of 100 bars. before being cooled.

Des rondelles de 6mm de diamètre sont alors découpées dans la plaque à l'aide d'un emporte-pièce, puis pesées exactement, au mg près (masse totale = 300-350 mg).Washers 6mm in diameter are then cut into the plate using a punch, and weighed exactly, to the nearest mg (total mass = 300-350 mg).

L'échantillon est placé dans la chambre de l'appareil, mise sous pression (hélium). Cette chambre est connectée au moyen d'une valve, à un réservoir de 5ml lui aussi sous pression. En début de test, les pressions dans la chambre et dans le réservoir sont identiques. Pendant le cycle de température, la valve s'ouvre et se ferme par intermittence, permettant l'établissement d'un nouvel équilibre lorsqu'elle est ouverte, puis la mesure de la nouvelle pression dans le réservoir, lorsqu'elle est fermée. L'évolution de la pression provient pour partie du dégagement du méthane, et pour partie de la variation dimensionnelle de la chambre avec la température. Une lecture en temps réel de la quantité de méthane dégagée nécessite donc un étalonnage préalable en faisant subir à la chambre le cycle de température envisagé.The sample is placed in the chamber of the apparatus, pressurized (helium). This chamber is connected by means of a valve, to a tank of 5ml also under pressure. At the beginning of the test, the pressures in the chamber and in the tank are identical. During the temperature cycle, the valve opens and closes intermittently, allowing a new equilibrium to be established when it is open, then measuring the new pressure in the tank when it is closed. The evolution of the pressure comes partly from the release of the methane, and partly from the dimensional variation of the chamber with the temperature. A real-time reading of the amount of methane released therefore requires a prior calibration by subjecting the chamber to the temperature cycle envisaged.

L'équipement permet des rampes de température contrôlées de 1°C/s, simulant les conditions de réticulation des différentes couches de polyéthylène en tube de vulcanisation.The equipment allows controlled temperature ramps of 1 ° C / s, simulating the crosslinking conditions of the different layers of polyethylene vulcanization tube.

Le cycle prévoit une chauffe depuis la température ambiante jusqu'à 250°C.The cycle provides heating from room temperature up to 250 ° C.

La différence entre les mesures de pression finale et initiale, à température identique, permet d'accéder au taux de méthane dégagé. La quantité de volatils (i.e. méthane) est exprimée en µmol/g de polyéthylène réticulé.The difference between the final and initial pressure measurements, at the same temperature, makes it possible to access the level of methane released. The amount of volatiles (i.e. methane) is expressed in μmol / g of cross-linked polyethylene.

Caractérisations sur plaque réticuléeCharacterizations on reticulated plate ● Densité de réticulation par mesure de fluage à chaud ● Cross-linking density by hot creep measurement

Des plaques de 1mm d'épaisseur sont moulées à partir des granulés de polyéthylène imprégnés. Le moulage se fait sous presse à 120°C, suivant un cycle de 2 minutes sans pression puis 3 minutes sous 100 bars. Les plaques sont ensuite refroidies sous une pression de 100 bars.1mm thick plates are molded from the impregnated polyethylene granules. The molding is done in a press at 120 ° C, following a cycle of 2 minutes without pressure and then 3 minutes under 100 bars. The plates are then cooled under a pressure of 100 bar.

L'étape de réticulation se fait sous presse, à la température de 190°C sous 100 bars de pression et dure 10 minutes. Les moules sont préalablement préchauffés à 190°C. L'étape de refroidissement se fait sous pression maintenue à 100 bars.The crosslinking step is carried out in a press at a temperature of 190 ° C. under 100 bar pressure and lasts 10 minutes. The molds are preheated to 190 ° C. The cooling step is carried out under pressure maintained at 100 bars.

La mesure du fluage à chaud d'un matériau sous contrainte mécanique, quant à elle, est déterminée selon la norme NF EN 60811-2-1.The measurement of the hot creep of a material under mechanical stress, as for it, is determined according to the standard NF EN 60811-2-1.

Ce test est communément désigné par l'anglicisme Hot Set Test (HST) et consiste à lester une extrémité d'une éprouvette de type haltère H2 avec une masse correspondant à l'application d'une contrainte équivalente à 0,2MPa, et à placer l'ensemble dans une étuve chauffée à 200+/-1°C pendant une durée de 15 minutes.This test is commonly referred to as the Anglicism Hot Set Test (HST) and consists of ballasting one end of a dumbbell type H2 specimen with a mass corresponding to the application of a stress equivalent to 0.2MPa, and to place the whole in an oven heated to 200 +/- 1 ° C for a period of 15 minutes.

