JP7747964B2 - Compositions containing 1-chloro-2,3,3-trifluoro-1-propene and water, and methods for storing the compositions - Google Patents

Description

One embodiment of the present invention relates to a composition comprising 1-chloro-2,3,3-trifluoro-1-propene and water, and a method for storing the composition.

In recent years, various hydrofluorocarbons and chlorofluorocarbons with low global warming potential (GWP) have been developed. One known example is 1-chloro-2,3,3-trifluoro-1-propene (see Patent Documents 1 and 2).

International Publication No. 2017/018412 International Publication No. 2017/122801

One embodiment of the present invention aims to provide a method for stably storing a composition containing 1-chloro-2,3,3-trifluoro-1-propene. Alternatively, one embodiment of the present invention aims to provide a composition containing 1-chloro-2,3,3-trifluoro-1-propene that can be stored for a long period of time.

One embodiment of the present invention is a composition comprising 1-chloro-2,3,3-trifluoro-1-propene, an additive, and water.

One embodiment of the present invention is a method for preserving a composition, comprising adding water and an additive to 1-chloro-2,3,3-trifluoro-1-propene.

One embodiment of the present invention is a composition comprising 1-chloro-2,3,3-trifluoro-1-propene and water.

Embodiments of the present invention enable a composition containing 1-chloro-2,3,3-trifluoro-1-propene to be stored stably for a long period of time. It is also possible to provide a composition containing 1-chloro-2,3,3-trifluoro-1-propene that can be stored stably for a long period of time.

Each embodiment of the present invention will be described below. However, the present invention can be implemented in various forms without departing from the spirit of the invention, and should not be construed as being limited to the description of the embodiments exemplified below. Furthermore, even if there are other effects different from those achieved by the aspects of the following embodiments, those that are clear from the description in this specification or that would be easily predictable by one of ordinary skill in the art are naturally considered to be achieved by the present invention.

Below, we will describe a composition containing 1-chloro-2,3,3-trifluoro-1-propene (hereinafter referred to as 1233yd), which relates to one embodiment of the present invention, and a method for stably storing this composition.

1. Composition The composition contains 1233yd represented by the following formula and water: The composition may further contain additives.

1-1.1233yd
1233yd, a type of chlorofluorocarbon, may be the E-isomer (1233yd(E)), the Z-isomer (1233yd(Z)), or a mixture thereof. In the case of a mixture, the ratio of the E-isomer to the Z-isomer can be selected arbitrarily. For example, the ratio of the E-isomer to the total amount of the E-isomer and the Z-isomer may be 1% or more and 99% or less, 1% or more and 50% or less, or 1% or more and 20% or less. The ratio of the E-isomer to the Z-isomer may be calculated by nuclear magnetic resonance spectroscopy (NMR), or may be determined from the area ratio of a chromatogram obtained by gas chromatography or liquid chromatography. When NMR is used, any of ¹ H-NMR, ¹⁹ F-NMR, and ¹³ C-NMR may be used, but it is preferable to use ¹ H-NMR or ¹⁹ F-NMR, which have high quantitative accuracy.

Due to 1233yd's high solubility in various solutes, its non-flammability, large heat of vaporization, and low boiling point, this composition can be used in a variety of applications, including as a solvent for applying lubricants (lubricant application liquid solvent), a heat transfer medium, a refrigerant, a foaming agent, a solvent, a cleaning agent, a propellant, and a fire extinguisher. Furthermore, because 1233yd has a low GWP, another major feature of this composition is that it is less likely to contribute to global warming than conventional compositions primarily containing hydrofluorocarbons or hydrochlorofluorocarbons.

There are no restrictions on the method for synthesizing 1233yd, but a highly efficient synthesis method is dehydrofluorination of 3-chloro-1,1,2,2-tetrafluoropropane (hereinafter referred to as 244ca) using a base, as shown in the following formula.

