EP2254126A1 - Organogel für elektrische Kabelisolierschichten - Google Patents

Organogel für elektrische Kabelisolierschichten Download PDF

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Publication number
EP2254126A1
EP2254126A1 EP09305468A EP09305468A EP2254126A1 EP 2254126 A1 EP2254126 A1 EP 2254126A1 EP 09305468 A EP09305468 A EP 09305468A EP 09305468 A EP09305468 A EP 09305468A EP 2254126 A1 EP2254126 A1 EP 2254126A1
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EP
European Patent Office
Prior art keywords
oil
mixture
electric cable
urea
cable according
Prior art date
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Application number
EP09305468A
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English (en)
French (fr)
Inventor
Steinar Ouren
Henricus Marie Janssen
Pieter Michel Fransen
Martijn Arnoldus Johannes Veld
Anja Rita Alberta Palmans
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Nexans SA
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Nexans SA
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Publication date
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Priority to EP09305468A priority Critical patent/EP2254126A1/de
Priority to EP10163155A priority patent/EP2254127A1/de
Priority to KR1020100047161A priority patent/KR20100125192A/ko
Priority to JP2010116402A priority patent/JP5646881B2/ja
Publication of EP2254126A1 publication Critical patent/EP2254126A1/de
Priority to KR1020170133096A priority patent/KR101990887B1/ko
Withdrawn legal-status Critical Current

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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
    • H01B3/20—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances liquids, e.g. oils
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B12/00—Superconductive or hyperconductive conductors, cables, or transmission lines
    • H01B12/14—Superconductive or hyperconductive conductors, cables, or transmission lines characterised by the disposition of thermal insulation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H01B13/22—Sheathing; Armouring; Screening; Applying other protective layers
    • H01B13/26—Sheathing; Armouring; Screening; Applying other protective layers by winding, braiding or longitudinal lapping
    • H01B13/2613—Sheathing; Armouring; Screening; Applying other protective layers by winding, braiding or longitudinal lapping by longitudinal lapping
    • H01B13/2626—Sheathing; Armouring; Screening; Applying other protective layers by winding, braiding or longitudinal lapping by longitudinal lapping of a coaxial cable outer conductor
    • 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
    • H01B3/20—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances liquids, e.g. oils
    • H01B3/22—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances liquids, e.g. oils hydrocarbons
    • 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
    • H01B3/302—Polyurethanes or polythiourethanes; Polyurea or polythiourea
    • 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
    • H01B3/303—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups H01B3/38 or H01B3/302
    • H01B3/305—Polyamides or polyesteramides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B9/00—Power cables

Definitions

  • the present invention relates to an electric cable comprising an electrically insulating layer impregnated with a dielectric fluid including an organogel.
  • the electric cable is a direct current transmission cable (DC transmission cable), more preferably a high voltage direct current cable (HVDC transmission cable) especially with a transmission capacity more than 1200 MW.
  • DC transmission cable direct current transmission cable
  • HVDC transmission cable high voltage direct current cable
  • a typical DC transmission cable includes a conductor and an insulation system comprising a plurality of layers, such as an inner semi-conductive shield, an insulation body and an outer semi-conductive shield.
  • the cable is also completed with casing, reinforcement, etc., to withstand water penetration and any mechanical wear or forces during production, installation and use. Almost all the DC cable systems supplied so far have been for submarine crossings or the land cable associated with them.
  • the insulation body is typically a wound body comprising an essentially all paper tape, i.e. a tape based on paper or cellulose fibers, but application of laminated tape materials, i.e. tape made of at least two layers adhered to each other, such as a laminated polypropylene paper tape, can be used as well.
  • the wound body is typically impregnated with an electric insulation oil or mass.
  • the document WO 99/33068 describes a DC cable having at least one conductor and an electrically insulating layer impregnated with a dielectric fluid.
  • the dielectric fluid comprises an oil and a gelling additive, wherein this gelling additive determines the viscosity and elasticity of the dielectric fluid.
  • the cable shall thus, in its impregnated insulating layer, comprise a dielectric fluid (i.e. oil plus gelling additive) with a sufficiently low viscosity at the (higher) impregnation temperature to ensure stable flow properties and flow behavior of this fluid, with a sufficiently high viscosity and elasticity at the (lower) operating temperature of the cable to ensure retention of the oil in the insulating layer, and with a sufficiently sharp viscosity increase on going from the impregnating to the operating temperature to enable the use of higher operating temperatures.
  • a dielectric fluid i.e. oil plus gelling additive
  • the gelling additive molecule can be selected among a very large variety of compounds that are characterized by a polar part capable of forming hydrogen bonds, wherein said gelling additive together with an oil form a polymer gel when the gelling additive is a polymer, or an organogel when the gelling additive is a compound which is not a polymer.
  • three gelling additives are respectively used in combination with an unspecified naphthenic mineral oil.
  • any gelling additive compound as defined in WO 99/33068
  • any unspecified naphthenic mineral oil does not provide a dielectric fluid with sufficiently stable dielectric properties within the electrically insulating layer.
  • the described gelling additive and the oil will form a phase separated mixture, either because the gelling additive is not soluble in the oil resulting in a suspension of the additive in the oil, or because the gelling additive and the oil form a phase separated mixture of a gel phase and an oil phase (this is also called 'bleeding').
