WO2021085134A1 - Composition comprising 1-chloro-2,3,3-trifluoro-1-propene and water, and method for storing composition - Google Patents
Composition comprising 1-chloro-2,3,3-trifluoro-1-propene and water, and method for storing composition Download PDFInfo
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- WO2021085134A1 WO2021085134A1 PCT/JP2020/038751 JP2020038751W WO2021085134A1 WO 2021085134 A1 WO2021085134 A1 WO 2021085134A1 JP 2020038751 W JP2020038751 W JP 2020038751W WO 2021085134 A1 WO2021085134 A1 WO 2021085134A1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
- C07C17/42—Use of additives, e.g. for stabilisation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C21/00—Acyclic unsaturated compounds containing halogen atoms
- C07C21/02—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds
- C07C21/18—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds containing fluorine
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/30—Materials not provided for elsewhere for aerosols
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/24—Hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/28—Organic compounds containing halogen
- C11D7/30—Halogenated hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/50—Solvents
Definitions
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- the ratio of E-form to Z-form can also be arbitrarily selected.
- 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.
- this composition is also characterized in that it is less likely to cause global warming than conventional compositions mainly containing hydrofluorocarbons and hydrochlorofluorocarbons.
- 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.
- 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.
- 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.
- phase transfer catalyst For defluorinated hydrogen, a phase transfer catalyst may be used.
- the phase transfer catalyst include quaternary ammonium salts, quaternary phosphonium salts, quaternary sulfonium salts, pyridine salts, crown ethers and the like.
- 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.
- defluorinated hydrogen 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.
- 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.
- alkene such as octene
- isomers may be present in alkenes, one isolated isomer may be used, or a mixture of two or more isomers may be used.
- 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.
- 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.
- a base such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, etc.
- the organic layer may be further washed with saturated saline.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- additives examples 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.
- nitro compounds include aliphatic or aromatic nitro compounds.
- 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.
- epoxy compound examples 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-.
- 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-.
- ethylhexyl glycidyl ether 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.
- phenol derivatives 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.
- 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.
- phenol derivatives such as methoxyphenol, p-methoxyphenol, eugenol, isoeugenol, butylhydroxyanisole, xylenol, t-butylcatechol, 2,5-di-t-aminohydroquinone, 2,5-di
- divalent phenol derivatives such as -t-butylhydroquinone.
- 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.
- 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, cyclo
- imidazole derivative examples 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.
- amines examples include pentylamine, hexylamine, diisopropylamine, diisobutylamine, di-n-propylamine, triethylamine, morpholine, N-methylmorpholine, benzylamine, dibenzylamine, ⁇ -methylbenzylamine, methylamine, and dimethylamine. , Trimethylamine, ethylamine, diethylamine, propylamine, isopropylamine, dipropylamine, butylamine, isobutylamine, dibutylamine, tributylamine, dipentylamine, trypentylamine, 2-ethylhexylamine, etc.
- aromatic amines such as aniline, N-methylaniline, N, N-dimethylaniline, N, N-diethylaniline, diphenylamine and triphenylamine, and nitrogen-containing heteroaromatic compounds such as pyridine.
- aromatic amines such as aniline, N-methylaniline, N, N-dimethylaniline, N, N-diethylaniline, diphenylamine and triphenylamine
- nitrogen-containing heteroaromatic compounds such as pyridine.
- it may be a polyfunctional amine such as ethylenediamine, propylenediamine, diethylenetriamine or tetraethylenepentamine, or it may be a herooxylamine such as diethylhydroxylamine.
- 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
- 1233yd is unstable to water and has been considered to be easily decomposed by water.
- 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. ..
- the additive when the additive is contained in the composition, the amount of water added in the composition can be reduced.
- 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.
- the stabilizer when synthesizing 1233 yd in the presence of a stabilizer, the stabilizer may not be completely removed from the generated 1233 yd.
- 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.
- the composition containing 1233 yd can be stabilized and stored for a long period of time.
- 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.
- an inert gas such as nitrogen or argon may be filled.
- the container 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.
- a glass ampoule 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.
- 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).
- the composition may be deoxidized by bubbling an inert gas such as nitrogen or argon.
- 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.
- 1233yd obtained by defluorinated hydrogen of 244ca was used as sample A
- 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. ..
- 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.
- concentration of octene in Sample B was low, 3.2 ppm by weight.
- 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.
- 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.
- the dehydration treatment was performed on sample A or B using a molecular sieve as a dehydrating agent.
- samples A1 and A2 the samples obtained by adding water and dehydrating the sample A
- samples B1 and B2 the samples obtained by adding water and dehydrating the sample B
- the amount of water contained in these samples A1, A2, B1 and B2 was measured using a Karl Fischer titer.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- Example 2 As described above, it was confirmed that the addition of water suppressed the decomposition of 1233 yd.
- 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.
- 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.
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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
本発明の実施形態の一つは、1-クロロ-2,3,3-トリフルオロ-1-プロペンと水とを含む組成物、およびこの組成物を保存する方法に関する。
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.
近年、地球温暖化能力(GWP)が低い種々のハイドロフルオロカーボンやクロロフルオロカーボンが開発されている。その一つの例として、1-クロロ-2,3,3-トリフルオロ-1-プロペンが知られている(特許文献1、2参照)。
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).
本発明の実施形態の一つは、1-クロロ-2,3,3-トリフルオロ-1-プロペンを含む組成物を安定的に保存するための方法を提供することを課題の一つとする。あるいは、本発明の実施形態の一つは、長期保存可能な1-クロロ-2,3,3-トリフルオロ-1-プロペンを含む組成物を提供することを課題の一つとする。
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.
本発明の実施形態の一つは、1-クロロ-2,3,3-トリフルオロ-1-プロペン、添加剤、および水を含む組成物である。
One of the embodiments of the present invention is a composition containing 1-chloro-2,3,3-trifluoro-1-propene, an additive, and water.
