WO2016052562A1 - 2-クロロ-1,3,3,3-テトラフルオロプロペン及び1-クロロ-3,3,3-トリフルオロプロペンを含有する共沸様組成物 - Google Patents
2-クロロ-1,3,3,3-テトラフルオロプロペン及び1-クロロ-3,3,3-トリフルオロプロペンを含有する共沸様組成物 Download PDFInfo
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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
- C11D7/5036—Azeotropic mixtures containing halogenated solvents
- C11D7/504—Azeotropic mixtures containing halogenated solvents all solvents being halogenated hydrocarbons
- C11D7/5045—Mixtures of (hydro)chlorofluorocarbons
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- 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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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/143—Halogen containing compounds
- C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
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- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
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- 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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- 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
- C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
- C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
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- 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
- C09K5/048—Boiling liquids as heat transfer materials
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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
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
- F25B1/00—Compression machines, plants or systems with non-reversible cycle
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
- C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
- C08J2203/144—Perhalogenated saturated hydrocarbons, e.g. F3C-CF3
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- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/20—Ternary blends of expanding agents
- C08J2203/202—Ternary blends of expanding agents of physical blowing agents
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/06—Polyurethanes from polyesters
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- 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
- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/10—Components
- C09K2205/12—Hydrocarbons
- C09K2205/126—Unsaturated fluorinated hydrocarbons
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/22—All components of a mixture being fluoro compounds
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- 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
- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/32—The mixture being azeotropic
Definitions
- the present invention relates to 2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe) and 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd) which have utility in many applications.
- HCFO-1224xe 2-chloro-1,3,3,3-tetrafluoropropene
- HCFO-1233zd 1-chloro-3,3,3-trifluoropropene
- azeotrope-like composition is useful as a cleaning agent, a solvent, a silicone solvent, a foaming agent, a refrigerant or a heat medium for a heat pump, a high-temperature working fluid, or the like.
- HFCs hydrofluorocarbons
- chlorine which is an ozone depleting element
- HCFO-1233zd 1-Chloro-3,3,3-trifluoropropene
- E form trans form
- Z form cis form
- HCFO-1233zd (Z) HCFO-1233zd
- the geometric isomers are not distinguished or in the case of a mixture, it may be called HCFO-1233zd.
- HCFO-1233zd (E) having a boiling point of 19 ° C. is commercially produced as a next-generation blowing agent.
- HCFO-1233zd (Z) having a boiling point of 39 ° C. has been proposed for use as a solvent and a cleaning agent (Patent Document 1).
- HCFO-1224xe 2-chloro-1,3,3,3-tetrafluoropropene
- E isomer trans isomer
- Z isomer a cis isomer
- E trans isomer
- Z HCFO-1224xe
- the geometric isomers are not distinguished or in the case of a mixture, it may be called HCFO-1224xe.
- physical properties such as isolation of the trans isomer (E isomer) and cis isomer (Z isomer) and their boiling points.
- CFCs and CFC substitutes (hereinafter sometimes referred to as CFCs), a mixed refrigerant in which two or more types of CFCs are mixed has been proposed.
- refrigerant numbers R502, R507A, R404A, R407C, R410A of the American Society of Heating, Refrigerating and Air Conditioning Engineers (ASHRAE) are well known as mixed refrigerants.
- These mixed refrigerants are improved in coefficient of performance, refrigeration cycle, incombustibility, global warming coefficient and the like by mixing two or more kinds of chlorofluorocarbons at a specific ratio.
- chlorofluorocarbons have volatility, when used as a mixture, if any of the chlorofluorocarbons evaporates unilaterally, the composition changes during use and the physical properties change. Therefore, an azeotropic or azeotropic-like composition that volatilizes at substantially the same composition as the liquid phase is preferable.
- R502 mixed refrigerant of R22 and R115
- R507A mixed refrigerant of R143a and R125
- R410A its constituent components R32 and R125 are non-azeotropic, but are widely used as azeotrope-like refrigerants because the composition of the gas phase part and the liquid phase part are substantially the same. .
- Such an azeotropic composition or azeotropic-like composition is theoretically difficult to obtain on a desk with the current state of the art, and is a composition obtained only after actual confirmation by experiments.
- An object of the present invention is to provide an azeotrope-like composition of fluorine-containing olefins that has little influence on global warming and the like.
- the present invention is as follows.
- An azeotrope-like composition comprising:
- Trans-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd (E)) is contained in an amount of 1 mol% to 99.999 mol%, and trans-2-chloro-1,3,3,3-tetra An azeotrope-like composition containing 0.001 mol% or more and 99 mol% or less of fluoropropene (HCFO-1224xe (E)).
- An azeotrope-like composition comprising:
- ⁇ Invention 5> Containing 0.001 mol% or more and 99.999 mol% or less of cis-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (Z)), and trans-1-chloro-3,3,3 An azeotrope-like composition comprising 0.001 mol or more and 99.999 mol% or less of trifluoropropene (HCFO-1233zd (E)).
- ⁇ Invention 7> It contains 90% mol or more and 99.9 mol% or less of trans-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (E)), and cis-1-chloro-3,3,3- An azeotrope-like composition containing trifluoropropene (HCFO-1233zd (Z)) in an amount of 0.1 mol% to 10 mol%.
- a cleaning agent comprising the azeotrope-like composition according to any one of Inventions 1 to 9.
- ⁇ Invention 12> A silicone solvent comprising the azeotrope-like composition of any one of inventions 1 to 9.
- a blowing agent comprising the azeotrope-like composition according to any one of Inventions 1 to 9.
- a heat conducting medium comprising the azeotrope-like composition according to any one of Inventions 1 to 9.
- Invention 14 An organic Rankine cycle system device using a heat conduction medium.
- a high-temperature heat pump cycle system using a heat conduction medium according to the fourteenth aspect of the present invention.
- the azeotrope-like composition of the present invention it is possible to provide a composition that is nonflammable, has a small influence on the environment, and has substantially the same composition in the liquid phase part and the gas phase part. . Further, by using the azeotrope-like composition of the present invention, a cleaning agent that is nonflammable, has a small impact on the environment, and the liquid phase part and the gas phase part have substantially the same composition, Solvents, silicone solvents, blowing agents, refrigerants or heat pump heat media, or hot working fluids can be provided.
- FIG. 3 is a diagram for explaining a process for producing 2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe) from fluorine-containing olefins.
- FIG. 3 is a diagram showing a vapor-liquid equilibrium curve of trans-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd (E)) in a mixture containing E)).
- Cis-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (Z)) and trans-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd It is a figure which shows the vapor-liquid equilibrium curve of cis-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (Z)) in the mixture containing E)). The boiling point of the composition with respect to the mass ratio of trans-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (Z)) is shown.
- FIG. 3 shows a vapor-liquid equilibrium curve of trans-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (E)) in a mixture containing Z)).
- FIG. 3 is a diagram showing a vapor-liquid equilibrium curve of cis-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (Z)) in a mixture containing Z)).
- Cis-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (Z)) and trans-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd It is a Ph diagram of an azeotrope-like composition containing E)).
- FIG. 2 is a Ph diagram of 2,2-dichloro-1,1,1-trifluoroethane (HCFC-123).
- FIG. 2 is a Ph diagram of 2,2-dichloro-1,1,1-trifluoroethane (HCFC-123).
- Cis-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (Z)) and trans-1-chloro-3,3,3-trifluoropropene HCFO-1233zd (E ) Is a Ph diagram of an azeotrope-like composition.
- FIG. 2 is a Ph diagram of 2,2-dichloro-1,1,1-trifluoroethane (HCFC-123).
- Cis-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (Z)) and trans-1-chloro-3,3,3-trifluoropropene HCFO-1233zd (E ) Is a Ts diagram of an azeotrope-like composition. It is a Ts diagram of 2,2-dichloro-1,1,1-trifluoroethane (HCFC-123).
- Cis-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (Z)) and trans-1-chloro-3,3,3-trifluoropropene HCFO-1233zd (E ) Is a Ts diagram of an azeotrope-like composition. It is a Ts diagram of 2,2-dichloro-1,1,1-trifluoroethane (HCFC-123).
- the azeotrope-like composition, cleaning agent, solvent and blowing agent according to the present invention will be described with reference to the drawings.
- the azeotrope-like composition, heat transfer composition, cleaning agent, cleaning agent and foaming method of the present invention are not construed as being limited to the description of the embodiments and examples shown below. .
- the same portions or portions having similar functions are denoted by the same reference numerals, and repetitive description thereof is omitted.
- An azeotrope-like composition according to the present invention comprises 2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe) and 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd). It is the composition which mixed. Since the azeotrope-like composition according to the present invention is such a mixture, it is nonflammable, and the compound constituting the composition contains a double bond in the molecule and should be released to the atmosphere. However, since the double bond and the OH radical in the atmosphere react and decompose quickly, the load on the environment is small.
- ⁇ Azeotropic composition In the azeotropic composition, the boiling point of the liquid composition is fixed under a predetermined pressure, and the composition of the vapor (gas phase) of the boiling liquid composition is the composition of the boiling liquid composition (liquid phase). It is characterized by being the same. That is, the azeotropic composition does not cause fractional distillation of the components of the liquid composition when the liquid composition boils.
- an azeotrope-like composition refers to a composition that behaves like an azeotrope composition, where the boiling point of the liquid composition is substantially fixed under a predetermined pressure, and the liquid composition is volatilized.
- the composition of the vapor (gas phase) of the boiling liquid composition is compared to the composition of the boiling liquid composition (liquid phase). It is characterized by changes that can only be ignored. That is, the azeotrope-like composition is unlikely to cause fractional distillation of the components of the liquid composition when the liquid composition boils.
- R410A mixed refrigerant of R32 and R125
- the composition of the gas phase part and the liquid phase part is substantially the same, so it is widely used as an azeotrope-like refrigerant. It is used.
- both azeotropic and azeotrope-like can be treated practically in the same way.
- both azeotropic and azeotrope-like compositions are called azeotrope-like compositions.
- non-azeotropic compositions that are not azeotropic-like are characterized in that the composition of the gas phase of the composition and the composition of the liquid phase of the composition change during evaporation or condensation.
- HCFO-1224xe 2-chloro-1,3,3,3-tetrafluoropropene
- HCFO-1233zd 1-chloro-3,3,3-trifluoropropene
- FIG. 1 is a diagram for explaining a process for producing 2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe) from fluorine-containing olefins.
- a process for producing 2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe) will be described with reference to FIG.
- HFO-1224xe 2-chloro-1,3,3,3-tetrafluoropropene
- HFO-1234ze 1,3,3,3-tetrafluoropropene
- 3-tetrafluoropropene trans isomer is HFO-1234ze (E)
- cis isomer is HFO-1234ze (Z)
- mixture and geometric isomers may be called HFO-1234ze) after chlorination It can be produced by dehydrochlorination. Since the geometrical isomer of HFO-1234ze as a starting material is not limited, HFO-1234ze (E), HFO-1234ze (Z), or a mixture thereof can be used.
- HCFC-234da 2,3-dichloro-1,1,1,3-tetrafluoropropane
- HCFO-1224xe is produced by bringing HCFC-234da into contact with a basic aqueous solution such as an aqueous potassium hydroxide solution.
- HCFO-1224xe (Z) and HCFO-1224xe (E) can be isolated.
- phase transfer catalyst When contacting HCFC-234da with a basic aqueous solution, it is preferable to use a phase transfer catalyst because by-products of 1,2-dichloro-3,3,3-trifluoropropene (HCFC-1223xd) can be suppressed. .
- HCFC-234da 2,3-dichloro-1,1,1,3-tetrafluoropropane
- HCFO-1224xe (Z) is generated as a main component, and an aqueous HCFC-234da threo body and an aqueous basic solution such as an aqueous potassium hydroxide solution are produced.
- HCFO-1224xe (E) is produced when the is contacted.
- HCFC-235da 2-chloro-1,1,1,3,3-pentafluoropropane
- a basic aqueous solution such as an aqueous potassium hydroxide solution
- HCFO— 1224xe (Z) can be obtained.
- HCFC-235da can be obtained as a by-product during the production of HCFO-1233zd.
- 1-chloro-3,3,3-trifluoropropene may be a commercially available product or may be obtained by manufacturing.
- the manufacturing method of HCFO-1233zd is obvious to those skilled in the art by taking into account the common general knowledge at the time of filing this application.
- trans-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd (E)) is 1,1,1,3,3-penta based on the description in JP-A-9-183740.
- HCFO-1233zd (Z) cis-1-chloro-3,3,3-trifluoropropene
- HCFO-1224xe 2-Chloro-1,3,3,3-tetrafluoropropene
- 1-chloro-3,3,3-trifluoropropene components of the azeotrope-like composition according to the present invention
- HCFO-1233zd may be a high-purity product, or one containing impurities contained during production or recycling.
- a high-purity azeotrope-like composition is required by a person skilled in the art, it is desirable to use high-purity HCFO-1224xe and HCFO-1233zd.
- a general-purpose product may be used or recycled. Product can be used.
- the azeotrope-like composition comprises 2-chloro-1,3,3,3-tetrafluoropropene HCFO-1224xe and 1-chloro-3,3,3-trifluoropropene (HCFO— HCFO-1224xe is a trans isomer (HCFO-1224xe (E)), and HCFO-1233zd is also preferably a trans isomer (HCFO-1233zd (E)).
