Haloolefin composition

Abstract

To provide a haloolefin composition that is inhibited from decomposition and oxidation and has high stability.SOLUTION: The haloolefin composition includes (a) haloolefins, (b) at least one kind of compounds selected from the group consisting of HFO-1234ze, HFC-254eb, HFO-1243zf, HFC-245eb, HFC-245fa, HFC-245cb, HFC-236ea, HFC-236fa, HFO-1225ye, 3,3,3-trifluoropropyne, HFC-23, HFC-32, HFC-125, HFC-143a, HFC-134a, FC-1216, HCFO-1233xf, HCFO-1233zd, HCFO-1232xf, HCFO-1223xd and chloromethane, and (c) water.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a haloolefin composition.

Background Art

[0002] Hydrofluorocarbons "HFCs" typified by HFC-125, HFC-32, etc. are widely used as important alternative substances to replace CFCs, HCFCs, etc. known as substances that destroy the ozone layer. As such alternative substances, "HFC-410A" which is a mixture of HFC-32 and HFC-125, "HFC-404A" which is a mixture of HFC-125, HFC-134a and HFC-143a, etc. are known.

[0003] The above alternative substances are used in a wide variety of applications such as heat transfer media, refrigerants, blowing agents, solvents, cleaning agents, propellants, fire extinguishing agents, etc., and the consumption is also large. On the other hand, all of these substances have a warming ability thousands of times that of CO 2 (so-called "GWP"), and there is concern that the spread of these substances has a great impact on global warming. As a measure against global warming, substance recovery after use is being carried out, but not all can be recovered, and diffusion due to leakage, etc. cannot be ignored. In the applications of refrigerants and heat transfer media, although alternatives using CO 2 or hydrocarbon-based substances are being considered, the CO 2 refrigerant itself has low efficiency, and the equipment also becomes larger, so there are many problems in reducing the total greenhouse gas emissions including energy consumption. In addition, hydrocarbon-based substances have problems in terms of safety due to their high flammability.

[0004] As substances to solve the above problems, hydrohaloolefins with a low global warming potential are currently attracting attention. Hydrohaloolefins are a general term for unsaturated hydrocarbons containing hydrogen, fluorine, and chlorine. For example, substances represented by the following chemical formulas are included. The numbers in parentheses after the chemical formulas represent the refrigerant numbers generally used in refrigerant applications. CF 3 CF=CF2 (Also known as HFO-1216yc, hexafluoropropene.) CF 3 CF=CHF (HFO-1225ye) CF 3 CF=CH 2 (HFO-1234yf) CF 3 CH=CHF (HFO-1234ze) CF 3 CH=CH 2 (HFO-1243zf) CF 3 CCl=CH 2 (HCFO-1233xf) CF 2 ClCCl=CH 2 (HCFO-1232xf) CF 3 CH=CHCl(HCFO-1233zd) CF 3 CCl=CHCl(HCFO-1223xd) CClF 2 CCl=CHCl(HCFO-1222xd) CFCl 2 CCl=CH 2 (HCFO-1231xf) CH 2 ClCCl=CCl 2 (HCO-1230xa) Among these, especially fluoropropenes are promising substances as candidates for low-GWP refrigerants and heat transfer media. However, they may gradually decompose over time, etc., and are not by any means highly stable substances. Therefore, when using such substances in various applications, there are problems such as the performance gradually decreasing depending on the usage situation or the usage environment.

[0005] As a method for enhancing the stability of fluoropropenes, a method of adding a phenolic compound to a composition containing HFO-1234yf and CF 3 I is known (see, for example, Patent Document 1, etc.).

Prior Art Documents

Patent Documents

[0006] Patent Document 1 International Publication No. 2005 / 103187 Summary of the Invention Problems to be Solved by the Invention

[0007] In the above method, although the stability of HFO-1234yf is improved by the action of the phenolic compound, problems still remain from the viewpoint of handling properties during compounding. Further, in the method of adding a phenolic compound as described above to improve stability, there is also a possibility that the performance of the fluoropropenes themselves may be degraded by the action of the phenolic compound, and problems still remain in terms of improving stability while maintaining performance.

