Hydrohaloolefin composition

Abstract

A hydrohaloolefin composition, whose main component is a hydrohaloolefin and also contains 1,1,2,3-tetrafluorobutane, and the content of the foregoing 1,1,2,3-tetrafluorobutane is 0.001 to 0.1% by mass relative to the total mass of the organic compound.

Description

Technical Field

[0001] The present disclosure relates to a hydrohaloolefin composition. Background Art

[0002] In order to prevent global warming and ozone layer depletion, hydrohaloolefins such as hydrofluoroolefins (HFO) and hydrochlorofluorolefins (HCFO) with a low global warming potential are expected as substitutes for chlorofluorocarbons.

[0003] Hydrohaloolefins sometimes decompose over time and cannot be said to have sufficient stability. If an acid is generated by decomposition, it may sometimes cause corrosion of metals.

[0004] Patent Document 1 describes an example in which the decomposition during storage is suppressed when a small amount of 1-chloro-2,2,3,3-tetrafluoropropane (HCFC-244ca) is added to 1-chloro-2,3,3-trifluoro-1-propene (HCFO-1233yd).

[0005] Patent Document 2 describes an example in which the decomposition during storage is suppressed when a small amount of water is added to a composition containing 2,3,3,3-tetrafluoropropene (HFO-1234yf) or 1,3,3,3-tetrafluoropropene (HFO-1234ze) and containing oxygen.

[0006] Prior Art Documents

[0007] Patent Documents

[0008] Patent Document 1: Japanese Unexamined Patent Application Publication No. 2020-172657

[0009] Patent Document 2: Japanese Patent No. 5962827 Summary of the Invention

[0010] Problems to be Solved by the Invention

[0011] In Patent Documents 1 and 2, HCFC-244ca or water is disclosed as a compound contributing to stability, and further technological enrichment is required.

[0012] An object of the present disclosure is to provide a hydrohaloolefin composition having good stability.

[0013] Means for Solving the Problems

[0014] The present disclosure includes the following aspects.

[0015] [1] A hydrohaloolefin composition, wherein the main component is a hydrohaloolefin, and further contains 1,1,2,3-tetrafluorobutane, and the content of the 1,1,2,3-tetrafluorobutane is 0.001 to 0.1% by mass based on the total amount of the organic compounds.

[0016] [2] The hydrohaloolefin composition according to [1], wherein the hydrohaloolefin contains 2,4,4,4-tetrafluoro-1-butene, and the total content of the foregoing 1,1,2,3-tetrafluorobutane and the foregoing 2,4,4,4-tetrafluoro-1-butene exceeds 0.001% by mass and is 0.4% by mass or less based on the total amount of the foregoing organic compounds.

[0017] [3] The hydrohaloolefin composition according to [1] or [2], wherein the main component is a hydrochlorofluoroolefin.

[0018] [4] The hydrohaloolefin composition according to [3], wherein the main component is 1-chloro-2,3,3,3-tetrafluoropropene.

[0019] [5] The hydrohaloolefin composition according to any one of [1] to [4], which is used as one or more selected from the group consisting of a working fluid, a foaming agent, a diluting solvent, a cleaning agent, a propellant, a fire extinguishing agent, a gas dielectric, an etching gas, and a molten metal covering gas.

[0020] [6] The hydrohaloolefin composition according to [5], which is in the form of an aerosol.

[0021] [7] The hydrohaloolefin composition according to [5], wherein the working fluid is a working fluid for a thermal cycle.

[0022] [8] The hydrohaloolefin composition according to [5], wherein the cleaning agent is a cleaning agent for removing at least one selected from the group consisting of carbon, grease, and dust attached thereby.

[0023] [9] The hydrohaloolefin composition according to [5], wherein the cleaning agent is a cleaning agent for an article formed of a metal, a resin, a rubber, a glass, a ceramic, a natural fiber, a synthetic fiber, or a composite material having two or more of them.

[0024]

[10] The hydrohaloolefin composition according to [5], wherein the propellant is one or more selected from the group consisting of a boosting agent and a spraying agent.

[0025]

[11] The hydrohaloolefin composition according to [5], wherein the gas dielectric contains one or more selected from the group consisting of a liquefied gas and a compressed gas.