本発明の実施形態の一つは、1-クロロ-2,3,3-トリフルオロ-1-プロペンに、水、および添加剤を添加することを含む、組成物を保存する方法である。
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.
本発明の実施形態の一つは、1-クロロ-2,3,3-トリフルオロ-1-プロペンと水を含む組成物である。
One of the embodiments of the present invention is a composition containing 1-chloro-2,3,3-trifluoro-1-propene and water.
本発明の実施形態により、1-クロロ-2,3,3-トリフルオロ-1-プロペンを含む組成物を安定的に長期にわたって保存することができる。また、安定的に長期保存可能な、1-クロロ-2,3,3-トリフルオロ-1-プロペンを含む組成物を提供することができる。
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.
以下、本発明の各実施形態について説明する。但し、本発明は、その要旨を逸脱しない範囲において様々な態様で実施することができ、以下に例示する実施形態の記載内容に限定して解釈されるものではない。また、以下の実施形態の態様によりもたらされる作用効果とは異なる他の作用効果であっても、本明細書の記載から明らかなもの、又は、当業者において容易に予測し得るものについては、当然に本発明によりもたらされるものと解される。
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.
以下、本発明の実施形態の一つに係る、1-クロロ-2,3,3-トリフルオロ-1-プロペン(以下、1233ydと記す)を含む組成物、およびこの組成物を安定的に保存する方法について説明する。
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.組成物
この組成物は、以下の式で表される1233ydと水を含む。組成物はさらに添加剤を含んでもよい。
1. 1. Composition This composition contains 1233 yd represented by the following formula and water. The composition may further include additives.
この組成物は、以下の式で表される1233ydと水を含む。組成物はさらに添加剤を含んでもよい。
1-1.1233yd
クロロフルオロカーボンの一種である1233ydは、E体(1233yd(E))であってもよく、Z体(1233yd(Z))であってもよく、あるいはこれらの混合物でも良い。混合物の場合、E体とZ体の割合も任意に選択することができる。例えばE体とZ体の総量に対するE体の割合は、1%以上99%以下、1%以上50%以下、あるいは1%以上20%以下でも良い。E体とZ体の割合は、核磁気共鳴分光法(NMR)で算出してもよく、あるいはガスクロマトグラフィーや液体クロマトグラフィーのクロマトグラムの面積比から求めてもよい。NMRを用いる場合、1H-NMR、19F-NMR、13C-NMRのいずれを用いてもよいが、定量性が高い1H-NMRまたは19F-NMRを用いることが好ましい。 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.
クロロフルオロカーボンの一種である1233ydは、E体(1233yd(E))であってもよく、Z体(1233yd(Z))であってもよく、あるいはこれらの混合物でも良い。混合物の場合、E体とZ体の割合も任意に選択することができる。例えばE体とZ体の総量に対するE体の割合は、1%以上99%以下、1%以上50%以下、あるいは1%以上20%以下でも良い。E体とZ体の割合は、核磁気共鳴分光法(NMR)で算出してもよく、あるいはガスクロマトグラフィーや液体クロマトグラフィーのクロマトグラムの面積比から求めてもよい。NMRを用いる場合、1H-NMR、19F-NMR、13C-NMRのいずれを用いてもよいが、定量性が高い1H-NMRまたは19F-NMRを用いることが好ましい。 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.
本組成物は、種々の溶質に対する1233ydの高い溶解力、不燃性、大きな気化熱、低い沸点などに起因し、潤滑剤を塗布する際に使用する溶剤(潤滑剤塗布液用溶剤)として、あるいは熱媒体、冷媒、発泡剤、溶媒、洗浄剤、噴射剤、消火剤など、様々な用途に利用することができる。また、1233ydはGWPが低いため、本組成物は、従来のハイドロフルオロカーボンやハイドロクロロフルオロカーボンを主に含む組成物と比較して、地球温暖化を招きにくい点も大きな特徴である。
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.
1233ydの合成方法に制約はないが、高効率な合成法として、以下の式に示す3-クロロ-1,1,2,2-テトラフルオロプロパン(以下、244caと記す)の塩基による脱フッ化水素が挙げられる。
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.
脱フッ化水素に用いられる塩基としては、ナトリウムやカリウム、リチウムなどのアルカリ金属若しくはマグネシウムやカルシウム、ストロンチウム、バリウムなどの第2族元素の水酸化物、炭酸塩、酸化物、アルコキシド、アミドなどが挙げられる。塩基は244caと1:1のモル比で反応することを考慮し、244caと等モル、あるいは244caよりも過剰量用いればよい。具体的には、塩基は244caに対して1.0当量以上3.0当量以下、1.0当量以上2.0当量以下、1.0当量以上1.5当量以下、あるいは1.0当量以上1.2当量以下の範囲から適宜選択される。
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.
塩基は水、メタノールやエタノール、イソプロパノール、1-ブタノールなどの炭素数1から4のアルコール、あるいはテトラヒドロフランやジオキサンなどのエーテルに溶解させ、この塩基溶液をバルクの1233yd、あるいは1233ydの溶液に滴下させることで脱フッ化水素を行うことができる。1233ydの溶液を構成する溶媒に制約はなく、上記炭素数1から4のアルコールやエーテル、あるいはトルエンやキシレンなどの芳香族炭化水素などが挙げられる。
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.
脱フッ化水素では、相間移動触媒を用いてもよい。相間移動触媒としては、第四級アンモニウム塩、第四級ホスホニウム塩、第四級スルホニウム塩、ピリジン塩、クラウンエーテル類などが例示される。第四級アンモニウム塩、第四級ホスホニウム塩、第四級スルホニウム塩、またはピリジン塩を用いる場合、カウンターアニオンとしては塩化物イオン、臭化物イオン、ヨウ化物イオン、水酸化物イオン、リン酸イオン、p-トルエンスルホン酸イオンなどが挙げられる。
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.