- the azeotrope-like composition according to an embodiment of the present invention has a gas phase part and a liquid phase part at an arbitrary composition ratio. This is because the compositions are substantially the same and can be used in a ratio desired by those skilled in the art.
- a preferred composition ratio of HCFO-1224xe (E) and HCFO-1233zd (E) in the azeotrope-like composition according to an embodiment of the present invention is such that HCFO-1224xe (E) is 0.001 mol% or more and 99 mol% or less. And HCFO-1233zd (E) is 1 mol% or more and 99.999 mol% or less.
- HCFO-1224xe (E) is 80 mol% or more and 99 mol% or less
- HCFO-1233zd (E) is 1 mol% or more and 20 mol% or less
- HCFO-1224xe (E) is 0.001 mol% or more and 40% or less. It is particularly preferable that it is not more than mol and the region where HCFO-1233zd (E) is not less than 60 mol% and not more than 99.999 mol% because the composition of the gas phase portion and the liquid phase portion is very close.
- the azeotrope-like composition comprises 2-chloro-1,3,3,3-tetrafluoropropene HCFO-1224xe and 1-chloro-3,3,3-trifluoropropene ( HCFO-1224xe is preferably a cis form (HCFO-1224xe (Z)), and HCFO-1233zd is preferably a trans form (HCFO-1233zd (E)).
- the azeotrope-like composition according to one embodiment of the present invention is HCFO-1224xe (E) and HCFO in the azeotrope-like composition. This is because the composition of the gas phase portion and the liquid phase portion is substantially the same regardless of the composition ratio to ⁇ 1233zd (E).
- the composition ratio of HCFO-1224xe (E) and HCFO-1233zd (E) in the azeotrope-like composition according to an embodiment of the present invention is such that HCFO-1224xe (Z) is 0.001 mol% or more and 99.999 mol% or less.
- HCFO-1233zd (E) is preferably 0.001 mol% or more and 99.999 mol% or less.
- the azeotrope-like composition comprises 2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe) and 1-chloro-3,3,3-tri Fluoropropene (HCFO-1233zd), HCFO-1224xe includes trans isomer (HCFO-1224xe (E)) and cis isomer (HCFO-1224xe (Z)), and HCFO-1233zd includes trans isomer (HCFO-1233zd ( E)) is preferred.
- a composition containing at least three components of HCFO-1224xe (E), HCFO-1224xe (Z), and HCFO-1233zd (E) is azeotropic with any composition.
- a preferred composition ratio of each component in the azeotrope-like composition according to an embodiment of the present invention is HCFO-1233zd (E) of 60 mol% or more and 99.999 mol% or less, and HCFO-1224xe of 0.001 mol% or more and 40 mol%. %.
- the ratio of HCFO-1224xe (E) to HCFO-1224xe (Z) is arbitrary, but the molar ratio of HCFO-1224xe (E) / HCFO-1224xe (Z) is from 0.0001 to 9999.9. Is preferred.
- the ratio of threo form / erythro form of HCFC-234da is about 2: 1.
- the ratio of HCFO-1224xe (E) / HCFO-1224xe (Z) is approximately 2: 1.
- 1224xe may be used in an azeotrope-like composition according to one embodiment of the present invention. This is because precise distillation separation between HCFO-1224xe (E) and HCFO-1224xe (Z) is not easy.
- the azeotrope-like composition comprises 2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe) and 1-chloro-3,3,3-tri It is preferable that HCFO-1224xe is a trans isomer (HCFO-1224xe (E)) and HCFO-1233zd is a cis isomer (HCFO-1233zd (Z)).
- the azeotrope-like composition according to an embodiment of the present invention has a gas phase part and a liquid phase part at an arbitrary composition ratio.
- the composition is substantially the same.
- a preferred composition ratio of HCFO-1224xe (E) to HCFO-1233zd (Z) in the azeotrope-like composition according to an embodiment of the present invention is such that HCFO-1224xe (E) is 90 mol% or more and 99.9 mol% or less.
- HCFO-1233zd (Z) is 0.1 mol% or more and 10 mol% or less.
- HCFO-1224xe (Z) cis-2-chloro-1,3,3,3-tetrafluoropropene
- HCFO-1224xe (Z) cis-1-chloro-3,3,3-trifluoropropene
- HCFO-1233zd (Z) a composition consisting solely of HCFO-1233zd (Z)
- HCFO-1224xe (Z) is preferentially volatilized during use, so that HCFO-1233zd (Z) is concentrated in the liquid phase part. There is a tendency.
- this composition which is not an azeotrope-like composition is not limited as desired by those skilled in the art.
- the azeotrope-like composition according to the present invention described above has excellent detergency.
- the field of cleaning using the azeotrope-like composition of the present invention is not particularly limited, but CFC-113 (chlorotrifluoromethane), HCFC-141b (1,1-dichloro-1-fluoroethane), HCFC-225 ( Of 3,3-dichloro-1,1,1,2,2-pentafluoropropane (HCFC-225ca) and 1,3-dichloro-1,1,2,2,3-pentafluoropropane (HCFC-225cb)
- the field in which the mixture) is used as a cleaning agent is preferred.
- dirt that can be removed by CFC-113, HCFC-141b, and HCFC-225 can be removed by optimizing the composition ratio of the azeotrope-like composition of the present invention.
- stains include particles, oil, grease, wax, flux, ink, and the like.
- the cleaning method is not particularly limited, and a conventionally used method can be employed. Specifically, immersion, spraying, boiling cleaning, ultrasonic cleaning, steam cleaning, or a combination thereof can be used. In particular, as shown in the examples described later, a method of removing dirt by dipping is particularly preferable.
- the dipping refers to bringing an object (object to be cleaned) on which dirt such as oil adheres with the azeotrope-like composition of the present invention.
- the dirt adhering to the object to be cleaned is dissolved in the azeotrope-like composition, whereby the dirt can be removed from the object to be cleaned.
- the said immersion operation can also be combined with other cleaning operations (boiling cleaning, ultrasonic cleaning, etc.).
- the liquid phase composition ratio in vapor-liquid equilibrium and the gas phase composition ratio are substantially the same, so even if volatilization occurs over time, the composition change is very small, and always A stable cleaning ability can be obtained. Moreover, the composition change in the storage container at the time of storage can also be avoided.
- various surfactants may be added to the cleaning agent containing the azeotrope-like composition of the present invention as necessary.
- the surfactant include sorbitan aliphatic esters such as sorbitan monooleate and sorbitan trioleate; polyoxyethylene sorbite fatty acid esters such as sorbit tetraoleate of polyoxyethylene; polyethylene such as polyoxyethylene monolaurate Glycol fatty acid esters; polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether; polyoxyethylene alkyl phenyl ethers such as polyoxyethylene nonylphenyl ether; polyoxyethylene alkylamine fatty acid amides such as polyoxyethylene oleic acid amide Nonionic surfactants such as the like.
- surfactants may be used alone or in combination of two or more.
- cationic surfactants and anionic surfactants are added to the detergent containing the azeotrope-like composition of the present invention in order to synergistically improve the detergency and interfacial action. May be.
- the amount of the surfactant used varies depending on the type of the surfactant, but may be any level that does not interfere with the azeotrope-like properties of the azeotrope-like composition. It is about mass% or less, and it is preferable to set it as about 0.3 mass% or more and 5 mass% or less.
- various stabilizers may be further added when used under severe conditions.
- the kind of the stabilizer is not particularly limited, but it is more preferable that the stabilizer is entrained by distillation or forms an azeotrope-like mixture.
- Such stabilizers include aliphatic nitro compounds such as nitromethane, nitroethane, and nitropropane; aromatic nitro compounds such as nitrobenzene, nitrotoluene, nitrostyrene, and nitroaniline; dimethoxymethane, 1,2-dimethoxyethane, Ethers such as 1,4-dioxane, 1,3,5-trioxane and tetrahydrofuran; Epoxides such as glycidol, methyl glycidyl ether, allyl glycidyl ether, 1,2-butylene oxide, phenyl glycidyl ether, cyclohexene oxide and epichlorohydrin; Unsaturated hydrocarbons such as hexene, heptene, pentadiene, cyclopentene, cyclohexene; Olefin alcohols such as allyl alcohol and 1-buten-3-ol
- phenols, amines, and benzotriazoles may be used in combination. These stabilizers may be used alone or in combination of two or more.
- the amount of the stabilizer used varies depending on the type of the stabilizer, but it is sufficient that it does not interfere with the azeotrope-like properties of the azeotrope-like composition, and usually 0.01% by mass or more in the azeotrope-like composition. It is about 10% by mass or less, and preferably about 0.1% by mass or more and 5% by mass or less.
- trans-1-chloro-3,3,3-trifluoropropene (molecular weight M: 130.5)) is commercially produced as a blowing agent, and HCFO-1233zd (E)
- HCFO-1233zd (molecular weight M: 130.5)
- 2-chloro-1,3,3,3-tetrafluoropropene (molecular weight M: 148.5))
- the product can be used as a blowing agent for the production of rigid polyurethane foam or polyisocyanurate foam.
- the production of rigid urethane foam or polyisocyanurate foam requires a premix, which is a mixture of a foaming agent, one or more polyols, a catalyst, a foam stabilizer, a flame retardant, and water. It is.
- the azeotrope-like composition according to the present invention as a foaming agent for this premix and reacting with isocyanate, the rigid polyurethane foam or polyisocyanurate foam which is the target product can be produced.
- addition of the above-mentioned substances to the azeotrope-like composition of the present invention is also within the technical scope of the present invention.
- Isocyanates include aromatic, cycloaliphatic, chain aliphatic and the like, and generally bifunctional ones are used.
- isocyanates include tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, tolylene diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, dicyclohexylmethane isocyanate.
- polyisocyanates such as these and prepolymer-type modified products, nurate-modified products, and urea-modified products. These are used alone or in a mixture.
- Polyols included in the premix include polyether polyols, polyester polyols, polyhydric alcohols, hydroxyl group-containing diethylene polymers, and polyether polyols are generally used. Moreover, a polyester-type polyol and a polyether-type polyol may be a main component, and other polyols may be used.
- Polyester polyols include condensed polyester polyols, lactone polyester polyols, polycarbonate polyols and the like in addition to compounds derived from phthalic anhydride, waste polyester, and castor oil.
- the hydroxyl value (OH value) of the polyester polyol is 100 mgKOH / g or more and 400 mgKOH / g or less, and the viscosity is 200 Pa ⁇ s / It is preferably 25 ° C. or higher and 4000 mPa ⁇ s / 25 ° C. or lower.
- Polyether-based polyols include polypropylene glycol, polytetramethylene glycol and their modified products, as well as compounds containing active hydrogen such as sugars, polyhydric alcohols, alkanolamines, etc., and propylene oxide, ethylene oxide, epichlorohydrin.
- a product obtained by adding a cyclic ether such as butylene oxide is preferably used.
- polyether polyol those having a hydroxyl value of 400 mgKOH / g or more and 1000 mgKOH / g or less are usually used.
- the catalyst contained in the premix includes an organometallic catalyst and an organic amine catalyst.
- an organometallic catalyst an organotin compound is preferably used, and stannous octoate, stannous laurate, dibutyltin dilaurate, dibutyltin dimaleate, dibutyltin diacetate, dioctyltin diacetate and the like can be mentioned.
- the organic amine catalyst include tertiary amines such as triethylenediamine, N-ethylmorpholine, bis (2-dimethylaminoethyl) ether, N, N ′, N′-triethylethanolamine and the like.
- an organosilicon compound-based surfactant is usually used, such as SH-193, SH-195, SH-200 or SRX-253 manufactured by Toray Silicone Co., Ltd., Shin-Etsu Silicone ( F-230, F-305, F-341, F-348, etc. manufactured by Nippon Unicar Co., Ltd., L-544, L-5310, L-5320, L-5420, L-5720 or Toshiba Silicone Co., Ltd. ) Manufactured by TFA-4200, TFA-4202, and the like.
- Flame retardants included in the premix are phosphate esters used in rigid polyurethane foams or polyisocyanurate foams, including tris (2-chloroethyl) phosphate, tris (2-chloropropyl) phosphate, tris (butoxyethyl) Examples include phosphate, trismethyl phosphate, trisethyl phosphate, triphenyl phosphate, and tris (isopropylphenyl) phosphate.
- additives added to the premix include additives for improving various physical properties of the rigid polyurethane foam or polyisocyanurate foam, such as an ultraviolet ray inhibitor, a scorch inhibitor, and a premix storage stabilizer.
- Addition of water contributes to the economic efficiency of rigid polyurethane foam or polyisocyanurate foam and lowering of the vapor pressure of the premix in order to reduce the amount of fluorine-based foaming agent used.
- epoxy compounds such as 1,2-epoxybutane, 1,2-epoxyhexane, epoxycyclohexane, ⁇ -methylstyrene, p-
- a stabilizer such as an unsaturated compound such as isopropenyltoluene or amylene or a nitro compound such as nitromethane, nitroethane, nitropropane, nitrotoluene, or nitrobenzene to the premix.
- the azeotrope-like composition of the present invention When used as a foaming agent, it is usually 5 parts by weight or more and 80 parts by weight or less, preferably 10 parts by weight or more and 70 parts by weight or less, more preferably 15 parts by weight or more per 100 parts by weight of polyol. Used at 60 parts by weight or less.
- a rigid urethane foam or polyisocyanate having a density of 20 kg / m 3 or more, particularly 30 kg / m 3 or more and 80 kg / m 3 or less. Nurate foam can be produced.