[0026] Advantages of the Invention

[0027] According to the present disclosure, a hydrohaloolefin composition with good stability can be obtained. Detailed Description of the Invention

[0028] The definitions of the following terms apply throughout this specification and the claims.

[0029] Hydrohaloolefins are a general term for unsaturated hydrocarbon compounds having one or more hydrogen atoms and selected from the group consisting of fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0030] Organic compounds are compounds containing carbon atoms and are a general term for compounds other than carbon oxides and metal carbonates.

[0031] The main component of a composition means the one having the largest mass relative to the total mass of the composition.

[0032] Sometimes, the abbreviation or alias of a compound is noted in parentheses after the name of the compound. Sometimes, the abbreviation or alias is used instead of the compound name.

[0033] In unsaturated hydrocarbon compounds, depending on the position of the substituents bonded to the carbon atoms having double bonds, there exist Z-isomers (cis-isomers) and E-isomers (trans-isomers) as geometric isomers. For compounds having Z-isomers and E-isomers, when the compound name or the abbreviation of the compound is used without special specification, it means the Z-isomer or the E-isomer, or a mixture of the Z-isomer and the E-isomer in any ratio. When (Z) or (E) is attached after the compound name or the abbreviation of the compound, it represents the Z-isomer or the E-isomer of each compound.

[0034] The numerical range represented by "~" means the numerical range with the values before and after ~ as the lower limit value and the upper limit value. In the numerically ranged described stepwise, the upper limit value or the lower limit value described by one numerical range can be replaced by the upper limit value or the lower limit value of the numerical range described in other steps. In addition, in the numerical range, the upper limit value or the lower limit value of the numerical range can be replaced by the value shown in the examples.

[0035] (Meth)acrylic acid means acrylic acid or methacrylic acid.

[0036] <Hydrohaloolefin composition>

[0037] The hydrohaloolefin composition of the present disclosure (hereinafter also referred to as the present composition.) contains two or more organic compounds, and the main component is a hydrohaloolefin.

[0038] Relative to the total mass of the present composition, the content of the main component is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, particularly preferably 90% by mass or more, and most preferably 99% by mass or more.

[0039] [Hydrohaloolefin]

[0040] As hydrohaloolefins, hydrofluoroolefins (HFO), hydrochlorofluorocarbons (HCFO), and hydrochloroolefins (HCO) can be exemplified. The hydrohaloolefins can be used alone or in combination of two or more.

[0041] Specific examples of the hydrofluoroolefin (HFO) as the main component include 1,1,2-trifluoroethylene (HFO-1123), 1-fluoropropene (HFO-1261ze), 1,2-difluoropropene (HFO-1252ye), 1,3,3,3-tetrafluoropropene (HFO-1234ze), 1,1,2,3-tetrafluoropropene (HFO-1234yc), 2,3,3,3-tetrafluoropropene (HFO-1234yf), 1,2,3,3-tetrafluoropropene (HFO-1234ye), 1,1,3,3-tetrafluoropropene (HFO-1234zc), 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), 2,4,4,4-tetrafluoro-1-butene (HFO-1354yf), 1,1,1,2,4,4,5,5,5-nonafluoropentene (HFO-1429myz), 1,1,1,4,4,5,5,5-octafluoropent-2-ene (HFO-1438mzz), 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), and 1,2,3,3,3-pentafluoro-1-propene (HFO-1225ye).

[0042] Specific examples of the hydrochlorofluorocarbon (HCFO) as the main component include 1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd), 1-chloro-2,3,3-trifluoropropene (HCFO-1233yd), 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), 2-chloro-1,1,3-trifluoropropene (HCFO-1233xc), 2-chloro-1,3,3-trifluoropropene (HCFO-1233xe), 1-chloro-1,2,3-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), 1,2-dichloro-3,3,3-trifluoropropene (HCFO-1223xd), 2-chloro-1,1,3,3-tetrafluoropropene (HCFO-1224xc), 2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe), 1,1-dichloro-2-fluoroethylene (HCFO-1121a), 1,2-dichloro-1-fluoroethylene (HCFO-1121), 1-chloro-1-fluoroethylene (HCFO-1131a), 1-chloro-2-fluoroethylene (HCFO-1131), and 1-chloro-2,2-difluoroethylene (HCFO-1122).