Bases used for dehydrofluorination include hydroxides, carbonates, oxides, alkoxides, and amides of alkali metals such as sodium, potassium, and lithium, or Group 2 elements such as magnesium, calcium, strontium, and barium. Considering that the base reacts with 244ca in a 1:1 molar ratio, it is sufficient to use an equimolar amount to 244ca or an excess amount relative to 244ca. Specifically, the amount of base used relative to 244ca is appropriately selected from the range of 1.0 to 3.0 equivalents, 1.0 to 2.0 equivalents, 1.0 to 1.5 equivalents, or 1.0 to 1.2 equivalents.

Dehydrofluorination can be carried out by dissolving the base in water, an alcohol having 1 to 4 carbon atoms such as methanol, ethanol, isopropanol, or 1-butanol, or an ether such as tetrahydrofuran or dioxane, and then adding this base solution dropwise to bulk 1233yd or a solution of 1233yd. There are no restrictions on the solvent that can be used to make the 1233yd solution, and examples include the above-mentioned alcohols or ethers having 1 to 4 carbon atoms, or aromatic hydrocarbons such as toluene and xylene.

A phase transfer catalyst may be used in the dehydrofluorination. Examples of phase transfer catalysts include quaternary ammonium salts, quaternary phosphonium salts, quaternary sulfonium salts, pyridine salts, and crown ethers. When a quaternary ammonium salt, quaternary phosphonium salt, quaternary sulfonium salt, or pyridine salt is used, examples of the counter anion include chloride ion, bromide ion, iodide ion, hydroxide ion, phosphate ion, and p-toluenesulfonate ion.

There are no restrictions on the temperature for dehydrofluorination and it can be selected appropriately from, for example, -40°C or higher and +80°C or lower, -20°C or higher and +60°C or lower, or 0°C or higher and +40°C or lower.

In dehydrofluorination, a stabilizer may be added to the reaction system. Examples of stabilizers include alkenes (olefins) such as hexene, heptene, octene, pentadiene, cyclopentene, and cyclohexene; aliphatic nitro compounds such as nitromethane, nitroethane, and nitropropane; aromatic nitro compounds such as nitrobenzene, nitrotoluene, and nitroaniline; ethers such as dimethoxymethane, 1,2-dimethoxyethane, 1,4-dioxane, 1,3,5-trioxane, and tetrahydrofuran; epoxy compounds such as glycidol, methyl glycidyl ether, allyl glycidyl ether, 1,2-butylene oxide, phenyl glycidyl ether, cyclohexene oxide, and epichlorohydrin; allyl alcohols such as phenol; olefinic alcohols such as 1-buten-3-ol; acetylenic alcohols such as 3-methyl-1-butyn-3-ol and 3-methyl-1-pentyn-3-ol; and acrylic esters such as methyl acrylate, ethyl acrylate, and butyl acrylate. Among these, alkenes such as octene are preferred because they are inexpensive, have relatively low reactivity, and are unlikely to adversely affect equipment used when using a composition containing 1233yd. Alkenes may have isomers, and an isolated single isomer may be used, or a mixture of two or more isomers may be used. For example, when octene is used as a stabilizer, 1-octene, 2-octene, 3-octene, 4-octene, 2-methyl-1-heptene, 2-methyl-2-heptene, 2-methyl-3-heptene, 3-methyl-1-heptene, 3-methyl-2-heptene, 3-methyl-3-heptene, 4-methyl-1-heptene, 4-methyl-2-heptene, 4-methyl-3-heptene, 5-methyl-1-heptene, 5-methyl-2-heptene, 5-methyl-3-heptene, 6-methyl-1-heptene, 6-methyl-2-heptene, 6-methyl-3-heptene, 2,3-dimethyl-1-hexene, 2,4-dimethyl-1-hexene, 2,5-dimethyl-1-hexene, 3,4-dimethyl-1-hexene, 3,5-dimethyl-1-hexene, 4,5-dimethyl-1-hexene, 3,3-dimethyl-1-hexene, 4,4-dimethyl-1-hexene, 5,5-dimethyl-1-hexene, 3-ethyl-1-hexene, 4-ethyl-1-hexene, 2,3-dimethyl-2-hexene, 2,4-dimethyl -2-hexene, 2,5-dimethyl-2-hexene, 3,4-dimethyl-2-hexene, 3,5-dimethyl-2-hexene, 4,5-dimethyl-2-hexene, 4,4-dimethyl-1-hexene, 5,5-dimethyl-1-hexene, 3-ethyl-2-hexene, 4-ethyl-2-hexene, 2,3-dimethyl-3-hexene, 2,4-dimethyl-3-hexene, 2,5-dimethyl-3-hexene, 3,4-dimethyl-3-hexene, 3,5-dimethyl-3-hexene, 2,2-dimethyl-3 Any one of 2,3,3-trimethyl-1-pentene, 2,3,4-trimethyl-1-pentene, 2,4,4-trimethyl-1-pentene, 3,3,4-trimethyl-1-pentene, 2,3,4-trimethyl-2-pentene, 2,4,4-trimethyl-2-pentene, 3,4,4-trimethyl-2-pentene, 3-ethyl-2-methyl-2-pentene, and 3-ethyl-4-methyl-2-pentene may be used, or a mixture of these may be used.

