WO2022085544A1 - 電気設備 - Google Patents

電気設備 Download PDF

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Publication number
WO2022085544A1
WO2022085544A1 PCT/JP2021/037954 JP2021037954W WO2022085544A1 WO 2022085544 A1 WO2022085544 A1 WO 2022085544A1 JP 2021037954 W JP2021037954 W JP 2021037954W WO 2022085544 A1 WO2022085544 A1 WO 2022085544A1
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Prior art keywords
dielectric
electrical equipment
group
isomer
hcfo
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PCT/JP2021/037954
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English (en)
French (fr)
Japanese (ja)
Inventor
環 チン曽我
正人 福島
洋輝 速水
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AGC Inc
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Asahi Glass Co Ltd
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Priority to JP2022557058A priority Critical patent/JPWO2022085544A1/ja
Priority to EP21882685.7A priority patent/EP4235702A4/en
Priority to CN202180071050.7A priority patent/CN116348968A/zh
Publication of WO2022085544A1 publication Critical patent/WO2022085544A1/ja
Priority to US18/295,922 priority patent/US12456851B2/en
Anticipated expiration legal-status Critical
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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
    • H01B3/56—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances gases
    • H—ELECTRICITY
    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02B—BOARDS, SUBSTATIONS OR SWITCHING ARRANGEMENTS FOR THE SUPPLY OR DISTRIBUTION OF ELECTRIC POWER
    • H02B13/00—Arrangement of switchgear in which switches are enclosed in, or structurally associated with, a casing, e.g. cubicle
    • H02B13/02—Arrangement of switchgear in which switches are enclosed in, or structurally associated with, a casing, e.g. cubicle with metal casing
    • H02B13/035—Gas-insulated switchgear
    • H02B13/055—Features relating to the gas

Definitions

  • This disclosure relates to electrical equipment.
  • HFO hydrofluoroolefin
  • HCFO hydrochlorofluoroolefin
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2018-525327
  • the isomerization reaction proceeds depending on the temperature conditions and coexisting metals.
  • Geometric isomers often have different boiling points. If the isomerization of the dielectric progresses in the electrical equipment and the boiling point of the dielectric changes, the insulation performance of the electrical equipment may deteriorate. For example, if the boiling point of the dielectric rises due to the isomerization of the dielectric, the condensation temperature of the dielectric rises, and the dielectric liquefies in the tank, which may deteriorate the insulation performance. Further, when the boiling point of the dielectric is lowered due to the isomerization of the dielectric, the pressure in the tank rises, so that there is a concern in terms of safety in the design of the equipment.
  • the present disclosure is made in view of the above problems, and an object of the present invention is to provide an electric facility in which isomerization of a dielectric used as an insulating gas is suppressed.
  • the present disclosure includes the following [1] to [6].
  • [1] It has a metal tank in which a conductor member is arranged, and the metal tank is filled with a dielectric.
  • the dielectric is at least one selected from the group consisting of 1-chloro-2,3,3,3-tetrafluoropropene and 1,1,1,4,4,4-hexafluoro-2-butene.
  • Including Electrical equipment in which the surface of the conductor member comprises one or more selected from the group consisting of metals and metal oxides.
  • the metal is at least one selected from the group consisting of aluminum, copper, silver, tin, zinc, iron, and chromium, or from aluminum, copper, silver, tin, zinc, iron, and chromium.
  • the electrical equipment according to [1] which is an alloy containing at least one selected from the group.
  • the dielectrics are the Z and E isomers of 1-chloro-2,3,3,3-tetrafluoropropene, and 1,1,1,4,4,4-hexafluoro-2.
  • the electrical equipment according to [1] or [2] comprising at least one selected from the group consisting of Z and E isomers of butene.
  • the dielectric contains the Z isomer and the E isomer of 1-chloro-2,3,3,3-tetrafluoropropene, and the 1-chloro-2,3,3,3-tetrafluoropropene.
  • the electrical equipment according to any one of [1] to [3], wherein the mass ratio represented by the Z isomer / E isomer in the total mass is 99/1 to 50/50.
