CA2684290A1 - Azeotropic and azeotrope-like compositions of e-1,1,1,4,4,4-hexafluoro-2-butene - Google Patents
Azeotropic and azeotrope-like compositions of e-1,1,1,4,4,4-hexafluoro-2-butene Download PDFInfo
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- CA2684290A1 CA2684290A1 CA002684290A CA2684290A CA2684290A1 CA 2684290 A1 CA2684290 A1 CA 2684290A1 CA 002684290 A CA002684290 A CA 002684290A CA 2684290 A CA2684290 A CA 2684290A CA 2684290 A1 CA2684290 A1 CA 2684290A1
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- azeotrope
- azeotropic
- hexafluoro
- butene
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
- 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
- C09K5/045—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 containing only fluorine as halogen
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- 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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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
- A62D1/0028—Liquid extinguishing substances
- A62D1/0057—Polyhaloalkanes
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
- A62D1/0071—Foams
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
- A62D1/0092—Gaseous extinguishing substances, e.g. liquefied gases, carbon dioxide snow
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- 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
- C08J9/141—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
- C08J9/142—Compounds containing oxygen but no halogen atom
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- 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
- C08J9/145—Halogen containing compounds containing carbon, halogen and hydrogen only only chlorine as halogen atoms
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- 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
- C08J9/146—Halogen containing compounds containing carbon, halogen and hydrogen only only fluorine as halogen atoms
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- 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
- C08J9/149—Mixtures of blowing agents covered by more than one of the groups C08J9/141 - C08J9/143
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/30—Materials not provided for elsewhere for aerosols
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- C—CHEMISTRY; METALLURGY
- 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
- C11D7/505—Mixtures of (hydro)fluorocarbons
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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
- C11D7/50—Solvents
- C11D7/5036—Azeotropic mixtures containing halogenated solvents
- C11D7/504—Azeotropic mixtures containing halogenated solvents all solvents being halogenated hydrocarbons
- C11D7/5054—Mixtures of (hydro)chlorofluorocarbons and (hydro) fluorocarbons
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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
- C11D7/5068—Mixtures of halogenated and non-halogenated solvents
- C11D7/5072—Mixtures of only hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/50—Solvents
- C11D7/5036—Azeotropic mixtures containing halogenated solvents
- C11D7/5068—Mixtures of halogenated and non-halogenated solvents
- C11D7/5077—Mixtures of only oxygen-containing solvents
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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
- C11D7/5068—Mixtures of halogenated and non-halogenated solvents
- C11D7/5077—Mixtures of only oxygen-containing solvents
- C11D7/5086—Mixtures of only oxygen-containing solvents the oxygen-containing solvents being different from alcohols, e.g. mixtures of water and ethers
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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
- C08J2203/02—CO2-releasing, e.g. NaHCO3 and citric acid
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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
- C08J2203/12—Organic compounds only containing carbon, hydrogen and oxygen atoms, e.g. ketone or alcohol
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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
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/16—Unsaturated hydrocarbons
- C08J2203/162—Halogenated unsaturated hydrocarbons, e.g. H2C=CF2
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- C08J2207/00—Foams characterised by their intended use
- C08J2207/04—Aerosol, e.g. polyurethane foam spray
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/10—Components
- C09K2205/12—Hydrocarbons
- C09K2205/126—Unsaturated fluorinated hydrocarbons
Abstract
Azeotropic or azeotrope-like compositions are disclosed. The azeotropic o r azeotrope-like compositions are mixtures of E-1,1,1,4,4,4-hexafluoro-2-but ene with methyl formate, n-pentane, 2-methylbutane,, trans-1,2-dichloroethyl ene, 1,1,1,3,3-pentafluoropropane, n-butane or isobutane. Also disclosed is a process of preparing a thermoplastic or thermoset foam by using such azeot ropic or azeotrope-like compositions as blowing agents. Also disclosed is a process of producing refrigeration by using such azeotropic or azeotrope-lik e compositions. Also disclosed is a process of using such azeotropic or azeo trope-like compositions as solvents. Also disclosed is a process of producin g an aerosol product by using such azeotropic or azeotrope-like compositions . Also disclosed is a process of using such azeotropic or azeotrope-like com positions as heat transfer media. Also disclosed is a process of extinguishi ng or suppressing a fire by using such azeotropic or azeotrope-like composit ions. Also disclosed is a process of using such azeotropic or azeotrope-like compositions as dielectrics.
Description
2 PCT/US2008/066621 TITLE OF INVENTION
AZEOTROPIC AND AZEOTROPE-LE~~~ COMPOSITIONS OF
E- 1,1: 1, 4,4.4-HEXAFLUOROk2-BUTENE
This applicatÃon claims priority of U.S. Patent ApplÃcations 60/934199 and 601934209 filed June 12,2007j U.S. Patent Application 60/936082 fi&ed June 18, 2007, U.S Patent Application 6019:7590 f~~~~
June 28, 2007, U.S. Patent ApplicatÃons 60i1-470387 and 60/970384 filed September 6, 2007> and U.S. PatentApplacation 601993241 filed September 11, 2007.
