EP4093834A1 - Dielectric compositions with improved properties - Google Patents

Dielectric compositions with improved properties

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Publication number
EP4093834A1
EP4093834A1 EP21706338.7A EP21706338A EP4093834A1 EP 4093834 A1 EP4093834 A1 EP 4093834A1 EP 21706338 A EP21706338 A EP 21706338A EP 4093834 A1 EP4093834 A1 EP 4093834A1
Authority
EP
European Patent Office
Prior art keywords
weight
composition
halogenated hydrocarbon
use according
chosen
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP21706338.7A
Other languages
German (de)
French (fr)
Inventor
Jeremie WALKER
Bernard Monguillon
Dominique Garrait
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Arkema France SA
Original Assignee
Arkema France SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Arkema France SA filed Critical Arkema France SA
Publication of EP4093834A1 publication Critical patent/EP4093834A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/08—Materials not undergoing a change of physical state when used
    • C09K5/10—Liquid materials
    • 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

Definitions

  • the present invention relates to dielectric fluids that can be used in various types of electrical or electronic equipment, and in particular in transformers, capacitors, cables, instrument transformers, bushings ("bushing" in English), load tap changers, to name just the main ones.
  • the dielectric fluids used today are insulating oils and having the characteristics of heat transfer fluids in order to dissipate the calories possibly generated by the operation of this equipment.
  • the problem currently encountered with the dielectric fluids commonly used in this electrical equipment is that these fluids generally have relatively low flash points, thus leading to high risks of fire, due to the relatively frequent electric discharges during the operation of these electrical equipment.
  • PCB PolyChloroBiphenyl type
  • the present invention relates to the use of a composition comprising: a) at least one dielectric fluid, and b) at least one halogenated hydrocarbon, as an insulating fluid in electrical equipment.
  • the composition comprises at least one dielectric fluid chosen from dielectric fluids well known to those skilled in the art. These dielectric fluids are mainly and most commonly chosen from mineral, synthetic and vegetable dielectric oils and their mixtures.
  • dielectric fluid is meant, within the meaning of the present invention, a fluid which does not conduct (or only slightly) electricity but allows electrostatic forces to be exerted.
  • the dielectric fluid comprises at least one dielectric fluid chosen from mineral dielectric oils and synthetic dielectric oils, vegetable oils, as well as their mixtures in all proportions. Synthetic dielectric oils are preferred.
  • the dielectric fluid comprises at least one mineral dielectric oil.
  • mineral dielectric oils include paraffinic oils and naphthenic oils, such as dielectric oils of the Nytro family, sold by the company Nynas (in particular Nytro Taurus, Nytro Libra, Nytro 4000X and Nytro 10XN), and Dalia, marketed by the Shell company.
  • the dielectric fluid is a synthetic dielectric oil.
  • oils Synthetic include aromatic hydrocarbons, aliphatic hydrocarbons, silicone oils, and esters, as well as mixtures of two or more of them in any proportion.
  • alkylbenzenes alkyldiphenylethanes (for example phenylxylylethane (PXE), phenylethylphenylethane (PEPE), mono-isopropyl-biphenyl (MIPB), 1, 1 -diphenylethane ( 1, 1 -DPE), alkylnaphthalenes (for example di-iso-propylnaphthalene (DIPN)), methylpolyarylmethanes (for example benzyltoluene (BT) and dibenzyltolulene DBT), and mixtures thereof.
  • PXE phenylxylylethane
  • PEPE phenylethylphenylethane
  • MIPB mono-isopropyl-biphenyl
  • 1, 1 -DPE alkylnaphthalenes
  • DIPN di-iso-propylnaphthalene
  • aromatic hydrocarbons it should be understood that 'at least one ring is aromatic and that, optionally, one or more other ring (s) present (s) may be partially or totally unsaturated.
  • dielectric fluids marketed by Soltex Inc, by the Arkema company under the name Jarylec ® , and SAS 60E from JX Nippon Chemical Texas Inc.
  • PAO poly (apha) olefins
  • PIB polyisobutene
  • olefins of vinylidene type such as those marketed for example by the company Soltex Inc.
  • silicone oils include, without limitation, linear polydimethylsiloxane silicone oils types, such as for example those sold by the company Wacker under the name Wacker ® AK.
  • esters of phthalic type such as dioctylphthalate (DOP) or di-isononylphthalate (DINP) (sold for example by the company BASF).
  • DOP dioctylphthalate
  • DINP di-isononylphthalate
  • esters resulting from the reaction between a polyalcohol and an organic acid in particular an acid chosen from organic acids in CA to C22, saturated or unsaturated.
  • organic acids mention may be made of undecanoic acid, heptanoic acid, octanoic acid, palmitic acid, and mixtures thereof.
  • polyols which can be used for the synthesis of the abovementioned esters mention may be made, by way of nonlimiting examples, of pentaerythytritol.
  • the synthetic esters resulting from the reaction between a polyalcohol and an organic acid are for example the products of the Midel ® range, such as for example Midel ® 7131, or of the Mivolt ® range, such as for example Mivolt ® DFK and Mivolt ® DF7 from the company M & l Materials, or the esters of the Nycodiel range from the company Nyco.
  • the composition further comprises at least one halogenated hydrocarbon.
  • the halogenated hydrocarbon can be of any type well known to a person skilled in the art chosen from halogenated hydrocarbons as such, fluorinated ketones, fluorinated ethers, and mixtures thereof, and preferably hydrocarbons comprising at least one d atom. halogen chosen from fluorine, chlorine, bromine and iodine, and more preferably chosen from fluorinated, chlorinated and fluorochlorinated hydrocarbons, and their mixtures in all proportions.
  • the term “halogenated hydrocarbon” is understood to mean a non-aromatic halogenated hydrocarbon, that is to say one not comprising an aromatic ring.
  • halogenated hydrocarbons is meant more particularly the aforementioned hydrocarbons, optionally oxygenated, and which comprise one or more halogen atoms, replacing one or more of the hydrogen atoms present in the hydrocarbon.
  • halogenated hydrocarbons we are talking about perhalogenated hydrocarbons.
  • halogenated hydrocarbons which can be used in the context of the present invention, mention may be made of hydrofluorocarbons, hydrochlorofluorocarbons, hydrofluoro-olefins, hydrochloro-olefins and hydrochlorofluoro-olefins.
  • hydrofluorocarbons hydrofluorocarbons, hydrochlorofluorocarbons, hydrofluoro-olefins, hydrochloro-olefins and hydrochlorofluoro-olefins.
  • halogenated hydrocarbons which can be of all types well known to those skilled in the art, those which meet the ANSI / ASHRAE 34-2019 standard (ISSN 1041-2336) are preferred, and in particular hydrocarbons.
  • halogenated not very flammable, even non-flammable, and more particularly those corresponding to classification A1, B1, A2L, B2L, A2 or B2.
  • the halogenated hydrocarbons are chosen from those having an A1 or B1 orA2L or B2L classification, and very particularly preferably from those having an A1 or B1 classification.
  • hydrofluorocarbons hydrofluorocarbons, hydrochlorofluorocarbons, hydrofluoro-olefins, hydrochloro-olefins and hydrochlorofluro-olefins.
  • the halogenated hydrocarbons include 1, 1, 1, 4,4,4-hexafluorobut-2-ene (HFO-1336mzz, E or Z isomer), 1 -chloro-
  • FIFO-1234ze isomer E or Z
  • difluoromethane FIFC-32
  • 1, 1, 2-tetrafluoroethane FIFC-134a
  • 1, 1, 2,2-tetrafluoroethane HFC- 134
  • 1, 1 -difluoroethane FIFC-152a
  • pentafluoroethane HFC-125
  • 1, 1, 3,3-pentafluorobutane FIFC-365mfc
  • fluoroethane HFC- 161
  • FIFC-227ea 1, 1, 1, 2,3,3,3-heptafluoropropane
  • HFC-263fb 1, 2-dichloroethylene
  • fluorinated ketones there may be mentioned, for example, fluorinated monocetones, perfluorinated monocetones such as 1, 1, 1, 2,2,4,5,5,5-nonafluoro-4- (trifluoromethyl) -3 -pentanone (Novec TM 649 from the company 3M TM).
  • fluorinated ethers examples include methoxynonafluorobutane (HFE7100), ethoxy-nonafluorobutane (HFE-7200), 1 -methoxyheptafluoropropane (FIFE-7000), Novec TM 7000, 7100 7200 from 3M TM), perfluoropolyethers of Galden ® range of Solvay, and mixtures of two or more of them, in all proportions.
  • the halogenated hydrocarbon used in the context of the present can comprise one or more, for example two, or three, or four or five, compounds, as described above.
  • halogenated hydrocarbons chosen from those having a low Global Warming Potential (PRP) or in English “Global Warming Potential” (GWP), as defined in European regulation F- Gas (EU) N ° 517/2014, in force in Europe since January 2015 and which aims to reduce greenhouse gas emissions, for halogenated hydrocarbons.
  • PRP Global Warming Potential
  • GWP Global Warming Potential
  • EU European regulation F- Gas
  • the preferred halogenated hydrocarbons of the present invention are chosen from those having a PRP strictly less than 2500, better still a PRP strictly less than 1500, more advantageously still a PRP strictly less than 1000, and in particular those having a PRP strictly less than 1000. less than 300 and very particularly preferably a GWP strictly less than 150, or even strictly less than 10.
  • the preferred halogenated hydrocarbons have a boiling point greater than or equal to 10 ° C and more preferably a boiling point greater than or equal to 18 ° C.
  • a particularly preferred mode according to the invention is the use of a halogenated hydrocarbon with a boiling point greater than or equal to 25 ° G
  • halogenated hydrocarbons known by the acronyms CFC, HCFO, HFC, HFE, HFO and in particular those chosen from 1, 1, 1, 4,4,4-hexafluorobut-2-ene (HFO-1336mzz , isomer E or Z), 1 -chloro-3,3,3-trifluoropropene (FICFO-1233zd, isomer E or Z), 3,3,4,4,4-pentafluorobut-1 -ene (FIFO-1345fz ), 2,4,4,4-tetrafluorobut-1 -ene (FIFO-1354mfy), 1, 1, 2-trifluoroethylene (HFO-1123), 1, 1, 1, 3,3-pentafluoropropane (HFC-245fa), 2,3,3,3-tetrafluoropropene (HFO-1234yf), 1, 3,3,3-tetrafluoropropene (HFO-1234ze, E or Z isomer), difluoromethane (HFC-3
  • the halogenated hydrocarbon comprises HFO-1233zd in E or Z form, and more preferably HFO-1233zd E.
  • the addition of at least one halogenated hydrocarbon in at least one dielectric fluid makes it possible to obtain a non-flammable composition, or at least with a very high flash point, while retaining the dielectric properties required in electrical equipment.
  • the amount of said at least one halogenated hydrocarbon is between 0 and 100%, limits excluded, preferably between 0 and 80%, limits excluded, more preferably between 0 and 65%, limits excluded, better still between 0 and 50%, limits excluded, relative to the total weight of the composition used as insulating fluid.
  • the amount of said at least one halogenated hydrocarbon is between 0.1% and 25%, limits included by weight relative to the total weight of the composition used as insulating fluid, preferably between 0.1% and 20% by weight, of more preferably between 0.1% and 15% by weight, more preferably between 0.1% and 10% by weight, advantageously between 0.5% and 10% by weight, better still between 1% and 10%, limits included , by weight relative to the total weight of the composition used as insulating fluid.
