CN107533878A - Electric insulation oil base oil for oil-filled electric equipment, electric insulation oil and oil-filled electric equipment containing it - Google Patents
Electric insulation oil base oil for oil-filled electric equipment, electric insulation oil and oil-filled electric equipment containing it Download PDFInfo
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- CN107533878A CN107533878A CN201680021478.XA CN201680021478A CN107533878A CN 107533878 A CN107533878 A CN 107533878A CN 201680021478 A CN201680021478 A CN 201680021478A CN 107533878 A CN107533878 A CN 107533878A
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- oil
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
- C10M101/02—Petroleum fractions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/02—Well-defined hydrocarbons
- C10M105/06—Well-defined hydrocarbons aromatic
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
- C10M105/32—Esters
- C10M105/34—Esters of monocarboxylic acids
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/20—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances liquids, e.g. oils
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/20—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances liquids, e.g. oils
- 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
Abstract
A kind of electric insulation oil base oil for oil-filled electric equipment, it contains the fatty acid ester (A) shown in following logical formula (I)s：R1‑COO‑R2... in (I) formula (I), R1It is the straight-chain of carbon number 5~17 or the branched alkyl of carbon number 5~17, R2It is the aralkyl of carbon number 6~10.In above-mentioned formula (I), preferably R1It is the branched alkyl of carbon number 5~17.
Description
Technical field
The present invention relates to for the electric insulation oil base oil of oil-filled electric equipment, the electric insulation oil containing it and it is oil-filled electrically
Equipment.
The Patent 2015-081805 CLAIM OF PRIORITYs that the present invention is filed an application based on April 13rd, 2015 in Japan, draw herein
With its content.
Background technology
Now, in the oil-filled electric equipments such as transformer, cable, breaker, capacitor, for the mesh of insulation or cooling
, using there is electric insulation oil.Oil-filled electric equipment due to being used under high electric field, therefore exist its it is internal occur shelf depreciation can
Can property.Therefore, for the insulating oil for oil-filled electric equipment, it is desirable to which it has excellent Characteristics of Partial Discharge, i.e. in high electricity
Shelf depreciation (partial discharge inception voltage is high) is not susceptible to off field, also can rapidly be extinguished even if generation shelf depreciation and (is locally put
Electric extinction voltage is high).
As the base oil of electric insulation oil, so far using having mineral oil, silicone oil, PCB (PCB), dibenzyl toluene etc..But
It is that the general biodegradable of these base oils is poor, being leaked to load when in environment turns into problem.Further, due to resource
Limited, the use to mineral oil from now on there is a possibility that to be restricted.The general viscosity of silicone oil is high and heat conductivity is also low.Cause
This, causes the cooling effect of oil-filled electric equipment poor, is not easy to minimize oil-filled electric equipment.
In recent years, there is the base oil that the excellent vegetable oil of biodegradable, fatty acid ester are used as electric insulation oil by research.Example
Such as, Patent Document 1 discloses a kind of electric insulation oil containing vegetable oil.Patent Document 2 discloses one kind to contain advanced fat
The higher fatty acids ester series solvent of fat ester compound can be effectively used to the purposes of electric insulation oil etc..
However, the technology of patent document 1, patent document 2 can not obtain sufficient Characteristics of Partial Discharge.
Prior art literature
Patent document 1：Japanese Patent Laid-Open 2010-287788 publications
Patent document 2：Japanese Patent Laid-Open 2004-149705 publications
The content of the invention
Invent problem to be solved
The present invention is to complete in view of the foregoing, excellent and can give birth to its object is to provide a kind of Characteristics of Partial Discharge
The excellent electric insulation oil base oil for oil-filled electric equipment of thing degradability.
The technical scheme solved the problems, such as
As a result the present inventor has found that the following electric insulation oil base oil for oil-filled electric equipment can by further investigation
Solve the above problems.
I.e. the present invention has following composition.
[1] a kind of electric insulation oil base oil for oil-filled electric equipment, it contains the fatty acid ester shown in following logical formula (I)s
(A)：
R1-COO-R2…(I)
In formula (I), R1It is the straight-chain of carbon number 5~17 or the branched alkyl of carbon number 5~17, R2It is carbon number
6~10 aralkyl.
[2] the electric insulation oil base oil for oil-filled electric equipment as described in [1], in above-mentioned formula (I), R1It is carbon number 5
~17 branched alkyl.
[3] the electric insulation oil base oil for oil-filled electric equipment as described in [1] or [2], it contains selected from by alkylbenzene, alkane
The compound (B) of at least one of the group that base naphthalene, diaryl alkane, triaryl alkane and mineral oil are formed.
[4] the electric insulation oil base oil for oil-filled electric equipment as described in [3], the matter represented by (A) composition/(B) composition
Amount is than being 90/10~20/80.
[5] a kind of electric insulation oil, it contains the electric insulation oil for oil-filled electric equipment described in any one in [1]~[4]
Base oil.
[6] a kind of oil-filled electric equipment, it contains the electric insulation oil described in [5].
Invention effect
The Characteristics of Partial Discharge of the electric insulation oil base oil for oil-filled electric equipment of the present invention is excellent and biological can drop
Solution property is excellent.
Brief description of the drawings
Fig. 1 is the sectional view of a capacitor.
Fig. 2 is the schematic diagram of a cable.
Symbol description
1 capacitor element
2 lead wire
3 metal shells
4 insulation materials
5 insulation media (electric insulation oil)
6 metal covers
7 external lead terminals
8 terminal boards
9 binding post rods
10 caulking gums
11 insulation boards
12 electric insulation oils
13 second semi-conductive layers
14 woven wires
15 protection sheaths
16 conductors
17 first semi-conductive layers
Embodiment
(the electric insulation oil base oil for being used for oil-filled electric equipment)
The electric insulation oil base oil (hereinafter also referred to as " electric insulation oil base oil ") for oil-filled electric equipment of the present invention contains
There is specific fatty acid ester ((A) composition).
The biodegradable of electric insulation oil base oil preferably more than 60%, more preferably more than 70%, further preferred 75% with
On, particularly preferred more than 80% or 100%.Above-mentioned biodegradable is according to European OECD's chemistry product examine
Survey pressure measurement respirometry experiment specified in guideline (OECD Guideline for Testing of chemicals)
Measure behind 28 days of (Manometric Respirometry Test) (guideline 301F, on July 17th, 1992) measure
Value.
Kinematic viscosity preferably 0.1~8mm of the electric insulation oil base oil at 40 DEG C2/ s, more preferably 0.5~4mm2/s.Electric insulation oil
The kinematic viscosity of base oil is easily obtained the cooling effect of oil-filled electric equipment in above-mentioned preferred scope.
In this specification, kinematic viscosity can be according to JIS K 2283:2000 (crude oil and oil product-movement viscosity test sides
Method and viscosity index (VI) computational methods) it is measured.
Preferably less than -25 DEG C, more preferably less than -35 DEG C of the pour point of electric insulation oil base oil.
The pour point of electric insulation oil base oil is easily obtained and used also not even in cold district etc. below above-mentioned higher limit
The excellent electric insulation oil of the versatility that is restricted.
In this specification, pour point can be according to JIS K 2269:1987 (pour point and oil product of crude oil and oil product are turbid
Experimental tests method) " 3. pourtest method " be measured.
" insulating properties " in this specification refers to according to JIS C 2101:2010 (electric insulation oil test methods) " 22. is exhausted
The property of breakdown voltage when edge breakdown voltage test " is measured in more than 40kV.
<(A) composition>
(A) composition is the fatty acid ester shown in following logical formula (I)s.The electric insulation oil base oil of the present invention by containing (A) composition,
Characteristics of Partial Discharge can be improved, and biodegradable can be improved.
R1-COO-R2…(I)
In formula (I), R1It is the straight-chain of carbon number 5~17 or the branched alkyl of carbon number 5~17, R2It is carbon number
6~10 aralkyl.
In formula (I), R1It is the straight-chain of carbon number 5~17 or the branched alkyl of carbon number 5~17, preferably carbon is former
The straight-chain of subnumber 5~11 or the branched alkyl of carbon number 5~11, the more preferably straight-chain of carbon number 5~9 or carbon are former
The branched alkyl of subnumber 5~9.R1Carbon number if above range, Characteristics of Partial Discharge can be improved.In addition, R1's
If carbon number is less than 5, become strong for the plasticity of resin component element, the possibility that resin component element deformation etc. be present.R1Carbon atom
If number is more than 17, kinematic viscosity uprises, and the possibility that can not obtain the sufficiently cooling effect to oil-filled electric equipment be present.