- the mixing temperature is 5 ° C or higher and 50 ° C or lower, preferably 10 ° C or higher and 40 ° C or lower, more preferably 15 ° C or higher and 35 ° C or lower.
- the azeotrope-like composition of the present invention has a vapor pressure and thus volatilizes at these temperatures.
- the composition of the gas-liquid phase is substantially the same, it is excellent in foam, heat insulation, shape stability at low temperature, etc. .
- the method for producing a rigid polyurethane foam or polyisocyanurate foam using the azeotrope-like composition of the present invention is not particularly limited, and various conventionally known methods can be employed. For example, it can be produced by a one-shot method or a prepolymer method.
- various foaming methods such as in-situ foaming, slab foaming, injection foaming (filling method, molding method), laminate foaming, and spray foaming can be employed.
- the azeotrope-like composition of the present invention has very good properties as a silicone solvent. That is, the azeotrope-like composition of the present invention has substantially zero ozone depletion coefficient and global warming coefficient, is nonflammable, has excellent volatility, and can arbitrarily dissolve various silicones. it can. In particular, since the azeotrope-like composition of the present invention has a wide azeotrope-like composition range, those skilled in the art can select an optimal composition according to various silicone compounds.
- azeotrope-like composition of the present invention is used as a silicone solvent.
- surface coating in order to protect the surface of an object and provide lubricity, the solvent is evaporated after applying a silicone coating solution obtained by dissolving silicone of a lubricant in a volatile solvent to the object.
- silicone coating solution obtained by dissolving silicone of a lubricant in a volatile solvent to the object.
- silicone is applied to the injection needle in order to improve slipperiness.
- silicones used for surface coating can be used.
- straight silicone oils such as dimethyl silicone oil, methyl phenyl silicone oil, and methyl hydrogen silicone oil bonded with methyl, phenyl, and hydrogen atoms as substituents, and components derived secondarily from straight silicone oil
- a silicone such as a reactive silicone oil or a modified silicone oil such as a non-reactive silicone oil may be used.
- silicones the reaction of aminoalkylsiloxane and dimethylsiloxane copolymer as a main component, reaction product of amino group-containing silane and epoxy group-containing silane, and polydiorganosiloxane containing silanol group Containing a product as a main component, a silicone mixture comprising a silicone and polydiorganosiloxane containing an amino group at the side chain or terminal, an amino group-containing alkoxysilane, an epoxy group-containing alkoxysilane, and silanol groups at both ends
- silicone mixture comprising a silicone and polydiorganosiloxane containing an amino group at the side chain or terminal, an amino group-containing alkoxysilane, an epoxy group-containing alkoxysilane, and silanol groups at both ends
- silicone mixture comprising a silicone and polydiorganosiloxane containing an amino group at the side chain or terminal, an amino group-containing alkoxysilane,
- the ratio of the azeotrope-like composition of the present invention as the silicone solvent in the coating silicone solution is preferably 0.1% by mass or more and 80% by mass or less, particularly preferably 1% by mass or more and 20% by mass or less.
- the azeotrope-like composition of the present invention in the coating silicone solution is less than 0.1% by mass, a coating film having a sufficient film thickness is difficult to be formed, and when it exceeds 80% by mass, a uniform coating film is obtained. Hateful.
- the silicone coating solution containing the azeotrope-like composition of the present invention is applied to the surface of the object, and the solvent composition containing the azeotrope-like composition of the present invention is evaporated and removed, thereby removing the silicone on the object surface.
- Form a film As an object to which the method of the present invention can be applied, it can be applied to various materials such as a metal member, a resin member, a ceramic member, and a glass member, and in particular, a needle tube portion of a syringe needle and a dispenser (liquid metering device). It can be applied to springs and spring parts.
- a silicone coating is formed on the needle tube portion of an injection needle, etc.
- the needle tube portion of the injection needle is immersed in a silicone coating solution and applied to the outer surface of the needle tube portion.
- a dip coating method may be applied in which the solvent composition containing the azeotrope-like composition of the present invention is evaporated at room temperature or under heating to form a silicone film.
- the azeotrope-like composition of the present invention has excellent heat transfer characteristics and is suitable as a heat transfer medium for refrigeration cycle systems, high-temperature heat pump systems, organic Rankine cycle systems, and the like.
- the “refrigeration cycle system” is a vapor compression refrigeration cycle system including at least an evaporator, a compressor, a condenser, and an expansion valve element device, and is a system mainly intended for cooling. Point to.
- the expansion valve is a device for expanding and contracting the heat transfer medium, and may be a capillary tube.
- the refrigeration cycle system may include an internal heat exchanger, a dryer (dryer), a liquid separator, an oil recovery unit, and a non-condensable gas separator in addition to the element devices.
- the refrigeration cycle system may be used as a refrigerator, an air conditioning system, or a cooling device.
- the “high temperature heat pump cycle system” is a vapor compression heat pump cycle system including at least an evaporator, a compressor, a condenser, and an expansion valve element device, and is mainly intended for heating.
- the expansion valve is a device for constricting and expanding the heat transfer medium, and may be a capillary tube.
- the high-temperature heat pump cycle system may include an internal heat exchanger, a dryer (dryer), a liquid separator, an oil recovery device, and a non-condensable gas separator in addition to the element devices.
- the high temperature heat pump cycle system may be used as a hot water supply system, a steam generation system, or a heating device.
- the high-temperature heat pump cycle system may use solar heat energy, factory waste heat, or the like as a heat source.
- the “organic Rankine cycle system” is a Rankine cycle system including at least an evaporator, an expander, a condenser, and an element device of a booster pump, and mainly converts thermal energy into electric energy.
- the organic Rankine cycle system may include an internal heat exchanger, a dryer (dryer), a liquid separator, an oil recovery unit, and a non-condensable gas separator in addition to the element devices.
- the organic Rankine cycle system may be used as a power generation device that recovers medium and low temperature heat.
- the organic Rankine cycle system may use solar heat energy, factory waste heat, or the like as a heat source.
- azeotrope-like composition of the present invention cis-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (Z)) and trans-1-chloro-3,3,3-trifluoro It is particularly preferred to use an azeotrope-like composition comprising propene (HCFO-1233zd (E)) as a heat transfer medium.
- a lubricant, a stabilizer, and a flame retardant may be added as necessary.
- the lubricating oil used in the compressor sliding portion is a mineral oil (paraffinic oil or naphthenic oil) or a synthetic oil alkylbenzene (AB). ), Poly (alpha-olefin), esters, polyol esters (POE), polyalkylene glycols (PAG) or polyvinyl ethers (PVE). These lubricating oils may be used independently and 2 or more types may be used together.
- the lubricant used in the expander sliding portion is a mineral oil (paraffinic oil or naphthenic oil) or a synthetic oil alkylbenzene (AB).
- AB synthetic oil alkylbenzene
- Poly (alpha-olefin), esters, polyol esters (POE), polyalkylene glycols (PAG) or polyvinyl ethers (PVE) can be used.
- These lubricating oils may be used independently and 2 or more types may be used together.
- Alkylbenzenes include n-octylbenzene, n-nonylbenzene, n-decylbenzene, n-undecylbenzene, n-dodecylbenzene, n-tridecylbenzene, 2-methyl-1-phenylheptane, 2-methyl- 1-phenyloctane, 2-methyl-1-phenylnonane, 2-methyl-1-phenyldecane, 2-methyl-1-phenylundecane, 2-methyl-1-phenyldodecane, 2-methyl-1-phenyltridecane Etc.
- Esters include aromatic esters such as benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid and mixtures thereof, dibasic acid esters, polyol esters, complex esters, carbonate esters, etc. It is done.
- Polyol esters are obtained by reacting polyhydric alcohols with carboxylic acids.
- the polyhydric alcohol used as a raw material for polyol esters include neopentyl glycol, trimethylol ethane, trimethylol propane, trimethylol butane, di- (trimethylol propane), tri- (trimethylol propane), pentaerythritol, di- Hindered alcohols such as (pentaerythritol) and tri- (pentaerythritol), ethylene glycol, 1,3-propanediol, propylene glycol, 1,4-butanediol, 1,2-butanediol, 2-methyl-1, 3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 2-ethyl-2-methyl-1,3-propanediol, 1,7-heptanediol, 2-methyl-2-propyl
- carboxylic acids used as starting materials for polyol esters include butanoic acid, 2-methylpropanoic acid, pentanoic acid, 2-methylbutanoic acid, 3-methylbutanoic acid, 2,2-dimethylpropanoic acid, 2-methylpentanoic acid, 3-methylpentanoic acid, Methylpentanoic acid, 4-methylpentanoic acid, 2,2-dimethylbutanoic acid, 2,3-dimethylbutanoic acid, 3,3-dimethylbutanoic acid, hexanoic acid, 2-methylhexanoic acid, 3-methylbutanoic acid, 4- Methylbutanoic acid, 5-methylbutanoic acid, 2,2-dimethylpentanoic acid, 2,3-dimethylpentanoic acid, 2,4-dimethylpentanoic acid, 3,3-dimethylpentanoic acid, 3,4-dimethylpentanoic acid, 4, 4-dimethylpentanoi
- Polyalkylene glycol is methanol, ethanol, linear or branched propanol, linear or branched butanol, linear or branched pentanol, linear or branched hexanol, etc. And a straight-chain or branched aliphatic alcohol having 1 to 18 carbon atoms and addition-polymerized with ethylene oxide, propylene oxide, butylene oxide and the like.
- Polyvinyl ethers include polymethyl vinyl ether, polyethyl vinyl ether, poly n-propyl vinyl ether, polyisopropyl vinyl ether and the like.
- the acid value of the lubricating oil contained in the heat transfer medium of the present invention is not particularly limited, in order to prevent corrosion of metals used in refrigeration cycle systems and the like and to prevent decomposition of the lubricating oil, the present invention In one embodiment, it is preferably 0.1 mgKOH / g or less, more preferably 0.05 mgKOH / g or less.
- an acid value means the acid value measured based on Japanese Industrial Standard JISK2501.
- the ash content of the lubricating oil contained in the heat transfer medium of the present invention is not particularly limited, in order to increase the thermal and chemical stability of the lubricating oil and suppress the generation of sludge, in one embodiment of the present invention, preferably It is 100 ppm or less, More preferably, it is 50 ppm or less.
- an ash content means the value of the ash content measured based on Japanese Industrial Standard JISK2272.
- the kinematic viscosity of the lubricating oil contained in the heat transfer medium of the present invention is not particularly limited, in one embodiment, the kinematic viscosity at 40 ° C. is preferably 3 mm 2 / s to 1000 mm 2 / s, more preferably. or less 4 mm 2 / s or more 500 mm 2 / s, and most preferably not more than 5 mm 2 / s or more 400 mm 2 / s.
- the kinematic viscosity at 100 ° C. is preferably 1 mm 2 / s to 100 mm 2 / s.
- a stabilizer can be used to improve thermal stability, oxidation resistance and the like.
- the stabilizer include nitro compounds, epoxy compounds, phenols, imidazoles, amines, hydrocarbons and the like.
- nitro compound a known compound may be used, and examples thereof include aliphatic and / or aromatic derivatives.
- examples of the aliphatic nitro compound include nitromethane, nitroethane, 1-nitropropane, 2-nitropropane and the like.
- aromatic nitro compounds 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- or p-nitrophenol, o -, M- or p-nitroanisole and the like can be mentioned.
- Examples of the epoxy compound include ethylene oxide, 1,2-butylene oxide, propylene oxide, styrene oxide, cyclohexene oxide, glycidol, epichlorohydrin, glycidyl methacrylate, phenyl glycidyl ether, allyl glycidyl ether, methyl glycidyl ether, butyl glycidyl ether, Mono-epoxy compounds such as 2-ethylhexyl glycidyl ether, polyepoxy compounds such as diepoxybutane, vinylcyclohexene dioxide, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, glycerin polyglycidyl ether, trimethylolpropane tolglycidyl ether Compounds and the like.
- the phenols include phenols containing various substituents such as an alkyl group, an alkenyl group, an alkoxy group, a carboxyl group, a carbonyl group, and a halogen in addition to the hydroxyl group.
- Monovalent phenol such as eugenol, isoeugenol, butylhydroxyanisole, phenol, xylenol or divalent such as t-butylcatechol, 2,5-di-t-aminohydroquinone, 2,5-di-t-butylhydroquinone Phenol and the like.
- imidazoles examples include 1-methylimidazole, 1-n-butylimidazole, straight chain or branched alkyl group having 1 to 18 carbon atoms, cycloalkyl group, or aryl group having N-position substituent.
- amines examples include pentylamine, hexylamine, diisopropylamine, diisobutylamine, di-n-propylamine, diallylamine, triethylamine, N-methylaniline, pyridine, morpholine, N-methylmorpholine, triallylamine, allylamine, ⁇ -methyl.
- hydrocarbons examples include ⁇ -methylstyrene, p-isopropenyltoluene, isoprenes, propadiene, terpenes and the like. These may be used alone, or two or more compounds may be used in combination.
- the stabilizer may be added in advance to one or both of the refrigerant and the lubricant, or may be added alone in the condenser.
