WO2021085134A1 - Composition comprising 1-chloro-2,3,3-trifluoro-1-propene and water, and method for storing composition - Google Patents

Abstract

One of the embodiments of the present invention addresses the problem of providing a method for storing a composition containing 1-chloro-2,3,3-trifluoro-1-propene stably, or providing a composition that contains 1-chloro-2,3,3-trifluoro-1-propene and can be stored for a long period. The composition comprises 1-chloro-2,3,3-trifluoro-1-propene, an additive, and water. The amount of water can be selected in a range larger than 200 ppm by weight and equal to or less than 1600 ppm by weight relative to the amount of 1-chloro-2,3,3-trifluoro-1-propene. The additive may be an unsubstituted alkene.

Description

A composition containing 1-chloro-2,3,3-trifluoro-1-propene and water, and a method for preserving the composition.

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

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

International Publication No. 2017/01/8412 International Publication No. 2017/12201

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

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

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

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

According to the embodiment of the present invention, the composition containing 1-chloro-2,3,3-trifluoro-1-propene can be stably stored for a long period of time. Further, it is possible to provide a composition containing 1-chloro-2,3,3-trifluoro-1-propene, which can be stably stored for a long period of time.

Hereinafter, each embodiment of the present invention will be described. However, the present invention can be implemented in various aspects without departing from the gist thereof, and is not construed as being limited to the description contents of the embodiments illustrated below. In addition, even if the action and effect are different from the action and effect brought about by the aspects of the following embodiments, those that are clear from the description of the present specification or those that can be easily predicted by those skilled in the art are of course. Is understood to be brought about by the present invention.

Hereinafter, a composition containing 1-chloro-2,3,3-trifluoro-1-propene (hereinafter referred to as 1233yd) according to one of the embodiments of the present invention, and this composition are stably stored. The method of doing this will be described.

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

1-1.1233yd
1233yd, which is a kind of chlorofluorocarbon, may be E-form (1233yd (E)), Z-form (1233yd (Z)), or a mixture thereof. In the case of a mixture, the ratio of E-form to Z-form can also be arbitrarily selected. For example, the ratio of E-form to the total amount of E-form and Z-form 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 E-form to Z-form may be calculated by nuclear magnetic resonance spectroscopy (NMR), or may be obtained from the area ratio of chromatograms of 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 having high quantification.}

This composition is due to its high dissolving power of 1233 yd to various solutes, nonflammability, large heat of vaporization, low boiling point, etc., and can be used as a solvent (solvent for lubricant coating liquid) used when applying a lubricant, or as a solvent for a lubricant coating liquid. It can be used for various purposes such as a heat medium, a refrigerant, a foaming agent, a solvent, a cleaning agent, a propellant, and a fire extinguishing agent. In addition, since 1233yd has a low GWP, this composition is also characterized in that it is less likely to cause global warming than conventional compositions mainly containing hydrofluorocarbons and hydrochlorofluorocarbons.

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

Bases used for defluorinated hydrogen include alkali metals such as sodium, potassium and lithium, or hydroxides of Group 2 elements such as magnesium, calcium, strontium and barium, carbonates, oxides, alkoxides and amides. Can be mentioned. Considering that the base reacts with 244ca in a molar ratio of 1: 1 it may be used in an equimolar amount of 244ca or in an excess amount of 244ca. Specifically, the base is 1.0 equivalent or more and 3.0 equivalent or less, 1.0 equivalent or more and 2.0 equivalent or less, 1.0 equivalent or more and 1.5 equivalent or less, or 1.0 equivalent or more with respect to 244ca. 1.2 Equivalent or less is appropriately selected.

The base is dissolved in water, an alcohol having 1 to 4 carbon atoms such as methanol, ethanol, isopropanol and 1-butanol, or an ether such as tetrahydrofuran and dioxane, and this base solution is added dropwise to a bulk solution of 1233 yd or 1233 yd. Defluorinated hydrogen can be carried out at. The solvent constituting the solution of 1233 yd is not limited, and examples thereof include the above-mentioned alcohols and ethers having 1 to 4 carbon atoms, and aromatic hydrocarbons such as toluene and xylene.

For defluorinated hydrogen, a phase transfer catalyst may be used. Examples of the phase transfer catalyst include quaternary ammonium salts, quaternary phosphonium salts, quaternary sulfonium salts, pyridine salts, crown ethers and the like. When a quaternary ammonium salt, a quaternary phosphonium salt, a quaternary sulfonium salt, or a pyridine salt is used, the counter anions include chloride ion, bromide ion, iodide ion, hydroxide ion, phosphate ion, and p. -Toluene sulfonate ion and the like can be mentioned.

