CN1160063A - Epoxy resin composition and insulating spacer - Google Patents

Epoxy resin composition and insulating spacer Download PDF

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Publication number
CN1160063A
CN1160063A CN96123199A CN96123199A CN1160063A CN 1160063 A CN1160063 A CN 1160063A CN 96123199 A CN96123199 A CN 96123199A CN 96123199 A CN96123199 A CN 96123199A CN 1160063 A CN1160063 A CN 1160063A
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epoxy resin
insulating spacer
composition
epoxy
resins
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小林稔幸
铃木重雄
大原周一
小山徹
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Hitachi Ltd
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Hitachi Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/40—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes epoxy resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
    • H01H33/00—High-tension or heavy-current switches with arc-extinguishing or arc-preventing means
    • H01H33/02—Details
    • H01H33/53—Cases; Reservoirs, tanks, piping or valves, for arc-extinguishing fluid; Accessories therefor, e.g. safety arrangements, pressure relief devices
    • H01H33/55—Oil reservoirs or tanks; Lowering means therefor
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Epoxy Resins (AREA)
  • Organic Insulating Materials (AREA)

Abstract

The present invention provides an epoxy resin compsn. having a low specific permittivity and excellent heat resistance, cracking resistance, and resistance to SF6 decomposition gas and to produce an insulating spacer and a gas insulated switch equipment therefor. This epoxy resin composition comprises a polyfunctional epoxy resin having an epoxy equivalent of 150 to 250, an acid anhydride curing agent, aluminum fluoride and alumina as a filler, and a flexibilizer. The amt. of the flexibilizer added is 3 to 30wt.% based on the epoxy resin and the acid anhydride curing agent. The aluminum fluoride to alumina mixing ratio is (9:1) to (5:5), and the amt. of the filler added is 30 to 65vol%.