R1Can be saturated hydrocarbyl or unsaturated alkyl.
As R1, the straight-chain of carbon number 5~17 or the alkyl of branched, alkenyl, alkynyl etc. can be enumerated.R1It can enumerate for example
Amyl group, hexyl, heptyl, different heptyl, octyl group, iso-octyl, nonyl, isononyl, decyl, undecyl, dodecyl, tridecane
Base, tridecylene base, myristyl, pentadecyl, 15 carbene bases, cetyl, heptadecyl, heptadecene base, 17
Carbon dialkylene, 17 carbon trialkenyls, aplotaxene base etc..
R1Preferably branched alkyl.R1For branched alkyl, it is easy to further improve low temperature flow.In addition, this hair
Branched alkyl in bright is also secondary containing the carbon atom combined such as 1- ethyl pentyl groups with the carbon atom of the carbonyl in formula (I)
The group of carbon atom.
In formula (I), R2It is the aralkyl of carbon number 6~10.R2Such as benzyl, 2- phenylethyls, 1- phenyl second can be enumerated
Base, 2- phenyl -1- propyl group, 3- phenyl -1- propyl group, 1- phenyl -1- butyl etc..Wherein, put based on being easily obtained good part
The viewpoint of electrical characteristics, R2Preferably benzyl, 2- phenylethyls, 1- phenylethyls.
As (A) composition, based on the further viewpoint for improving partial discharge extinction voltage, preferably benzyl hexanoate, caproic acid 2-
Phenyl chlorocarbonate, caproic acid 1- phenyl chlorocarbonates, caproic acid 2- phenyl -1- propyl ester, caproic acid 3- phenyl -1- propyl ester, caproic acid 1- phenyl -1- fourths
Ester, enanthic acid benzyl ester, enanthic acid 2- phenyl chlorocarbonates, enanthic acid 1- phenyl chlorocarbonates, enanthic acid 2- phenyl -1- propyl ester, enanthic acid 3- phenyl -1- third
Ester, enanthic acid 1- phenyl -1- butyl esters, sad benzyl ester, sad 2- phenyl chlorocarbonates, sad 1- phenyl chlorocarbonates, sad 2- phenyl -1- third
Ester, sad 3- phenyl -1- propyl ester, sad 1- phenyl -1- butyl esters, isooctyl acid benzyl ester, isooctyl acid 2- phenyl chlorocarbonates, isooctyl acid 1- benzene
Base ethyl ester, isooctyl acid 2- phenyl -1- propyl ester, isooctyl acid 3- phenyl -1- propyl ester, isooctyl acid 1- phenyl -1- butyl esters, different n-nonanoic acid benzyl
Ester, different n-nonanoic acid 2- phenyl chlorocarbonates, different n-nonanoic acid 1- phenyl chlorocarbonates, different n-nonanoic acid 2- phenyl -1- propyl ester, different n-nonanoic acid 3- phenyl -1- propyl ester,
Different n-nonanoic acid 1- phenyl -1- butyl esters, capric acid benzyl ester, capric acid 2- phenyl chlorocarbonates, capric acid 1- phenyl chlorocarbonates, capric acid 2- phenyl -1- propyl ester,
Capric acid 3- phenyl -1- propyl ester, capric acid 1- phenyl -1- butyl esters, isodecyl acid benzyl ester, isodecyl acid 2- phenyl chlorocarbonates, isodecyl acid 1- phenyl
Ethyl ester, isodecyl acid 2- phenyl -1- propyl ester, isodecyl acid 3- phenyl -1- propyl ester, isodecyl acid 1- phenyl -1- butyl esters, nutmeg oleic acid benzyl
Ester, nutmeg oleic acid 2- phenyl chlorocarbonates, nutmeg oleic acid 1- phenyl chlorocarbonates, nutmeg oleic acid 2- phenyl -1- propyl ester, mace oil
Sour 3- phenyl -1- propyl ester, nutmeg oleic acid 1- phenyl -1- butyl esters, palmitoleic acid benzyl ester, palmitoleic acid 2- phenyl chlorocarbonates, palm
Oleic acid 1- phenyl chlorocarbonates, palmitoleic acid 2- phenyl -1- propyl ester, palmitoleic acid 3- phenyl -1- propyl ester, palmitoleic acid 1- phenyl -1-
Butyl ester, oleic acid benzyl ester, oleic acid 2- phenyl chlorocarbonates, oleic acid 1- phenyl chlorocarbonates, oleic acid 2- phenyl -1- propyl ester, oleic acid 3- phenyl -1- third
Ester, oleic acid 1- phenyl -1- butyl esters, linoleic acid benzyl ester, linoleic acid 2- phenyl chlorocarbonates, linoleic acid 1- phenyl chlorocarbonates, linoleic acid 2- benzene
Base -1- propyl ester, linoleic acid 3- phenyl -1- propyl ester, linoleic acid 1- phenyl -1- butyl esters, flax acid benzyl ester, leukotrienes 2- phenyl second
Ester, leukotrienes 1- phenyl chlorocarbonates, leukotrienes 2- phenyl -1- propyl ester, leukotrienes 3- phenyl -1- propyl ester, leukotrienes 1- phenyl -1- fourths
Ester, elaidic acid benzyl ester, elaidic acid 2- phenyl chlorocarbonates, elaidic acid 1- phenyl chlorocarbonates, elaidic acid 2- phenyl -1- propyl ester, elaidic acid 3-
Phenyl -1- propyl ester, elaidic acid 1- phenyl -1- butyl esters, vaccenic acid benzyl ester, vaccenic acid 2- phenyl chlorocarbonates, vaccenic acid 1- phenyl chlorocarbonates,
Vaccenic acid 2- phenyl -1- propyl ester, vaccenic acid 3- phenyl -1- propyl ester, vaccenic acid 1- phenyl -1- butyl esters, stearidonic acid benzyl ester,
Parinaric acid 2- phenyl chlorocarbonates, parinaric acid 1- phenyl chlorocarbonates, parinaric acid 2- phenyl -1- propyl ester, 18
Carbon tetraenoic acid 3- phenyl -1- propyl ester, parinaric acid 1- phenyl -1- butyl esters.
Wherein, based on partial discharge extinction voltage is improved, and the viewpoint of good low temperature flow can be obtained, more preferably oneself
Acid benzyl ester, caproic acid 2- phenyl chlorocarbonates, caproic acid 1- phenyl chlorocarbonates, caproic acid 2- phenyl -1- propyl ester, caproic acid 3- phenyl -1- propyl ester, caproic acid
1- phenyl -1- butyl esters, enanthic acid benzyl ester, enanthic acid 2- phenyl chlorocarbonates, enanthic acid 1- phenyl chlorocarbonates, enanthic acid 2- phenyl -1- propyl ester, enanthic acid 3-
Phenyl -1- propyl ester, enanthic acid 1- phenyl -1- butyl esters, sad benzyl ester, sad 2- phenyl chlorocarbonates, sad 1- phenyl chlorocarbonates, sad 2- benzene
It is base -1- propyl ester, sad 3- phenyl -1- propyl ester, sad 1- phenyl -1- butyl esters, isooctyl acid benzyl ester, isooctyl acid 2- phenyl chlorocarbonates, different
It is sad 1- phenyl chlorocarbonates, isooctyl acid 2- phenyl -1- propyl ester, isooctyl acid 3- phenyl -1- propyl ester, isooctyl acid 1- phenyl -1- butyl esters, different
N-nonanoic acid benzyl ester, different n-nonanoic acid 2- phenyl chlorocarbonates, different n-nonanoic acid 1- phenyl chlorocarbonates, different n-nonanoic acid 2- phenyl -1- propyl ester, different n-nonanoic acid 3- phenyl -
1- propyl ester, different n-nonanoic acid 1- phenyl -1- butyl esters, capric acid benzyl ester, capric acid 2- phenyl chlorocarbonates, capric acid 1- phenyl chlorocarbonates, capric acid 2- phenyl -
1- propyl ester, capric acid 3- phenyl -1- propyl ester, capric acid 1- phenyl -1- butyl esters.
These (A) compositions can be used alone any, or be used in combination of two or more.
[manufacture method of (A) composition]
As the manufacture method of (A) composition, the alcohol that can enumerate such as (i) grease and the aralkyl with carbon number 6~10 enters
Method that aliphatic acid is esterified by the method for row ester exchange, (ii) by the alcohol of the aralkyl with carbon number 6~10,
(iii) method that the alcohol of fatty acid ester and the aralkyl with carbon number 6~10 carries out ester exchange etc..