  • the electrical equipment further comprises equipment selected from the group consisting of switches, circuit breakers, disconnectors, transformers, resistors, reactors, capacitors, and insulated cables [1]-[. 4]
  • the electrical equipment described in any one of. [6] It has a metal tank in which a conductor member is arranged, and the metal tank is filled with a dielectric.
  • the dielectric is at least one selected from the group consisting of 1-chloro-2,3,3,3-tetrafluoropropene and 1,1,1,4,4,4-hexafluoro-2-butene.
  • FIG. 1 is a cross-sectional view showing a configuration example of the electrical equipment of the present disclosure.
  • FIG. 1 illustrates a gas-insulated switchgear as an example of gas electrical equipment.
  • the electrical equipment 10 shown in FIG. 1 has a metal tank 11 in which a conductor member 12 is arranged.
  • the metal tank 11 is filled with a dielectric (not shown) as an insulating gas.
  • the conductor member 12 is supported by the support member 13 in a state of being insulated from the metal tank 11.
  • the metal tank 11 is an airtight container, a space, or the like. A high voltage is applied to the conductor member 12.
  • the surface of the conductor member 12 contains one or more selected from the group consisting of metals and metal oxides.
  • the metal may be at least one selected from the group consisting of aluminum, copper, silver, tin, zinc, iron and chromium, or the group consisting of aluminum, copper, silver, tin, zinc, iron and chromium.
  • An alloy containing at least one selected is preferred.
  • the metal oxide may be an oxide obtained by oxidizing the above-mentioned metal or an oxide of another metal.
  • the metal oxide is preferably one or more selected from the group consisting of zinc oxide, iron oxide, and aluminum oxide.
  • the conductor member may be made of a plurality of materials.
  • the core portion (inside the conductor member) may be made of a material other than metal and metal oxide.
  • the core portion of the conductor member is made of another material, at least a portion of the surface of the conductor member is covered with one or more selected from the group consisting of metals and metal oxides.
  • At least a part of the surface of the conductor member in contact with the dielectric filled inside the metal tank 11 is selected from the group consisting of metal and metal oxide 1. It is preferably one or more.
  • the electrical equipment 10 may contain an adsorbent desiccant, an acid supplement, or the like in the equipment in order to maintain the dielectric purity and the equipment performance.
  • the adsorbent preferably adsorbs an organic substance in the dielectric and a decomposition product of the dielectric generated with use.
  • the adsorbent for example, activated carbon, activated alumina, silica gel, zeolite, a metal oxide having an adsorption function, a porous substance and the like can be used, and in particular, zeolite, a metal oxide having an adsorption function and a porous substance are preferable. ..
  • the adsorbent may be used alone or in combination of two or more.
  • Examples of the zeolite include synthetic zeolite having a silica / alumina molar ratio of 5 or more (high silica synthetic zeolite), synthetic zeolite having a proton (H) as a cation (proton exchange synthetic zeolite), and the like.
  • Examples of the metal oxide having an adsorption function include CuO, Co3O4 , MnO2 and the like.
  • Examples of the porous substance include a porous substance coated with calcium carbonate.
  • the desiccant is preferably one that efficiently adsorbs water in the dielectric, for example, calcium, calcium sulfate, particularly dry erite, calcium carbonate, calcium hydride, calcium chloride, potassium carbonate, potassium hydroxide, copper sulfate.
  • the desiccant may be used alone or in combination of two or more.
  • the dielectrics to be filled inside the metal tank 11 are 1-chloro-2,3,3,3-tetrafluoropropene (hereinafter, also referred to as HCFO-1224yd) and 1,1. , 1,4,4,4-Hexafluoro-2-butene (hereinafter, also referred to as HFO-1336mzz), which comprises at least one selected from the group.
  • the surface material of the conductor member 12 described above is at least one selected from the group consisting of HFO and HCFO filled as a dielectric inside the metal tank 11 in a high temperature environment depending on the combination of the types of dielectrics to be filled. Acts as a catalyst for the isomerization reaction of. As a result, it is considered that the isomerization reaction of HFO and HCFO can proceed.
  • the inventors of the present application use at least one selected from the group consisting of HCFO-1224yd and HFO-1336mzz as the dielectric to be filled inside the metal tank 11, and the surface material of the conductor member is predetermined.