There is no restriction on the temperature of defluorinated hydrogen, and for example, it is appropriately selected from -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.

For defluorinated hydrogen, a stabilizer may be added to the reaction system. 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, tetrahydrofuran, glycidol, methylglycidyl ether, allylglycidyl ether, 1,2-butylene oxide, phenylglycidyl ether, Epoxy compounds such as cyclohexene oxide and epichlorohydrin, allyl alcohols such as phenol, olefinic alcohols such as 1-buten-3-ol; 3-methyl-1-butin-3-ol, 3-methyl-1-pentin-3-3 Examples thereof include acetylene-based alcohols such as oars, and acrylic acid esters such as methyl acrylate, ethyl acrylate, and butyl acrylate. Among them, an alkene such as octene, which is inexpensive, has relatively low reactivity, and has a low possibility of adversely affecting an apparatus used when using a composition containing 1233 yd, is preferable. Although isomers may be present in alkenes, one isolated 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-hepten, 2-methyl-2-hepten, 2-methyl-3. -Hexene, 3-Methyl-1-Hexene, 3-Methyl-2-Hexene, 3-Methyl-3-Hexene, 4-Methyl-1-Hexene, 4-Methyl-2-Hexene, 4 -Methyl-3-hexene, 5-methyl-1-hexene, 5-methyl-2-hepten, 5-methyl-3-hexene, 6-methyl-1-hepten, 6-methyl-2- Heptene, 6-methyl-3-hexene, 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-hexene, 3-ethyl-3-hexene, 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- Any one of 2-pentene, 3,4,4-trimethyl-2-pentene, 3-ethyl-2-methyl-2-pentene, 3-ethyl-4-methyl-2-pentene may be used, or A mixture of these may be used.

After defluorinated hydrogen, the organic layer is extracted, washed with an aqueous solution of a base such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, etc., and then washed with water. The organic layer may be further washed with saturated saline. Then, a crude product of 1233 yd can be obtained by simply dehydrating with a dehydrating agent such as magnesium sulfate or sodium sulfate. The composition may be prepared without purifying the crude product, or the composition may be prepared using 1233 yd isolated by distillation purification.

Although a small amount of oxygen is present in the unpurified 1233 yd and the 1233 yd purified by distillation, a treatment for removing oxygen from the 1233 yd (for example, a deoxidizing treatment such as degassing treatment or bubbling of an inert gas). There is no need to do. As shown in Examples, the composition can be stably stored for a long period of time by adding water or water and an additive without performing the oxygen scavenging treatment of 1233 yd.

1-2. The amount of water contained in the water composition is 1233 yd obtained by distillation purification, or water is added to the crude product containing 1233 yd obtained by simple dehydration by any method, or dehydration treatment is performed. It can be adjusted by. When water is added, the distilled 1233 yd or the simply dehydrated 1233 yd crude product may be weighed and water may be dropped using a micropipette or a microsyringe. When the dehydration treatment is performed, an appropriate amount (for example, 5% by weight) of a dehydrating agent such as molecular sieves may be added and filtered. The amount of water constituting the composition is higher than 200 ppm by weight and 1600 ppm by weight or less, higher than 200 wt ppm and 1400 wt ppm or less, higher than 200 wt ppm and 1200 wt ppm or less, 200 wt ppm or less with respect to 1233 yd. It is selected from a range higher than 1000 ppm by weight or greater than 200 ppm by weight and less than 500 ppm by weight. The amount of water constituting the composition is 260 wt ppm or more and 1600 wt ppm or less, 260 wt ppm or more and 1400 wt ppm or less, 260 wt ppm or more and 1200 wt ppm or less, 260 wt ppm or more and 1000 wt ppm or less. It may be selected from the following range, or a range of 260 ppm by weight or more and 500 wt ppm or less. The amount of water in the composition can be determined using, for example, a coulometric titration method. Water is preferably added to 1233 yd after being distilled, filtered, extracted, treated with an ion exchange resin or activated carbon.

1-3. Additives When the composition contains additives, the amount is 2 wt ppm or more and 5 wt% or less, 10 wt ppm or more and 2 wt% or less, 10 wt ppm or more and 1 wt% or less, or 10 wt ppm with respect to 1233 yd. Additives are added so as to be in the range of 0.5% by weight or less. Additives may be added in the same manner as when water is added. When the additive and the stabilizer used for defluorinated hydrogen are the same, the stabilizer remaining in the crude product may be used as the additive without adding the additive separately.