As the grease in above-mentioned (i) method, olive oil, cupu oil, perilla herb oil, camellia oil, peanut oil, soybean can be enumerated
Oil, rapeseed oil, mustard oil, dehydrated castor oil, tung oil, safflower oil, linseed oil, corn oil, sunflower oil, corn oil, cottonseed
Oil, sesame oil, rice bran oil, hemp-seed oil, evening primrose oil, palm oil, palm-kernel oil, coconut oil etc..In addition, as above-mentioned oil
Fat, edible grade for grease can be recycled.Wherein, the viewpoint based on excellent oxidation stability, preferably palm oil, palm-kernel oil, coconut palm
Seed oil.Based on the viewpoint for the Characteristics of Partial Discharge for being easier to improve (A) composition, more preferably palm-kernel oil, coconut oil.
Above-mentioned (i) method can be carried out with existing known method.
Aliphatic acid in above-mentioned (ii) method, can enumerate caproic acid, enanthic acid, octanoic acid, isooctyl acid, different n-nonanoic acid, capric acid, isodecyl
Acid, hendecanoic acid, laurate, tridecanoic acid, myristic acid, pentadecanoic acid, nutmeg oleic acid, palmitic acid, palmitoleic acid, 17
Alkanoic acid, stearic acid, oleic acid, linoleic acid, leukotrienes, elaidic acid, vaccenic acid, parinaric acid etc..In addition, as above-mentioned fat
Acid, edible grade for aliphatic acid can be recycled.
It is the preferred caproic acid of above-mentioned aliphatic acid, enanthic acid, octanoic acid, different based on the viewpoint for the Characteristics of Partial Discharge for being easier to improve (A) composition
Sad, different n-nonanoic acid, capric acid, isodecyl acid, nutmeg oleic acid, palmitoleic acid, oleic acid, linoleic acid, leukotrienes, elaidic acid, vaccenic acid,
Parinaric acid.Wherein, based on the Characteristics of Partial Discharge for being easy to improve (A) composition, and it is easily obtained good low temperature fluidity
Viewpoint, more preferably caproic acid, enanthic acid, octanoic acid, isooctyl acid, different n-nonanoic acid, capric acid.
Above-mentioned (ii) method can be carried out with known method, such as can be carried out in the following way：From normal temperature rank
While section property is warming up to 200 DEG C, 0.7KPa is decompressed to from atmospheric phase, removes water byproduct.
The catalyst used in above-mentioned (ii) method is not particularly limited, and can enumerate such as sulfuric acid, p-methyl benzenesulfonic acid (p-TS), benzene sulphur
The acid catalyst such as sour (BS), methanesulfonic acid；ZrO2、TiO2、SiO2、PO4、Al2O3, the inorganic oxide catalyst such as ZnO；Lithium, caesium,
The base catalysts such as the hydroxide such as sodium, potassium, magnesium, barium, calcium, bicarbonate, carbonate, sodium methoxide, potassium methoxide；The isopropyl of metatitanic acid four
The organic titanic compound catalyst such as ester, tetra-n-butyl titanate, metatitanic acid tetrem hydramine, metatitanic acid tetrastearate；Zirconium-n-propylate, zirconium
Organic zirconate catalyst such as sour N-butyl, four acetylacetone,2,4-pentanedione zirconiums, single acetyl acetone zirconium etc..
Fatty acid ester in above-mentioned (iii) method, the ester compounds for the aliphatic acid that can be enumerated in (ii) method.As above-mentioned
Ester compounds, preferably by the ester compounds with preferable aliphatic acid identical Fatty acid compositions in (ii) method.
Above-mentioned (iii) method can be carried out with known method, such as can be carried out in the following way：From normal temperature rank
While section property is warming up to 200 DEG C, 0.7KPa is decompressed to from atmospheric phase, removes accessory substance alcohols.
The catalyst used in above-mentioned (iii) method is not particularly limited, and can enumerate the hydrogen such as lithium, caesium, sodium, potassium, magnesium, barium, calcium
Oxide；The base catalysts such as bicarbonate, carbonate, sodium methoxide, potassium methoxide；Tetraisopropyl titanate, tetra-n-butyl titanate, titanium
The organic titanic compound catalyst such as sour tetrem hydramine, metatitanic acid tetrastearate；Zirconium-n-propylate, zirconium-n-butylate, four levulinics
Organic zirconate catalyst such as ketone zirconium, single acetyl acetone zirconium etc..
As the manufacture method of (A) composition, based on the viewpoint for improving the electrical characteristics such as Characteristics of Partial Discharge, preferably removed
Go alcohol, separation glycerine, removing inorganic constituents, neutralization, washing, distillation, adsorption treatment, degassing process etc. refined.Wherein, preferably
Carry out adsorption treatment and/or degassing process.If carrying out adsorption treatment, the acid number of electric insulation oil base oil reduces, and is easy to improve
Electrical characteristic.If being de-gassed processing, the amount of moisture of electric insulation oil base oil reduces, and is easy to improve electrical characteristic.
Adsorption treatment can be carried out in the following way：In reaction solution after terminating to reaction, activated clay or work are added
The adsorbents such as property aluminum oxide, after being allowed to Xi Fu Swam from aliphatic acid or acid catalyst etc., by being filtered to remove above-mentioned adsorbent.
As above-mentioned adsorbent, the Inorganic synthese adsorbent for principal component with Mg, Al, Si etc. can be enumerated, such as Association and chemical industry
KYOWARD 100,200,300,400,500,600,700,1000,2000 (being trade name above) of Co., Ltd.'s manufacture etc.
KYOWAMAG 30,150 (being trade name above) of KYOWARD series, Association and the manufacture of chemical industry Co., Ltd. etc.
TOMITA AD100,500,600,700 (being trade name above) of serial, the rich Tanabe Selyaku Co., Ltd's manufactures of KYOWAMAG etc.
TOMITA AD series etc..
Relative to the ester compounds of 100 mass parts reaction gained, 0.01~5 mass parts adsorbent is preferably added.In addition, at absorption
The temperature of liquid to be treated is preferably set to 20~160 DEG C by reason, under air, under the inert gas environment gas such as nitrogen or argon gas or
Handled 10 minutes~5 hours under reduced pressure.
By the adsorption treatment, the acid number of (A) composition is preferably reduced to 0.0001~0.01mgKOH/g, more preferably 0.0001
~0.005mgKOH/g, can further improve electrical characteristic.
It is explained, acid number can use JIS C 2101:The method of " 16. acid value test " of 2010 (electric insulation oil test methods)
It is measured.
Degassing process can be carried out in the following way：To carrying out nitrogen displacement in reactor, in 20~160 DEG C, vacuum
Depressurized 10 minutes~5 hours under degree 0.1kPa~80kPa, evaporation removing moisture, air from reacted reaction solution.Now,
It is the azeotrope with water such as 0.1~3 mole of toluene, isopropanol, ethanol, pyridine that can add relative to the moisture in above-mentioned reaction solution
Compound carry out azeotropic.
By the degassing process, the amount of moisture in (A) composition can preferably be reduced to 0.1~100ppm, more preferably 0.1~
50ppm。
Amount of moisture can use JIS C 2101:The method of " 20. moisture test " of 2010 (electric insulation oil test methods) is surveyed
It is fixed.
After being de-gassed processing, in order to not allow (A) composition to reabsorb moisture, preferably protect in a nitrogen environment or under dry air
Deposit.In addition, (A) composition can add 0.1~30 mass parts 4A molecular sieves relative to 100 mass parts (A) composition
Preserved under dehydrating agents such as (Molecular Sieve) (trade name, Junsei Chemical Co., Ltd.'s systems).Accordingly, will during can growing
Amount of moisture maintains above-mentioned preferable scope.
Relative to the gross mass of electric insulation oil base oil, the content of (A) composition is preferably more than 10 mass % more preferably 20
More than quality %, further preferred more than 40 mass % or 100 mass %, i.e. electric insulation oil base oil only by (A) into
Divide and form.(A) content of composition is easy to improve Characteristics of Partial Discharge and biodegradable more than above-mentioned lower limit.
Relative to the gross mass of electric insulation oil base oil, the content of (A) composition is preferably 10~100 mass %, more preferably 20~
90 mass %, further preferred 40~80 mass %.
<(B) composition>
(B) composition is in the group being made up of alkylbenzene, alkylnaphthalene, diaryl alkane, triaryl alkane and mineral oil
At least one compound.
By using (B) composition, it is easy to improve partial discharge extinction voltage.It is also easy to improve low temperature flow.
Alkylbenzene is the aromatic hydrocarbon that alkyl is combined with 1 phenyl ring.Abovementioned alkyl can be straight-chain or branched.This
Outside, 1 alkyl or multiple alkyl can be combined on phenyl ring.Alkylbenzene can enumerate monoalkyl benzene, dialkyl benzene, trialkyl benzene, four
Alkylbenzene etc..