BACKGROUND OF TH~E INVENTION
Field of the Disclosure The present disclosure relates to azeotropic or azeotrape-Ãi~~
compositions of E 1,1, 1,4,4;4-hexafIuoro-26butene.
Description of Related Art Manv industries have beenworkÃnc~ for the past tewr decades to find replacements for the ozone depIetÃng chlorofluorocarbons (CFCs) and hydrocftrofluorocar'bons (HCFCs)- Tt~~ CFCs ~~~d HC.~C,,,, have been employed in a vAde range ot appiications, including the#r cÃse as aerosol propellants, refrsgerants, cIeaning agents, expansion agents for thermoplastic and thermoset foams, heat transfer media, gaseous dielect6z,s, fire extinguishing and suppression agents, power cyc1e, t~+orkiiig flLIÃds, poIyme6zatÃon media, particulate removal fluids, carrier f1uidsF
buffing abrasive agents, and displacement drying agents. In the search for replacements for these versatile compounds, many industr~~s, have turned to the Lise of hydrofluorocarbons (NFCs):
The HFCs do not contribute to the destruction of strat~~pheri'c ozone, but are of concern due to their contribution to the "gr~~~~oLÃse effect", i.e., they contribute to global warmÃng_ As a result of their contrÃbutioÃi to globaf warming, the HFCs have come under scÃLitmny, and WO 2008/154612' PCT/US2008/066621 their widespread use may also be limited in the future. "-'hÃvÃs; there is a need for compositions that do not coritr#bute to the destruction of stratospherc ozone and also have low global warming patentmals (GWPs).
Gei-taan hyd#'r.tfluor~~~efinsy such as 1,1t1r4,4,4-hexafluoro-2,butene (CF'w~~~~HCFw, FG-1 336Ã~z7-): are believed to meet both goaes, This application includes seven different types of azeotropic or azeotrope-lske Ãr~ixtures.
This di5c:;asz i;~ provides a compos3}:on consisting essentÃalIy of (a) E-FC-1 336rrzz. ar-;d (b) methyl formate, wherein the methyl forrÃiat~ is present in an effective amount to forÃTi an azeotrope-lÃke mÃxtLiÃe with E-FC-1336mzz.
This disclosure also provides a composition consisting essentially of (a) E-FC-~ ~36mxz and (b) n-pentane; wherein the n-pentane is present in an effective amount to form an azeotropic or azeotrope-like mixture with E-FC-1336n-az.
This d, is^l;.~sure also provides a composition consÃstÃzig essentially of (a) E-FC 13; 6Ãt~~z and (b) 2-methylbutane (Ãsopentane); wherein the isopentane is present iti an effective amount to form an azeotropic or azeotrope-like mixture, with E-FO- 1336Ãnzz:
This disclosure also provides a composition consisting essentially of (a) E-FC-1336mzz and (b) trans-1,2-dichIoroethylene; wherein the traÃ~s-1,2-dichloroethylene is Present in an effective amount to form an azeotrope-ftk~ n,,ixtui-e with E-FC-1336mzz_ This 6sdc7sure also provides a composition consisting essentially oà (a) E-FC-13. 36mzz and (b) 1:1,1r3r3-pent~fluoropropane (C: F-,~,C'HzCFyH, E-4FC_245fia), wherein the HFC-245fa is present iÃi an effective amount to form an azeotrope-like mixture vrith EYFC-1336Ãtizz_ The dÃ~~~~sure also prevides a composition: consisting essentially of (a) E-FC-1 336mzz and (b) n-butane; wherein the n-butane is present in an effective amoont to form an azeotropic or azeotrope-like mixture with E-FC~~ ~~6mzz.
WO 2008/154612' PCT/US2008/066621 The d#scIosure also provides a composit~on~ coaisisting essentially of (a) E-FC-1336mzz and (b) 2-methy1-proparie (isobutane); wherein the 2-methylpropane is present in an effective amount to form ari azeotropic or azeotrope-like mixture with E-FC-1336mzz:
~r BRI~~ SUMMARY OF THE DP;AWI~~S
FIG, I y FIG, 1 is a graphical representatÃrar, of azeotropeulike com-positions consisting essentialiy of E-FC-1,336mizz and methyl formate at, a temperature of about 20,0 ' C.
FIG, 2 - F1G. 2 is a graphical representation of an azeotrope and ~~~otrope-~ike compositions consisting essentially of ~-F~~~ 336mzz and nNpentane at a temperatur~ of about 20.0 C
FIG, 3 - FIG, 3Ãs a graphical representation of an azeotrope and azeotrope-like compositions consÃsting essentially ofE-FC-1336rnz.~ and isopentane at a temperature of about 20.0 C.
FIG, 4 - FIG. 4 is a grapliical representation of azeotrope-like compositions consisting essentially of E-FC-1336mzz and trans-1,2-~ichloroethylene at a temperatureof about 20.0'-C.
