Hydrohaloolefin composition

Abstract

A hydrohaloolefin composition comprising: a hydrohaloolefin as a main component; and 1,1,2,3-tetrafluorobutane, wherein the contained amount of the 1,1,2,3-tetrafluorobutane is 0.001-0.1 mass% with respect to the total mass of organic compounds.

Description

Technical Field

[0001] The present disclosure relates to hydrohaloolefin compositions.

Background Art

[0002] In order to prevent global warming and ozone layer depletion, hydrohaloolefins such as hydrofluoroolefins (HFOs) and hydrochlorofluoroolefins (HCFOs) with a low global warming potential are expected as alternatives to chlorofluorocarbons. Hydrohaloolefins may decompose over time and their stability is not sufficient. The generation of acid due to decomposition may cause corrosion of metals in some cases. Patent Document 1 describes an example in which adding a small amount of 1-chloro-2,2,3,3-tetrafluoropropane (HCFC-244ca) to 1-chloro-2,3,3-trifluoro-1-propene (HCFO-1233yd) suppresses decomposition during storage. Patent Document 2 describes an example in which adding a small amount of water to a composition containing 2,3,3,3-tetrafluoropropene (HFO-1234yf) or 1,3,3,3-tetrafluoropropene (HFO-1234ze) and oxygen suppresses decomposition during storage.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0004] In Patent Documents 1 and 2, HCFC-244ca or water is disclosed as a compound contributing to stability, but further enrichment of technology is required. The present disclosure aims to provide a hydrohaloolefin composition having good stability.

Means for Solving the Problems

[0005] The present disclosure includes the following aspects. [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. [2] The hydrohaloolefin composition according to [1], wherein the hydrohaloolefin 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 is more than 0.001% to 0.4% by mass based on the total amount of the organic compounds. [3] The hydrohaloolefin composition according to [1] or [2], wherein the main component is a hydrochlorofluorolefin. [4] The hydrohaloolefin composition according to [3], wherein the main component is 1-chloro-2,3,3,3-tetrafluoropropene. [5] The hydrohaloolefin composition according to any one of [1] to [4], wherein the use is one or more selected from the group consisting of a working fluid, a blowing 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. [6] The hydrohaloolefin composition according to [5], which is in the form of an aerosol. [7] The hydrohaloolefin composition according to [5], wherein the working fluid is a working fluid for a thermal cycle. [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 adhering thereto. [9] The hydrohaloolefin composition according to [5], wherein the cleaning agent is a cleaning agent for an article made of a composite material having metal, resin, rubber, glass, ceramics, natural fiber, synthetic fiber, or two or more of these materials.

[10] The hydrohaloolefin composition according to [5], wherein the propellant contains at least one selected from the group consisting of a pressure booster and a spraying agent.

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

Advantages of the Invention

[0006] According to the present disclosure, a hydrohaloolefin composition having good stability can be obtained.

Modes for Carrying Out the Invention

[0007] The following definitions of terms apply throughout this specification and the claims. Hydrohaloolefin is a general term for unsaturated hydrocarbon compounds containing a hydrogen atom and at least one selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Organic compound is a general term for compounds containing a carbon atom, excluding carbon oxides and metal carbonates. The main component of a composition means that the content mass is the largest with respect to the total mass of the composition. The abbreviation or alias of a compound may be indicated in parentheses after the name of the compound. The abbreviation or alias may be used instead of the compound name. In an unsaturated hydrocarbon compound, depending on the position of the substituent bonded to the carbon having a double bond, there are geometric isomers, the Z-isomer (cis-isomer) and the E-isomer (trans-isomer). For a compound in which the Z-isomer and the E-isomer exist, when using the compound name or the abbreviation of the compound without particular notice, 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 indicates the Z-isomer or the E-isomer of each compound. The numerical range represented by "~" means a numerical range with the numerical values before and after "~" as the lower limit value and the upper limit value. In a numerically described range in steps, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of another numerically described range in steps. Also, in a numerical range, the upper limit value or the lower limit value of that numerical range may be replaced with the value shown in the examples. (Meth)acrylic means acrylic or methacrylic.