The preferred carbon number 1~30 of alkyl possessed by alkylbenzene, more preferably carbon number 3~30, further preferred carbon atom
Number 4~24, particularly preferred carbon number 10~20.
As alkylbenzene, 1~4 alkyl is preferably combined with phenyl ring.In addition, as alkylbenzene, the alkane preferably combined with phenyl ring
The total carbon atom number of base is 3~30, and more preferably the total carbon atom number of alkyl is 4~24, the entire carbon atom of further preferred alkyl
Number is 10~20.In electric insulation oil base oil if alkylbenzene mixture, it is easy to improve low temperature flow.
Abovementioned alkyl can enumerate methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl,
Dodecyl, tridecyl, myristyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, two
Dodecyl, tricosyl, tetracosyl, pentacosyl, cerul, heptacosane base, octacosyl, two
Nonadecyl, melissyl etc..These alkyl can be straight-chain or branched.
As alkylbenzene, based on the viewpoint for being easy to improve partial discharge extinction voltage, the alkyl preferably combined with phenyl ring
Total carbon atom number is 10~20.In addition, abovementioned alkyl be preferably the decyl of straight-chain or branched, undecyl, dodecyl,
Tridecyl, myristyl, heptadecyl, octadecyl, nonadecyl, eicosyl.
Alkylbenzene can be used alone any one or be applied in combination two or more.
As the concrete example of alkylbenzene, decyl benzene, undecyl benzene, detergent alkylate, tridane, 14 can be enumerated
Alkylbenzene, heptadecyl benzene, octadecyl benzene, nonadecyl benzene, eicosyl benzene etc..
The manufacture method of alkylbenzene is not particularly limited, and can enumerate known method.As above-mentioned manufacture method, example can be enumerated
Such as benzene,toluene,xylene, ethylbenzene, ethyl methyl benzene, diethylbenzene and their mixture raw material are entered by alkylating agent
The method of row alkylation.Abovementioned alkyl agent can be enumerated：Pass through the polymerization of the lower monoolefinics such as ethene, propylene, butylene, isobutene
The straight-chain of acquisition or the alkene of branched；Obtained by the thermal decomposition of wax, heavy oil, petroleum distillate, polyethylene, polypropylene etc.
The alkene of straight-chain or branched；Or positive structure chain hydrocarbon is separated from the petroleum distillates such as kerosene, light oil, it is passed through into catalyst alkene
Straight-chain alkene obtained by hydrocarbonylation；And their mixture etc..
Alkylnaphthalene is the aromatic hydrocarbon that alkyl is combined with 1 naphthalene nucleus.
Abovementioned alkyl can enumerate the alkyl identical group with being combined on abovementioned alkyl benzene.On naphthalene nucleus can combine 1 alkyl or
Multiple alkyl.
The preferred carbon number 1~30 of alkyl possessed by alkylnaphthalene, more preferably carbon number 3~30, further preferred carbon atom
Number 10~25, particularly preferred carbon number 14~20.As alkylnaphthalene, with reference to the compound of 1~4 alkyl preferably on naphthalene nucleus.
In addition, as alkylnaphthalene, based on the viewpoint for being easy to improve partial discharge extinction voltage, the total carbon of the alkyl preferably combined with naphthalene nucleus
Atomicity is 3~30, and more preferably the total carbon atom number of alkyl is 6~24, the total carbon atom number of further preferred alkyl for 14~
20。
Alkylnaphthalene can be used alone or be applied in combination two or more.
The concrete example of alkylnaphthalene can enumerate decyl naphthalene, undecyl naphthalene, dodecyl naphthalene, tridecyl naphthalene, myristyl
Naphthalene, heptadecyl naphthalene, octadecyl naphthalene, nonadecyl naphthalene, eicosyl naphthalene etc..
The manufacture method of alkylnaphthalene is not particularly limited, and can be manufactured with various known methods.It can enumerate and for example exist
The solid acid such as the inorganic acids such as sulfuric acid, phosphoric acid, silico-tungstic acid, hydrofluoric acid, acid clay, activated clay material or aluminium chloride, chlorination
In the presence of the acid catalysts such as the friedel-craft catalysts of the metal halides such as zinc, by the halide of the hydrocarbon of carbon number 14~20,
The olefines of carbon number 14~20 and the method for naphthalene addition etc..
As diaryl alkane, alkane compound of the intramolecular with 2 aryl radicals can be enumerated, such as hexichol can be enumerated
Methylmethane, benzyl toluene, benzylxylene, phenyl sec-butylbenzene methylmethane, di-sec-butyl diphenyl methane, diphenylethane,
Phenyl ethyl phenyl ethane, phenyl cumyl ethane, diisopropyl phenyl ethane, phenyltoluene base ethane, di-sec-butyl phenyl second
Alkane, di-tert-butyl-phenyl ethane, phenyl xylyl ethane, phenyl secondary butyl phenenyl ethane, diphenyl propane, diphenyl fourth
Alkane, xylyl ethane, two (xylyl) octanes, two (xylyl) decane etc..
Wherein, preferably phenyl ethyl phenyl ethane, phenyl xylyl ethane.
As phenyl ethyl phenyl ethane, 1- phenyl -1- (2- ethylphenyls) ethane, 1- phenyl -1- (3- ethylo benzenes can be enumerated
Base) ethane, 1- phenyl -1- (4- ethylphenyls) ethane, 1- phenyl -2- (2- ethylphenyls) ethane etc..As phenyl dimethylbenzene
Base ethane, 1- phenyl -1- (2,3- 3,5-dimethylphenyl) ethane, 1- phenyl -1- (2,4- 3,5-dimethylphenyl) ethane, 1- benzene can be enumerated
Base -1- (2,5- 3,5-dimethylphenyls) ethane, 1- phenyl -1- (2,6- 3,5-dimethylphenyls) ethane, 1- phenyl -1- (3,4- dimethyl
Phenyl) ethane, 1- phenyl -1- (3,5- 3,5-dimethylphenyls) ethane, 1- phenyl -2- (2,3- 3,5-dimethylphenyls) ethane etc..
The total carbon atom number of diaryl alkane preferably 13~30, more preferably 13~20.
Diaryl alkane can be used alone or be applied in combination two or more.
As triaryl alkane, alkane compound of the intramolecular with 3 aryl radicals can be enumerated.Such as dibenzyl can be enumerated
Base benzene, dibenzyl toluene, dibenzylxylene and their alkyl substituents etc..
The total carbon atom number of triaryl alkane preferably 19~30, more preferably 19~26.
Triaryl alkane can be used alone or be applied in combination two or more.
As mineral oil, can enumerate from heavy oil distillation it is refined obtained by material.As above-mentioned mineral oil, it is for example right to enumerate
The lubricating oil that paraffin base system crude oil, middle base system crude oil or cycloalkanes base system crude oil obtain via air-distillation and vacuum distillation evaporates
Point, implement solvent deasphalting, solvent extraction, hydrogenation cracking, solvent dewaxing, catalytic dewaxing, hydrofining, sulfuric acid cleaned, clay
Paraffin mineral oil or cycloalkanes hydrocarbon system mineral oil obtained by one or more kinds of refined means of processing.Wherein, based on heat
The viewpoint of excellent in stability, preferably highly refined mineral oil.As above-mentioned mineral oil, can enumerate by paraffin base system crude oil, in
Between base system crude oil or cycloalkanes base system crude oil atmospheric distillation or as air-distillation residue oil be evaporated under reduced pressure obtained by distillate oil, according to
Refined oil obtained from conventional method is refined, further implement depth dewaxed oil obtained by depth dewaxing treatment after refining, implement
Hydrogenated oil and fat obtained by hydrogenation treatment etc..
It is 0.1~100mm preferably in 40 DEG C of kinematic viscosity as mineral oil2/ s, more preferably 0.1~50mm2/ s, further
It is preferred that 0.1~10mm2/s.Above-mentioned kinematic viscosity can be adjusted with a kind of mineral oil and formed, and can also be mixed with two or more
The mineral oil regulation of different motion viscosity forms.
As (B) composition, based on (A) composition and the Characteristics of Partial Discharge of used time and the balancing good of biodegradable
Viewpoint, preferably alkylbenzene, alkylnaphthalene, more preferably alkylbenzene.Among alkylbenzene, particularly preferably with carbon number 10~20
The monoalkyl benzene of straight-chain alkyl.
(B) composition can be used alone or be applied in combination and be two or more.