After dehydrofluorination, the organic layer is extracted and washed with an aqueous solution of a base such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, or potassium bicarbonate, followed by water. The organic layer may be further washed with saturated saline. A crude product of 1,233 yd is then obtained by simple dehydration using a dehydrating agent such as magnesium sulfate or sodium sulfate. The present composition may be prepared from this crude product without purification, or the present composition may be prepared using 1,233 yd isolated by distillation purification.

Although trace amounts of oxygen are present in unpurified 1233yd and in 1233yd purified by distillation, there is no need to subject 1233yd to oxygen removal treatment (e.g., degassing or oxygen removal treatment such as bubbling with an inert gas). As shown in the examples, this composition can be stored stably for long periods of time by adding water or water and additives, even without deoxygenating 1233yd.

1-2. Water The amount of water contained in the composition can be adjusted by adding water to the 1233yd obtained by distillation purification or the crude product containing 1233yd obtained by simple dehydration, or by performing a dehydration treatment. When adding water, the distilled 1233yd or the simply dehydrated 1233yd crude product is weighed and water is added dropwise using a micropipette or microsyringe. When performing a dehydration treatment, an appropriate amount (e.g., 5% by weight) of a dehydrating agent such as molecular sieves is added and filtered. The amount of water constituting the composition is selected from the following ranges relative to the 1233yd: greater than 200 ppm by weight to 1600 ppm by weight, greater than 200 ppm by weight to 1400 ppm by weight, greater than 200 ppm by weight to 1200 ppm by weight, greater than 200 ppm by weight to 1000 ppm by weight, or greater than 200 ppm by weight to 500 ppm by weight. The amount of water contained in the composition may be selected from the range of 260 ppm by weight to 1600 ppm by weight, 260 ppm by weight to 1400 ppm by weight, 260 ppm by weight to 1200 ppm by weight, 260 ppm by weight to 1000 ppm by weight, or 260 ppm by weight to 500 ppm by weight, relative to 1233 yd. The amount of water in the composition can be determined, for example, using coulometric titration. It is preferable to add water to 1233 yd after distillation, filtration, extraction, or treatment with an ion exchange resin or activated carbon.

1-3. Additives When the composition contains additives, the additives are added in an amount of 2 ppm by weight or more and 5% by weight or less, 10 ppm by weight or more and 2% by weight or less, 10 ppm by weight or more and 1% by weight or less, or 10 ppm by weight or more and 0.5% by weight or less, relative to 1233 yd. The addition of the additives may be carried out in the same manner as the addition of water. When the additive and the stabilizer used during dehydrofluorination are the same, the stabilizer remaining in the crude product may be used as the additive without adding a separate additive.

Additives include, for example, nitro compounds, epoxy compounds, phenol derivatives, ethers, alcohols, imidazole derivatives, amines, unsaturated hydrocarbons, etc. These may be used alone or in combination with two or more types of additives.

