Hydrohaloolefin Composition

Abstract

To provide a hydrohaloolefin composition that is primarily composed of 1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224 yd) and has excellent stability.SOLUTION: A hydrohaloolefin composition is primarily composed of HCFO-1224 yd and further contains at least one selected from the group consisting of HFC-245fa, HFC-254fb, HCFC-244bb, HFO-1354yf, HFO-1234yf, HCFO-1233xf, HCFO-1224xe, CFO-1214ya, 3-chloro-1,1,1,2,2,3-hexafluoropropane (HCFC-226ca), 1-chloro-1,1,2,3,3,3-hexafluoropropane (HCFC-226ea), and 2-chloro-1,1,1,3,3-pentafluoropropane (HCFC-235da).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to hydrohaloolefin compositions. [Background technology]

[0002] To prevent global warming and ozone layer depletion, hydrohaloolefins such as hydrofluoroolefins (HFOs) and hydrochlorofluoroolefins (HCFOs), which have low global warming potential, are expected to be substitutes for fluorocarbons. For example, Patent Document 1 describes uses of hydrohaloolefins such as heat transfer media, refrigerants, foaming agents, solvents, cleaning agents, propellants, and fire extinguishing agents. Hydrohaloolefins are not sufficiently stable, as they may gradually decompose over time, etc. Therefore, when used in various applications, there are problems such as a gradual deterioration in performance depending on the conditions or environment of use. Patent Document 1 describes an example in which a small amount of water is added to 2,3,3,3-tetrafluoropropene (HFO-1234yf) or 1,3,3,3-tetrafluoropropene (HFO-1234ze) to improve stability. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent No. 5962827 Summary of the Invention [Problem to be solved by the invention]

[0004] It is also desirable to improve the stability of hydrohaloolefins other than HFO-1234yf or HFO-1234ze described in Patent Document 1. An object of the present invention is to provide a hydrohaloolefin composition that contains 1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd) as a main component and has good stability. [Means for solving the problem]

[0005] The present invention has the following aspects. [1] The main component is 1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd), and further includes 1,1,1,3,3-pentafluoropropane (HFC-245fa), 1,1,1,3-tetrafluoropropane (HFC-254fb), 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb), 2,4,4,4-tetrafluoro-1-butene (HFO-1354yf), 2,3,3,3-tetrafluoropropene (HFO-1234yf), 2-chloro-3,3,3-trifluoropropene (HCFO-1 2-chloro-1,3,3,3-tetrafluoropropene (HCFC-1224xf), 2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe), 1,1-dichloro-2,3,3,3-tetrafluoropropene (CFO-1214ya), 3-chloro-1,1,1,2,2,3-hexafluoropropane (HCFC-226ca), 1-chloro-1,1,2,3,3,3-hexafluoropropane (HCFC-226ea), and 2-chloro-1,1,1,3,3-pentafluoropropane (HCFC-235da). [2] The amount of the 1,1,1,3,3-pentafluoropropane (HFC-245fa), the 1,1,1,3-tetrafluoropropane (HFC-254fb), the 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb), the 2,4,4,4-tetrafluoro-1-butene (HFO-1354yf), the 2,3,3,3-tetrafluoropropene (HFO-1234yf), the 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), and the 2-chloro- The hydrohaloolefin composition of [1], wherein the total content of 1,3,3,3-tetrafluoropropene (HCFO-1224xe), the 1,1-dichloro-2,3,3,3-tetrafluoropropene (CFO-1214ya), the 3-chloro-1,1,1,2,2,3-hexafluoropropane (HCFC-226ca), the 1-chloro-1,1,2,3,3,3-hexafluoropropane (HCFC-226ea), and the 2-chloro-1,1,1,3,3-pentafluoropropane (HCFC-235da) is less than 10.0% by mass. [3] The hydrohaloolefin composition according to [1], which is used as a working fluid. [4] The hydrohaloolefin composition according to [1], which is used as a blowing agent. [5] The hydrohaloolefin composition according to [1], which is used as a dilution solvent. [6] The hydrohaloolefin composition according to [1], which is used as a detergent. [7] The hydrohaloolefin composition according to [1], which is used as a propellant. [8] The hydrohaloolefin composition of [1], which is used as a fire extinguishing agent. [9] The hydrohaloolefin composition of [1], which is for use as a gaseous dielectric.