- the usage-amount of a stabilizer is not specifically limited, 0.001 mass% or more and 10 mass% or less are preferable with respect to a main refrigerant
- the high-pressure part pressure of the heat transfer medium containing the azeotrope-like composition of the present invention is determined by the composition of the heat transfer medium and the condensation temperature. That is, in the refrigeration cycle system or the high temperature heat pump cycle system, the high-pressure part pressure of the heat transfer medium becomes equal to the saturated vapor pressure of the heat transfer medium at the condensation temperature.
- the high-pressure part pressure of the heat transfer medium containing the azeotrope-like composition of the present invention is determined by the composition of the heat transfer medium and the evaporation temperature.
- the high-pressure part pressure of the heat transfer medium is equal to the saturated vapor pressure of the heat transfer medium at the evaporation temperature.
- the high-pressure part pressure can be made lower than 5.0 MPa, and known compressors, expanders, heat exchangers, and piping parts can be used.
- the heat transfer medium containing the azeotrope-like composition of the present invention is nonflammable, has a low environmental load, and has excellent thermal cycle characteristics. Therefore, heat medium for high-temperature heat pump used for generating pressurized hot water or superheated steam, working fluid for organic Rankine cycle used for power generation system, refrigerant for vapor compression refrigeration cycle system, absorption heat pump, heat pipe Or a cleaning agent for cycle cleaning of a cooling system or a heat pump system.
- the heat transfer medium containing the azeotrope-like composition of the present invention is not limited to package-type small devices (such as Rankine cycle systems and heat pump cycle systems), but also factory-scale large-scale power generation systems, heat pump hot water supply systems, It can be applied to a heat pump steam generation system or the like.
- HCFO-1224xe ⁇ Method for Producing 2-Chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe)>
- HCFO-1224xe a method for synthesizing 2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe) 1224 will be specifically described below.
- the synthesis method of HCFO-1224xe is not limited to the method described below.
- trans-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd (E)) is produced based on Japanese Patent Application Laid-Open No. 2014-028800.
- Cis-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd (Z)) was produced based on Japanese Patent Application Laid-Open No. 2014-024821, and each had a purity of 99.99%. It was.
- HCFO-1224xe (E) and HCFO-1233zd (E) ⁇ Azeotropic-like composition by combination of HCFO-1224xe (E) and HCFO-1233zd (E)>
- the inventors of the present invention have analyzed trans-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (E)) and cis-1-chloro-3, The composition of the gas phase part and the liquid phase part in the mixture with 3,3-trifluoropropene (HCFO-1233zd (E)) was examined.
- HCFO-1233zd E
- injection cylinder made of polypropylene
- seal part and plunger part made of polyethylene
- FIG. 2 shows a vapor-liquid equilibrium curve of HCFO-1233zd (E) in a mixture containing HCFO-1224xe (E) and HCFO-1233zd (E) according to the present invention.
- a mixture containing a combination of HCFO-1233zd (E) and HCFO-1224xe (E) has substantially the same composition or difference between the gas phase part and the liquid phase part. Even if there was, it was negligible. Therefore, a mixture containing HCFO-1224xe (E) in the range of 0.001 mol% to 99 mol% and HCFO-1233zd (E) in the range of 1 mol% to 99.999 mol% is a co-polymer according to the present invention. It turns out that it is preferable as a boiling-like composition.
- HCFO-1224xe (Z) and HCFO-1233zd (E) ⁇ Azeotropic-like composition by combination of HCFO-1224xe (Z) and HCFO-1233zd (E)>
- the inventors of the present invention have conducted cis-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (Z)) and trans-1-chloro-3, The composition of the gas phase part and the liquid phase part in the mixture with 3,3-trifluoropropene (HCFO-1233zd (E)) was examined.
- a vial (head space vial) having a capacity of 20 mL was measured for mass with a precision balance, and HCFO-1233zd (Z) and HCFO-1224xe (E) in a predetermined mole percentage (mol%) were charged.
- Gas chromatographic analysis by the headspace method was performed in the same procedure as described above.
- FIG. 3 shows a vapor-liquid equilibrium curve of HCFO-1224xe (Z) in a mixture containing HCFO-1224xe (Z) and HCFO-1233zd (E) according to the present invention.
- the composition containing the combination of HCFO-1224xe (Z) and HCFO-1233zd (E) had substantially the same composition in the gas phase part and the liquid phase part. Therefore, a mixture containing HCFO-1224xe (Z) in the range of 0.001 mol% to 99.999 mol% and HCFO-1233zd (E) in the range of 0.001 mol% to 99.999 mol% is It can be seen that the azeotrope-like composition according to the invention is preferred.
- HCFO-1224xe (Z) cis-2-chloro-1,3,3,3-tetrafluoropropene
- trans-1-chloro-3,3,3-trifluoropropene The boiling point of the mixture with HCFO-1233zd (E) was measured.
- a pressure vessel made of SUS316 equipped with a strain gauge pressure transducer was added to cis-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (Z)) and trans-1-chloro-3, A two-component composition containing 3,3-trifluoropropene (HCFO-1233zd (E)) was charged.
- the air remaining in the pressure vessel was removed using a vacuum pump while the composition was cooled and solidified with liquid nitrogen.
- the pressure-resistant container was left still in a constant temperature water tank, and the temperature of the constant temperature water tank was changed so that the pressure of the said composition might become standard atmospheric pressure (101.3 kPa).
- the temperature of the composition was measured with a platinum resistance thermometer, and the temperature (boiling point) when the pressure of the composition reached 101.3 kPa was measured.
- Table 3 shows the boiling points of the compositions.
- FIG. 4 shows the boiling point of the composition relative to the mass ratio of HCFO-1224xe (Z).
- the two-component composition containing HCFO-1224xe (Z) and HCFO-1233zd (E) has a mass ratio of HCFO-1224xe (Z) / HCFO-1233zd (E) ⁇ 91.1 / 8.
- HCFO-1224xe (Z) was more than 0% by mass and up to 100% by mass
- the boiling point change of the composition was 1.4 ° C. or less. Accordingly, it can be seen that the composition forms an azeotropic composition and / or an azeotrope-like composition in the composition range.
- the change in boiling point of the composition was 0.5 ° C. or less in a composition in which HCFO-1224xe (Z) was more than 55.7% by mass and up to 100% by mass.
- HCFO-1224xe (Z) and HCFO-1233zd (E) forms a more preferred azeotrope and / or azeotrope-like composition.
- HCFO-1224xe (E) and HCFO-1233zd (Z) ⁇ Azeotropic-like composition by combination of HCFO-1224xe (E) and HCFO-1233zd (Z)>
- the inventors of the present invention have analyzed trans-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (E)) and cis-1-chloro-3, The composition of the gas phase part and the liquid phase part in the mixture with 3,3-trifluoropropene (HCFO-1233zd (Z)) was examined.
- a vial (head space vial) having a capacity of 20 mL was measured for mass with a precision balance, and charged with a predetermined mole percentage (mol%) of HCFO-1233zd (E) and HCFO-1224xe (Z).
- mol%) of HCFO-1233zd (E) and HCFO-1224xe (Z) was measured for mass with a precision balance, and charged with a predetermined mole percentage (mol%) of HCFO-1233zd (E) and HCFO-1224xe (Z).
- Gas chromatographic analysis by the headspace method was performed in the same procedure as described above.
- FIG. 5 shows a vapor-liquid equilibrium curve of HCFO-1224xe (E) in a mixture containing HCFO-1224xe (E) and HCFO-1233zd (Z) according to the present invention.
- the mixture containing the combination of HCFO-1224xe (E) and HCFO-1233zd (Z) contains HCFO-1224xe (E) in the range of 90 mol% or more and 99.9 mol% or less. Further, it can be seen that a mixture containing HCFO-1233zd (Z) in the range of 0.1 mol% to 10 mol% is preferable as the azeotrope-like composition according to the present invention.
- a mixture containing a combination of HCFO-1224xe (Z) and HCFO-1233zd (Z) has a composition ratio of HCFO-1224xe (Z) and HCFO-1233zd (Z) in the mixture. Regardless, it turns out to be non-azeotropic.
- HCFO-1224xe 2-chloro-1,3,3,3-tetrafluoropropene
- HCFO-1233zd 1-chloro-3,3,3-trifluoropropene
- Example 1 ⁇ Cleaning test A> A commercially available 25 cc graduated cylinder was cut with an 11 cc scale. After measuring the mass of a clean glass rod having a diameter of about 7.2 mm and a length of about 40 mm, it was immersed in the oil listed in the table for 2 minutes and then drained for 10 minutes (excess oil was removed). The mass (glass rod + initially attached oil) was measured and then placed in the graduated cylinder. An azeotrope-like composition comprising Compound A and Compound B described in Table 6 below was charged to a liquid level of 10 cc, and was set up at the center of a small ultrasonic cleaner (SW5800 manufactured by Citizen) filled with 20 ° C. water. .
- SW5800 small ultrasonic cleaner
- the azeotrope-like composition volatilized with time, and when it reached the 8 cc scale, the liquid in the graduated cylinder was analyzed with a gas chromatograph.
- the liquid composition before and after the cleaning was substantially the same even though 2 cc was volatilized. That is, in the actual machine cleaning, the composition comprising Compound A and Compound B used in Examples 1-a to 1-j is an azeotrope in which the composition of the residual liquid does not substantially change even if it partially volatilizes. It was shown to be a like composition.
- the glass rod is dried and the mass (total mass of the glass rod and the remaining oil) is measured to obtain the oil removal rate (the mass of the residual oil / the mass of the initial adhered oil ⁇ 100 [%]) and enlarged.
- the surface of the glass was observed with a mirror.
- the oil removal rate was 100% in all the examples, and the results of magnifying glass observation were judged to be good because no residual oil was observed.
- Table 7 The results of each Example and Comparative Example are shown in Table 7 below.
- HFC-365mfc CH 3 CF 2 CH 2 CF 3 , manufactured by Solvay Japan
- HFC-43-10mee which are commercially available fluorine-based cleaning agents
- Example 2 ⁇ Cleaning test B> HCFO-1224xe (Z) (51.2354GC%), HCFO-1233zd (E) (31.451GC%), HCFO-1224xe (Z) (13.5412GC%), HCFO-1233zd (Z) (3.2741GC%)
- the same experiment (cutting oil (Lube Cut B-35)) as in Example 1-a was conducted except that an azeotrope-like composition consisting of As a result, the composition of the liquid after washing was HCFO-1224xe (Z) (51.2349GC%), HCFO-1233zd (E) (31.8422GC%), HCFO-1224xe (Z) (13.5913GC%), HCFO It was ⁇ 1233zd (Z) (3.2743 GC%), and it was substantially the same as the initial composition even though 2 cc was volatilized. The oil removal rate was 100%, and the result of magnifying glass observation was also judged to be good because
- Example 3 ⁇ Cleaning test C> Instead of cutting oil (Lube Cut B-35), spindle oil (Pure Safety C-80), hydraulic oil (Super Clean SC-41), lubricating oil (Suniso 4GS), silicone oil (SH-193), straight silicone oil (KF-96) and a modified silicone oil (MDX4-4159) were used to conduct the same experiment as Example 2 (four-type azeotrope-like composition). Then, as in Example 2, the oil removal rate was 100%, and the result of magnifying glass observation was also judged to be good because no residual oil was observed.
- Example 4 ⁇ Cleaning test D> The SUS316 test piece was left in a dusty work room for a week. After blowing with nitrogen, when observed with a microscope (magnification: 100 times and 1000 times), many particles were observed.
- the same experiment was performed using HFC-365mfc, and as a result, residual particles were observed.
- Example 5 ⁇ Cleaning test E> After applying the oil described in Table 9 below to a stainless steel wire mesh (60 mesh), it was drained for 10 minutes and added to the azeotrope-like composition of the present invention having the composition described in Table 8 below for 5 seconds. It was dipped, pulled up and dried, and the oil removal rate was determined by mass measurement before and after Example 1 (Example 5-a to Example 5-c).
- HFE-7100 CH 3 OCF 2 CF 2 CF 2 CF 3 , manufactured by Sumitomo 3M
- HFC-365mfc CF 3 CH 2 CF 3 CF 3 (manufactured by Solvay Japan)
- HCFC-225 a mixture of HCFC-225ca (CF 3 CF 2 CHCl 2 ) and HCFC-225cb (CCIF 2 CF 2 CHClF), manufactured by Asahi Glass
- Table 9 an oil removal rate of 95% to 100% is indicated by ⁇ , 80% or more but less than 95% is indicated by ⁇ , and 0% or more and less than 80% is indicated by ⁇ .
- Example 7 ⁇ Cleaning test G> Using an azeotrope-like composition consisting of HCFO-1224ex (E) (95 mol%) and HCFO-1233zd (Z) (5 mol%), the acrylic plate was washed with an ultrasonic cleaner for 10 minutes. As a result of visual observation and observation with a magnifying glass, the surface was clean, and the acrylic plate showed the same gloss as when it was not washed. As a comparative example, using only HCFO-1233zd (Z), the acrylic plate was washed with an ultrasonic washer for 10 minutes in the same manner as in Example 7. As a result of visual observation and observation with a magnifying glass, when only HCFO-1233zd (Z) was used, the glossiness of the acrylic plate was lost.
- E HCFO-1224ex
- Z HCFO-1233zd
- HCFO-1224xe 2-chloro-1,3,3,3-tetrafluoropropene
- HCFO-1233zd 1-chloro-3,3,3-trifluoropropene
- Example 8 ⁇ Solubility test with oil>
- the azeotrope-like compositions A to H shown in Table 10 below were prepared by mixing HCFO-1224xe and HCFO-1233zd in a volume ratio.
