WO2006040888A1 - Huile isolante électrique - Google Patents

Huile isolante électrique Download PDF

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Publication number
WO2006040888A1
WO2006040888A1 PCT/JP2005/016312 JP2005016312W WO2006040888A1 WO 2006040888 A1 WO2006040888 A1 WO 2006040888A1 JP 2005016312 W JP2005016312 W JP 2005016312W WO 2006040888 A1 WO2006040888 A1 WO 2006040888A1
Authority
WO
WIPO (PCT)
Prior art keywords
acid
ester
electrical insulating
insulating oil
oil
Prior art date
Application number
PCT/JP2005/016312
Other languages
English (en)
Japanese (ja)
Inventor
Takashi Kaimai
Yoshiyuki Morishima
Original Assignee
Japan Energy Corporation
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 Japan Energy Corporation filed Critical Japan Energy Corporation
Priority to KR1020077003563A priority Critical patent/KR101230701B1/ko
Priority to CN2005800250504A priority patent/CN1993775B/zh
Priority to JP2006540849A priority patent/JP4994846B2/ja
Publication of WO2006040888A1 publication Critical patent/WO2006040888A1/fr

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Classifications

    • 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

Definitions

  • the present invention relates to an electrical insulating oil excellent in electrical characteristics and biodegradability.
  • Natural circulation cooling type transformers, etc. have low viscosity at low temperatures as well as the above biodegradability and normal insulation performance. Even if a small amount of moisture is mixed in, the deterioration in insulation performance is small.
  • the electric insulating oil composed of the rapeseed oil ester is not satisfactory in terms of pour point and viscosity at low temperature.
  • Various commercially available electric insulating oils also have electric characteristics, pour point and low temperature. There is a problem with either the viscosity or biodegradability of this material, and most of them are found to be satisfactory.
  • the present invention solves the above-mentioned problems, is excellent in biodegradability, has low viscosity at low temperature, and has a sufficient electric characteristic that the deterioration in insulation performance is small even when some moisture is mixed.
  • the present invention provides:
  • (1) Mainly composed of neopentyldaricol and one or more esters of linear or branched carboxylic acids with 7 to 10 carbon atoms, with kinematic viscosity at 0 ° C of 10 to 200 mm 2 / s, dielectric breakdown Electrical insulating oil with a voltage of 30 kV or higher, biodegradability of 60% or higher, and a pour point of 30 ° C or lower, (2) The ester power of neopentyl glycol and n-heptanoic acid, n-octanoic acid, n-nonanoic acid, n-decanoic acid, 2-ethylhexanoic acid and 3,5,5-trimethylhexanoic acid.
  • the electrical insulating oil according to (1) above which contains at least one ester.
  • Phenolic compounds and Z or amine compounds as antioxidants, triazole compounds as antistatic agents, and carposimide and Z or epoxy compounds as hydrolysis inhibitors are added in an amount of 1% by mass or less,
  • the electrical insulating oil of the present invention is excellent in biodegradability, it is rapidly decomposed by microorganisms even if it leaks, and the load on the natural environment is small. Natural circulation cooling function can be exhibited even outdoors, and even if some rainwater or other water is mixed in, it has sufficient electrical characteristics that the deterioration of insulation performance is small and excellent in practical performance. There is a special effect.
  • An ester comprising neopentyl glycol, which is a main component of the electrical insulating oil of the present invention, and one or more of a straight chain or branched carboxylic acid having 7 to 10 carbon atoms is a non-catalyst of the above-mentioned dalicol and carboxylic acid.
  • it can be produced by esterification by a usual method in the presence of a strong acid catalyst such as sulfuric acid or alkylsulfonic acid, or a metal chloride catalyst such as tin chloride or titanium chloride.
  • the obtained ester may be purified by a series of treatments such as deoxidation, washing with water, dehydration, decoloration, and filtration, as in the case of purifying ordinary esters.