  • composition which can be used in the context of the present invention may further comprise one or more additives and / or fillers well known to those skilled in the art, and for example chosen from, without limitation, antioxidants, passivators , pour point depressants, decomposition inhibitors, fragrances and flavors, colors, preservatives, and the like and mixtures thereof.
  • a particularly preferred dielectric fluid comprises a decomposition inhibitor.
  • antioxidants which can be advantageously used in the dielectric fluid, mention may be made, by way of nonlimiting examples, of phenolic antioxidants, such as for example dibutylhydroxytoluene, butylhydroxyanisole, tocopherols, as well as the acetates of these phenolic antioxidants; but also amine-type antioxidants, such as for example phenyl-a- naphthylamine, of the diamine type, for example N, N'-di- (2-naphthyl) -para-phenylenediamine, but also ascorbic acid and its salts, esters of ascorbic acid, alone or as mixtures of two or more of them or with other components, such as for example green tea extracts, coffee extracts.
  • phenolic antioxidants such as for example dibutylhydroxytoluene, butylhydroxyanisole, tocopherols, as well as the acetates of these phenolic antioxidants
  • amine-type antioxidants such as for example pheny
  • a particularly suitable antioxidant that is commercially available from Brenntag under the lonol ® trade name.
  • the passivators which can be used as additives in the dielectric fluid which can be used in the context of the present invention are of any type known to those skilled in the art and are advantageously chosen from triazole derivatives, benzimidazoles, imidazoles, thiazole, benzothiazole.
  • triazole derivatives benzimidazoles, imidazoles, thiazole, benzothiazole.
  • dioctylaminomethyl-2,3-benzotriazole and 2-dodécyldithio-imidazole can be mentioned.
  • the fatty acid esters of sucrose the fatty acids.
  • acrylic polymers such as poly (alkyl methacrylate) or even poly (alkyl acrylate).
  • Preferred acrylic polymers are those whose molecular weight is between 50,000 g mol 1 and 500,000 g mol 1 .
  • Examples of such acrylic polymers include polymers which may contain linear alkyl groups comprising from 1 to 20 carbon atoms.
  • the dielectric fluid which can be used in the context of the present invention comprises at least one decomposition inhibitor, as an additive.
  • the decomposition inhibitor can be of any type well known to those skilled in the art and in particular can be chosen from carbodi-imide derivatives such as diphenyl carbodi-imide, di-tolylcarbodi-imide, bis (isopropylphenyl).
  • carbodi-imide bis (butylphenyl) carbodi-imide, but also from phenylglycidyl ethers, or esters, alkylglycidyl ethers, or esters, 3,4-epoxycyclohexylmethyl- (3,4-epoxycyclohexane) carboxylate, compounds of the anthraquinone family, such as for example b-methylanthraquinone marketed under the name “BMAQ”, epoxy derivatives such as vinylcyclohexene diepoxides, 3,4-epoxy-6-methylcyclohexylmethyl- (3,4-epoxy-) carboxylate 6-methylhexane), phenol novolak type epoxy resins, bisphenol A epoxy diglycidyl ether, such as DGEBA or CEL 2021 P, available in particular from the company Whyte Chemicals.
  • BMAQ b-methylanthraquinone marketed under the name “BMAQ”
  • the dielectric fluid which can be used in the context of the present invention comprises at least one decomposition inhibitor.
  • the content by weight of the additive, or of the additives optionally present (s) in the composition which can be used as an insulating fluid in the context of the present invention can range from 0.0001% to 5% by weight, preferably of 0.001% to 3% by weight, more preferably from 0.01% to 2% by weight, limits included, relative to the total weight of the composition.
  • composition according to the invention can be used in any type of electrical equipment.
  • electrical equipment any type of electrical or electronic equipment, whether it is transformers, storage equipment in electrostatic form, elements for transporting electricity or electrical connections, such as as power transformers, distribution transformers, traction transformers, instrument transformers, special transformers, circuit breakers, capacitors, distributors, capacitive dividers, cables, bushings, load tap changers changers ”in English), and others, to name only the main electrical or electronic equipment comprising an insulating fluid.
  • the use of the present invention is characterized in particular by the fact that the insulating fluid is used just like the dielectric fluid, that is to say that the insulating fluid comprising at least one halogenated hydrocarbon advantageously replaces the dielectric fluid commonly used so far.
  • the insulating fluid retains the dielectric properties of said at least one dielectric fluid present in the composition, while exhibiting the desired flammability properties. Furthermore, it has been observed, also quite surprisingly, that the insulating fluid comprising at least one dielectric fluid and at least one halogenated hydrocarbon has improved permittivity, and in particular a higher permittivity than the intrinsic permittivity. dielectric fluid or mixture of dielectric fluids present in the composition.
  • the present invention relates to a composition
  • a composition comprising: a) at least one dielectric fluid, and b) at least one halogenated hydrocarbon, as they have just been defined.
  • the amount of said at least one dielectric fluid is between 0 and 100%, limits excluded, preferably from 20% to 99.5%, preferably from 40% to 99. %, and more preferably from 40% to 98% by weight relative to the total weight of the composition.
  • this content can be from 20% to 25%, or from 25% to 30%, or from 30% to 35%, or from 35 to 40%, or from 40% to 45%, or from 45% to 50%, or 50% to 55%, or 55% to 60%, or 60% to 65%, or 65% to 70%, or 70% to 75%, or 75% at 80%, or from 80% to 85% or from 85% to 90%, limits included, by weight relative to the total weight of the composition according to the invention.
  • the amount of said at least one halogenated hydrocarbon is between 0 and 100%, limits excluded, of preferably between 0 and 80%, limits excluded, more preferably between 0 and 65%, limits excluded, better still between 0 and 50%, limits excluded, by weight relative to the total weight of the composition according to the invention.
  • the amount of said at least one halogenated hydrocarbon is between 0.1% and 45%, limits included by weight relative to the total weight of the composition according to the invention, preferably between 0.1% and 30% by weight, more preferably between 0.1% and 20% by weight, better still between 0.1% and 15%, more preferably between 0.1% and 12% by weight, more preferably between 0.1% and 10%, advantageously between 0.5% and 10% by weight, better still between 1% and 10%, limits included, by weight relative to the total weight of the composition of the invention.
  • composition according to the invention can be prepared by any means well known to those skilled in the art, for example by simply mixing the various components of the composition according to the invention.
  • composition according to the present invention can be prepared by mixing with stirring, preferably cold, preferably at a temperature below the boiling point of the halogenated hydrocarbon, either under atmospheric pressure or under slight pressure , preferably at atmospheric pressure.
  • Light pressure is understood to mean an absolute pressure of maximum 5 bars and at 60 ° C. and preferably an absolute pressure of 2 bars at 25 ° C.
  • the dielectric fluid is first cooled to a temperature slightly below the boiling point of the halogenated hydrocarbon.
  • the halogenated hydrocarbon is added slowly into the dielectric fluid while maintaining the temperature of the medium at a temperature below the boiling point of the halogenated hydrocarbon.
  • the medium is homogenized for a period of a few seconds to several minutes.
  • the homogenization is carried out in a few minutes.
  • Very preferred compositions in the context of the present invention comprise at least one dielectric fluid chosen from synthetic oils and at least one fluorinated or fluorochlorinated hydrocarbon.
  • a particularly suitable composition comprises a mixture of benzyltoluene and dibenzyltoluene (as Jarylec ® from Arkema) and at least one fluorinated or fluorochlorohydrocarbon, such as for example, but are not limiting a fluoropropane, a fluoropropene, a chlorofluoropropane, a chlorofluoropropene, and others as well as their mixtures of two or more of them in all proportions.
  • fluorinated or fluorochlorohydrocarbon such as for example, but are not limiting a fluoropropane, a fluoropropene, a chlorofluoropropane, a chlorofluoropropene, and others as well as their mixtures of two or more of them in all proportions.
  • composition according to the invention can of course comprise one or more additives and / or fillers, as already described above.
  • Very preferred compositions in the context of the present invention are liquid and can be handled at room temperature and at atmospheric pressure. Completely preferred compositions have a low GWP and totally preferably a GWP strictly less than 150. Very preferred compositions according to the scope of the invention are single-phase, very preferably in the liquid state, and have dielectric characteristics suitable for use in electrical equipment.
  • the composition of the present invention can be used in all types of equipment, in particular electrical equipment, but also as a heat transfer fluid for solar oven uses. , thermal power stations (natural, fossil or nuclear fuel), industrial heating systems (boilers, exchangers, synthesis reactors and others) and for the transport of heat in general.
  • a composition was prepared by mixing 15.55% by weight of HCFO-1233zd E and 84.45% by weight of Jarylec ® C101 from Arkema under the conditions shown in Table 1 below below.
  • composition was prepared by mixing 90.16% weight of HCFO-1233zd and E 9.84% by weight of Jarylec ® C101 from Arkema under the conditions shown in Table 2 below . - Table 2 -
  • compositions of dielectric fluids and halogenated hydrocarbons are prepared by mixing the halogenated hydrocarbon in the dielectric fluid at a temperature 5 ° C lower than that of the boiling point of halogenated hydrocarbon and at atmospheric pressure.
  • the mixture of the products is homogeneous and liquid at ambient temperature and atmospheric pressure. Part of the liquid is taken and then introduced into the flash point measuring device.
  • the flash point measurement is carried out according to ISO 3679 and ISO 3680 standards, determination of the flash point, rapid closed cup equilibrium method.
  • the flash point measurement temperature range is between 140 ° C and 290 ° C, with a rise of 20 ° C each time the flash point dies and a stabilization time of 2 minutes.
  • the dielectric fluid is Jarylec ® C101 and the halogenated hydrocarbon is either HCFO-1233zd Z or HCFO-1233zd E.
  • the flash points are measured at temperatures of 140 ° C, 160 ° C, 180 ° C, 200 ° C, 220 ° C, 240 ° C, 260 ° C, 280 ° c and 290 ° C for HCFO-32zd E and from 140 ° c to 290 ° C with jumps of 10 ° C at each measurement for HCF01233zd Z.
  • the boiling points of the halogenated hydrocarbons used are: for HCFO-1233zd Z: 40 ° C at atmospheric pressure, and for HCFO-1233zd E: 18 ° C at atmospheric pressure.
  • the results of flash point measurements according to ISO 3679 and ISO standards are: for HCFO-1233zd Z: 40 ° C at atmospheric pressure, and for HCFO-1233zd E: 18 ° C at atmospheric pressure.
  • compositions are measured according to IEC 61620.
  • the following compositions are prepared by mixing at room temperature and Jarylec ® C101 atmospheric pressure and HCFO-1233zd Z, both in liquid form.
  • Table 4 The results of Table 4 above show that the addition of a halogenated hydrocarbon, even in small quantity, in a dielectric fluid makes it possible to make the flash point undetectable, under the test conditions, which corresponds to a non-flammable composition. Moreover, the addition of a halogenated hydrocarbon, even in a small amount, in a dielectric fluid does not lead to a decrease in the permittivity of the composition, but on the contrary makes it possible to increase the permittivity of said composition, by comparison with the permittivity of the dielectric fluid alone.

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Abstract

The present invention relates to the use of a composition comprising a) at least one dielectric fluid, and b) at least one halogenated hydrocarbon, as insulating fluid in electrical equipment. The invention also relates to a composition comprising a) at least one dielectric fluid, and b) at least one halogenated hydrocarbon, the amount of said at least one dielectric fluid being between 0 and 100%, limits excluded, by weight relative to the total weight of the composition.