Examples of nitro compounds include aliphatic or aromatic nitro compounds. Aliphatic nitro compounds include nitromethane, nitroethane, 1-nitropropane, and 2-nitropropane. Aromatic nitro compounds include nitrobenzene, o-, m-, or p-dinitrobenzene, trinitrobenzene, o-, m-, or p-nitrotoluene, o-, m-, or p-ethylnitrobenzene, 2,3-, 2,4-, 2,5-, 2,6-, 3,4-, or 3,5-dimethylnitrobenzene, o-, m-, or p-nitroacetophenone, o-, m-, or p-nitrophenol, and o-, m-, or p-nitroanisole.

Examples of epoxy compounds include monoepoxy compounds such as ethylene oxide, 1,2-butylene oxide, propylene oxide, styrene oxide, cyclohexene oxide, glycidol, epichlorohydrin, glycidyl methacrylate, allyl glycidyl ethers such as phenyl glycidyl ether, methyl glycidyl ether, butyl glycidyl ether, and 2-ethylhexyl glycidyl ether, as well as polyfunctional epoxy compounds such as diepoxybutane, vinylcyclohexene dioxide, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, glycerin polyglycidyl ether, and trimethylolpropane triglycidyl ether.

Phenol derivatives include unsubstituted phenols as well as compounds having various substituents on the aromatic ring, such as alkyl groups, alkenyl groups, alkoxy groups, carboxyl groups, carbonyl groups, and halogens, in addition to a phenolic hydroxyl group. Examples of such phenol derivatives include monohydric phenol derivatives such as 2,6-di-t-butyl-p-cresol, o-cresol, m-cresol, p-cresol, thymol, p-t-butylphenol, o-methoxyphenol, m-methoxyphenol, p-methoxyphenol, eugenol, isoeugenol, butylhydroxyanisole, and xylenol, as well as dihydric phenol derivatives such as t-butylcatechol, 2,5-di-t-aminohydroquinone, and 2,5-di-t-butylhydroquinone.

Examples of ethers include ethers in which an aliphatic substituent is bonded to oxygen, such as dimethyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dipentyl ether, diisopentyl ether, ethyl methyl ether, ethyl propyl ether, ethyl isopropyl ether, ethyl isobutyl ether, ethyl isopentyl ether, ethyl vinyl ether, ethyl propargyl ether, 1,4-dioxane, 1,3-dioxane, 1,3,5-trioxane, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol methyl ether, trimethoxyethane, triethoxyethane, and tetrahydrofuran, as well as ethers in which at least one aromatic substituent is bonded to oxygen, such as ethyl phenyl ether, diphenyl ether, ethyl naphthyl ether, ethylene glycol monophenyl ether, ethylene glycol diphenyl ether, anisole, and anethole.

Alcohols include methanol, ethanol, 1-propanol, isopropanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 1-ethyl-1-propanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 4-methyl-2-pentanol, 2-ethyl-1-butanol, 1-heptanol, 2-heptanol, 3- Examples of the alcohol include heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, 1-nonanol, 3,5,5-trimethyl-1-hexanol, 1-decanol, 1-undecanol, 1-dodecanol, benzyl alcohol, cyclohexanol, 1-methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 4-methylcyclohexanol, α-terpineol, 2,6-dimethyl-4-heptanol, nonyl alcohol, tetradecyl alcohol, and 2-propyn-1-ol. Among these alcohols, alcohols having 1 to 3 carbon atoms, such as methanol, ethanol, isopropanol, and 2-propyn-1-ol, are preferred.

Imidazole derivatives include unsubstituted imidazole, as well as 1-methylimidazole, 1-n-butylimidazole, 1-phenylimidazole, 1-benzylimidazole, 1-(β-oxyethyl)imidazole, 1-methyl-2-propylimidazole, 1-methyl-2-isobutylimidazole, 1-n-butyl-2-methylimidazole, 1,2-dimethylimidazole, 1,4-dimethylimidazole, 1,5-dimethylimidazole, 1,2,5-trimethylimidazole, 1,4,5-trimethylimidazole, and 1-ethyl-2-methylimidazole, which have an alkyl group, cycloalkyl group, or aryl group having 1 to 18 carbon atoms as a substituent on the nitrogen.