[10] The hydrohaloolefin composition according to [1], which is used as an etching gas.

[11] The hydrohaloolefin composition of [1], which is used as a molten metal cover gas. [Effects of the Invention]

[0006] According to the present invention, a hydrohaloolefin composition having excellent stability and containing 1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd) as a main component can be obtained. DETAILED DESCRIPTION OF THE INVENTION

[0007] The following definitions of terms apply throughout the specification and claims. Hydrohaloolefin is a general term for unsaturated hydrocarbon compounds containing a hydrogen atom and a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. An organic compound is a general term for compounds containing carbon atoms, excluding oxides of carbon and carbonates of metals. The main component of a composition means a compound that is contained in the largest amount relative to the total mass of the composition. The abbreviation or alias of a compound may be written in parentheses after the compound name. The abbreviation or alias may be used instead of the compound name. In unsaturated hydrocarbon compounds, geometric isomers, Z (cis) and E (trans), exist depending on the position of the substituent attached to the carbon atom with the double bond. For compounds that exist in both Z and E forms, when the compound name or abbreviation is used without any special mention, it means either the Z or E form, or a mixture of Z and E forms in any proportion. When a compound name or abbreviation is followed by (Z) or (E), it indicates that it is the Z or E form of the respective compound. A numerical range expressed with "to" means that the numerical values before and after "to" are the lower and upper limits of the numerical range.

[0008] <Hydrohaloolefin composition> The hydrohaloolefin composition of this embodiment (hereinafter also referred to as the present composition) contains two or more organic compounds, and the main component is 1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd). HCFO-1224yd may be HCFO-1224yd(Z), HCFO-1224yd(E), or a mixture thereof. The Z / E ratio, which represents the mass ratio of the Z isomer content to the E isomer content in HCFO-1224yd, may be from 100 / 0 to 0 / 100, preferably from 99.9 / 0.1 to 50 / 50, more preferably from 99.9 / 0.1 to 70 / 30, and even more preferably from 99.9 / 0.1 to 99.0 / 1.0. The content of the main component relative to the total mass of the composition is, for example, more than 90 mass%, and may be 93.5 mass% or more, preferably 96.0 mass% or more, more preferably 98.5 mass% or more, even more preferably 99.0 mass% or more, and particularly preferably 99.5 mass% or more.

[0009] In addition to the main component HCFO-1224yd, this composition contains 1,1,1,3,3-pentafluoropropane (HFC-245fa), 1,1,1,3-tetrafluoropropane (HFC-254fb), 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb), 2,4,4,4-tetrafluoro-1-butene (HFO-1354yf), 2,3,3,3-tetrafluoropropene (HFO-1234yf), 2-chloro-3,3,3-trifluoropropene (HCFO-1233x ... -Contains one or more compounds (hereinafter also referred to as Compound A) selected from the group consisting of 1,3,3,3-tetrafluoropropene (HCFO-1224xe), 1,1-dichloro-2,3,3,3-tetrafluoropropene (CFO-1214ya), 3-chloro-1,1,1,2,2,3-hexafluoropropane (HCFC-226ca), 1-chloro-1,1,2,3,3,3-hexafluoropropane (HCFC-226ea), and 2-chloro-1,1,1,3,3-pentafluoropropane (HCFC-235da). Table 1 shows the structural formula of compound A and the content of each compound.

[0010] [Table 1]

[0011] The total content of compound A relative to the total mass of the composition is preferably less than 10.0 mass%, more preferably 2.0 mass% or less, even more preferably 0.8 mass% or less, and particularly preferably 0.5 mass% or less. Furthermore, when the total content of compound A relative to the total mass of the composition is less than 10.0 mass%, a hydrohaloolefin composition having good stability and metal corrosion resistance can be provided.