[0043] Specific examples of the hydrochloroolefin (HCO) as the main component include vinyl chloride and 1,2-dichloroethylene.

[0044] The main component of this composition is preferably a hydrochlorofluorocarbon (HCFO), more preferably HCFO-1224yd.

[0045] HCFO-1224yd can be HCFO-1224yd(Z), can be HCFO-1224yd(E), or can be a mixture thereof. The Z / E ratio representing the mass ratio of the content of the Z isomer to the content of the E isomer in HCFO-1224yd can be 100 / 0 to 0 / 100, preferably 99.9 / 0.1 to 50 / 50, more preferably 99.9 / 0.1 to 70 / 30, and further preferably 99.9 / 0.1 to 99.0 / 1.0.

[0046] In addition to the hydrohaloolefin as the main component, this composition further contains 1,1,2,3-tetrafluorobutane (HFC-374pee).

[0047] The content of HFC-374pee is 0.001 to 0.1% by mass, preferably 0.001 to 0.05% by mass, more preferably 0.001 to 0.01% by mass, relative to the total mass of the organic compounds in the present composition. When within the above ranges, the stability of the present composition is excellent.

[0048] The hydrohaloolefin may contain 2,4,4,4-tetrafluoro-1-butene (HFO-1354yf). When HFO-1354yf is contained, the total content of HFC-374pee and HFO-1354yf is preferably more than 0.001% by mass and 0.4% by mass or less, more preferably 0.001 to 0.2% by mass, further preferably 0.01 to 0.1% by mass, relative to the total mass of the organic compounds in the present composition. When within the above ranges, the stability of the present composition is excellent.

[0049] It should be noted that when the present composition contains HFO-1354yf, the main component is a hydrohaloolefin other than HFO-1354yf.

[0050] The present composition may contain one or more hydrohaloolefins (which may contain HFO-1354yf) as the main component, and other organic compounds other than HFC-374pee.

[0051] Examples of other organic compounds include chlorofluoroolfins (CFO), fluoroolefins, chloroolefins, olefins, hydrofluorocarbons (HFC) other than HFC-374pee, hydrochlorofluorocarbons (HCFC), chlorofluorocarbons (CFC), chlorocarbons, fluorocarbons (FC), hydrocarbons (HC), hydrofluoroethers (HFE), chlorofluoroacetylenes, alcohols, ethers, ketones, organic acids, and saturated hydrocarbons.

[0052] Furthermore, it may also contain one or more halogenated methanes containing one or more selected from the group consisting of bromine atoms and iodine atoms, as needed.

[0053] Specific examples of chlorofluoroolfins (CFO) include 1,1-dichloro-2,3,3,3-tetrafluoropropene (CFO-1214ya), 1,1,2-trichloro-2-fluoroethylene, 1,1,2-trifluoro-2-chloroethylene (HCFO-1113), and 2-chloro-1,1,3,3,3-pentafluoro-1-propene (CFO-1215xc).

[0054] Specific examples of fluoroolefins include hexafluoropropene (FO-1216), and octafluoro-2-butene (FO-1318my).

[0055] Specific examples of chloroolefins include tetrachloroethylene.

[0056] As specific examples of the olefin, ethylene and propylene can be cited.

[0057] As specific examples of hydrofluorocarbons (HFCs) other than HFC-374pee, 1,1,1,3,3-pentafluoropropane (HFC-245fa), 1,1,1,2,2-pentafluoropropane (HFC-245cb), 1,1,2,2,3-pentafluoropropane (HFC-245ca), 1,1,1,2,3-pentafluoropropane (HFC-245eb), 1,1,1,2,3,3,3-pentafluoropropane (HFC-227ea), 1,1,1,2-tetrafluoropropane (HFC-254eb), 1,1,1,3-tetrafluoropropane (HFC-254fb), 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-281ea), 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb), 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) can be cited.

[0058] As specific examples of hydrochlorofluorocarbons (HCCs), chloroform, 1,1,1,2,3-pentachloropropane (HCC-240db), and 2-chloropropane can be cited.

[0059] As specific examples of hydrochlorofluorocarbons (HCFCs), 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-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), 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb), 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) can be cited.