Description

Composition epoxy resin and insulating spacer
The present invention relates to utilize for example sulfur hexafluoride (SF of insulating gas 6) as a kind of insulation system of the electric installation of dielectric, relating in particular to a kind of composition epoxy resin, it is a kind of material that is used to support and make the container insulating insulating spacer of energized conductor and sealing.
This gas isolated switching device comprises: the container of a sealing (wherein is filled with for example SF of certain insulating gas 6), and be installed in the sealed vessel, be used for the supporting strap electric conductor and make its container with sealing be in the insulating spacer of electric insulating state.Usually, this insulating spacer is cast and is heating and curing by the Resins, epoxy that contains various fillers and makes.
For example, adopt silicon-dioxide (SiO 2) during the filler of class, this class problem that the dissociating gas that electric arc produced in the time of then should solving by shut-off circuit causes insulating property to reduce.Therefore, general with having anti-preferably SF 6The aluminum oxide of the performance of dissociating gas is as filler.
At present, for the volume that reduces gas isolated switching device and improve its capacity, consider the design of electric field, require insulating spacer to have low specific inductivity and better heat-resisting.The current capacity of common air insulating device is the highest to be 8,000A, even and when rated current the temperature of high-voltage conductor be not higher than 100 ℃.Therefore, the second-order transition temperature of common insulating spacer, promptly resistance toheat index is about 105 ℃.
But, when being increased to, current capacity is at least 8, and during 000A, the temperature of high-voltage conductor reaches 135 ℃ under rated current.Therefore, require to have the insulating spacer of high glass-transition temperature, because the temperature of insulating spacer is when surpassing its second-order transition temperature, the physical strength of insulating spacer significantly reduces.Requiring the physical strength (this moment be meant bending strength) of insulating spacer in the time of 135 ℃ is 5kg/mm at least 2
Normally, the filler of being made by the mixture of aluminum fluoride and aluminum oxide is used as and has low-k and anti-preferably SF 6The insulating spacer of the performance of dissociating gas for example is disclosed in JP-A-57-203508 (1982), JP-A-57-203511 (1982), and among the JP-A-2-97553 (1990).Yet, in these examples, do not fully take into account insulating spacer physical strength at high temperature.
Document JP-A-3-200858 (1991) has provided the prescribed value of epoxy equivalent (weight), but the physical strength when not considering 135 ℃.
Document JP-A-4-341711 (1992) discloses a kind of epoxy resin mould product of being made by the mixture of aluminum oxide/boron nitride, it is mixed making the second-order transition temperature of mixture be higher than 130 ℃, will consider thermotolerance simultaneously and with cycloaliphatic epoxy resin and bisphenol-based epoxy resin.Under this situation, should in mixture, add a large amount of boron nitrides to reach desired low-k.But, because boron nitride is flaky, the mixture thickness significantly that in the process of kneading and cast, just becomes, therefore, just comparison is difficult a large amount of boron nitrides (for example volume ratio is 40～65%) to be sneaked into mixture.And expensive is that another has problem to be solved.
One of purpose of the present invention provides a kind of composition epoxy resin, and it has better heat-resisting, and crumpling resistance is anti--SF 6The performance of dissociating gas, and low-k; And provide a kind of insulating spacer and a kind of a kind of gas isolated switching device of using above-mentioned substance.
Main points of the present invention are a kind of composition epoxy resin, and it is used to make a kind of insulating spacer, and this insulating spacer insulation and supporting are installed on the conductor in the sealed vessel.This composition epoxy resin comprises that a kind of epoxy equivalent (weight) is 150～250 multi-functional epoxy resin, a kind of anhydride hardener, a kind of filler of making by the mixture of aluminum fluoride and aluminum oxide, and a kind of toughner, wherein the add-on of toughner accounts for 3～30% of Resins, epoxy and anhydride hardener gross weight, the ratio of mixture of aluminum fluoride/aluminum oxide in filler is in 9/1～5/5 scope, and filler accounts for 30～65% of total epoxy composition cumulative volume to the ratio of mixture of composition epoxy resin.