[0012] The present composition may contain one or more organic compounds other than HCFO-1224yd and compound A. Examples of other organic compounds include hydrofluoroolefins (HFOs), hydrochlorofluoroolefins (HCFOs), hydrochloroolefins (HCOs), chlorofluoroolefins (CFOs), fluoroolefins, chloroolefins, olefins, hydrofluorocarbons (HFCs), hydrochlorocarbons (HCCs), hydrochlorofluorocarbons (HCFCs), chlorofluorocarbons (CFCs), chlorocarbons, fluorocarbons (FCs), hydrocarbons (HCs), hydrofluoroethers (HFEs), alcohols, ethers, ketones, organic acids, and saturated hydrocarbons. Furthermore, halogenated methane containing a bromine atom or an iodine atom may be included as needed.

[0013] Specific examples of hydrofluoroolefins (HFOs) include 1,1,2-trifluoroethylene (HFO-1123), 1-fluoropropene (HFO-1261ze), 1,2-difluoropropane (HFO-1252ye), 1,3,3,3-tetrafluoropropene (HFO-1234ze), 1,1,2,3-tetrafluoropropene (HFO-1234yc), 1,2,3,3-tetrafluoropropene (HFO-1234ye), and 1,1,3,3-tetrafluoropropene (HFO-1234ze). zc), 1,1,2,3,3-pentafluoropropene (HFO-1225yc), 1,1,3,3,3-pentafluoropropene (HFO-1225zc), 1,1,2-trifluoropropene (HFO-1243yc), 1,2,3-trifluoropropene (HFO-1243ye), 3,3,3-trifluoropropene (HFO-1243zf), 1,3,3-trifluoropropene (HFO-1243ze), 3,3-difluoropropene (HFO-1252zf), 2-fluoropropene (HFO -1261yf), 1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz), 2,3,3,4,4,4-hexafluoro-1-butene (HFO-1336mcyf), 1,3,3,4,4,4-hexafluoro-1-butene (HFO-1336ze), tetrafluorobutene (HFO-1354), 1,1,1,2,4,4,5,5,5-nonafluoropentene (HFO-1429myz), 1,1,1,4,4,5,5,5-octafluoropent-2-ene (HFO-143 8mzz), 1,3,4,4,4-pentafluoro-3-trifluoromethyl-1-butene (HFO-1438ezy), (C2F5)(CF3)C=CH2, (CF3)2CFCH=CF2, (CF3)2CFCF=CHF, 1,1-difluoroethylene (HFO-1132a), 1,2-difluoroethylene (HFO-1132), 1,2,3,3,3-pentafluoro-1-propene (HFO-1225ye), and 1,1,2,3,3-pentafluoropropene (HFO-1225yc).

[0014] Specific examples of hydrochlorofluoroolefins (HCFOs) other than 1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd) include 1-chloro-2,3,3-trifluoropropene (HCFO-1233yd), 2-chloro-1,1,3-trifluoropropene (HCFO-1233xc), 2-chloro-1,3,3-trifluoropropene (HCFO-1233xe), 1-chloro-1,2,3-tetrafluoropropene (HCFO-1224yd), ...tetrafluoropropene (HCFO-1224yd), 1-chloro-2,3,3-trifluoropropene (HCFO-1224yd), 2-chloro-1,1,3-trifluoropropene (HCFO-1233xc), 2-chloro-1,3,3-trifluoropropene (HCFO-1233x Trifluoropropene (HCFO-1233yb), 1-chloro-1,3,3-trifluoropropene (HCFO-1233zb), 3-chloro-1,1,3-trifluoropropene (HCFO-1233zc), 3-chloro-1,3,3-trifluoropropene (HCFO-1233ze), 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd), 2,3,3-trichloro-3-fluoropropene (HCFO -1231xf), 2,3-dichloro-3,3-difluoropropene (HCFO-1232xf), 2,3-dichloro-3,3-difluoropropene (HCFO-1232xf), 1,2-dichloro-3,3,3-trifluoropropene (HCFO-1223xd), 2-chloro-1,1,3,3-tetrafluoropropene (HCFO-1224xc), 1,1-dichloro-2-fluoroethylene (HCFO-1121a), 1, Examples include 2-dichloro-1-fluoroethylene (HCFO-1121), 1-chloro-1-fluoroethylene (HCFO-1131a), 1-chloro-2-fluoroethylene (HCFO-1131), 1-chloro-2,2-difluoroethylene (HCFO-1122), 1,1,2-trifluoro-2-chloroethylene (HCFO-1113), and 1-chloro-3,3,3-trifluoro-1-propyne (CF3-C≡CCl).