  • the electrical insulating oil of the present invention has a predetermined property by appropriately mixing, ie, physically mixing, the above-mentioned darlicol and each carboxylic acid separately and separately. May be used, or two or more in advance so as to have a predetermined property It is also possible to use what was obtained by the so-called chemical mixing, in which the above carboxylic acid was appropriately blended and reacted with the above-mentioned Daricol and esterification.
  • the ester that is useful in the present invention may be a partial ester in which some of the hydroxyl groups of neopentyldaricol remain without being esterified, but all the hydroxyl groups of the alcohol (glycol). Is preferably esterified.
  • the hydroxyl value of the above ester is preferably 50 mgKOH / g or less, particularly preferably 10 mgKOH / g or less.
  • the linear or branched carboxylic acid having 7 to 10 carbon atoms is represented by R-COOH, has one carboxyl group, and R is a linear or branched alkyl group having 6 to 9 carbon atoms.
  • R is a linear or branched alkyl group having 6 to 9 carbon atoms.
  • n-heptanoic acid, n-octanoic acid, n-nonanoic acid, n_decanoic acid, 2-ethylhexanoic acid and 3,5,5-trimethylhexanoic acid are preferred.
  • the carboxylic acid a branched carboxylic acid having 8 or 9 carbon atoms is more preferable.
  • 2-ethylhexanoic acid or 3,5,5-trimethylhexanoic acid is preferably used.
  • the branched carboxylic acid is preferably 5 mol% or more, particularly 15 mol% or more, more preferably 25 mol% or more in full strength rubonic acid.
  • carboxylic acid in best carboxylic acid hexanoic acid 2- Echiru. 5 to: L 00 mole 0/0, especially ⁇ This. 15 to: L00 mole 0/0, further ⁇ This 50 to: L00 mol It is preferable to use it so that it may become%.
  • the above ester is included as the main component of the base oil! / Will be good! In particular, all the required performances such as viscosity at low temperature, pour point, biodegradability and electrical properties are better. From the point of view, if the balance is surely satisfied, the ester is preferably contained in an amount of 50% by mass or more based on the total amount of the base oil, and more preferably 80% by mass or more, more preferably 90% by mass or more. It is most preferable that the above ester, which is more preferably contained, is 100% by mass of the base oil.
  • the base oil of the electrical insulating oil of the present invention includes hydrocarbon oils such as mineral oil, olefin polymers, alkylbenzenes, polydaricol, polybule ethers, ketones, polyphenyl ethers, silicones in addition to the above esters. , Polysiloxane, perfluoroether, Oxygen-containing synthetic oils such as esters and ethers other than the above esters may be used.
  • Electrical insulating oil of the present invention has a kinematic viscosity at 0 ° C is required to be in the range of 10 to 200 mm 2 / s, is less than 10 mm 2 / s, poor flame resistance flash point is lowered If it exceeds 200 mm 2 / s, the circulation of the insulating oil in the transformer becomes insufficient, resulting in incomplete cooling and heating.
  • the kinematic viscosity at 0 ° C. is preferably in the range of 10 to 100 mm 2 / s, particularly 10 to 50 mm 2 / s.
  • the electrical insulating oil of the present invention needs to have a biodegradability of 60% or more and a biodegradability of 85% or more in order to reduce the influence on the natural environment. It is preferable. This biodegradability is after 28 days measured by the method specified in OECD 301B.
  • the electrical insulating oil of the present invention has a pour point of 30 ° C or lower. Unless the pour point of electrical insulating oil is 30 ° C or less, it cannot withstand use in cold regions.
  • the dielectric breakdown voltage according to JIS C 2101 needs to be 30 kV or more, and preferably 50 kV or more.
  • the electrical insulating oil of the present invention preferably has a dielectric loss tangent (80 ° C.) according to JIS C 2101 of 5% or less, particularly 2% or less.
  • the electrical insulating oil of the present invention preferably has a total acid value of 0.1 mgKOH / g or less in order to ensure good stability! /.
  • the base oil mainly composed of ester has a high dielectric constant close to that of insulating paper as compared with a mineral oil-based base oil, so that the transformer can be miniaturized.
  • the base oil mainly composed of ester has a high saturated water content, the dielectric breakdown voltage can be maintained at 30 kV or higher even when the water concentration reaches 500 ppm.