  • the isomerization reaction is remarkable as compared with other HCFOs and HFOs, for example, 1-chloro-3,3,3 trifluoropropene (hereinafter, also referred to as HCFO-1233zd) used in Examples described later. It was found that it was suppressed.
  • HCFO-1224yd has a geometric isomer, and the boiling point of the Z isomer of HCFO-1224yd (hereinafter, also referred to as HCFO-1224yd (Z)) is 15 ° C., and that of HCFO-1224yd.
  • the boiling point of the E isomer (hereinafter, also referred to as HCFO-1224yd (E)) is 17 ° C.
  • a composition of HCFO-1224yd (Z) and HCFO-1224yd (E) can be obtained by a known production method, and both can be separated by distillation.
  • HCFO-1224yd may use only one of the Z isomer or the E isomer, or one containing both the Z isomer and the E isomer. May be.
  • HCFO-1224yd (Z) having a lower boiling point is preferable because it is difficult to liquefy in the electric equipment.
  • a composition containing a Z isomer and an E isomer it is preferable to use an isomer composition having a high proportion of HCFO-1224yd (Z) in consideration of productivity.
  • the mass ratio (Z / E ratio) represented by HCFO-1224yd (Z) / HCFO-1224yd (E) is 99 in the total mass of HCFO-1224yd to be filled as a dielectric. It is preferably 1/1 to 50/50, more preferably 99/1 to 80/20, and even more preferably 99/1 to 95/5.
  • Examples of the method for producing HCFO-1224yd include (1) a method of dehydrochlorinating 1,2-dichloro-2,3,3,3-tetrafluoropropane (hereinafter, also referred to as HCFC-234bb). (2) Examples thereof include a method of hydrogen-reducing 1,1-dichloro-2,3,3,3-tetrafluoropropene (hereinafter, also referred to as CFO-1214ya).
  • CFO-1214ya hydrogen-reducing 1,1-dichloro-2,3,3,3-tetrafluoropropene
  • HCFC-234bb is brought into contact with a base dissolved in a solvent (that is, a base in a solution state) to carry out a dehydrochlorination reaction of HCFC-234bb.
  • HCFC-234bb can be produced, for example, by reacting 2,3,3,3-tetrafluoropropene (hereinafter, also referred to as HFO-1234yf) with chlorine in a solvent.
  • CFO-1214ya is reduced to HFO-1234yf by reducing it with hydrogen in the presence of a catalyst. Then, HCFO-1224yd is obtained as an intermediate for the reduction reaction to HFO-1234yf. Further, in the reduction reaction to HFO-1234yf, many kinds of fluorine-containing compounds other than HCFO-1224yd are by-produced.
  • CFO-1214ya is made from, for example, 3,3-dichloro-1,1,1,2,2-pentafluoropropane or the like in an alkaline aqueous solution in the presence of a phase transfer catalyst, or chromium, iron, copper, activated carbon.
  • a method is known in which a hydrogen fluoride reaction is carried out by a gas phase reaction in the presence of a catalyst such as the above.
  • HFO-1336mzz has a geometric isomer
  • the boiling point of the Z isomer of HFO-1336mzz (hereinafter, also referred to as HFO-1336mzz (Z)) is 33 ° C.
  • the boiling point of the E isomer (hereinafter, also referred to as HFO-1336mzz (E)) is 7.5 ° C.
  • a composition containing HFO-1336 mzz (Z) and HFO-1336 mzz (E) can be obtained by a known production method, and both can be separated by distillation.
  • HFO-1336mzz may be either Z isomer or E isomer, or may contain Z isomer and E isomer.
  • HFO-1336 mzz (E) having a lower boiling point is preferable because it is difficult to liquefy in the electric equipment.
  • CF 3 -CCl CCl-CF in the presence of a catalyst.
  • HFO-1336mzz can also be prepared by contacting CF 3 -CHCl 2 with copper in the presence of an amide solvent and 2,2'-bipyridine, as disclosed in US Pat. No. 8,436,216. ..