[0015] Specific examples of hydrochloroolefins (HCO) include chloroethylene and 1,2-dichloroethylene.

[0016] Specific examples of chlorofluoroolefins (CFOs) include 1,1,2-trichloro-2-fluoroethylene and 2-chloro-1,1,3,3,3-pentafluoro-1-propene (CFO-1215xc).

[0017] Specific examples of the fluoroolefin include hexafluoropropene (FO-1216) and octafluoro-2-butene (FO-1318my).

[0018] A specific example of the chloroolefin is tetrachloroethylene.

[0019] Specific examples of the olefin include ethylene and propylene.

[0020] Specific examples of hydrofluorocarbons (HFCs) include 1,1,2,3-tetrafluorobutane (HFC-374pee), 1,1,1,2,2-pentafluoropropane (HFC-245cb), 1,1,2,2,3-pentafluoropropane (HFC-245ca), 1,1,1,2,3-pentafluoropropane (HFC-245eb), and 1,1,1,2,3,3,3 -Heptafluoropropane (HFC-227ea), 1,1,1,2-tetrafluoropropane (HFC-254eb), 1,1,1-trifluoropropane (HFC-263fb), 1,1,1,2,3,3-hexafluoropropane (HFC-236ea), 1,1,1,3,3,3-hexafluoropropane (HFC-236fa), 2-fluoropropane (HFC-28 1ea), 1,1,2,2-tetrafluoroethane (HFC-134), 1,1,1,2-tetrafluoroethane (HFC-134a), 1,2-difluoroethane (HFC-152), 1,1-difluoroethane (HFC-152a), difluoromethane (HFC-32), 1,1,1,2,2-pentafluoroethane (HFC-125), 1,1,2-trifluoroethane ( HFC-143), 1,1,1-trifluoroethane (HFC-143a), 1,1,1,3,3-pentafluorobutane (HFC-365mfc), fluoroethane (HFC-161), 1,1,1,2,2,3,4,5,5,5-decafluoropentane (HFC-43-10mee), trifluoromethane (HFC-23), and fluoromethane (HFC-41).

[0021] Specific examples of hydrochlorocarbons (HCCs) include chloroform, 1,1,1,2,3-pentachloropropane (HCC-240db), and 2-chloropropane.

[0022] Specific examples of hydrochlorofluorocarbons (HCFCs) include chlorodifluoromethane (HCFC-22), chlorofluoromethane (HCFC-31), trichlorodifluoroethane (HCFC-122), 1,1,2-trichloro-1,2-difluoroethane (HCFC-122a), 1,1,1-trichloro-2,2-difluoroethane (HCFC-122b), 2,2-dichloro-1,1,1-trifluoroethane (HCFC-123), 2-chloro-1,1,1,2-tetrafluoroethane (HCFC-124), 1-chloro-1,1,2,2-tetrafluoroethane (HCFC-124a), 2-chloro-1,1,1-trifluoroethane (HCFC-133a), 1,1-dichloro- Examples of suitable fluorocarbons include 1-fluoroethane (HCFC-141b), 1,1-difluoro-2-chloroethane (HCFC-142), 1-chloro-1,2-difluoroethane (HCFC-142a), 1-chloro-1,1-difluoroethane (HCFC-142b), 3,3-dichloro-1,1,1,2,2-pentafluoropropane (HCFC-225ca), 1,3-dichloro-1,1,2,2,3-pentafluoropropane (HCFC-225cb), 2,2-dichloro-1,1,1-trifluoropropane (HCFC-243ab), 2,3-dichloro-1,1,1-trifluoropropane (HCFC-243db), and 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb).