脱フッ化水素の温度に制約はなく、例えば-40℃以上+80℃以下、-20℃以上+60℃以下、あるいは0℃以上+40℃以下から適宜選択される。
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.
脱フッ化水素では、反応系に安定化剤を加えてもよい。安定化剤としては、ヘキセン、ヘプテン、オクテン、ペンタジエン、シクロペンテン、シクロヘキセンなどのアルケン(オレフィン)、ニトロメタンやニトロエタン、ニトロプロパンなどの脂肪族ニトロ化合物、ニトロベンゼンやニトロトルエン、ニトロアニリンなどの芳香族ニトロ化合物、ジメトキシメタンや1,2-ジメトキシエタン、1,4-ジオキサン、1,3,5-トリオキサン、テトラヒドロフランなどのエーテル、グリシドールやメチルグリシジルエーテル、アリルグリシジルエーテル、1,2-ブチレンオキシド、フェニルグリシジルエーテル、シクロヘキセンオキシド、エピクロルヒドリンなどのエポキシ化合物、フェノールなどのアリルアルコール、1-ブテン-3-オールなどのオレフィン系アルコール;3-メチル-1-ブチン-3-オール、3-メチル-1-ペンチン-3-オールなどのアセチレン系アルコール、アクリル酸メチル、アクリル酸エチル、アクリル酸ブチルなどのアクリル酸エステルが挙げられる。なかでも、オクテンのような安価であり、比較的反応性が低く、1233ydを含む組成物を利用する際に用いられる装置に対して悪影響を及ぼす可能性の低いアルケンが好ましい。アルケンには異性体が存在する場合があるが、単離された一種類の異性体を用いてもよく、あるいは二種類以上の異性体の混合物を用いてもよい。例えばオクテンを安定化剤として使用する場合、1-オクテン、2-オクテン、3-オクテン、4-オクテン、2-メチル-1-へプテン、2-メチル-2-へプテン、2-メチル-3-へプテン、3-メチル-1-へプテン、3-メチル-2-へプテン、3-メチル-3-へプテン、4-メチル-1-へプテン、4-メチル-2-へプテン、4-メチル-3-へプテン、5-メチル-1-へプテン、5-メチル-2-へプテン、5-メチル-3-へプテン、6-メチル-1-へプテン、6-メチル-2-へプテン、6-メチル-3-へプテン、2,3-ジメチル-1-ヘキセン、2,4-ジメチル-1-ヘキセン、2,5-ジメチル-1-ヘキセン、3,4-ジメチル-1-ヘキセン、3,5-ジメチル-1-ヘキセン、4,5-ジメチル-1-ヘキセン、3,3-ジメチル-1-ヘキセン、4,4-ジメチル-1-ヘキセン、5,5-ジメチル-1-ヘキセン、3-エチル-1-ヘキセン、4-エチル-1-ヘキセン、2,3-ジメチル-2-ヘキセン、2,4-ジメチル-2-ヘキセン、2,5-ジメチル-2-ヘキセン、3,4-ジメチル-2-ヘキセン、3,5-ジメチル-2-ヘキセン、4,5-ジメチル-2-ヘキセン、4,4-ジメチル-1-ヘキセン、5,5-ジメチル-1-ヘキセン、3-エチル-2-ヘキセン、4-エチル-2-ヘキセン、2,3-ジメチル-3-ヘキセン、2,4-ジメチル-3-ヘキセン、2,5-ジメチル-3-ヘキセン、3,4-ジメチル-3-ヘキセン、3,5-ジメチル-3-ヘキセン、2,2-ジメチル-3-ヘキセン、3-エチル-3-ヘキセン、2,3,3-トリメチル-1-ペンテン、2,3,4-トリメチル-1-ペンテン、2,4,4-トリメチル-1-ペンテン、3,3,4-トリメチル-1-ペンテン、2,3,4-トリメチル-2-ペンテン、2,4,4-トリメチル-2-ペンテン、3,4,4-トリメチル-2-ペンテン、3-エチル-2-メチル-2-ペンテン、3-エチル-4-メチル-2-ペンテンのいずれか一種を用いてもよく、あるいはこれらの混合物でもよい。
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.
脱フッ化水素の後、有機層を抽出し、水酸化ナトリウムや水酸化カリウム、炭酸ナトリウム、炭酸水素ナトリウム、炭酸カリウム、炭酸水素カリウムなどの塩基の水溶液で洗浄し、その後水で洗浄する。有機層をさらに飽和食塩水で洗浄してもよい。その後、硫酸マグネシウムや硫酸ナトリウムなどの脱水剤を用いて簡易的に脱水することで1233ydの粗生成物が得られる。この粗生成物を精製することなく本組成物を調製してもよく、あるいは蒸留精製によって単離される1233ydを用いて本組成物を調製してもよい。
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.
未精製の1233yd、および蒸留によって精製される1233ydには微量の酸素が存在するが、1233ydに対して酸素を除去するための処理(例えば脱気処理や不活性ガスのバブリングなどの脱酸素処理)を行う必要は無い。実施例で示すように、1233ydの脱酸素処理を行わなくても、水、あるいは水と添加剤を添加することで、本組成物を長期にわたって安定的に保存することが可能である。
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.水
組成物に含まれる水の量は、蒸留精製して得られる1233yd、または簡易的な脱水で得られる1233ydを含む粗生成物に対して任意の方法で水を添加する、あるいは脱水処理を行うことで調整することができる。水を添加する場合には、蒸留された1233yd、または簡易脱水された1233yd粗生成物を秤量し、マイクロピペットやマイクロシリンジなどを用いて水を滴下すればよい。脱水処理を行う場合にはモレキュラーシーブスなどの脱水剤を適切な量(例えば5重量%)加えてろ過すればよい。組成物を構成する水の量は、1233ydに対して200重量ppmよりも高く1600重量ppm以下、200重量ppmよりも高く1400重量ppm以下、200重量ppmよりも高く1200重量ppm以下、200重量ppmよりも高く1000重量ppm以下の範囲、あるいは200重量ppmよりも高く500重量ppm以下の範囲から選択される。また、組成物を構成する水の量は、1233ydに対して260重量ppm以上1600重量ppm以下、260重量ppm以上1400重量ppm以下、260重量ppm以上1200重量ppm以下、260重量ppm以上1000重量ppm以下の範囲、あるいは260重量ppm以上500重量ppm以下の範囲から選択されてもよい。組成物中の水の量は、例えば電量滴定法などを用いて求めることができる。なお、水は蒸留や濾過、抽出、イオン交換樹脂や活性炭との処理を行った後に1233ydに添加することが好ましい。 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.