- a glass vial (10 cc) was charged with the eutectic composition and oil as described in Table 11, shaken 10 times, and allowed to stand for 24 hours (Example 8-a to Example 8-x).
- Example 8-a to Example 8-x As a comparative example, the same experiment was performed using a commercially available fluorine-based solvent instead of the azeotrope-like composition (Comparative Examples 8a to 8-f). The visual results are shown in Table 11.
- HCFO-1224xe 2-chloro-1,3,3,3-tetrafluoropropene
- HCFO-1233zd 1-chloro-3,3,3-trifluoropropene
- Example 9 ⁇ Coating and drying test>
- the azeotrope-like composition H of Example 8 and the silicone oil described in Table 12 below were mixed at a volume ratio of 95: 5. As a result, it became uniform quickly. Even if the obtained silicone coating solution was stored for 1 month, no alteration such as two-layer separation was observed.
- a mirror-finished SUS316 disk was immersed in this silicone coating solution, and then dried using a spin coater. Specifically, it was rotated at 1000 rpm for 30 seconds. Table 12 shows the drying property and the state of the coating film.
- HCFO-1224xe 2-chloro-1,3,3,3-tetrafluoropropene
- HCFO-1233zd 1-chloro-3,3,3-trifluoropropene
- Example 10 As a comparative example, the same experiment as in Example 10 was performed, except that HCFO-1233zd (E) (99.9999GC%) was used as the foaming agent. As a result, a foam having a gelation time of 18 seconds and an excellent appearance was obtained. When the core portion was cut out and visually observed, dense and homogeneous cells were formed. When measured with a thermal conductivity measuring device (TCA-8 manufactured by Anacon) in accordance with JIS A-1412, the thermal conductivity of the foam was 20.90 mW / mK.
- TCA-8 thermal conductivity measuring device
- An azeotrope-like composition of the present invention containing 2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe) and 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd)
- HCFO-1224xe 2-chloro-1,3,3,3-tetrafluoropropene
- HCFO-1233zd 1-chloro-3,3,3-trifluoropropene
- HCFO-1224xe 2-chloro-1,3,3,3-tetrafluoropropene
- 1-chloro-3,3,3-trifluoropropene of the present invention were obtained.
- An azeotrope-like composition containing (HCFO-1233zd) is non-flammable, has little influence on the environment, and has substantially the same composition in the liquid phase part and the gas phase part. It turns out that it is excellent as a solvent and is useful as a material of a foaming agent.
- HCFO-1224xe 2-chloro-1,3,3,3-tetrafluoropropene
- HCFO-1233zd 1-chloro-3,3,3-trifluoropropene
- COP R coefficient of performance
- the compression process of the compressor is assumed to be isentropic compression.
- the throttle expansion process in the expansion valve is an isoenthalpy expansion.
- C Ignore heat loss and pressure loss in piping and heat exchangers.
- D The compressor efficiency ⁇ is set to 0.7.
- HCFC-123 2,2-dichloro-1,1,1-trifluoroethane
- HCFC-123 is nonflammable and has an allowable concentration of 10 ppm.
- HCFC-123 has a boiling point of 27.8 ° C. under atmospheric pressure, an atmospheric life of 1.3 years, a global warming potential (GWP) of 77 (IPCC Fourth Assessment Report 2007), and an ozone depletion potential (ODP). Is 0.02.
- Table 15 shows the calculation results of the refrigeration cycle system coefficient of performance (COP R ) of Example 12 and Comparative Example 12.
- Example 15 the values of the first component and the second component of the azeotrope-like composition of the present invention used in Example 12 are shown in mass percentage.
- the first component of the azeotrope-like composition is cis-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (Z)) and the second component is trans-1-chloro-3, 3,3-trifluoropropene (HCFO-1233zd (E)).
- the relative COP R and relative CAP R of Example 12 in Table 15 were calculated as relative values in which COP R and CAP R of Comparative Example 12 were each set to 1.00.
- the azeotrope-like composition of the present invention has a coefficient of performance (COP R ) equivalent to that of 2,2-dichloro-1,1,1-trifluoroethane (HCFC-123) conventionally used. It can be seen that It has also been found that the volume capacity of the azeotrope-like composition of the present invention is 40-46% greater than the volume capacity of HCFC-123. These results show that when designing a refrigeration cycle system for 2-chloro-1,3,3,3-tetrafluoropropene having the same cooling capacity as that of the refrigeration cycle system for HCFC-123, This means that the size of the entire system can be reduced as compared with the system.
- the heat transfer medium comprising the azeotrope-like composition of the present invention has been found to be comparable to the operating pressure, pressure ratio, and pressure differential of HCFC-123, and as a more environmentally friendly alternative composition It can be seen that it is used.
- COP H high temperature heat pump cycle system coefficient of performance
- Table 17 shows the calculation results of the high temperature heat pump cycle system coefficient of performance (COP H ) of Example 13 and Comparative Example 13.
- Example 17 the values of the first component and the second component of the azeotrope-like composition of the present invention used in Example 13 are shown in mass percentage.
- the first component of the azeotrope-like composition is cis-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (Z)) and the second component is trans-1-chloro-3, 3,3-trifluoropropene (HCFO-1233zd (E)).
- the relative COP H and relative CAP H of Example 13 shown in Table 17 were calculated as relative values with COP H and CAP H of Comparative Example 13 being 1.00, respectively.
- the azeotrope-like composition of the present invention has a coefficient of performance (COP H ) equivalent to that of 2,2-dichloro-1,1,1-trifluoroethane (HCFC-123) conventionally used. It can be seen that It was also found that the volume capacity (CAP H ) of the heat transfer medium of the present invention was 33-36% greater than the volume capacity of HCFC-123. These results show that when designing a high temperature heat pump cycle system for 2-chloro-1,3,3,3-tetrafluoropropene having the same level of heating capability as the high temperature heat pump cycle system for HCFC-123, This means that the size of the entire system can be further reduced as compared with the 123 system.
- the heat transfer medium comprising the azeotrope-like composition of the present invention has been found to be comparable to the operating pressure, pressure ratio, and pressure differential of HCFC-123, and as a more environmentally friendly alternative composition It can be seen that it is used.
- Table 19 shows the calculation results of the high temperature heat pump cycle system coefficient of performance (COP H ) of Example 14 and Comparative Example 14.
- Example 19 the values of the first component and the second component of the azeotrope-like composition of the present invention used in Example 14 are shown in mass percentage.
- the first component of the azeotrope-like composition is cis-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (Z)) and the second component is trans-1-chloro-3, 3,3-trifluoropropene (HCFO-1233zd (E)).
- the relative COP H and relative CAP H of Example 14 shown in Table 19 were calculated as relative values with COP H and CAP H of Comparative Example 14 being 1.00, respectively.
- the heat transfer medium of the present invention has a coefficient of performance (COP H ) equivalent to that of 2,2-dichloro-1,1,1-trifluoroethane (HCFC-123) conventionally used.
- COP H coefficient of performance
- CAP H volume capacity of the heat transfer medium of the present invention is 23-25% greater than the volume capacity of HCFC-123.
- the organic Rankine cycle system condition 4 assumes that the temperature of the heat source water supplied to the evaporator is 90 ° C. and the temperature of the cooling water supplied to the condenser is 30 ° C.
- the basic formula for calculating the power generation cycle efficiency ( ⁇ cycle ) of the organic Rankine cycle system will be described in detail.
- the basic formula is Ebara Times No. 211 (2006-4), p.
- the calculation formula of “Development of waste heat power generation equipment (examination of working medium and expansion turbine)” on page 11 was used.
- FIG. 13 shows a Ts diagram in Example 15 (azeotropic-like composition containing HCFO-1224xe (Z) and HCFO-1233zd (E)).
- cycle points 1, 2, 3, and 4 indicate organic Rankine cycle system calculation condition 4.
- Table 21 shows the calculation results of the organic Rankine cycle system performance ( ⁇ cycle and SP) of Example 15 and Comparative Example 15.
- the values of the first component and the second component of the heat transfer medium (working fluid) of Example 5 in Table 21 are shown in mass percentage.
- the first component of the heat transfer medium (working fluid) is cis-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (Z)), and the second component is trans-1-chloro- 3,3,3-tetrafluoropropene (HCFO-1233zd (E)).
- Example 16 ⁇ Heat Conductive Medium Containing HCFO-1224xe (Z) and HCFO-1233zd (E)> Cis-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (Z)) and trans-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd (E))
- the power generation cycle efficiency and the expander size parameter were calculated under the conditions shown in Table 23.
- the Ts diagram in FIG. 15 and Example 16 is shown.
- the organic Rankine cycle system calculation condition 5 is shown in Table 23 below.
- Table 24 shows the calculation results of the organic Rankine cycle system performance ( ⁇ cycle and SP) of Example 16 and Comparative Example 16.
- the values of the first component and the second component of the heat transfer medium (working fluid) of Example 16 in Table 24 are shown in mass percentage.
- the first component of the heat transfer medium (working fluid) is cis-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (Z)), and the second component is trans-1-chloro- 3,3,3-tetrafluoropropene (HCFO-1233zd (E)).
- Example 16 Regarding the expander inlet volume flow rate, expander outlet volume flow rate, power generation cycle efficiency and SP value of Example 16 shown in Table 24, 2,2-dichloro-1,1,1-trifluoroethane of Comparative Example 16 was used. The relative values are shown in Table 25 as 1.
- the 2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe) and 1-chloro-3,3,3-trifluoropropene of the present invention were obtained. It can be seen that the azeotrope-like composition containing (HCFO-1233zd) is useful as a heat transfer medium for use in heat transfer devices such as refrigeration cycle systems, high temperature heat pump cycle systems, and organic Rankine cycle system devices.
- the present invention relates to 2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe) and 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd) which have utility in numerous applications.
- HCFO-1224xe 2-chloro-1,3,3,3-tetrafluoropropene
- HCFO-1233zd 1-chloro-3,3,3-trifluoropropene
- azeotrope-like composition By using the azeotrope-like composition of the present invention, a cleaning agent that is nonflammable or slightly flammable, has little influence on the environment, and has substantially the same composition in the liquid phase part and the gas phase part.