[0023] Specific examples of chlorofluorocarbons (CFCs) include trichlorofluoromethane (CFC-11), dichlorodifluoromethane (CFC-12), chlorotrifluoromethane (CFC-13), trichlorotrifluoroethane (CFC-113), 1,2-dichloro-1,1,2,2-tetrafluoroethane (CFC-114), 1,1-dichloro-1,2,2,2-tetrafluoroethane (CFC-114a), chloropentafluoroethane (CFC-115), dichlorohexafluoropropane (CFC-216), 2,2,3,3-tetrachlorohexafluorobutane (CFC-316), and dichlorooctafluorobutane (CFC-318).

[0024] Specific examples of chlorocarbons include dichloromethane (methylene chloride) and trichloroethane.

[0025] Specific examples of fluorocarbons (FC) include 1,1,1,2,2,2-hexafluoroethane (FC-116), octafluoropropane (FC-218), and 1,1,1,2,2,3,3-heptafluoropropane (FC-227ca).

[0026] Specific examples of hydrocarbons (HC) include methane, ethane, propane, n-butane, isobutane, n-pentane, isopentane, neopentane, cyclopentane, n-hexane, isohexane, and heptane.

[0027] Specific examples of hydrofluoroethers (HFEs) include CHF2-O-CHF2, CHF2-O-CH2F, CH2F-O-CH2F, CH2F-O-CH3, cyclo-CF2-CH2-CF2-O, cyclo-CF2-CF2-CH2-O, CHF2-O-CF2-CHF2, CF3-CF2-O-CH2F, CHF2-O-CHF-CF3, CHF2-O-CF2-CHF2, CH2F-O-CF2-CHF2, CF3-O-CF2-CH3, CHF2-CHF-O-CHF2, CF3-O-CHF-CH2F, CF3-CHF-O-CH2F C Examples include F3-O-CHF-CH3, CF3-CHF-O-CH3, CHF2-O-CH2-CHF2, CF3-O-CH2-CH2F, CF3-CH2-O-CH2F, CF2H-CF2-CF2-O-CH3, CF3CF2CF2-O-CH3, and C4H9-O-CH3.

[0028] Specific examples of alcohols include methanol, ethanol, propanol, and isopropanol.

[0029] Specific examples of ethers include dimethyl ether, methyl ethyl ether, diethyl ether, methyl propyl ether, methyl isopropyl ether, ethyl propyl ether, ethyl isopropyl ether, dipropyl ether, diisopropyl ether, dimethoxymethane, diethoxyethane, dipropoxymethane, and dibutoxymethane.

[0030] Specific examples of the ketone include methyl ethyl ketone, methyl isobutyl ketone, and perfluoroethyl isopropyl ketone.

[0031] Specific examples of organic acids include methyl formate, ethyl formate, and formic acid.

[0032] Specific examples of saturated hydrocarbons include methane, ethane, propane, butane, isobutane, pentane, isopentane, cyclopentane, and hexane.

[0033] The content of other organic compounds relative to the total mass of the composition is preferably 1.5 mass % or less, more preferably 1.0 mass % or less, and even more preferably 0.5 mass % or less.

[0034] In addition to the organic compound, the composition may contain an inert gas, such as carbon dioxide, nitrogen, oxygen, air (nitrogen: about 80% by volume, oxygen: about 20% by volume), argon, or helium. When the composition is filled into a sealed container, the inert gas may be present in an amount of 20% by volume or less, preferably 15% by volume or less, more preferably 10% by volume or less, even more preferably 5% by volume or less, and particularly preferably 1.5% by volume or less, relative to the total volume of the gas phase.

[0035] Specific examples of halogenated methanes containing a bromine atom or an iodine atom include (mono)iodomethane (CHI), diiodomethane (CHI), dibromomethane (CHBr), bromomethane (CHBr), dichloromethane (CHCl), chloroiodomethane (CHClI), dibromochloromethane (CHBrCl), tetraiodomethane (CI), carbon tetrabromide (CBr), bromotrichloromethane (CBrCl), dibromodichloromethane (CBrCl), tribromofluoromethane (CBrF), fluoroiodomethane (CHFI), difluorodiiodomethane (CFI), dibromodifluoromethane (CBrF), trifluoroiodomethane (CFI), and the like.