[0060] As specific examples of chlorofluorocarbons (CFCs), trichlorofluoromethane (CFC-11), dichlorodifluoromethane (CFC-12), chlorotrifluoromethane (CFC-13), trichlorotrifluoroethane (CFC-113), 1,1,1-trichloro-2,2,2-trifluoroethane (CFC-113a), 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) can be cited.

[0061] As specific examples of chlorocarbons, dichloromethane (methylene chloride) and trichloroethane can be cited.

[0062] As specific examples of fluorocarbons (FCs), 1,1,1,2,2,2-hexafluoroethane (FC-116), octafluoropropane (FC-218), and 1,1,1,2,2,3,3-pentafluoropropane (FC-227ca) can be cited.

[0063] As specific examples of hydrocarbons (HCs), methane, ethane, propane, n-butane, isobutane, n-pentane, isopentane, neopentane, cyclopentane, n-hexane, isohexane, and heptane can be cited.

[0064] As specific examples of hydrofluoroethers (HFEs), 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, CF3-O-CH2-CHF2, CHF2-O-CH2-CF3, CHF2-CF2-O-CH2F, CHF2-O-CF2-CH3, CHF2-CF2-O-CH3, CH2F-O-CHF-CH2F, CHF2-CHF-O-CH2F, CF3-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 can be cited.

[0065] As a specific example of a chlorofluoroacetylene, 1-chloro-3,3,3-trifluoro-1-propyne (CF3-C≡CCl) can be cited.

[0066] As specific examples of alcohols, methanol, ethanol, propanol, and isopropanol can be cited.

[0067] As specific examples of ethers, 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 can be cited.

[0068] As specific examples of ketones, ketone, methyl ethyl ketone, methyl isobutyl ketone, and perfluoroethyl isopropyl ketone can be cited.

[0069] As specific examples of the organic acid, methyl formate, ethyl formate, and formic acid can be cited.

[0070] As specific examples of the saturated hydrocarbon, methane, ethane, propane, butane, isobutane, pentane, isopentane, cyclopentane, and hexane can be cited.

[0071] As specific examples of the halogenated methane containing one or more selected from the group consisting of a bromine atom and an iodine atom, (mono)iodomethane (CH3I), diiodomethane (CH2I2), dibromomethane (CH2Br2), bromomethane (CH3Br), dichloromethane (CH2Cl2), chloroiodomethane (CH2ClI), dibromochloromethane (CHBr2Cl), tetraiodomethane (CI4), carbon tetrabromide (CBr4), bromotrichloromethane (CBrCl3), dibromodichloromethane (CBr2Cl2), tribromofluoromethane (CBr3F), fluoroiodomethane (CHFI2), difluoroiodomethane (CF2I2), dibromodifluoromethane (CBr2F2), and trifluoroiodomethane (CF3I) can be cited.

[0072] Relative to the total mass of the organic compounds in the present composition, the content of other organic compounds is preferably 1.5% by mass or less, more preferably 1.0% by mass or less, and further preferably 0.5% by mass or less.

[0073] The present composition may further contain an inert gas in addition to the organic compounds. As specific examples of the inert gas, carbon dioxide, nitrogen, oxygen, air (nitrogen: about 80% by volume, oxygen: about 20% by volume), argon, and helium can be cited.

[0074] Relative to the total volume of the gas phase when the present composition is filled into a closed container, the inert gas may be 20% by volume or less, preferably 15% by volume or less, more preferably 10% by volume or less, further preferably 5% by volume or less, and particularly preferably 1.5% by volume or less.

[0075] The present composition may further contain water in addition to the organic compounds. Relative to the total amount of the organic compounds in the present composition, the content of water may be 200 mass ppm or less, preferably 150 mass ppm or less, more preferably 100 mass ppm, and further preferably 20 mass ppm.

[0076] <Manufacturing method>

[0077] The hydrohaloolefin contained in the present composition can be produced by a known production method.

[0078] For example, HCFO-1224yd is obtained as an intermediate in the step of reducing CFO-1214ya with hydrogen (hydrogen reduction reaction) in the presence of a catalyst to obtain HFO-1234yf.

