EP1059643A1 - Dielectric composition having an improved gas absorbtion - Google Patents

Dielectric composition having an improved gas absorbtion Download PDF

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EP1059643A1
EP1059643A1 EP00401546A EP00401546A EP1059643A1 EP 1059643 A1 EP1059643 A1 EP 1059643A1 EP 00401546 A EP00401546 A EP 00401546A EP 00401546 A EP00401546 A EP 00401546A EP 1059643 A1 EP1059643 A1 EP 1059643A1
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Prior art keywords
mixture
formula
isomers
products
compositions
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German (de)
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EP1059643B1 (en
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Noelle Berger
Raymond Commandeur
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Arkema France SA
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Atofina SA
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • 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 a dielectric composition with mineral oil base for electrical equipment with absorption of improved gas.
  • Mineral oils are widely used as oils insulators in various electrical materials such as transformers, capacitors, and cables.
  • mineral oils include natural compounds different such as paraffin chains, cyclic compounds saturated naphthenic, aromatic structures whose polyaromatic condensed.
  • Aromatic compounds give mineral oils better dielectric properties such as better breakdown voltage or so-called gassing properties.
  • the absorption of gas is characteristic of the behavior of a oil under high electric field.
  • the oil can either produce more gas in which case, it is called “gas-evolving” (gas producer), or absorb hydrogen, it is then called “gas-absorbing” (absorber of gas).
  • Condensed polyaromatics are diverse and varied in nature, but most are considered carcinogenic. Also, in order to reduce the polyaromatic content in mineral oils, these undergo hydrogenation treatment. This treatment however has the disadvantage of making others disappear completely aromatic considered as not very toxic.
  • the Applicant has found that the use of small amounts of compounds of the polyarylalkane family made it possible to improve the gas absorption property of mineral oils.
  • the compositions (I) can contain product (A) with 2 rings, (methylbenzyl) xylene, and product (A) with 3 rings which is designated by bis (methylbenzyl) xylene.
  • compositions (I) usable according to the present invention mention will be made of the polyarylalkane composition sold by ELF ATOCHEM S.A. under the designation JARISOL XX having a content by weight of compounds with 2 and 3 aromatic rings greater than 99%.
  • compositions can be obtained by methods described in patents EP 136 230-B1, EP 299 867-B1, EP 384 818-B1, EP 500 435-B1 incorporated into the present invention, by references, which consist of chlorinating toluene or xylene then to perform a Friedel and Crafts type condensation either on toluene, either on xylene (mixture of isomers), or on a toluene and xylene mixture, either on benzene or on a mixture benzene and toluene.
  • the reaction is finished, the or reagents not transformed by distillation then the crude product can be subjected to a dechlorination treatment as described in the patent EP 306 398-B1.
  • compositions (II) can be obtained by a process described in patent EP 136 230-B1 which consists, in a first step, in reacting chlorine on toluene by radical reaction in the presence of free radical generator at a temperature between 50 ° C and 110 ° C then in a second step, the reaction product from the first step is subjected to a condensation reaction with toluene in the presence of FeCl 3 at a temperature between 50 ° C and 100 ° C.
  • compositions (I) can be obtained according to a process described in patent EP 0 50 435-B1 which consists in carrying out the condensation of (methyl) benzyl chloride with xylene in the presence of FeCl 3 .
  • the dielectric compositions according to the invention have the advantage of having improved gas behavior (improved gassing).
  • the interface between a column of liquid and a volume of hydrogen is subjected to electrical discharges between 2 electrodes placed at different potentials.
  • the evolution of the gas volume is monitored as a function of time.
  • the gassing expressed in ⁇ l / min, is positive if gas is released and is negative if gas is absorbed.