組成物に含まれる水の量は、蒸留精製して得られる1233yd、または簡易的な脱水で得られる1233ydを含む粗生成物に対して任意の方法で水を添加する、あるいは脱水処理を行うことで調整することができる。水を添加する場合には、蒸留された1233yd、または簡易脱水された1233yd粗生成物を秤量し、マイクロピペットやマイクロシリンジなどを用いて水を滴下すればよい。脱水処理を行う場合にはモレキュラーシーブスなどの脱水剤を適切な量(例えば5重量%)加えてろ過すればよい。組成物を構成する水の量は、1233ydに対して200重量ppmよりも高く1600重量ppm以下、200重量ppmよりも高く1400重量ppm以下、200重量ppmよりも高く1200重量ppm以下、200重量ppmよりも高く1000重量ppm以下の範囲、あるいは200重量ppmよりも高く500重量ppm以下の範囲から選択される。また、組成物を構成する水の量は、1233ydに対して260重量ppm以上1600重量ppm以下、260重量ppm以上1400重量ppm以下、260重量ppm以上1200重量ppm以下、260重量ppm以上1000重量ppm以下の範囲、あるいは260重量ppm以上500重量ppm以下の範囲から選択されてもよい。組成物中の水の量は、例えば電量滴定法などを用いて求めることができる。なお、水は蒸留や濾過、抽出、イオン交換樹脂や活性炭との処理を行った後に1233ydに添加することが好ましい。 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.添加剤
組成物に添加剤が含まれる場合、その量は1233ydに対して2重量ppm以上5重量%以下、10重量ppm以上2重量%以下、10重量ppm以上1重量%以下、あるいは10重量ppm以上0.5重量%以下の範囲となるように添加剤が加えられる。添加剤の添加も、水の添加と同様の方法で行えばよい。添加剤と脱フッ化水素の際に用いられる安定化剤が同一の場合、添加剤を別途添加せず、粗生成物中に残留する安定化剤を添加剤として用いてもよい。 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.
組成物に添加剤が含まれる場合、その量は1233ydに対して2重量ppm以上5重量%以下、10重量ppm以上2重量%以下、10重量ppm以上1重量%以下、あるいは10重量ppm以上0.5重量%以下の範囲となるように添加剤が加えられる。添加剤の添加も、水の添加と同様の方法で行えばよい。添加剤と脱フッ化水素の際に用いられる安定化剤が同一の場合、添加剤を別途添加せず、粗生成物中に残留する安定化剤を添加剤として用いてもよい。 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.
添加剤としては、例えば、ニトロ化合物、エポキシ化合物、フェノール誘導体、エーテル、アルコール、イミダゾール誘導体、アミン、不飽和炭化水素等が挙げられる。また、これらは単独で用いてもよく、2種類以上の添加剤を併用してもよい。
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.
ニトロ化合物としては、例えば、脂肪族または芳香族ニトロ化合物が挙げられる。脂肪族ニトロ化合物としては、例えば、ニトロメタン、ニトロエタン、1-ニトロプロパン、2-ニトロプロパンなどが挙げられる。芳香族ニトロ化合物としては、例えば、ニトロベンゼン、o-、m-、またはp-ジニトロベンゼン、トリニトロベンゼン、o-、m-、またはp-ニトロトルエン、o-、m-、またはp-エチルニトロベンゼン、2,3-、2,4-、2,5-、2,6-、3,4-、または3,5-ジメチルニトロベンゼン、o-、m-、またはp-ニトロアセトフェノン、o-、m-、またはp-ニトロフェノール、o-、m-、またはp-ニトロアニソールなどが挙げられる。
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.
エポキシ化合物としては、例えばエチレンオキシド、1,2-ブチレンオキシド、プロピレンオキシド、スチレンオキシド、シクロヘキセンオキシド、グリシドール、エピクロルヒドリン、グリシジルメタクリレート、フェニルグリシジルエーテルなどのアリルグリシジルエーテル、メチルグリシジルエーテル、ブチルグリシジルエーテル、2-エチルヘキシルグリシジルエーテルなどに例示されるモノエポキシ化合物に加え、ジエポキシブタン、ビニルシクロヘキセンジオキシド、ネオペンチルグリコールジグリシジルエーテル、エチレングリコールジグリシジルエーテル、グリセリンポリグリシジルエーテル、トリメチロールプロパントルグリシジルエーテルなどの多官能性エポキシ化合物等が挙げられる。
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.
フェノール誘導体としては、無置換のフェノールのほか、例えば、フェノール性水酸基とともにアルキル基、アルケニル基、アルコキシ基、カルボキシル基、カルボニル基、ハロゲンなど各種の置換基を芳香環上に有する化合物が挙げられる。このようなフェノール誘導体としては、例えば、2,6-ジ-t-ブチル-p-クレゾール、o-クレゾール、m-クレゾール、p-クレゾール、チモール、p-t-ブチルフェノール、o-メトキシフェノール、m-メトキシフェノール、p-メトキシフェノール、オイゲノール、イソオイゲノール、ブチルヒドロキシアニソール、キシレノールなどの1価のフェノール誘導体に加え、t-ブチルカテコール、2,5-ジ-t-アミノヒドロキノン、2,5-ジ-t-ブチルヒドロキノンなどの2価のフェノール誘導体などが挙げられる。
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.