  • the present invention seeks to solve the above-mentioned problems of the prior art, and proposes to optimize the dielectric stability as well as the non-bleeding properties (i.e. the stability) of the dielectric fluid that is used to impregnate the electrically insulating layer of an electric cable.
  • An object of the present invention is to provide an electric cable comprising at least one conductor, and an electrically insulating layer impregnated with a dielectric fluid, said insulating layer surrounding said conductor, the dielectric fluid comprising an organogel including an oil and an organo-gelator, characterized in that the oil is a non-polar oil with a flash point inferior or equal to 200°C.
  • the non-polarity of the oil is essential to have satisfactory dielectric properties of the impregnated electrically insulating layer.
  • the non-polar oil has a low content of aromatics (C A ) according to the ASTM D 2140 standard, so that the weight percentage of C A is preferably inferior to 12%, more preferably inferior to 10%, and even more preferably C A is inferior to 6%.
  • the non-polar oil has a low weight percentage that can be extracted from it with DMSO (a polar solvent), after the oil has been diluted with cyclohexane.
  • DMSO a polar solvent
  • the DMSO-extractable weight percentage is inferior to 3%, preferably inferior to 2%, and more preferably inferior or equal to 1.5%.
  • the non-polar oil has a low content of aromatics (C A ) according to the ASTM D 2140 standard (first variant) and a low percentage of DMSO-extractibles according to the IP 346 test (second variant).
  • the combination of the organo-gelator with the specific oil of the invention provides clear and homogeneous organogels without any precipitate, with optimized stable dielectric properties (e.g. very high breakdown voltages), that do not exhibit bleeding phenomena.
  • the flash point of the oil indicates how volatile the oil is.
  • the flash point is typically determined by the Pensky Marten (PM) closed cup method ASTM D 93 A, or similar tests such as the ASTM D92 or ASTM D93 tests.
  • the flash point is reached when the oil releases enough gases to make the gas mixture above the oil ignitable in the presence of an open flame.
  • the flash point of the oil is preferably inferior or equal to 180°C and even more preferably inferior or equal to 160°C.
  • the flash point of the oil is preferably superior or equal to 95°C, more preferably superior or equal to 110°C and even more preferably superior or equal to 120°C.
  • the non-polar oil can preferably be selected among a hydrocarbon oil, a silicon oil, a fluoro-oil and a natural oil (e.g. vegetable oils, terpene derived oils), or mixtures thereof, and is more preferably a hydrocarbon oil.
  • hydrocarbon oils one can select a naphthenic oil, a paraffinic oil or an isoparaffinic oil, or mixtures thereof, where these may be mineral oils, semi-synthetic mineral oils (such as hydrotreated mineral oils) or synthetic oils (such as hydrogenated poly-alpha-olefines). Even more preferred are semi-synthetic hydrotreated mineral oils (either naphthenic, paraffinic or isoparaffinic).
  • the non-polar oil of the invention may be provided by any supplier or distributor, such as Nynas, Shell, Renkert Oil, Neste Oil, etc.
  • the oil viscosity is inferior to 40 cSt (centistokes) at 40 °C, preferably inferior to 20 cSt at 40 °C, and more prefereably inferior to 10 cSt at 40 °C.
  • the oil viscosity is determined in measuring the kinematic viscosity in cSt by Ubbelhode capillary according to ASTM D445 standard.
  • the non-polar oil used in the invention preferably contain molecules that are branched and/or cyclic.
  • heptamethylnonane is preferred over n-hexadecane
  • decaline is preferred over n-dodecane.
  • Other examples are (branched) alkyl cyclohexanes or (branched) alkyl decalines (i.e. these are hydrogenated alkyl benzenes and hydrogenated alkyl naphthalenes). Branching usually implies that various isomers are present in the oil, and this is preferred as the oil is preferably composed of a mixture of molecules. As a result, an oil composed of a mixture of primarily linear structures is also possible (i.e. paraffinic oils).
  • the organo-gelator is the organo-gelator
  • Organo-gelators are molecules that self-assemble in solution, by supramolecular interactions, usually by hydrogen bonding interactions and/or by ⁇ - ⁇ interactions.
  • the organization of the organo-gelator molecules primarily takes place in one direction, so that long supramolecular structures are formed. Interactions between these structures, that become important as of a sufficiently high concentration of the organo-gelator molecules, cause the gelation of the solution.
  • the supramolecular structure is not a polymer, and indeed, by heating the solution, the supramolecular structures disintegrate reversibly, giving a solution of individual molecules or very small aggregates of a few molecules, resulting in a sharp viscosity drop, and enabling easy processing at higher temperatures.
  • the organo-gelator is selected among urea-based compounds, a mixture of urea-based compounds, amide-based compounds, and a mixture of amide-based compounds, or mixtures thereof.
  • Said organo-gelator is particularly suited to prepare stable organogels that are of interest in electrical cable insulation applications.
  • Said organo-gelator in combination with the oil according to the invention, is capable of producing clear, homogeneous and stable organogels.
  • organo-gelators are not organo-gelators, also not among molecules that bear a non-polar segment and that have a polar segment that can form hydrogen bonds.
  • organo-gelators may be able to produce organogels, but these organogels may not be stable in time (precipitation or bleeding may occur).
  • an organo-gelator composition comprising from 2 up to 1000 different molecules, preferably from 2 up to 250, more preferably 4 up to 100, and most preferably from 6 up to 60 molecules.
  • the ratio in which the molecules are present may vary invariably.