  • a phenolic compound and Z or amine compound as an antioxidant, carposimide and Z or epoxy as a hydrolysis inhibitor are added to the base oil mainly composed of the ester. It is preferable to add 1% by mass or less of one or more of the compound and triazol compound as an antistatic agent.
  • the phenolic compound and the amine compound as the acid / antioxidant include di-tert-butyl-p-cresol, 4,4'-methylene-bis- (2,6-di-tert- (Butylphenol), Bisphenol 8, Phenol-naphthylamine, ⁇ ⁇ , ⁇ ⁇ -Di (2-naphthyl) -p-Phenol-diamino And dioctyldiphenylamine.
  • the triazole compound as the antistatic agent include benzotriazole, benzotriazole derivatives, and thiadiazole.
  • carbodiimide as the hydrolysis inhibitor, diphenylcarbodiimide, ditolylcarbodiimide, bis (isopropylpropyl) carbodiimide, bis (diisopropylphenol) carbodiimide, bis (triisopropylpropyl) carbodiimide.
  • Bis (alkylphenol) carbodiimide such as bis (butylphenol) carbodiimide
  • epoxy compounds as the hydrolysis inhibitor include phenol glycidyl ether, phenol glycidyl ester, carbon Examples thereof include alkyl glycidyl ethers having 5 to 18 carbon atoms and alkyl glycidyl esters having 5 to 18 carbon atoms.
  • antioxidants may be added depending on the individual required performance.
  • the amount added should be 1% by mass or less for each additive, based on the total mass of the electrical insulating oil. If it exceeds 1% by mass, sludge generation and coloration will occur during deterioration.
  • acid and water inhibitors and hydrolysis inhibitors 0.05 to 1% by weight, especially 0.1 to 0.5% by weight, and for antistatic agents, 5 to: LOOOppm, especially 5 to 5 Oppm I prefer to do that!
  • the electrical insulating oil of the present invention includes an antiwear agent such as zinc dithiophosphate, an extreme pressure agent such as a sulfur compound, a viscosity index improver, a pour point depressant, and a cleaning dispersant.
  • an antiwear agent such as zinc dithiophosphate
  • an extreme pressure agent such as a sulfur compound
  • a viscosity index improver such as a viscosity index improver
  • a pour point depressant such as a a pour point depressant
  • a cleaning dispersant such as a metal deactivator can be added alone or in combination.
  • additives such as a metal deactivator can be added alone or in combination.
  • the addition amount of these additives is not particularly limited, but is preferably 1% by mass or less based on the total amount of the electrical insulating oil.
  • Neopentyl glycol is used as alcohol, and n-heptanoic acid (nC7), n-octanoic acid (nC8), n-nonanoic acid (nC9), n-decanoic acid (nCIO), 2-ethyl Hexanoic acid ( ⁇ 8), 3,5,5-trimethylhexanoic acid (1 ⁇ 9), 11-butanoic acid 4), 11-dodeca Using acid (nC12), and for comparison, using trimethylolpropane (TMP) or pentaerythritol (PE) as the alcohol, esters were prepared at the ratios shown in Table 1, and the test oil and did.
  • TMP trimethylolpropane
  • PE pentaerythritol
  • An ester using two or more kinds of carboxylic acids is prepared by chemical mixing, that is, by mixing carboxylic acids at a predetermined ratio and esterifying them with alcohol.
  • test oils 1 to 7 according to the present invention are balanced in terms of the performance of the electrical insulating oil having good kinematic viscosity, biodegradability, low temperature fluidity, combustibility, and thermal stability.
  • sample oil 8 for comparison has a low kinematic viscosity and flash point
  • sample oil 9 has a too high pour point
  • sample oil 10 has a high kinematic viscosity and is biodegradable.
  • Low test oil 11 is low in biodegradability
  • Sample oil 12 and 13 are high in pour point and low in biodegradability
  • Sample oil 14 is high in pour point The
  • DBPC 2,6-di-butyl- ⁇ -taresol
  • PNA phenol- ⁇ -naphthylamine
  • BTA benzotriazole
  • the electrical insulating oil of the present invention is excellent in biodegradability, has low viscosity at low temperature, and has sufficient electrical characteristics that the deterioration of the insulation performance is small even if some moisture is mixed.
  • it is extremely useful as an electrical insulating oil for pole transformers for power distribution, but it is also useful as an insulating oil for various electrical equipment such as other transformers, cables, capacitors, and circuit breakers.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Organic Insulating Materials (AREA)
  • Lubricants (AREA)