[0036] The composition may contain water in addition to the organic compound. The water content may be 200 ppm by mass or less, preferably 150 ppm by mass or less, more preferably 100 ppm by mass or less, and even more preferably 20 ppm by mass or less, based on the total mass of the composition.

[0037] <Manufacturing method> The main component, HCFO-1224yd, is obtained as an intermediate in the process of reducing CFO-1214ya with hydrogen in the presence of a catalyst (hydrogen reduction reaction) to obtain HFO-1234yf. The raw material CFO-1214ya can be produced, for example, by using HCFC-225ca as the raw material and subjecting it to a dehydrofluorination reaction with an alkaline aqueous solution such as an aqueous potassium hydroxide solution in the presence of a phase transfer catalyst such as tetrabutylammonium bromide, or by subjecting it to a dehydrofluorination reaction in a gas phase in the presence of a catalyst such as chromium, iron, copper, or activated carbon. The reaction mixture obtained by the hydrogen reduction reaction is distilled using a conventional distillation method or the extractive distillation method described in WO 2017 / 146190 to separate unreacted CFO-1214ya and HFO-1234yf from HCFO-1224yd, thereby obtaining a purified composition containing HCFO-1224yd at a high concentration. This purified composition may contain by-products produced in the hydrogen reduction reaction.

[0038] Compound A contained in the present composition may be one contained in a purified composition obtained by producing HCFO-1224yd, distilling and purifying it, or may be added separately, or may be a combination of these. The organic compounds contained in the composition and their content can be analyzed and identified using a GC-MS system.

[0039] <Application> The composition has good stability and can be used in applications known for hydrohaloolefins. Furthermore, the composition is unlikely to corrode metals even when it comes into contact with metals, making it suitable for applications in which it comes into contact with metals. Examples of uses of the present composition include working fluids, foaming agents, diluting solvents, cleaning agents, propellants, fire extinguishing agents, gaseous dielectrics, etching gases, and molten metal cover gases. The present composition may be used for one or more purposes.

[0040] Examples of working fluids using the present composition include refrigerants for refrigerators, refrigerants for air conditioners, working fluids for power generation systems (such as waste heat recovery power generation), working fluids for latent heat transport devices (such as heat pipes), and working fluids for heat cycles such as secondary cooling fluids.

[0041] Examples of foaming agents using the present composition include physical foaming agents used in the production of thermoplastic resin foams and thermosetting resin foams. Specific examples of thermoplastic resins contained in the thermoplastic resin foam include polycarbonate resin, polystyrene resin, polyphenylene ether resin, acrylonitrile-butadiene-styrene resin, polyolefin resin, polyvinyl chloride resin, (meth)acrylic resin, polyester resin, modified polyphenylene ether resin, polyacetal resin, polyetherimide resin, polyethersulfone resin, polyamide resin, polysulfone resin, polyetheretherketone resin, and polyetherketone resin. Specific examples of thermosetting resin foams include polyurethane foams, polyisocyanurate foams, and phenolic resin foams. Specific examples of polyurethane foams include rigid urethane foams, flexible urethane foams, semi-rigid urethane foams, and integral skin foams.

[0042] Examples of dilution solvents using the present composition include solvents for coating film-forming compositions containing functional components such as lubricants (silicone-based lubricants, fluorine-based lubricants, etc.), rust inhibitors (mineral oil, synthetic oil, etc.), moisture-proof coating agents for water-repellent treatment, and antifouling coating agents for antifouling treatment (fingerprint removal and adhesion prevention agents), solvents for diluting functional components such as insecticides, insect repellents, and preservatives, and dilution solvents for chemical processes (extraction solvents, polymerization solvents), etc. The dilution solvent can be used in the form of an aerosol, etc.