  • HFO-1336mzz (1) in the presence of a catalyst containing ruthenium, CCl 3 -CF 3 is brought into contact with hydrogen to 1316mxx (2,3-dichloro-1,1,1,4,4,4-). Hexafluoro-2-butene) is produced; (2) E- or Z-1326mxz (1) by contacting 1316mxx with hydrogen in the presence of a catalyst containing copper, nickel, copper-nickel, or copper-palladium. , 1,1,4,4,4-hexafluoro-2-chloro-2-butene); (3) in the presence of a quaternary alkylammonium salt, 1326mxz is contacted with an aqueous solution of alkali metal hydroxide. (4) Contacting hexafluoro-2-butin with hydrogen and a catalyst (in order from (1) above to (4) above). It can be prepared by, as disclosed in WO 2015/120250. It may include steps other than (1) to (4).
  • HFO-1336mzz as disclosed in International Publication No. 2015/142981, (1) 3,3,3-trifluoro-1-propene is brought into contact with carbon tetrachloride to cause 2,4,4. , 4-Tetrachloro-1,1,1-trifluorobutane; (2) Can be prepared by contacting 2,4,4,4-tetrachloro-1,1,1-trifluorobutane. ..
  • HCFO-1224yd As the dielectric to be filled in the metal tank 11, only one of HCFO-1224yd or HFO-1336mzz may be contained, or both may be contained. As the dielectric to be filled inside the metal tank 11, HCFO-1224yd is liquefied in the electric equipment because the difference in boiling points between the Z-form and the E-form is small even when the isomerization reaction proceeds in the electric equipment. It is preferable because it is difficult.
  • the total volume of HCFO-1224yd and HFO-1336mzz filled inside the metal tank 11 is such that HCFO-1224yd and HFO-1336mzz are in a vapor phase state with respect to the total volume of the dielectric filled inside the metal tank 11. From the viewpoint of realizing the condensation temperature required to exist only, 70% by volume or less, 60% by volume or less, 50% by volume or less, 40% by volume or less, 30% by volume or less, 25% by volume or less, 20% by volume or less. , 15% by volume or less, 10% by volume or less, or 5% by volume or less is preferable.
  • the total volume of HCFO-1224yd and HFO-1336mzz is 1% by volume or more and 2% by volume with respect to the total volume of the dielectric filled in the metal tank 11 from the viewpoint of insulation performance and arc extinguishing performance.
  • the above, or 3% by volume or more is preferable.
  • the dielectric filled in the metal tank 11 may contain other dielectrics in addition to HCFO-1224yd and HFO-1336mzz. Specific examples of other dielectrics are shown below. Other dielectrics include difluoroethylene, trifluoroethylene, 2,3,3,3-tetrafluoro-1-propene, (E) -1,3,3,3-tetrafluoropropene and (Z) -1. , 3, 3, 3-Tetrafluoropropene.
  • (E) -1-chloro-3,3,3-trifluoropropene, 2,3,3,3-tetrafluoro-1-propen, (E) -1,3,3,3- Tetrafluoropropene and (Z) -1,3,3,3-tetrafluoropropene are preferred.
  • the isomerization reaction is more likely to proceed as compared with HCFO-1224yd and HFO-1336mzz, so that the other dielectric inside the metal tank 11 is used. If the filling amount is large, the effect on the electrical equipment due to the isomerization of other dielectrics becomes a problem. Therefore, among the dielectrics filled in the metal tank 11, the molar ratio of the other dielectrics is preferably 30% or less, more preferably 20% or less, further preferably 10% or less, and particularly preferably 5% or less.
  • Fluorocarbon refers to a saturated hydrocarbon compound containing a fluorine atom as a halogen atom in the molecule but not a chlorine atom. Fluorocarbons may or may not contain hydrogen atoms in their molecules. Chlorofluorocarbon refers to a saturated hydrocarbon compound containing a fluorine atom and a chlorine atom as halogen atoms in the molecule. The chlorofluorocarbon may or may not contain a hydrogen atom in the molecule.
  • the fluoroolefin is an ethylene hydrocarbon compound containing a fluorine atom as a halogen atom but not a chlorine atom in the molecule. The fluoroolefin may or may not contain a hydrogen atom in the molecule.
  • the chlorofluoroolefin is an ethylene hydrocarbon compound containing a fluorine atom and a chlorine atom as halogen atoms in the molecule.
  • the chlorofluoroolefin may or may not contain a hydrogen atom in the molecule.