Amines include aliphatic amines such as pentylamine, hexylamine, diisopropylamine, diisobutylamine, di-n-propylamine, triethylamine, morpholine, N-methylmorpholine, benzylamine, dibenzylamine, α-methylbenzylamine, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, propylamine, isopropylamine, dipropylamine, butylamine, isobutylamine, dibutylamine, tributylamine, dipentylamine, tripentylamine, and 2-ethylhexylamine, as well as aromatic amines such as aniline, N-methylaniline, N,N-dimethylaniline, N,N-diethylaniline, diphenylamine, and triphenylamine, and nitrogen-containing heteroaromatic compounds such as pyridine. Alternatively, polyfunctional amines such as ethylenediamine, propylenediamine, diethylenetriamine, and tetraethylenepentamine may also be used, as well as hydroxylamines such as diethylhydroxylamine.

Unsaturated hydrocarbons include pentene isomers such as 1-pentene, 2-pentene, 2-methyl-1-butene, 3-methyl-1-butene, and 2-methyl-2-butene; hexene isomers such as 1-hexene, 2-hexene, 3-hexene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 2-ethyl-1-butene, 3-ethyl-1-butene, 3-ethyl-2-butene, 2-methyl-2-pentene, 3-methyl-2-pentene, 4-methyl-2-pentene, and 2,3-dimethyl-2-butene; heptene isomers such as 1-heptene, 2-heptene, 3-heptene, 4-heptene, and 3-ethyl-2-pentene; 1-octene, 2-octene, 3-octene, 4-octene, and 2 -methyl-1-heptene, 2-methyl-2-heptene, 2-methyl-3-heptene, 3-methyl-1-heptene, 3-methyl-2-heptene, 3-methyl-3-heptene, 4-methyl-1-heptene, 4-methyl-2-heptene, 4-methyl-3-heptene, 5-methyl-1-heptene, 5-methyl-2-heptene, 5-methyl-3-heptene, 6-methyl-1-heptene, 6-methyl-2-heptene, 6-methyl-3-heptene, 2,3-dimethyl-1-hexene, 2,4-dimethyl-1-hexene, 2,5-dimethyl-1-hexene, 3,4-dimethyl-1-hexene, 3,5-dimethyl-1-hexene, 4,5-dimethyl-1-hexene, 3,3-dimethyl-1-hexene, 4,4-dimethyl ethyl-1-hexene, 5,5-dimethyl-1-hexene, 3-ethyl-1-hexene, 4-ethyl-1-hexene, 2,3-dimethyl-2-hexene, 2,4-dimethyl-2-hexene, 2,5-dimethyl-2-hexene, 3,4-dimethyl-2-hexene, 3,5-dimethyl-2-hexene, 4,5-dimethyl-2-hexene, 4,4-dimethyl-1-hexene, 5,5-dimethyl-1-hexene, 3-ethyl-2-hexene, 4-ethyl-2-hexene, 2,3-dimethyl-3-hexene, 2,4-dimethyl-3-hexene, 2,5-dimethyl-3-hexene, 3,4-dimethyl-3-hexene, 3,5-dimethyl-3-hexene, 2,2-dimethyl-3-hexene, 3-ethyl-3-hexene octene isomers such as 2,3,3-trimethyl-1-pentene, 2,3,4-trimethyl-1-pentene, 2,4,4-trimethyl-1-pentene, 3,3,4-trimethyl-1-pentene, 2,3,4-trimethyl-2-pentene, 2,4,4-trimethyl-2-pentene, 3,4,4-trimethyl-2-pentene, 3-ethyl-2-methyl-2-pentene, and 3-ethyl-4-methyl-2-pentene; nonene isomers such as 1-nonene; dienes such as butadiene, isoprene, hexadiene, heptadiene, and octadiene; and unsaturated cyclic compounds such as cyclohexene, cyclohexadiene, cycloheptene, cycloheptadiene, cyclooctene, and cyclooctadiene.