Multi-functional epoxy resin comprises dihydroxyphenyl propane/F type Resins, epoxy, or bisphenol f type epoxy resin.
Multi-functional epoxy resin can comprise cycloaliphatic epoxy resin, and can use dihydroxyphenyl propane/F type Resins, epoxy or bisphenol f type epoxy resin and cycloaliphatic epoxy resin simultaneously.
In order to improve thermotolerance, be 150～250 multi-functional epoxy resin in the present invention with epoxy equivalent (weight).As epoxy equivalent (weight) is 150～250 multi-functional epoxy resin, considers thermotolerance with flexible, and dihydroxyphenyl propane/F type Resins, epoxy or bisphenol f type epoxy resin meet the requirements.When using epoxy equivalent (weight) to be higher than 250 multi-functional epoxy resin, then can not satisfy desired thermotolerance, and owing to the high viscosity before solidifying makes the processibility variation.
If epoxy equivalent (weight) in 150～250 scopes, then available bifunctional epoxy resin such as bisphenol A type epoxy resin, dihydroxyphenyl propane D type Resins, epoxy, phenol type phenolic resin varnish type epoxy resin, bisphenol A-type phenolic resin varnish type epoxy resin or the like.
In order to improve thermotolerance, can use the cycloaliphatic epoxy resin of epoxy equivalent (weight) in 150～250 scopes simultaneously.Use cycloaliphatic epoxy resin to reduce the viscosity of solidifying preceding resin simultaneously, thereby processibility can improve.
Can be used for cycloaliphatic epoxy resin of the present invention and for example comprise, 3,4-epoxycyclohexyl methyl-(3, the 4-epoxy) cyclohexane carboxylate, 4-(1, the 2-epoxypropyl)-1, the 2-epoxy cyclohexane, 2-(3, the 4-epoxy) cyclohexyl-5,5-spiral shell (3, the 4-epoxy)-hexanaphthene--diox, 3,4-epoxy-6-methyl cyclohexane ylmethyl-4-epoxy-6-methylcyclohexanecarboxylic acid ester, or the like.
The anhydride hardener that is suitable among the present invention is without any special restriction, as long as it is the acid anhydrides of using always.Acid anhydrides comprises, for example, and methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, Tetra Hydro Phthalic Anhydride, nadic anhy-dride, methylnadic anhydride, dodecyl succinic anhydride, succinyl oxide, the octadecyl succinyl oxide, maleic anhydride, the benzophenone tetracarboxylic anhydride, or the like.Above-claimed cpd can be used separately or mix and use.
The filler of using among the present invention is to be made by the mixture of aluminum fluoride and aluminum oxide, and its ratio of mixture (aluminum fluoride/aluminum oxide) is in 9/1～5/5 scope.The consumption that increases aluminum fluoride can reduce physical strength, and the consumption of minimizing aluminum fluoride can make specific inductivity raise.The consumption of filler preferably be adjusted to make resin itself specific inductivity in the 3.5-5.4 scope, this value is lower than the specific inductivity (5.5～6.5) that only adds aluminum oxide and obtain.
Requiring the average particle size maximum of filler is 80 μ m, preferably in the scope of 3～20 μ m.Consider that physical strength and sedimentation do not wish average particle size greater than above-mentioned scope, and average particle size will make the processibility variation because of increasing of its viscosity less than above-mentioned scope.
Except that above-mentioned filler, following compounds can be used simultaneously with above-mentioned filler: magnesium oxide, and lime carbonate, magnesiumcarbonate, rhombspar, calcium hydroxide, magnesium hydroxide, calcium sulfate, barium sulfate, Calcium Fluoride (Fluorspan), magnesium fluoride, or the like.But silica containing compound such as talcum and mica should not be used, because it resists-SF 6The poor performance of dissociating gas.
According to the present invention, be necessary to add toughner because adopt low to 150～250 epoxy equivalent (weight) to improve thermotolerance.Can be used for toughner requirement of the present invention and Resins, epoxy is immiscible and for sea-land type structure, crumpling resistance can improve because the reduction of the second-order transition temperature of cured body is less.