エーテルとしては、ジメチルエーテル、ジエチルエーテル、ジプロピルエーテル、ジイソプロピルエーテル、ジブチルエーテル、ジペンチルエーテル、ジイソペンチルエーテル、エチルメチルエーテル、エチルプロピルエーテル、エチルイソプロピルエーテル、エチルイソブチルエーテル、エチルイソペンチルエーテル、エチルビニルエーテル、エチルプロパルギルエーテル、1,4-ジオキサン、1,3-ジオキサン、1,3,5-トリオキサン、エチレングリコールモノメチルエーテル、エチレングリコールモノブチルエーテル、エチレングリコールモノベンジルエーテル、エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジプロピレングリコールメチルエーテル、トリメトキシエタン、トリエトキシエタン、テトラヒドロフランなどの脂肪族置換基が酸素に結合されたエーテルのほか、エチルフェニルエーテル、ジフェニルエーテル、エチルナフチルエーテル、エチレングリコールモノフェニルエーテル、エチレングリコールジフェニルエーテル、アニソール、アネトールなどの芳香族置換基が少なくとも一つ酸素に結合されたエーテルでも良い。
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.
アルコールとしては、メタノール、エタノール、1-プロパノール、イソプロパノール、1-ブタノール、2-ブタノール、2-メチル-1-プロパノール、2-メチル-2-プロパノール、1-ペンタノール、2-ペンタノール、1-エチル-1-プロパノール、2-メチル-1-ブタノール、3-メチル-1-ブタノール、3-メチル-2-ブタノール、ネオペンチルアルコール、1-ヘキサノール、2-メチル-1-ペンタノール、4-メチル-2-ペンタノール、2-エチル-1-ブタノール、1-ヘプタノール、2-ヘプタノール、3-ヘプタノール、1-オクタノール、2-オクタノール、2-エチル-1-ヘキサノール、1-ノナノール、3,5,5-トリメチル-1-ヘキサノール、1-デカノール、1-ウンデカノール、1-ドデカノール、ベンジルアルコール、シクロヘキサノール、1-メチルシクロヘキサノール、2-メチルシクロヘキサノール、3-メチルシクロヘキサノール、4-メチルシクロヘキサノール、α-テルピネオール、2,6-ジメチル-4-ヘプタノール、ノニルアルコール、テトラデシルアルコール、2-プロピン-1-オールなどが挙げられる。これらのアルコールなかでも、炭素数が1から3のアルコールであるメタノール、エタノール、イソプロパノール、2-プロピン-1-オールが好ましい。
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.
イミダゾール誘導体としては、未置換のイミダゾールのほか、炭素数1から18のアルキル基、シクロアルキル基、またはアリール基を窒素上の置換基として有する1-メチルイミダソール、1-n-ブチルイミダゾール、1-フェニルイミダゾール、1-ベンジルイミダゾール、1-(β-オキシエチル)イミダゾール、1-メチル-2-プロピルイミダゾール、1-メチル-2-イソブチルイミダゾール、1-n-ブチル-2-メチルイミダゾール、1,2-ジメチルイミダゾール、1,4-ジメチルイミダゾール、1,5-ジメチルイミダゾール、1,2,5ートリメチルイミダゾール、1,4,5-トリメチルイミダゾール、1-エチル-2-メチルイミダゾールなどが挙げられる。
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.
アミンとしては、ペンチルアミン、ヘキシルアミン、ジイソプロピルアミン、ジイソブチルアミン、ジ-n-プロピルアミン、トリエチルアミン、モルホリン、N-メチルモルホリン、ベンジルアミン、ジベンジルアミン、α-メチルベンジルアミン、メチルアミン、ジメチルアミン、トリメチルアミン、エチルアミン、ジエチルアミン、プロピルアミン、イソプロピルアミン、ジプロピルアミン、ブチルアミン、イソブチルアミン、ジブチルアミン、トリブチルアミン、ジペンチルアミン、トリペンチルアミン、2-エチルヘキシルアミンなどに例示される脂肪族アミンに加え、アニリン、N-メチルアニリン、N,N-ジメチルアニリン、N,N-ジエチルアニリン、ジフェニルアミン、トリフェニルアミンなどの芳香族アミン、ピリジンなどの含窒素ヘテロ芳香族化合物が挙げられる。あるいはエチレンジアミンやプロピレンジアミン、ジエチレントリアミン、テトラエチレンペンタミンなどの多官能性アミンでも良よく、ジエチルヒドロキシルアミンなどのヒロロキシルアミンでもよい。
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.