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Insulating Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Lubricants (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

A small quantity of polyarylalkane compounds is introduced to improve the gassing properties of the dielectric composition. A dielectric oil mixture comprises 99 - 70% of a mineral oil and 1 - 30% of a polyarylalkane composition selected from :- -compositions (I) consisting of a mixture of products of formula (A) :- -in which n1 and n2 = 0 or 1, containing products(A) such that n1 + n2 = 0 , and products (A) in which n2 = 1 ; and products(B) of formula :- -compositions (II) consisting of a mixture of two products (C) and (D) where :- product (C) is a mixture of isomers of formula :- -in which p1 and p2 = 0, 1 or 2, with p1 + p2 is less than or equal to 3 ; and product (D) is a mixture of isomers of formula :- p<1>1, p<2>1 and p4 = 0, 1 or 2 and p<1>1+p<2>1+p<1>2+p<2>2+ p3+p4+p5 =2 or less -compositions(III) comprising a mixture of two products (A1) and (A2) such that :- (A1) is a mixture of isomers of formula :- -m1 and m2 = 0. 1 or 2, and m1 + m2 is less than or equal to 3 ; (A2) is a mixture of isomers of formula :- -q1 and q2 = 0, 1 or 2 and q1 + q+2 is less than or equal to 3 ; At least one of compounds (A1) and (A2) is an isomer having three benzene nuclei ; and -compositions(IV) comprising two products (A1) and (A2) with the addition of a compound (E1), (E2) or (E3) as follows :- (E1) is a mixture of isomers of formula :- -r<1>1, r<2>1 and R4 = 0, 1 or 2 ; r<1>2, r<2>2, r3, r<1>3 and r5 = 0 or 1 ; and r<1>1 + r<2>1 + r<1>2 + r<2>2 + r3 + r<1>3 + r4 + r5 is less than or equal to 2 ; R1 and R2 = H ; (E2) is an isomer or isomer mixture of formula (E1), save that R1 and R2 are Me and coefficients r are replaced by s of similar significance ; (E3) is an iosomer or isomer mixture of formula(E1) save that R1 and R2 are different and represent H or Me and coefficients r are replaced by t of similar significance ;

Description

La présente invention concerne une composition diélectrique à base d'huile minérale pour matériel électrique ayant une absorption de gaz améliorée.The present invention relates to a dielectric composition with mineral oil base for electrical equipment with absorption of improved gas.

Les huiles minérales sont largement utilisées comme huiles isolantes dans différents matériels électriques tels que transformateurs, condensateurs, et cables.Mineral oils are widely used as oils insulators in various electrical materials such as transformers, capacitors, and cables.

Ces huiles minérales comprennent des composés de natures différentes tels que chaínes paraffiniques, des composés cycliques saturés désignés naphténiques, des structures aromatiques dont les polyaromatiques condensés.These mineral oils include natural compounds different such as paraffin chains, cyclic compounds saturated naphthenic, aromatic structures whose polyaromatic condensed.

Les composés aromatiques donnent aux huiles minérales de meilleures propriétés diélectriques telle que meilleure tension de claquage ou des propriétés dites de gassing.Aromatic compounds give mineral oils better dielectric properties such as better breakdown voltage or so-called gassing properties.

L'absorption de gaz est caractéristique du comportement d'une huile sous champ électrique élevé.The absorption of gas is characteristic of the behavior of a oil under high electric field.

En présence d'hydrogène gazeux, l'huile peut soit produire plus de gaz auquel cas, elle est dite "gas-évolving" (productrice de gaz), soit absorber l'hydrogène, elle est alors dite "gas-absorbing" (absorbeur de gaz).In the presence of hydrogen gas, the oil can either produce more gas in which case, it is called "gas-evolving" (gas producer), or absorb hydrogen, it is then called "gas-absorbing" (absorber of gas).

Il est recherché pour le matériel électrique des huiles dites "gas-absorbing".It is sought after for electrical equipment called "gas-absorbing" oils.

Les polyaromatiques condensés sont de nature diverse et variée, mais la plupart sont considérés comme cancérigènes. Aussi, afin de réduire la teneur en polyaromatiques dans les huiles minérales, celles-ci subissent un traitement d'hydrogénation. Ce traitement cependant présente l'inconvénient de faire disparaítre totalement les autres aromatiques considérés comme peu toxiques.Condensed polyaromatics are diverse and varied in nature, but most are considered carcinogenic. Also, in order to reduce the polyaromatic content in mineral oils, these undergo hydrogenation treatment. This treatment however has the disadvantage of making others disappear completely aromatic considered as not very toxic.

La demanderesse a constaté que l'utilisation de faibles quantités de composés de la famille des polyarylalcanes permettait d'améliorer la propriété d'absorption de gaz des huiles minérales.The Applicant has found that the use of small amounts of compounds of the polyarylalkane family made it possible to improve the gas absorption property of mineral oils.