[0008] The present invention has been made in view of the above, and an object thereof is to provide a highly stable halogenated olefins composition in which decomposition and oxidation are suppressed. Means for Solving the Problems

[0009] As a result of intensive studies to achieve the above object, the present inventors have found that the above object can be achieved by allowing a trace amount of moisture to be present in a mixture containing halogenated olefins and other specific substances, and have completed the present invention.

[0010] That is, the present invention relates to the following halogenated olefins composition. 1. (a) Halogenated olefins, and (b) At least one compound selected from the group consisting of HFO-1234ze, HFC-254eb, HFO-1243zf, HFC-245eb, HFC-245fa, HFC-245cb, HFC-236ea, HFC-236fa, HFO-1225ye, 3,3,3-trifluoropropene, HFC-23, HFC-32, HFC-125, HFC-143a, HFC-134a, FC-1216, HCFO-1233xf, HCFO-1233zd, HCFO-1232xf, HCFO-1223xd, and chloromethane, (c) water, and A halogenolefin composition characterized by comprising 2. The composition according to item 1 above, wherein the content of the (c) water is 200 ppm by weight or less with respect to the total amount of the (a) halogenolefins. 3. The composition according to item 1 or 2 above, further comprising (d) oxygen. 4. The composition according to item 3 above, wherein the content of the (d) oxygen is 0.35 mol% or less with respect to the total amount of the (a) halogenolefins. 5. The composition according to any one of items 1 to 4 above, wherein the (a) halogenolefins are tetrafluoropropene. 6. The composition according to item 5 above, wherein the tetrafluoropropene is 2,3,3,3-tetrafluoropropene. 7. The composition according to item 5 above, wherein the tetrafluoropropene is 1,3,3,3-tetrafluoropropene. 8. The composition according to any one of items 1 to 7 above, further comprising at least one of (e) polyalkylene glycol and polyol ether. 9. (a) Halogenolefins, (c) water, (e) at least one of polyalkylene glycol and polyol ether, and A halogenolefin composition characterized by comprising 10. The composition according to item 9 above, wherein the content of the (c) water is 200 ppm by weight or less with respect to the total amount of the (a) halogenolefins. 11. The composition according to item 9 or 10 above, wherein the (a) haloolefins are tetrafluoropropene. 12. The composition according to item 11 above, wherein the tetrafluoropropene is 2,3,3,3 - tetrafluoropropene. 13. The composition according to item 11 above, wherein the tetrafluoropropene is 1,3,3,3 - tetrafluoropropene.

Advantages of the Invention

[0011] According to the haloolefin composition of the present invention, by containing moisture, the stability of the haloolefins contained in the composition is improved. That is, the intramolecular double bond of the haloolefins can exist stably, and the oxidation of the haloolefins is also less likely to occur, so the performance of the haloolefins is less likely to be impaired over a long period of time.

Modes for Carrying Out the Invention

[0012] Hereinafter, embodiments of the present invention will be described in detail.

[0013] The haloolefin composition contains (a) haloolefins, (b) at least one compound selected from the group consisting of HFO - 1234ze, HFC - 254eb, HFO - 1243zf, HFC - 245eb, HFC - 245fa, HFC - 245cb, HFC - 236ea, HFC - 236fa, HFO - 1225ye, 3,3,3 - trifluoropropene, HFC - 23, HFC - 32, HFC - 125, HFC - 143a, HFC - 134a, FC - 1216, HCFO - 1233xf, HCFO - 1233zd, HCFO - 1232xf, HCFO - 1223xd, and chloromethane, which are by - products produced in the production of the (a) haloolefins (hereinafter abbreviated as "component (b)"), and (c) water.