不飽和炭化水素としては、1-ペンテン、2-ペンテン、2-メチル-1-ブテン、3-メチル-1-ブテン、2-メチル-2-ブテンなどのペンテン異性体、1-ヘキセン、2-ヘキセン、3-ヘキセン、2-メチル-1-ペンテン、3-メチル-1-ペンテン、4-メチル-1-ペンテン、2-エチル-1-ブテン、3-エチル-1-ブテン、3-エチル-2-ブテン、2-メチル-2-ペンテン、3-メチル-2-ペンテン、4-メチル-2-ペンテン、2,3-ジメチル-2-ブテンなどのヘキセン異性体、1-ヘプテン、2-ヘプテン、3-ヘプテン、4-ヘプテン、3-エチル-2-ペンテンなどのへプテン異性体、1-オクテン、2-オクテン、3-オクテン、4-オクテン、2-メチル-1-へプテン、2-メチル-2-へプテン、2-メチル-3-へプテン、3-メチル-1-へプテン、3-メチル-2-へプテン、3-メチル-3-へプテン、4-メチル-1-へプテン、4-メチル-2-へプテン、4-メチル-3-へプテン、5-メチル-1-へプテン、5-メチル-2-へプテン、5-メチル-3-へプテン、6-メチル-1-へプテン、6-メチル-2-へプテン、6-メチル-3-へプテン、2,3-ジメチル-1-ヘキセン、2,4-ジメチル-1-ヘキセン、2,5-ジメチル-1-ヘキセン、3,4-ジメチル-1-ヘキセン、3,5-ジメチル-1-ヘキセン、4,5-ジメチル-1-ヘキセン、3,3-ジメチル-1-ヘキセン、4,4-ジメチル-1-ヘキセン、5,5-ジメチル-1-ヘキセン、3-エチル-1-ヘキセン、4-エチル-1-ヘキセン、2,3-ジメチル-2-ヘキセン、2,4-ジメチル-2-ヘキセン、2,5-ジメチル-2-ヘキセン、3,4-ジメチル-2-ヘキセン、3,5-ジメチル-2-ヘキセン、4,5-ジメチル-2-ヘキセン、4,4-ジメチル-1-ヘキセン、5,5-ジメチル-1-ヘキセン、3-エチル-2-ヘキセン、4-エチル-2-ヘキセン、2,3-ジメチル-3-ヘキセン、2,4-ジメチル-3-ヘキセン、2,5-ジメチル-3-ヘキセン、3,4-ジメチル-3-ヘキセン、3,5-ジメチル-3-ヘキセン、2,2-ジメチル-3-ヘキセン、3-エチル-3-ヘキセン、2,3,3-トリメチル-1-ペンテン、2,3,4-トリメチル-1-ペンテン、2,4,4-トリメチル-1-ペンテン、3,3,4-トリメチル-1-ペンテン、2,3,4-トリメチル-2-ペンテン、2,4,4-トリメチル-2-ペンテン、3,4,4-トリメチル-2-ペンテン、3-エチル-2-メチル-2-ペンテン、3-エチル-4-メチル-2-ペンテンなどのオクテン異性体、1-ノネンなどのノネン異性体、また、ブタジエン、イソプレン、ヘキサジエン、ヘプタジエン、オクタジエンなどのジエン、シクロヘキセン、シクロヘキサジエン、シクロヘプテン、シクロヘプタジエン、シクロオクテン、シクロオクタジエンなどの不飽和環状化合物が挙げられる。
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.
特許文献1に開示されているように、1233ydは水に対して不安定であり、水によって容易に分解すると考えられてきた。しかしながら実施例に示すように、1233ydを含む組成物に水を添加することにより、1233ydの分解が効果的に抑制され、その結果、長期にわたって1233ydを含む組成物を安定的に保存することができる。また、添加剤が組成物に含まれる場合、組成物中の水の添加量を減少させることができる。具体的には、水と添加剤の両者が存在する条件下では、水と添加剤の量が1233ydに対してそれぞれ数百重量ppmであっても1233ydの安定性が大幅に向上し、その分解を効果的に抑制することができる。
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.
また、安定化剤の存在下で1233ydの合成を行う場合、生成した1233ydから安定化剤を完全に除去できない場合がある。この場合、安定化剤は1233ydを含む組成物の添加剤として機能することができるが、必ずしも残留する安定化剤だけでは1233ydの分解を抑制することはできない。しかしながら、数百重量ppm程度の水、あるいはそれ以上の量の水を添加することで、1233ydを含む組成物を安定化させ、長期にわたる保存が可能となる。
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.組成物の保存
1233ydと水を含む組成物、および1233yd、水、ならびに添加剤を含む組成物は、例えばポリエチレン、ポリテトラフルオロエチレン、テトラフルオロエチレン/パーフルオロアルコキシエチレン共重合体、ステンレスや鉄などの金属、またはガラスなどを材料として含む容器内で密閉することによって保存することができる。容器内部はコーティング処理などをしなくてもよく、容器内で組成物が上記材料と接してもよい。あるいは、ステンレスまたは鉄などの金属で作製され、内表面がガラスコーティングされた容器を用いてもよい。容器内に組成物を注入した後に窒素やアルゴンなどの不活性ガスを封入してもよい。なお、ガラスを材料として選択する場合には、紫外線や可視光を遮蔽するための遮光フィルムで容器を覆う、あるいは酸化鉄を含むガラスを材料として用いたガラス容器を用いてもよい。また、少量(例えば数mLから数百mL)の組成物を保存する場合には、容器としてガラス製のアンプルを用い、アンプル内に組成物を注入した後に一部を溶融して封止してもよい。 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.
1233ydと水を含む組成物、および1233yd、水、ならびに添加剤を含む組成物は、例えばポリエチレン、ポリテトラフルオロエチレン、テトラフルオロエチレン/パーフルオロアルコキシエチレン共重合体、ステンレスや鉄などの金属、またはガラスなどを材料として含む容器内で密閉することによって保存することができる。容器内部はコーティング処理などをしなくてもよく、容器内で組成物が上記材料と接してもよい。あるいは、ステンレスまたは鉄などの金属で作製され、内表面がガラスコーティングされた容器を用いてもよい。容器内に組成物を注入した後に窒素やアルゴンなどの不活性ガスを封入してもよい。なお、ガラスを材料として選択する場合には、紫外線や可視光を遮蔽するための遮光フィルムで容器を覆う、あるいは酸化鉄を含むガラスを材料として用いたガラス容器を用いてもよい。また、少量(例えば数mLから数百mL)の組成物を保存する場合には、容器としてガラス製のアンプルを用い、アンプル内に組成物を注入した後に一部を溶融して封止してもよい。 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.
組成物を容器内に密閉する前に、脱酸素処理を行ってもよい。これにより、酸素による1233ydの分解をさらに抑制することができる。脱酸素処理は、例えば液体窒素やドライアイスなどを用いて容器内で組成物を固化し、その後容器内を減圧して(例えば10Pa以上300Pa)密閉し、外部環境温度に戻るまで静置する。この操作を数回(例えば2回から5回)繰り返せばよい。あるいは組成物に対して窒素やアルゴンなどの不活性ガスをバブリングすることで脱酸素処理を行ってもよい。
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.