FIG. 5 - FIG, 5 is a graphical representation of azeotrope-like compositions consisting essentially of E-FC-1 336mzz and HFC-245fa at a temperature of about 20.0 C") FIG, 6 - FIG. 6 is a g:aphicW representation ofr ar) azeotrope arid azeofrope-li~~ ~ompositioais c.a;IsisrÃng essentially of E-FC-~ 336mzz and n-butane at a temperature of about 20.0 C.
FIG. 7 - FlG 7 is a graphical representation of an azze-otr~~~ and azeotrope-fike compositions consisting essentially of E-FC-1 336mzz at-sd isobutane at a tempe:@{-sÃe of aibout 20>0 'C<
DETAILED DESC6~IPT!O~ OF THE INVENTION
In many applicatÃons, the useof a pure sing}e component or afi azeotropic or azeotrope-like mixture is desirab@e. For example, when a blowing ~~enY composition (also known as foam expansion agents or foam ~~parnsian compositions) is ~~~~ a pure single component or an ~~eolropic or azeotrope-li~e mixture, the composition may change during its
AZEOTROPIC AND AZEOTROPE-LE~~~ COMPOSITIONS OF
E- 1,1: 1, 4,4.4-HEXAFLUOROk2-BUTENE
This applicatÃon claims priority of U.S. Patent ApplÃcations 60/934199 and 601934209 filed June 12,2007j U.S. Patent Application 60/936082 fi&ed June 18, 2007, U.S Patent Application 6019:7590 f~~~~
June 28, 2007, U.S. Patent ApplicatÃons 60i1-470387 and 60/970384 filed September 6, 2007> and U.S. PatentApplacation 601993241 filed September 11, 2007.
BACKGROUND OF TH~E INVENTION
Field of the Disclosure The present disclosure relates to azeotropic or azeotrape-Ãi~~
compositions of E 1,1, 1,4,4;4-hexafIuoro-26butene.
Description of Related Art Manv industries have beenworkÃnc~ for the past tewr decades to find replacements for the ozone depIetÃng chlorofluorocarbons (CFCs) and hydrocftrofluorocar'bons (HCFCs)- Tt~~ CFCs ~~~d HC.~C,,,, have been employed in a vAde range ot appiications, including the#r cÃse as aerosol propellants, refrsgerants, cIeaning agents, expansion agents for thermoplastic and thermoset foams, heat transfer media, gaseous dielect6z,s, fire extinguishing and suppression agents, power cyc1e, t~+orkiiig flLIÃds, poIyme6zatÃon media, particulate removal fluids, carrier f1uidsF
buffing abrasive agents, and displacement drying agents. In the search for replacements for these versatile compounds, many industr~~s, have turned to the Lise of hydrofluorocarbons (NFCs):
The HFCs do not contribute to the destruction of strat~~pheri'c ozone, but are of concern due to their contribution to the "gr~~~~oLÃse effect", i.e., they contribute to global warmÃng_ As a result of their contrÃbutioÃi to globaf warming, the HFCs have come under scÃLitmny, and WO 2008/154612' PCT/US2008/066621 their widespread use may also be limited in the future. "-'hÃvÃs; there is a need for compositions that do not coritr#bute to the destruction of stratospherc ozone and also have low global warming patentmals (GWPs).
Gei-taan hyd#'r.tfluor~~~efinsy such as 1,1t1r4,4,4-hexafluoro-2,butene (CF'w~~~~HCFw, FG-1 336Ã~z7-): are believed to meet both goaes, This application includes seven different types of azeotropic or azeotrope-lske Ãr~ixtures.
This di5c:;asz i;~ provides a compos3}:on consisting essentÃalIy of (a) E-FC-1 336rrzz. ar-;d (b) methyl formate, wherein the methyl forrÃiat~ is present in an effective amount to forÃTi an azeotrope-lÃke mÃxtLiÃe with E-FC-1336mzz.
This disclosure also provides a composition consisting essentially of (a) E-FC-~ ~36mxz and (b) n-pentane; wherein the n-pentane is present in an effective amount to form an azeotropic or azeotrope-like mixture with E-FC-1336n-az.
This d, is^l;.~sure also provides a composition consÃstÃzig essentially of (a) E-FC 13; 6Ãt~~z and (b) 2-methylbutane (Ãsopentane); wherein the isopentane is present iti an effective amount to form an azeotropic or azeotrope-like mixture, with E-FO- 1336Ãnzz:
This disclosure also provides a composition consisting essentially of (a) E-FC-1336mzz and (b) trans-1,2-dichIoroethylene; wherein the traÃ~s-1,2-dichloroethylene is Present in an effective amount to form an azeotrope-ftk~ n,,ixtui-e with E-FC-1336mzz_ This 6sdc7sure also provides a composition consisting essentially oà (a) E-FC-13. 36mzz and (b) 1:1,1r3r3-pent~fluoropropane (C: F-,~,C'HzCFyH, E-4FC_245fia), wherein the HFC-245fa is present iÃi an effective amount to form an azeotrope-like mixture vrith EYFC-1336Ãtizz_ The dÃ~~~~sure also prevides a composition: consisting essentially of (a) E-FC-1 336mzz and (b) n-butane; wherein the n-butane is present in an effective amoont to form an azeotropic or azeotrope-like mixture with E-FC~~ ~~6mzz.
