Composition

Abstract

To provide a novel composition suitable for use as an insulating medium or a refrigerant.SOLUTION: A composition comprises hexafluoroazomethane and at least one substance selected from the group consisting of hydrofluorocarbons, hydrofluoroolefins, hydrochlorofluoroolefins, chlorofluoroolefins, perfluoroolefins, nitrogen, oxygen, and carbon dioxide.SELECTED DRAWING: None

Description

Technical Field

[0001] The present disclosure relates to a composition.

Background Art

[0002] Sulfur hexafluoride has been widely used as an insulating medium for gas-insulated switchgear, gas circuit breakers, etc. because of its excellent insulating performance. However, since sulfur hexafluoride has a high global warming potential, an alternative is desired. For example, Patent Document 1 describes that hexafluoroazomethane has insulating performance.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] The present disclosure has been made in view of such circumstances, and an object to be solved by one embodiment of the present invention is to provide a novel composition useful as an insulating medium or a refrigerant.

Means for Solving the Problems

[0005] The present disclosure includes the following aspects. <1> Hexafluoroazomethane, and At least one substance selected from the group consisting of hydrofluorocarbons, hydrofluoroolefins, hydrochlorofluoroolefins, chlorofluoroolefins, perfluoroolefins, nitrogen, oxygen, and carbon dioxide, and A composition containing the same. <2> The composition according to <1>, wherein the substance contains 2,3,3,3-tetrafluoropropene. <3> The substance is the composition according to <2>, which further contains at least one selected from difluoromethane, fluoroethane, 1,1-difluoroethane, 1,1,1,2-tetrafluoroethane, 1,1,2,2-tetrafluoroethane, 1,1,1,2-tetrafluoropropane, 1,1,1,2,3-pentafluoropropane, 3,3,3-trifluoropropene, 1,1,1,3,3-pentafluoropropene, 1,2,3,3,3-pentafluoropropene, (E)-1,3,3,3-tetrafluoropropene, (Z)-1,3,3,3-tetrafluoropropene, 1-chloro-2,3,3,3-tetrafluoropropene, oxygen, and carbon dioxide. <4> The substance is the composition according to <1>, which contains difluoromethane. <5> The substance is the composition according to <4>, which further contains at least one selected from fluoroethane, 1,1-difluoroethane, 2,3,3,3-tetrafluoropropene, 1,1,1,2-tetrafluoroethane, 1,1,2,2-tetrafluoroethane, 1,1,1,2-tetrafluoropropane, 1,1,1,2,3-pentafluoropropane, 3,3,3-trifluoropropene, 1,1,1,3,3-pentafluoropropene, 1,2,3,3,3-pentafluoropropene, (E)-1,3,3,3-tetrafluoropropene, (Z)-1,3,3,3-tetrafluoropropene, 1-chloro-2,3,3,3-tetrafluoropropene, oxygen, and carbon dioxide. <6> The substance is the composition according to <1>, which contains 1,1-difluoroethane. <7> The composition according to <6>, wherein the substance further contains at least one selected from difluoromethane, fluoroethane, 2,3,3,3-tetrafluoropropene, 1,1,1,2-tetrafluoroethane, 1,1,2,2-tetrafluoroethane, 1,1,1,2-tetrafluoropropane, 1,1,1,2,3-pentafluoropropane, 3,3,3-trifluoropropene, 1,1,1,3,3-pentafluoropropene, 1,2,3,3,3-pentafluoropropene, (E)-1,3,3,3-tetrafluoropropene, (Z)-1,3,3,3-tetrafluoropropene, 1-chloro-2,3,3,3-tetrafluoropropene, oxygen, and carbon dioxide. <8> The composition according to any one of <1> to <7>, wherein the content of hexafluoroazomethane is 10 to 95% by mass based on the total amount of the composition. <9> The composition according to any one of <1> to <8>, which is used as an insulating medium. <10> The composition according to any one of <1> to <8>, which is used as a refrigerant. [Advantages of the Invention]

[0006] According to the present disclosure, a novel composition useful as an insulating medium or a refrigerant is provided. [Embodiments for Carrying Out the Invention]

[0007] [Composition] The composition of the present disclosure contains hexafluoroazomethane and at least one substance selected from the group consisting of hydrofluorocarbons (HFCs), hydrofluoroolefins (HFOs), hydrochlorofluoroolefins (HCFOs), chlorofluoroolefins (CFOs), perfluoroolefins (PFOs), nitrogen, oxygen, and carbon dioxide.

[0008] Hereinafter, at least one substance selected from the group consisting of HFCs, HFOs, HCFOs, CFOs, PFOs, nitrogen, oxygen, and carbon dioxide is also referred to as a "specific substance".