Description

COMPOSITIONS DIÉLECTRIQUES À PROPRIÉTÉS AMÉLIORÉES DIELECTRIC COMPOSITIONS WITH IMPROVED PROPERTIES
[0001] La présente invention concerne des fluides diélectriques utilisables dans divers types d’équipements électriques ou électroniques, et en particulier dans les transformateurs, les condensateurs, les câbles, les transformateurs de mesure, les traversées (« bushing » en langue anglaise), les changeurs de prise en charge (« load tap changers » en langue anglaise), pour ne citer que les principaux d’entre eux. The present invention relates to dielectric fluids that can be used in various types of electrical or electronic equipment, and in particular in transformers, capacitors, cables, instrument transformers, bushings ("bushing" in English), load tap changers, to name just the main ones.
[0002] Les fluides diélectriques utilisés aujourd’hui sont des huiles isolantes et possédant des caractéristiques de fluide caloporteurs afin de permettre de dissiper les calories générées éventuellement par les fonctionnements de ces équipements. [0003] Le problème rencontré actuellement avec les fluides diélectriques communément utilisés dans ces équipements électriques est que ces fluides présentent généralement des points éclair relativement bas, conduisant ainsi à des risques élevés d’incendie, en raison des décharges électriques relativement fréquentes lors du fonctionnement de ces équipements électriques. [0002] The dielectric fluids used today are insulating oils and having the characteristics of heat transfer fluids in order to dissipate the calories possibly generated by the operation of this equipment. The problem currently encountered with the dielectric fluids commonly used in this electrical equipment is that these fluids generally have relatively low flash points, thus leading to high risks of fire, due to the relatively frequent electric discharges during the operation of these electrical equipment.
[0004] Ce problème d’inflammabilité ne se présentait pas avec les fluides diélectriques de type PolyChloroBiphényles (PCB), qui étaient d’usage courant jusque dans les années 70, et qui sont maintenant interdits en raison de leur persistance dans le milieu animal (bio-accumulation) et dans l’environnement. [0005] Ces PCB sont maintenant remplacés par d’autres fluides diélectriques qui sont le plus souvent des composés ou compositions avec des points éclairs ne permettant pas d’éviter tout risque d’incendie dans les équipements électriques, comme explicité ci-dessus. This flammability problem did not arise with dielectric fluids of PolyChloroBiphenyl type (PCB), which were in common use until the 1970s, and which are now prohibited due to their persistence in the animal environment ( bio-accumulation) and in the environment. [0005] These PCBs are now replaced by other dielectric fluids which are most often compounds or compositions with flash points that do not make it possible to avoid any risk of fire in electrical equipment, as explained above.
[0006] Or, pour des raisons évidentes de sécurité incendie, notamment dans des endroits confinés ou en souterrain, la non-inflammabilité est une propriété indispensable pour un fluide diélectrique présent dans un équipement électrique. [0007] Par ailleurs un fluide diélectrique doit présenter une certaine permittivité, afin d’optimiser le fonctionnement des appareils électriques tout en maintenant à un niveau acceptable les pertes de puissance par échauffement. [0008] Il reste donc aujourd’hui un besoin pour des fluides diélectriques peu inflammables voir non inflammables et présentant des caractéristiques de permittivité compatibles avec les équipements électriques. [0006] However, for obvious reasons of fire safety, in particular in confined places or underground, non-flammability is an essential property for a dielectric fluid present in electrical equipment. [0007] Furthermore, a dielectric fluid must have a certain permittivity, in order to optimize the operation of electrical devices while maintaining at an acceptable level the power losses by heating. [0008] There therefore remains today a need for dielectric fluids that are not very flammable or even non-flammable and have permittivity characteristics compatible with electrical equipment.
[0009] Les inventeurs ont maintenant découvert de manière surprenant que les objectifs précités peuvent être atteints en totalité ou au moins en partie grâce à l’invention dont la description suit. [0009] The inventors have now surprisingly discovered that the aforementioned objectives can be achieved in whole or at least in part by virtue of the invention, the description of which follows.
[0010] Ainsi, et selon un premier aspect, la présente invention concerne l’utilisation d’une composition comprenant : a) au moins un fluide diélectrique, et b) au moins un hydrocarbure halogéné, comme fluide isolant dans un équipement électrique. [0010] Thus, and according to a first aspect, the present invention relates to the use of a composition comprising: a) at least one dielectric fluid, and b) at least one halogenated hydrocarbon, as an insulating fluid in electrical equipment.
[0011] Il a en effet été découvert que grâce à l’utilisation de cette composition, les risques d’incendie sont grandement diminués, voire supprimés. En outre, les propriétés diélectriques notamment en terme de permittivité sont le plus souvent conservées, voire améliorées. [0011] It has in fact been discovered that thanks to the use of this composition, the risk of fire is greatly reduced or even eliminated. In addition, the dielectric properties, in particular in terms of permittivity, are most often retained, or even improved.
[0012] Selon la présente invention, la composition comprend au moins un fluide diélectrique choisi parmi les fluides diélectriques bien connus de l’homme du métier. Ces fluides diélectriques sont principalement et le plus communément choisis parmi les huiles diélectriques minérales, synthétiques et végétales et leurs mélanges. Par « fluide diélectrique », on entend, au sens de la présente invention, un fluide qui ne conduit pas (ou peu) l'électricité mais laisse s'exercer les forces électrostatiques. [0013] De préférence, le fluide diélectrique comprend au moins un fluide diélectrique choisi parmi les huiles diélectriques minérales et les huiles diélectriques synthétiques, les huiles végétales, ainsi que leurs mélanges en toutes proportions. Les huiles diélectriques synthétiques sont préférées. [0012] According to the present invention, the composition comprises at least one dielectric fluid chosen from dielectric fluids well known to those skilled in the art. These dielectric fluids are mainly and most commonly chosen from mineral, synthetic and vegetable dielectric oils and their mixtures. By “dielectric fluid” is meant, within the meaning of the present invention, a fluid which does not conduct (or only slightly) electricity but allows electrostatic forces to be exerted. Preferably, the dielectric fluid comprises at least one dielectric fluid chosen from mineral dielectric oils and synthetic dielectric oils, vegetable oils, as well as their mixtures in all proportions. Synthetic dielectric oils are preferred.
[0014] Selon un mode de réalisation de l’invention, le fluide diélectrique comprend au moins une huile diélectrique minérale. Des exemples non limitatifs de telles huiles diélectriques minérales comprennent les huiles paraffiniques et les huiles naphténiques, telles que les huiles diélectriques de la famille Nytro, commercialisés par le société Nynas (en particulier Nytro Taurus, Nytro Libra, Nytro 4000X et Nytro 10XN), et Dalia, commercialisé par la société Shell. [0014] According to one embodiment of the invention, the dielectric fluid comprises at least one mineral dielectric oil. Nonlimiting examples of such mineral dielectric oils include paraffinic oils and naphthenic oils, such as dielectric oils of the Nytro family, sold by the company Nynas (in particular Nytro Taurus, Nytro Libra, Nytro 4000X and Nytro 10XN), and Dalia, marketed by the Shell company.
[0015] Selon un autre mode de réalisation de l’invention, le fluide diélectrique est une huile diélectrique synthétique. Des exemples non limitatifs de telles huiles synthétiques comprennent les hydrocarbures aromatiques, les hydrocarbures aliphatiques, les huiles silicones, et les esters, ainsi que les mélanges de deux ou plusieurs d’entre elles en toutes proportions. According to another embodiment of the invention, the dielectric fluid is a synthetic dielectric oil. Nonlimiting examples of such oils Synthetic include aromatic hydrocarbons, aliphatic hydrocarbons, silicone oils, and esters, as well as mixtures of two or more of them in any proportion.
[0016] Parmi les hydrocarbures aromatiques, on peut citer, de manière non limitative, les alkylbenzènes, les alkyldiphényléthanes (par exemple phénylxylyléthane (PXE), phényléthylphényléthane (PEPE), mono-isopropyl- biphényle (MIPB), 1 ,1 -diphényléthane (1 ,1 -DPE), les alkylnaphtalènes (par exemple di-iso-propylnaphtalène (DIPN)), les méthylpolyarylméthanes (par exemple benzyltoluène (BT) et dibenzyltolulène DBT), et leurs mélanges. Dans lesdits hydrocarbures aromatiques, il doit être compris qu’au moins un cycle est aromatique et que, éventuellement, un ou plusieurs autres cycle(s) présent(s) peuvent être partiellement ou totalement insaturé(s). Des exemples tout particulièrement préférés sont les fluides diélectriques commercialisés par Soltex Inc, par la société Arkema sous le nom de Jarylec®, et le SAS 60E de la société JX Nippon Chemical Texas Inc. Among the aromatic hydrocarbons, there may be mentioned, without limitation, alkylbenzenes, alkyldiphenylethanes (for example phenylxylylethane (PXE), phenylethylphenylethane (PEPE), mono-isopropyl-biphenyl (MIPB), 1, 1 -diphenylethane ( 1, 1 -DPE), alkylnaphthalenes (for example di-iso-propylnaphthalene (DIPN)), methylpolyarylmethanes (for example benzyltoluene (BT) and dibenzyltolulene DBT), and mixtures thereof. In said aromatic hydrocarbons, it should be understood that 'at least one ring is aromatic and that, optionally, one or more other ring (s) present (s) may be partially or totally unsaturated. Very particularly preferred examples are the dielectric fluids marketed by Soltex Inc, by the Arkema company under the name Jarylec ® , and SAS 60E from JX Nippon Chemical Texas Inc.
[0017] Parmi les hydrocarbures aliphatiques, on peut citer de manière non limitative, les poly (apha)oléfines (PAO), par exemple les polyisobutène (PIB) ou les oléfines de type vinylidène, telles que celles commercialisées par exemple par la société Soltex Inc. Among aliphatic hydrocarbons, there may be mentioned in a nonlimiting manner, poly (apha) olefins (PAO), for example polyisobutene (PIB) or olefins of vinylidene type, such as those marketed for example by the company Soltex Inc.
[0018] Parmi les huiles silicones, on peut citer de manière non limitative, les huiles silicones linéaires de types polydiméthylsiloxanes, telles que par exemple celles commercialisées par la société Wacker sous la dénomination Wacker® AK. [0018] Among the silicone oils include, without limitation, linear polydimethylsiloxane silicone oils types, such as for example those sold by the company Wacker under the name Wacker ® AK.
[0019] Parmi les esters synthétiques, on peut citer de manière non limitative les esters de type phtalique tels que le dioctylphtalate (DOP) ou le di-isononylphtalate (DINP) (commercialisé par exemple par la société BASF). Among the synthetic esters, mention may be made without limitation of esters of phthalic type such as dioctylphthalate (DOP) or di-isononylphthalate (DINP) (sold for example by the company BASF).
[0020] On peut également citer de manière non limitative les esters issus de la réaction entre un polyalcool et un acide organique, en particulier un acide choisi parmi les acides organiques en CA à C22, saturés ou insaturés. À titre d’exemples non limitatifs de tels acides organiques, on peut citer l’acide undécanoïque, l’acide heptanoïque, l’acide octanoïque, l’acide palmitique, et leurs mélanges. Parmi les polyols qui peuvent être utilisés pour la synthèse des esters précités, on peut citer, à titre d’exemples non limitatifs, le pentaérhytritol. [0021] Ainsi les esters synthétiques issus de la réaction entre un polyalcool et un acide organique sont par exemple les produits de la gamme Midel®, comme par exemple le Midel® 7131 , ou de la gamme Mivolt®, comme par exemple le Mivolt® DFK et le Mivolt® DF7 de la société M&l Materials, ou encore les esters de la gamme Nycodiel de la société Nyco. Mention may also be made, in a nonlimiting manner, of the esters resulting from the reaction between a polyalcohol and an organic acid, in particular an acid chosen from organic acids in CA to C22, saturated or unsaturated. By way of nonlimiting examples of such organic acids, mention may be made of undecanoic acid, heptanoic acid, octanoic acid, palmitic acid, and mixtures thereof. Among the polyols which can be used for the synthesis of the abovementioned esters, mention may be made, by way of nonlimiting examples, of pentaerythytritol. Thus the synthetic esters resulting from the reaction between a polyalcohol and an organic acid are for example the products of the Midel ® range, such as for example Midel ® 7131, or of the Mivolt ® range, such as for example Mivolt ® DFK and Mivolt ® DF7 from the company M & l Materials, or the esters of the Nycodiel range from the company Nyco.