[0079] CFO-1214ya as a raw material can be produced, for example, by subjecting HCFC-225ca as a raw material to a dehydrofluorination reaction in an aqueous alkali 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 reaction in the presence of a catalyst such as chromium, iron, copper, or activated carbon.

[0080] The reaction solution obtained by the aforementioned hydrogen reduction reaction is distilled using a conventional distillation method or the extractive distillation method described in International Publication No. 2017 / 146190, whereby unreacted CFO-1214ya and HFO-1234yf are separated from HCFO-1224yd, and a purified composition containing HCFO-1224yd at a high concentration is obtained. This purified composition may contain by-products generated in the aforementioned hydrogen reduction reaction.

[0081] HFC-374pee contained in this composition may be contained in a purified composition obtained by producing and purifying a hydrohaloolefin, may be added additionally, or may be a combination thereof.

[0082] HFO-1354yf that may be contained in this composition may be contained in a purified composition of a hydrohaloolefin, may be added additionally, or may be a combination thereof.

[0083] The types and contents of the organic compounds contained in this composition can be analyzed and identified using a GC-MS system.

[0084] As shown in the examples described later, the decomposition of the hydrohaloolefin is suppressed and the stability is improved by the composition mainly composed of a hydrohaloolefin containing HFC-374pee. The reason is not clear yet, but it is considered as follows.

[0085] HFC-374pee has the properties of an HFC, and although not necessarily clear, it is presumed to have a free radical scavenging action. By this action, it functions as a stabilizer to suppress the decomposition of hydrohaloolefins such as HCFO-1224yd and stabilize them.

[0086] <Use>

[0087] This composition has good stability and can be used for known uses as a hydrohaloolefin. In addition, this composition is not likely to corrode metals even when in contact with metals, and can be applied to uses in contact with metals.

[0088] Examples of the uses of the present composition include working fluids, foaming agents, diluting solvents, cleaning agents, propellants, fire extinguishing agents, gas dielectrics, etching gases, and molten metal covering gases. The uses of the present composition may be one type or two or more types. The present composition can be used in the form of an aerosol.

[0089] Examples of the working fluid using the present composition include cooling media for refrigerators, cooling media for air-conditioning machines, working fluids for power generation systems (such as waste heat recovery power generation), working fluids for latent heat transfer devices (such as heat pipes), and working fluids for heat cycles such as secondary cooling media.

[0090] Examples of the foaming agent using the present composition include physical foaming agents used in the production of thermoplastic resin foams and thermosetting resin foams.

[0091] Specific examples of the thermoplastic resin 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.

[0092] Specific examples of the thermosetting resin foam include polyurethane foam, polyisocyanurate foam, and phenolic resin foam.

[0093] Specific examples of the polyurethane foam include rigid urethane foam, flexible urethane foam, semi-rigid urethane foam, and integral skin foam.

[0094] Examples of the diluting solvent using the present composition include solvents for coating composition formation containing functional components such as lubricants (silicone-based lubricants, fluorine-based lubricants, etc.), rust preventives (mineral oils, synthetic oils, etc.), moisture-proof coating agents for performing water repellent treatment, antifouling coating agents for performing antifouling treatment (fingerprint removal adhesion preventives), etc., solvents for diluting functional components such as insecticides, insect repellents, preservatives, etc., and diluting solvents for chemical processes (extraction solvents, polymerization solvents, etc.). The diluting solvent can be used in the form of an aerosol or the like.

[0095] Examples of the cleaning agent using the present composition include degreasing cleaning, flux cleaning, precision cleaning, dry cleaning agents, pipe cleaning, glass cleaners, heat exchanger cleaners for refrigeration and air-conditioning machines, oil stain cleaning, flux cleaning, precision cleaning, dry cleaning, etc. for removing hydrophobic substances, and cleaning agents for stain removal cleaning of clothing, etc. The cleaning agent can be used in the form of an aerosol or the like.