[0014] Here, HFO - 1234ze is 1,3,3,3 - tetrafluoropropene, and HFC - 254eb is 1, 1,1,2-Tetrafluoropropane, HFO-1243zf; 3,3,3-trifluoropropene, HFC-245eb; 1,1,1,2,3-pentafluoropropane, HFC-245fa; 1,1,1,3,3-pentafluoropropane, HFC-245cb; 1,1,1,2,2-pentafluoro propane, HFC-236ea; 1,1,1,2,3,3-hexafluoropropane, HFC-236fa; 1,1,1,3,3,3-hexafluoropropane, HFO-1225ye; 1,2,3,3,3-pentafluoropropene, HFC-23; trifluoromethane, HFC-32; methylene difluoride, HFC-125; 1,1,1,2,2-pentafluoroethane, HFC-143a; 1,1,1-tri fluoroethane, HFC-134a; 1,1,1,2-tetrafluoroethane, FC-1216; hexa fluoropropene, HCFO-1233xf; 2-chloro-3,3,3-trifluoropropene, HCFO-1233zd; 1-chloro-3,3,3-trifluoropropene, HCFO-1232xf; 3,3-dif luoro-propene, HCFO-1223xd; 1,2-dichloro-3,3,3-trifluoropropene are as follows.

[0015] The component of (b) is, for example, a by-product in the production of (a) haloolefins. Therefore, the component of (b) is a compound different from (a) haloolefins.

[0016] The above-mentioned haloolefin composition (hereinafter sometimes abbreviated as "composition") contains moisture, so that the intramolecular double bond of haloolefins can stably exist, and the oxidation of haloolefins is also less likely to occur. As a result, the stability of haloolefins is improved.

[0017] The above-mentioned haloolefins refer to unsaturated hydrocarbons having halogen atoms such as fluorine and chlorine as substituents. Also, all hydrogens in the haloolefins may be substituted with halogen atoms, or some hydrogens may be substituted with halogen atoms. The number of carbon atoms in the haloolefins is not particularly limited, but for example, it is 3 to 10. The number of carbon atoms in the haloolefins is preferably 3 to 8, and particularly preferably 3 to 6, in terms of further enhancing the stability of the haloolefins in the composition. The haloolefins contained in the composition may be only one kind of compound or two or more different compounds.

[0018] Particularly preferred haloolefins include tetrafluoropropene, pentafluoroprop ene, and trifluoropropene. For all of these compounds, the types of their isomers are not particularly limited. Specific examples of particularly preferred haloolefins include 2,3,3,3-tetrafluoropropene (HFO-1234yf), 1,3,3,3-tetrafluoropropene (HFO-1234ze), 1,2,3,3-tetrafluoropropene (HFO-1234ye), 1,1,2,3-tetrafluoropropene (HFO-1234yc), 1,2,3,3,3-pentafluoropropene (HFO-1225ye), 1,1,3,3,3-pentafluoropropene (HFO-1225zc), 3,3,3-trifluoropropene (HFO-1243zf), 1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz), 1,1,1,2,4,4,5,5,5-nonafluoropentene (HFO-1429myz), etc.