Examples of the additive include nitro compounds, epoxy compounds, phenol derivatives, ethers, alcohols, imidazole derivatives, amines, unsaturated hydrocarbons and the like. Further, these may be used alone or in combination of two or more kinds of additives.

Examples of nitro compounds include aliphatic or aromatic nitro compounds. Examples of the aliphatic nitro compound include nitromethane, nitroethane, 1-nitropropane, 2-nitropropane and the like. Aromatic nitro compounds include, for example, 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-, Alternatively, p-nitrophenol, o-, m-, p-nitroanisole and the like can be mentioned.

Examples of the epoxy compound include allyl glycidyl ethers such as ethylene oxide, 1,2-butylene oxide, propylene oxide, styrene oxide, cyclohexene oxide, glycidol, epichlorohydrin, glycidyl methacrylate and phenylglycidyl ether, methyl glycidyl ether, butyl glycidyl ether and 2-. In addition to monoepoxy compounds exemplified by ethylhexyl glycidyl ether and the like, many such as diepoxybutane, vinylcyclohexendioxide, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, glycerin polyglycidyl ether, trimethylol propanthrglycidyl ether and the like. Examples include functional epoxy compounds.

Examples of the phenol derivative include an unsubstituted phenol and a compound having various substituents such as an alkyl group, an alkenyl group, an alkoxy group, a carboxyl group, a carbonyl group and a halogen together with a phenolic hydroxyl group on the aromatic ring. Examples of such phenol derivatives include 2,6-di-t-butyl-p-cresol, o-cresol, m-cresol, p-cresol, timol, pt-butylphenol, o-methoxyphenol, m. -In addition to monovalent phenol derivatives such as methoxyphenol, p-methoxyphenol, eugenol, isoeugenol, butylhydroxyanisole, xylenol, t-butylcatechol, 2,5-di-t-aminohydroquinone, 2,5-di Examples thereof include divalent phenol derivatives such as -t-butylhydroquinone.

Examples of ethers include 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 and ethyl vinyl ether. , Ethylpropargyl 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, In addition to ethers in which aliphatic substituents such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol methyl ether, trimethoxyethane, triethoxyethane, and tetrahydrofuran are bonded to oxygen, ethylphenyl ether, diphenyl ether, ethylnaphthyl ether, etc. An ether in which at least one aromatic substituent such as ethylene glycol monophenyl ether, ethylene glycol diphenyl ether, anisole, or anetol is bonded to oxygen may be used.

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-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, Examples thereof include α-terpineol, 2,6-dimethyl-4-heptanol, nonyl alcohol, tetradecyl alcohol, 2-propin-1-ol and the like. Among these alcohols, methanol, ethanol, isopropanol, and 2-propin-1-ol, which are alcohols having 1 to 3 carbon atoms, are preferable.

Examples of the imidazole derivative include unsubstituted imidazole, 1-methylimidazole having an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, or an aryl group as a substituent on nitrogen, 1-n-butylimidazole, and the like. 1-Phenylimidazole, 1-benzylimidazole, 1- (β-oxyethyl) imidazole, 1-methyl-2-propylimidazole, 1-methyl-2-isobutylimidazole, 1-n-butyl-2-methylimidazole, 1, Examples thereof include 2-dimethylimidazole, 1,4-dimethylimidazole, 1,5-dimethylimidazole, 1,2,5-trimethylimidazole, 1,4,5-trimethylimidazole and 1-ethyl-2-methylimidazole.

Examples of amines include pentylamine, hexylamine, diisopropylamine, diisobutylamine, di-n-propylamine, triethylamine, morpholine, N-methylmorpholine, benzylamine, dibenzylamine, α-methylbenzylamine, methylamine, and dimethylamine. , Trimethylamine, ethylamine, diethylamine, propylamine, isopropylamine, dipropylamine, butylamine, isobutylamine, dibutylamine, tributylamine, dipentylamine, trypentylamine, 2-ethylhexylamine, etc. Examples include 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, it may be a polyfunctional amine such as ethylenediamine, propylenediamine, diethylenetriamine or tetraethylenepentamine, or it may be a herooxylamine such as diethylhydroxylamine.