Au terme de ce délai, on relève l'allongement maximal à chaud sous contrainte de l'éprouvette, exprimé en %.At the end of this time, the maximum heat stress elongation of the test piece, expressed in%, is recorded.

La masse suspendue est alors retirée, et l'éprouvette est maintenue dans l'étuve pendant 5 nouvelles minutes.The suspended mass is then removed, and the test piece is kept in the oven for another 5 minutes.

L'allongement permanent restant, également appelé rémanence (ou élongation rémanente), est alors mesuré avant d'être exprimé en %.The remaining permanent elongation, also called remanence (or remanent elongation), is then measured before being expressed in%.

On rappelle que plus un matériau est réticulé, plus les valeurs d'allongement maximal sous contrainte et de rémanence seront faibles.It is recalled that the more a material is crosslinked, the higher the values of maximum elongation under stress and remanence will be low.

On précise par ailleurs que dans le cas où une éprouvette viendrait à se rompre en cours d'essai, sous l'action conjuguée de la contrainte mécanique et de la température, le résultat au test serait alors logiquement considéré comme un échec.It is also specified that in the case where a test piece breaks during the test, under the combined action of the mechanical stress and the temperature, the test result would then logically be considered a failure.

Dans le cas qui nous intéresse, une valeur d'allongement sera considérée comme conforme aux exigences si celle-ci n'excède pas 100%. Au delà de cette valeur, au même titre qu'une rupture, la tenue au test sera considérée comme non conforme.In this case, an elongation value will be considered as meeting the requirements if it does not exceed 100%. Beyond this value, in the same way as a break, the test will be considered as non-compliant.

L'ensemble des résultats concernant les caractérisations des plaques non réticulées et réticulées provenant des compositions réticulables C1 à C4 est rassemblé dans le tableau 2 ci-après. Tableau 2 Compositions réticulables C1 C2 C3 C4 MH (dN.m) 3,2 2,9 3,4 3,2 ML à 130°C (unités Mooney) 9,4 9,7 9,7 7,5 t0 (ML + 0) (min) 15 17 22 31 t1 (ML + 1) (min) 45 49 52 69 t2 (ML + 2) (min) 66 79 74 102 CH4 Sievert (µmol/g XLPE) 113 104 101 69 Hot set à 200°C Allongement maximal (%) 70-75 70-95 50-65 60-65 Rémanence (%) 0 0 0 0 The set of results relating to the characterizations of the non-crosslinked and crosslinked plates from the crosslinkable compositions C1 to C4 are collated in Table 2 below. <b><u> Table 2 </ u></b> Crosslinkable compositions C1 C2 C3 C4 MH (dN.m) 3.2 2.9 3.4 3.2 ML at 130 ° C (Mooney units) 9.4 9.7 9.7 7.5 t0 (ML + 0) (min) 15 17 22 31 t1 (ML + 1) (min) 45 49 52 69 t2 (ML + 2) (min) 66 79 74 102 CH 4 Sievert (μmol / g XLPE) 113 104 101 69 Hot set at 200 ° C Maximum elongation (%) 70-75 70-95 50-65 60-65 Remanence (%) 0 0 0 0

A propriétés thermomécaniques équivalentes (voir les résultats de l'allongement maximal et de la rémanence - cf. Hot Set Test à 200°C), la quantité de peroxyde aliphatique utilisée dans la composition réticulable C2 de l'invention est bien moins importante que celle utilisée dans la composition réticulable C1 (1,25 pour C2 contre 1,42 pour C1).With equivalent thermomechanical properties (see the results of the maximum elongation and the remanence - see Hot Set Test at 200 ° C.), the quantity of aliphatic peroxide used in the crosslinkable composition C2 of the invention is much smaller than that used in the crosslinkable composition C1 (1.25 for C2 against 1.42 for C1).

En comparant les compositions réticulables C1 et C2, la quantité de méthane dégagé pendant la réticulation passe de 113 à 104µmol/g de XLPE.By comparing the crosslinkable compositions C1 and C2, the amount of methane released during the crosslinking increases from 113 to 104μmol / g of XLPE.