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Abstract
Description
2-クロロ-1,3,3,3-テトラフルオロプロペン(HCFO-1224xe)と1-クロロ-3,3,3-トリフルオロプロペン(HCFO-1233zd)とを含有する共沸様組成物。
トランス-2-クロロ-1,3,3,3-テトラフルオロプロペン(HCFO-1224xe(E))とトランス-1-クロロ-3,3,3-トリフルオロプロペン(HCFO-1233zd(E))とを含む共沸様組成物。
トランス-1-クロロ-3,3,3-トリフルオロプロペン(HCFO-1233zd(E))を1mol%以上99.999mol%以下含み、且つトランス-2-クロロ-1,3,3,3-テトラフルオロプロペン(HCFO-1224xe(E))を0.001mol%以上99mol%以下含む共沸様組成物。
シス-2-クロロ-1,3,3,3-テトラフルオロプロペン(HCFO-1224xe(Z))とトランス-1-クロロ-3,3,3-トリフルオロプロペン(HCFO-1233zd(E))とを含む共沸様組成物。
シス-2-クロロ-1,3,3,3-テトラフルオロプロペン(HCFO-1224xe(Z))を0.001mol%以上99.999mol%以下含み、且つトランス-1-クロロ-3,3,3-トリフルオロプロペン(HCFO-1233zd(E))を0.001mol以上99.999mol%以下含む共沸様組成物。
トランス-2-クロロ-1,3,3,3-テトラフルオロプロペン(HCFO-1224xe(E))とシス-1-クロロ-3,3,3-トリフルオロプロペン(HCFO-1233zd(Z))とを含む共沸様組成物。
トランス-2-クロロ-1,3,3,3-テトラフルオロプロペン(HCFO-1224xe(E))を90%mol以上99.9mol%以下含み、且つシス-1-クロロ-3,3,3-トリフルオロプロペン(HCFO-1233zd(Z))を0.1mol%以上10mol%以下含む共沸様組成物。
トランス-2-クロロ-1,3,3,3-テトラフルオロプロペン(HCFO-1224xe(E))とシス-2-クロロ-1,3,3,3-テトラフルオロプロペン(HCFO-1224xe(Z))とトランス-1-クロロ-3,3,3-トリフルオロプロペン(HCFO-1233zd(E))とを含む共沸様組成物。
トランス-2-クロロ-1,3,3,3-テトラフルオロプロペン(HCFO-1224xe(E))とシス-2-クロロ-1,3,3,3-テトラフルオロプロペン(HCFO-1224xe(Z))とトランス-1-クロロ-3,3,3-トリフルオロプロペン(HCFO-1233zd(E))とシス-1-クロロ-3,3,3-トリフルオロプロペン(HCFO-1233zd(Z))とを含む共沸様組成物。
発明1~発明9のいずれかの共沸様組成物を含む洗浄剤。
発明1~発明9のいずれかの共沸様組成物を含む溶媒。
発明1~発明9のいずれかの共沸様組成物を含むシリコーン溶剤。
発明1~発明9のいずれかの共沸様組成物を含む発泡剤。
発明1~発明9のいずれかの共沸様組成物を含む熱伝導媒体。
発明14の、熱伝導媒体を用いた熱伝導装置。
共沸組成物は、所定の圧力下で液体組成物の沸点が固定されており、沸騰中の該液体組成物の蒸気(気相)の組成が沸騰中の液体組成物(液相)の組成と同一であることを特徴とする。即ち、共沸組成物は、液体組成物の沸騰時に該液体組成物の成分の分留が起こらない。それに対して、共沸様組成物は、共沸組成物と同様の挙動をする組成物を指し、所定の圧力下で液体組成物の沸点が実質的に固定されており、液体組成物が揮発する際に、液体の組成と実質的に同一の組成で揮発するため、沸騰中の該液体組成物の蒸気(気相)の組成が沸騰中の液体組成物(液相)の組成に対して無視できる程度にしか変化しないことを特徴とする。即ち、共沸様組成物は、液体組成物の沸騰時に該液体組成物の成分の分留が起こりにくい。例えば、上述したように、R410A(R32とR125との混合冷媒)は非共沸であるが、気相部と液相部との組成が実質的に同じであるため、共沸様冷媒として広く用いられている。フロン代替品用途においては、共沸でも共沸様でも実用上、同一に扱うことができる。本明細書においては、フロン代替品用途において、共沸組成物でも共沸様組成物でも、実用上、厳密に区別する必要がない場合が多いので、共沸または共沸様をともに共沸様と呼び、共沸組成物または共沸様組成物をともに共沸様組成物と呼ぶ。一方、共沸様でない非共沸組成物は、蒸発又は凝縮の間に組成物の気相の組成と組成物の液相の組成とが変化することを特徴とする。
2-クロロ-1,3,3,3-テトラフルオロプロペン(HCFO-1224xe)及び1-クロロ-3,3,3-トリフルオロプロペン(HCFO-1233zd)の製造方法は特に限定されない。HCFO-1224xeは、工業的に製造されている含フッ素オレフィン類から製造することができる。
上述したように、共沸もしくは共沸様組成を理論的に算出することは現在の技術水準では困難である。そのため、本発明者らは、2-クロロ-1,3,3,3-テトラフルオロプロペン(HCFO-1224xe)の幾何異性体(E体およびZ体)とトランス-1-クロロ-3,3,3-トリフルオロプロペン(HCFO-1233zd)とを調合し、試行錯誤した結果、以下に述べる共沸様組成を見出した。
本発明の一実施形態において、共沸様組成物は、2-クロロ-1,3,3,3-テトラフルオロプロペンHCFO-1224xeと1-クロロ-3,3,3-トリフルオロプロペン(HCFO-1233zd)とを含み、HCFO-1224xeはトランス体(HCFO-1224xe(E))であり、HCFO-1233zdもトランス体(HCFO-1233zd(E))であることが好ましい。少なくともHCFO-1224xe(E)及びHCFO-1233zd(E)の両方が含まれる場合、本発明の一実施形態に係る共沸様組成物は、任意の組成比で気相部と液相部との組成が実質的に同一であり、当業者が所望する比率で使用可能であるためである。本発明の一実施形態に係る共沸様組成物におけるHCFO-1224xe(E)とHCFO-1233zd(E)との好ましい組成比は、HCFO-1224xe(E)が0.001mol%以上99mol%以下であり、HCFO-1233zd(E)が1mol%以上99.999mol%以下である。さらに、HCFO-1224xe(E)が80mol%以上99mol%以下であり、HCFO-1233zd(E)が1mol%以上20mol%以下である領域と、HCFO-1224xe(E)が0.001mol%以上40%mol以下であり、HCFO-1233zd(E)が60mol%以上99.999mol%以下である領域とは、気相部と液相部との組成が非常に近いため、特に好ましい。
本発明の別の一実施形態において、共沸様組成物は、2-クロロ-1,3,3,3-テトラフルオロプロペンHCFO-1224xeと1-クロロ-3,3,3-トリフルオロプロペン(HCFO-1233zd)とを含み、HCFO-1224xeはシス体(HCFO-1224xe(Z))であり、HCFO-1233zdはトランス体(HCFO-1233zd(E))であることが好ましい。少なくともHCFO-1224xe(Z)及びHCFO-1233zd(E)の両方が含まれる場合、本発明の一実施形態に係る共沸様組成物は、共沸様組成物におけるHCFO-1224xe(E)とHCFO-1233zd(E)との組成比にかかわらず、気相部と液相部との組成が実質的に同じであるためである。本発明の一実施形態に係る共沸様組成物におけるHCFO-1224xe(E)とHCFO-1233zd(E)との組成比は、HCFO-1224xe(Z)が0.001mol%以上99.999mol%以下であり、HCFO-1233zd(E)が0.001mol%以上99.999mol%以下であることが好ましい。
本発明のさらに別の一実施形態において、共沸様組成物は、2-クロロ-1,3,3,3-テトラフルオロプロペン(HCFO-1224xe)と1-クロロ-3,3,3-トリフルオロプロペン(HCFO-1233zd)とを含み、HCFO-1224xeはトランス体(HCFO-1224xe(E))及びシス体(HCFO-1224xe(Z))を含み、HCFO-1233zdはトランス体(HCFO-1233zd(E))であることが好ましい。少なくともHCFO-1224xe(E)とHCFO-1224xe(Z)とHCFO-1233zd(E)との3成分を含む組成物は、任意の組成で共沸様である。本発明の一実施形態に係る共沸様組成物における各成分の好ましい組成比は、HCFO-1233zd(E)が60mol%以上99.999mol%以下であり、HCFO-1224xeが0.001mol%以上40mol%である。このとき、HCFO-1224xe(E)とHCFO-1224xe(Z)との比率は任意であるが、HCFO-1224xe(E)/HCFO-1224xe(Z)のモル比は0.0001以上9999.9以下が好ましい。一般にHFO-1234zeの塩素付加によってHCFC-234daを合成した場合、HCFC-234daのトレオ体/エリトロ体の比率が概ね2:1となる。トレオ体とエリトロ体とを分離せずに、塩基性水溶液と接触した場合は、HCFO-1224xe(E)/HCFO-1224xe(Z)の比率はおよそ2:1となるため、その比率のHCFO-1224xeを本発明の一実施形態に係る共沸様組成物に用いてもよい。なぜならば、HCFO-1224xe(E)とHCFO-1224xe(Z)との精密な蒸留分離は容易ではないからである。
本発明のさらに別の一実施形態において、共沸様組成物は、2-クロロ-1,3,3,3-テトラフルオロプロペン(HCFO-1224xe)と1-クロロ-3,3,3-トリフルオロプロペン(HCFO-1233zd)とを含み、HCFO-1224xeはトランス体(HCFO-1224xe(E))であり、HCFO-1233zdはシス体(HCFO-1233zd(Z))であることが好ましい。少なくともHCFO-1224xe(E)及びHCFO-1233zd(Z)の両方が含まれる場合、本発明の一実施形態に係る共沸様組成物は、任意の組成比で気相部と液相部との組成が実質的に同一である。本発明の一実施形態に係る共沸様組成物におけるHCFO-1224xe(E)とHCFO-1233zd(Z)との好ましい組成比は、HCFO-1224xe(E)が90mol%以上99.9mol%以下であり、HCFO-1233zd(Z)が0.1mol%以上10mol%以下である。
上述した本発明に係る共沸様組成物は、いずれも沸点まで不燃であり、消防法上における非危険物である。
上述した本発明に係る共沸様組成物は優れた洗浄力を有する。本発明の共沸様組成物を用いる洗浄の分野は特に限定されないが、従来にCFC-113(クロロトリフルオロメタン)、HCFC-141b(1,1-ジクロロ-1-フルオロエタン)、HCFC-225(3,3-ジクロロ-1,1,1,2,2-ペンタフルオロプロパン(HCFC-225ca)及び1,3-ジクロロ-1,1,2,2,3-ペンタフルオロプロパン(HCFC-225cb)の混合物)が洗浄剤として使用された分野が好適である。具体的には、電子部品(プリント基板、液晶表示器、磁気記録部品、半導体材料等)、電機部品、精密機械部品、樹脂加工部品、光学レンズ、衣料品等の洗浄が挙げられる。汚れの種類も限定されないが、CFC-113、HCFC-141b、HCFC-225で除去可能な汚れは、本発明の共沸様組成物の組成比を最適化することで除去することが可能であり、そのような汚れとしてはパーティクル、油、グリース、ワックス、フラックス、インキ等が挙げられる。
本発明の共沸様組成物を発泡剤として用いる場合について詳細に述べる。
本発明の共沸様組成物はシリコーンの溶剤として非常に優れた特性を有する。即ち、本発明の共沸様組成物は、オゾン層破壊係数及び地球温暖化係数が実質的にゼロで、不燃性であり、揮発性に優れ、かつ、種々のシリコーンを任意で溶解させることができる。特に、本発明の共沸様組成物は、広い共沸様組成範囲を持つので、当業者は各種のシリコーン化合物に応じた最適の組成を選定することができる。
本発明の共沸様組成物は、熱伝達特性にすぐれており、冷凍サイクルシステム、高温ヒートポンプシステム、及び有機ランキンサイクルシステムなどの熱伝達媒体として好適である。
本発明の熱伝達媒体を冷凍サイクルシステムまたは高温ヒートポンプの冷媒に用いる場合、圧縮機摺動部で使用する潤滑油は、鉱物油(パラフィン系油またはナフテン系油)または合成油のアルキルベンゼン類(AB)、ポリ(アルファ-オレフィン)、エステル類、ポリオールエステル類(POE)、ポリアルキレングリコール類(PAG)またはポリビニルエーテル類(PVE)を用いることができる。これらの潤滑油は単独で用いられてもよく、2種以上が併用されてもよい。
また、本発明の共沸様組成物を熱伝達媒体として用いる場合、熱安定性、耐酸化性等を改善するために安定剤を用いることができる。安定剤としては、ニトロ化合物、エポキシ化合物、フェノール類、イミダゾール類、アミン類、炭化水素類等が挙げられる。
先ず、以下に2-クロロ-1,3,3,3-テトラフルオロプロペン(HCFO-1224xe)1224の合成方法を、具体的に説明する。しかしながら、HCFO-1224xeの合成方法は、以下に説明する方法に限定されるわけではない。
トランス-1,3,3,3-テトラフルオロプロペン(HFO-1234ze(E))(777.45g,6.81mol)を、ドライアイス-アセトンバスで冷却したガラス製洗気瓶(1000cc)に仕込んだ。紫外線ランプを照射し、洗気瓶内の1HFO-234ze(E)を磁石式撹拌子で攪拌しながら、塩素ガスを2g/分の速度で483.58g(6.81mol)投入した。最終的に純度98.54GC面積%の2,3-ジクロロ-1,1,1,3-テトラフルオロプロパン(HCFC-234da)を1222.59g得た。この操作を繰り返して原料を確保した。
ジムロート(冷媒温度:-15℃)、300mL滴下ロート、温度計、攪拌子を備えた四つ口フラスコ(2000cc)に、テトラブチルアンモニウムブロミド4.57g(0.014mol)、1139.19g(6.16mol)のHCFC-234daを仕込み、0℃の氷水浴に浸し攪拌を開始した。滴下ロートより、25重量%水酸化ナトリウム水溶液1054.59g(HCFC-234daに対して1.07当量)を149分間かけて滴下した。ジムロート、滴下ロートを外し、30cmのヴィグリュー管を備えた単蒸留装置に組み替え、蒸留回収したところ575.75gの有機物を回収した。ガスクロマトグラフィーによって組成を分析したところ、HCFO-1224xe(Z)が56.053GC面積%、HCFO-1224xe(E)が35.68GC面積%であった。得られた生成物は、ヘリパックNo.2を充填した理論段数46段の蒸留塔を用いて、HCFO-1224xe(E)とHCFO-1224xe(Z)とに単離した。結果として、HCFO-1224xe(Z)(純度:99.47GC面積%)269.92g、HCFO-1224xe(E)(純度:99.56%)49.33gをそれぞれ得た。さらに、これらのサンプルの一部を精密蒸留して99.9GC面積%以上のHCFO-1224xe(Z)及びHCFO-1224xe(E)を得た。この操作を繰り返して高純度のトランス-2-クロロ-1,3,3,3-テトラフルオロプロペン(HCFO-1224xe(E))及びシス-2-クロロ-1,3,3,3-テトラフルオロプロペン(HCFO-1224xe(Z))のサンプルを確保し、本発明に係る共沸様組成物の調合に用いた。