Examples of unsaturated hydrocarbons include penten isomers such as 1-pentene, 2-pentene, 2-methyl-1-butene, 3-methyl-1-butene, and 2-methyl-2-butene, 1-hexene, and 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- Hexene isomers such as 2-butene, 2-methyl-2-pentene, 3-methyl-2-pentene, 4-methyl-2-pentene, 2,3-dimethyl-2-butene, 1-heptene, 2-heptene , 3-Hexene, 4-Hexene, Hexene isomers such as 3-ethyl-2-pentene, 1-octene, 2-octene, 3-octene, 4-octene, 2-methyl-1-hepten, 2- To Methyl-2-hexene, 2-Methyl-3-Hexene, 3-Methyl-1-Hexene, 3-Methyl-2-Hexene, 3-Methyl-3-Hexene, 4-Methyl-1- Pten, 4-Methyl-2-Hexene, 4-Methyl-3-Hexene, 5-Methyl-1-Hexene, 5-Methyl-2-Hexene, 5-Methyl-3-Hexene, 6-Methyl -1-Heptene, 6-methyl-2-hepten, 6-methyl-3-hepten, 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-hexene, 3-ethyl-3-hexene, 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 Octene isomers such as -methyl-2-pentene and 3-ethyl-4-methyl-2-pentene, nonene isomers such as 1-nonene, and diene such as butadiene, isoprene, hexadiene, heptadiene and octadiene, cyclohexene, Examples thereof include unsaturated cyclic compounds such as cyclohexadiene, cycloheptene, cycloheptadiene, cyclooctene, and cyclooctadiene.

As disclosed in Patent Document 1, 1233yd is unstable to water and has been considered to be easily decomposed by water. However, as shown in the examples, by adding water to the composition containing 1233 yd, the decomposition of 1233 yd is effectively suppressed, and as a result, the composition containing 1233 yd can be stably stored for a long period of time. .. Further, when the additive is contained in the composition, the amount of water added in the composition can be reduced. Specifically, under the condition that both water and the additive are present, the stability of 1233 yd is significantly improved even if the amount of water and the additive is several hundred ppm by weight with respect to 1233 yd, and the decomposition thereof. Can be effectively suppressed.

Further, when synthesizing 1233 yd in the presence of a stabilizer, the stabilizer may not be completely removed from the generated 1233 yd. In this case, the stabilizer can function as an additive for the composition containing 1233 yd, but the residual stabilizer alone cannot necessarily suppress the decomposition of 1233 yd. However, by adding water of about several hundred weight ppm or more, the composition containing 1233 yd can be stabilized and stored for a long period of time.

2. Preservation of Composition The composition containing 1233 yd and water, and the composition containing 1233 yd, water, and additives include, for example, polyethylene, polytetrafluoroethylene, tetrafluoroethylene / perfluoroalkoxyethylene copolymer, stainless steel, iron, and the like. It can be stored by sealing it in a container containing the metal, glass, or the like as a material. The inside of the container does not have to be coated, and the composition may come into contact with the above-mentioned material inside the container. Alternatively, a container made of a metal such as stainless steel or iron and having a glass-coated inner surface may be used. After injecting the composition into the container, an inert gas such as nitrogen or argon may be filled. When glass is selected as the material, the container may be covered with a light-shielding film for shielding ultraviolet rays or visible light, or a glass container using glass containing iron oxide as the material may be used. When storing a small amount (for example, several mL to several hundred mL) of the composition, use a glass ampoule as a container, inject the composition into the ampoule, and then melt and seal a part of the composition. May be good.

The composition may be deoxidized before being sealed in the container. Thereby, the decomposition of 1233 yd by oxygen can be further suppressed. In the deoxidizing treatment, the composition is solidified in a container using, for example, liquid nitrogen or dry ice, then the inside of the container is depressurized (for example, 10 Pa or more and 300 Pa), sealed, and allowed to stand until the temperature returns to the external environmental temperature. This operation may be repeated several times (for example, 2 to 5 times). Alternatively, the composition may be deoxidized by bubbling an inert gas such as nitrogen or argon.

As shown in the examples, the decomposition of 1233yd is suppressed by adding water to 1233yd. Therefore, by constructing the composition so as to contain water, the composition can function as a solvent for a lubricant coating liquid, a heat medium, a refrigerant, a foaming agent, a solvent, a cleaning agent, a propellant, or a fire extinguisher for a long period of time. Not only can it be maintained, but it can also prevent corrosion, deterioration, and damage to the equipment that uses the composition.