En outre, l'alcool cumylique en tant que sous-produits de réticulation est remplacé par la formation de tertiobutanol dans la composition C2, lors de la réticulation. Le tertiobutanol, comme tout alcool tertiaire, peut bien entendu se déshydrater pour former de l'isobutène et de l'eau. Toutefois, l'isobutène étant nettement moins stabilisé que l'alpha-méthyl styrène formé dans le cadre de la réaction de déshydratation de l'alcool cumylique, cette réaction est nettement défavorisée, et la formation d'eau ralentie.In addition, the cumyl alcohol as cross-linking by-products is replaced by the formation of tertiobutanol in the composition C2, during the crosslinking. Tertiobutanol, like any tertiary alcohol, can of course dehydrate to form isobutene and water. However, isobutene being significantly less stabilized than the alpha-methyl styrene formed in the context of the dehydration reaction of cumyl alcohol, this reaction is markedly disadvantaged, and the formation of water slowed down.

Ces différences sont d'autant plus significatives en comparant les compositions C3 et C4. Toujours à propriétés thermomécaniques équivalentes, on observe une diminution significative de la quantité de méthane pour la composition C4 de l'invention par rapport à la composition C3. En outre, les valeurs des temps de grillage sont bien meilleures pour la composition C4 que pour la composition C3. Enfin, la composition C4 ne comprenant pas de peroxyde cumylique, la formation d'eau est nettement ralentie dans cette composition.These differences are even more significant by comparing the C3 and C4 compositions. Still having equivalent thermomechanical properties, there is a significant decrease in the amount of methane for the composition C4 of the invention relative to the composition C3. In addition, the values of the roasting times are much better for the composition C4 than for the composition C3. Finally, the composition C4 does not include cumyl peroxide, the formation of water is significantly slowed down in this composition.

Claims (13)

  1. An electric cable (1) comprising an electric conductor (2), a first semiconducting layer (3) surrounding the electric conductor (2), a second electrically insulating layer (4), surrounding the first layer (3), and a third semiconducting layer (5) surrounding the second layer (4), at least one of these three layers (3, 4, 5) is a cross-linked layer obtained from a cross-linkable composition comprising at least one polyolefin, and an aliphatic peroxide as a cross-linking agent, characterized in that the cross-linkable composition further comprises an aromatic compound comprising at least one aromatic ring and a single reactive function able to be grafted onto the polyolefin.
  2. The cable according to claim 1, characterized in that the cross-linkable composition further comprises at least one cross-linking co-agent including at least two reactive functions, either identical or different, which are able to be grafted on to the polyolefin on the one hand, and to participate in the cross-linking of the polyolefin on the other hand.
  3. The cable according to claim 2, characterizing that one of both of these reactive functions is a vinyl function of the CH2=CH2 type.
  4. An electric cable (1) comprising an electric conductor (2), a first semiconducting layer (3) surrounding the electric conductor (2), a second electrically insulating layer (4), surrounding the first layer (3), and a third semiconducting layer (5) surrounding the second layer (4), at least one of these three layers (3, 4, 5) is a cross-linked layer obtained from a cross-linkable composition comprising at least one polyolefin, and an aliphatic peroxide as a cross-linking agent, characterized in that the cross-linkable composition further comprises at least one cross-linking co-agent including at least two reactive functions, either identical or different, which are able to be grafted onto the polyolefin on the one hand, and to participate in the cross-linking of the polyolefin on the other hand, one of both of these reactive functions being a vinyl function of the CH2=CH2 type.
  5. The cable according to claim 4, characterized in that the cross-linkable composition further comprises an aromatic compound comprising at least the one aromatic ring and a single reactive function able to be grafted onto the polyolefin.
  6. The cable according to one of any preceding claims, characterizing that the aliphatic peroxide is selected from aliphatic peroxycarbonates, tertiary dialkyl aliphatic peroxides, aliphatic peroxyacetals, and aliphatic peroxyesters, or one of their mixtures.
  7. The cable according to one of any preceding claims, characterized in that the polyolefin is an ethylene polymer.
  8. The cable according to claim 7, characterizing that the ethylene polymer is a low density polyethylene (LDPE).
  9. The cable according to any of the preceding claims, characterized in that the cross-linkable composition comprises more than 50.0 parts by weight of polyolefin for 100 parts by weight of polymer in the composition.
  10. The cable according to claim 2, 3, 4, characterized in that said at least two reactive functions of the co-agent are vinyl functions of the CH2=CH2 type.
  11. The cable according to claim 1 or 5, characterized in that the single reactive function of the aromatic compound is a vinyl function.
  12. The cable according to any of the preceding claims, characterized in that the cross-linked layer is an electrically insulating layer.
  13. The cable according to any of the preceding claims, characterized in that the three layers of the cable are cross-linked layers.
EP20120158603 2011-03-08 2012-03-08 low and middle voltage electric cable Revoked EP2498263B1 (en)