[0019] The above-mentioned haloolefins can be those produced by known production methods. As an example of such a production method, there is a method of dehydrogenating a fluoroalkane in the presence of a catalyst (for example, the method described in JP-T-2012-500182). The number of carbon atoms of the fluoroalkane is not particularly limited, but is preferably 3 to 8, and particularly preferably 3 to 6. For example, if the haloolefin is tetrafluoropropene, pentafluoropropane can be used as a raw material, and tetrafluoropropene can be produced by subjecting this to a dehydrogenation reaction in the presence of a catalyst. Specifically, if the haloolefin is 2,3,3,3-tetrafluoropropene (HFO-1234yf), 1,1,1,2,3-pentafluoropropane or 1,1,1,2,2-pentafluoropropane can be used as a raw material, and 2,3,3,3-tetrafluoropropene (HFO-1234yf) can be obtained by subjecting this to a dehydrogenation reaction in the presence of a catalyst. Further, if the haloolefin is 1,3,3,3-tetrafluoropropene (HFO-1234ze), 1,1,1,3,3-pentafluoropropane can be used as a raw material, and 1,3,3,3-tetrafluoropropene (HFO-1234ze) can be obtained by subjecting this to a dehydrogenation reaction in the presence of a catalyst. In the above production method, as the catalyst, a chromium catalyst such as chromium oxide or fluorinated chromium oxide, or other metal catalysts can be used, and the reaction temperature can be carried out within the range of 200 to 500°C.

[0020] Incidentally, when producing, for example, 2,3,3,3-tetrafluoropropene by the above manufacturing method, E-form and Z-form 1,3,3,3-tetrafluoropropene (HFO-1234ze), etc. are generated as by-products. In this case, it is normal to remove the above by-products by purifying the obtained product, etc., to obtain the target 2,3,3,3-tetrafluoropropene. However, the E-form and Z-form 1,3,3,3-tetrafluoropropene by-produced by the above manufacturing method is not only a by-product but also a component (b) in the composition. Therefore, when producing 2,3,3,3-tetrafluoropropene by the above method, since the component (b) which is an essential component in the composition of this form can also be obtained, there is an advantage that it can be used in a state containing by-products without purification. Of course, not limited to 2,3,3,3-tetrafluoropropene, when producing other haloolefins by the above manufacturing method, as long as the by-product is also a component (b), it can be used as haloolefins in the composition as it is without purification. Therefore, when haloolefins are produced by a method of dehydrogenating hydrogen fluoride from fluoroalkane in the presence of a catalyst, the haloolefins may be in a state containing by-products.

[0021] The component (b) in the composition is a compound selected from the group consisting of HFO-1234ze, HFC-254eb, HFO-1243zf, HFC-245eb, HFC-245fa, HFC-245cb, HFC-236ea, HFC-236fa, HFO-1225ye, 3,3,3-trifluoropropyne, HFC-23, HFC-32, HFC-125, HFC-143a, HFC-134a, FC-1216, HCFO-1233xf, HCFO-1233zd, HCFO-1232xf, HCFO-1223xd, and chloromethane. It may be one of these alone or two or more of them. When there are two or more, the combination is not particularly limited.

[0022] As the component (b), those produced by known production methods may be used, or as described above, those by-produced in the production of haloolefins may be used as the component (b).

[0023] The type of water is not particularly limited, and purified water such as distilled water, ion-exchanged water, filtered water, tap water, and ultrapure water obtained by commercially available pure water generators can be used. However, if the water contains acid components such as HCl, it may corrode the equipment or reduce the effect of stabilizing haloolefins. Therefore, it is preferable to remove HCl and the like to a level below the detection limit in the commonly adopted analysis methods. In this case, the content of acid components is preferably 10 ppm by weight or less, more preferably 1 ppm by weight or less, based on the total amount of the components (a), (b), and (c) contained in the composition.

[0024] The pH of the water is not particularly limited, but it is usually sufficient if it is in the range of 6 to 8. If the acid content in the water is within the above range, the pH of the water should usually be within this range.

[0025] The water content in the composition is preferably 200 ppm by weight or less based on the total amount of (a) haloolefins. In this case, the action of stabilizing haloolefins is sufficiently exerted. Further, if the water content is 200 ppm by weight or less, more preferably less than 30 ppm by weight, based on the total amount of haloolefins, it becomes easier to prevent corrosion of the equipment or promotion of decomposition of haloolefins. The lower limit of the water content in the composition is not limited as long as the effects of the present invention are exhibited. For example, it can be 0.1 ppm by weight, more preferably 3 ppm by weight. Within this range, the stability of haloolefins in the composition is further improved.