  • the chlorofluoroalkyne is an acetylene-based hydrocarbon compound containing a fluorine atom and a chlorine atom as halogen atoms in the molecule.
  • the chlorofluoroalkyne may or may not contain a hydrogen atom in the molecule.
  • Fluorocarbons include 1,1,1,2-tetrafluoropropane, 1,1,1,3-tetrafluoropropane, 1,1,1,3,3-pentafluoropropane, 1,1,1,2, Included are 2,3,3-heptafluoropropane, tetrafluoromethane, trifluoromethane and fluoroethane.
  • chlorofluorocarbons include 1,3-dichloro-1,1,2,2,3-pentafluoropropane, 2-chloro-1,1,1,2-tetrafluoropropane, and 3,3-dichloro-1,1. , 1,2,2-pentafluoropropane and chlorotrifluoromethane.
  • fluoroolefins other than HFO-1336 mzz examples include 2,4,4,4-tetrafluoro-1-butene and tetrafluoroethylene.
  • chlorofluoroolefins other than HCFO-1224yd examples include 1,1-dichloro-2,3,3,3-tetrafluoropropene, 2-chloro-3,3,3-trifluoropropene, and (Z) -2-chloro. -1,3,3,3-tetrafluoropropene, (E) -2-chloro-1,3,3,3-tetrafluoropropene and 2-chloro-1,1,3,3,3-pentafluoro- 1-Propene can be mentioned.
  • chlorofluoroalkynes examples include 1,1-dichloro-2,3,3,3-tetrafluoropropene and 1-chloro-3,3,3-trifluoro-1-propyne.
  • examples include solvents.
  • the dielectric to be filled inside the metal tank 11 is selected from the group consisting of chlorine, hydrogen fluoride, hydrogen chloride, acetic acid, carbonyl fluoride, phosgene, trifluoroacetate fluoride, formyl chloride and chloroform as the second trace component. It may contain at least one of the above.
  • the mass-based content of the second trace component is 5000 ppm or less with respect to the entire dielectric filled in the metal tank 11 from the viewpoint of ensuring further stability.
  • the mass-based content of the second trace component is set with respect to the entire dielectric filled in the metal tank 11. 5 ppm or more is preferable, and 10 ppm or more is more preferable.
  • the preferred combination of the dielectric and the diluting gas is (E) -1-chloro-2,3,3,3-tetrafluoropropene. And (Z) a combination of at least one of -1-chloro-2,3,3,3-tetrafluoropropene and at least one selected from the group consisting of air, nitrogen, oxygen and carbon dioxide and the like. ..
  • the electrical equipment 10 shown in FIG. 1 may be provided with various equipment electrically in series or in parallel along an electric circuit (electric circuit) including a conductor member 12.
  • Examples of the above-mentioned equipment include switches, circuit breakers, disconnectors, etc. for cutting the electric circuit; transformers, resistors, reactors, capacitors, etc. for changing the voltage of the electric circuit; and insulated cables.
  • the dielectric and diluting gas filled inside the metal tank 11 and hydrogen. Helium, SF 6 , or a mixed gas thereof may be used.
  • a solid insulating material, an insulating oil, a gel-like insulating material or the like may be used for the internal or external insulation of the above equipment.
  • the inside or outside of the above equipment may be insulated by a vacuum state.
  • the solid insulator include an insulating resin material and the like.
  • the insulating resin material include a thermoplastic resin and a thermosetting resin.
  • the thermoplastic resin include vinyl chloride-based, polyester-based, and nylon-based resins.
  • the thermosetting resin include epoxy-based and urethane-based resins.
  • the insulating oil include mineral oil, vegetable oil, animal oil, fluorine-based oil and the like.
  • the electrical equipment of the present disclosure contains in the dielectric and the amount of change ⁇ Z from the initial value of the peak area of the Z isomer contained in the dielectric, which is measured by a gas chromatograph after 100 hours under the temperature condition of 160 ° C.