[0096] In the cleaning method of the cleaning agent using this composition, as the stains to be removed by cleaning, there can be cited carbon, grease, and dust adhering to various objects to be cleaned and adhering by means of them. As the grease, there can be cited flux, processing oil, mold release agent, sebum, food oil, and cosmetics. As the processing oil, there can be cited cutting oil, quenching oil, rolling oil, lubricating oil, machine oil, pressure processing oil, punching oil, drawing oil, assembly oil, wire drawing oil, brake fluid, etc. As the cosmetics, there can be cited nail polish, lipstick, etc. Two or more of the above-mentioned stains can adhere to various objects to be cleaned. Compared with HFC, HFE, etc. which are conventional solvent compositions, this solvent composition of the present disclosure is preferably used in the cleaning of stains formed by these oils in terms of excellent solubility in these oils.

[0097] As the materials of the articles to which the cleaning agent using this composition can be applied, there can be cited metals, resins, rubbers, glasses, ceramics, natural fibers, and synthetic fibers. In addition, as the articles, there can be articles containing composite materials having two or more of these materials. As the composite materials, there can be cited laminates of metals and resins, etc. In particular, this solvent composition of the present disclosure can also be used for articles containing rubber materials such as SBR and resin materials affected by HCFO-1224yd.

[0098] The propellant using this composition can be mixed with one or more selected from the group consisting of pressure boosters and spray agents as functional components. Specifically, there can be exemplified compressed gas as a pressure booster, and pesticides, deodorants, lubricants, rust preventives, antistatic agents, extreme pressure agents, antifogging agents, penetrants, wetting agents, coatings, cleaning agents, cosmetics, external medications, dyes, antifouling agents, water repellents, and oil repellents as spray agents. The propellant can be used in the form of an aerosol, etc.

[0099] The gas dielectric using this composition can be mixed with one or more selected from the group consisting of liquefied gases and compressed gases and used in electrical devices. As specific examples of electrical devices, there can be exemplified circuit breakers, current interruption devices, gas-insulated transmission lines, gas-insulated transformers, gas-insulated substations, gas-insulated switchgear, gas-insulated circuit breakers, and gas-insulated load break switches.

[0100] As an example of the use of the etching gas using this composition, there can be exemplified the process of forming a circuit pattern of a semiconductor integrated circuit.

[0101] As an example of the use of the molten metal covering gas using this composition, there can be exemplified a gas (protective atmosphere) that prevents oxidation and evaporation of the molten metal in the crucible and covers the molten metal.

[0102] Examples

[0103] The embodiments of the present disclosure will be described in more detail below using examples, but the embodiments of the present disclosure are not limited to these examples.

[0104] <Evaluation method>

[0105] [Stability test · Metal corrosion resistance test]

[0106] Prepare 1 sheet each of metal sheets made of SS400, Cu, and Al (length of one side: 20 mm × 30 mm, thickness: 2 mm), for a total of 3 sheets.

[0107] Put the 3 aforementioned metal sheets into a stainless steel pressure-resistant container with a capacity of 200 mL and seal it. Perform vacuum evacuation and fill 60 g of the hydrogen halide olefin composition to be tested.

[0108] Next, keep the sealed pressure-resistant container in a constant temperature bath at 175°C for 14 days, and then let it stand until it reaches room temperature (25°C).

[0109] Prepare a device in which 100 mL of pure water is placed in each of 4 absorption bottles and connected in series with a conduit. Connect the aforementioned device with the absorption bottles to the pressure-resistant container at room temperature (25°C), slowly open the valve of the pressure-resistant container, introduce the gas in the pressure-resistant container into the water in the absorption bottles, and extract the acid components contained in the aforementioned gas.

[0110] For the water in the absorption bottles after extraction, in the case where the first and second absorption bottles are combined starting from the side close to the pressure-resistant container, add 1 drop of an indicator (BTB: bromothymol blue), and perform titration using a 1 / 100N NaOH alkali standard solution as the measured value. In addition, combine the water in the third and fourth absorption bottles and perform titration in the same manner as a measurement blank. Based on these measured values and the value of the measurement blank, calculate the acid components contained in the hydrogen halide olefin composition to be tested in the form of HCl conversion concentration.

[0111] Based on the value of the calculated acid components (HCl conversion concentration), evaluate the stability according to the following criteria.

[0112] S (excellent): The acid components are less than 1 mass ppm.

[0113] A (good): The acid components are 1 mass ppm or more and less than 5 mass ppm.

[0114] B (slightly poor): The acid components are 5 mass ppm or more.