[0026] The water content in the composition is particularly preferably more than 3 ppm by weight and less than 30 ppm by weight. In this case, the stability of the haloolefins in the composition is further improved. Also, when the water content in the composition is less than 30 ppm by weight, it is also possible to suppress the inhibition of the refrigerant performance.

[0027] The content of the component (b) contained in the composition is preferably contained in an amount of 0.1 ppm by weight or more and less than 10,000 ppm by weight with respect to the total amount of the haloolefins. If it is within this range, the risk of inhibiting the stabilizing action of the haloolefins is small.

[0028] The composition may contain other known additives as long as the effects of the present invention are not inhibited. The other additives are preferably 50% by weight or less, and more preferably 40% by weight or less, based on the total amount of the composition.

[0029] The method for preparing the composition is not particularly limited. For example, each component can be prepared and the composition can be obtained by mixing them in a predetermined blending amount.

[0030] In the above composition, due to the presence of water, the double bond of the haloolefins is stably present and oxidation etc. hardly occurs, so the stability of the haloolefins is high. Therefore, it becomes possible to store for a longer period compared to ordinary haloolefins. Moreover, since the stability of the haloolefins is high, the risk of impairing the performance of the haloolefins is also small. Therefore, for example, even if the composition is used as a refrigerant or a heat medium, due to the high stability of the haloolefins, the performance as a refrigerant or a heat medium becomes excellent.

[0031] The above composition can further contain (d) oxygen. When the composition contains (d) oxygen, the content of (d) oxygen is 0.35 mol% or less with respect to the total amount of (a) haloolefins It is preferable. If the oxygen content is within this range, the stability of the haloolefins in the composition is further improved. From this perspective, the lower the oxygen content in the composition, the better. However, as described above, since the composition contains water, if the oxygen amount is within the above range, the stability of the haloolefins can be maintained by the action of the water. The lower limit of the oxygen content in the composition can be, for example, 1 ppm, which is the detection limit of gas chromatography.

[0032] When the composition is used as a refrigerant or a heat medium as described above, as the haloolefins, 2,3,3,3 - tetrafluoropropene (HFO - 1234yf), 1,3,3,3 - tetrafluoropropene (HFO - 1234ze), 1,2,3,3 - tetrafluoropropene (HFO - 1234ye), 1,2,3,3,3 - pentafluoropropene (HFO - 1225ye), 3,3,3 - trifluoropropene (HFO - 1243zf), etc. are particularly advantageous.

[0033] When the composition is used as a refrigerant or a heat medium, as the lubricating oil, at least one of (e) polyalkylene glycol and polyol ether may be contained in the composition. When the composition contains at least one of polyalkylene glycol and polyol ether, the component of (b) above may or may not be contained in the composition. When the component of (b) above is not contained in the composition, the composition comprises (a) haloolefins, (c) water, and (e) at least one of polyalkylene glycol and polyol ether. Note that (a) haloolefins and (c) water are the same as the above-described configurations.

[0034] The lubricating oil can be contained in an amount of 10 to 50% by mass based on the total amount of the components (a), (b), and (c) contained in the composition. However, since it varies depending on the specifications of the oil tank of the refrigerator, it is not particularly limited to this range. If it is within this range, there is no risk of impairing the stability of the haloolefins. Further, the lubricating oil may further contain polyvinyl ether (PVE), or may be composed of polyvinyl ether alone.

[0035] Examples of the polyalkylene glycol (PAG) include "SUNICE P56" manufactured by Nippon Sun Oil Co., Ltd. Examples of the polyol ether (POE) include "Ze-GLES RB32" manufactured by JX Nippon Mining & Energy Corporation.

[0036] Even when the composition contains a lubricating oil, (d) oxygen can also be contained in the composition. When the composition contains (d) oxygen, for the same reasons as described above, the content of (d) oxygen is preferably 0.35 mol% or less based on the total amount of (a) haloolefins.