Relative to the gross mass of electric insulation oil base oil, content preferably 0~80 mass %, more preferably 10~80 matter of (B) composition
Measure %, further preferred 20~70 mass %, particularly preferred 35~65 mass %.
(B) content of composition is easy to further improve partial discharge extinction voltage, further carried more than above-mentioned lower limit
High/low temperature mobility.
When containing (B) composition in electric insulation oil base oil, mass ratio [(A) composition represented by (A) composition/(B) composition
Relative to the mass ratio of (B) composition] preferably 90/10~20/80, more preferably 80/20~30/70, further preferred 65/35~
35/65。
(A) mass ratio represented by composition/(B) composition is if above range, is easily obtained Characteristics of Partial Discharge and can biology
The excellent electric insulation oil base oil of degradability.
Relative to the gross mass of electric insulation oil base oil, the total content preferably 80 mass % of (A) composition and (B) composition with
On, more preferably more than 90 mass %, further preferred more than 95 mass % or 100 mass %, i.e. electric insulation oil basis
Oil is only made up of (A) composition and (B) composition.(A) total content of composition and (B) composition is easy in above-mentioned preferred scope
Improve Characteristics of Partial Discharge and biodegradable.
The electric insulation oil base oil of the present invention is preferably comprised selected from by benzyl hexanoate, caproic acid 2- phenyl chlorocarbonates, caproic acid 1- benzene
Base ethyl ester, caproic acid 2- phenyl -1- propyl ester, caproic acid 3- phenyl -1- propyl ester, caproic acid 1- phenyl -1- butyl esters, enanthic acid benzyl ester, enanthic acid 2-
Phenyl chlorocarbonate, enanthic acid 1- phenyl chlorocarbonates, enanthic acid 2- phenyl -1- propyl ester, enanthic acid 3- phenyl -1- propyl ester, enanthic acid 1- phenyl -1- fourths
Ester, sad benzyl ester, sad 2- phenyl chlorocarbonates, sad 1- phenyl chlorocarbonates, sad 2- phenyl -1- propyl ester, sad 3- phenyl -1- third
Ester, sad 1- phenyl -1- butyl esters, isooctyl acid benzyl ester, isooctyl acid 2- phenyl chlorocarbonates, isooctyl acid 1- phenyl chlorocarbonates, isooctyl acid 2- benzene
Base -1- propyl ester, isooctyl acid 3- phenyl -1- propyl ester, isooctyl acid 1- phenyl -1- butyl esters, different n-nonanoic acid benzyl ester, different n-nonanoic acid 2- phenyl second
Ester, different n-nonanoic acid 1- phenyl chlorocarbonates, different n-nonanoic acid 2- phenyl -1- propyl ester, different n-nonanoic acid 3- phenyl -1- propyl ester, different n-nonanoic acid 1- phenyl -1- fourths
Ester, capric acid benzyl ester, capric acid 2- phenyl chlorocarbonates, capric acid 1- phenyl chlorocarbonates, capric acid 2- phenyl -1- propyl ester, capric acid 3- phenyl -1- propyl ester
At least one of the group formed with capric acid 1- phenyl -1- butyl esters fatty acid ester (A), and selected from by alkylbenzene, alkyl
The compound (B) of at least one of the group that naphthalene, diaryl alkane, triaryl alkane and mineral oil are formed.
The electric insulation oil base oil of the present invention is preferably comprised selected from by sad benzyl ester, capric acid benzyl ester, palm oil fatty acid benzyl
The fatty acid ester (A) of at least one of the group that ester and isooctyl acid benzyl are formed, and selected from by alkylbenzene, alkylnaphthalene,
The compound (B) of at least one of the group that dibenzyl toluene and phenyl xylyl ethane are formed.
The electric insulation oil base oil of the present invention is preferably comprised selected from by sad benzyl ester, capric acid benzyl ester, palm oil fatty acid benzyl
The fatty acid ester (A) of at least one of the group that ester and isooctyl acid benzyl ester are formed, and selected from by alkylbenzene, alkylnaphthalene,
The compound (B) of at least one of the group that dibenzyl toluene and phenyl xylyl ethane are formed,
Relative to the gross mass of electric insulation oil base oil, the content of composition (A) is 20~100 mass %,
Relative to the gross mass of electric insulation oil base oil, the content of composition (B) is 0~80 mass %,
The total amount of composition (A) and composition (B) is no more than 100 mass %.
The electric insulation oil base oil of the present invention is preferably comprised by selected from by sad benzyl ester, capric acid benzyl ester, palm oil fatty acid
The fatty acid ester (A) of at least one of the group that benzyl ester and isooctyl acid benzyl ester are formed.
The electric insulation oil base oil of the present invention is preferably comprised selected from by sad benzyl ester, capric acid benzyl ester, palm oil fatty acid benzyl
The fatty acid ester (A) of at least one of the group that ester and isooctyl acid benzyl ester are formed, and selected from by alkylbenzene, alkylnaphthalene,
The compound (B) of at least one of the group that dibenzyl toluene and phenyl xylyl ethane are formed,
Relative to the gross mass of electric insulation oil base oil, the content of composition (A) is 20~90 mass %,
Relative to the gross mass of electric insulation oil base oil, the content of composition (B) is 10~80 mass %,
The total amount of composition (A) and composition (B) is no more than 100 mass %.
(electric insulation oil for being used for oil-filled electric equipment)
The electric insulation oil for oil-filled electric equipment of the present invention contains above-mentioned electric insulation (below also referred to as " electric insulation oil ")
Oil base oil.
Relative to the gross mass of electric insulation oil, the content of electric insulation oil base oil is preferably more than 80 mass %, more preferably 90 matter
Measure more than %, further preferred more than 95 mass % or 100 mass %.The content of electric insulation oil base oil is above-mentioned
More than lower limit, it is easy to improve the Characteristics of Partial Discharge and biodegradable of electric insulation oil.
The biodegradable of electric insulation oil preferably more than 60%, more preferably more than 70%, further preferred more than 75%, especially
It is preferred that more than 80% or 100%.Above-mentioned biodegradable can be with the biodegradable of electric insulation oil base oil
Assay method similarly measures.
Kinematic viscosity preferably 0.1~8mm of the electric insulation oil at 40 DEG C2/ s, more preferably 0.5~4mm2/s.The motion of electric insulation oil
Viscosity is easily obtained the cooling effect for oil-filled electric equipment if above-mentioned preferred scope.
Preferably less than -25 DEG C, more preferably less than -35 DEG C of the pour point of electric insulation oil.The pour point of electric insulation oil above-mentioned higher limit with
If lower, good usability can be also even obtained in cold district etc., the versatility of electric insulation oil is improved.
In electric insulation oil, in addition to above-mentioned electric insulation oil base oil, also containing usually used its in electric insulation oil
His composition.As other compositions, the base oil and antioxidant, pour point that can be enumerated beyond for example above-mentioned (A) composition and (B) composition
The additives such as depressant, matal deactivator, decomposing inhibitor.But based on the better Characteristics of Partial Discharge of acquisition and Ke Sheng
The viewpoint of thing degradability, relative to the gross mass of electric insulation oil, the content of the base oil beyond (A) composition and (B) composition is preferred
Below 20 mass %, more preferably below 10 mass %, further preferred below 5 mass % or 0 mass %.
As above-mentioned antioxidant, the phenol system antioxygen such as dibutyl hydroxy toluene, butylated hydroxy anisole can be enumerated
Agent；The amine system antioxidant such as phenyl-α-naphthylamine, N, N- bis- (2- naphthyls)-p-phenylenediamine；Tocopherol, d- tocopherols, dl-
The vitamin E classes such as alpha-tocopherol, α-D-α-tocopherol acetate, dl- α-D-α-tocopherol acetate, tocopherol acetate, alpha-tocopherol；Vitamin C
The vitamin c class such as acid, ascorbic acid salt, ascorbyl stearate；Green-tea extract；Green coffee extract；Sesamol；Sesame
Plain phenol of fiber crops etc..Wherein, based on to the excellent viewpoint of electric insulation oil base oil dissolubility, preferably phenol system antioxidant.Electric exhausted
If antioxidant being mixed in edge oil, oxidation stability when being easy to improve when preserving and using for a long time.
Antioxidant can be used alone or be applied in combination two or more.
When the electric insulation oil of the present invention contains antioxidant, relative to the mass parts of electric insulation oil base oil 100, antioxidant contains
Amount is preferably 0.01~5 mass parts.
As above-mentioned pour point depressant, such as sucrose fatty ester, polyalkyl methacrylate or polypropylene can be enumerated
Acrylic acid series polymeric compounds such as acid alkyl ester etc..Aforesaid propylene acid based polymer preferably has about 5,000~500,000 weight average molecular weight.