実施例で示されるように、1233ydに水を添加することで1233ydの分解が抑制される。したがって、水を含むように組成物を構成することで、組成物の潤滑剤塗布液用溶剤、熱媒体、冷媒、発泡剤、溶媒、洗浄剤、噴射剤、あるいは消火剤としての機能を長期にわたって維持できるのみならず、組成物を使用する装置の腐食や劣化、破損を防止することができる。
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.
以下の実施例では、244caの脱フッ化水素によって得られた1233ydを試料A、試料Aを精密蒸留して得られた1233ydを試料Bとして用いた。1233ydに対しては脱気処理などの脱酸素処理は行わなかった。試料A、Bの有機成分に対する分析は、FID検出器を備えたガスクロマトグラフィー(アジレント社製、型番7890B)を用いて行い、クロマトグラムにおける各有機成分の面積比に基づいて成分比を決定した。
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. ..
試料A、Bのイオン成分の分析は、イオンクロマトグラフ(Thermo Fisher Scientific社製Aquion、カラム:AS-22、溶離液:炭酸系溶離液)を用いて行い、クロマトグラムにおける各イオンの面積比に基づいて成分比を決定した。具体的には、4gの試料AまたはBを超純水4gで抽出し、この溶液をイオンクロマトグラフで分析した。
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.
試料A、Bの組成を表1に示す。試料Aには、脱フッ化水素時に添加されたオクテンが添加剤として含まれ、試料A中のオクテンの総量は2.0重量%であった。一方、精密蒸留によってオクテンの大部分が除去されるため、試料Bにはオクテンの濃度は低く、3.2重量ppmであった。なお、オクテンには少なくとも4種類の異性体が含まれており、表1に示すように、これらの異性体はOctene-1からOctene-4として検出した。Octene-1からOctene-4として検出された個々のオクテンの同定は行わなかった。
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.
これらの試料A、Bに対し、それぞれ水の添加処理と脱水処理を行った。水の添加処理は、30gの試料AまたはBに対して水をマイクロシリンジで添加することで行った。一方、脱水処理は、試料AまたはBに対して、脱水剤としてモレキュラーシーブを用いて行った。以下、試料Aに対して水添加処理と脱水処理した試料をそれぞれ試料A1、A2、試料Bに対して水添加処理と脱水処理した試料をそれぞれ試料B1、B2と呼ぶ。これらの試料A1、A2、B1、B2に含まれる水の量はカールフィッシャー水分計を用いて測定した。
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.実施例1
本実施例では、試料A1、A2、B1、B2をガラス容器内に封入して保存試験を行った結果を述べる。 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.
本実施例では、試料A1、A2、B1、B2をガラス容器内に封入して保存試験を行った結果を述べる。 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.
まず、試料A1、A2、B1、B2をそれぞれガラスバイアル(内径約3.5mm、長さ約6.5cm)に注入し、封入された試料を遮光下、55℃の温度で6日間静置した。その後ガラスバイアルを開封し、試料をイオンクロマトグラフで分析した。分析結果を表2に示す。
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.
表1に示されるように、保存試験開始前の試料A、Bでは、いずれもフッ化物イオンやCHF2CO2
-イオン、塩化物イオン、CF3CO2
-イオンの濃度は極めて低い。添加剤としてオクテンを2.0%含む試料A1、A2では、水の量に依存せず、保存試験後もイオンの濃度の増大は殆ど確認されなかった。特許文献2では、1233ydに対して不飽和炭化水素などの安定化剤を添加することで1233ydが安定化され、分解によるイオン成分濃度の増大が抑制されることが開示されている。したがって、試料A1、A2の結果は、特許文献2の開示と一致するともいえる。
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.
しかしながら試料B1では、添加剤であるオクテンが特許文献2が開示する安定化剤の最適濃度である0.001重量%から0.1重量%(すなわち、10ppmから1000ppm)の濃度で含まれているにもかかわらず、イオンの濃度が大幅に増大している。また、特許文献1に開示されているように、1233ydは水に対して不安定であり、水の含有量は1000ppm未満、好ましくは100ppm未満にすることが求められていた。しかし試料B1においては、水の濃度はこの範囲を満足しているにもかかわらず、イオン濃度の大幅な増大が見られることから、この結果は、特許文献1、2に開示された条件下では1233ydの分解が必ずしも抑制できないことを意味している。
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.
これに対し、水添加処理によって得られる飽和濃度の水(1600重量ppm)を含む試料B2では、塩化物イオンがわずかに増大したにとどまっていることが分かった。このことから、水を一定以上の濃度となるように添加することで、添加剤の濃度に大きく依存することなく、1233ydの分解が抑制され、1233ydを含む組成物を安定的に保存できることが分かった。
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.
なお、特開2016-216477(以下、参考文献)には、ハイドロフルオロカーボンである2,3,3,3-テトラフルオロプロペン(以下、1234yf)や1,3,3,3-テトラフルオロプロペン(以下、1234ze)の高濃度酸素存在下における安定性に対する水の添加効果が記載されている。この文献の記載によると、1234yfや1234zeの精製は蒸留で行っているため、脱酸素処理は行われていない。したがって、1234yfや1234zeには微量の酸素が含まれるが、微量の酸素を含む1234yfや1234zeは安定であり、水の添加の有無にかかわらず、150℃で1週間静置してもイオン成分は検知されないことがこの参考文献から理解される。このことはすなわち、この参考文献は、微量の酸素を含むハイドロフルオロカーボンやフルオロクロロカーボンの安定性に対し、水はなんら影響を及ぼさないことを教示していることを示唆している。
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.