[0043] Examples of cleaning agents using the present composition include cleaning agents for degreasing, flux cleaning, precision cleaning, dry cleaning, pipe cleaning, glass cleaners, heat exchanger cleaners for refrigeration and air conditioning equipment, cleaning agents for removing hydrophobic substances such as oil stains, flux cleaning, precision cleaning, and dry cleaning, and cleaning agents for removing stains from clothing, etc. The cleaning agent can be used in the form of an aerosol, etc.

[0044] In cleaning methods using the present composition, the dirt to be removed by cleaning includes carbon, flux, processing oil, release agent, sebum, food oil, cosmetics, and other oils and fats attached to various objects, as well as dust attached via these. Examples of processing oils include cutting oil, quenching oil, rolling oil, lubricating oil, machine oil, press processing oil, punching oil, drawing oil, assembly oil, wire drawing oil, and brake fluid. Examples of cosmetics include nail polish and lipstick. Two or more of the above-mentioned dirt may be attached to various objects. Compared to conventional solvent compositions such as HFC and HFE, the present composition has superior solubility in these oils, and is therefore preferably used to clean dirt made of these oils.

[0045] Materials for articles to which the cleaning agent containing the present composition can be applied include metals, resins, rubbers, glass, ceramics, natural fibers, and synthetic fibers. The article may also be made of a composite material containing two or more of these materials. Examples of composite materials include laminates of metals and resins. In particular, the present composition can be used for articles containing rubber materials such as SBR or resin materials that are affected by HCFO-1224yd.

[0046] The propellant using the present composition may be mixed with a pressure booster and a spray agent as functional components. Specific examples of the pressure booster include compressed gas, and examples of the spray agent include insecticides, deodorants, lubricants, rust inhibitors, antistatic agents, extreme pressure agents, antifogging agents, penetrating agents, wetting agents, paints, detergents, cosmetics, topical medications, dyes, antifouling agents, water repellents, and oil repellents. The propellant can be used in the form of an aerosol, etc.

[0047] The gas dielectric using the composition may be mixed with a liquefied gas or compressed gas and used in electrical devices, such as circuit breakers, current interrupting equipment, gas-insulated power lines, gas-insulated transformers, gas-insulated substations, gas-insulated switchgears, gas-insulated disconnecting switches, and gas-insulated load break switches.

[0048] An example of the use of an etching gas containing the present composition is in the process of forming a circuit pattern for a semiconductor integrated circuit.

[0049] An example of the use of a molten metal cover gas using the present composition is a gas (protective atmosphere) that covers molten metal in a crucible to prevent oxidation and evaporation of the molten metal. [Example]

[0050] The present invention will be explained in more detail below using examples, but the present invention is not limited to these examples. <Evaluation method> [Stability test / metal corrosion resistance test] Prepare three metal pieces (20mm x 30mm, 2mm thick) made of SS400, Cu, and Al, one each. Three of the metal pieces are placed in a 200 mL stainless steel pressure vessel and sealed. The vessel is evacuated and filled with 60 g of the hydrohaloolefin composition to be tested. The sealed pressure-resistant container is then stored in a thermostatic chamber at 175°C for 14 days, and then allowed to stand until it cools to room temperature.

[0051] Prepare four absorption bottles, each filled with 100 mL of pure water, connected in series with a conduit. The absorption bottle connected to the pressure vessel is connected to a pressure vessel that has been cooled to room temperature, and the valve of the pressure vessel is gradually opened to introduce the gas in the pressure vessel into the water in the absorption bottle, thereby extracting the acid contained in the gas. After extraction, the water in the first and second absorption bottles, starting from the side closest to the pressure vessel, is combined, one drop of indicator (BTB: Bromothymol Blue) is added, and titration is performed using a 1 / 100N NaOH alkaline standard solution to obtain the measured value. The water in the third and fourth absorption bottles is combined and titrated in the same way to obtain a measurement blank. From these measured values and the measurement blank value, the acid content in the hydrohaloolefin composition being tested is calculated as an HCl-equivalent concentration. Based on the calculated acid content (HCl equivalent concentration), stability is evaluated according to the following criteria. A (Excellent): Acid content is less than 2 ppm. B (Good): Acid content is 2 ppm or more and less than 10 ppm.