Aforesaid propylene acid based polymer can enumerate the polymer of straight-chain or branched-chain alkyl with carbon number 1~20, such as can
Enumerate PMA, polymethyl methacrylate, polyacrylic acid propyl ester, polypropylmethacryla,es, polyacrylic acid heptyl ester,
Polymethyl heptyl heptylate, polyacrylic acid nonyl ester, polymethylacrylic acid nonyl ester, polyacrylic acid hendecane base ester, polymethyl
It is sour hendecane base ester, polyacrylic acid tridecane base ester, polymethylacrylic acid tridecane base ester, polyacrylic acid pentadecane base ester, poly-
Methacrylic acid pentadecane base ester, polyacrylic acid heptadecane base ester, polymethylacrylic acid heptadecane base ester etc..Aforesaid propylene acid esters
Polymer can use commercially available product.As above-mentioned commercially available product, the excellent viewpoint of reducing effect and operation treatability based on pour point,
It is preferred that Sanyo Chemical Industries, Ltd.'s manufacture the series of Acrube 100 (Acrube 132,133,136,137,138,146,
160, be trade name above).
When the electric insulation oil of the present invention contains pour point depressant, relative to the mass parts of electric insulation oil base oil 100, pour point depressant
Content preferably 0.01~5 mass parts, more preferably 0.01~3 mass parts.The content of pour point depressant is more than above-mentioned lower limit
If, it is easy to improve low temperature flow.The content of pour point depressant is easy to suppress electric insulation oil below above-mentioned higher limit
High viscosity.
As above-mentioned matal deactivator, such as BTA, 4- methyl-BTA, 4- ethyls-BTA can be enumerated
Deng 4- alkyl-benzotriazole；5- alkyl-the benzotriazoles such as 5- methyl-BTA, 5- ethyls-BTA；1- bis- is pungent
1- alkyl-the benzotriazoles such as base amino methyl -2,3- BTAs；The 1- such as 1- dioctylamino methyl -2,3- tolytriazoles
The benzotriazole derivatives such as alkyl-tolytriazole class；Benzimidazole, 2- (sulphur of octyl group two)-benzimidazole, 2- (sulphur of decyl two)-
2- (sulphur of the alkyl two)-benzimidazoles such as benzimidazole, 2- (sulphur of dodecyl two)-benzimidazole；2- (sulphur of octyl group two)-toluene
And 2- (sulphur of alkyl two)-toluene such as imidazoles, 2- (sulphur of decyl two)-first benzimidazole, 2- (sulphur of dodecyl two)-first benzimidazole
And the benzimidizole derivatives such as imidazoles；Thiazole, benzothiazole, 2-mercaptobenzothiazole derivative, 2- (sulphur of hexyl two) benzo
2- (sulphur of the alkyl two) benzothiazoles such as thiazole, 2- (sulphur of octyl group two) benzothiazole；2- (sulphur of hexyl two) first benzothiazole, 2-
(sulphur of octyl group two) first benzothiazole etc. 2- (sulphur of alkyl two) first benzothiazoles；2- (N, N- diethyl-dithio carbamyl oxygen
Base) benzothiazole, 2- (N, N- dibutyl dithio carbamoyloxy)-benzothiazole, 2- (N, N- dihexyl dithiocarbamates
Formyloxy) 2- (N, the N- dialkyl dithio carbamoyloxy) benzothiazoles such as-benzothiazole；2- (N, N- diethyl
Dithiocarbamates formyloxy) first benzothiazole, 2- (N, N- dibutyl dithio carbamoyloxy) first benzothiazole, 2-
(N, N- dihexyl dithiocarbamates formyloxy) first benzothiazole etc. 2- (N, N- dialkyl dithio carbamoyloxy)-first
Benzothiazole derivants such as benzothiazoles etc..Wherein, it is excellent based on the viewpoint that can also obtain the effect as flowing antistatic additive
Select benzotriazole derivatives.
Matal deactivator can be used alone or be applied in combination two or more.
When the electric insulation oil of the present invention contains matal deactivator, relative to the mass parts of electric insulation oil base oil 100, matal deactivator
Content preferably 0.0001~0.5 mass parts, further preferred 0.0005~0.1 mass parts.
As above-mentioned decomposing inhibitor, diphenyl carbodiimide, xylyl carbodiimide, two (cumenes can be enumerated
Base) carbodiimide compound such as two (alkyl phenyl) carbodiimides such as carbodiimide, two (butyl phenyl) carbodiimides；Phenyl contracts
Water glycerin ether, phenyl glycidyl ester, alkyl glycidyl ether, alkyl glycidyl ester, 3,4- epoxycyclohexyl-methyls (3,4-
7-oxa-bicyclo[4.1.0) carboxylate, vinylcyclohexene diepoxide, 3,4- epoxy radicals -6- methylcyclohexylmethyl (3,4- epoxies
Base -6- methyl hexanes) carboxylate, bisphenol-A diglycidyl ether-type epoxide novolak type epoxy compounds；It is adjacent
Epoxides such as cresol-novolak type epoxy compound etc..If the electric insulation oil of the present invention contains decomposing inhibitor, it is easy to
Suppress deterioration caused by heat, oxygen etc..
The electric insulation oil of the present invention can be manufactured by existing known manufacture method.System as the electric insulation oil of the present invention
The method of making can be enumerated for example adds other compositions into electric insulation oil base oil, the method being mixed.
The electric insulation oil of the present invention can use as the insulating oil of oil-filled electric equipment.
(oil-filled electric equipment)
The oil-filled electric equipment of the present invention has above-mentioned electric insulation oil.As oil-filled electric equipment, can enumerate such as transformer,
Reactor, tap changer, cable, sleeve pipe, converter, capacitor, current transformer etc..
Fig. 1 capacitor has：Formed what winding formed using polypropylene screen etc. as dielectric medium, using metal foil etc. as electrode
Capacitor element 1；From the derived lead wire 2 formed by copper foil etc. of capacitor element 1；Having for storage capacitor element 1 is opened
The metal shell 3 of oral area；The insulation material 4 being configured between metal shell and capacitor element 1；For by metal shell 3 with electricity
The insulation media (electric insulation oil) 5 being full of inside metal shell that container component 1 insulate；The metal cover 6 of sealing metal shell 3；
It is configured at the top of metal cover 6, external lead terminals 7 for being connected with external power source；For by metal cover 6 and outside lead
Terminal board 8 that terminal 7 insulate, being formed by thermosetting resin etc.；Be configured at it is under metal cover 6, by lead wire 2 with it is outside
The binding post rod 9 that lead terminal 7 is electrically connected；And it is configured under metal cover 6, metal cover 6 and binding post rod 9 is exhausted
Edge and the preventing media (electric insulation oil) 5 that insulate spill the caulking gum 10 of metal shell.
Fig. 2 cable possesses：Conductor 16, the first semi-conductive layer 17 being configured at around conductor 16, it is configured at the first semi-conductive layer
Containing for outside is soaked with the layer of electric insulation oil 12, is configured at containing the second semi-conductive layer being soaked with the outside of the layer of electric insulation oil 12, configures
Woven wire 14 on the outside of the second semi-conductive layer and the protection sheath 15 for being configured at the outside of woven wire 14.
As mentioned above, electric insulation oil base oil of the invention is due to excellent containing (A) composition, its Characteristics of Partial Discharge
It is different, and biodegradable is excellent.
Embodiment
Embodiment used below illustrates in more detail to the present invention, but the present invention is not limited to these embodiments.This
" % " in embodiment unless otherwise noted, that is, represents " quality % ".
The raw material used in the present embodiment is as described below.
<(A) composition>
A-1：Sad benzyl ester, is prepared as follows and forms.
A-2：Capric acid benzyl ester, is prepared as follows and forms.
A-3：Palm oil fatty acid benzyl ester, is prepared as follows and forms.
A-4：Isooctyl acid benzyl ester, is prepared as follows and forms.
<(B) composition>
B-1：Alkylbenzene (there is the monoalkyl benzene of the alkyl of carbon number 10~13, JX Kuang Shi energy Co., Ltd. to manufacture,
Trade name " Alkene L ").
B-2：Alkylnaphthalene (the monoalkyl naphthalene of the alkyl with carbon number 16~18, Lion Corporation's system, trade name " diffusion
Pump oil (Expansion dissipates Port Application プ oil) A ").
B-3：Dibenzyl toluene (Japan is comprehensive to grind scientific and technological Co. Ltd. system, trade name " NeoSK-OIL ").