As disclosed in Patent Document 1, 1233yd is believed to be unstable in water and to be easily decomposed by water. However, as shown in the examples, adding water to a composition containing 1233yd effectively inhibits the decomposition of 1233yd, allowing the composition to be stably stored for long periods of time. Furthermore, when an additive is included in the composition, the amount of water added to the composition can be reduced. Specifically, in the presence of both water and additives, the stability of 1233yd is significantly improved, and its decomposition can be effectively inhibited, even when the amounts of water and additives are each several hundred ppm by weight relative to 1233yd.

Furthermore, when synthesizing 1233yd in the presence of a stabilizer, it may not be possible to completely remove the stabilizer from the resulting 1233yd. In this case, the stabilizer can function as an additive to the composition containing 1233yd, but the remaining stabilizer alone cannot necessarily suppress the decomposition of 1233yd. However, adding water in the range of several hundred ppm by weight or more can stabilize the composition containing 1233yd, enabling it to be stored for long periods of time.

2. Storage of Compositions Compositions containing 1233yd and water, and compositions containing 1233yd, water, and additives, can be stored by sealing them in a container made of, for example, polyethylene, polytetrafluoroethylene, tetrafluoroethylene/perfluoroalkoxyethylene copolymer, metals such as stainless steel and iron, or glass. The interior of the container does not need to be coated, and the composition may be in contact with the above-mentioned material inside the container. Alternatively, a container made of a metal such as stainless steel or iron with a glass-coated inner surface may be used. After the composition is poured into the container, an inert gas such as nitrogen or argon may be sealed inside. When glass is selected as the material, the container may be covered with a light-shielding film to block ultraviolet and visible light, or a glass container made of glass containing iron oxide may be used. Furthermore, when storing a small amount of composition (e.g., a few mL to several hundred mL), a glass ampoule may be used as the container, and the composition may be poured into the ampoule and then partially melted to seal it.

The composition may be deoxidized before being sealed in a container. This can further suppress decomposition of 1233yd by oxygen. Deoxidation is performed by solidifying the composition in a container using, for example, liquid nitrogen or dry ice, then reducing the pressure inside the container (for example, 10 Pa to 300 Pa), sealing it, and leaving it to cool until it returns to the external ambient temperature. This operation can be repeated several times (for example, two to five times). Alternatively, deoxidation can be performed by bubbling an inert gas such as nitrogen or argon through the composition.

As shown in the examples, adding water to 1233yd inhibits the decomposition of 1233yd. Therefore, by configuring the composition to contain water, the composition's functionality as a solvent for lubricant coating solutions, heat transfer medium, refrigerant, foaming agent, solvent, cleaning agent, propellant, or fire extinguishing agent can be maintained for a long period of time, and corrosion, deterioration, and damage to equipment using the composition can be prevented.

In the following examples, 1233 yd obtained by dehydrofluorination of 244 ca was used as Sample A, and 1233 yd obtained by precision distillation of Sample A was used as Sample B. No degassing or other deoxygenation treatments were performed on the 1233 yd. Analysis of the organic components of Samples A and B was performed using a gas chromatograph (Agilent, Model No. 7890B) equipped with an FID detector, and the component ratios were determined based on the area ratios of each organic component in the chromatogram.

Analysis of the ionic components of samples A and B was performed using an ion chromatograph (Thermo Fisher Scientific Aquion, column: AS-22, eluent: carbonate-based eluent), and the component ratios were determined based on the area ratio of each ion in the chromatogram. Specifically, 4 g of sample A or B was extracted with 4 g of ultrapure water, and this solution was analyzed using the ion chromatograph.

The compositions of Samples A and B are shown in Table 1. Sample A contained octene as an additive added during dehydrofluorination, and the total amount of octene in Sample A was 2.0 wt%. On the other hand, because most of the octene was removed by precision distillation, the octene concentration in Sample B was low, at 3.2 wt ppm. Octene contains at least four isomers, and as shown in Table 1, these isomers were detected as Octene-1 to Octene-4. The individual octenes detected as Octene-1 to Octene-4 were not identified.