Above-mentioned desired toughner for example has, carboxyl end group perbutan, amine end groups perbutan, acrylic rubber, styrene-butadiene rubber(SBR), acrylonitrile-butadiene-styrene resin, methyl methacrylate-butadiene-styrene resin, or the like.Any single structure class, and the above-mentioned toughner of core-shell can be used.
The add-on of toughner at most only accounts for 40% of Resins, epoxy and acid anhydrides gross weight, preferably in the scope of 3～30wt%.If the add-on of toughner is higher than above-mentioned scope, then can reduce second-order transition temperature, and if the add-on of toughner is lower than above-mentioned scope, then the advantage of cracking resistance is less.
Need, when resin combination solidifies, curing catalysts can be added in the composition epoxy resin of the present invention.Curing catalysts is not limited to specific catalyst, but it must have the effect of solidifying multi-functional epoxy resin.The curing catalysts that adds in the composition epoxy resin is generally 0.01～5wt%.
The example of curing catalysts for example has: tertiary amines such as Trimethylamine 99, and triethylamine, tetramethyl butane diamine, triethylene amine, or the like; Amine such as dimethylaminoethanol, the dimethylamino amylalcohol, three (dimethylamino methyl) monoethanolamine, N-methylmorpholine, or the like; Quaternary ammonium salt such as cetyl trimethylammonium bromide, palmityl trimethyl ammonium chloride, cetyl trimethyl ammonium iodide, Trimethyllaurylammonium bromide, Dodecyl trimethyl ammonium chloride, dodecyl trimethylammonium ammonium iodide, benzyl dimethyl tetradecyl ammonium chloride, the benzyl dimethyl Tetradecylammonium bromide, the allyl group Trimethyllaurylammonium bromide, benzyl dimethyl stearyl brometo de amonio, stearyl trimethyl ammonium chloride, benzyl dimethyl tetradecyl acetylize ammonium, or the like; Imidazoles such as glyoxal ethyline, 2-ethyl imidazol(e), 2-undecyl imidazole, 2-heptadecyl imidazoles, 2-methyl-4-ethyl imidazol(e), 1-butyl imidazole, 1-propyl group-glyoxal ethyline, 1 benzyl 2 methyl imidazole, 1-cyano ethyl-2-phenylimidazole, 1-1-cyanoethyl-2-methylimidazole, 1-cyano ethyl-2-undecyl imidazole, 1-azine-glyoxal ethyline, 1-azine-2-undecyl or the like; Metal-salt such as certain amine and zinc octoate or cobalt; Amine tetraphenyl borate salts class is as 1,8-diaza-dicyclo (5,4,0)-undecylene-7; N methyl piperazine, tetramethyl butyl guanidine, triethyl tetraphenyl ammonium borate, 2-ethyl-4-methyl tetraphenyl borate salts; 1,8-diaza-dicyclo (5,4,0)-undecylene-7-tetraphenyl borate salts; or the like, triphenylphosphine, tetraphenyl boric acid triphenyl phosphonium; trialkyl etheric acid aluminium, triacetyl etheric acid aluminium, aluminum alcoholate; acidylate aluminium, alcoholization sodium, mixture of boron trifluoride and amine or the like.
Be described in detail to these and other objects of the present invention from following with reference to accompanying drawing, feature and advantage solve clearer, wherein,
Fig. 1 is the part cross section that utilizes the main part of the air insulating device that relates to insulating spacer of the present invention, and
Fig. 2 is a structural representation, and the SF that relates to insulating spacer of the present invention is adopted in expression 6The composition of gas-insulated switching device.
Relating to insulating spacer of the present invention can follow these steps to make: with epoxy equivalent (weight) is 150～250 multi-functional epoxy resin, anhydride hardener, aluminum fluoride and the aluminum oxide used as filler, and toughner mixes according to a conventional method, stir for some time, inject mould, and the sclerosis casting matrix.
The gained insulating spacer for example is used to the air insulating device shown in Fig. 1.Fig. 1 represents to utilize the part cross section of the main part of the air insulating device that relates to insulating spacer of the present invention.With bolt 6 insulating spacer 1 is fixed on the flange 5 of sealed vessel 3.Conductor 4 is inserted in the insulating spacer 1, and with the conductor 2 of supporting strap high voltage electric and make conductor 2 and container 3 insulation, wherein conductor 2 links to each other with conductor 4.SF 6Air seal is in container 3.Shown taper partition example among Fig. 1.But the partition that the present invention is suitable for all kinds of shapes is the cylindricality partition for example, the disc partition, or the like.