  • the most abundant species may preferably be present from 1 mol% up to 99 mol%, more preferably from 3 mol% up to 60 mol% and most preferably from 5 mol% up to 40%.
  • the least abundant species is preferably present from 0.01 mol% to 49 mol%, preferably from 0.05 mol% to 25 mol%, and most preferably from 0.1 mol% to 15 mol%.
  • the organo-gelator is selected among urea-based compounds or a mixture of urea-based compounds, and amide-based compounds or a mixture of amide-based compounds.
  • the mixtures according to the present invention are preferably composed of alike type of organo-gelator molecules, meaning that mono-ureas are mixed with other mono-ureas, aromatic tri-amides are mixed with other aromatic tri-amides, etc. Even more particularly, for mixtures that contain multifunctional amide structures (or for mixtures that contain multifunctional urea structures), the spacer between the amide- or urea functions is preferably identical for all the mixed organo-gelator molecules.
  • tri-alkyl benzene-1,3,5-tri-carboxamides are mixed with other tri-alkyl benzene-1,3,5-tricarboxamides; or, in another example, 2,4-bis-urea toluenes are mixed with other 2,4-bis-urea toluenes; or, in yet another example, 1,2-bis-urea (S,S)-cyclohexanes are mixed with other 1,2-bis-urea (S,S)-cyclohexanes.
  • the mixtures of organo-gelators can be made by physically mixing a set of individually synthesized organo-gelators. For example, a particular, or several particular, 2,4-bis-(di-alkyl-ureido)-toluene(s) is/are physically mixed in a selected ratio with another, or with several other, 2,4-bis-(di-alkyl-ureido)-toluene(s).
  • the mixtures can also be synthesized by taking one specific multifunctional reactant, and allowing this building block to react with a mixture of mono-functional reactants.
  • 2,4-toluene di-isocyanate (the specific multifunctional reactant) is reacted with a mixture of primary amine reactants (the mono-functional reactants) to produce a mixture of 2,4-bis-(di-alkyl-ureido)-toluenes; or, in another example, (S,S)-1,2-diamino cyclohexane is reacted with a mixture of mono-isocyanates to produce a mixture of (S,S)-1,2-bis-urea cyclohexanes.
  • the nature of the mono-functional reactants e.g. linear alkyl, branched, cyclic, alkylaryl, etc.
  • Particular and well-suited mixtures of mono-functional reactants are racemates, such as for example racemates of primary amines, racemates of carboxylic acids or derivatives thereof, or racemates of isocyanates.
  • mixtures according to the invention it is possible to surprisingly prepare an organo-gelator by mixing molecules that individually are not capable of gelating or thickening oils.
  • said mixtures allow to optimize properties of the organogels (e.g. with respect to viscosity, gel point, stability, etc.), by altering the specific composition of the mixture.
  • these urea functions can be regular ureas (-NH-CO-NH-), or thio-ureas (-NH-CS-NH-). Regular ureas are preferred.
  • both nitrogen atoms in one urea moiety can be substituted with hydrogens, or one of these nitrogen atoms can be alkylated or arylated.
  • both nitrogen atoms in the urea moiety are substitued with hydrogens, giving a -NH-CO-NH- urea moiety (or a -NH-CS-NH- thio-urea moiety) that is capable of engaging in hydrogen bonding interactions.
  • urea-based compounds these can be selected among mono-ureas or a mixture of mono-ureas, bis-ureas or a mixture of bis-ureas, and tris-ureas or a mixture of tris-ureas, and more preferably among mono-ureas or a mixture of mono-ureas, and bis-ureas or a mixture of bis-ureas. Most preferred are bis-ureas or a mixture of bis-ureas.
  • urea-based compound When the urea-based compound is substituted by at least two different R-groups, said compound is called an "asymmetric" urea-based compound. When all of the urea functions are substituted by identical R-groups, said compound is called a “symmetric" urea-based compound.
  • R-groups are not spacer groups that connect different urea-functions.
  • said mixture can comprise:
  • urea formulas as described hereafter concern regular ureas.
  • thio-ureas (not represented) can be as well considered instead of regular ureas.
  • the mono-ureas (or a mixture of mono-ureas) or the bis-ureas (or a mixture of bis-ureas) can respectively comply with the following formulas Ia and Ib, respectively: in which:
  • R1 and/or R2 are independently selected among 2-ethyl-hexyl; 1,5-dimethyl-hexyl; 3,7-dimethyl-octyl; 1-methyl-hexyl; other branched C 3 -C 8 alkyls, linear C 4 -C 18 alkyls, benzyls, cyclohexyl, alkoxy alkyls and hydroxy-alkyls.
  • R1 and/or R2 can be independently selected among 2-ethyl-hexyl; 1,5-dimethyl-hexyl; 1-methyl-hexyl; branched C 3 -C 6 alkyls; and linear C 4 -C 10 , C 16 and C 18 alkyls.
  • the most preferred is the 2-ethyl-hexyl radical.
  • these groups are preferably racemic groups (or more accurately stated, these R1 and/or R2 groups are then originated from racemic reactants, such as for example racemic primary amines, or racemic isocyanates).
  • R1 in the cases where R1 is different from R2 in order to have an asymmetric mono-urea compound, R1 (or R2) can preferably be selected among aryl or benzyl derived C 6 to C 15 carbon-based radicals, optionally containing from 1 to 3 heteroatoms chosen from O, S, F and N, and combinations thereof, and R2 (or R1) can be selected among hydrogen, linear, branched or cyclic, saturated or unsaturated C 1 -C 24 alkyl radicals optionally containing from 1 to 3 heteroatoms chosen from O, S, F and N.