[0008] <Hydrohaloolefin composition> The hydrohaloolefin composition of the present disclosure (hereinafter also referred to as "this composition") contains two or more organic compounds, and the main component is a hydrohaloolefin. 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 extremely preferably 99% by mass or more with respect to the total mass of this composition.

[0009] [Hydrohaloolefin] Examples of the hydrohaloolefin include hydrofluoroolefin (HFO), hydrochlorofluorolefin (HCFO), and hydrochloroolefin (HCO). The hydrohaloolefin may be used alone or in combination of two or more.

[0010] Specific examples of hydrofluoroolefins (HFOs) as main components 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-octafluoropenta-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).

[0011] Specific examples of hydrochlorofluorolefins (HCFOs) 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).

[0012] Specific examples of hydrochloroolefins (HCOs) as the main component include chloroethylene and 1,2-dichloroethylene.

[0013] The main component of this composition is preferably a hydrochlorofluorolefin (HCFO), and more preferably 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.

[0014] In addition to the hydrohaloolefin which is the main component, this composition contains 1,1,2,3-tetrafluorobutane (HFC-374pee). With respect to the total mass of the organic compounds in this composition, the content of HFC-374pee is 0.001 to 0.1% by mass, preferably 0.001 to 0.05% by mass, and more preferably 0.001 to 0.01% by mass. When within the above range, the composition has excellent stability. The hydrohaloolefin may contain 2,4,4,4-tetrafluoro-1-butene (HFO-1354yf). When HFO-1354yf is contained, with respect to the total mass of the organic compounds in this composition, the total content of HFC-374pee and HFO-1354yf is preferably more than 0.001% to 0.4% by mass, more preferably 0.001 to 0.2% by mass, and even more preferably 0.01 to 0.1% by mass. When within the above range, the composition has excellent stability. In addition, when this composition contains HFO-1354yf, the main component is a hydrohaloolefin other than HFO-1354yf.

[0015] This composition may contain one or more other organic compounds in addition to the hydrohaloolefin (which may contain HFO-1354yf) as the main component and HFC-374pee. Examples of other organic compounds include chlorofluoroolfins (CFOs), fluoroolfins, chloroolefins, olefins, hydrofluorocarbons (HFCs) excluding HFC-374pee, hydrochlorocarbons (HCCs), hydrochlorofluorocarbons (HCFCs), chlorofluorocarbons (CFCs), chlorocarbons, fluorocarbons (FCs), hydrocarbons (HCs), hydrofluoroethers (HFEs), chlorofluoroalkynes, alcohols, ethers, ketones, organic acids, and saturated hydrocarbons. Furthermore, halogenated methane containing one or more selected from the group consisting of bromine atoms and iodine atoms may be included as needed.

[0016] Specific examples of chlorofluoroolfins (CFOs) 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).

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

[0018] Specific examples of chloroolefins include tetrachloroethylene.

[0019] Specific examples of olefins include ethylene and propylene.

[0020] Specific examples of hydrofluorocarbons (HFCs) excluding HFC-374pee include 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-heptafluoropropane (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).

[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-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).

[0023] Specific examples of chlorofluorocarbons (CFCs) include 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).

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

[0025] Specific examples of fluorocarbons (FCs) 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 (HCs) include methane, ethane, propane, n-butane, isobutane, n-pentane, isopentane, neopentane, cyclopentane, n-hexane, isohexane, and heptane.

[0027] Specific examples of hydrofluoroethers (HFE) 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, 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.

[0028] Specific examples of chlorofluoroalkynes include 1-chloro-3,3,3-trifluoro-1-propyne (CF3-C≡CCl).

[0029] Specific examples of alcohols include methanol, ethanol, propanol, and isopropanol.

[0030] 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.

[0031] Specific examples of ketones include ketone, methyl ethyl ketone, methyl isobutyl ketone, and perfluoroethyl isopropyl ketone.

[0032] Specific examples of the organic acid include methyl formate, ethyl formate, and formic acid.

[0033] Specific examples of the saturated hydrocarbon include methane, ethane, propane, butane, isobutane, pentane, isopentane, cyclopentane, and hexane.