L'invention a donc pour objet une composition diélectrique pour appareils électriques, caractérisée en ce qu'elle comprend de 99 % à 70 % en poids et, de préférence, de 99 % à 80 % d'une huile minérale et de 1 % à 30 % en poids et, de préférence de 1 % à 20 % d'au moins une composition de polyarylalcanes choisie parmi :

  • les compositions (I) comprenant un mélange de produits de formule (A) :
    Figure 00020001
    dans laquelle n1 et n2 = 0 ou 1 qui contient des produits (A) tels que n1 + n2 = 0 et des produits (A) tels que n1 + n2 = 1 et de produits de formule (B) :
    Figure 00020002
  • les compositions (II) comprenant un mélange de deux produits (C) et (D) dans lequel :
    • le produit (C) est un mélange d'isomères de formule :
      Figure 00020003
      avec p1 et p2 = 0,1 et 2, sachant que p1 + p2 ≤ 3, et
    • le produit (D) est un mélange d'isomères de formule :
      Figure 00030001
      avec
         p'1, p"1 et p4 = 0,1 et 2
         P'2, p"2, p3 et p5 = 0 et 1 sachant que p'1 + p"1 + p'2 + p"2 + p3 + p'3 + p4 + p5 ≤ 2.
  • les compositions (III) comprenant un mélange de deux produits (A1) et (A2), tels que :
    • le produit (A1) est un mélange d'isomères de formule :
      Figure 00030002
      avec m1 et m2 = 0, 1 ou 2 sachant que m1 + m2 ≤ 3,
    • le produit (A2) est un mélange d'isomères de formule :
      Figure 00030003
      avec q1 et q2 = 0, 1 ou 2 sachant que q1 + q2 ≤ 3,
      l'un au moins des composés (A1) et (A2) comprenant un isomère ayant trois noyaux benzéniques.
  • les compositions (IV) comprenant les deux produits (A1) et (A2) et, en outre, au moins un composé choisi parmi les produits (E1), (E2) ou (E3) suivants :
    • (E1) est un isomère ou un mélange d'isomères de formule :
      Figure 00040001
      avec
         r'1, r"1 et r4 = 0, 1 ou 2
         r'2, r"2, r3, r'3 et r5 = 0 et 1
      sachant que r'1 + r"1 + r'2 + r"2 + r3 + r'3 + r4 + r5 est inférieur ou égal à 2.
         R1 et R2 représentent un atome d'hydrogène.
    • (E2) est un isomère ou un mélange d'isomères de même formule générale que (E1), sauf que R1 et R2 représentent un méthyle et les coefficients r sont remplacés par s et ont la même signification.
    • (E3) est un isomère ou un mélange d'isomères de même formule générale que (E1), sauf que R1 et R2 sont différents et représentent un atome d'hydrogène ou un radical méthyle et les coefficients r sont remplacés par t et ont la même signification.
The subject of the invention is therefore a dielectric composition for electrical devices, characterized in that it comprises from 99% to 70% by weight and, preferably, from 99% to 80% of a mineral oil and from 1% to 30% by weight and preferably from 1% to 20% of at least one polyarylalkane composition chosen from:
  • the compositions (I) comprising a mixture of products of formula (A):
    Figure 00020001
    in which n 1 and n 2 = 0 or 1 which contains products (A) such as n 1 + n 2 = 0 and products (A) such as n 1 + n 2 = 1 and products of formula (B) :
    Figure 00020002
  • the compositions (II) comprising a mixture of two products (C) and (D) in which:
    • product (C) is a mixture of isomers of formula:
      Figure 00020003
      with p 1 and p 2 = 0.1 and 2, knowing that p 1 + p 2 ≤ 3, and
    • product (D) is a mixture of isomers of formula:
      Figure 00030001
      with
      p ' 1 , p " 1 and p 4 = 0.1 and 2
      P ' 2 , p " 2 , p 3 and p 5 = 0 and 1 knowing that p' 1 + p" 1 + p ' 2 + p " 2 + p 3 + p' 3 + p 4 + p 5 ≤ 2.
  • the compositions (III) comprising a mixture of two products (A1) and (A2), such as:
    • the product (A1) is a mixture of isomers of formula:
      Figure 00030002
      with m 1 and m 2 = 0, 1 or 2 knowing that m 1 + m 2 ≤ 3,
    • the product (A2) is a mixture of isomers of formula:
      Figure 00030003
      with q 1 and q 2 = 0, 1 or 2 knowing that q 1 + q 2 ≤ 3,
      at least one of the compounds (A1) and (A2) comprising an isomer having three benzene rings.
  • the compositions (IV) comprising the two products (A1) and (A2) and, in addition, at least one compound chosen from the following products (E1), (E2) or (E3):
    • (E1) is an isomer or a mixture of isomers of formula:
      Figure 00040001
      with
      r ' 1 , r " 1 and r 4 = 0, 1 or 2
      r ' 2 , r " 2 , r 3 , r' 3 and r 5 = 0 and 1
      knowing that r ' 1 + r " 1 + r' 2 + r" 2 + r 3 + r ' 3 + r 4 + r 5 is less than or equal to 2.
      R 1 and R 2 represent a hydrogen atom.
    • (E2) is an isomer or a mixture of isomers with the same general formula as (E1), except that R 1 and R 2 represent a methyl and the coefficients r are replaced by s and have the same meaning.
    • (E3) is an isomer or a mixture of isomers of the same general formula as (E1), except that R 1 and R 2 are different and represent a hydrogen atom or a methyl radical and the coefficients r are replaced by t and have the same meaning.