  • R1 in the cases where R1 is different from R2 in order to have an asymmetric bis-urea-based compound, R1 (or R2) can preferably be selected among saturated or unsaturated, non-cyclic, branched C 3 to C 15 carbon-based radicals, optionally containing from 1 to 3 heteroatoms chosen from O, S, F and N, and combinations thereof, and R2 (or R1) can be selected among hydrogen, linear, branched or cyclic, saturated or unsaturated C 1 -C 24 alkyl radicals optionally containing from 1 to 3 heteroatoms chosen from O, S, F and N.
  • all the molecules in said mixture preferably have one specific identical R1-group, preferably a specific aryl-derived group, or a specific benzyl-derived group.
  • R1-group preferably a specific aryl-derived group, or a specific benzyl-derived group.
  • a mixture that is composed of only 1-benzyl-mono-ureas preferably a mixture that is composed of only 1-benzyl-mono-ureas.
  • all the molecules in said mixture preferably have the same spacer A.
  • the spacer A in all molecules of a mixture of structures Ib is a R,R-1,2-cyclohexylene spacer.
  • the urea-based compound can be an aromatic bis-urea (or a mixture of aromatic bis-ureas) complying with the following formula II: Aromatic bis-urea (II) in which R1 and R2 are defined as above, and R3 is a hydrogen atom or a linear or branched C 1 to C 4 alkyl radical.
  • urea groups are preferably connected with the same aromatic spacer.
  • metha-bis-ureas are mixed with other metha-bisureas
  • para-bis-ureas are mixed with other para-bis-ureas
  • ortho-bis-ureas are mixed with other ortho-bis-ureas.
  • the aromatic bis-urea can be a bis-urea substituted toluene (or a mixture of bis-urea substituted toluenes) complying with the following formula III: Bis-urea substituted toluene (III) in which R1 and R2 are defined as above.
  • the urea groups in structures II are also metha-substituted onto the ring.
  • these amide functions can be regular amides (-NH-CO-), or thio-amides (-NH-CS-). Regular amides are preferred.
  • the nitrogen atom in the amide moiety can be substituted with a hydrogen, giving -NH-CO-amide moiety (or -NH-CS- thio-amide moiety) that is capable of engaging in hydrogen bonding interactions.
  • these can be selected among di-amides or a mixture of di-amides, tri-amides or a mixture of tri-amides, and tetra-amides or a mixture of tetra-amides.
  • amide-based compound When the amide-based compound is substituted by at least two different R-groups, said compound is called an "asymmetric" amide-based compound. When all of the amide functions are substituted by identical R-groups, said compound is called a “symmetric" amide-based compound. R-groups are not spacer groups that connect different amide functions.
  • said mixture can comprise:
  • amide formulas as described hereafter concern regular amides.
  • thio-amides (not represented) can be as well considered instead of regular amides.
  • R4 and/or R5, and R7 and/or R8 can be different or identical, and can independently be selected among hydrogen, linear, branched or cyclic, saturated or unsaturated C 1 -C 36 alkyl, alkylaryl or arylalkyl
  • R4 and/or R5 are preferably, and independently, selected among hydrogen, 2-ethyl-hexyl; 1,5-dimethyl-hexyl; 3,7-dimethyl-octyl; 1-methyl-hexyl; other branched C 3 -C 8 alkyls, linear C 4 -C 18 alkyls, benzyls, cyclohexyl, alkoxy alkyls (e.g. 3-methoxypropyl) and hydroxy-alkyls.
  • R7 and/or R8 these are preferably, and independently, selected among 1-ethyl-pentyl; 1-methyl-ethyl; 1-methyl-propyl; tert-butyl; 1-ethyl-propyl; 2,6-dimethyl-heptyl; other branched C 3 -C 7 alkyls; C 12 -C 36 1-alkyl-alkyls, linear C 4 -C 18 alkyls, benzyls, cyclohexyls, and alkoxy-alkyls.
  • these groups are preferably racemic groups.
  • racemic reactants such as for example from racemic primary amine reactants (for IV) or from racemic carboxylic acid derived reactants (for V).
  • the moiety B is an non-aromatic or aromatic spacer, preferably selected among a linear alkylene, a cyclohexylene, a camphorylene, a phenylene, a bis-phenylene, a naphthalene, and a glutamic or aspartic acid derived spacer.
  • Spacer B can also represent a direct covalent bond between the two carbons.
  • the moiety C is a non-aromatic or aromatic spacer, preferably selected among a linear alkylene, a cyclohexylene (preferably a R,R- or a S,S-1,2-cyclohexylene), a 4,4'-methylene-bis-cyclohexylene, a 4,4'-methylene-bis-phenylene, a 4,4'-oxy-bis-phenylene, a benzylene, a naphthalene, tris-(2-ethylene)-amine, an isophoronylene, a para-menthylene and a lysine-derived spacer.
  • Spacer C can also represent a direct covalent bond between the two nitrogen atoms.
  • all molecules in said mixtures preferably have the same spacer B (for the mixture of structures IV), or the same spacer C (for the mixture of structures V).
  • the spacer C in all molecules of a mixture of structures V is a R,R-1,2-cyclohexylene spacer.