[0052] After measuring the acid content, remove the three metal pieces from the pressure vessel and visually inspect their appearance. Compare their appearance with that of unused metal pieces and evaluate the metal corrosion resistance according to the following criteria. A (Excellent): All three metal pieces have the same luster as unused items, and none of them have rust. B (Good): There is one or more pieces of metal that have lost their luster, but no rust.

[0053] <Examples 1 to 5> HCFC-225ca was used as the raw material and mixed with an aqueous metal hydroxide solution in the presence of a phase transfer catalyst, followed by a dehydrofluorination reaction to obtain CFO-1214ya. The resulting CFO-1214ya was used as the raw material and contacted in the gas phase with hydrogen and nitrogen and a catalyst consisting of palladium supported on activated carbon to undergo a hydrogen reduction reaction, yielding a reaction liquid containing HFO-1234yf and HCFO-1224yd. The resulting reaction liquid was purified by distillation to obtain the hydrohaloolefin composition shown in Table 2. The composition of the obtained hydrohaloolefin composition was analyzed using a GC-MS system, and the results are shown in Table 2. In Table 2, "<0.001" means below the detection limit. The resulting hydrohaloolefin compositions were tested and evaluated for stability and metal corrosion resistance using the methods described above. The results are shown in Table 2.

[0054] [Table 2]

Claims

1. The main component is 1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd), and 1,1,1,3,3-pentafluoropropane (HFC-245fa), 1,1,1,3-tetrafluoropropane (HFC-254fb), 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb), 2,4,4,4-tetrafluoro-1-butene (HFO-1354yf), 2,3,3,3-tetrafluoropropene (HFO-1234yf), 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), 2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe), 1,1-dichloro-2,3,3,3-tetrafluoropropene (CFO-1214ya), 3-chloro-1,1,1,2,2,3-hexafluoropropane (HCFC-226ca), 1-chloro-1,1,2,3,3,3-hexafluoropropane (HCFC-226ea), and A hydrohaloolefin composition comprising compound A, which is one or more compounds selected from the group consisting of 2-chloro-1,1,1,3,3-pentafluoropropane (HCFC-235da), The compound A contains at least the HFC-254fb, the HCFC-244bb, the HFO-1354yf, and the HCFO-1224xe in an amount of 0.001 mass% or more, based on the total mass of the hydrohaloolefin composition; A hydrohaloolefin composition, wherein the content of said HCFO-1224yd is 96% by mass or more and the total content of said compound A is 2.0% by mass or less, relative to the total mass of said hydrohaloolefin composition.

2. The hydrohaloolefin composition according to claim 1, wherein the Z / E ratio, which represents the mass ratio of the Z isomer content to the E isomer content in the HCFO-1224yd, is 100 / 0 to 70 / 30.

3. The compound A contains HFC-245fa in an amount of 0.001 mass% or more relative to the total mass of the hydrohaloolefin composition, The hydrohaloolefin composition according to claim 1, wherein the content of HCFO-1224yd is 98.5% by mass or more and the total content of compound A is 0.8% by mass or less, relative to the total mass of the hydrohaloolefin composition.

4. The hydrohaloolefin composition according to claim 3, wherein the Z / E ratio, which represents the mass ratio of the Z isomer content to the E isomer content in said HCFO-1224yd, is 100 / 0 to 99.0 / 1.

0.

5. 10. The hydrohaloolefin composition of claim 1, which is for use as a working fluid.

6. The hydrohaloolefin composition according to claim 1, which is used as a blowing agent.

7. 10. The hydrohaloolefin composition of claim 1, which is for use as a diluent solvent.

8. The hydrohaloolefin composition of claim 1, which is used as a detergent.

9. 10. The hydrohaloolefin composition of claim 1, which is for use as a propellant.

10. The hydrohaloolefin composition according to claim 1, which is used as a fire extinguishing agent.

11. 10. The hydrohaloolefin composition of claim 1, which is for use as a gaseous dielectric.

12. The hydrohaloolefin composition according to claim 1, which is used as an etching gas.

13. 10. The hydrohaloolefin composition of claim 1 for use as a molten metal cover gas.

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