Selon la présente invention, les compositions (I) peuvent contenir du produit (A) à 2 noyaux, le (méthylbenzyl)xylène, et du produit (A) à 3 noyaux que l'on désigne par bis(méthylbenzyl)xylène. Ce produit (A) à 3 noyaux peut être du produit tel que n1 = 1 et n2 = 0, du produit tel que n1 = 0 et n2 = 1 ou un mélange de ces deux derniers. La composition de polyarylalcanes peut aussi contenir des produits tels que n1 = 1 et n2 = 1. According to the present invention, the compositions (I) can contain product (A) with 2 rings, (methylbenzyl) xylene, and product (A) with 3 rings which is designated by bis (methylbenzyl) xylene. This product (A) with 3 cores can be a product such as n 1 = 1 and n 2 = 0, a product such as n 1 = 0 and n 2 = 1 or a mixture of the latter two. The polyarylalkane composition can also contain products such as n 1 = 1 and n 2 = 1.

A titre d'illustration de compositions (I) utilisables selon la présente invention, on citera la composition de polyarylalcanes vendue par la Société ELF ATOCHEM S.A. sous la désignation JARISOL XX ayant une teneur pondérale en composés à 2 et 3 noyaux aromatiques supérieure à 99 %.By way of illustration of compositions (I) usable according to the present invention, mention will be made of the polyarylalkane composition sold by ELF ATOCHEM S.A. under the designation JARISOL XX having a content by weight of compounds with 2 and 3 aromatic rings greater than 99%.

A titre d'illustration de compositions (II) utilisables selon la présente invention, on citera la composition de polyarylalcanes vendue par la Société ELF ATOCHEM S.A. sous la désignation JARYLEC C100 qui est constitué essentiellement par 70 % à 80 % en poids d'un mélange d'isomères de benzyltoluène (produit (C), p1 = p2 = 0) et par 20 % à 30 % en poids d'isomères de dibenzyltoluène (produit (C), p1 = 1, p2 = 0 ou p1 = 0 et p2 = 1) et de ditolylphénylméthane (produit (D), p'1 + p"1 + p'2 + p"2 + p3 + p'3 + p4 + p5 = 0).By way of illustration of compositions (II) which can be used according to the present invention, mention will be made of the polyarylalkane composition sold by the company ELF ATOCHEM SA under the designation JARYLEC C100 which consists essentially of 70% to 80% by weight of a mixture of benzyltoluene isomers (product (C), p 1 = p 2 = 0) and by 20% to 30% by weight of dibenzyltoluene isomers (product (C), p 1 = 1, p 2 = 0 or p 1 = 0 and p 2 = 1) and ditolylphenylmethane (product (D), p ' 1 + p " 1 + p' 2 + p" 2 + p 3 + p ' 3 + p 4 + p 5 = 0).