[0115] After measuring the acid components, take out the 3 metal sheets from the pressure-resistant container and observe the appearance visually. Compare the appearance with each of the unused metal sheets and evaluate the metal corrosion resistance according to the following criteria.

[0116] S (Excellent): All three metal sheets have the same luster as unused products, and there is no rusty metal sheet.

[0117] A (Good): There is one or more metal sheets that have lost their luster, and there is no rusty metal sheet.

[0118] B (Slightly Poor): There is one or more metal sheets with slightly rusty surfaces, but there is no metal sheet with rust covering the entire surface.

[0119] Example 1 is a comparative example, and Examples 2 to 5 are examples.

[0120] <Examples 1 - 5>

[0121] Using HCFC-225ca as a raw material, it is mixed with an aqueous solution of metal hydroxide in the presence of a phase transfer catalyst, and dehydrofluorination reaction is carried out to obtain CFO-1214ya. Using the obtained CFO-1214ya as a raw material, hydrogen and nitrogen are brought into contact with a catalyst having palladium supported on activated carbon or metal oxide in the gas phase, and thus a hydrogen reduction reaction is carried out to obtain a reaction solution containing HFO-1234yf and HCFO-1224yd. The obtained reaction solution is distilled and purified to obtain a purified composition containing HCFO-1224yd at a high concentration. In Example 1, the obtained purified composition is used as a hydrohaloolefin composition. In Examples 2 to 5, HFC-374pee is added to the obtained purified composition to obtain the hydrohaloolefin compositions shown in Table 1.

[0122] The composition of the obtained hydrohaloolefin composition is analyzed using a GC-MS system. The contents (unit: mass%) of HCFO-1224yd (Z), HCFO-1224yd (E), HFC-374pee, HFO-1354yf, and other organic compounds relative to the total mass of the organic compounds in the hydrohaloolefin composition are shown in Table 1. "<0.001" in Table 1 means below the detection limit.

[0123] Taking the obtained hydrohaloolefin composition as the test object, its stability and metal corrosion resistance are evaluated by the above method. The results are shown in Table 1.

[0124] [Table 1]

[0125]

[0126] The entire disclosure of Japanese Patent Application No. 2020-212127 is incorporated herein by reference in its entirety.

[0127] All documents, patent applications, and technical standards described in this specification are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard were specifically and separately recited.

Claims

1. A hydrohaloolefin composition, whose main component is 1-chloro-2,3,3,3-tetrafluoropropene, further contains 1,1,2,3-tetrafluorobutane, and the content of the 1,1,2,3-tetrafluorobutane is 0.001 to 0.1% by mass relative to the total amount of the organic compounds.

2. The hydrohaloolefin composition according to claim 1, wherein, The hydrohaloolefin composition contains 2,4,4,4-tetrafluoro-1-butene, and the total content of the 1,1,2,3-tetrafluorobutane and the 2,4,4,4-tetrafluoro-1-butene exceeds 0.001% by mass and is 0.4% by mass or less relative to the total amount of the organic compounds.

3. The hydrohaloolefin composition according to claim 1, and its use is one or more selected from the group consisting of working fluids, blowing agents, diluting solvents, cleaning agents, propellants, fire extinguishing agents, gas dielectrics, etching gases, and molten metal covering gases.

4. The hydrohaloolefin composition according to claim 3, and it is in the form of an aerosol.

5. The hydrohaloolefin composition according to claim 3, wherein The working fluid is a working fluid for thermal cycling.

6. The hydrohaloolefin composition according to claim 3, wherein, The cleaning agent is a cleaning agent for removing at least one selected from the group consisting of carbon, grease, and dust adhering thereto.

7. The hydrohaloolefin composition according to claim 3, wherein The cleaning agent is a cleaning agent for articles formed of metal, resin, rubber, glass, ceramics, natural fiber, synthetic fiber, or a composite material having two or more of them.

8. The hydrohaloolefin composition according to claim 3, wherein, The propellant is one or more selected from the group consisting of boosting agents and spraying agents.

9. The hydrohaloolefin composition according to claim 3, wherein The gas dielectric contains one or more selected from the group consisting of liquefied gases and compressed gases.

Images