[0022] Parmi les esters naturels et les huiles végétales, on peut citer de manière non limitative, les produits issus de graines huileuses ou d’autres sources d’origine naturelle. On peut citer à titre d’exemple et de manière non limitative le FR3™ ou encore l’Envirotemp™ commercialisés par la société Cargill ou encore le Midel eN 1215 commercialisé par la société M&l Materials. [0022] Among the natural esters and vegetable oils, mention may be made, without limitation, of products derived from oily seeds or other sources of natural origin. Mention may be made, by way of example and in a nonlimiting manner, of FR3 ™ or even Envirotemp ™ marketed by the company Cargill or else the Midel eN 1215 marketed by the company M & l Materials.
[0023] Dans l’utilisation selon la présente invention, la composition comprend en outre au moins un hydrocarbure halogéné. L’hydrocarbure halogéné peut être de tout type bien connu de l’homme du métier choisi parmi les hydrocarbures halogénés en tant que tels, les cétones fluorées, les éthers fluorés, et leurs mélanges, et de préférence les hydrocarbures comprenant au moins un atome d’halogène choisi parmi fluor, chlore, brome et iode, et de préférence encore choisi parmi les hydrocarbures fluorés, chlorés, fluorochlorés, et leurs mélanges en toutes proportions. Au sens de la présente invention, par « hydrocarbure halogéné », on entend un hydrocarbure halogéné non aromatique, c’est-à-dire ne comportant pas de cycle aromatique. [0023] In the use according to the present invention, the composition further comprises at least one halogenated hydrocarbon. The halogenated hydrocarbon can be of any type well known to a person skilled in the art chosen from halogenated hydrocarbons as such, fluorinated ketones, fluorinated ethers, and mixtures thereof, and preferably hydrocarbons comprising at least one d atom. halogen chosen from fluorine, chlorine, bromine and iodine, and more preferably chosen from fluorinated, chlorinated and fluorochlorinated hydrocarbons, and their mixtures in all proportions. For the purposes of the present invention, the term “halogenated hydrocarbon” is understood to mean a non-aromatic halogenated hydrocarbon, that is to say one not comprising an aromatic ring.
[0024] Par « hydrocarbures halogénés » on entend plus particulièrement les hydrocarbures précités, éventuellement oxygénés, et qui comprennent un ou plusieurs atomes d’halogène, venant en substitution d’un ou plusieurs des atomes d’hydrogène présents dans l’hydrocarbure. Lorsque tous les atomes d’hydrogène sont substitués par des atomes d’halogène, on parle alors d’hydrocarbures perhalogénés. By "halogenated hydrocarbons" is meant more particularly the aforementioned hydrocarbons, optionally oxygenated, and which comprise one or more halogen atoms, replacing one or more of the hydrogen atoms present in the hydrocarbon. When all of the hydrogen atoms are substituted by halogen atoms, we are talking about perhalogenated hydrocarbons.
[0025] Parmi les hydrocarbures halogénés qui peuvent être utilisés dans le cadre de la présente invention, on peut citer les hydrofluorocarbures, les hydrochlorofluorocarbures, les hydrofluoro-oléfines, les hydrochloro-oléfines et les hydrochlorofluoro-oléfines. Parmi les hydrocarbures halogénés, qui peuvent être de tous types bien connus de l’homme du métier, on préfère ceux qui répondent à la norme ANSI/ASHRAE 34-2019 (ISSN 1041 -2336) et notamment les hydrocarbures halogénés peu inflammables, voire ininflammables, et plus particulièrement ceux répondant à la classification A1 , B1 , A2L, B2L, A2 ou B2. Among the halogenated hydrocarbons which can be used in the context of the present invention, mention may be made of hydrofluorocarbons, hydrochlorofluorocarbons, hydrofluoro-olefins, hydrochloro-olefins and hydrochlorofluoro-olefins. Among the halogenated hydrocarbons, which can be of all types well known to those skilled in the art, those which meet the ANSI / ASHRAE 34-2019 standard (ISSN 1041-2336) are preferred, and in particular hydrocarbons. halogenated, not very flammable, even non-flammable, and more particularly those corresponding to classification A1, B1, A2L, B2L, A2 or B2.
[0026] De manière préféré, les hydrocarbures halogénés sont choisis parmi ceux ayant une classification A1 ou B1 ouA2L ou B2L, et de manière tout particulièrement préférée parmi ceux ayant une classification A1 ou B1. Preferably, the halogenated hydrocarbons are chosen from those having an A1 or B1 orA2L or B2L classification, and very particularly preferably from those having an A1 or B1 classification.
[0027] Parmi les hydrocarbures halogénés, on peut citer les hydrofluorocarbures, les hydrochlorofluorocarbures, les hydrofluoro-oléfines, les hydrochloro-oléfines et les hydrochlorofluro-oléfines. Among the halogenated hydrocarbons, mention may be made of hydrofluorocarbons, hydrochlorofluorocarbons, hydrofluoro-olefins, hydrochloro-olefins and hydrochlorofluro-olefins.
[0028] À titre d’exemples non limitatifs, les hydrocarbures halogénés comprennent le 1 ,1 ,1 ,4,4,4-hexafluorobut-2-ène (HFO-1336mzz, isomère E ou Z), le 1 -chloro-[0028] By way of non-limiting examples, the halogenated hydrocarbons include 1, 1, 1, 4,4,4-hexafluorobut-2-ene (HFO-1336mzz, E or Z isomer), 1 -chloro-
3.3.3-trifluoropropène (HCFO-1233zd, isomère E ou Z), le 3,3,4,4,4-pentafluorobut- 1-ène (FIFO-1345fz), le 2,4,4,4-tétrafluorobut-1 -ène (FIFO-1354mfy), le 1 ,1 ,2- trifluoroéthylène (FIFO-1123), le 1 ,1 ,1 ,3,3-pentafluoropropane (FIFC-245fa), le3.3.3-trifluoropropene (HCFO-1233zd, E or Z isomer), 3,3,4,4,4-pentafluorobut-1-ene (FIFO-1345fz), 2,4,4,4-tetrafluorobut-1 -ene (FIFO-1354mfy), 1, 1, 2-trifluoroethylene (FIFO-1123), 1, 1, 1, 3,3-pentafluoropropane (FIFC-245fa),
2.3.3.3-tétrafluoropropène (FIFO-1234yf), le 1 ,3,3,3-tétrafluoropropène2.3.3.3-tetrafluoropropene (FIFO-1234yf), 1, 3,3,3-tetrafluoropropene
(FIFO-1234ze, isomère E ou Z), le difluorométhane (FIFC-32), le 1 ,1 ,1 ,2-tétra- fluoroéthane (FIFC-134a), le 1 ,1 ,2,2-tétrafluoroéthane (HFC-134), le 1 ,1 -difluoro- éthane (FIFC-152a), le pentafluoroéthane (HFC-125), le 1 ,1 ,1 ,3,3-pentafluoro- butane (FIFC-365mfc), le fluoroéthane (HFC-161 ), le 1 ,1 ,1 ,2,3,3,3-heptafluoro- propane (FIFC-227ea), le 1 ,1 ,1 -trifluoropropane (HFC-263fb), le 1 ,2-dichloro- éthylene (E ou Z), et les mélanges de deux ou plusieurs d’entre eux, en toutes proportions. (FIFO-1234ze, isomer E or Z), difluoromethane (FIFC-32), 1, 1, 1, 2-tetrafluoroethane (FIFC-134a), 1, 1, 2,2-tetrafluoroethane (HFC- 134), 1, 1 -difluoroethane (FIFC-152a), pentafluoroethane (HFC-125), 1, 1, 1, 3,3-pentafluorobutane (FIFC-365mfc), fluoroethane (HFC- 161), 1, 1, 1, 2,3,3,3-heptafluoropropane (FIFC-227ea), 1, 1, 1 -trifluoropropane (HFC-263fb), 1, 2-dichloroethylene ( E or Z), and mixtures of two or more of them, in all proportions.
[0029] Parmi les cétones fluorées, on peut citer par exemple les monocétones fluorées, les monocétones perfluorées tels que la 1 ,1 ,1 ,2,2,4,5,5,5-nonafluoro-4- (trifluorométhyl)-3-pentanone (Novec™ 649 de la société 3M™). Among the fluorinated ketones, there may be mentioned, for example, fluorinated monocetones, perfluorinated monocetones such as 1, 1, 1, 2,2,4,5,5,5-nonafluoro-4- (trifluoromethyl) -3 -pentanone (Novec ™ 649 from the company 3M ™).
[0030] Parmi les éthers fluorés, on peut citer par exemple les hydrofluoroéthers tel que le méthoxynonafluorobutane (HFE7100), l’éthoxy-nonafluorobutane (HFE- 7200), le 1 -méthoxyheptafluoropropane (FIFE-7000), les Novec™ 7000, 7100, 7200 de la société 3M™), les perfluoropolyéthers de la gamme Galden® de la société Solvay, et les mélanges de deux ou plusieurs d’entre eux, en toutes proportions. [0031] L’hydrocarbure halogéné utilisé dans le cadre de la présente peut comprendre un ou plusieurs, par exemple deux, ou trois, ou quatre ou cinq, composés, tels que décrits ci-dessus. [0032] Selon encore un autre mode de réalisation préféré de la présente invention, on préfère les hydrocarbures halogénés choisis parmi ceux présentant un bas Potentiel de Réchauffement Planétaire (PRP) ou en langue anglaise « Global Warming Potential » (GWP), comme défini dans la réglementation européenne F- Gaz (UE) N°517/2014, en vigueur en Europe depuis Janvier 2015 et qui vise à réduire les émissions de gaz à effet de serre, pour les hydrocarbures halogénés. [0033] Avantageusement, les hydrocarbures halogénés préférés de la présente invention sont choisis parmi ceux ayant PRP strictement inférieur à 2500, mieux encore un PRP strictement inférieur à 1500, plus avantageusement encore un PRP strictement inférieur à 1000, et notamment ceux ayant un PRP strictement inférieur à 300 et de manière tout particulièrement préférée un PRP strictement inférieur à 150, voire strictement inférieur à 10. Among the fluorinated ethers, mention may be made, for example, of hydrofluoroethers such as methoxynonafluorobutane (HFE7100), ethoxy-nonafluorobutane (HFE-7200), 1 -methoxyheptafluoropropane (FIFE-7000), Novec ™ 7000, 7100 7200 from 3M ™), perfluoropolyethers of Galden ® range of Solvay, and mixtures of two or more of them, in all proportions. The halogenated hydrocarbon used in the context of the present can comprise one or more, for example two, or three, or four or five, compounds, as described above. According to yet another preferred embodiment of the present invention, preferred are halogenated hydrocarbons chosen from those having a low Global Warming Potential (PRP) or in English "Global Warming Potential" (GWP), as defined in European regulation F- Gas (EU) N ° 517/2014, in force in Europe since January 2015 and which aims to reduce greenhouse gas emissions, for halogenated hydrocarbons. Advantageously, the preferred halogenated hydrocarbons of the present invention are chosen from those having a PRP strictly less than 2500, better still a PRP strictly less than 1500, more advantageously still a PRP strictly less than 1000, and in particular those having a PRP strictly less than 1000. less than 300 and very particularly preferably a GWP strictly less than 150, or even strictly less than 10.