  • R10 and R11 can be different or identical, and can independently be selected among hydrogen, linear, branched or cyclic, saturated or unsaturated C 1 -C 24 alkyl, alkylaryl or arylalkyl carbon-based radicals, more particularly saturated al
  • R10 and R11 are derived from amino-acid residues, such as hydrogen, benzyl, alkyl, branched alkyl or alkyl residues containing alkyl-ester or alcohol groups.
  • R10 and/or R11 groups contain stereocenters
  • these groups are preferably racemic groups.
  • all molecules in this mixture preferably have the same configuration for the 6-membered ring, i.e. all molecules have the same R,R- or the same S,S-configuration.
  • the amide-based compound can be an aromatic tri-amide.
  • the aromatic tri-amide (or a mixture of aromatic tri-amides) is a benzene-1,3,5-tricarboxamide (BTA) (or a mixture of BTAs) complying with the following formula VII: Benzene-1,3,5-tricarboxamide (BTA) (VII)
  • the aromatic tri-amide (or a mixture of aromatic tri-amides) can comply with the following formula VIII:
  • R4, R5 and/or R6 of formula VII are preferably, and independently, selected among 2-ethyl-hexyl; 1,5-dimethyl-hexyl; 3,7-dimethyl-octyl; 1-methyl-hexyl; other branched C 3 -C 8 alkyls, linear C 4 -C 18 alkyls, benzyls, cyclohexyl, alkoxy alkyls (e.g. 3-methoxy-propyl) and hydroxy-alkyls.
  • R7, R8 and/or R9 of formula VIII are preferably, and independently, selected among 1-ethyl-pentyl; 1-methyl-ethyl; 1-methyl-propyl; tert-butyl; 1-ethyl-propyl; 2,6-dimethyl-heptyl; other branched C 3 -C 7 alkyls; C 12 -C 36 1-alkyl-alkyls, linear C 4 -C 18 alkyls, benzyls, cyclohexyls, and alkoxy-alkyls.
  • R4, R5 and/or R6 groups of formula VII, or the R7, R8 and/or R9 groups of formula VIII contain stereocenters, these groups are preferably racemic groups. Or more accurately stated, are originated from racemic reactants.
  • the tri-amide (or a mixture of tri-amides) can comply with the following formula IX: in which R4, R5 and R6 are defined as above for structure VII.
  • R4, R5 and/or R6 groups of formula IX contain stereocenters
  • these groups are preferably racemic groups. Or more accurately stated, are originated from racemic reactants.
  • all molecules in this mixture preferably have the same configuration for the 1,3,5-cyclohexylene ring, i.e. all molecules have the same R,R,R or the same S,S,S-configuration.
  • Tetra-amides can be pyromellitamide compounds or mixtures thereof, such as for example benzene-1,2,4,5-tetra-carboxamides.
  • formulas Ia, Ib, II, III, IV, V, VI, VII, VIII and IX formulas Ia, Ib, III, V and VII are preferred. Most preferred are III and VII.
  • an organo-gelator that is a mixture of alike compounds is preferred, as opposed to an organo-gelator that is composed of a single compound.
  • Mixtures of alike structures according to formula Ia, or to formula Ib, or to formula III, or to formulas II and III, or to formula V, or to formula VII are preferred.
  • Most preferred are mixtures of alike structures according to formula III, according to formulas II and III, or according to formula VII.
  • the present invention introduces a class of organo-gelators that can be used to effectively and stably thicken or gelate oils that are applied in electrical cable insulation.
  • organo-gelators from mixtures of alike molecules can further be applied to other type of molecular structures with (multiple) pendant alkyl groups, such as for example, metal-salts (e.g. mono- or di-nuclear metal diketonates or tetra carboxylic acids, di- or trivalent metal salts of fatty acids or phosphoric acids), sugar or poly-ol based compounds (e.g sorbitol derivatives, cholic acid derivatives), steroid derivatives (such as cholesterol derivatives), amino acid derivatives or oligopeptides, mellitic acid derivatives (e.g. mellitamides), systems that aggregate due to ⁇ - ⁇ -interactions (e.g.
  • metal-salts e.g. mono- or di-nuclear metal diketonates or tetra carboxylic acids, di- or trivalent metal salts of fatty acids or phosphoric acids
  • sugar or poly-ol based compounds e.g sorbitol derivatives
  • porphyrines phthalocyanins, phenylenevinylidenes, fluorenes, azo-phenylenes, other dyes, anthraquinones
  • two-component systems e.g acid-base systems, pyrimidine-barbituric acid systems, or similar systems based on melamines or triazines, systems based on cyclodextrins, donor-acceptor based systems
  • multivalent urethanes e.g based on N-benzyl-3,4-dihydroxy-pyrrolidine
  • bola-amphiphilic structures molecules with mesogenic groups (such as tri-alkyl gallic acid derivatives, 4-alkoxy benzoic acid derivatives).
  • the organogel The organogel
  • the dielectric fluid of the invention comprises the organo-gelator and the oil that both are described in detail above.
  • a fluid in a vial is considered as a gel when inverting the vial does not result in flowing of the fluid on the time scale of seconds or minutes, whereas a very viscous solution will flow slowly in seconds, and a low viscous solution will flow fast immediately.
  • the dielectric fluid of the invention is preferably clear (or transparent), as opposed to being turbid or white. Additionally, it is preferably macroscopically homogeneous, as opposed to being a mixture having a precipitate (a suspension), or a mixture exhibiting any other type of phase separation, such as a mixture of a gel and a phase separated liquid.