Insulating spacer with cracking resistance and thermotolerance preferably (especially in the time of 135 ℃ physical strength) preferably can be that 150～250 the multi-functional epoxy resin and the composition epoxy resin of toughner prepare with containing epoxy equivalent (weight).In addition, this insulating spacer also has low specific inductivity and resists-SF preferably 6The performance of the gas of gaseous dissociation is because it also contains common aluminum fluoride and aluminum oxide as filler.Therefore, utilize and to relate to insulating spacer of the present invention and can obtain small-sized and reliable SF 6Gas isolated switching device.
In the following embodiment, multi-functional epoxy resin, anhydride hardener, curing catalysts, it is as follows to reach the used abbreviation of toughner:
PY-302-2: dihydroxyphenyl propane/F type Resins, epoxy (epoxy equivalent (weight) 175),
EP-807: bisphenol f type epoxy resin (epoxy equivalent (weight) 170),
EP-1001: bisphenol A type epoxy resin (epoxy equivalent (weight) 450),
EP-1002: the Resins, epoxy of bisphenol A-type (epoxy equivalent (weight) 600),
CEL-2021:3,4-epoxycyclohexyl methyl-(3, the 4-epoxy) cyclohexane carboxylates (epoxy equivalent (weight) 138),
MHAC-P:methylnadic acid anhydride (anhydride equivalent 178),
2E4MZ-CN:1-(2-cyanoethyl)-2-ethyl-4-methylimidazole,
CTBN1300X13: carboxyl end group paracril; Bonded vinyl cyanide 27%,
ATBN1300X16: amine end groups is in nitrile rubber; Bonded vinyl cyanide 16.5%,
EXL: methyl methacrylate-butadiene-styrene resin,
ALF 3: mean diameter 10.3 μ m, the size of particles cumulative distribution is lower than 50 μ m100%,
Al 2O 3: mean diameter 10.3 μ m, the size of particles cumulative distribution is lower than 50 μ m100%,
The title on the colon left side is trade(brand)name or industrial name normally.(embodiment 1)
A kind of composition epoxy resin (as shown in table 1) that is used for insulating spacer makes by mixing following each composition: as the PY-302-2100 weight part of multi-functional epoxy resin, MHAC-P 100.65 weight parts as anhydride hardener, 2E4MZ-CN 0.26 weight part as curing catalysts, as the CTBN1300X1311 weight part of toughner, and AlF 3300 weight parts and Al 2O 3100 weight parts (both are used separately as filler) stir under the decompression down at 90 ℃.This mixture is injected pressure cast pattern, make taper partition 1 shown in Figure 1 (diameter 720mm) heating curing in 15 hours with this mixture heating up 17 hours and under 170 ℃ under 90 ℃.(embodiment 2～10)
With in the embodiment 1 similarly partition by with embodiment 1 in the same procedure preparation, just change the add-on of toughner, and mix the adding ratio of filler when, as shown in table 1.(Comparative Examples 1～4)
With with embodiment 1 in similar partition in the preparation of identical method and the embodiment 1, just change mixing element, as shown in table 2.
Table 1
Embodiment ?????1 ?????2 ????3 ????4 ????6
Resins, epoxy RY-302-2 ????100 ????100 ????100 ????100 ????100
EP-807 ????- ????- ????- ????- ????-
CEL-2021 ????- ????- ????- ????- ????-
Hardn. 1) MHAC-p ????100.65 ????100.65 ????100.65 ????100.65 ????100.65
Cur.a. 2) 2E4MZ-CN ????0.26 ????0.26 ????0.26 ????0.26 ????0.26
Toughner CTBN 3) ????11 ????23 ????50 ????23 ????23
ATBN 4) ????- ????- ????- ????- ????-
EXL ????- ????- ????- ????- ????-
Filler AlF 3 ????300 ????306 ????342 ????204 ????196.5
Al 2O 3 ????100 ????102 ????114 ????204 ????65.5
Ratio of mixture (AlF 3/Al 2O 3) ????3/1 ????3/1 ????3/1 ????5/5 ????3/1
Adding?ratio 5)(vol/％) ????40 ????40 ????40 ????40 ????30
Adding??amount 6)(wt.％) ????5.5 ????11.5 ????24.9 ????11.5 ????11.5
Flexural strength (kg/mm under 135 ℃ 2) ????7 ????6 ????5 ????6 ????7
Second-order transition temperature (℃) ????152 ????150 ????147 ????150 ????152
Cracking resistance ????5 ????6 ????6 ????6 ????4
Spec.dielectric constant 7) ????4.4 ????4.5 ????4.5 ????4.8 ????4.2
Table 1 (continuing)
Embodiment ????6 ????7 ????8 ????9 ????10
Resins, epoxy RY-302-2 ????100 ????80 ????- ????100 ????100
Ep-807 ????- ????- ????100 ????- ????-
CEL-2021 ????- ????20 ????- ????- ????-
Hardn. 1) MHAC-P ????100.65 ????100.65 ????100.65 ????100.65 ????100.65
Cur.a. 2) 2E4MZ-CN ????0.26 ????0.26 ????0.26 ????0.26 ????0.26
Toughner CTBN 3) ????23 ????23 ????23 ????- ????-
ATBN 4) ????- ????- ????- ????23 ????-
EXL ????- ????- ????- ????- ????23
Filler AlF 3 ????851.4 ????306 ????306 ????306 ????306
Al 2O 3 ????283.8 ????102 ????102 ????102 ????102
Ratio of mixture (AlF 3/Al 2O 3) ????3/1 ????3/1 ????3/1 ????3/1 ????3/1
Adding?ratio 5)(vol/％) ????65 ????40 ????40 ????40 ????30
Adding?amount 6)(wt.％) ????11.5 ????11.5 ????11.5 ????11.5 ????11.5