Ces compositions peuvent être obtenues par des procédés décrits dans les brevets EP 136 230-B1, EP 299 867-B1, EP 384 818-B1, EP 500 435-B1 incorporés dans la présente invention, par références, qui consistent à effectuer la chloration du toluène ou du xylène puis d'effectuer une condensation de type Friedel et Crafts soit sur du toluène, soit sur du xylène (mélange d'isomères), soit sur un mélange toluène et xylène, soit sur du benzène, soit sur un mélange benzène et toluène. La réaction terminée, on élimine directement le ou les réactifs non transformés par distillation puis le produit brut peut être soumis à un traitement de déchloration tel que décrit dans le brevet EP 306 398-B1.These compositions can be obtained by methods described in patents EP 136 230-B1, EP 299 867-B1, EP 384 818-B1, EP 500 435-B1 incorporated into the present invention, by references, which consist of chlorinating toluene or xylene then to perform a Friedel and Crafts type condensation either on toluene, either on xylene (mixture of isomers), or on a toluene and xylene mixture, either on benzene or on a mixture benzene and toluene. When the reaction is finished, the or reagents not transformed by distillation then the crude product can be subjected to a dechlorination treatment as described in the patent EP 306 398-B1.

Ainsi, par exemple, les compositions (II) peuvent être obtenues par un procédé décrit dans le brevet EP 136 230-B1 qui consiste dans une première étape, à faire réagir du chlore sur du toluène par réaction radicalaire en présence de générateur de radicaux libres à une température comprise entre 50°C et 110°C puis dans une seconde étape, on soumet le produit de réaction de la première étape à une réaction de condensation avec le toluène en présence de FeCl3 à une température comprise entre 50°C et 100°C.Thus, for example, the compositions (II) can be obtained by a process described in patent EP 136 230-B1 which consists, in a first step, in reacting chlorine on toluene by radical reaction in the presence of free radical generator at a temperature between 50 ° C and 110 ° C then in a second step, the reaction product from the first step is subjected to a condensation reaction with toluene in the presence of FeCl 3 at a temperature between 50 ° C and 100 ° C.

Les compositions (I) peuvent être obtenues selon un procédé décrit dans le brevet EP 0 50 435-B1 qui consiste à réaliser la condensation du chlorure de (methyl)benzyl avec du xylène en présence de FeCl3.The compositions (I) can be obtained according to a process described in patent EP 0 50 435-B1 which consists in carrying out the condensation of (methyl) benzyl chloride with xylene in the presence of FeCl 3 .

Les compositions diélectriques selon l'invention présentent l'avantage d'avoir un comportement gazeux amélioré (gassing amélioré). The dielectric compositions according to the invention have the advantage of having improved gas behavior (improved gassing).

Les exemples qui suivent illustrent l'invention.The following examples illustrate the invention.

La propriété de "gassing" a été évaluée en utilisant la méthode décrite dans la norme 628 de la commission électrotechnique internationale (CEI).The property of "gassing" was evaluated using the method described in standard 628 of the electrotechnical commission international (CEI).

Selon cette méthode, l'interface entre une colonne de liquide et un volume d'hydrogène est soumise à des décharges électriques entre 2 électrodes placées à des potentiels différents.According to this method, the interface between a column of liquid and a volume of hydrogen is subjected to electrical discharges between 2 electrodes placed at different potentials.

On suit l'évolution du volume gazeux en fonction du temps.The evolution of the gas volume is monitored as a function of time.

Le gassing, exprimé en µl/min, est positif si du gaz est libéré et est négatif si du gaz est absorbé.The gassing, expressed in µl / min, is positive if gas is released and is negative if gas is absorbed.

Différents mélanges d'un huile minérale de type paraffinique "gas-evolving" et du produit JARISOL XX (ci-après désigné par XX), ont été préparés puis évalués selon la méthode CEI 628-A à 80°C.Different mixtures of a paraffinic mineral oil "gas-evolving" and the JARISOL XX product (hereinafter referred to as XX), have have been prepared and then evaluated according to the IEC 628-A method at 80 ° C.

Les résultats de qassinq sont reportés dans le tableau 1. COMPOSITION (% EN POIDS) GASSING Huile minérale XX EN µl/min 100 % - + 5,4 : 98 % 2 % - 5 95 % 5 % - 12,8 90 % 10 % - 22,7 The results of qassinq are reported in Table 1. COMPOSITION (% BY WEIGHT) GASSING Mineral oil XX IN µl / min 100% - + 5.4: 98% 2% - 5 95% 5% - 12.8 90% 10% - 22.7

Différents mélanges d'huiles minérales de type naphténique plus ou moins hydrogénées "gaz evolving" (gassing positif) et du produit JARYLEC C100 (ci-après désigné par C100) ont été préparés, puis évalués selon la méthode CEI 628-A- à 80°C.Different mixtures of mineral oils of naphthenic type plus or less hydrogenated "evolving gas" (positive gassing) and of the product JARYLEC C100 (hereinafter referred to as C100) have been prepared, then evaluated according to the IEC 628-A- method at 80 ° C.