  • An organogel is a visco-elastic solution, implying that it has both elastic (i.e. solid-like) and viscous (i.e. liquid-like) properties.
  • the gel point (Tgel) of an organogel is the temperature below which the organogel has a more elastic or solid-like nature, and above which it has a more liquid-like behavior.
  • the gel point of an organogel can be determined by rheological measurements, or more particularly by complex viscosity measurements or by viscoelastic measurements.
  • Rheological measurements are typically performed with a dynamic rheometer in oscillatory mode such as a Brookfield rheometer.
  • the gel point of the present invention is measured under dynamic oscillation of 0,095 Hz.
  • the organogel is placed in a concentric cylinder cup with a cone inside, and heated from 4°C to 110°C at 0,5 °C/min under a dynamic oscillation of 0,095 Hz and under a strain of 0,01%.
  • rheological parameters such as the storage modulus (G', in Pa, reflecting the solid-like nature of the gel), loss modulus (G", in Pa, reflecting the liquid-like nature of the gel) and the complex viscosity ⁇ * (in Pa.s) can be recorded.
  • the gel point is then defined as the temperature at which the storage modulus G' is equal to the loss modulus G".
  • the impregnating temperature of the cable is preferably higher than the gel point of the applied organogel in the insulating layer, whereas the operating temperature of the cable is preferably lower than or not much higher than this gel point.
  • the gel point of the organogel can be chosen from 45°C to 90 °C. This specific gel point range allows for an organogel that gives the impregnated electrically insulating layer of the invention all the advantageous properties.
  • a gel point higher than 90°C is preferably not desired as this implicates that too high impregnating temperatures have to be used.
  • a gel point less than 45°C induces a risk of creating cavities in the electrically insulating layer due to polarity reversal of the cable at operating temperatures.
  • Polarity reversal induces a temperature change in the cable, and said temperature change can modify the dielectric fluid structure, possibly resulting in cavity formation (i.e. small gas bubble formation).
  • cavity formation i.e. small gas bubble formation.
  • Such cavities can severely increase the chance on a breakdown (failure) of the cable.
  • the rheological behaviour of the dielectric fluid of the invention can be characterized by a "solid" (elastic) behaviour from 0°C to approximately 60°C, and a more viscous behaviour from 60 °C to 100°C.
  • the complex viscosity at 0°C can be about 100 to 5000 Pa.s.
  • the viscosity can be about 50 to 2000 Pa.s, and at 100°C, the viscosity can be about 0,01 to 2 Pa.s.
  • the well-know method to characterize the organogel complex viscosity in Pa.s is to use a dynamical rheometer in oscillatory mode, as mentioned and described above, by use of e.g. a Brookfield rheometer.
  • the dielectric fluid of the invention displays a sharp complex viscosity drop somewhere in the temperature window between 45 °C and 110 °C.
  • the complex viscosity drop is preferably more than 2 decades (e.g. from 200 Pa.s to 2 Pa.s) within 40 °C, more preferably more than 3 decades within 35 °C, and even more preferably more than 3 decades within 30 °C.
  • Said complex viscosity drop is preferably larger than 100 Pa.s, more preferably larger than 250 Pa.s, most preferably larger than 500 Pa.s.
  • the organogel can include to the maximum 20% by weight of organo-gelator, more preferably include to the maximum 10% by weight of organo-gelator.
  • the dielectric fluid can include at least 2% by weight of organo-gelator.
  • the organogel can include from 3% to 7% by weight of the organo-gelator.
  • the organogel preferably only contains the oil and the organo-gelator according to the invention.
  • the dielectric fluid can further comprise additional components, such as for example rheology modifiers, anti-oxidants, metal deactivators or hydrogen scavengers.
  • additional components such as for example rheology modifiers, anti-oxidants, metal deactivators or hydrogen scavengers.
  • the dielectric fluid preferably comprises more than 97% by weight of organogel.
  • rheology modifiers are elastomers to make the gel more elastic, said elastomer being not more than 2% by weight in the dielectric fluid.
  • the addition of more than 2% by weight of said elastomer may induce a rheological problem due to the compatibility between said elastomer and the organo-gelator, as well as a risk of bleeding.
  • the elastomer can be polyisobutene (PIB), more preferably a low molecular weight polyisobutene (LMWPIB) such as a molecular weight inferior to 10000 g/mol, and more preferably inferior to 2000 g/mol.
  • PIB polyisobutene
  • LMWPIB low molecular weight polyisobutene
  • anti-oxidants are phenol derived anti-oxidants, such as 2,6-di-tert-butyl-4-methylphenol (BHT), or Irganox type of anti-oxidants as commercialized by Ciba (these are sometimes also phenol derivatives).
  • BHT 2,6-di-tert-butyl-4-methylphenol
  • Irganox type of anti-oxidants as commercialized by Ciba (these are sometimes also phenol derivatives).
  • the electrically insulating layer can typically be a porous, fibrous and/or laminated structure, such as tape, based preferably on cellulose or paper fibers.
  • laminated structure a structure including at least three layers, in which the intermediate layer is based on cellulose or paper fibers and the two other layers are different layers such as atactic polypropylene layers (i.e. polypropylene layers stretched in random direction).
  • the electrically insulating layer of the invention is impregnated with the dielectric fluid, such that essentially all voids of said electrically insulating layer are filled with the dielectric impregnating fluid.