[0009] <Hexafluoroazomethane> The composition of the present disclosure contains hexafluoroazomethane. Hexafluoroazomethane can be obtained, for example, by reacting silver fluoride after mixing cyanogen bromide and tetrabutylammonium tribromide in an organic solvent. Examples of the solvent include acetonitrile, chloroform, and dichloromethane.

[0010] The hexafluoroazomethane contained in the composition of the present disclosure may be the Z isomer, the E isomer, or a mixture of the Z isomer and the E isomer.

[0011] The content of hexafluoroazomethane is preferably 10 to 95% by mass, more preferably 30 to 90% by mass, based on the total amount of the composition of the present disclosure.

[0012] <Specific substance> The composition of the present disclosure contains a specific substance. The specific substance may be only one kind or two or more kinds.

[0013] Examples of HFCs include Fluoromethane (HFC-41), Difluoromethane (HFC-32), Trifluoromethane (HFC-23), Fluoroethane (HFC-161), 1,1-Difluoroethane (HFC-152a), Pentafluoroethane (HFC-125), 1,1,1-Trifluoroethane (HFC-143a), 1,1,1,2-Tetrafluoroethane (HFC-134a), 1,1,2,2-Tetrafluoroethane (HFC-134), 1,1,1,2,2-Pentafluoropropane (HFC-245cb), 1,1,1,2,2,3,3-Heptafluoropropane (HFC-227ca), 1,1,1,2,3,3,3 - heptafluoropropane (HFC - 227ea), 1,1,1 - trifluoropropane (HFC - 263fb), 1,1,1,2 - tetrafluoropropane (HFC - 254eb), 1,1,1,2,3 - pentafluoropropane (HFC - 245eb), 1,1,1,3,3 - pentafluoropropane (HFC - 245fa), 1,1,2,2,3 - pentafluoropropane (HFC - 245ca) and 1,1,1,3 - tetrafluoropropane (HFC - 254fb) may be mentioned.

[0014] Examples of HFOs include, for example, 2,3,3,3 - tetrafluoropropene (HFO - 1234yf), 3,3 - difluoropropene (HFO - 1252zf), 3,3,3 - trifluoropropene (HFO - 1243zf) 1,1,1,3,3 - pentafluoropropene (HFO - 1225zc), 1,2,3,3,3 - pentafluoropropene (HFO - 1225ye), (E) - 1,3,3,3 - tetrafluoropropene (HFO - 1234ze(E)), (Z) - 1,3,3,3 - tetrafluoropropene (HFO - 1234ze(Z)), (E) - 1,1,3,3 - tetrafluoropropene (HFO - 1234zc(E)), (Z) - 1,1,3,3 - tetrafluoropropene (HFO - 1234zc(Z)), (E) - 1,1,1,4,4,4 - hexafluorobutene (HFO - 1336mzz(E)), (Z) - 1,1,1,4,4,4 - hexafluorobutene (HFO - 1336mzz(Z)) and 1,2,3,3 - tetrafluoropropene (HFO - 1234ye) may be mentioned.

[0015] Examples of HCFOs include 2-chloro-1,1,3,3,3-pentafluoropropene (HCFO-1215xc), 1-chloro-1,2,3,3,3-pentafluoropropene (HCFO-1215yb), 2-chloro-1,3,3-trifluoropropene (HCFO-1233xf), 1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd), 3-chloro-1,2,3,3-tetrafluoropropene (HCFO-1224ye), 1-chloro-1,2,3,3-tetrafluoropropene (HCFO-1224yb), 1-chloro-2,3,3-trifluoropropene (HCFO-1233yd), 2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe), 2-chloro-1,1,3,3-tetrafluoropropene (HCFO-1224xc), 1,2-dichloro-3,3,3-trifluoropropene (HCFO-1223xd), 1,1-dichloro-2,3,3-trifluoropropene (HCFO-1223ya) and 1,1-dichloro-3,3,3-trifluoropropene (HCFO-1223za). Examples thereof include.

[0016] Examples of CFOs include 1,1-dichloro-2,3,3,3-tetrafluoropropene (CFO-1214ya), 1,2-dichloro-1,3,3,3-tetrafluoropropene (CFO-1214xb) and 1,3-dichloro-1,2,3,3-tetrafluoropropene (CFO-1214yb).

[0017] Examples of PFOs include tetrafluoroethylene, perfluoro-2-butyne, perfluoro-2-butene, and perfluorobutadiene.

[0018] Among them, HFC, HFO, HCHO, CFO, and PFO preferably have 1 to 4 carbon atoms.