Flexural strength (kg/mm under 135 ℃ 2) ????6 ????6 ????8 ????5 ????6
Second-order transition temperature (℃) ????150 ????150 ????154 ????148 ????151
Cracking resistance ????5 ????5 ????4 ????5 ????5
Spec.dielectric constant 7) ????5.1 ????4.5 ????4.4 ????4.5 ????4.5
Table 2
Comparative Examples ????1 ????2 ????3 ????4 ????6
Resins, epoxy EP-1001 ????100 ????80 ????- ????- ????-
Ep-1002 ????- ????- ????100 ????80 ????-
CEL-2021 ????- ????20 ????- ????20 ????-
PY302-2 ????- ????- ????- ????- ????100
Hardn. 1) MHAC-P ????40 ????40 ????30 ????30
Cur.a. 2) 2E4MZ-CN ????0.2 ????0.2 ????0.2 ????0.2 ????0.26
Filler AlF 3 ????191.4 ????191.4 ????191.4 ????191.4 ????274.2
Al 2O 3 ????63.8 ????63.8 ????63.8 ????63.8 ????91.4
Ratio of mixture (AlF 3/Al 2O 3) ????3/1 ????3/1 ????5/5 ????3/1 ????3/1
Adding?ratio 5)(vol/％) ????40 ????40 ????40 ????40 ????40
135 ℃ flexural strength (kg/mm 2) ????1 ????2 ????1 ????1 ????7
Second-order transition temperature (℃) ????106 ????110 ????104 ????107 ????155
Cracking resistance ????4 ????3 ????4 ????3 ????1
Spec.dielectric constant 7) ????4.4 ????4.5 ????4.5 ????4.5 ????4.3
Note: 1) anhydride hardener, 2) curing catalysts, 3) CTBN 1300X13,4) ATBN 1300X16,5) filler is to the adding ratio of composition epoxy resin, 6) toughner is to the add-on of Resins, epoxy and anhydride hardener sum, 7) compare specific inductivity.
Table 3
Times of thermal cycle Thermal cycle conditions
Low temperature High temperature
????1 0 ℃/1 hour 100 ℃/1 hour
????2 -10 ℃/1 hour 100 ℃/1 hour
????3 -20 ℃/1 hour 100 ℃/1 hour
????4 -30 ℃/1 hour 100 ℃/1 hour
????5 -40 ℃/1 hour 100 ℃/1 hour
????6 -50 ℃/1 hour 100 ℃/1 hour
By the flexural strength of the insulating spacer of above-mentioned embodiment and Comparative Examples preparation with than specific inductivity is to measure by the standard method of JIS K6911 defined.Flexural strength is measured down at 135 ℃.Second-order transition temperature is measured with hot machine analyser (TMA).The condition determination of cracking resistance is: batten diameter 28mm, and long 50mm, wherein the steel double-screw bolt of the length 40 of a M12 is embedded in the sample center, and it is carried out the fracture number of thermal cycling test as shown in table 3 and counting generation.
Anti--SF 6Dissociative gas is estimated by the following step: with SF 6Gas is enclosed in the discharger, carries out continuous 5 hours discharge with pin-plate (needle-us-plate) electrode, measures surface resistivity with the standard method of JIS K6911 defined.Almost do not observe the reduction of surface resistivity, and obtain result preferably.
The insulating spacer that makes by embodiment of the present invention, the flexural strength under 135 ℃ is 5kg/mm at least 2, have cracking resistance preferably, and lower ratio specific inductivity.
Otherwise the flexural strength of the insulating spacer that makes in the Comparative Examples under 135 ℃ is lower than 5kg/mm 2, and sample can not use at 135 ℃.And the insulating spacer that makes in the Comparative Examples 5 does not possess required cracking resistance, because it does not contain toughner.
Fig. 2 is the SF that utilizes the insulating spacer that makes by the present embodiment 6The structural representation of gas-insulated switching device.This SF 6The gas-insulated switching device comprises sleeve 7, wiring 8, isolator 9, current transformer 10, isolating switch 11, grounding switch 12, and main line 13.Isolating switch 11 is installed between each current transformer 10, and insulating spacer of the present invention 1 offers SF with the form of single partition 6Gas isolated switching device.
The switching device of insulating spacer 1 of the present invention is housed, and the insulating reliability is improved, and this is because of its low ratio specific inductivity, better heat-resisting and cracking resistance, and to SF 6The stability of gas isolated switching device.In addition, utilize insulating spacer of the present invention, SF 6The diameter of the sealed vessel of gas isolated switching device can reduce 10%.
According to the present invention, can obtain to have better heat-resisting and cracking resistance, desired to SF 6The stability of the dissociation product of gas, and the composition epoxy resin of low ratio specific inductivity, and the insulating spacer of making by this composition epoxy resin.
And, by utilizing insulating spacer of the present invention, SF 6The size of gas isolated switching device can reduce, and the reliability of equipment can be improved.