Applications Claiming Priority (1)

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FR1151892A FR2972559B1 (en) 2011-03-08 2011-03-08 ELECTRICAL CABLE WITH MEDIUM OR HIGH VOLTAGE

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EP2498263A1 EP2498263A1 (en) 2012-09-12
EP2498263B1 true EP2498263B1 (en) 2014-11-19

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FR3024797B1 (en) * 2014-08-07 2016-07-29 Nexans CABLE COMPRISING A RETICULATED LAYER
CN107068272A (en) * 2016-02-25 2017-08-18 杨攀 A kind of high-pressure coaxial cable
CA3019189C (en) * 2016-03-30 2024-01-16 Dow Global Technologies Llc Crosslinkable polymeric compositions with methyl-radical scavengers and articles made therefrom
GB2565587A (en) 2017-08-18 2019-02-20 Addivant Switzerland Gmbh Insulation composition

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US2426111A (en) * 1938-09-13 1947-08-19 Mertens Willi Method of producing hard electrically insulating articles from polyisobutylene, styrene, and divinyl benzene
DE1946927C3 (en) * 1969-09-17 1975-11-20 Kabel- Und Metallwerke Gutehoffnungshuette Ag, 3000 Hannover High-voltage-resistant insulation for electrical cables containing voltage stabilizers
DE3244704C2 (en) * 1982-12-03 1985-01-31 Licentia Patent-Verwaltungs-Gmbh, 6000 Frankfurt Electrical insulation with stabilizer
DE3702209A1 (en) * 1987-01-26 1988-08-04 Licentia Gmbh PLASTIC INSULATION AND METHOD FOR THEIR PRODUCTION
JP3175297B2 (en) 1991-06-24 2001-06-11 日本油脂株式会社 Ethylene-based polymer crosslinking composition, crosslinking method and power cable
US5378539A (en) * 1992-03-17 1995-01-03 E. I. Du Pont De Nemours And Company Cross-linked melt processible fire-retardant ethylene polymer compositions
JPH06135927A (en) * 1992-07-16 1994-05-17 Nippon Oil & Fats Co Ltd Dialkylperoxide, composition using the same, crosslinking method and electric cable
SE9802386D0 (en) * 1998-07-03 1998-07-03 Borealis As Composition for electric cables
FR2809226B1 (en) * 2000-05-19 2002-07-26 Sagem CROSSLINKABLE SEMICONDUCTOR COMPOSITION AND ELECTRICAL CABLE WITH SEMICONDUCTOR FILM
KR100727207B1 (en) * 2006-02-24 2007-06-13 주식회사 엘지화학 Cross-linked polyethylene having excellent inhibition of sweat-out and insulation properties
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BRPI0915738B1 (en) * 2008-07-10 2019-09-24 Borealis Ag RETICULABLE POLYMER COMPOSITION, ARTICLE UNDERSTANDING A POLYMER COMPOSITION, PROCESS FOR PRODUCING A RETICULABLE CABLE AND CABLE
CN101445627A (en) * 2008-12-11 2009-06-03 上海交通大学 High-voltage DC cable insulating material and a preparation method thereof
JP5836368B2 (en) * 2010-06-18 2015-12-24 ユニオン カーバイド ケミカルズ アンド プラスティックス テクノロジー エルエルシー Conductive olefin multi-block copolymer composition

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KR20180061101A (en) 2018-06-07
CN102682904B (en) 2017-05-17
FR2972559A1 (en) 2012-09-14
AU2012201230A1 (en) 2012-09-27
CN102682904A (en) 2012-09-19
ES2530362T3 (en) 2015-03-02
KR20120103498A (en) 2012-09-19
FR2972559B1 (en) 2017-11-24

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