本実施例の結果を再度参酌すると、いずれの試料に対しても脱気処理や窒素バブリングなどの脱酸素処理を行っていないため、試料A1からB2には微量の酸素が含まれると考えられる。したがって、本実施例の結果は、酸素濃度が低い場合では、水を添加することで1233ydの分解が抑制できることを意味している。1233ydは水の存在下では速やかに分解が生じるという知見を考慮すると、水を添加することで1233ydを含む組成物の安定性が向上するという点は予想できない効果であると考えられる。
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.実施例2
上述したように、水を加えることで1233ydの分解を抑制することが確認された。本実施例では、添加剤としてオクテンを用い、水存在下における添加剤の濃度効果を詳細に検討した結果を述べる。 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.
上述したように、水を加えることで1233ydの分解を抑制することが確認された。本実施例では、添加剤としてオクテンを用い、水存在下における添加剤の濃度効果を詳細に検討した結果を述べる。 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.
実験は、試料Bに対して1-オクテンを加え、1-オクテンの含有量の異なる試料として試料B3からB10を調製した。これらの試料を実施例1と同様にガラスバイアルに加え、遮光下、55℃で保存した。その後ガラスバイアルを開封し、試料をイオンクロマトグラフで分析した。3日間保存した結果を表3に、6日間保存した結果を表4にそれぞれ示す。
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.
表3、表4に示すように、約150重量ppmから2重量%の範囲において、1233ydの安定性に対する添加剤の量の依存性は顕著に観察されず、約150重量ppmの添加剤を加えることで、水濃度が数百重量ppm程度であっても1233ydは安定に存在することが分かった。すなわち、添加剤の濃度が約150ppm以上であれば、水の濃度が約200ppmから500ppmとなるように調整することで、1233ydの分解が抑制可能である。したがって、例えば組成物を使用する際に用いられる装置や設備が高濃度の水に対して耐久性が低い、あるいは劣化が生じるなどの場合には、添加剤と水を含むように組成物を構成することで、装置や設備に対する悪影響を防止することが可能となる。
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.実施例3
本実施例では、1233ydを含む組成物をステンレスを材料として含む容器内で保存した結果について述べる。 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.
本実施例では、1233ydを含む組成物をステンレスを材料として含む容器内で保存した結果について述べる。 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.
上述した試料A、B1、B2(各60g)を120ccの容積を有するオートクレーブ(耐圧硝子社製)内に密閉し、55℃で7日間静置した。その後、オートクレーブを開放し、試料をイオンクロマトグラフで分析した。分析結果を表5に示す。
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.
実施例1と同様、1233ydがステンレスと接する環境下でも、水の濃度が50重量ppmと低い場合には、保存試験後にフッ化物イオンやCHF2CO2
-イオン、塩化物イオン、CF3CO2
-イオンの濃度が増大することが分かった。しかしながら水の量が1600重量ppmとなるように水を添加した試料B2では、これらのイオン濃度の増大が大幅に抑制されることが分かった。特に添加剤としてオクテンを2.0%含む試料Aでは、濃度が260重量ppmとなるように水の量を調整することにより、1233ydの分解がほぼ完全に抑制できることが分かった。
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-クロロ-2,3,3-トリフルオロ-1-プロペン、添加剤、および水を含む組成物。 A composition containing 1-chloro-2,3,3-trifluoro-1-propene, additives, and water.
- 潤滑剤塗布液用溶剤、熱媒体、冷媒、発泡剤、溶媒、洗浄剤、噴射剤、および消火剤から選ばれる少なくとも一種に用いられる、請求項1に記載の組成物。 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.
- 前記水の量は、1-クロロ-2,3,3-トリフルオロ-1-プロペンに対して200重量ppmよりも高く1600重量ppm以下である、請求項1に記載の組成物。 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.
- 前記添加剤の量は、1-クロロ-2,3,3-トリフルオロ-1-プロペンに対して10重量ppm以上2重量%以下である、請求項1に記載の組成物。 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.
- 前記添加剤は無置換アルケンである、請求項4に記載の組成物。 The composition according to claim 4, wherein the additive is an unsubstituted alkene.
- 前記無置換アルケンは、少なくとも1-オクテン、2-オクテン、3-オクテン、および4-オクテンのいずれかを含む、請求項5に記載の組成物。 The composition according to claim 5, wherein the unsubstituted alkene contains at least one of 1-octene, 2-octene, 3-octene, and 4-octene.
- 1-クロロ-2,3,3-トリフルオロ-1-プロペンに、水、および添加剤を添加することを含む、組成物を保存する方法。 A method of preserving a composition comprising adding water and additives to 1-chloro-2,3,3-trifluoro-1-propene.
- 前記組成物は、潤滑剤塗布液用溶剤、熱媒体、冷媒、発泡剤、溶媒、洗浄剤、噴射剤、および消火剤から選ばれる少なくとも一種に用いられる、請求項7に記載の方法。 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.
- 前記水の添加は、前記水の量が1-クロロ-2,3,3-トリフルオロ-1-プロペンに対して200重量ppmよりも高く1600重量ppm以下となるように行われる、請求項7に記載の方法。 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.
- 前記組成物は、ポリエチレン、ポリテトラフルオロエチレン、テトラフルオロエチレン/パーフルオロアルコキシエチレン共重合体、ステンレス、鉄、またはガラスを含む容器に保存される、請求項7に記載の方法。 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.
- 前記添加剤の添加は、前記添加剤の量が1-クロロ-2,3,3-トリフルオロ-1-プロペンに対して10重量ppm以上2重量%以下となるように行われる請求項7に記載の方法。 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.
- 前記添加剤は無置換アルケンである、請求項11に記載の方法。 The method according to claim 11, wherein the additive is an unsubstituted alkene.
- 前記無置換アルケンは、少なくとも1-オクテン、2-オクテン、3-オクテン、および4-オクテンのいずれかを含む、請求項12に記載の方法。 The method of claim 12, wherein the unsubstituted alkene comprises at least one of 1-octene, 2-octene, 3-octene, and 4-octene.
- 1-クロロ-2,3,3-トリフルオロ-1-プロペンと水を含む組成物。 A composition containing 1-chloro-2,3,3-trifluoro-1-propene and water.
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