Les résultats de gassing sont reportés dans le tableau 2.

Figure 00060001
The gassing results are reported in Table 2.
Figure 00060001

Claims (4)

Composition diélectrique pour appareils électriques, caractérisée en ce qu'elle comprend de 99 % à 70 % en poids d'une huile minérale et de 1 % à 30 % en poids d'au moins une composition de polyarylalcanes choisie parmi : les compositions (I) comprenant un mélange de produits de formule (A) :
Figure 00070001
dans laquelle n1 et n2 = 0 ou 1 qui contient des produits (A) tels que n1 + n2 = 0 et des produits (A) tels que n1 + n2 = 1 ; et de produits de formule (B) :
Figure 00070002
 les compositions (II) comprenant un mélange de deux produits (C) et (D) dans lequel : le produit (C) est un mélange d'isomères de formule :
Figure 00070003
avec p1 et p2 = 0,1 et 2, sachant que p1 + p2 ≤ 3, et le produit (D) est un mélange d'isomères de formule :
Figure 00080001
avec
   p'1, p"1 et p4 = 0,1 et 2
   p'2, p"2, p3 et p5 = 0 et 1
sachant que p'1 + p"1 + p'2 + p2 + p3 + p'3 + p4 + p5 ≤ 2. les compositions (III) comprenant un mélange de deux produits (A1) et (A2), tels que : le produit (A1) est un mélange d'isomères de formule :
Figure 00080002
avec m1 et m2 = 0, 1 ou 2 sachant que m1 + m2 ≤ 3, le produit (A2) est un mélange d'isomères de formule :
Figure 00080003
avec q1 et q2 = 0, 1 ou 2 sachant que q1 + q2 ≤ 3,
l'un au moins des composés (A1) et (A2) comprenant un isomère ayant trois noyaux benzéniques. les compositions (IV) comprenant les deux produits (A1) et (A2) et, en outre, au moins un composé choisi parmi les produits (E1), (E2) ou (E3) suivants : (E1) est un isomère ou un mélange d'isomères de formule :
Figure 00090001
avec
   r'1, r"1 et r4 = 0, 1 ou 2
   r'2, r"2, r3, r'3 et r5 = 0 et 1
sachant que r'1 + r"1 + r'2 + r"2 + r3 + r'3 + r4 + r5 est inférieur ou égal à 2.
   R1 et R2 représentent un atome d'hydrogène. (E2) est un isomère ou un mélange d'isomères de même formule générale que (E1), sauf que R1 et R2 représentent un méthyle et les coefficients r sont remplacés par s et ont la même signification. (E3) est un isomère ou un mélange d'isomères de même formule générale que (E1), sauf que R1 et R2 sont différents et représentent un atome d'hydrogène ou un radical méthyle et les coefficients r sont remplacés par t et ont la même signification. Dielectric composition for electrical devices, characterized in that it comprises from 99% to 70% by weight of a mineral oil and from 1% to 30% by weight of at least one polyarylalkane composition chosen from: the compositions (I) comprising a mixture of products of formula (A):
Figure 00070001
in which n 1 and n 2 = 0 or 1 which contains products (A) such as n 1 + n 2 = 0 and products (A) such as n 1 + n 2 = 1; and of products of formula (B):
Figure 00070002
 the compositions (II) comprising a mixture of two products (C) and (D) in which: product (C) is a mixture of isomers of formula:
Figure 00070003
with p 1 and p 2 = 0.1 and 2, knowing that p 1 + p 2 ≤ 3, and product (D) is a mixture of isomers of formula:
Figure 00080001
with
p ' 1 , p " 1 and p 4 = 0.1 and 2
p ' 2 , p " 2 , p 3 and p 5 = 0 and 1
knowing that p ' 1 + p " 1 + p' 2 + p 2 + p 3 + p ' 3 + p 4 + p 5 ≤ 2. the compositions (III) comprising a mixture of two products (A1) and (A2), such as: the product (A1) is a mixture of isomers of formula:
Figure 00080002
with m 1 and m 2 = 0, 1 or 2 knowing that m 1 + m 2 ≤ 3, the product (A2) is a mixture of isomers of formula:
Figure 00080003
with q 1 and q 2 = 0, 1 or 2 knowing that q 1 + q 2 ≤ 3,
at least one of the compounds (A1) and (A2) comprising an isomer having three benzene rings. the compositions (IV) comprising the two products (A1) and (A2) and, in addition, at least one compound chosen from the following products (E1), (E2) or (E3): (E1) is an isomer or a mixture of isomers of formula:
Figure 00090001
with
r ' 1 , r " 1 and r 4 = 0, 1 or 2
r ' 2 , r " 2 , r 3 , r' 3 and r 5 = 0 and 1
knowing that r ' 1 + r " 1 + r' 2 + r" 2 + r 3 + r ' 3 + r 4 + r 5 is less than or equal to 2.
R 1 and R 2 represent a hydrogen atom. (E2) is an isomer or a mixture of isomers with the same general formula as (E1), except that R 1 and R 2 represent a methyl and the coefficients r are replaced by s and have the same meaning. (E3) is an isomer or a mixture of isomers of the same general formula as (E1), except that R 1 and R 2 are different and represent a hydrogen atom or a methyl radical and the coefficients r are replaced by t and have the same meaning. Composition selon la revendication 1, caractérisée en ce que les compositions (I) ont une teneur pondérale en composés à 2 et 3 noyaux aromatiques supérieure à 99 %. Composition according to Claim 1, characterized in that the compositions (I) have a content by weight of compounds 2 and 3 aromatic nuclei greater than 99%. Composition selon la revendication 1 caractérisée en ce que les compositions (II) sont constituées essentiellement par 70 % à 80 % en poids d'un mélange d'isomères de benzyltoluène (produit (C), p1 = p2 = 0) et par 20 % à 30 % en poids d'isomères de dibenzyltoluène (produit (C) ; p1 = 1, p2 = 0 ou p1 = 0, p2 = 1) et d'isomères du ditolylphénylméthane (produit (D)).Composition according to Claim 1, characterized in that the compositions (II) consist essentially of 70% to 80% by weight of a mixture of benzyltoluene isomers (product (C), p 1 = p 2 = 0) and by 20% to 30% by weight of dibenzyltoluene isomers (product (C); p 1 = 1, p 2 = 0 or p 1 = 0, p 2 = 1) and isomers of ditolylphenylmethane (product (D)) . Composition selon l'une des revendications 1 à 3, caractérisée en ce qu'elle comprend de 99 % à 80 % en poids d'une huile minérale et de 1 % à 20 % en poids d'au moins une composition de polyarylalcanes choisie parmi les compositions (I), (II), (III) ou (IV).Composition according to one of claims 1 to 3, characterized in what it includes from 99% to 80% by weight of a mineral oil and from 1% to 20% by weight of at least one composition of polyarylalkanes chosen from compositions (I), (II), (III) or (IV).
EP00401546A 1999-06-07 2000-05-31 Dielectric composition having an improved gas absorbtion Expired - Lifetime EP1059643B1 (en)