[0034] Selon encore un autre mode de réalisation de l’invention, les hydrocarbures halogénés préférés présentent un point d’ébullition supérieur ou égal à 10° C et de manière plus préférée un point d’ébullition supérieur ou égal à 18°C. Un mode particulièrement préféré selon l’invention est l’utilisation d’hydrocarbure halogéné avec un point d’ébullition supérieur ou égal à 25°G [0034] According to yet another embodiment of the invention, the preferred halogenated hydrocarbons have a boiling point greater than or equal to 10 ° C and more preferably a boiling point greater than or equal to 18 ° C. A particularly preferred mode according to the invention is the use of a halogenated hydrocarbon with a boiling point greater than or equal to 25 ° G
[0035] On préfère tout particulièrement les hydrocarbures halogénés connus sous les acronymes CFC, HCFO, HFC, HFE, HFO et notamment ceux choisis parmi le 1 ,1 ,1 ,4,4,4-hexafluorobut-2-ène (HFO-1336mzz, isomère E ou Z), le 1 -chloro-3,3,3- trifluoropropène (FICFO-1233zd, isomère E ou Z), le 3,3,4,4,4-pentafluorobut-1 -ène (FIFO-1345fz), le 2,4,4,4-tétrafluorobut-1 -ène (FIFO-1354mfy), le 1 ,1 ,2-trifluoro- éthylène (HFO-1123), le 1 ,1 ,1 ,3,3-pentafluoropropane (HFC-245fa), le 2,3,3,3-tétrafluoropropène (HFO-1234yf), le 1 ,3,3,3-tétrafluoropropène (HFO-1234ze, isomère E ou Z), le difluorométhane (HFC-32), le 1 , 1 ,1 ,2- tétrafluoroéthane (HFC-134a), le 1 ,1 ,2,2-tétrafluoroéthane (HFC-134), le 1 ,1 - difluoroéthane (HFC-152a), le pentafluoroéthane (HFC-125), le 1 ,1 ,1 ,3,3- pentafluorobutane (HFC-365mfc), le fluoroéthane (HFC-161 ), le 1 ,1 ,1 ,2,3,3,3 heptafluoropropane (HFC-227ea), le 1 ,1 ,1 -trifluoropropane (HFC-263fb), les HFE Novec™ 7000, Novec™ 7200, les cétones halogénées Novec™ 649 et les mélanges de deux ou plusieurs d’entre eux en toutes proportions, pour ne citer que les hydrocarbures halogénés principaux, et plus particulièrement encore ceux choisis parmi les HFO F1233zd E, F1233zd Z, F1336mz Z, les HFE Novec™ 7000, Novec™ 7200, les cétones halogénées Novec™ 649, les perfluoropolyéthers de la gamme Galden®, notamment HT55 à H270, ainsi que les mélanges de deux ou plusieurs de ces hydrocarbures halogénés principaux, en toutes proportions. Most particularly preferred are halogenated hydrocarbons known by the acronyms CFC, HCFO, HFC, HFE, HFO and in particular those chosen from 1, 1, 1, 4,4,4-hexafluorobut-2-ene (HFO-1336mzz , isomer E or Z), 1 -chloro-3,3,3-trifluoropropene (FICFO-1233zd, isomer E or Z), 3,3,4,4,4-pentafluorobut-1 -ene (FIFO-1345fz ), 2,4,4,4-tetrafluorobut-1 -ene (FIFO-1354mfy), 1, 1, 2-trifluoroethylene (HFO-1123), 1, 1, 1, 3,3-pentafluoropropane (HFC-245fa), 2,3,3,3-tetrafluoropropene (HFO-1234yf), 1, 3,3,3-tetrafluoropropene (HFO-1234ze, E or Z isomer), difluoromethane (HFC-32) , 1, 1, 1, 2-tetrafluoroethane (HFC-134a), 1, 1, 2,2-tetrafluoroethane (HFC-134), 1, 1 - difluoroethane (HFC-152a), pentafluoroethane (HFC- 125), 1, 1, 1, 3,3-pentafluorobutane (HFC-365mfc), fluoroethane (HFC-161), 1, 1, 1, 2,3,3,3 heptafluoropropane (HFC-227ea), 1, 1, 1 -trifluoropropane (HFC-263fb), HFE Novec ™ 7000, Novec ™ 7200, halogenated ketones No vec ™ 649 and mixtures of two or more of them in all proportions, to mention only the main halogenated hydrocarbons, and more particularly still those chosen from HFOs F1233zd E, F1233zd Z, F1336mz Z, HFE Novec ™ 7000 , Novec ™ 7200, the halogenated ketones Novec ™ 649, the perfluoropolyethers of the Galden ® range, in particular HT55 to H270, as well as mixtures of two or more of these main halogenated hydrocarbons, in all proportions.
[0036] Dans un mode de réalisation tout particulièrement préféré, l’hydrocarbure halogéné comprend le HFO-1233zd sous forme E ou Z, et de préférence encore le HFO-1233zd E. In a very particularly preferred embodiment, the halogenated hydrocarbon comprises HFO-1233zd in E or Z form, and more preferably HFO-1233zd E.
[0037] Il a été observé de manière surprenante que l’ajout d’au moins un hydrocarbure halogéné dans au moins un fluide diélectrique permet d’obtenir une composition ininflammable, ou tout au moins avec un point éclair très élevé, tout en conservant les propriétés diélectriques requises dans les équipements électriques. [0038] Dans un mode de réalisation préféré de l’invention, la quantité dudit au moins un hydrocarbure halogéné est comprise entre 0 et 100%, bornes exclues, de préférence entre 0 et 80%, bornes exclues, de préférence encore entre 0 et 65%, bornes exclues, mieux entre 0 et 50%, bornes exclues, par rapport au poids total de la composition utilisée comme fluide isolant. Avantageusement la quantité dudit au moins un hydrocarbure halogéné est comprise entre 0,1% et 25%, bornes incluses en poids par rapport au poids total de la composition utilisée comme fluide isolant, préférentiellement entre 0,1 % et 20% en poids, de préférence encore entre 0,1 % et 15% en poids, de préférence encore entre 0, 1 % et 10% en poids, avantageusement entre 0,5% et 10% en poids, mieux encore entre 1 % et 10%, bornes incluses, en poids par rapport au poids total de la composition utilisée comme fluide isolant. [0039] La composition utilisable dans le cadre de la présente invention peut en outre comprendre un ou plusieurs additifs et/ou charges bien connus de l’homme du métier, et par exemple choisis parmi, de manière non limitative, les antioxydants, les passivateurs, les abaisseurs de point d’écoulement, les inhibiteurs de décomposition, les parfums et arômes, les colorants, les conservateurs, et autres et leurs mélanges. Un fluide diélectrique tout particulièrement préféré comprend un inhibiteur de décomposition. It was surprisingly observed that the addition of at least one halogenated hydrocarbon in at least one dielectric fluid makes it possible to obtain a non-flammable composition, or at least with a very high flash point, while retaining the dielectric properties required in electrical equipment. In a preferred embodiment of the invention, the amount of said at least one halogenated hydrocarbon is between 0 and 100%, limits excluded, preferably between 0 and 80%, limits excluded, more preferably between 0 and 65%, limits excluded, better still between 0 and 50%, limits excluded, relative to the total weight of the composition used as insulating fluid. Advantageously, the amount of said at least one halogenated hydrocarbon is between 0.1% and 25%, limits included by weight relative to the total weight of the composition used as insulating fluid, preferably between 0.1% and 20% by weight, of more preferably between 0.1% and 15% by weight, more preferably between 0.1% and 10% by weight, advantageously between 0.5% and 10% by weight, better still between 1% and 10%, limits included , by weight relative to the total weight of the composition used as insulating fluid. The composition which can be used in the context of the present invention may further comprise one or more additives and / or fillers well known to those skilled in the art, and for example chosen from, without limitation, antioxidants, passivators , pour point depressants, decomposition inhibitors, fragrances and flavors, colors, preservatives, and the like and mixtures thereof. A particularly preferred dielectric fluid comprises a decomposition inhibitor.
[0040] Parmi les antioxydants qui peuvent être avantageusement utilisés dans le fluide diélectrique, on peut citer, à titre d’exemples non limitatifs les antioxydants phénoliques, tels que par exemple le dibutylhydroxytoluène, le butylhydroxyanisole, les tocophérols, ainsi que les acétates de ces anti-oxydants phénoliques ; mais aussi les antioxydants de type amine, tels que par exemple la phényl-a- naphtylamine, de type diamine, par exemple la N,N’-di-(2-naphtyl )-para- phénylènediamine, mais aussi l’acide ascorbique et ses sels, les esters de l’acide ascorbique, seuls ou en mélanges de deux ou plusieurs d’entre eux ou avec d’autres composants, comme par exemple les extraits de thé vert, les extraits de café. Among the antioxidants which can be advantageously used in the dielectric fluid, mention may be made, by way of nonlimiting examples, of phenolic antioxidants, such as for example dibutylhydroxytoluene, butylhydroxyanisole, tocopherols, as well as the acetates of these phenolic antioxidants; but also amine-type antioxidants, such as for example phenyl-a- naphthylamine, of the diamine type, for example N, N'-di- (2-naphthyl) -para-phenylenediamine, but also ascorbic acid and its salts, esters of ascorbic acid, alone or as mixtures of two or more of them or with other components, such as for example green tea extracts, coffee extracts.
[0041] Un antioxydant tout particulièrement adapté est celui disponible dans le commerce auprès de la société Brenntag sous la dénomination commerciale lonol®. [0042] Les passivateurs qui peuvent être utilisés comme additifs dans le fluide diélectrique utilisable dans le cadre de la présente invention sont de tout type connu de l’homme du métier et sont avantageusement choisis parmi les dérivés du triazole, les benzimidazoles, les imidazoles, le thiazole, le benzothiazole. À titre d’exemple et de manière non limitative, le dioctylaminométhyl-2,3-benzotriazole et le 2-dodécyldithio-imidazole peuvent être mentionnés. [0041] A particularly suitable antioxidant that is commercially available from Brenntag under the lonol ® trade name. The passivators which can be used as additives in the dielectric fluid which can be used in the context of the present invention are of any type known to those skilled in the art and are advantageously chosen from triazole derivatives, benzimidazoles, imidazoles, thiazole, benzothiazole. By way of example and in a nonlimiting manner, dioctylaminomethyl-2,3-benzotriazole and 2-dodécyldithio-imidazole can be mentioned.
[0043] Parmi les abaisseurs de point d’écoulement qui peuvent être présents dans le fluide diélectrique utilisable dans le cadre de la présente invention, on peut citer, à titres d’exemples non limitatifs, les esters d’acides gras de sucrose, les polymères acryliques tels que le poly(méthacrylate d’alkyle) ou encore le poly(acrylate d’alkyle). Among the pour point depressants which may be present in the dielectric fluid which can be used in the context of the present invention, there may be mentioned, by way of nonlimiting examples, the fatty acid esters of sucrose, the fatty acids. acrylic polymers such as poly (alkyl methacrylate) or even poly (alkyl acrylate).