Samples A and B were each subjected to water addition and dehydration. Water addition was performed by adding water to 30 g of sample A or B using a microsyringe. Dehydration, on the other hand, was performed on sample A or B using molecular sieves as a dehydrating agent. Hereinafter, samples A subjected to water addition and dehydration will be referred to as samples A1 and A2, respectively, and samples B subjected to water addition and dehydration will be referred to as samples B1 and B2, respectively. The amount of water contained in these samples A1, A2, B1, and B2 was measured using a Karl Fischer moisture meter.

1. Example 1
In this example, the results of a storage test in which samples A1, A2, B1, and B2 were sealed in glass containers will be described.

First, samples A1, A2, B1, and B2 were each poured into a glass vial (inner diameter approximately 3.5 mm, length approximately 6.5 cm), and the sealed samples were left to stand at 55°C for six days in the dark. The glass vials were then opened, and the samples were analyzed by ion chromatography. The analytical results are shown in Table 2.

As shown in Table 1, the concentrations of fluoride ions, _CHF2CO2- ^ions , chloride ions, and _CF3CO2- ^ions were extremely low in both Samples A _and B before the start of the storage test. In Samples A1 and A2, which contained 2.0% octene as an additive, almost no increase in _ion concentration was observed even after the storage test, regardless of the amount of water. Patent Document 2 discloses that adding a stabilizer such as an unsaturated hydrocarbon to 1233yd stabilizes 1233yd and suppresses the increase in ion component concentration due to decomposition. Therefore, the results of Samples A1 and A2 can be said to be consistent with the disclosure of Patent Document 2.

However, in sample B1, the ion concentration significantly increased, even though the additive octene was contained at a concentration of 0.001% by weight to 0.1% by weight (i.e., 10 ppm to 1000 ppm), which is the optimal stabilizer concentration disclosed in Patent Document 2. Furthermore, as disclosed in Patent Document 1, 1233yd is unstable in water, and the water content is required to be less than 1000 ppm, preferably less than 100 ppm. However, in sample B1, even though the water concentration satisfies this range, a significant increase in ion concentration was observed. This result indicates that the decomposition of 1233yd cannot necessarily be suppressed under the conditions disclosed in Patent Documents 1 and 2.

In contrast, sample B2, which contained saturated water (1,600 ppm by weight) obtained by the water addition process, showed only a slight increase in chloride ions. This indicates that by adding water to a certain concentration or higher, the decomposition of 1233yd can be suppressed without being significantly dependent on the additive concentration, and compositions containing 1233yd can be stored stably.

Incidentally, Japanese Patent Application Laid-Open No. 2016-216477 (hereinafter referred to as the Reference Document) describes the effect of adding water on the stability of hydrofluorocarbons 2,3,3,3-tetrafluoropropene (hereinafter referred to as 1234yf) and 1,3,3,3-tetrafluoropropene (hereinafter referred to as 1234ze) in the presence of high concentrations of oxygen. According to this document, 1234yf and 1234ze are purified by distillation, and therefore no deoxygenation treatment is performed. Therefore, it can be understood from this reference that although 1234yf and 1234ze contain trace amounts of oxygen, 1234yf and 1234ze containing trace amounts of oxygen are stable, and no ionic components are detected even when left standing at 150°C for one week, regardless of whether water is added. This suggests that this reference document teaches that water has no effect on the stability of hydrofluorocarbons and fluorochlorocarbons containing trace amounts of oxygen.

Reconsidering the results of this example, it is believed that samples A1 to B2 contain trace amounts of oxygen because none of the samples were subjected to deoxygenation treatments such as degassing or nitrogen bubbling. Therefore, the results of this example indicate that when the oxygen concentration is low, the decomposition of 1233yd can be suppressed by adding water. Considering the knowledge that 1233yd decomposes rapidly in the presence of water, the fact that the addition of water improves the stability of compositions containing 1233yd is believed to be an unexpected effect.

2. Example 2
As described above, it was confirmed that the decomposition of 1233yd was suppressed by adding water. In this example, octene was used as an additive, and the effect of additive concentration in the presence of water was examined in detail.