[0037] Refrigerants and heat transfer media mainly composed of haloolefins are likely to decompose and oxidize when they come into contact with metals, etc., and the performance as refrigerants and heat transfer media is likely to be impaired. However, if the above composition is used as a refrigerant or heat transfer media, due to the high stability of the haloolefins, a decrease in the performance of the refrigerant or heat transfer media is suppressed.

[0038] Therefore, the composition according to the present invention can be used not only for the above refrigerant and heat transfer media applications but also for various other applications. When the composition is used for such applications, specific examples of the haloolefins include 2,3,3,3-tetrafluoropropene (HFO-1234yf), 1,3,3,3-tetrafluoropropene (HFO-1234ze), 1,2,3,3-tetrafluoropropene (HFO-1234ye), 1,1,2,3-tetrafluoropropene (HFO-1234yc), 1,2,3,3,3-pentafluoropropene (HFO-1225ye), 1,1,3,3,3-pentafluoropropene (HFO-1225 zc), 3,3,3-trifluoropropene (HFO-1243zf), 1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz), 1,1,1,2,4,4,5,5,5-nonafluoropentene (HFO-1429myz), etc. can be mentioned.

Examples

[0039] Hereinafter, the present invention will be described more specifically by way of examples, but the present invention is not limited to the aspects of these examples. It is not defined.

[0040] (Example 1) 2,3,3,3-Tetrafluoropropene (hereinafter abbreviated as "HFO-1234yf") and water were prepared, and by blending these, three types of haloolefin compositions with water contents of 10 ppm by weight, 200 ppm by weight, and 10,000 ppm by weight with respect to HFO-1234yf were prepared. The above HFO-1234yf was produced, for example, by the method shown in Example 1 of JP-A-2012-500182 and JP-A-2009-126803. The HF generated at this time was deacidified by a water washing tower and an alkali tower of an aqueous NaOH solution. The obtained haloolefin composition may contain by-products (for example, 1,3,3,3-tetrafluoropropene (HFO-1234ze), that is, the component of (b)) generated in the production of HFO-1234yf.

[0041] (Example 2) 1,3,3,3-Tetrafluoropropene (hereinafter abbreviated as "HFO-1234ze") and water were prepared, and by blending these, three types of haloolefin compositions with water contents of 10 ppm by weight, 200 ppm by weight, and 10,000 ppm by weight with respect to HFO-1234ze were prepared. The above HFO-1234ze was obtained, for example, by dehydrofluorination of HFC-245eb by the method described in JP-A-2012-500182 to obtain HFO-1234y It was obtained together with f. The generated HF was deacidified by a water washing tower and an alkali tower of an aqueous NaOH solution. HFO-1234yf is a component of (b).

[0042] (Comparative Example 1) A haloolefin composition was obtained in the same manner as in Example 1 except that water was not blended.

[0043] (Comparative Example 2) A haloolefin composition was obtained in the same manner as in Example 2 except that water was not blended.

[0044] (Stability Test 1 of Haloolefins) For each of the haloolefin compositions obtained in the above Examples and Comparative Examples, a stability test of haloolefins was conducted as follows. A glass tube (ID8 mmΦ × OD12 mmΦ × L300 mm) with one side already sealed was charged with the haloolefin composition so that the content of haloolefins was 0.01 mol. The tube was sealed by melting to make it airtight. This tube was left standing in a constant temperature bath under an atmosphere of 150 °C and held in this state for one week. Then, it was taken out from the constant temperature bath and cooled, and the stability of haloolefins was evaluated by analyzing the acid content in the gas inside the tube.