  • the gel point of the organogel of the invention can be from 45 to 80°C, and more preferably from 50 to 75°C, most preferably from 55 °C to 65°C.
  • the gel point of the organogel of the invention can be from 80 to 90°C.
  • the electric cable according to the invention can be an electric direct current transmission cable comprising a first semi-conducting layer surrounding said conductor, the insulating layer surrounding said first layer; a second semi-conducting layer surrounding said insulating layer, and a protective sheath surrounding said second layer.
  • a metallic screen can be positioned between the second semi-conductive layer and the protective sheath along the electric cable.
  • Figure 1 illustrates a DC cable comprising from the center and outwards:
  • the DC cable can be a single conductor DC cable having a multi-wire core as shown in Figure 1 or a DC cable with two or more conductors.
  • a DC cable comprising two or more conductors can be of any known type with the conductors placed side-by-side in a flat cable arrangement, or in a two-conductor arrangement with one first central conductor surrounded by a concentrically arranged second outer conductor, i.e. a coaxial two-conductor cable.
  • oils referenced in table 1 are commercialized by Nynas, except for heptamethylnonane (CAS 4390-04-9), a non-aromatic oil that can be bought from sources such as Aldrich.
  • Bis-urea substituted toluenes can be prepared according to the following scheme:
  • the 2,4-toluene di-isocyanate, or tolylene-2,4-diisocyanate, (TDI) that is used in the experiments described below is of 95% purity. According to the specifications of the supplier (Aldrich T39853; CAS 584-84-9) it contains about 4% of the 2,6-toluene di-isocyanate isomer. As a result, the described bis-urea (or diurea) products will also contain a small percentage of 2,6-diureido isomers.
  • this organo-gelator OG1 contains 4 different 2,4-bis-(2-ethylhexylureido)-toluene isomer compounds (the R,R-, S,S-, R,S- and S,R-isomers), as well as small amounts of 3 different 2,6-bis-(2-ethylhexylureido)-toluene isomer compounds (the R,R-, the S,S- and the R,S-isomers). Therefore, OG1 is composed of in total 7 compounds, where the 2,4-isomers are examples of structures (III), while the 2,6-isomers are examples of the structures (II).
  • Organo-gelators EHUT (OG1) and DMHUT (OG2) have been mixed in a weight ratio of 4-to-1.
  • the mixture was homogenized by dissolution in a mixture of chloroform and methanol, after which these solvents were removed again by vaccuum evaporation.
  • the product is a white solid.
  • Organogel formation from OG1 to OG5 in oils as detailed in Table 1 was tested by stirring the oil and the organo-gelator at elevated temperatures (about 80 to 100 °C), overnight or during a few hours, and inspecting the solution after cooling down to room temperature.
  • OG1 was used to prepare clear, macroscopically homogeneous and stable 5 w/w% and 10 w/w% organogels in heptamethylnonane, Nynas S8,5 and Nyflex 800. Furthermore, 2.5 w/w% and 15 w/w% organogels were prepared in heptamethylnonane.
  • the vials containing these OG1-organogels can be kept up-side down and no flowing of the gel-solution is observed. In the time scale of hours, flow can be recorded, so the organogels are visco-elastic.
  • the 5 w/w% organogel has elastic properties, while the 10 w/w% organogel is also elastic, but is harder in nature.
  • the 5 w/w% organogels from OG1 in heptamethylnonane and Nynas S8,5 have been monitored during at least 2 and a half years and remain stable, as inverting the vials does not result in flowing, the organogels remain clear, no precipitation or bleeding is observed, and stirring with a pipet in the organogel does not induce bleeding or precipitation.
  • OG2, OG3, OG4 and OG5 were used to prepare clear, stable and homogeneous 5 w/w% organogels in heptamethylnonane, Nynas S8,5 and Nyflex 800.
  • organo-gelators OG1 and OG3 could not be properly dissolved at elevated temperatures in the Nynas S100B or the Nynas T110 oil, not even at further heating to about 120 °C, and on cooling further precipitation occured, leaving inhomogeneous mixtures at room temperature.
  • Benzene-1,3,5-tricarboxamides can be prepared according to the following scheme:
  • This organo-gelator is therefore composed of 4 different BTA-compounds: the S,S,S-, the S,S,R-, the S,R,R- and the R,R,R-isomer.
  • BTAs are examples of structures VII.
  • Organo-gelator 7 (OG7):
  • This organo-gelator is therefore composed of only 1 BTA-compound: the S,S,S-isomer.
  • BTAs benzene-1,3,5-tricarboxamides
  • C4-BTA n-butyl
  • C6-BTA n-hexyl
  • C8-BTA n-octyl
  • C10-BTA n-decyl
  • C12-BTA n-dodecyl
  • C14-BTA n-tetradecyl
  • Organo-gelator OG8 was then prepared by mixing C4-BTA, C6-BTA, C8-BTA, C10-BTA, C12-BTA and C14-BTA in an even molar ratio.
  • the organo-gelator OG9 was prepared by reacting benzene-1,3,5-tricarboxylic acid chloride with a mixture of primary amines R-NH 2 in the presence of triethylamine base.
  • BTAs benzene-1,3,5-tricarboxamides
  • the five primary amine reactants n-hexyl amine, n-octyl amine, n-decyl amine, n-dodecyl amine and cyclohexyl amine were applied in a 1:1:1:1:4 molar ratio.