Claims (9)

1. be used to insulate in order to making and support the composition epoxy resin of the insulating spacer that is installed on the conductor in the container that is filled with insulating gas, said composition contains:
The Resins, epoxy equivalent is 150～250 multi-functional epoxy resin,
Anhydride hardener,
As the aluminum fluoride of filler and the mixture of aluminum oxide, and
Toughner, wherein
The add-on of described toughner in 3～30wt% scope of described Resins, epoxy and described anhydride hardener sum,
The ratio of mixture of aluminum fluoride/aluminum oxide is in 9/1～5/5 weight ratio scope in the described filler, and
Described filler compares in the scope of 30～65vol% the adding of described composition epoxy resin.
2. desired composition epoxy resin in the claim 1, wherein
Described multi-functional epoxy resin composition contains any in dihydroxyphenyl propane/F type Resins, epoxy and the bisphenol f type epoxy resin.
3. each desired composition epoxy resin in the claim 1 and 2, wherein
Described multi-functional epoxy resin composition contains cycloaliphatic epoxy resin.
4. be used to insulate and support the insulating spacer that is installed on the conductor in the container that is filled with insulating gas, made by the cured body of composition epoxy resin, composition epoxy resin comprises
The Resins, epoxy equivalent is 150～250 multi-functional epoxy resin,
Anhydride hardener,
As the aluminum fluoride of filler and the mixture of aluminum oxide, and
Toughner, wherein
The add-on of described toughner in 3～30wt% scope of described Resins, epoxy and described anhydride hardener sum, and
Described filler compares in 30～65vol% scope the adding of described composition epoxy resin.
5. the insulating spacer that requires in the claim 4, wherein
Described multi-functional epoxy resin contains any of dihydroxyphenyl propane/F type Resins, epoxy and bisphenol f type epoxy resin.
6. each desired insulating spacer in the claim 4 and 5, wherein
Described multi-functional epoxy resin contains cycloaliphatic epoxy resin.
7. gas isolated switching device, it comprises
Be installed on the isolator in the container that is filled with insulating gas, and
Be used to insulate and support the insulating spacer that has high voltage electric, remains the insulating conductor, wherein
Described insulating spacer is to be made by the cured body of composition epoxy resin, and composition epoxy resin comprises
The Resins, epoxy equivalent is 150～250 multi-functional epoxy resin,
Anhydride hardener,
As the aluminum fluoride of filler and the mixture of aluminum oxide, and
Toughner,
The add-on of described toughner in 3～30wt% scope of described Resins, epoxy and described anhydride hardener sum,
The ratio of mixture of aluminum fluoride/aluminum oxide is in 9/1～5/5 weight ratio scope in the described filler, and
Described filler compares in 30～65wt% scope the adding of described composition epoxy resin.
8. desired gas isolated switching device in the claim 7, wherein
The multi-functional epoxy resin composition of described insulating spacer contains any of dihydroxyphenyl propane/F type Resins, epoxy and bisphenol f type epoxy resin.
9. the desired gas isolated switching device of each in the claim 7 and 8, wherein
The multi-functional epoxy resin composition of described insulating spacer contains alicyclic Resins, epoxy.
CN96123199A 1995-12-28 1996-12-27 Epoxy resin composition and insulating spacer Pending CN1160063A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP7342194A JPH09176288A (en) 1995-12-28 1995-12-28 Epoxy resin composition and insulating spacer
JP342194/95 1995-12-28

Publications (1)

Publication Number Publication Date
CN1160063A true CN1160063A (en) 1997-09-24

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KR (1) KR970042810A (en)
CN (1) CN1160063A (en)

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US20030059618A1 (en) * 2001-03-23 2003-03-27 Hideyuke Takai Method of producing epoxy compound, epoxy resin composition and its applications, ultraviolet rays-curable can-coating composition and method of producing coated metal can
EP1541567A4 (en) 2002-09-05 2010-11-17 Daicel Chem Process for preparation of alicyclic diepoxy compounds, curable epoxy resin compositions, epoxy resin compositions for the encapsulation of electronic components, stabilizers for electrical insulating oils, and casting epoxy resin compositions for electrical insulation
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CN104292767B (en) * 2014-01-13 2017-02-15 国家电网公司 Vacuum casting mold material used for electrical insulation parts, and preparation method of mold
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CN105344992A (en) * 2015-11-19 2016-02-24 苏州紫光伟业激光科技有限公司 Metallurgy powder composition

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JPH09176288A (en) 1997-07-08

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