Abstract

La présente invention concerne une huile isolante électrique qui possède une excellente biodégradabilité, une faible viscosité à basse température et qui, même lorsqu'une quantité d'humidité y est mélangée, détériore lentement le rendement de l’isolation, procurant des caractéristiques électriques satisfaisantes. En particulier, l’invention concerne une huile isolante électrique comprenant comme composant principal un ester composé d’un néopentyle glycol et au moins un acide carboxylique linéaire ou ramifié en C7 à C10 et ayant une viscosité cinématique à 0 °C allant de 10 à 200 mm2/s, une tension disruptive égale ou supérieure à 30 kV, une biodégradabilité égale ou supérieure à 60 % et un point de liquide égal ou inférieur à -30 °C.
PCT/JP2005/016312 2004-10-13 2005-09-06 Huile isolante électrique WO2006040888A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
KR1020077003563A KR101230701B1 (ko) 2004-10-13 2005-09-06 전기 절연유
CN2005800250504A CN1993775B (zh) 2004-10-13 2005-09-06 电绝缘油
JP2006540849A JP4994846B2 (ja) 2004-10-13 2005-09-06 自然循環冷却方式の変圧器用電気絶縁油

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2004298427 2004-10-13
JP2004-298427 2004-10-13

Publications (1)

Publication Number Publication Date
WO2006040888A1 true WO2006040888A1 (fr) 2006-04-20

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2005/016312 WO2006040888A1 (fr) 2004-10-13 2005-09-06 Huile isolante électrique

Country Status (4)

Country Link
JP (1) JP4994846B2 (fr)
KR (1) KR101230701B1 (fr)
CN (1) CN1993775B (fr)
WO (1) WO2006040888A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011063734A (ja) * 2009-09-18 2011-03-31 Jx Nippon Oil & Energy Corp 電動モータ油組成物
WO2014078156A1 (fr) * 2012-11-13 2014-05-22 E. I. Du Pont De Nemours And Company Compositions d'huile mélangée utiles comme compositions de fluide diélectrique et procédés de préparation de ces dernières
GB2525281A (en) * 2014-02-13 2015-10-21 M & I Materials Ltd Improvements in and relating to dielectric fluids
WO2016132156A1 (fr) * 2015-02-20 2016-08-25 M&I Materials Limited Compositions de fluide diélectrique à basse température
JP2016204760A (ja) * 2015-04-15 2016-12-08 株式会社日立製作所 電気絶縁紙およびそれを用いた静止誘導電器
GB2541929A (en) * 2015-09-04 2017-03-08 M&I Mat Ltd Ester compositions for dielectric fluids

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5165307B2 (ja) * 2007-08-23 2013-03-21 Ｊｘ日鉱日石エネルギー株式会社 電気絶縁油及びその製造方法
CN110079276B (zh) * 2014-02-20 2022-01-14 Ａｇｃ株式会社 热循环系统用组合物以及热循环系统
CN105296051B (zh) * 2015-10-20 2018-08-24 中国石油化工股份有限公司 一种可生物降解绝缘油及其制备方法
CN107903985A (zh) * 2017-10-23 2018-04-13 中国科学院长春应用化学研究所 一种合成酯类牵引变压器油组合物及其制备方法
CN116478754B (zh) * 2022-01-13 2024-07-12 中国石油天然气股份有限公司 一种具有高水解稳定性的酯型变压器油组合物
CN115449418B (zh) * 2022-09-29 2023-12-01 国网湖南省电力有限公司 一种防火绝缘油