[0034] Specific examples of the halogenated methane containing one or more selected from the group consisting of a bromine atom and an iodine atom include (mono)iodomethane (CH3I), diiodomethane (CH2I2), dibromomethane (CH2Br2), bromomethane (CH3Br), dichloromethane (CH2Cl2), chloroiodomethane (CH2ClI), dibromochloromethane (CHBr2Cl), carbon tetraiodide (CI4), carbon tetrabromide (CBr4), bromotrichloromethane (CBrCl3), dibromodichloromethane (CBr2Cl2), tribromofluoromethane (CBr3F), fluorodiiodomethane (CHFI2), difluorodiiodomethane (CF2I2), dibromodifluoromethane (CBr2F2), and trifluoroiodomethane (CF3I).

[0035] With respect 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 still more preferably 0.5% by mass or less.

[0036] The present composition may contain an inert gas in addition to the organic compounds. Specific examples of the inert gas include carbon dioxide, nitrogen, oxygen, air (nitrogen: about 80% by volume, oxygen: about 20% by volume), argon, and helium. With respect to the total volume of the gas phase part when the present composition is filled in a sealed container, the inert gas may be 20% by volume or less, preferably 15% by volume or less, more preferably 10% by volume or less, still more preferably 5% by volume or less, and particularly preferably 1.5% by volume or less.

[0037] In addition to organic compounds, the composition may contain water. With respect to the total amount of organic compounds in the composition, the water content may be 200 mass ppm or less, preferably 150 mass ppm or less, more preferably 100 mass ppm, and even more preferably 20 mass ppm.

[0038] <Manufacturing method> The hydrohaloolefin contained in the composition can be produced by known production methods. 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. The raw material CFO-1214ya can be produced, for example, by using HCFC-225ca as a raw material and subjecting it to a dehydrofluorination reaction with 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. The reaction solution obtained from the hydrogen reduction reaction is distilled using a normal distillation method or the extractive distillation method described in International Publication No. 2017 / 146190 to separate unreacted CFO-1214ya and HFO-1234yf 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 hydrogen reduction reaction. HFC-374pee contained in the composition may be contained in a purified composition obtained by producing and purifying a hydrohaloolefin, may be added separately, or may be a combination of these. HFO-1354yf, which may be contained in the composition, may be contained in a purified composition of a hydrohaloolefin, may be added separately, or may be a combination of these. The types and contents of the organic compounds contained in the composition can be analyzed and identified using a GC-MS system.

[0039] As shown in the examples described below, when a composition mainly composed of hydrohaloolefins contains HFC-374pee, the decomposition of the hydrohaloolefins is suppressed and the stability is improved. The reason is not clear, but it is considered as follows. HFC-374pee has properties as an HFC and is presumed to have an action of capturing radicals, although it is not always clear. It is considered that due to this action, it exhibits a function as a stabilizer that suppresses and stabilizes the decomposition of hydrohaloolefins such as HCFO-1224yd.

[0040] <Use> This composition has good stability and can be used in applications known as uses of hydrohaloolefins. In addition, this composition is less likely to corrode metals even when in contact with them, and can be applied to uses in contact with metals. Examples of the uses of this composition include working fluids, blowing agents, diluting solvents, cleaning agents, propellants, fire extinguishing agents, gas dielectrics, etching gases, and molten metal covering gases. The use of this composition may be one type or two or more types. This composition may be used in the form of an aerosol or the like.

[0041] Examples of the working fluid using this composition include refrigerants for refrigerators, refrigerants for air conditioning equipment, 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 media.

[0042] Examples of the blowing agent using this composition include physical blowing agents used in the production of thermoplastic resin foams and thermosetting resin foams. 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. Specific examples of the thermosetting resin foam include polyurethane foam, polyisocyanurate foam, and phenolic resin foam. Specific examples of the polyurethane foam include rigid urethane foam, flexible urethane foam, semi-rigid urethane foam, and integral skin foam.

[0043] Examples of the diluting solvent using this composition include solvents for forming a coating film 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 water-repellent treatment, antifouling coating agents for antifouling treatment (fingerprint removal and adhesion prevention agents, etc.), solvents for diluting functional components such as insecticides, insect repellents, and preservatives, 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.