[0019] From the perspective of using the composition of the present disclosure as a refrigerant, the boiling points of HFC, HFO, HCHO, CFO, and PFO are preferably close to the boiling point of hexafluoroazomethane (-32°C). Specifically, the boiling points of HFC, HFO, HCHO, CFO, and PFO are preferably 0 to -60°C, more preferably -10 to -45°C. The boiling point is the value at atmospheric pressure (101.325 kPa).

[0020] The specific substance may be nitrogen, oxygen, or carbon dioxide. Further, the composition of the present disclosure may contain hexafluoroazomethane and air.

[0021] The composition of the present disclosure preferably contains HFO-1234yf, and further preferably contains at least one selected from HFC-32, HFC-161, HFC-152a, HFC-134a, HFC-134, HFC-254eb, HFC-245eb, HFO-1243zf, HFO-1225zc, HFO-1225ye, HFO-1234ze(E), HFO-1234ze(Z), HCFO-1224yd, oxygen, and carbon dioxide.

[0022] Also, the composition of the present disclosure preferably contains HFC-32, and further preferably contains at least one selected from HFC-161, HFC-152a, HFO-1234yf, HFC-134a, HFC-134, HFC-254eb, HFC-245eb, HFO-1243zf, HFO-1225zc, HFO-1225ye, HFO-1234ze(E), HFO-1234ze(Z), HCFO-1224yd, oxygen, and carbon dioxide.

[0023] Further, the composition of the present disclosure preferably contains HFC-152a, and further preferably contains at least one selected from the group consisting of HFC-32, HFC-161, HFO-1234yf, HFC-134a, HFC-134, HFC-254eb, HFC-245eb, HFO-1243zf, HFO-1225zc, HFO-1225ye, HFO-1234ze(E), HFO-1234ze(Z), HCFO-1224yd, oxygen, and carbon dioxide.

[0024] When the composition of the present disclosure is used as a refrigerant, the specific substance is preferably at least one selected from the group consisting of HFO-1234yf, HFC-32, HFC-161, HFC-152a, HFC-134a, HFC-134, HFC-254eb, HFC-245eb, HFO-1243zf, HFO-1225zc, HFO-1225ye, HFO-1234ze(E), HFO-1234ze(Z), and HCFO-1224yd, and more preferably HFO-1234yf, HFC-32, or HFC-152a.

[0025] When the composition of the present disclosure is used as an insulating medium, from the viewpoint of reacting and removing the soot generated by discharge when a discharge phenomenon occurs in the device during use, the specific substance preferably contains oxygen or carbon dioxide in addition to HFO-1234yf, HFC-32, or HFC-152a.

[0026] From the viewpoint of using the composition of the present disclosure as an insulating medium, the specific substance is preferably at least one selected from the group consisting of HFO-1234yf, HFC-32, HFC-161, HFC-152a, HFC-134a, HFC-134, HFC-254eb, HFC-245eb, HFO-1243zf, HFO-1225zc, HFO-1225ye, HFO-1234ze(E), HFO-1234ze(Z), HCFO-1224yd, oxygen, nitrogen, and carbon dioxide, and more preferably HFO-1234yf, HFC-32, HFC-152a, oxygen, or carbon dioxide.

[0027] The content of the specific substance varies depending on the function it serves. For example, in the case of a specific substance added for the purpose of improving insulation characteristics and gas-liquid equilibrium characteristics when used as an insulating medium or refrigerant, 5 to 90% by mass is preferable, and 10 to 70% by mass is more preferable, based on the total amount of the composition of the present disclosure. On the other hand, for the purpose of removing soot generated by the discharge phenomenon when used as an insulating medium, or for the purpose of addition as a stabilizer to suppress performance deterioration due to self-decomposition reaction of the main component, etc., even an addition at the ppm level exhibits an effect, so an addition of 10% by mass or less is preferable, and 5% by mass or less is more preferable.

[0028] The composition of the present disclosure may contain components other than hexafluoroazomethane and the specific substance. Examples of other components include lubricants, stabilizers, etc. when used as a refrigerant.

[0029] <Use> Since the composition of the present disclosure contains hexafluoroazomethane, it has excellent insulation performance and is preferably used as an insulating medium. For the composition of the present disclosure, for example, it is preferable that the breakdown voltage is 30 kV or more. The breakdown voltage is measured, for example, as the breakdown voltage between electrodes with a width of 0.1 inches under normal temperature (23°C) and normal pressure (1 atm) conditions based on ASTM D2477-07(2012).

[0030] Also, since the composition of the present disclosure contains hexafluoroazomethane, it has excellent refrigeration capacity and is preferably used as a refrigerant. For the composition of the present disclosure, for example, the boiling point is 0°C or lower.

Examples

[0031] The present invention will be described in more detail below using examples, but the present invention is not limited to these examples.