WO 2008/154612' PCT/US2008/066621 The d#scIosure also provides a composit~on~ coaisisting essentially of (a) E-FC-1336mzz and (b) 2-methy1-proparie (isobutane); wherein the 2-methylpropane is present in an effective amount to form ari azeotropic or azeotrope-like mixture with E-FC-1336mzz:
~r BRI~~ SUMMARY OF THE DP;AWI~~S
FIG, I y FIG, 1 is a graphical representatÃrar, of azeotropeulike com-positions consisting essentialiy of E-FC-1,336mizz and methyl formate at, a temperature of about 20,0 ' C.
FIG, 2 - F1G. 2 is a graphical representation of an azeotrope and ~~~otrope-~ike compositions consisting essentially of ~-F~~~ 336mzz and nNpentane at a temperatur~ of about 20.0 C
FIG, 3 - FIG, 3Ãs a graphical representation of an azeotrope and azeotrope-like compositions consÃsting essentially ofE-FC-1336rnz.~ and isopentane at a temperature of about 20.0 C.
FIG, 4 - FIG. 4 is a grapliical representation of azeotrope-like compositions consisting essentially of E-FC-1336mzz and trans-1,2-~ichloroethylene at a temperatureof about 20.0'-C.
FIG. 5 - FIG, 5 is a graphical representation of azeotrope-like compositions consisting essentially of E-FC-1 336mzz and HFC-245fa at a temperature of about 20.0 C") FIG, 6 - FIG. 6 is a g:aphicW representation ofr ar) azeotrope arid azeofrope-li~~ ~ompositioais c.a;IsisrÃng essentially of E-FC-~ 336mzz and n-butane at a temperature of about 20.0 C.
FIG. 7 - FlG 7 is a graphical representation of an azze-otr~~~ and azeotrope-fike compositions consisting essentially of E-FC-1 336mzz at-sd isobutane at a tempe:@{-sÃe of aibout 20>0 'C<
DETAILED DESC6~IPT!O~ OF THE INVENTION
In many applicatÃons, the useof a pure sing}e component or afi azeotropic or azeotrope-like mixture is desirab@e. For example, when a blowing ~~enY composition (also known as foam expansion agents or foam ~~parnsian compositions) is ~~~~ a pure single component or an ~~eolropic or azeotrope-li~e mixture, the composition may change during its
3 WO 2008/154612' PCT/US2008/066621 appÃicatÃon. in the foam forming process. Such change in composition could detrimentally affect processing or cause poor performance in the application. Also, in refrigeration applications, a refrigerant is often lost during operation through leaks in shaft seals, hose connections, soldered joints and broken lines. In addition, the refrigerant may be released to the atmosphere dLirÃÃ:Ãg maintenance procedures on refrigeration ~~Liipment. If the refrigerant is not a pure single component or an azeotropic or azeotrope-like composÃtion, the refrager~~~~t composition may chaÃ~~e when leaked or discharged to the atmosphere from the refrigeration equÃpmetit.
The change in refrigerant composition may cause the refrigerant to become flammable or to have poor refrigeration perfbrmance. Accordingly, there is a need for using azeotropic or ~~eotrope-ÃÃke mixtures in these and other appiicatsons: for example azeotropic or azeotrope-like mixtures containing E-1 ,1 1, 1Ar,4.4-hexafluoroy~~butene (E-CF,CH=CHCF;,., E-FC-1336mzz).
Before addressing details of embodiments described below, some terms are defined or cIarÃfÃed:
FC- 1 336mzz may exist asone of two configurational isomers. E or Z. FC-1336mzz as used herein refers to the isomers, Z-FC-1336mzz or E-FC-1 336mzz, as well as any combinations or mixtures of such isomers.
As used herein, the terms <<comprises.,, <;comprisanq,:: ,:includes,=, ÃnciLsding\,. ,fhas,;; "having,. or any o+her variation thereof, are intended to cover a non-exclusive incÃLrsion. Fo: example, a process, method, art.icie., or apparatus that comprises aÃÃst of elements a.s not ~er-essariiy limited to only those elements but may include other elements not expressfy listed or inherent to such process, method, aÃ'tÃrÃe; or appaÃ~~tus. Further, unless expressly statp-d to ti'le cO:1rary, "or" refers to an inclusive or and not to an exclusive or. For exampÃe, a condition A or B is satisfied by any one of the fdÃnwing; A is true (or present) and B is false (or not present), A is, false (or not present) and B is trLre (or present), and both A and B are trup- (or present).
Also, use of "a" or "an" are employed to describe elements and components descrþ>~d herein. This is dorie merely for convenience and to give a generaI sense of the scope of the invention. This description
The change in refrigerant composition may cause the refrigerant to become flammable or to have poor refrigeration perfbrmance. Accordingly, there is a need for using azeotropic or ~~eotrope-ÃÃke mixtures in these and other appiicatsons: for example azeotropic or azeotrope-like mixtures containing E-1 ,1 1, 1Ar,4.4-hexafluoroy~~butene (E-CF,CH=CHCF;,., E-FC-1336mzz).