In the experiment, 1-octene was added to sample B to prepare samples B3 to B10 with different 1-octene contents. These samples were added to glass vials in the same manner as in Example 1 and stored at 55°C in the dark. The glass vials were then opened and the samples analyzed by ion chromatography. The results after three days of storage are shown in Table 3, and the results after six days of storage are shown in Table 4.

As shown in Tables 3 and 4, the stability of 1233yd did not show a significant dependency on the amount of additive in the range of approximately 150 ppm by weight to 2% by weight. It was found that adding approximately 150 ppm by weight of additive ensured that 1233yd remained stable even when the water concentration was several hundred ppm by weight. In other words, if the additive concentration was approximately 150 ppm or higher, adjusting the water concentration to approximately 200 ppm to 500 ppm could suppress the decomposition of 1233yd. Therefore, for example, if the equipment or facilities used in the composition have low durability or are prone to deterioration in the presence of high concentrations of water, formulating the composition to contain both additive and water can prevent adverse effects on the equipment or facilities.

3. Example 3
In this example, the results of storing a composition containing 1233yd in a container containing stainless steel are described.

The above-mentioned samples A, B1, and B2 (60 g each) were sealed in a 120 cc autoclave (manufactured by Taiatsu Glass Co., Ltd.) and left to stand at 55°C for 7 days. The autoclave was then opened, and the samples were analyzed by ion chromatography. The analytical results are shown in Table 5.

As in Example 1, even in an environment where 1233yd is in contact with stainless _steel , when the water concentration is as low as 50 ppm by weight, it was found that the concentrations of fluoride ions, _CHF2CO2- ^ions , chloride ions, _{and CF3CO2-} ^ions increase after the storage test. However, it was found that the increase in the concentrations of these ions was significantly suppressed in Sample B2, to which water was added so that the amount of water was 1600 ppm by weight. In particular, it was found that the decomposition of 1233yd could be almost completely suppressed in Sample A, which contained 2.0% octene as an additive, by adjusting the amount of water so that the concentration was 260 ppm by weight.

Claims (7)

comprising 1-chloro-2,3,3-trifluoro-1-propene, an additive, and water;
the amount of water is greater than 260 ppm by weight and less than or equal to 1600 ppm by weight relative to 1-chloro-2,3,3-trifluoro-1-propene ;
the amount of the additive is 10 ppm by weight or more and 2% by weight or less relative to 1-chloro-2,3,3-trifluoro-1-propene,
The composition, wherein the additive is an unsubstituted alkene . The composition according to claim 1 is used in at least one selected from the group consisting of a solvent for a lubricant coating liquid, a heat transfer medium, a refrigerant, a foaming agent, a solvent, a cleaning agent, a propellant, and a fire extinguishing agent. 2. The composition of claim 1 , wherein the unsubstituted alkene comprises at least any of 1-octene, 2-octene, 3-octene, and 4-octene. adding water and an additive to 1-chloro-2,3,3-trifluoro-1-propene;
the addition of water is carried out so that the amount of water is more than 260 ppm by weight and not more than 1600 ppm by weight relative to 1-chloro-2,3,3-trifluoro-1-propene ;
the additive is added so that the amount of the additive is 10 ppm by weight or more and 2% by weight or less relative to 1-chloro-2,3,3-trifluoro-1-propene;
A method for preserving a composition, wherein the additive is an unsubstituted alkene . The method according to claim 4 , wherein the composition is used for at least one selected from the group consisting of a solvent for a lubricant coating liquid, a heat transfer medium, a refrigerant, a foaming agent, a solvent, a cleaning agent, a propellant, and a fire extinguisher. 5. The method of claim 4 , wherein the composition is stored in a container comprising polyethylene, polytetrafluoroethylene, tetrafluoroethylene/perfluoroalkoxyethylene copolymer, stainless steel, iron, or glass. The method according to claim 4 , wherein the unsubstituted alkene comprises at least any of 1-octene, 2-octene, 3-octene, and 4-octene.