Applications Claiming Priority (4)

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FR9907143 1999-06-07
FR9907143A FR2794566B1 (en) 1999-06-07 1999-06-07 DIELECTRIC COMPOSITION HAVING IMPROVED GAS ABSORPTION
FR0001880A FR2794567A1 (en) 1999-06-07 2000-02-16 DIELECTRIC COMPOSITION HAVING IMPROVED GAS ABSORPTION
FR0001880 2000-02-16

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US9051419B2 (en) * 2002-06-14 2015-06-09 Richard H. Hall Polymer
US20060100466A1 (en) * 2004-11-08 2006-05-11 Holmes Steven A Cycloalkane base oils, cycloalkane-base dielectric liquids made using cycloalkane base oils, and methods of making same
US7531083B2 (en) * 2004-11-08 2009-05-12 Shell Oil Company Cycloalkane base oils, cycloalkane-base dielectric liquids made using cycloalkane base oils, and methods of making same
KR20170139696A (en) * 2010-11-25 2017-12-19 프리즈미안 에스피에이 Energy Cable Having a Voltage Stabilized Thermoplastic Electrically Insulating Layer
FR3008708B1 (en) * 2013-07-19 2016-09-23 Arkema France COMPOSITION OF DIELECTRIC FLUID OR CALOPORATOR
CN106675733A (en) * 2017-01-05 2017-05-17 广东美商工业材料有限公司 Capacitor oil applied to oil-immersed capacitor and preparation method of capacitor oil
FR3078711B1 (en) * 2018-03-08 2020-07-31 Arkema France USE OF A MIXTURE AS A DIELECTRIC FLUID