[0044] Les polymères acryliques préférés sont ceux dont le poids moléculaire est compris entre 50000 g mol 1 et 500000 g mol 1. Des exemples de ces polymères acryliques incluent des polymères pouvant contenir des groupes alkyles linéaires comprenant de 1 à 20 atomes de carbone. Preferred acrylic polymers are those whose molecular weight is between 50,000 g mol 1 and 500,000 g mol 1 . Examples of such acrylic polymers include polymers which may contain linear alkyl groups comprising from 1 to 20 carbon atoms.
[0045] Parmi ceux-ci, et toujours à titre d’exemples non limitatifs, on peut citer le poly(acrylate de méthyle), le poly(méthacrylate de méthyle), le poly(acrylate d’heptyle), le poly(méthacrylate d’heptyle), le poly(acrylate de nonyle), le poly(méthacrylate de nonyle), le poly(acrylate de undécyle), le poly(méthacrylate de undécyle), le poly(acrylate de tridécyle), le poly(méthacrylate de tridécyle), le poly(acrylate de pentadécyle), le poly(méthacrylate de pentadécyle), le poly(acrylate d’heptadécyle), et le poly(méthacrylate d’heptadécyle). Among these, and still by way of nonlimiting examples, mention may be made of poly (methyl acrylate), poly (methyl methacrylate), poly (heptyl acrylate), poly (methacrylate heptyl), poly (nonyl acrylate), poly (nonyl methacrylate), poly (undecyl acrylate), poly (undecyl methacrylate), poly (tridecyl acrylate), poly (undecyl methacrylate), tridecyl), poly (pentadecyl acrylate), poly (pentadecyl methacrylate), poly (heptadecyl acrylate), and poly (heptadecyl methacrylate).
[0046] Un exemple d’un tel abaisseur de point d’écoulement est disponible dans le commerce auprès de la société Sanyo Chemical Industries, Ltd, sous la dénomination commerciale Aclube. [0047] Selon un aspect tout particulièrement préféré, le fluide diélectrique utilisable dans le cadre de la présente invention comprend au moins un inhibiteur de décomposition, en tant qu’additif. L’inhibiteur de décomposition peut être de tout type bien connu de l’homme du métier et en particulier peut être choisi parmi les dérivés carbodi-imides tels que le diphényle carbodi-imide, le di-tolylcarbodi-imide, le bis(isopropylphényl)carbodi-imide, le bis(butylphényl)carbodi-imide, mais aussi parmi les phénylglycidyl éthers, ou esters, les alkylglycidyl éthers, ou esters, le carboxylate de 3,4-époxycyclohexylméthyle-(3,4-époxycyclohexane), les composés de la famille des anthraquinones, tels que par exemple la b- méthylanthraquinone commercialisée sous le nom « BMAQ », les dérivés époxydés tels que les vinylcyclohexène diépoxydes, le carboxylate de 3,4-époxy-6- méthylcyclohexylméthyle-(3,4-époxy-6-méthylhexane), les résines époxy type phénol novolak, les diglycidyl éther époxy de bisphénol A, tels que la DGEBA ou la CEL 2021 P, disponibles notamment auprès de la société Whyte Chemicals. An example of such a pour point depressor is commercially available from Sanyo Chemical Industries, Ltd., under the trade name Aclube. According to a very particularly preferred aspect, the dielectric fluid which can be used in the context of the present invention comprises at least one decomposition inhibitor, as an additive. The decomposition inhibitor can be of any type well known to those skilled in the art and in particular can be chosen from carbodi-imide derivatives such as diphenyl carbodi-imide, di-tolylcarbodi-imide, bis (isopropylphenyl). carbodi-imide, bis (butylphenyl) carbodi-imide, but also from phenylglycidyl ethers, or esters, alkylglycidyl ethers, or esters, 3,4-epoxycyclohexylmethyl- (3,4-epoxycyclohexane) carboxylate, compounds of the anthraquinone family, such as for example b-methylanthraquinone marketed under the name “BMAQ”, epoxy derivatives such as vinylcyclohexene diepoxides, 3,4-epoxy-6-methylcyclohexylmethyl- (3,4-epoxy-) carboxylate 6-methylhexane), phenol novolak type epoxy resins, bisphenol A epoxy diglycidyl ether, such as DGEBA or CEL 2021 P, available in particular from the company Whyte Chemicals.
[0048] Selon un mode de réalisation particulier de l’invention, le fluide diélectrique utilisable dans le cadre de la présente invention comprend au moins un inhibiteur de décomposition. [0048] According to a particular embodiment of the invention, the dielectric fluid which can be used in the context of the present invention comprises at least one decomposition inhibitor.
[0049] La teneur en poids de l’additif, ou des additifs éventuellement présent(s) dans la composition utilisable comme fluide isolant dans le cadre de la présente invention peut aller de 0,0001 % à 5% en poids, de préférence de 0,001 % à 3% en poids, plus préférentiellement de 0,01 % à 2% en poids, bornes incluses, par rapport au poids total de la composition. The content by weight of the additive, or of the additives optionally present (s) in the composition which can be used as an insulating fluid in the context of the present invention can range from 0.0001% to 5% by weight, preferably of 0.001% to 3% by weight, more preferably from 0.01% to 2% by weight, limits included, relative to the total weight of the composition.
[0050] La composition selon l’invention est utilisable dans tout type d’équipements électrique. The composition according to the invention can be used in any type of electrical equipment.
[0051] Par équipement électrique, on entend tout type d’équipement électrique ou électronique, qu’il s’agisse de transformateurs, d’équipements de stockage sous forme électrostatique, d’éléments de transport d’électricité ou de connectique électrique, tel que transformateurs de puissance, transformateurs de distribution, transformateurs de traction, transformateurs de mesure, transformateurs spéciaux, disjoncteurs, condensateurs, répartiteurs, diviseurs capacitifs, câbles, traversées (« bushing » en langue anglaise), changeurs de prise en charge (« load tap changers » en langue anglaise), et autres, pour ne citer que les principaux équipements électriques ou électroniques comprenant un fluide isolant. [0052] L’utilisation de la présente invention se caractérise notamment par le fait que le fluide isolant est utilisé tout comme le fluide diélectrique, c’est-à-dire que le fluide isolant comprenant au moins un hydrocarbure halogéné remplace avantageusement le fluide diélectrique utilisé couramment jusqu’à présent. By electrical equipment is meant any type of electrical or electronic equipment, whether it is transformers, storage equipment in electrostatic form, elements for transporting electricity or electrical connections, such as as power transformers, distribution transformers, traction transformers, instrument transformers, special transformers, circuit breakers, capacitors, distributors, capacitive dividers, cables, bushings, load tap changers changers ”in English), and others, to name only the main electrical or electronic equipment comprising an insulating fluid. The use of the present invention is characterized in particular by the fact that the insulating fluid is used just like the dielectric fluid, that is to say that the insulating fluid comprising at least one halogenated hydrocarbon advantageously replaces the dielectric fluid commonly used so far.
[0053] Comme indiqué précédemment, il a été observé que le fluide isolant conserve les propriétés diélectriques dudit au moins un fluide diélectrique présent dans la composition, tout en présentant les propriétés d’ininflammabilité souhaitées. [0054] Par ailleurs, il a été observé, également de manière tout à fait surprenante, que le fluide isolant comprenant au moins un fluide diélectrique et au moins un hydrocarbure halogéné présent une permittivité améliorée, et notamment une permittivité plus élevée que la permittivité intrinsèque du fluide diélectrique ou du mélange de fluides diélectriques présent(s) dans la composition. As indicated above, it has been observed that the insulating fluid retains the dielectric properties of said at least one dielectric fluid present in the composition, while exhibiting the desired flammability properties. Furthermore, it has been observed, also quite surprisingly, that the insulating fluid comprising at least one dielectric fluid and at least one halogenated hydrocarbon has improved permittivity, and in particular a higher permittivity than the intrinsic permittivity. dielectric fluid or mixture of dielectric fluids present in the composition.
[0055] Cette augmentation de permittivité trouve une application tout à fait intéressante en ce qu’elle permet de pouvoir augmenter la tension aux bornes de l’équipement électrique, sans en modifier la taille. Par exemple, dans le cas d’un condensateur haute-tension, un gain de 10% en permittivité du fluide isolant pourrait permettre d’augmenter la tension dudit condensateur d’environ 3%. This increase in permittivity finds a very interesting application in that it makes it possible to be able to increase the voltage at the terminals of the electrical equipment, without modifying its size. For example, in the case of a high-voltage capacitor, a gain of 10% in the permittivity of the insulating fluid could increase the voltage of said capacitor by about 3%.
[0056] Selon un autre aspect, la présente invention concerne une composition comprenant : a) au moins un fluide diélectrique, et b) au moins un hydrocarbure halogéné, tels qu’ils viennent d’être définis. According to another aspect, the present invention relates to a composition comprising: a) at least one dielectric fluid, and b) at least one halogenated hydrocarbon, as they have just been defined.
[0057] Dans un mode de réalisation de l’invention, la quantité dudit au moins un fluide diélectrique est comprise entre 0 et 100%, bornes exclues, de préférence de 20% à 99,5%, de préférence de 40% à 99%, et encore de préférence de 40% à 98 % en poids par rapport au poids total de la composition. In one embodiment of the invention, the amount of said at least one dielectric fluid is between 0 and 100%, limits excluded, preferably from 20% to 99.5%, preferably from 40% to 99. %, and more preferably from 40% to 98% by weight relative to the total weight of the composition.
[0058] Par exemple, cette teneur peut être de 20% à 25%, ou de 25% à 30%, ou de 30% à 35%, ou de 35 à 40%, ou de 40% à 45%, ou de 45% à 50%, ou de 50% à 55%, ou de 55% à 60%, ou de 60% à 65%, ou de 65% à 70%, ou de 70% à 75%, ou de 75% à 80%, ou de 80% à 85% ou de 85% à 90%, bornes incluses, en poids par rapport au poids total de la composition selon l’invention. For example, this content can be from 20% to 25%, or from 25% to 30%, or from 30% to 35%, or from 35 to 40%, or from 40% to 45%, or from 45% to 50%, or 50% to 55%, or 55% to 60%, or 60% to 65%, or 65% to 70%, or 70% to 75%, or 75% at 80%, or from 80% to 85% or from 85% to 90%, limits included, by weight relative to the total weight of the composition according to the invention.
[0059] Dans un autre mode de réalisation de l’invention, la quantité dudit au moins un hydrocarbure halogéné est comprise entre 0 et 100%, bornes exclues, de préférence entre 0 et 80%, bornes exclues, de préférence encore entre 0 et 65%, bornes exclues, mieux entre 0 et 50%, bornes exclues, en poids par rapport au poids total de la composition selon l’invention. Avantageusement, la quantité dudit au moins un hydrocarbure halogéné est comprise entre 0,1 % et 45%, bornes incluses en poids par rapport au poids total de la composition selon l’invention, préférentiellement entre 0,1 % et 30% en poids, de préférence encore entre 0,1 % et 20% en poids, mieux encore entre 0,1 % et 15%, de préférence encore entre 0,1 % et 12% en poids, plus préférentiellement entre 0,1 % et 10%, avantageusement entre 0,5% et 10% en poids, mieux encore entre 1 % et 10%, bornes incluses, en poids par rapport au poids total de la composition de l’invention. In another embodiment of the invention, the amount of said at least one halogenated hydrocarbon is between 0 and 100%, limits excluded, of preferably between 0 and 80%, limits excluded, more preferably between 0 and 65%, limits excluded, better still between 0 and 50%, limits excluded, by weight relative to the total weight of the composition according to the invention. Advantageously, the amount of said at least one halogenated hydrocarbon is between 0.1% and 45%, limits included by weight relative to the total weight of the composition according to the invention, preferably between 0.1% and 30% by weight, more preferably between 0.1% and 20% by weight, better still between 0.1% and 15%, more preferably between 0.1% and 12% by weight, more preferably between 0.1% and 10%, advantageously between 0.5% and 10% by weight, better still between 1% and 10%, limits included, by weight relative to the total weight of the composition of the invention.