本発明者らは、ヘッドスペース法によるガスクロマトグラフィー分析により、トランス-2-クロロ-1,3,3,3-テトラフルオロプロペン(HCFO-1224xe(E))とシス-1-クロロ-3,3,3-トリフルオロプロペン(HCFO-1233zd(E))との混合物における気相部と液相部との組成を調べた。
20mLの容量を有するバイアル(ヘッドスペースバイアル、アジレント社製)を、PTFE/白シリコンセプタムのアルミキャップ(アジレント社製)で閉めた後、22ゲージの注射針を備えた100mLシリンジ(注射筒:ポリプロピレン製、シール部及びプランジャー部:ポリエチレン製)を用いて、該バイアル瓶内を減圧した。次いで、22ゲージの注射針を備えた10mLシリンジ(注射筒:ポリプロピレン製、シール部及びプランジャー部:ポリエチレン製)に、HCFO-1233zd(E)を約5mL採取して該シリンジ内の空気抜きを行った後、該バイアル瓶内に仕込んだ。
その後、このバイアル瓶を25℃に制御された湯浴に浸し、試料温度を25℃にして静置した。気液平衡に達した後、バイアル内部の気相部を10mLガスタイトシリンジで1mLを採取して、ガスクロマトグラフィーで分析した。さらに、22ゲージの注射針を備えた5mLシリンジ(注射筒:ポリプロピレン製、シール部及びプランジャー部:ポリエチレン製)で液相部を1mL採取して、氷で冷却した2mLサンプル瓶に移し、この液に対して、ガスクロマトグラフィー(島津製作所製GC-17A)を用いて組成を分析した。
上述した[手順1]で使用したバイアル瓶内の全液量が5mLとなるように、22ゲージの注射針を備えた10mLシリンジ(注射筒:ポリプロピレン製、シール部及びプランジャー部:ポリエチレン製)を用いて、任意の割合となるようにHCFO-1233zd(E)及びHCFO-1224xe(E)を添加し、[手順2]の方法と同様にしてサンプリング及びガスクロマトグラフィー分析を行った。なお、少量のHCFO-1224xe(E)を添加する際には、該10mLシリンジの代わりに、10μLガスクロマトグラフィー分析用シリンジを用いた。また、HCFO-1233zd(E)が少ない組成については、[手順1]においてHCFO-1233zd(E)の代わりにHCFO-1224xe(E)を加えること以外は[手順1]と同様の操作を行い、次いで[手順2]と同様の方法でサンプリングし、ガスクロマトグラフィー(島津製作所製GC-17A)を用いて組成を分析した。
以上に述べた[手順1]~[手順3]の方法で得られたHCFO-1233zd(E)の気相部及び液相部の測定ピーク面積(GC%)による比から、予めピーク面積とモル比に対する検量線を作成し、測定ピーク面積からモル比を導き出した。これらの結果を表1に示す。
本発明者らは、ヘッドスペース法によるガスクロマトグラフィー分析により、シス-2-クロロ-1,3,3,3-テトラフルオロプロペン(HCFO-1224xe(Z))とトランス-1-クロロ-3,3,3-トリフルオロプロペン(HCFO-1233zd(E))との混合物における気相部と液相部との組成を調べた。
本発明者らは、ヘッドスペース法によるガスクロマトグラフィー分析により、トランス-2-クロロ-1,3,3,3-テトラフルオロプロペン(HCFO-1224xe(E))とシス-1-クロロ-3,3,3-トリフルオロプロペン(HCFO-1233zd(Z))との混合物における気相部と液相部との組成を調べた。
本発明者らは、ヘッドスペース法によるガスクロマトグラフィー分析により、シス-2-クロロ-1,3,3,3-テトラフルオロプロペン(HCFO-1224xe(Z))とシス-1-クロロ-3,3,3-トリフルオロプロペン(HCFO-1233zd(Z))との混合物における気相部と液相部との組成を調べた。ヘッドスペース法によるガスクロマトグラフィー分析は、上述の手順と同様の手順で行った。図6は、HCFO-1224xe(Z)及びHCFO-1233zd(Z)からなる混合物におけるHCFO-1224xe(Z)の気液平衡曲線を示し、表5は、気相及び液相におけるHCFO-1224xe(Z)(沸点24℃)とびHCFO-1233zd(Z)(沸点19℃)との混合物のモル百分率(mol%)及びガスクロマトグラフィーの分析の結果(GC%)を示す。
<洗浄試験A>
市販の25ccメスシリンダーを11ccの目盛り線で切断した。直径:約7.2mm×長さ:約40mmの清浄な硝子棒の質量を測定後、表記載のオイルに2分間浸漬し、10分間立てて液切した(過剰についたオイルを除去した)後、質量(硝子棒+初期付着オイル)を測定後、前記のメスシリンダーに入れた。以下の表6に記載の化合物Aと化合物Bからなる共沸様組成物を10ccの液面まで仕込み、20℃の水を満たした小型超音波洗浄機(シチズン製SW5800)の中央部に立てた。超音波を照射すると時間と共に共沸様組成物が揮発し、8ccの目盛り線になった時点で、メスシリンダー内の液をガスクロマトグラフで分析した。その結果、全ての実施例1-a~実施例1-jにおいて、2cc揮発したにも関わらず、洗浄前後の液組成は実質に同一であった。すなわち、実機洗浄において、実施例1-a~実施例1-jで用いた化合物A及び化合物Bからなる組成物は、部分的に揮発しても残液の組成が実質的に変化しない共沸様組成であることが示された。次にガラス棒を乾燥させて質量(硝子棒と残存オイルとの総質量)を測定して、油除去率(残存オイルの質量÷初期付着オイルの質量×100[%])を求めると共に、拡大鏡で硝子の表面を観察した。その結果、全ての実施例において油除去率が100%であり、拡大鏡観察結果においては、油分の残存が認められなかったため良好と判断された。各実施例及び比較例の結果を以下の表7に示す。
<洗浄試験B>
HCFO-1224xe(Z)(51.2354GC%)、HCFO-1233zd(E)(31.8451GC%)、HCFO-1224xe(Z)(13.5412GC%)、HCFO-1233zd(Z)(3.2741GC%)からなる共沸様組成物を用いることを除いて、実施例1-aと同様の実験(切削油(ルブカットB-35))を行った。その結果、洗浄後の液の組成はHCFO-1224xe(Z)(51.2349GC%)、HCFO-1233zd(E)(31.8422GC%)、HCFO-1224xe(Z)(13.5913GC%)、HCFO-1233zd(Z)(3.2743GC%)であり、2cc揮発したにも関わらず、実質的に初期組成と同一であった。また、油除去率は100%であり、拡大鏡観察結果も残存油分が認められなかったので良好と判断された。
<洗浄試験C>
切削油(ルブカットB-35)の代わりに、スピンドル油(ピュアセーフティ C-80)、作動油(スーパークリーン SC-41)、潤滑油(スニソ 4GS)、シリコーン油(SH-193)、ストレートシリコーン油(KF-96)、変性シリコーン油(MDX4-4159)を用いて実施例2と同様の実験(4種混合の共沸様組成物)を行った。すると、実施例2と同様に、油除去率は100%であり、拡大鏡観察結果も残存油分が認められなかったので良好と判断された。
<洗浄試験D>
SUS316テストピースを埃が多い工作室に1週間放置した。窒素でブローした後、顕微鏡(倍率:百倍と千倍)で観察したところ、多くのパーティクルが観察された。これを、本発明の共沸様組成物:HCFO-1224xe(Z)(33vol%)-HCFO-1224xe(E)(33vol%)-HCFO-1233zd(E)(33vol%)-HCFO-1233zd(Z)(1vol%)(4種混合の共沸様組成物)で30秒間の超音波洗浄と、30秒間の蒸気洗浄を行い、自然乾燥した後、再び顕微鏡(倍率:百倍と千倍)で観察した結果、残存パーティクルが認められなかった。比較例として、HFC-365mfcを用いて同様の実験を行った結果、残存パーティクルが認められた。
<洗浄試験E>
ステンレススチール製金網(60メッシュ)に以下の表9に記載のオイルを塗布後、10分間立てて液切し、以下の表8に記載した組成を有する本発明の共沸様組成物に5秒間浸漬して引き上げて、乾燥し、実施例1と同様に前後の質量測定によって油除去率を求めた(実施例5-a~実施例5-c)。比較例として、共沸様組成物の代わりに市販のフッ素系洗浄剤であるHFE-7100(CH3OCF2CF2CF2CF3、住友スリーエム社製)、HFC-365mfc(CF3CH2CF3CF3、日本ソルベイ社製),HCFC-225(HCFC-225ca(CF3CF2CHCl2)とHCFC-225cb(CClF2CF2CHClF)との混合物、旭硝子社製)を用いて同様の試験を行った(比較例5-a~比較例5-c)。その結果を以下の表9に示す。
<洗浄試験F>
HCFO-1224xe(Z)(80mol%)及びHCFO-1233zd(E)(20mol%)からなる共沸様組成物(200g)を小型超音波洗浄機に入れて、硝子製レンズを10分間洗浄した。10分後の洗浄液の温度は17.5℃であった。この温度は、この共沸様組成物の蒸発温度を表す。レンズを熱風乾燥した後、目視、および拡大鏡で観察したが、良好に洗浄されていた。
<洗浄試験G>
HCFO-1224ex(E)(95mol%)及びHCFO-1233zd(Z)(5mol%)からなる共沸様組成物を用いて、超音波洗浄機でアクリル板を10分洗浄した。目視および拡大鏡で観察した結果、表面は清浄であり、アクリル板も未洗浄時と同様の光沢を示していた。比較例として、HCFO-1233zd(Z)のみを用いて、実施例7と同様に超音波洗浄機でアクリル板を10分洗浄した。目視および拡大鏡で観察した結果、HCFO-1233zd(Z)のみを用いた場合、アクリル板の光沢が失われていた。
<オイルとの溶解性試験>
容量比でHCFO-1224xe,HCFO-1233zdを混合して以下の表10に示す共沸様組成物A~Hを調製した。硝子製バイアル(10cc)に、共弗様組成物とオイルを表11に記載のとおり仕込み、10回振った後、24時間静置した(実施例8-a~実施例8-x)。また、比較例として、共沸様組成物の代わりに市販されているフッ素系溶剤を用いて同じ実験を行った(比較例8a~比較例8-f)。その目視結果は表11の通りである。
<塗布及び乾燥性試験>
前述の実施例8の共沸様組成物Hと以下の表12に記載のシリコーン油を容量比95:5で混合した。その結果、速やかに均一となった。得られたシリコーン塗布溶液は、1ヶ月保管しても二層分離等の変質は認められなかった。このシリコーン塗布溶液に鏡面仕上げしたSUS316製ディスクを浸漬したあと、スピンコーターを用いて乾燥させた。具体的には1000rpmで30秒間回転させた。乾燥性、塗布膜の状態を表12に記載した。
<発泡試験>
以下の組成のプレミックスを調製した。
エステル系ポリオール(東邦理化製 OH価:314mgKOH/g):50質量部
ポリエーテル系ポリオール(住化バイエルウレタン製 OH価:467mgKOH/g:50質量部
整泡剤(ダウコーニング東レ製SF2937F):1.5質量部
整泡剤(GE東芝シリコーン製 TFA-4200):0.5質量部
酢酸カリウム:0.5質量部
触媒(エアプロダクツ製 PC-41):1.5質量部
イオン交換水:2質量部
発泡剤(HCFO-1224xe(Z)(33vol%)-HCFO-1224xe(E)(33vol%)-HCFO-1233zd(E)(33vol%)-HCFO-1233zd(Z)(1vol%)):35質量部
<HCFO-1224xe(Z)とHCFO-2333zd(E)を含む熱伝達媒体>
シス-2-クロロ-1,3,3,3-テトラフルオロプロペン(HCFO-1224xe(Z))およびトランス-1-クロロ-3,3,3-トリフルオロプロペン(HCFO-1233zd(E))を含む共沸様組成物を熱伝達媒体として用いた冷凍サイクルシステムの性能評価において、表14に示す条件で成績係数を算出した。熱伝達媒体の物性値は、米国国立標準技術研究所(NIST)のREFPROP ver.9.0により求めた。冷凍サイクルシステム計算条件1を以下の表14に示す。
(A)圧縮機の圧縮過程は等エントロピー圧縮とする。
(B)膨張弁における絞り膨張過程は等エンタルピー膨張とする。
(C)配管および熱交換器における熱損失、圧力損失は無視する。
(D)圧縮機効率ηを0.7とする。
QEVA=G×(h1-h4)・・・(1)
であり、凝縮器における放熱量QCONは、
QCON=G×(h2-h3)・・・(2)
となる。
h2=h1+(h2th-h1)/η・・・(3)
となる。
W=G×(h2-h1)・・・(4)
となる。
COPR=QEVA/W=(h1-h4)/(h2-h1)・・・(5)
となる。
COPH=QCON/W=(h2-h3)/(h2-h1)・・・(6)
となる。
CAPR=ρ2×QEVA=ρ2×(h1-h4)・・・(7)
となる。
CAPH=ρ2×QCON=ρ2×(h2-h3)・・・(8)
となる。
G :熱伝達用組成物循環量
W :圧縮仕事
QEVA :入熱量
QCON :放熱量
COPR:成績係数(冷却)
COPH:成績係数(加熱)
CAPR:体積能力(冷却)
CAPH:体積能力(加熱)
h :比エンタルピー
1,2,3,4:サイクルポイント
2th :等エントロピー圧縮後のサイクルポイント
<2,2-ジクロロ-1,1,1-トリフルオロエタン>
2,2-ジクロロ-1,1,1-トリフルオロエタン(HCFC-123)は、不燃性であり、許容濃度が10ppmである。なお、HCFC-123の沸点は、大気圧下において27.8℃、大気寿命は1.3年、地球温暖化係数(GWP)は77(IPCC4次評価報告書 2007)、オゾン破壊係数(ODP)は0.02である。
<HCFO-1224xe(Z)およびHCFO-1233zd(E)を含む熱伝達媒体>
シス-2-クロロ-1,3,3,3-テトラフルオロプロペン(HCFO-1224xe(Z))およびトランス-1-クロロ-3,3,3-トリフルオロプロペン(HCFO-1233zd(E))を含む共沸様組成物を熱伝達媒体として用いた高温ヒートポンプサイクルシステムの性能評価において、表16に示す条件で成績係数を算出した。熱伝達媒体の物性値は、米国国立標準技術研究所(NIST)のREFPROP ver.9.0により求めた。高温ヒートポンプサイクルシステム計算条件2を以下の表16に示す。
(A)圧縮機の圧縮過程は等エントロピー圧縮とする。
(B)膨張弁における絞り膨張過程は等エンタルピー膨張とする。