Before addressing details of embodiments described below, some terms are defined or cIarÃfÃed:
FC- 1 336mzz may exist asone of two configurational isomers. E or Z. FC-1336mzz as used herein refers to the isomers, Z-FC-1336mzz or E-FC-1 336mzz, as well as any combinations or mixtures of such isomers.
As used herein, the terms <<comprises.,, <;comprisanq,:: ,:includes,=, ÃnciLsding\,. ,fhas,;; "having,. or any o+her variation thereof, are intended to cover a non-exclusive incÃLrsion. Fo: example, a process, method, art.icie., or apparatus that comprises aÃÃst of elements a.s not ~er-essariiy limited to only those elements but may include other elements not expressfy listed or inherent to such process, method, aÃ'tÃrÃe; or appaÃ~~tus. Further, unless expressly statp-d to ti'le cO:1rary, "or" refers to an inclusive or and not to an exclusive or. For exampÃe, a condition A or B is satisfied by any one of the fdÃnwing; A is true (or present) and B is false (or not present), A is, false (or not present) and B is trLre (or present), and both A and B are trup- (or present).
Also, use of "a" or "an" are employed to describe elements and components descrþ>~d herein. This is dorie merely for convenience and to give a generaI sense of the scope of the invention. This description
4 WO 2008/154612' PCT/US2008/066621 should be read to include oÃie or at least orie aÃid the singular also includes th:e plural unless it is obvious that it is meanituthertivise-UnIess otherwise defined, all teChnicaI and sceent3fÃc termsused herein ~ave. the saÃiie meaning as c-r=mmonIy understood by one of ordinary sk:-1 ;n the art to which this invention belongs. Aithough mettiods and materials similar or eqLÃÃvaient to those described herein caÃ~ be used in the practice or testing of embodiments of the present invention, suitable methods and materials are described ~~~ow, All publications, patent applications, patents, and other ~~~~~~~~~~ mentioned herein ar~
incorporated by reference in their entirety; unless a paÃticLÃlar passage is C.ited. In case of conflict, the present specification, including definrtions;
will control. In ~dditiori, the materials, methods, and examples are illustrative only an~.~ not intended to be lirriiting;
E-FC-1336mzz is a known compound, and its pFepara#ion method has been dÃsciosed, fbr example, in Dawoodi, et, al., JoÃ:Ãrnal of the Chemical Society, ~~emmcal: Communications (1982), (12), 696-8., hereby incorporated by reference in its entirety.
This application includes azeotropic or azeotrcapeYlake compositions comprising E-FC-~ ~~6mzz.
In some embodiments of this invention, the composition consists essentially of (a) E-FC-1 336mzz and (b) methyl formate; wherein the methyl formate is present in an effbctÃ~~ amount to form an azeotrope-(Ãke mixture with E-FC-1 ~~6mzz.
In some embodiments of this invention, the composition consists esseait#alIy of (a) E-~~-1336~~~~ and (b) n-pentane; wherein the n-pentane is pr'esentin an effective aÃ~~ountte,:? fo3r~ ~ an azeotropic or a.~eot--ope-#ike mixture with E-FC ~1 336ruz.
In some embodiments of this invention, : the composition consists essentially of (a) E-FC-1 336mzx and (b) asopeÃitanez wherein the isopentane is present in an effective amoLÃnt to form an azeotrnpic or azeotrope-Itke mixture with E-FC-1336mzz:
In some embodiments of this invention, the compositior: consists essen*;~~ly of (a) E-FC-1336Ã~~zz and (b) trans-I
incorporated by reference in their entirety; unless a paÃticLÃlar passage is C.ited. In case of conflict, the present specification, including definrtions;
will control. In ~dditiori, the materials, methods, and examples are illustrative only an~.~ not intended to be lirriiting;
E-FC-1336mzz is a known compound, and its pFepara#ion method has been dÃsciosed, fbr example, in Dawoodi, et, al., JoÃ:Ãrnal of the Chemical Society, ~~emmcal: Communications (1982), (12), 696-8., hereby incorporated by reference in its entirety.
This application includes azeotropic or azeotrcapeYlake compositions comprising E-FC-~ ~~6mzz.
In some embodiments of this invention, the composition consists essentially of (a) E-FC-1 336mzz and (b) methyl formate; wherein the methyl formate is present in an effbctÃ~~ amount to form an azeotrope-(Ãke mixture with E-FC-1 ~~6mzz.
In some embodiments of this invention, the composition consists esseait#alIy of (a) E-~~-1336~~~~ and (b) n-pentane; wherein the n-pentane is pr'esentin an effective aÃ~~ountte,:? fo3r~ ~ an azeotropic or a.~eot--ope-#ike mixture with E-FC ~1 336ruz.