[0032] <Synthesis of Hexafluoroazomethane> In a glove box filled with argon, 21 mg (0.2 mmol) of cyanogen bromide (95.0+%, manufactured by Fujifilm Wako Pure Chemical Corporation), 48 mg (0.1 mmol) of tetrabutylammonium tribromide (98%, manufactured by TCI), and 1 mL of acetonitrile-d3 (>99%, manufactured by Tokyo Chemical Industry Co., Ltd.) were added in this order to a 10 mL glass scintillation vial containing a stirring bar coated with PTFE (polytetrafluoroethylene). Next, while stirring vigorously, 102 mg (0.7 mmol) of silver(II) fluoride (≧98%, manufactured by Merck Millipore) was added all at once. When the black silver(II) salt dissolved, the reaction mixture exhibited a color ranging from orange to yellowish-brown. Next, the vial was capped, placed in an opaque secondary container to protect it from light, and stirred vigorously for 90 minutes. After 90 minutes, the reaction mixture appeared as a yellow supernatant on top of a large amount of orange precipitate. The supernatant was separated by syringe filtration through a 0.45 micron PTFE membrane disk and placed directly into an NMR tube containing 0.1 mmol of hexafluorobenzene as an internal standard. For this crude product 19 By 19F-NMR (376 MHz) measurement, the yield of hexafluoroazomethane was 46%, and the molar ratio of the E-isomer to the Z-isomer (E / Z) was 15 / 85.

[0033] <Preparation of Composition> Hexafluoroazomethane and HFO-1234yf were mixed at a ratio of 70:30 (mass ratio) to prepare a composition.

[0034] The boiling point of the obtained composition was -31°C, and it was found to be useful as a refrigerant. The breakdown voltage of the obtained composition was 30 kV or more, and it was found to be useful as an insulating medium.

Claims

1. Hexafluoroazomethane and, at least one substance selected from the group consisting of hydrofluorocarbons, hydrofluoroolefins, hydrochlorofluoroolefins, chlorofluoroolefins, perfluoroolefins, nitrogen, oxygen, and carbon dioxide. A composition containing the same.

2. The composition according to claim 1, wherein the substance contains 2,3,3,3-tetrafluoropropene.

3. The composition according to claim 2, wherein the substance further contains at least one selected from difluoromethane, fluoroethane, 1,1-difluoroethane, 1,1,1,2-tetrafluoroethane, 1,1,2,2-tetrafluoroethane, 1,1,1,2-tetrafluoropropane, 1,1,1,2,3-pentafluoropropane, 3,3,3-trifluoropropene, 1,1,1,3,3-pentafluoropropene, 1,2,3,3,3-pentafluoropropene, (E)-1,3,3,3-tetrafluoropropene, (Z)-1,3,3,3-tetrafluoropropene, 1-chloro-2,3,3,3-tetrafluoropropene, oxygen, and carbon dioxide.

4. The composition according to claim 1, wherein the substance contains difluoromethane.

5. The composition according to claim 4, wherein the substance further contains at least one selected from fluoroethane, 1,1-difluoroethane, 2,3,3,3-tetrafluoropropene, 1,1,1,2-tetrafluoroethane, 1,1,2,2-tetrafluoroethane, 1,1,1,2-tetrafluoropropane, 1,1,1,2,3-pentafluoropropane, 3,3,3-trifluoropropene, 1,1,1,3,3-pentafluoropropene, 1,2,3,3,3-pentafluoropropene, (E)-1,3,3,3-tetrafluoropropene, (Z)-1,3,3,3-tetrafluoropropene, 1-chloro-2,3,3,3-tetrafluoropropene, oxygen, and carbon dioxide.

6. The composition according to claim 1, wherein the substance contains 1,1-difluoroethane.

7. The composition according to claim 6, wherein the substance further contains at least one selected from difluoromethane, fluoroethane, 2,3,3,3-tetrafluoropropene, 1,1,1,2-tetrafluoroethane, 1,1,2,2-tetrafluoroethane, 1,1,1,2-tetrafluoropropane, 1,1,1,2,3-pentafluoropropane, 3,3,3-trifluoropropene, 1,1,1,3,3-pentafluoropropene, 1,2,3,3,3-pentafluoropropene, (E)-1,3,3,3-tetrafluoropropene, (Z)-1,3,3,3-tetrafluoropropene, 1-chloro-2,3,3,3-tetrafluoropropene, oxygen, and carbon dioxide.

8. The composition according to any one of claims 1 to 7, wherein the content of the hexafluoroazomethane is 10 to 95% by mass based on the total amount of the composition.

9. The composition according to any one of claims 1 to 7, which is used as an insulating medium.

10. The composition according to any one of claims 1 to 7, which is used as a refrigerant.