B-4：Phenyl xylyl ethane (JIS C 2320,5 kind of No. 2 insulating oil).
<(A ') composition：(A) the comparison composition of composition>
A’-1：Methyl caprylate (Lion Corporation manufacture, trade name " Pastel M-8 ").
A’-2：Palm oil fatty acid methyl esters (Lion Corporation manufacture, trade name " Pastel M-182 ").
A’-3：Sad 2- ethylhexyls (Lion Corporation's manufacture, trade name " Pastel 2H-08 ").
A’-4：Rapeseed oil (Co., Ltd. Kanden Engineering Corporation manufactures, trade name " Sun-Ohm
ECO”)。
[preparation example of sad benzyl ester]
To being provided with the 5L four-hole boiling flasks of mixer, thermometer, fractional condensing tube and complete solidifying pipe, sad 2100g (the Japanese Northeast is added
KCC's system), benzyl alcohol (Japanese Kanto Kagaku K. K.'s system) 1653g (mol ratios 1：1.05), p-methyl benzenesulfonic acid
Monohydrate (Tokyo HuaCheng Industry Co., Ltd's system) 0.5g, and carry out nitrogen displacement.Thereafter, it is passed through with 1mL/ points of flow
While nitrogen, liquid temperature is warming up to 140 DEG C of progress esterifications, the water of reaction generation is distilled off.After removing water, further
While slowly 0.6kPa is decompressed to, 200 DEG C are warming up to, it is below 1 mass % to obtain unreacted octanoic acid and benzyl alcohol
Rough thing.Then, diatomite (Hyflo Super-Cel) of the 33.1g as filtration adjuvant is added to the above-mentioned rough things of 3310g
(Junsei Chemical Co., Ltd.'s system), after stirring makes it be uniformly dispersed in 10 minutes, filtered at 80 DEG C, obtain sad benzyl ester.
7 [preparation examples of capric acid benzyl ester]
It is sad to be replaced using capric acid (Japanese Kanto Kagaku K. K.'s system), and the mol ratio of capric acid and benzyl alcohol is capric acid：Benzyl
Alcohol=1：1.2, in addition, capric acid benzyl ester is obtained in the same manner as the preparation example of above-mentioned sad benzyl ester.
[preparation example of palm oil fatty acid benzyl ester]
Octanoic acid, palm oil are replaced using palm oil fatty acid methyl esters (trade name " Pastel M-182 ", Lion Corporation's system)
The mol ratio of fatty acid methyl ester and benzyl alcohol is palm oil fatty acid methyl esters：Benzyl alcohol=1：1.2, it is in addition, and above-mentioned pungent
The preparation example of acid benzyl ester similarly obtains palm oil fatty acid benzyl ester.
[preparation example of isooctyl acid benzyl ester]
It is sad to be replaced using isooctyl acid (manufacture of KH NeoChem Co., Ltd.), and the mol ratio of isooctyl acid and benzyl alcohol is different pungent
Acid：Benzyl alcohol=1：1.2, in addition, isooctyl acid benzyl ester is obtained in the same manner as the preparation example of above-mentioned sad benzyl ester.
(embodiment 1~10, comparative example 1~9)
The electric insulation oil base oil of embodiment 1 is used as using above-mentioned (A-1).In addition, the composition shown according to table 1~2, in mixing
(A) composition and (B) composition are stated, manufactures the electric insulation oil base oil of embodiment 2~10.
Using above-mentioned (B-4), (B-1), (B-3), (A ' -1), (A ' -2), (A ' -3) as comparative example 1~6 electric insulation oil
Base oil.In addition to using (A ') composition to replace (A) composition, the electric insulation of comparative example 7~9 is manufactured similarly to Example 2
Oil base oil.
The composition (blending constituent, content (quality %)) of the electric insulation oil base oil of each example of gained is shown in table 1~2.
In table, empty column represents not mixing the blending constituent.
To the electric insulation oil base oil of each example, according to evaluating its Characteristics of Partial Discharge (partial discharge inception voltage, office as follows
Portion's discharge quenching voltage), biodegradable.Evaluation result is shown in Table 1~2.
In addition, by the pour point for the electric insulation oil base oil for determining each example as follows, kinematic viscosity.Measurement result is shown in Table 1~2.
(evaluation of Characteristics of Partial Discharge)
<The evaluation of partial discharge inception voltage>
The partial discharge inception voltage of the electric insulation oil base oil of each example is determined according to JEC-0401-1990.Specifically, using office
Portion electric discharge analyzer (E.R.A.Discharge Detector Model5Type700, Robinson Instruments companies
Manufacture), when application voltage is slowly improved under assigned voltage, measure exceedes prescribed level and (size of discharge pulse, frequency occurs
Rate) the voltage (partial discharge inception voltage) that starts of shelf depreciation.With electric insulation oil base oil (the phenyl diformazan of comparative example 1
Diphenylphosphino ethane：JIS C 2320,5 kind of No. 2 insulating oil) partial discharge inception voltage measured value on the basis of (100%), try to achieve
Relative to the relative value of the measured value of each example partial discharge inception voltage of said determination value.Above-mentioned relative value is pressed into commentary valency
Criteria classification, evaluate the partial discharge inception voltage of the electric insulation oil base oil of each example.AA, A are qualified.
[evaluation criterion]
AA：More than 100%.
A：95~100%.
B：Less than 95%.
<The evaluation of partial discharge extinction voltage>
The partial discharge extinction voltage of the electric insulation oil base oil of each example is determined according to JEC-0401-1990.Specifically, using office
Portion electric discharge analyzer (E.R.A.Discharge Detector Model5Type700, Robinson Instruments companies
Manufacture), when slowly dropping low applied voltage under assigned voltage, measure exceedes prescribed level and (size of discharge pulse, frequency occurs
Rate) shelf depreciation extinguish voltage (partial discharge extinction voltage).With the shelf depreciation of the electric insulation oil base oil of comparative example 1
On the basis of the measured value of starting voltage (100%), the part of each example electric insulation oil base oil relative to said determination value is tried to achieve
The relative value of the measured value of discharge quenching voltage.Above-mentioned relative value is pressed and states evaluation criterion classification, evaluates the electric insulation of each example
The partial discharge extinction voltage of oil base oil.AAA, AA, A are qualified.It is explained, the B in following evaluation criterions is evaluated as office
Portion's electric discharge is not extinguished, can not be practical.
[evaluation criterion]
AAA：More than 50%.
AA：45~50%.
A：40% less than 45%.
B：Less than 40%.
(evaluation of biodegradable)
According to European OECD's chemicals detection guideline (OECD Guideline for Testing of
Chemicals pressure measurement respirometry specified in) tests (Manometric Respirometry Test) (guideline
301F, on July 17th, 1992), implement the biodegradable experiment of the electric insulation oil base oil of each example.The following institute of experimental condition
State.
Experimental condition：Tested material concentration 100mg/L, activated sludge concentration 30mg/L (for suspended sediment concentration), experiment liquid measure
During 300mL, 25 ± 1 DEG C of experimental liquid cultivation temperature, experimental liquid culture 28 days (under lucifuge).
The measure of biochemical oxygen required amount (BOD) is carried out by closed oxygen consumption amount determining device, calculates resolution.Obtain
More than 60% biodegradable it is as qualified.
(measure of pour point)
According to JIS K 2269:1987 (pour points and oil product cloud test method of crude oil and oil product) " 3. incline
Experimental tests method " determines the pour point of each example electric insulation oil base oil.
The pour point of the electric insulation oil base oil of each example is pressed and states evaluation criterion classification, evaluates pour point.Even if AA, A are evaluated as
Cold district etc. also can be used well, and versatility is excellent.
[evaluation criterion]
AA：Pour point is less than -35 DEG C.
A：Pour point is -35~-25 DEG C.
B：Pour point is more than -25 DEG C.
(measure of kinematic viscosity)
According to JIS K 2283:2000 (crude oil and oil product-movement viscosity test methods and viscosity index (VI) computational methods), make
With Kan Nong-Fen Sike (Cannon-Fenske) kinematic viscosity pipe, the electric insulation oil base oil for determining each example glues in 40 DEG C of motion
Degree.
The kinematic viscosity of the electric insulation oil base oil of each example is pressed and states evaluation criterion classification, evaluates kinematic viscosity.AA, A are evaluated
To be easily obtained good cooling effect to oil-filled electric equipment.
[evaluation criterion]
AA：4mm2/ below s.
A：More than 4mm2/s and 8mm2/ below s.