In some embodiments of this invention, : the composition consists essentially of (a) E-FC-1 336mzx and (b) asopeÃitanez wherein the isopentane is present in an effective amoLÃnt to form an azeotrnpic or azeotrope-Itke mixture with E-FC-1336mzz:
In some embodiments of this invention, the compositior: consists essen*;~~ly of (a) E-FC-1336Ã~~zz and (b) trans-I
5 WO 2008/154612' PCT/US2008/066621 wherein the t#'ans-1,2-dichÃoroethyfene is present in an effective amount to form an azeotr-ope-like mixt(ire with EYFC-131 6ttizz.
Iri some embodiments of this invention, the composition c.oÃas#sts c~~~eMial.ly of (a) E-FG-1336mzz and (b) l-iFCw24511a; :vhere#n the HFC-245ra;~s r)resent in an effective, amount to form er azootrope-Iike mixture with E-FCw~ ~~6mz:z, In some embodiments of this invention, the composition consists ~~~enkially of (a) E-FC-1 336mz2 and (b) ti-butane; wherein the n-butane is present in an effective amount to form an azeottopic or azeotrope-lik:e mixture with E-FC-1336mzz.
ln some embodiments of this invention, the composition consists ~~~en¾;aI'ly of (a) E-FC-1336mzz a.ric1 (b) 2-methyl-~~~opene (isobutane);
wherein the 2-m thylproparie ss present in an effective amount to form an azeotropic or azeotrope-like mixture with E-FC- I 336mzz:
By effective amount is meant ar) amount; which, when combined with ~~~C-'~~~~mzz, results in the formation ofan azeotropic or azeotropewlike mÃxtLire. This definition includes the amounts of each component, which amounts may vary depending on the pressure applied to the composition so long as the azeotropic or azeotropesslike compositions continue to exist at the different pressures, bLit wifit) possible differerit boilirig poirits: Therefore, effective amount ir~~ludes t~~~
amounts, such as may be expressed in weight or src>i~; percentages, of each component of th:e compositions of the 3rÃstant Bnventoon which form a.zeotropic or azeotrope-like compositions at t~~~~~~~~tures, or pressures other than as described hereÃn.
As recognized in the art, an azeotropic composition is an admixture of two or more different components which, when in liquid form under a given pressure, will boil at a substantially constant temperature, which temperature may be higher or lower then the boiling temperatures of the individual components, and which will provide a vapor composittosl essentially identical to the overall fiquEd composition undergoing boilÃng.
(see, e,g,: M. F. Dot~erty arid M.F. Malone, Concept.ual Design of Distillation Systems, McGraw-Hill (New York), 2001, 185> 186, 351..359):
Accordiaigly, the essential features of an azeotropic composition are that at a given pr~~sure, the boÃl#ng point of the liquid compgsÃt#or~ is fixed and that the composition of the vapor above the boiling composition is
Iri some embodiments of this invention, the composition c.oÃas#sts c~~~eMial.ly of (a) E-FG-1336mzz and (b) l-iFCw24511a; :vhere#n the HFC-245ra;~s r)resent in an effective, amount to form er azootrope-Iike mixture with E-FCw~ ~~6mz:z, In some embodiments of this invention, the composition consists ~~~enkially of (a) E-FC-1 336mz2 and (b) ti-butane; wherein the n-butane is present in an effective amount to form an azeottopic or azeotrope-lik:e mixture with E-FC-1336mzz.
ln some embodiments of this invention, the composition consists ~~~en¾;aI'ly of (a) E-FC-1336mzz a.ric1 (b) 2-methyl-~~~opene (isobutane);
wherein the 2-m thylproparie ss present in an effective amount to form an azeotropic or azeotrope-like mixture with E-FC- I 336mzz:
By effective amount is meant ar) amount; which, when combined with ~~~C-'~~~~mzz, results in the formation ofan azeotropic or azeotropewlike mÃxtLire. This definition includes the amounts of each component, which amounts may vary depending on the pressure applied to the composition so long as the azeotropic or azeotropesslike compositions continue to exist at the different pressures, bLit wifit) possible differerit boilirig poirits: Therefore, effective amount ir~~ludes t~~~
amounts, such as may be expressed in weight or src>i~; percentages, of each component of th:e compositions of the 3rÃstant Bnventoon which form a.zeotropic or azeotrope-like compositions at t~~~~~~~~tures, or pressures other than as described hereÃn.
As recognized in the art, an azeotropic composition is an admixture of two or more different components which, when in liquid form under a given pressure, will boil at a substantially constant temperature, which temperature may be higher or lower then the boiling temperatures of the individual components, and which will provide a vapor composittosl essentially identical to the overall fiquEd composition undergoing boilÃng.