[0044] Examples of the cleaning agent using this composition include degreasing cleaning, flux cleaning, precision cleaning, dry cleaning agents, pipe cleaning, glass cleaners, heat exchanger cleaners for refrigeration and air conditioning equipment, oil stain cleaning, flux cleaning, precision cleaning, cleaning for removing hydrophobic substances such as dry cleaning, and cleaning agents for stain removal cleaning of clothes and the like. The cleaning agent can be used in the form of an aerosol or the like.

[0045] In the method for cleaning a cleaning agent using this composition, examples of the dirt to be removed by cleaning include carbon, oil and fat, and dust adhering through these, which adhere to various objects to be cleaned. Examples of the oil and fat include flux, processing oil, release agent, sebum, food oil, and cosmetics. Examples of the processing oil include cutting oil, quenching oil, rolling oil, lubricating oil, machine oil, press working oil, punching oil, drawing oil, assembly oil, wire drawing oil, brake fluid, etc. Examples of the cosmetics include nail polish, lipstick, etc. Two or more of the above-mentioned dirt may adhere to various objects to be cleaned. Since the solvent composition of the present disclosure is superior in solubility to these oils compared to conventional solvent compositions such as HFC and HFE, it is preferably used for cleaning dirt composed of these oils.

[0046] Examples of the materials of the articles to which the cleaning agent using this composition can be applied include metal, resin, rubber, glass, ceramics, natural fiber, and synthetic fiber. Also, the article may be an article made of a composite material having two or more of these materials. Examples of the composite material include a laminate of metal and resin. In particular, the solvent composition of the present disclosure can also be used for articles containing rubber materials and resin materials such as SBR that are affected by HCFO-1224yd.

[0047] The propellant using this composition may be mixed with one or more selected from the group consisting of a pressure booster and a spraying agent as functional components. Specifically, examples of the pressure booster include compressed gas, and examples of the spraying agent include insecticide, deodorant, lubricant, rust preventive, antistatic agent, extreme pressure agent, antifogging agent, penetrant, wetting agent, paint, cleaning agent, cosmetic, external medicine, dye, antifouling agent, water repellent, and oil repellent. The propellant can be used in the form of an aerosol.

[0048] The gas dielectric using this composition may be mixed with one or more selected from the group consisting of liquefied gas and compressed gas and used in an electrical device. Specific examples of the electrical device include circuit breaker, current interruption equipment, gas insulated transmission line, gas insulated transformer, gas insulated substation, gas insulated switchgear, gas insulated circuit breaker, and gas insulated load switch.

[0049] As an example of the use of the etching gas using this composition, a process of forming a circuit pattern of a semiconductor integrated circuit can be exemplified.

[0050] As an example of the use of the molten metal covering gas using this composition, a gas (protective atmosphere) for covering the molten metal can be exemplified in order to prevent oxidation and evaporation of the metal melted in the crucible.

Examples

[0051] Hereinafter, the embodiments of the present disclosure will be described in more detail using examples, but the embodiments of the present disclosure are not limited to these examples. <Evaluation method> [Stability test · Metal corrosion resistance test] Prepare one metal piece each made of SS400, Cu, and Al (length of one side 20 mm × 30 mm, thickness 2 mm), for a total of 3 pieces. Put the 3 metal pieces into a stainless steel pressure-resistant container with a capacity of 200 mL and seal it. Exhaust the air to vacuum and fill it with 60 g of the hydrohaloolefin composition to be tested. Next, the sealed pressure-resistant container is stored in a constant temperature bath at 175 °C for 14 days, and then left to stand until it reaches room temperature (25 °C).