[0060] La composition selon l’invention peut être préparée selon tout moyen bien connu de l’homme du métier, par exemple par simple mélange des divers composants de la composition selon l’invention. The composition according to the invention can be prepared by any means well known to those skilled in the art, for example by simply mixing the various components of the composition according to the invention.
[0061] Ainsi, la composition selon la présente invention peut être préparée par mélange sous agitation, de préférence à froid, de préférence à une température inférieure au point d’ébullition de l’hydrocarbure halogéné, soit sous pression atmosphérique, soit sous légère pression, de préférence à pression atmosphérique. [0062] On entend par légère pression, une pression absolue de 5 bars maximum et à 60° C et de manière préférée une pression absoUe de 2 bars à 25 °C. Thus, the composition according to the present invention can be prepared by mixing with stirring, preferably cold, preferably at a temperature below the boiling point of the halogenated hydrocarbon, either under atmospheric pressure or under slight pressure , preferably at atmospheric pressure. Light pressure is understood to mean an absolute pressure of maximum 5 bars and at 60 ° C. and preferably an absolute pressure of 2 bars at 25 ° C.
[0063] Selon un mode de réalisation préféré, le fluide diélectrique est tout d’abord refroidi à une température légèrement inférieure à la température d’ébullition de l’hydrocarbure halogéné. L’hydrocarbure halogéné est additionné doucement dans le fluide diélectrique en maintenant la température du milieu à une température inférieure à la température d’ébullition de l’hydrocarbure halogéné. À la fin de l’addition de l’hydrocarbure halogéné dans le fluide diélectrique le milieu est homogénéisé pendant une période de quelques secondes à plusieurs minutes. De manière préférée l’homogénéisation est effectuée en quelques minutes [0064] Des compositions tout à fait préférées dans le cadre de la présente invention comprennent au moins un fluide diélectrique choisi parmi les huiles synthétiques et au moins un hydrocarbure fluoré ou fluorochloré. [0063] According to a preferred embodiment, the dielectric fluid is first cooled to a temperature slightly below the boiling point of the halogenated hydrocarbon. The halogenated hydrocarbon is added slowly into the dielectric fluid while maintaining the temperature of the medium at a temperature below the boiling point of the halogenated hydrocarbon. Upon completion of the addition of the halogenated hydrocarbon to the dielectric fluid, the medium is homogenized for a period of a few seconds to several minutes. Preferably, the homogenization is carried out in a few minutes. Very preferred compositions in the context of the present invention comprise at least one dielectric fluid chosen from synthetic oils and at least one fluorinated or fluorochlorinated hydrocarbon.
[0065] Une composition particulièrement adaptée comprend un mélange de benzyltoluène et de dibenzyltoluène (tel que Jarylec® de la société Arkema) et au moins un hydrocarbure fluoré ou fluorochloré, tel que par exemple, de manière non limitative un fluoropropane, un fluoropropène, un chlorofluoropropane, un chlorofluoropropène, et autres ainsi que leurs mélanges de deux ou plusieurs d’entre eux en toutes proportions. [0065] A particularly suitable composition comprises a mixture of benzyltoluene and dibenzyltoluene (as Jarylec ® from Arkema) and at least one fluorinated or fluorochlorohydrocarbon, such as for example, but are not limiting a fluoropropane, a fluoropropene, a chlorofluoropropane, a chlorofluoropropene, and others as well as their mixtures of two or more of them in all proportions.
[0066] La composition selon l’invention peut bien entendu comprendre un ou plusieurs additifs et/ou charges, comme déjà décrit plus haut. The composition according to the invention can of course comprise one or more additives and / or fillers, as already described above.
[0067] Des compositions tout à fait préférées dans le cadre de la présente invention sont liquides et manipulables à température ambiante et à pression atmosphérique. Des compositions tout à fait préférées ont un GWP bas et de manière totalement préférée un GWP strictement inférieur à 150. [0068] Des compositions tout à fait préférées selon le cadre de l’invention sont monophasique, très préférentiellement à l’état liquide, et présentent des caractéristiques diélectriques appropriées pour être utilisées dans les équipements électriques. Very preferred compositions in the context of the present invention are liquid and can be handled at room temperature and at atmospheric pressure. Completely preferred compositions have a low GWP and totally preferably a GWP strictly less than 150. Very preferred compositions according to the scope of the invention are single-phase, very preferably in the liquid state, and have dielectric characteristics suitable for use in electrical equipment.
[0069] Comme indiqué précédemment, en raison de son caractère peu inflammable, voire ininflammable, la composition de la présente invention peut être utilisée dans tous types d’équipements, notamment équipements électriques, mais aussi en tant que fluide caloporteur pour les utilisations fours solaires, centrales thermiques (à combustible naturel, fossile, ou nucléaire), systèmes de chauffage industriels (chaudières, échangeurs, réacteurs de synthèse et autres) et pour le transport des calories en général. As indicated above, due to its low flammability, even non-flammable nature, the composition of the present invention can be used in all types of equipment, in particular electrical equipment, but also as a heat transfer fluid for solar oven uses. , thermal power stations (natural, fossil or nuclear fuel), industrial heating systems (boilers, exchangers, synthesis reactors and others) and for the transport of heat in general.
Exemples : Examples:
[0070] Une composition a été préparée par mélange de 15,55% en poids de HCFO-1233zd E et de 84,45% en poids de Jarylec®C101 , de la société Arkema, dans les conditions présentées dans le Tableau 1 ci-dessous. [0070] A composition was prepared by mixing 15.55% by weight of HCFO-1233zd E and 84.45% by weight of Jarylec ® C101 from Arkema under the conditions shown in Table 1 below below.
- Tableau 1 - - Table 1 -
[0071] Une autre composition a été préparée par mélange de 90,16% poids de HCFO-1233zd E et 9,84% en poids de Jarylec®C101 , de la société Arkema, dans les conditions présentées dans le tableau 2 ci-dessous. -- Tableau 2 -- [0071] Another composition was prepared by mixing 90.16% weight of HCFO-1233zd and E 9.84% by weight of Jarylec ® C101 from Arkema under the conditions shown in Table 2 below . - Table 2 -
Mesure du point éclair Flash point measurement
[0072] Dans les exemples ci-après, les compositions de fluides diélectriques et d’hydrocarbures halogénés sont préparées par mélange de l’hydrocarbure halogéné dans le fluide diélectrique à une température inférieure de 5°C à celle de la température d’ébullition de l’hydrocarbure halogéné et sous pression atmosphérique. Le mélange des produits est homogène et liquide à température ambiante et pression atmosphérique. [0073] Une partie du liquide est prélevée puis introduite dans l’appareil de mesure de point éclair. La mesure du point éclair est effectuée selon les normes ISO 3679 et ISO 3680, détermination du point éclair, méthode rapide à l’équilibre en vase clos (« closed cup » en langue anglaise). In the examples below, the compositions of dielectric fluids and halogenated hydrocarbons are prepared by mixing the halogenated hydrocarbon in the dielectric fluid at a temperature 5 ° C lower than that of the boiling point of halogenated hydrocarbon and at atmospheric pressure. The mixture of the products is homogeneous and liquid at ambient temperature and atmospheric pressure. Part of the liquid is taken and then introduced into the flash point measuring device. The flash point measurement is carried out according to ISO 3679 and ISO 3680 standards, determination of the flash point, rapid closed cup equilibrium method.
[0074] La gamme de température de mesure du point éclair est comprise entre 140°C et 290 °C, avec une montée de 20 °C à chaque meure du point éclair et un temps de stabilisation de 2 minutes. The flash point measurement temperature range is between 140 ° C and 290 ° C, with a rise of 20 ° C each time the flash point dies and a stabilization time of 2 minutes.
[0075] Dans les exemples qui suivent, le fluide diélectrique est le Jarylec® C101 et l’hydrocarbure halogéné est soit du HCFO-1233zd Z, soit du HCFO-1233zd E. Les points éclairs sont mesurés à des températures de 140°C, 160°C,180°C, 200 °C, 220 °C, 240 °C, 260 °C, 280 °c et 290 °C pour le HCFO-32zd E et de 140°c à 290 °C avec des sauts de 10 ° C à chaque mesure pour le HCF01233zd Z. In the following examples, the dielectric fluid is Jarylec ® C101 and the halogenated hydrocarbon is either HCFO-1233zd Z or HCFO-1233zd E. The flash points are measured at temperatures of 140 ° C, 160 ° C, 180 ° C, 200 ° C, 220 ° C, 240 ° C, 260 ° C, 280 ° c and 290 ° C for HCFO-32zd E and from 140 ° c to 290 ° C with jumps of 10 ° C at each measurement for HCF01233zd Z.
[0076] Les points d’ébullition des hydrocarbures halogénés utilisés sont : pour le HCFO-1233zd Z : 40° C à pression atmosphéifque, et pour le HCFO-1233zd E : 18°C à pression atmosphéifque. [0077] Les résultats des mesures de point éclair selon les normes ISO 3679 et ISOThe boiling points of the halogenated hydrocarbons used are: for HCFO-1233zd Z: 40 ° C at atmospheric pressure, and for HCFO-1233zd E: 18 ° C at atmospheric pressure. The results of flash point measurements according to ISO 3679 and ISO standards
3680 sont présentées dans le tableau 3 ci-dessous : -- Tableau 3 -- 3680 are shown in Table 3 below: - Table 3 -
Mesure de la permittivité Permittivity measurement
[0078] La permittivité des compositions est mesurée selon la norme IEC 61620. [0079] Les compositions suivantes sont préparées par mélange à température ambiante et à pression atmosphérique de Jarylec® C101 et de HCFO-1233zd Z, tous deux sous forme liquide. [0078] The permittivity of the compositions is measured according to IEC 61620. [0079] The following compositions are prepared by mixing at room temperature and Jarylec ® C101 atmospheric pressure and HCFO-1233zd Z, both in liquid form.
-- Tableau 4 -- [0080] Les résultats du tableau 4 ci-dessus montrent que l’ajout d’un hydrocarbure halogéné, même en faible quantité, dans un fluide diélectrique permet de rendre indétectable le point éclair, dans les conditions du test, ce qui correspond à une composition ininflammable. Par ailleurs, l’ajout d’un hydrocarbure halogéné, même en faible quantité, dans un fluide diélectrique n’entraîne pas une diminution de la permittivité de la composition, mais au contraire permet d’augmenter la permittivité de ladite composition, par comparaison avec la permittivité du fluide diélectrique seul. - Table 4 - The results of Table 4 above show that the addition of a halogenated hydrocarbon, even in small quantity, in a dielectric fluid makes it possible to make the flash point undetectable, under the test conditions, which corresponds to a non-flammable composition. Moreover, the addition of a halogenated hydrocarbon, even in a small amount, in a dielectric fluid does not lead to a decrease in the permittivity of the composition, but on the contrary makes it possible to increase the permittivity of said composition, by comparison with the permittivity of the dielectric fluid alone.

Claims

REVENDICATIONS 1. Utilisation d’une composition comprenant : a) au moins un fluide diélectrique, et b) au moins un hydrocarbure halogéné, comme fluide isolant dans un équipement électrique. CLAIMS 1. Use of a composition comprising: a) at least one dielectric fluid, and b) at least one halogenated hydrocarbon, as an insulating fluid in electrical equipment.