(see, e,g,: M. F. Dot~erty arid M.F. Malone, Concept.ual Design of Distillation Systems, McGraw-Hill (New York), 2001, 185> 186, 351..359):
Accordiaigly, the essential features of an azeotropic composition are that at a given pr~~sure, the boÃl#ng point of the liquid compgsÃt#or~ is fixed and that the composition of the vapor above the boiling composition is
6 WO 2008/154612' PCT/US2008/066621 essentially that of the overaii boiling liquid composition (i.e:; no fÃ`acficnatiori of the components of the liquid composition takes place). It is also recognized in the art that both the boiling point and the weight percentages of each component of the azeofropic composition may change when the azec~~op;c i;c mpositioii is sukijected to boilir~g ait different pressures. Thus, an azeotropic composition may be defined in terms of the Linique reIationshiptf~~~ exists among the components or in terms of the compositional ranges of the components or in terms of exact weight percentages of each component of the composition characterized bya fixed boiling point at a specified pressure.
For the purpose of this invention, an azeotrope-ÃÃke composition means a compositioti that behaves, like ar~ aze.otr~~ic composition {Ã:e., has constant boiling characteristics or a tendency not to tÃactÃoriate upon boiling or evaporation). Hence, dunng boiling or evaporation, the vapor and liquid compositions, if they change at all, change only to a minimal or np 'gligible exteÃit. This is to be contrasted with non-azeotrape-1ike compositions in which during boiling or evaporation, the vapor and liquid compositions change to a sLebstantial degree.
Additionaliy, azeotrc~pe-like compositions exhibit dew point pressure and bubble point pressure with virtually no pr~~sLire dÃfferential. That is to say that the difference iÃi the dew point pressure and bubble point pressure at a given temperature will be a small value. IÃi this invention, compositions with a difference in dew point pressure and bubble pomÃit pressure of less than or equal to 5 percent (based upon the bubble point pressure) is considered to be azeotrope-~ik-e.
It is recognized in this fÃefki that wheti the re'tati.~e volatility of a system approaches 1.0, the system is defined as forrt;ing an azeotropic or azeotrope-like composition. Relative volatility is the ratio of the volatility of component I to the volatiiify of component 2. The ratso of the mo1e fraction of a cor~iponeÃit iÃ) vapor tothaf in liquid is the volatility of the component.
To determine the relative vofatÃlÃty of any two compcunds, a method known as the PTx method can be used. In th:s procedure, the total absolute pressure a~ a cell of known volume is rrieasuÃ'ed at a constant
For the purpose of this invention, an azeotrope-ÃÃke composition means a compositioti that behaves, like ar~ aze.otr~~ic composition {Ã:e., has constant boiling characteristics or a tendency not to tÃactÃoriate upon boiling or evaporation). Hence, dunng boiling or evaporation, the vapor and liquid compositions, if they change at all, change only to a minimal or np 'gligible exteÃit. This is to be contrasted with non-azeotrape-1ike compositions in which during boiling or evaporation, the vapor and liquid compositions change to a sLebstantial degree.
Additionaliy, azeotrc~pe-like compositions exhibit dew point pressure and bubble point pressure with virtually no pr~~sLire dÃfferential. That is to say that the difference iÃi the dew point pressure and bubble point pressure at a given temperature will be a small value. IÃi this invention, compositions with a difference in dew point pressure and bubble pomÃit pressure of less than or equal to 5 percent (based upon the bubble point pressure) is considered to be azeotrope-~ik-e.
It is recognized in this fÃefki that wheti the re'tati.~e volatility of a system approaches 1.0, the system is defined as forrt;ing an azeotropic or azeotrope-like composition. Relative volatility is the ratio of the volatility of component I to the volatiiify of component 2. The ratso of the mo1e fraction of a cor~iponeÃit iÃ) vapor tothaf in liquid is the volatility of the component.
To determine the relative vofatÃlÃty of any two compcunds, a method known as the PTx method can be used. In th:s procedure, the total absolute pressure a~ a cell of known volume is rrieasuÃ'ed at a constant
7 WO 2008/154612' PCT/US2008/066621 temperature for uarioÃt~ compositions of the two co#`r;pc=s:nds. Use of the PTx Method i~ described in detail in "Phase Equilik~~uti-~ in Process Des,gn",W#(ey .intersc#ence Publ~sher, 1970, written by Harold R. Null, on pages 124 to 126, hereby incorporated by reference.
These measurements can be converted into equilibrium vapor and liquid com~~sftions in the PTx cef! by using an activity coef~~c'ieÃit eqtÃation model, such as the Non-Random, Two-Liquid (NRTL) equation, to represe;zt. Eiquid phase nonidealities. Use of an activity coefficient equation, such as the NRTL equation is described in detail in "The Properlies of Gases and Liquids," 4th edition, pLrb=#sEied by McGraw Hiil: written by Reid, Prausnitz and Poling, on pa~eo> 241 to 387, and in "Phase Equilibria iri Chemical Engineering," ptiblishec~ by ButterNvorth PÃibI#shers, 1985, w##tte#~) by Stanley M. Walas, pages 165 to 244, Both aforemetifior~~d references are hereby incorporated by reference. Without w~sh#ng to be bound by any theory or explanation, it is believed that the NR"fL equation, together with the PTx cell data, can suffi~~entIy predict the relative volatilities of the E-1,1,1,4,4,4w hexaFluoro-=2-butene-containing compositions of the ~~rp-sent invention and can therefore predFct the behavior of these mix4ures in multi-stage, sepa~rn.:on equipment such as distillation columns.