In the following examples, 1233yd obtained by defluorinated hydrogen of 244ca was used as sample A, and 1233yd obtained by precision distillation of sample A was used as sample B. No deoxidizing treatment such as degassing treatment was performed on 1233yd. The analysis of the organic components of the samples A and B was performed using gas chromatography equipped with a FID detector (manufactured by Agilent, model number 7890B), and the component ratio was determined based on the area ratio of each organic component in the chromatogram. ..

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

Table 1 shows the compositions of samples A and B. Sample A contained octene added at the time of hydrogen fluoride as an additive, and the total amount of octene in sample A was 2.0% by weight. On the other hand, since most of the octene was removed by precision distillation, the concentration of octene in Sample B was low, 3.2 ppm by weight. In addition, octene contains at least four kinds of isomers, and as shown in Table 1, these isomers were detected as Octene-1 to Octene-4. No individual octenes detected as Octene-4 from Octene-1 were identified.

These samples A and B were subjected to water addition treatment and dehydration treatment, respectively. The water addition treatment was performed by adding water to 30 g of sample A or B with a microsyringe. On the other hand, the dehydration treatment was performed on sample A or B using a molecular sieve as a dehydrating agent. Hereinafter, the samples obtained by adding water and dehydrating the sample A will be referred to as samples A1 and A2, respectively, and the samples obtained by adding water and dehydrating the sample B 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 titer.

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

First, samples A1, A2, B1 and B2 were each injected into a glass vial (inner diameter of about 3.5 mm and length of about 6.5 cm), and the enclosed sample was allowed to stand at a temperature of 55 ° C. for 6 days under shading. .. The glass vial was then opened and the sample analyzed by ion chromatography. The analysis results are shown in Table 2.

As shown in Table 1, in the samples A and B before the start of the storage test, _{the concentrations of fluoride ion, CHF 2} CO ₂ ^- ion, chloride ion, and CF ₃ CO ₂ ^- ion are extremely low. In the samples A1 and A2 containing 2.0% of octene as an additive, an increase in the ion concentration was hardly confirmed 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 1233 yd stabilizes 1233 yd and suppresses an increase in ionic component concentration due to decomposition. Therefore, it can be said that the results of the samples A1 and A2 are consistent with the disclosure of Patent Document 2.

However, in sample B1, the additive octene is contained at a concentration of 0.001% by weight to 0.1% by weight (that is, 10ppm to 1000ppm), which is the optimum concentration of the stabilizer disclosed in Patent Document 2. Nevertheless, the concentration of ions has increased significantly. Further, as disclosed in Patent Document 1, 1233yd is unstable with respect to water, and the water content is required to be less than 1000 ppm, preferably less than 100 ppm. However, in sample B1, although the water concentration satisfies this range, a significant increase in the ion concentration is observed. Therefore, this result is obtained under the conditions disclosed in Patent Documents 1 and 2. This means that the decomposition of 1233 yd cannot always be suppressed.

On the other hand, it was found that in sample B2 containing saturated water (1600 ppm by weight) obtained by the water addition treatment, chloride ions increased only slightly. From this, it was found that by adding water so as to have a concentration of a certain level or higher, the decomposition of 1233 yd was suppressed without being greatly dependent on the concentration of the additive, and the composition containing 1233 yd could be stably stored. It was.

In addition, Japanese Patent Application Laid-Open No. 2016-216477 (hereinafter, reference) describes hydrofluorocarbons 2,3,3,3-tetrafluoropropene (hereinafter, 1234yf) and 1,3,3,3-tetrafluoropropene (hereinafter, reference). , 1234ze), the effect of adding water on stability in the presence of high oxygen concentrations is described. According to the description in this document, since the purification of 1234yf and 1234ze is performed by distillation, the deoxidizing treatment is not performed. Therefore, 1234yf and 1234ze contain a trace amount of oxygen, but 1234yf and 1234ze containing a trace amount of oxygen are stable, and the ionic component remains even if the mixture is allowed to stand at 150 ° C. for one week regardless of the addition of water. It is understood from this reference that it is not detected. This suggests that this reference teaches that water has no effect on the stability of hydrofluorocarbons and fluorochlorocarbons, which contain trace amounts of oxygen.