(C)配管および熱交換器における熱損失、圧力損失は無視する。
(D)圧縮機効率ηを0.7とする。
<2,2-ジクロロ-1,1,1-トリフルオロエタン>
実施例13における本発明の熱伝達媒体の代わりに、2,2-ジクロロ-1,1,1-トリフルオロエタン(HCFC-123)を熱伝達媒体として用いた高温ヒートポンプサイクルシステムの性能評価において、表16に示した条件で成績係数を算出した。なお、図10において、比較例13(HCFC-123)におけるPh線図を示す。
<HCFO-1224xe(Z)およびHCFO-1233zd(E)を含む熱伝達媒体>
シス-2-クロロ-1,3,3,3-テトラフルオロプロペン(HCFO-1224xe(Z))およびトランス-1-クロロ-3,3,3-トリフルオロプロペン(HCFO-1233zd(E))を含む共沸様組成物を熱伝達媒体として用いた高温ヒートポンプサイクルの性能評価において、表18に示す条件で成績係数を算出した。高温ヒートポンプサイクルシステム計算条件3を以下の表18に示す。
<2,2-ジクロロ-1,1,1-トリフルオロエタン>
実施例14における本発明の熱伝達媒体の代わりに、2,2-ジクロロ-1,1,1-トリフルオロエタン(HCFC-123)を熱伝達媒体として用いた高温ヒートポンプサイクルシステムの性能評価において、表18に示す条件で成績係数を算出した。なお、図12に、比較例3(HCFC-123)におけるPh線図を示す。
<HCFO-1224xe(Z)およびHCFO-1233zd(E)を含む熱伝達媒体>
シス-2-クロロ-1,3,3,3-テトラフルオロプロペン(HCFO-1224xe(Z))およびトランス-1-クロロ-3,3,3-トリフルオロプロペン(HCFO-1233zd(E))を含む共沸様組成物を熱伝達媒体(作動流体)として用いた有機ランキンサイクルシステムの性能評価において、表20に示す条件で発電サイクル効率および膨張機サイズパラメーターを算出した。有機ランキンサイクルシステム計算条件4を以下の表20に示す。
(A)ランキンサイクルの理想的な膨張過程は等エントロピー膨張とし、実機損失を考慮し、膨張機断熱効率ηTを導入する。
(B)膨張機による発電機損失を発電機効率ηGで考慮する。
(C)循環ポンプ動力は発電電気で駆動し、モータ効率を含めポンプ効率ηPを導入する。ポンプはキャンド型で、損失分は熱としてサイクルに含める。
(D)軸受潤滑油の循環ポンプ動力は微小であるため無視する。
(E)配管の熱損失、圧力損失は無視する。
(F)蒸発器出口の作動流体は飽和蒸気とする。
(G)凝縮器出口の作動流体は飽和液とする。
LTth=G×(h1-h2th)・・・(9)
となる。
LT=LTth×ηT=G×(h1-h2)・・・(10)
となる。
EG=LT×ηG・・・(11)
となる。
LPth=(PE-PC)×G/ρ3・・・(12)
となる。
EP=LPth/ηP=G×(h4-h3)・・・(13)
となる。
Ecycle=EG-EP・・・(14)
となる。
QE=G×(h1-h4)
=G×(h1-h3)-(PE-PC)×G/(ρ3×ηP)・・・(15)
となる。
ηcycle=(EG-EP)×100/QE・・・(16)
となる。
V2th=G/ρ2th・・・(17)
となる。
ΔHth=h1-h2th・・・(18)
となる。
SP=(V2th)0.5/(ΔHth)0.25・・・(19)
となる。
G: 作動流体循環量
LTth: 膨張機の理論発生動力
LT: 膨張機の発生動力
EG: 発電量
EP: 循環ポンプ必要電力
PC: 凝縮器圧力
PE: 蒸発器圧力
LPth: 循環ポンプの稼動に必要な理論動力
Ecycle: 有効発電量
QE: 入熱量
ηcycle: 発電サイクル効率
V2th: 膨張機出口の理論体積流量
ΔHth: 膨張機の理論断熱熱落差
SP: 膨張機サイズパラメーター
ρ: 作動流体の密度
h: 比エンタルピー
1,2,3,4: サイクルポイント
<2,2-ジクロロ-1,1,1-トリフルオロエタン>
実施例15における本発明の熱伝達媒体(作動流体)の代わりに、2,2-ジクロロ-1,1,1-トリフルオロエタン(HCFC-123)を作動流体として用いた有機ランキンサイクルシステムの性能評価において、表20に示す条件で発電サイクル効率および膨張機サイズパラメーターを算出した。なお、図14に、比較例15におけるTs線図を示す。
<HCFO-1224xe(Z)およびHCFO-1233zd(E)を含む熱伝導媒体>
シス-2-クロロ-1,3,3,3-テトラフルオロプロペン(HCFO-1224xe(Z))およびトランス-1-クロロ-3,3,3-トリフルオロプロペン(HCFO-1233zd(E))を含む共沸様組成物を熱伝達媒体(作動流体)として用いた有機ランキンサイクルシステムの性能評価において、表23に示す条件で発電サイクル効率および膨張機サイズパラメーターを算出した。なお、図15、実施例16におけるTs線図を示す。
<2,2-ジクロロ-1,1,1-トリフルオロエタン>
実施例16における本発明の熱伝達媒体(作動流体)の代わりに、2,2-ジクロロ-1,1,1-トリフルオロエタン(HCFC-123)を作動流体として用いた有機ランキンサイクルシステムの性能評価において、表23に示す条件で発電サイクル効率および膨張機サイズパラメーターを算出した。なお、図16に、比較例16におけるTs線図を示す。
Claims (18)
- 2-クロロ-1,3,3,3-テトラフルオロプロペン及び1-クロロ-3,3,3-トリフルオロプロペンを含有する共沸様組成物。
- トランス-2-クロロ-1,3,3,3-テトラフルオロプロペン及びトランス-1-クロロ-3,3,3-トリフルオロプロペンを含む請求項1に記載の共沸様組成物。
- 前記トランス-1-クロロ-3,3,3-トリフルオロプロペンを1mol%以上99.999mol%以下含み、且つ前記トランス-2-クロロ-1,3,3,3-テトラフルオロプロペンを0.001mol%以上99mol%以下含む請求項2に記載の共沸様組成物。
- シス-2-クロロ-1,3,3,3-テトラフルオロプロペン及びトランス-1-クロロ-3,3,3-トリフルオロプロペンを含む請求項1に記載の共沸様組成物。
- 前記シス-2-クロロ-1,3,3,3-テトラフルオロプロペンを0.001mol%以上99.999mol%以下含み、且つ前記トランス-1-クロロ-3,3,3-トリフルオロプロペンを0.001mol以上99.999mol%以下含む請求項4に記載の共沸様組成物。
- トランス-2-クロロ-1,3,3,3-テトラフルオロプロペン及びシス-1-クロロ-3,3,3-トリフルオロプロペンを含む請求項1に記載の共沸様組成物。
- 前記トランス-2-クロロ-1,3,3,3-テトラフルオロプロペンを90%mol以上99.9mol%以下含み、且つ前記シス-1-クロロ-3,3,3-トリフルオロプロペンを0.1mol%以上10mol%以下含む請求項6に記載の共沸様組成物。
- トランス-2-クロロ-1,3,3,3-テトラフルオロプロペン、シス-2-クロロ-1,3,3,3-テトラフルオロプロペン及びトランス-1-クロロ-3,3,3-トリフルオロプロペンを含む請求項1に記載の共沸様組成物。
- トランス-2-クロロ-1,3,3,3-テトラフルオロプロペン、シス-2-クロロ-1,3,3,3-テトラフルオロプロペン、トランス-1-クロロ-3,3,3-トリフルオロプロペン及びシス-1-クロロ-3,3,3-トリフルオロプロペンを含む請求項1に記載の共沸様組成物。
- 請求項1に記載の共沸様組成物を含む洗浄剤。
- 請求項1に記載の共沸様組成物を含む溶媒。
- 請求項1に記載の共沸様組成物を含むシリコーン溶剤。
- 請求項1に記載の共沸様組成物を含む発泡剤。
- 請求項1に記載の共沸様組成物を含む熱伝達媒体。
- 請求項14に記載の熱伝達媒体を用いた熱伝達装置。
- 請求項14に記載の熱伝達媒体を用いた有機ランキンサイクルシステム装置。
- 請求項14に記載の熱伝達媒体を用いた高温ヒートポンプサイクルシステム。
- 請求項14に記載の熱伝達媒体を用いた冷凍サイクルシステム。
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CN201580049480.3A CN106715669B (zh) | 2014-10-02 | 2015-09-29 | 含有2-氯-1,3,3,3-四氟丙烯和1-氯-3,3,3-三氟丙烯的类共沸组合物 |
JP2016552097A JP6575526B2 (ja) | 2014-10-02 | 2015-09-29 | 2−クロロ−1,3,3,3−テトラフルオロプロペン及び1−クロロ−3,3,3−トリフルオロプロペンを含有する共沸様組成物 |
EP15848096.2A EP3202882B1 (en) | 2014-10-02 | 2015-09-29 | Azeotropic like composition containing 2-chloro-1,3,3,3-tetrafluoropropene and 1-chloro-3,3,3-trifluoropropene |
US15/475,271 US10047326B2 (en) | 2014-10-02 | 2017-03-31 | Azeotropic like composition containing 2-chloro-1,3,3,3-tetrafluoropropene and 1-chloro-3,3,3-trifluoropropene |
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US15/475,271 Continuation US10047326B2 (en) | 2014-10-02 | 2017-03-31 | Azeotropic like composition containing 2-chloro-1,3,3,3-tetrafluoropropene and 1-chloro-3,3,3-trifluoropropene |
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EP (1) | EP3202882B1 (ja) |
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CN109790445A (zh) * | 2016-09-19 | 2019-05-21 | 阿科玛法国公司 | 包含1-氯-3,3,3-三氟丙烯的组合物 |
JP2020132784A (ja) * | 2019-02-22 | 2020-08-31 | セントラル硝子株式会社 | 溶剤組成物 |
JPWO2019117100A1 (ja) * | 2017-12-15 | 2020-12-24 | セントラル硝子株式会社 | Z−1,2−ジクロロ−3,3,3−トリフルオロプロペンを構成成分とする共沸様組成物 |
WO2022038861A1 (ja) * | 2020-08-17 | 2022-02-24 | セントラル硝子株式会社 | 組成物、組成物を含むエアゾール組成物、洗浄剤、溶媒、シリコーン溶剤、発泡剤、熱伝達媒体、消火剤、および燻蒸剤、熱伝達媒体を含む熱伝達装置、ならびに熱伝達装置が含まれるシステム |
WO2022145387A1 (ja) * | 2020-12-28 | 2022-07-07 | Agc株式会社 | モノクロロトリフルオロプロペンと安定剤とを含む組成物およびその用途 |
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WO2014117014A2 (en) | 2013-01-25 | 2014-07-31 | Trane International Inc. | Refrigerant additives and compositions |
CN113993969A (zh) * | 2019-06-07 | 2022-01-28 | Agc株式会社 | 共沸组合物、类共沸组合物、组合物、清洗剂、溶剂、热传递介质 |
JPWO2021187369A1 (ja) * | 2020-03-19 | 2021-09-23 | ||
US20220169816A1 (en) * | 2020-11-30 | 2022-06-02 | Honeywell International Inc. | AZEOTROPE OR AZEOTROPE-LIKE COMPOSITIONS OF Z-1-CHLORO-2,3,3,3-TETRAFLUOROPROPENE (HCFO-1224yd(Z)) |
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CN109790445A (zh) * | 2016-09-19 | 2019-05-21 | 阿科玛法国公司 | 包含1-氯-3,3,3-三氟丙烯的组合物 |
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JPWO2019117100A1 (ja) * | 2017-12-15 | 2020-12-24 | セントラル硝子株式会社 | Z−1,2−ジクロロ−3,3,3−トリフルオロプロペンを構成成分とする共沸様組成物 |
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JP7212835B2 (ja) | 2019-02-22 | 2023-01-26 | セントラル硝子株式会社 | 溶剤組成物 |
WO2022038861A1 (ja) * | 2020-08-17 | 2022-02-24 | セントラル硝子株式会社 | 組成物、組成物を含むエアゾール組成物、洗浄剤、溶媒、シリコーン溶剤、発泡剤、熱伝達媒体、消火剤、および燻蒸剤、熱伝達媒体を含む熱伝達装置、ならびに熱伝達装置が含まれるシステム |
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EP3202882A1 (en) | 2017-08-09 |
CN106715669A (zh) | 2017-05-24 |
US10047326B2 (en) | 2018-08-14 |
JP6575526B2 (ja) | 2019-09-18 |
US20170218311A1 (en) | 2017-08-03 |
JPWO2016052562A1 (ja) | 2017-08-31 |
EP3202882B1 (en) | 2019-09-18 |
CN106715669B (zh) | 2019-05-10 |
EP3202882A4 (en) | 2018-05-30 |
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