2. Utilisation selon la revendication 1 , dans laquelle le fluide diélectrique comprend au moins un fluide diélectrique choisi parmi les huiles diélectriques minérales et les huiles diélectriques synthétiques, les huiles végétales, ainsi que leurs mélanges en toutes proportions. 2. Use according to claim 1, in which the dielectric fluid comprises at least one dielectric fluid chosen from mineral dielectric oils and synthetic dielectric oils, vegetable oils, as well as their mixtures in all proportions.
3. Utilisation selon la revendication 1 ou la revendication 2, dans laquelle le fluide diélectrique est une huile diélectrique synthétique choisie parmi les hydrocarbures aromatiques, les hydrocarbures aliphatiques, les huiles silicones, et les esters, ainsi que les mélanges de deux ou plusieurs d’entre elles en toutes proportions. 3. Use according to claim 1 or claim 2, wherein the dielectric fluid is a synthetic dielectric oil selected from aromatic hydrocarbons, aliphatic hydrocarbons, silicone oils, and esters, as well as mixtures of two or more of. between them in all proportions.
4. Utilisation selon l’une quelconque des revendications précédentes, dans laquelle le fluide diélectrique est choisi parmi les alkylbenzènes, les alkyldiphényléthanes, les phényléthylphényléthane, le mono-isopropylbiphényle, le 1,1-diphényléthane, les alkylnaphtalènes, les méthylpolyarylméthanes, et leurs mélanges. 4. Use according to any one of the preceding claims, in which the dielectric fluid is chosen from alkylbenzenes, alkyldiphenylethanes, phenylethylphenylethane, mono-isopropylbiphenyl, 1,1-diphenylethane, alkylnaphthalenes, methylpolyarylmethanes, and their mixtures. .
5. Utilisation selon l’une quelconque des revendications précédentes, dans laquelle l’hydrocarbure halogéné est choisi parmi les hydrocarbures halogénés en tant que tels, les cétones fluorées, les éthers fluorés, et leurs mélanges, et de préférence les hydrocarbures comprenant au moins un atome d’halogène choisi parmi fluor, chlore, brome et iode, et de préférence encore choisi parmi les hydrocarbures fluorés, chlorés, fluorochlorés, et leurs mélanges en toutes proportions. 5. Use according to any one of the preceding claims, in which the halogenated hydrocarbon is chosen from halogenated hydrocarbons as such, fluorinated ketones, fluorinated ethers, and mixtures thereof, and preferably hydrocarbons comprising at least one. halogen atom chosen from fluorine, chlorine, bromine and iodine, and more preferably chosen from fluorinated, chlorinated and fluorochlorinated hydrocarbons, and their mixtures in all proportions.
6. Utilisation selon l’une quelconque des revendications précédentes, dans laquelle l’hydrocarbure halogéné est choisi parmi les hydrofluorocarbures, les hydrochlorofluorocarbures, les hydrofluoro-oléfines, les hydrochloro-oléfines et les hydrochlorofluoro-oléfines. 6. Use according to any one of the preceding claims, wherein the halogenated hydrocarbon is selected from hydrofluorocarbons, hydrochlorofluorocarbons, hydrofluoroolefins, hydrochloroolefins and hydrochlorofluoroolefins.
7. Utilisation selon l’une quelconque des revendications précédentes, dans laquelle l’hydrocarbure halogéné est choisi parmi les hydrocarbures halogénés connus sous les acronymes CFC, HCFO, HFC, HFE, HFO et notamment ceux choisis parmi le 1 ,1 ,1 ,4,4,4-hexafluorobut-2-ène, le 1 -chloro-3,3,3-trifluoropropène, le 3,3,4,4,4-pentafluorobut-1 -ène, le 2,4,4,4-tétrafluorobut-1 -ène, le 1 ,1 ,2-trifluoro- éthylène, le 1 ,1 ,1 ,3,3-pentafluoropropane, le 2,3,3, 3-tétrafluoropropène, le 1 , 3,3,3- tétrafluoropropène, le difluorométhane, le 1 ,1 ,1 ,2-tétrafluoroéthane, le 1 , 1 ,2,2- tétrafluoroéthane, le 1 ,1 -difluoroéthane, le pentafluoroéthane, le 1 ,1 ,1 ,3,3- pentafluorobutane, le fluoroéthane, le 1 ,1 , 1 ,2, 3, 3, 3 heptafluoropropane, le 1 ,1 ,1 - trifluoropropane, et les mélanges de deux ou plusieurs d’entre eux en toutes proportions. 7. Use according to any one of the preceding claims, in which the halogenated hydrocarbon is chosen from halogenated hydrocarbons known by the acronyms CFC, HCFO, HFC, HFE, HFO and in particular those chosen from among 1, 1, 1, 4. , 4,4-hexafluorobut-2-ene, 1 -chloro-3,3,3-trifluoropropene, 3,3,4,4,4-pentafluorobut-1 -ene, 2,4,4,4- tetrafluorobut-1 -ene, 1, 1, 2-trifluoroethylene, 1, 1, 1, 3,3-pentafluoropropane, 2,3,3, 3-tetrafluoropropene, 1, 3,3,3- tetrafluoropropene, difluoromethane, 1, 1, 1, 2-tetrafluoroethane, 1, 1, 2,2- tetrafluoroethane, 1, 1 -difluoroethane, pentafluoroethane, 1, 1, 1, 3,3-pentafluorobutane, fluoroethane, 1, 1, 1, 2, 3, 3, 3 heptafluoropropane, 1, 1, 1 - trifluoropropane, and mixtures of two or more of them in all proportions.
8. Utilisation selon l’une quelconque des revendications précédentes, dans laquelle la quantité dudit au moins un hydrocarbure halogéné est comprise entre 0 et 100%, bornes exclues, de préférence entre 0 et 80%, bornes exclues, de préférence encore entre 0 et 65%, bornes exclues, mieux entre 0 et 50%, bornes exclues, par rapport au poids total de la composition. 8. Use according to any one of the preceding claims, in which the amount of said at least one halogenated hydrocarbon is between 0 and 100%, limits excluded, preferably between 0 and 80%, limits excluded, more preferably between 0 and 65%, limits excluded, better still between 0 and 50%, limits excluded, relative to the total weight of the composition.
9. Utilisation selon l’une quelconque des revendications précédentes, dans laquelle la quantité dudit au moins un hydrocarbure halogéné est comprise entre 0,1 % et 25%, bornes incluses en poids par rapport au poids total de la composition utilisée comme fluide isolant, préférentiellement entre 0,1 % et 20% en poids, de préférence encore entre 0,1 % et 15% en poids, de préférence encore entre 0,1 % et 10% en poids, avantageusement entre 0,5% et 10% en poids, mieux encore entre 1% et 10%, bornes incluses, en poids par rapport au poids total de la composition. 9. Use according to any one of the preceding claims, in which the amount of said at least one halogenated hydrocarbon is between 0.1% and 25%, limits included by weight relative to the total weight of the composition used as insulating fluid, preferably between 0.1% and 20% by weight, more preferably between 0.1% and 15% by weight, more preferably between 0.1% and 10% by weight, advantageously between 0.5% and 10% by weight weight, better still between 1% and 10%, limits included, by weight relative to the total weight of the composition.
10. Utilisation selon l’une quelconque des revendications précédentes, comprenant en outre un ou plusieurs additifs choisis parmi, de manière non limitative, les antioxydants, les passivateurs, les abaisseurs de point d’écoulement, les inhibiteurs de décomposition, les parfums et arômes, les colorants, les conservateurs, et autres et leurs mélanges. 10. Use according to any one of the preceding claims, further comprising one or more additives selected from, without limitation, antioxidants, passivators, pour point depressants, decomposition inhibitors, perfumes and flavors. , dyes, preservatives, and the like and mixtures thereof.
11. Utilisation selon l’une des revendications précédentes, comprenant en outre un ou plusieurs additifs dont la teneur va de 0,0001 % à 5% en poids, de préférence de 0,001 % à 3% en poids, plus préférentiellement de 0,01 % à 2% en poids, bornes incluses, par rapport au poids total de la composition. 11. Use according to one of the preceding claims, further comprising one or more additives whose content ranges from 0.0001% to 5% by weight, preferably from 0.001% to 3% by weight, more preferably from 0.01. % to 2% by weight, limits included, relative to the total weight of the composition.
12. Utilisation selon l’une quelconque des revendications précédentes, dans tout type d’équipement électrique ou électronique, choisis parmi transformateurs, équipements de stockage sous forme électrostatique, éléments de transport d’électricité ou de connectique électrique. 12. Use according to any one of the preceding claims, in any type of electrical or electronic equipment, chosen from transformers, storage equipment in electrostatic form, elements for transporting electricity or electrical connections.
13. Utilisation selon la revendication 12, dans laquelle l’équipement électronique ou électronique est choisi parmi transformateurs de puissance, transformateurs de distribution, transformateurs de traction, transformateurs de mesure, transformateurs spéciaux, disjoncteurs, condensateurs, répartiteurs, diviseurs capacitifs, câbles, traversées, changeurs de prise en charge. 13. Use according to claim 12, in which the electronic or electronic equipment is chosen from power transformers, distribution transformers, traction transformers, instrument transformers, special transformers, circuit breakers, capacitors, distributors, capacitive dividers, cables, bushings. , take-over changers.
14. Composition telle que définie dans l’une quelconque des revendications 1 à 11 , comprenant : a) au moins un fluide diélectrique, et b) au moins un hydrocarbure halogéné, tels qu’ils sont définis dans les revendications 1 à 11 , et dans laquelle la quantité dudit au moins un hydrocarbure halogéné est comprise entre 0 et 100%, bornes exclues, de préférence entre 0 et 80%, bornes exclues, de préférence encore entre 0 et 65%, bornes exclues, mieux entre 0 et 50%, bornes exclues, en poids par rapport au poids total de la composition selon l’invention. 14. A composition as defined in any one of claims 1 to 11, comprising: a) at least one dielectric fluid, and b) at least one halogenated hydrocarbon, as defined in claims 1 to 11, and in which the amount of said at least one halogenated hydrocarbon is between 0 and 100%, limits excluded, preferably between 0 and 80%, limits excluded, more preferably between 0 and 65%, limits excluded, better still between 0 and 50% , limits excluded, by weight relative to the total weight of the composition according to the invention.
15. Composition selon la revendication 14, dans laquelle la quantité dudit au moins un hydrocarbure halogéné est comprise entre 0,1% et 45%, bornes incluses en poids par rapport au poids total de la composition selon l’invention, préférentiellement entre 0,1 % et 30% en poids, de préférence encore entre 0,1 % et 20% en poids, mieux encore entre 0,1% et 15%, de préférence encore entre 0,1% et 12% en poids, plus préférentiellement entre 0,1% et 10%, avantageusement entre 0,5% et 10% en poids, mieux encore entre 1% et 10%, bornes incluses, en poids par rapport au poids total de la composition de l’invention. 15. Composition according to claim 14, in which the amount of said at least one halogenated hydrocarbon is between 0.1% and 45%, limits included by weight relative to the total weight of the composition according to the invention, preferably between 0, 1% and 30% by weight, more preferably between 0.1% and 20% by weight, better still between 0.1% and 15%, more preferably between 0.1% and 12% by weight, more preferably between 0.1% and 10%, advantageously between 0.5% and 10% by weight, better still between 1% and 10%, limits included, by weight relative to the total weight of the composition of the invention.
EP21706338.7A 2020-01-20 2021-01-19 Dielectric compositions with improved properties Withdrawn EP4093834A1 (en)

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