[0045] (Stability Test 2 of Haloolefins) For each of the haloolefin compositions obtained in the above Examples and Comparative Examples, a stability test of haloolefins was conducted as follows. A glass tube (ID8 mmΦ × OD12 mmΦ × L300 mm) was charged with the haloolefin composition so that the content of haloolefins was 0.01 mol. Then, oxygen was enclosed in the tube by adjusting the oxygen concentration to a predetermined molar concentration (0.010 mol%, 0.115 mol% or 0.345 mol%) with respect to the number of moles of haloolefins charged. This tube was left standing in a constant temperature bath under an atmosphere of 150 °C and held in this state for one week. Then, it was taken out from the constant temperature bath and cooled, and the stability of haloolefins was evaluated by analyzing the acid content in the gas inside the tube.

[0046] Here, the analysis of the acid content in the gas was performed by the following method. After the above cooling, the tube was completely solidified with the gas retained in the tube using liquid nitrogen. Then, the tube was opened and gradually thawed to recover the gas into a Tedlar bag. 5 g of pure water was injected into this Tedlar bag, and the acid content was extracted into the pure water while being in good contact with the recovered gas. The extract was detected by ion chromatography to measure the content (weight ppm) of fluoride ion (F - ) and trifluoroacetate ion (CF3COO - ).

[0047] The test results are shown in Table 1. In Table 1, "yf" and "ze(E)" represent "HFO-1234yf" and "HFO-1234ze", respectively. Also, (E) in "ze(E)" indicates that HFO-1234ze is the E-isomer.

[0048]

Table 1

[0049] In Table 1, Nos. 5 to 8 all have an oxygen addition amount of 0.010 mol%. However, in No. 5, since it is a composition that does not contain water, it can be seen that the acid content is higher compared to Nos. 6 to 8 that contain water. That is, in No. 5, due to the high acid content, the decomposition and oxidation of HFO-1234yf, which is a haloolefin, in Nos. 6 to 8 It can be seen that it is promoted as compared with . From this result, it can be seen that in the composition containing water, HFO-1234yf, which is a hydrochlorofluoroolefin, is stabilized. Also, in all of No. 9 to 12, the oxygen addition amount is 0.115 mol%, and in all of No. 13 to 16, the oxygen addition amount is 0.345 mol%, but the same tendency as in the case of the oxygen addition amount of 0.115 mol% was observed. Furthermore, the same tendency was observed even when the hydrochlorofluoroolefins were HFO-1234ze (No. 21 to 24, 25 to 28, 29 to 32). Incidentally, in all of No. 1 to 4 and No. 17 to 20, the acid content is less than 1 weight ppm, and it can be seen that the decomposition of the hydrochlorofluoroolefins hardly proceeds. This is presumably because oxygen was not added to the system and oxidation or the like did not occur. Therefore, in a system where almost no oxygen exists, regardless of whether water is contained in the composition or not, all hydrochlorofluoroolefins are in a stable state.

[0050] From the above, it is clear that the water contained in the composition stabilizes the hydrochlorofluoroolefins as in the present invention.

Claims

1. (a) HFO-1243zf or HFO-1225ye, (b) at least one compound selected from the group consisting of HFO-1234ze, HFC-254eb, HFO-1243zf, HFC-245eb, HFC-245fa, HFC-245cb, HFC-236ea, HFC-236fa, HFO-1225ye, 3,3,3-trifluoropropyne, HFC-23, HFC-32, HFC-125, HFC-143a, HFC-134a, FC-1216, HCFO-1233xf, HCFO-1233zd, HCFO-1232xf, HCFO-1223xd, and chloromethane; (c) water; (d) oxygen; Including, The content of the water (c) is 0.1 ppm by weight or more and 200 ppm by weight or less based on the total amount of the component (a), The content of (b) is 0.1 ppm by weight or more and less than 10,000 ppm by weight based on the total amount of (a), A haloolefin composition, wherein the content of the oxygen (d) is 0.35 mol % or less based on the total amount of the oxygen (a).

2. The composition of claim 1 , further comprising (e) at least one of a polyalkylene glycol and a polyol ester.

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