B：More than 8mm2/s。
[table 1]
[table 2]
From the result shown in table 1~2 it has been confirmed that using embodiments of the invention 1~10 electric insulation oil base oil, its
Characteristics of Partial Discharge (partial discharge inception voltage, partial discharge extinction voltage) is excellent, and biodegradable is excellent.Enter one
Step, the pour point and kinematic viscosity of the electric insulation oil base oil of embodiment 1~10 are low, are be evaluated as the usability in cold district etc.
It is excellent with the cooling effect to oil-filled electric equipment.
On the other hand, the electric insulation oil base oil (comparative example 1) comprising (B-4), the electric insulation oil base oil (ratio comprising (B-3)
Compared with example 3) there is no sufficient biodegradable.
Electric insulation oil base oil (comparative example 2), (A ') composition comprising (B-1) and (B-1) and electric insulation oil base oil (compare
Compared with example 8, comparative example 9) there is no sufficient Characteristics of Partial Discharge (partial discharge inception voltage, partial discharge extinction voltage).
Electric insulation oil base oil (comparative example 4~6) comprising (A ') composition there is no sufficient Characteristics of Partial Discharge and (locally put
Electric extinction voltage).
(A ') composition and (B-4) and electric insulation oil base oil (comparative example 7) there is no sufficient Characteristics of Partial Discharge (office
Portion's discharge quenching voltage) and biodegradable.
Result more than confirms, and using the electric insulation oil base oil of the present invention, its Characteristics of Partial Discharge is excellent, and can give birth to
Thing degradability is excellent.
Utilization possibility in industry
Be used for excellent and excellent biodegradable it is an object of the invention to provide a kind of Characteristics of Partial Discharge is oil-filled
The electric insulation oil base oil of electrical equipment.
Claims (6)
1. a kind of electric insulation oil base oil for oil-filled electric equipment, it contains the fatty acid ester shown in following logical formula (I)s
(A)：
R1-COO-R2…(I)
In formula (I), R1It is the straight-chain of carbon number 5~17 or the branched alkyl of carbon number 5~17, R2It is carbon number 6
~10 aralkyl.
2. the electric insulation oil base oil according to claim 1 for oil-filled electric equipment, in the formula (I), R1It is carbon original
The branched alkyl of subnumber 5~17.
3. the electric insulation oil base oil according to claim 1 or 2 for oil-filled electric equipment, it contains selected from by alkyl
The compound (B) of at least one of the group that benzene, alkylnaphthalene, diaryl alkane, triaryl alkane and mineral oil are formed.
4. the electric insulation oil base oil according to claim 3 for oil-filled electric equipment, (A) composition/(B) composition institute table
The mass ratio shown is 90/10~20/80.
5. a kind of electric insulation oil for oil-filled electric equipment, it contains in Claims 1 to 4 and is used to fill described in any one
The electric insulation oil base oil of oily electrical equipment.
6. a kind of oil-filled electric equipment, it has the electric insulation oil for oil-filled electric equipment described in claim 5.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015081805 | 2015-04-13 | ||
| JP2015-081805 | 2015-04-13 | ||
| PCT/JP2016/061409 WO2016167176A1 (en) | 2015-04-13 | 2016-04-07 | Electrically insulating oil base oil for oil-filled electrical device, electrically insulating oil containing same, and oil-filled electrical device |
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| Publication Number | Publication Date |
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| CN107533878A true CN107533878A (en) | 2018-01-02 |
| CN107533878B CN107533878B (en) | 2020-03-10 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201680021478.XA Active CN107533878B (en) | 2015-04-13 | 2016-04-07 | Electric insulating oil base oil for oil-filled electrical equipment, electric insulating oil containing same, and oil-filled electrical equipment |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP6655607B2 (en) |
| CN (1) | CN107533878B (en) |
| WO (1) | WO2016167176A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111149796A (en) * | 2019-12-31 | 2020-05-15 | 苏州丰倍生物科技有限公司 | Pesticide solvent and preparation method and application thereof |
| CN111944227A (en) * | 2020-08-17 | 2020-11-17 | 东莞市赛美塑胶制品有限公司 | Plastic defoaming master batch and preparation method thereof |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR3078711B1 (en) | 2018-03-08 | 2020-07-31 | Arkema France | USE OF A MIXTURE AS A DIELECTRIC FLUID |
| JP7360240B2 (en) * | 2018-03-30 | 2023-10-12 | 住友化学株式会社 | Method for evaluating the degradability of chemical substances, and test containers and oxygen consumption measurement devices used in the method |
| FR3093729A1 (en) | 2019-03-13 | 2020-09-18 | Total Marketing Services | Use of an ester in a cooling composition |
| JP7171514B2 (en) * | 2019-06-20 | 2022-11-15 | 株式会社日立製作所 | electrical equipment |
| EP4186967A1 (en) * | 2020-07-22 | 2023-05-31 | Idemitsu Kosan Co., Ltd | Lubricating oil composition |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4108789A (en) * | 1975-08-28 | 1978-08-22 | Rhone-Poulenc Industries | Dielectric compositions containing benzyl esters |
| JPS5772203A (en) * | 1980-10-24 | 1982-05-06 | Nippon Petrochemicals Co Ltd | Method of degassing electrically insulating oil |
| JPS6199211A (en) * | 1984-10-22 | 1986-05-17 | 日石三菱株式会社 | Electric insulation oil |
| WO2007029724A1 (en) * | 2005-09-09 | 2007-03-15 | Lion Corporation | Base agent for electrical insulating oil |
| CN101784646A (en) * | 2007-07-31 | 2010-07-21 | 雪佛龙美国公司 | Electric insulation oil composition and preparation thereof |
| CN102682869A (en) * | 2012-04-11 | 2012-09-19 | 中国电力科学研究院 | Vegetable insulating oil, and preparation method of vegetable insulating oil |
| CN103988266A (en) * | 2011-10-07 | 2014-08-13 | 纳幕尔杜邦公司 | Liquid compositions used as insulating and heat transfer means, electrical devices containing said compositions and preparation methods for such compositions |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2322435A1 (en) * | 1975-08-28 | 1977-03-25 | Rhone Poulenc Ind | NEW DIELECTRIC LIQUIDS |
| JPH088016B2 (en) * | 1987-03-03 | 1996-01-29 | 東燃料株式会社 | Electrical insulating oil |
| JP2000090740A (en) * | 1998-09-14 | 2000-03-31 | Kansai Tech Corp | Ester insulating oil and manufacture thereof and electrical equipment |
-
2016
- 2016-04-07 WO PCT/JP2016/061409 patent/WO2016167176A1/en active Application Filing
- 2016-04-07 CN CN201680021478.XA patent/CN107533878B/en active Active
- 2016-04-07 JP JP2017512281A patent/JP6655607B2/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4108789A (en) * | 1975-08-28 | 1978-08-22 | Rhone-Poulenc Industries | Dielectric compositions containing benzyl esters |
| JPS5772203A (en) * | 1980-10-24 | 1982-05-06 | Nippon Petrochemicals Co Ltd | Method of degassing electrically insulating oil |
| JPS6199211A (en) * | 1984-10-22 | 1986-05-17 | 日石三菱株式会社 | Electric insulation oil |
| WO2007029724A1 (en) * | 2005-09-09 | 2007-03-15 | Lion Corporation | Base agent for electrical insulating oil |
| CN101784646A (en) * | 2007-07-31 | 2010-07-21 | 雪佛龙美国公司 | Electric insulation oil composition and preparation thereof |
| CN103988266A (en) * | 2011-10-07 | 2014-08-13 | 纳幕尔杜邦公司 | Liquid compositions used as insulating and heat transfer means, electrical devices containing said compositions and preparation methods for such compositions |
| CN102682869A (en) * | 2012-04-11 | 2012-09-19 | 中国电力科学研究院 | Vegetable insulating oil, and preparation method of vegetable insulating oil |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111149796A (en) * | 2019-12-31 | 2020-05-15 | 苏州丰倍生物科技有限公司 | Pesticide solvent and preparation method and application thereof |
| CN111149796B (en) * | 2019-12-31 | 2021-10-22 | 苏州丰倍生物科技有限公司 | Pesticide solvent and preparation method and application thereof |
| CN111944227A (en) * | 2020-08-17 | 2020-11-17 | 东莞市赛美塑胶制品有限公司 | Plastic defoaming master batch and preparation method thereof |
| CN111944227B (en) * | 2020-08-17 | 2022-07-15 | 东莞市赛美塑胶制品有限公司 | Plastic defoaming master batch and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6655607B2 (en) | 2020-02-26 |
| JPWO2016167176A1 (en) | 2017-12-07 |
| CN107533878B (en) | 2020-03-10 |
| WO2016167176A1 (en) | 2016-10-20 |
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