[0052] Prepare 4 absorption bottles, each filled with 100 mL of pure water, and connect them in series with a conduit. Connect the absorption bottles to the pressure-resistant container that has reached room temperature (25 °C), gradually 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 content contained in the gas. For the water in the absorption bottles after extraction, add 1 drop of indicator (BTB: bromothymol blue) to the combined first and second bottles from the side close to the pressure-resistant container, and titrate with 1 / 100N NaOH alkali standard solution to obtain the measured value. Also, titrate the combined water in the third and fourth absorption bottles in the same way to obtain the measurement blank. From these measured values and the measurement blank value, the acid content contained in the hydrohaloolefin composition to be tested is determined as the HCl conversion concentration. Based on the obtained value of the acid content (HCl conversion concentration), the stability is evaluated according to the following criteria. S (excellent): Acid content is less than 1 mass ppm. A (Good): The acid content is 1 ppm by mass or more and less than 5 ppm by mass. B (Slightly defective): The acid content is 5 ppm by mass or more.

[0053] After measuring the acid content, three metal pieces are taken out from the pressure-resistant container, and the appearance is visually observed. The appearance is compared with each unused metal piece, and the metal corrosion resistance is evaluated according to the following criteria. S (Excellent): All of the three metal pieces have the same luster as the unused products, and none of them have rust. A (Good): There is one or more metal pieces with lost luster, but none of them have rust. B (Slightly defective): One or more of the surfaces are slightly rusted, but none of them are completely rusted.

[0054] Example 1 is a comparative example, and Examples 2 to 5 are examples. <Examples 1 - 5> Using HCFC-225ca as a raw material, it was mixed with an aqueous metal hydroxide solution in the presence of a phase-interchange catalyst and subjected to a dehydrofluorination reaction to obtain CFO-1214ya. Using the obtained CFO-1214ya as a raw material, it was subjected to a hydrogen reduction reaction by contacting it with hydrogen and nitrogen in the gas phase and a catalyst in which palladium was supported on activated carbon or a metal oxide to obtain a reaction solution containing HFO-1234yf and HCFO-1224yd. The obtained reaction solution was distilled and purified to obtain a purified composition containing HCFO-1224yd at a high concentration. In Example 1, the obtained purified composition was used as a hydrohaloolefin composition. In Examples 2 to 5, HFC-374pee was added to the obtained purified composition to obtain the hydrohaloolefin compositions shown in Table 1. The composition of the obtained hydrohaloolefin composition was analyzed using a GC-MS system. Table 1 shows the contents (unit: mass%) of HCFO-1224yd(Z), HCFO-1224yd(E), HFC-374pee, HFO-1354yf, and other organic compounds with respect to the total mass of the organic compounds in the hydrohaloolefin composition. In Table 1, "<0.001" means that it is below the detection limit. The obtained hydrohaloolefin composition was used as the test object, and its stability and metal corrosion resistance were evaluated by the above method. The results are shown in Table 1.

[0055]

Table 1

[0056] The disclosure of Japanese Patent Application No. 2020-212127 is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards described in this specification are hereby incorporated by reference into this specification to the same extent as if each individual document, patent application, and technical standard were specifically and individually indicated to be incorporated by reference.

Claims

1. The main component is a hydrohaloolefin, further containing 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. The hydrohaloolefin 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 is more than 0.001% to 0.4% by mass based on the total amount of the organic compounds. The main component is 1 - chloro - 2,3,3,3 - tetrafluoropropene. A hydrohaloolefin composition in which the content of other organic compounds other than 1 - chloro - 2,3,3,3 - tetrafluoropropene and 1,1,2,3 - tetrafluorobutane is 1.5% by mass or less.

2. The hydrohaloolefin composition according to Claim 1, wherein the content of the main component is 99.2 to 99.9% by mass.

3. The hydrohaloolefin composition according to Claim 1 or 2, wherein the use is one or more selected from the group consisting of a working fluid, a blowing 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.

4. The hydrohaloolefin composition according to Claim 3, which is in the form of an aerosol.

5. The hydrohaloolefin composition according to Claim 3, wherein the working fluid is a working fluid for a thermal cycle.

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 through these.

7. The hydrohaloolefin composition according to Claim 3, wherein the cleaning agent is a cleaning agent for an article made of metal, resin, rubber, glass, ceramics, natural fiber, synthetic fiber, or a composite material having two or more of these materials.

8. The hydrohaloolefin composition according to Claim 3, wherein the propellant contains one or more selected from the group consisting of a pressure increasing agent and a spraying agent.

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

Images