  • the isolated organo-gelator was a white solid material.
  • Organo-gelator 10 (OG10) :
  • the organo-gelator was prepared in a similar way as OG9.
  • the five primary amine reactants n-hexyl amine, n-octyl amine, n-decyl amine, n-dodecyl amine and racemic 2-ethyl-hexyl amine were applied in a 1:1:1:1:4 molar ratio.
  • the isolated organo-gelator was a white solid material.
  • organogel formation of OG6 to OG10 in oils as detailed in Table 1 was tested by stirring the oil and the organo-gelator at elevated temperatures (about 80 to 100 °C), overnight or during a few hours, and inspecting the solution after cooling down to room temperature.
  • organogels were prepared from organo-gelator OG6 in the heptamethylnonane, Nynas S8,5, Nyflex 800 and Nynas T9 oils.
  • organo-gelators OG6 and OG7 could not be properly dissolved at elevated temperatures in the Nynas S100B or the Nynas T110 oil, and on cooling further precipitation occured, leaving inhomogeneous mixtures at room temperature.
  • Organo-gelator 11 1-benzyl-3-octyl urea
  • Octyl isocyanate (1,38g) was added to a solution of benzyl amine (1g) in toluene (50 mL). The reaction mixture was stirred overnight at room temperature under an inert nitrogen atmosphere, and was then diluted with hexane to induce precipitation of the white product. The solid was collected by filtration, was then washed with several portions of hexane, and dried.
  • Organo-gelator 12 (OG12) :
  • DDBS Dimethyldibenzylidene sorbitol
  • Organo-gelators OG11 and OG12 could not be dissolved in the Nynas T110 or Nynas S100B oils. Stirring at room temperature showed no swelling or thickening of the mixture, and subsequent heating to about 100 °C, and thereafter over 100 °C, did also not result in dissolution, leaving a suspension of organo-gelator and oil after cooling to room temperature. OG11 was tested on a 5w/w% level, while OG12 was tested on a 2w/w% level.
  • BHT butyl hydroxytoluene; 2,6-di-tert-butyl-4-methylphenol, CAS 128-37-0
  • a known anti-oxidant and stabilizer was stirred in the Nynas S8,5 oil at room temperature to give a 0.2 w/w% BHT solution.
  • This solution and the appropriate amount of EHUT (OG1) was stirred at room temperature (swelling was observed), and then at about 100 °C for several hours. Cooling to room temperature produced a clear 5 w/w% dielectric fluid containing the BHT anti-oxidant.
  • OG1 EHUT
  • Nyflex 800 was stirred in Nyflex 800 at room temperature to produce a 0.25 w/w% PIB solution.
  • This solution and the appropriate amount of EHUT (OG1) was stirred overnight at about 80 °C, and was then cooled to room temperature to produce a clear 5 w/w% dielectric fluid containing PIB and OG1-organogel.
  • the gel point is determined thanks to a Brookfield rheometer.
  • the viscosity measurements are done from 4°C to 110°C at 0,5 °C/min under oscillation of 0,095 Hz and under a strain of 0,01%.
  • Figure 2 represents the storage modulus G' and the loss modulus G" curves as well as the complex viscosity respectively in function of the temperature of the 5 w/w% organogel of EHUT (OG1) in Nyflex 800.
  • the gel point of said organogel is the intersection of the G' curve and the G" curve, which is at 55-60°C.
  • the complex viscosity drop between 45 °C and 90°C is from about 800 Pa.s to less than 0,2 Pa.s, and a complex viscosity drop of more than three decades and more than 500 Pa.s is observed within 30 °C.
  • the impregnation step consists on impregnating the insulating paper tape after this latter is applied around the conductor.
  • the insulating paper tape is wound around the conductor to form an electric cable and this latter is introduced into a vessel in presence of the organogel.
  • the impregnation step into the vessel is done at a temperature superior to the gel point of the organogel (superior to 60°C). Said temperature range allows to optimize the impregnation from the organogel to the insulating paper. Then the organogel excess in the vessel is pumped through a heat exchanger and, after the vessel is cooled, an impregnated insulating paper tape is obtained.
  • the organo-gelator EHUT (OG1) can stably gelate non-polar Nynas oils, as the impregnated insulating paper tape does not show bleeding (i.e. bleeding is phase separation between an oil phase and a gel phase), even after standing for 6 months.
  • the breakdown voltage of the organogel is measured according to IEC 156 standard.
  • the high breakdown properties of the insulating paper impregnated with organogel is obtained in using two electrodes with three layers of impregnated DC-paper of 70 micron each in between.
  • a Haefely DC generator is used to apply voltage steps of 5 kV (during 1 minute) until a DC breakdown appears in the impregnated insulating paper tape.
  • the DC breakdown is measured at 60 °C, and the DC breakdown occurs at a value superior to 200 kV/mm.

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EP3466398A1 (de) 2017-10-05 2019-04-10 Rhodia Operations N-hydrocarbyldiamid-zusammensetzung mit gelierenden eigenschaften
EP3640953A1 (de) * 2018-10-19 2020-04-22 Rolls-Royce Corporation Koaxialkabelsystem für gasturbinenmotor
US11348705B2 (en) 2018-10-19 2022-05-31 Rolls-Royce Corporation Coaxial cable system for gas turbine engine
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EP2254127A1 (de) 2010-11-24
KR20100125192A (ko) 2010-11-30

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