  • the amount of change ⁇ E from the initial value of the peak area of the Z isomer to be formed satisfies the following equations 1 and 2. Equation 1: ⁇ 1.0 area% ⁇ ⁇ Z ⁇ 1.0 area% Equation 2: ⁇ 1.0 area% ⁇ ⁇ E ⁇ 1.0 area%
  • Equation 1-2 -0.7area% ⁇ ⁇ Z ⁇ 0.7area%
  • Equation 2-2 -0.7area% ⁇ ⁇ E ⁇ 0.7area%
  • the ⁇ Z and the ⁇ E are measured using a gas chromatograph.
  • a gas chromatograph for example, a GC system 7890A manufactured by Agilent Technologies can be used, and as a GC column, DB-1 can be used.
  • ⁇ Z and the ⁇ E The calculation method of the ⁇ Z and the ⁇ E will be described below.
  • An electric facility filled with a dielectric to be measured (hereinafter referred to as a measurement target) is installed in a constant temperature bath and then heated to 40 ° C.
  • a gas sample of the gas phase part (gas containing a dielectric; the same shall apply hereinafter) in the measurement target is taken and measured by a gas chromatograph.
  • the peak areas (unit is "area%") of the Z isomer contained in the dielectric and the E isomer contained in the dielectric in the chromatogram are calculated, and each peak area is used as an initial value. ..
  • the initial value of the peak area of the Z isomer is Z 0
  • the initial value of the peak area of the E isomer is E 0
  • a gas sample is taken from the gas phase portion in the measurement target and measured by a gas chromatograph.
  • the area of the peak of the Z isomer contained in the dielectric Z1008 and the area of the peak of the E isomer contained in the dielectric E1008 are calculated. do.
  • the amount of change ⁇ Z (Z 1008 ⁇ Z 0 ) from the initial value of the peak area of the Z isomer and the amount of change ⁇ E (Z 1008 ⁇ Z 0 ) from the initial value of the peak area of the E isomer are calculated.
  • Example 1 and Example 2 are examples, and Example 3 is a comparative example. However, the present disclosure is not limited to these examples.
  • An internal intubation made of Pyrex (registered trademark) whose mass was measured in advance was inserted into a pressure vessel made of stainless steel (SUS316) having an internal volume of 200 cc (maximum working temperature 300 ° C., maximum working pressure 20 MPa).
  • Example 1 the decrease in HCFO-1224yd (Z) due to isomerization indicated by ⁇ Z and the increase in HCFO-1224yd (E) due to isomerization indicated by ⁇ E were slight.
  • Example 2 a decrease in HFO-1336 mzz (Z) due to the isomerization indicated by ⁇ Z could hardly be confirmed.
  • Example 3 the decrease by HCFO-1233zd (E) due to the isomerization indicated by ⁇ E and the increase by HCFO-1233zd (Z) due to the isomerization indicated by ⁇ Z were remarkable.
  • Example 1 it is shown that the isomerization of the dielectric is suppressed even when HCFO-1224yd having a purity of 99.4% is used as the dielectric. Further, in Example 2, it is shown that the isomerization of the dielectric is suppressed even when HFO-1336 mzz having a purity of 99.9% is used as the dielectric. Therefore, the concentrations of HCFO-1224yd and HFO-1336mzz contained in the dielectric are 70% by volume or less, 60% by volume or less, 50% by volume or less, 40% by volume or less, 30% by volume or less, 25% by volume or less, 20% by volume. Below, it can be seen that the isomerization of the dielectric is suppressed even when the volume is as low as 15% by volume or less, 10% by volume or less, or 5% by volume or less.

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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EP21882685.7A EP4235702A4 (en) 2020-10-22 2021-10-13 ELECTRICAL EQUIPMENT
CN202180071050.7A CN116348968A (zh) 2020-10-22 2021-10-13 电气设备
US18/295,922 US12456851B2 (en) 2020-10-22 2023-04-05 Gas-insulated switching device using C3HCIF4 or C4H2F6

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JP2012008524A (ja) * 2010-02-26 2012-01-12 Canon Inc 光学用部材、ポリイミド、およびその製造方法
US8399721B2 (en) 2008-12-22 2013-03-19 E I Du Pont De Nemours And Company Method of hydrodechlorination to produce dihydrofluorinated olefins
US8436216B2 (en) 2008-03-19 2013-05-07 E I Du Pont De Nemours And Company Process for making 1,1,1,4,4,4-Hexafluoro-2-butene
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