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Publication number Priority date Publication date Assignee Title
JPS63310502A (ja) * 1987-06-12 1988-12-19 Nippon Oil & Fats Co Ltd 電気絶縁油
JPS63310503A (ja) * 1987-06-12 1988-12-19 Nippon Oil & Fats Co Ltd 電気絶縁油
JPH04183788A (ja) * 1990-11-16 1992-06-30 Hitachi Ltd 冷凍装置
JP2003073681A (ja) * 2001-09-03 2003-03-12 Hitachi Ltd 冷蔵庫用作動媒体組成物又は該組成物を用いた冷蔵庫
JP2005276714A (ja) * 2004-03-26 2005-10-06 Japan Energy Corp 電気絶縁油

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KR100293318B1 (ko) * 1998-08-27 2001-10-26 이종훈 전기절연유의전산값간이측정용시약의제조방법및측정용기구와이를이용한전산값측정방법
JP3849482B2 (ja) 2001-10-10 2006-11-22 新日本理化株式会社 潤滑油

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63310502A (ja) * 1987-06-12 1988-12-19 Nippon Oil & Fats Co Ltd 電気絶縁油
JPS63310503A (ja) * 1987-06-12 1988-12-19 Nippon Oil & Fats Co Ltd 電気絶縁油
JPH04183788A (ja) * 1990-11-16 1992-06-30 Hitachi Ltd 冷凍装置
JP2003073681A (ja) * 2001-09-03 2003-03-12 Hitachi Ltd 冷蔵庫用作動媒体組成物又は該組成物を用いた冷蔵庫
JP2005276714A (ja) * 2004-03-26 2005-10-06 Japan Energy Corp 電気絶縁油

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KOLWZAN B AND GRYGLEWICZ S.: "Synthesis and Biodegradability of Some Adipic and Sebacic Esters.", J SYNTHETIC LUBRICATION., vol. 20, no. 2, July 2003 (2003-07-01), pages 99 - 107, XP002995036 *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011063734A (ja) * 2009-09-18 2011-03-31 Jx Nippon Oil & Energy Corp 電動モータ油組成物
WO2014078156A1 (fr) * 2012-11-13 2014-05-22 E. I. Du Pont De Nemours And Company Compositions d'huile mélangée utiles comme compositions de fluide diélectrique et procédés de préparation de ces dernières
CN104798143A (zh) * 2012-11-13 2015-07-22 纳幕尔杜邦公司 可用作介电流体组合物的共混的油组合物及其制备方法
GB2525281A (en) * 2014-02-13 2015-10-21 M & I Materials Ltd Improvements in and relating to dielectric fluids
WO2016132156A1 (fr) * 2015-02-20 2016-08-25 M&I Materials Limited Compositions de fluide diélectrique à basse température
GB2548421A (en) * 2015-02-20 2017-09-20 M&I Mat Ltd Low Temperature Dielectric Fluid Compositions
JP2016204760A (ja) * 2015-04-15 2016-12-08 株式会社日立製作所 電気絶縁紙およびそれを用いた静止誘導電器
GB2541929A (en) * 2015-09-04 2017-03-08 M&I Mat Ltd Ester compositions for dielectric fluids
EP3138893A1 (fr) * 2015-09-04 2017-03-08 M&I Materials Limited Compositions d'ester pour fluides diélectriques
GB2541929B (en) * 2015-09-04 2018-05-09 M&I Mat Limited Ester compositions for dielectric fluids

Also Published As

Publication number Publication date
KR101230701B1 (ko) 2013-02-07
JPWO2006040888A1 (ja) 2008-05-15
KR20070064587A (ko) 2007-06-21
CN1993775B (zh) 2012-09-05
CN1993775A (zh) 2007-07-04
JP4994846B2 (ja) 2012-08-08

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