When the results of this example are taken into consideration again, it is considered that the samples A1 to B2 contain a small amount of oxygen because none of the samples have been degassed or deoxidized such as nitrogen bubbling. Therefore, the result of this example means that when the oxygen concentration is low, the decomposition of 1233 yd can be suppressed by adding water. Considering the finding that 1233 yd rapidly decomposes in the presence of water, it is considered that the addition of water improves the stability of the composition containing 1233 yd, which is an unpredictable effect.

2. Example 2
As described above, it was confirmed that the addition of water suppressed the decomposition of 1233 yd. In this example, octene is used as an additive, and the result of detailed examination of the concentration effect of the additive in the presence of water will be described.

In the experiment, 1-octene was added to sample B, and samples B3 to B10 were prepared as samples having different 1-octene contents. These samples were added to a glass vial in the same manner as in Example 1 and stored at 55 ° C. under shading. The glass vial was then opened and the sample analyzed by ion chromatography. Table 3 shows the results stored for 3 days, and Table 4 shows the results stored for 6 days.

As shown in Tables 3 and 4, in the range of about 150 wt ppm to 2 wt%, the dependence of the amount of additive on the stability of 1233 yd was not significantly observed, and about 150 wt ppm of additive was added. Therefore, it was found that 1233 yd exists stably even when the water concentration is about several hundreds by weight ppm. That is, when the concentration of the additive is about 150 ppm or more, the decomposition of 1233 yd can be suppressed by adjusting the concentration of water to be about 200 ppm to 500 ppm. Therefore, for example, when the equipment or equipment used when using the composition has low durability against high-concentration water or deterioration occurs, the composition is configured to contain additives and water. By doing so, it is possible to prevent adverse effects on the equipment and facilities.

3. 3. Example 3
In this example, the result of storing the composition containing 1233 yd in a container containing stainless steel as a material will be described.

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

Similar to Example 1, even in an environment where 1233yd is in contact with stainless steel, if the concentration of water is as low as 50 ppm by weight, fluoride ions, CHF ₂ CO ₂ ^- ion, chloride ions, CF ₃ CO _{2 after the storage test} ^- it was found that the concentration of ions increases. However, it was found that the increase in these ion concentrations was significantly suppressed in the sample B2 in which water was added so that the amount of water was 1600 ppm by weight. In particular, in Sample A containing 2.0% of octene as an additive, it was found that the decomposition of 1233 yd can be almost completely suppressed by adjusting the amount of water so that the concentration becomes 260 ppm by weight.

Claims (14)

1. A composition containing 1-chloro-2,3,3-trifluoro-1-propene, additives, and water.
2. The composition according to claim 1, which is used for at least one selected from a solvent for a lubricant coating liquid, a heat medium, a refrigerant, a foaming agent, a solvent, a detergent, a propellant, and a fire extinguisher.
3. The composition according to claim 1, wherein the amount of the water is higher than 200 ppm by weight and 1600 ppm by weight or less with respect to 1-chloro-2,3,3-trifluoro-1-propene.
4. The composition according to claim 1, wherein the amount of the additive is 10% by weight or more and 2% by weight or less with respect to 1-chloro-2,3,3-trifluoro-1-propene.
5. The composition according to claim 4, wherein the additive is an unsubstituted alkene.
6. The composition according to claim 5, wherein the unsubstituted alkene contains at least one of 1-octene, 2-octene, 3-octene, and 4-octene.
7. A method of preserving a composition comprising adding water and additives to 1-chloro-2,3,3-trifluoro-1-propene.
8. The method according to claim 7, wherein the composition is used for at least one selected from a solvent for a lubricant coating liquid, a heat medium, a refrigerant, a foaming agent, a solvent, a detergent, a propellant, and a fire extinguisher.
9. The addition of the water is carried out so that the amount of the water is higher than 200 ppm by weight and 1600 ppm by weight or less with respect to 1-chloro-2,3,3-trifluoro-1-propene. The method described in.
10. The method according to claim 7, wherein the composition is stored in a container containing polyethylene, polytetrafluoroethylene, tetrafluoroethylene / perfluoroalkoxyethylene copolymer, stainless steel, iron, or glass.
11. The addition of the additive is carried out so that the amount of the additive is 10% by weight or more and 2% by weight or less with respect to 1-chloro-2,3,3-trifluoro-1-propene. The method described.
12. The method according to claim 11, wherein the additive is an unsubstituted alkene.
13. The method of claim 12, wherein the unsubstituted alkene comprises at least one of 1-octene, 2-octene, 3-octene, and 4-octene.
14. A composition containing 1-chloro-2,3,3-trifluoro-1-propene and water.