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1579679A (en) * 1976-07-16 1980-11-19 British Petroleum Co Electro-erosion process using dielectric liquids
EP0443899A1 (en) * 1990-02-20 1991-08-28 Elf Atochem S.A. Process for synthetising oligomers of (methylbenzyl)xylene and their use as dielectric
EP0444989A1 (en) * 1990-02-27 1991-09-04 Elf Atochem S.A. Dielectric compositions comprising benzyltoluene and (methylbenzyl)xylene
EP0446086A1 (en) * 1990-02-27 1991-09-11 Elf Atochem S.A. Composition comprising methyl and benzyl derivatives of diphenylmethane and its use as dielectricum
EP0544571A1 (en) * 1991-11-26 1993-06-02 Elf Atochem S.A. Composition based on benzyltoluene and benzylxylene, his application as dielectric
EP0704861A1 (en) * 1994-09-30 1996-04-03 Elf Atochem S.A. Dielectric composition based on polyarylalkanes with improved dielectric properties

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4914320B1 (en) * 1969-03-31 1974-04-06
JPS553762B2 (en) * 1973-07-11 1980-01-26
JPS5078899A (en) * 1973-11-16 1975-06-26
JPS5086699A (en) * 1973-12-06 1975-07-12
JPS5086700A (en) * 1973-12-06 1975-07-12
JPS5086698A (en) * 1973-12-06 1975-07-12
US4189391A (en) 1976-05-01 1980-02-19 Nippon Oil Co., Ltd. Electrical insulating oil compositions
FR2552423B1 (en) * 1983-09-23 1985-10-25 Ugine Kuhlmann POLYARYLALCAN OLIGOMER COMPOSITIONS AND THEIR MANUFACTURING METHOD
GR850003B (en) * 1984-07-11 1985-05-06 Siemens Ag
FR2643366B1 (en) * 1989-02-20 1991-09-06 Atochem POLYPHENYLMETHANE COMPOSITIONS, THEIR MANUFACTURING PROCESS AND THEIR APPLICATION AS DIELECTRIC
AU4427493A (en) * 1992-08-03 1994-02-10 Becton Dickinson & Company Solid phase assay
KR101579679B1 (en) * 2014-04-22 2015-12-22 한밭대학교 산학협력단 Nozzle apparatus for vertical type parylene monomer

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1579679A (en) * 1976-07-16 1980-11-19 British Petroleum Co Electro-erosion process using dielectric liquids
EP0443899A1 (en) * 1990-02-20 1991-08-28 Elf Atochem S.A. Process for synthetising oligomers of (methylbenzyl)xylene and their use as dielectric
EP0444989A1 (en) * 1990-02-27 1991-09-04 Elf Atochem S.A. Dielectric compositions comprising benzyltoluene and (methylbenzyl)xylene
EP0446086A1 (en) * 1990-02-27 1991-09-11 Elf Atochem S.A. Composition comprising methyl and benzyl derivatives of diphenylmethane and its use as dielectricum
EP0544571A1 (en) * 1991-11-26 1993-06-02 Elf Atochem S.A. Composition based on benzyltoluene and benzylxylene, his application as dielectric
EP0704861A1 (en) * 1994-09-30 1996-04-03 Elf Atochem S.A. Dielectric composition based on polyarylalkanes with improved dielectric properties

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TWI257383B (en) 2006-07-01
CA2311250C (en) 2007-10-30
CN1144844C (en) 2004-04-07
DE60003757T2 (en) 2004-05-27
EP1059643B1 (en) 2003-07-09
FR2794567A1 (en) 2000-12-08
KR100375357B1 (en) 2003-03-08
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JP2004143468A (en) 2004-05-20
KR20010007272A (en) 2001-01-26
CN1292402A (en) 2001-04-25
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DE60003757D1 (en) 2003-08-14

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