It was four{d through experiments that E-FC-1 336mzz and ~~
~entane form azeotropic or azeotrope-like compositions.
To determine ttie relative voIar,l t;' of this binary pair, the PTx method described above was u~ed, The total absolute pressure in a PTx cell of known volume was measured at constant te-imperature f~r'Various binary compositions. These measurements were then reduced to ~quiii>,~num vapor and liquid compositions in the ~~ell LisÃr~~ ~~c- NRTL
equation.
The vapor :1#-es5ure measured versus the compositions in the PTx cell for is sE~owÃi in FJG. 2, which graphically illustrates the formation of an azeotropic and azeotrope-like composition consisting ~sssentially of E-Pf:-1336mzz and n_pentane as i~~di~~~~d by a mixture of about 84.6 mole % E-1,1,1,4As4-hexaf1uoro-2_.
These measurements can be converted into equilibrium vapor and liquid com~~sftions in the PTx cef! by using an activity coef~~c'ieÃit eqtÃation model, such as the Non-Random, Two-Liquid (NRTL) equation, to represe;zt. Eiquid phase nonidealities. Use of an activity coefficient equation, such as the NRTL equation is described in detail in "The Properlies of Gases and Liquids," 4th edition, pLrb=#sEied by McGraw Hiil: written by Reid, Prausnitz and Poling, on pa~eo> 241 to 387, and in "Phase Equilibria iri Chemical Engineering," ptiblishec~ by ButterNvorth PÃibI#shers, 1985, w##tte#~) by Stanley M. Walas, pages 165 to 244, Both aforemetifior~~d references are hereby incorporated by reference. Without w~sh#ng to be bound by any theory or explanation, it is believed that the NR"fL equation, together with the PTx cell data, can suffi~~entIy predict the relative volatilities of the E-1,1,1,4,4,4w hexaFluoro-=2-butene-containing compositions of the ~~rp-sent invention and can therefore predFct the behavior of these mix4ures in multi-stage, sepa~rn.:on equipment such as distillation columns.
It was four{d through experiments that E-FC-1 336mzz and ~~
~entane form azeotropic or azeotrope-like compositions.
To determine ttie relative voIar,l t;' of this binary pair, the PTx method described above was u~ed, The total absolute pressure in a PTx cell of known volume was measured at constant te-imperature f~r'Various binary compositions. These measurements were then reduced to ~quiii>,~num vapor and liquid compositions in the ~~ell LisÃr~~ ~~c- NRTL
equation.
The vapor :1#-es5ure measured versus the compositions in the PTx cell for is sE~owÃi in FJG. 2, which graphically illustrates the formation of an azeotropic and azeotrope-like composition consisting ~sssentially of E-Pf:-1336mzz and n_pentane as i~~di~~~~d by a mixture of about 84.6 mole % E-1,1,1,4As4-hexaf1uoro-2_.
8 WO 2008/154612' PCT/US2008/066621 butene and 15A mole % n-pentane Eiaving the hilghest prec'sur~ over the range of compositi~ns. at this tempeÃ'attire. Based upon these findings, it has been caIcu1ated tha:t E-FC-1336mzz and nw pentane form azeotropic compositions ranging from about 82.2 mo(e percent to about 953 mole percent E-~~~ 1 336mzz and from at)otÃt 17 8 moIe percent to ~~~~~t 4.~.~
rTiole percent nwpentarte (which form azeotropic compositions boiling at a ~emperatÃ.Ãre of from about v20 OC to about 80 "C and at a pressure of from about 4.5 pspa, (31 kPa) to about 139 psia ~'951 kPa)). ~ome embodiments of azeotropic ~ompo. ;t:ans are lÃstedr in TabIQ 1_ TabE~ I Azeotropic compositions ............. ................................................. ----- ------- -------- -------- -----------Azec~~roptc Azeotropic E-FC-1336nizz r#-Pentane Temperature Pressure (Ps,a, ,,--roa L'~} (mole %) '-------------- ~!...---------------------------- '-"-'-- ---------..................... -'--" --------- '-------- I ........-'----------------'~
~Ã~,~3 ~,~~ ~3~.~ ~'.~
................................................ .............
....................... ......... ......... ........................;
10:0 7.36 i 7;5 0.0 11.4 17.0 -------- -------- ,~ --------- ------ 17.0 --------- -------- 83.7 --------- --------1~.~
7 . _______- ______ _________ t ... _____- -------- ________- - _______- -----_- ________- I _______- ^----- ________- -20.0 24.6 84.6 1;?A
............... _......................................
_.,,........................ .................... _..._._ ......... .........
....................i 30,0 34s6 85:7 14.3 ........ ......~.} .........._ ~ ............... j{'[ i.iM,........................ 1............. y~
.)...................... ......... ...)....f..~.............. .q `"&.~ `.'l`~t .~ ~Y .L.71~.LT
50.0 63:8 88.6 11.4 60.0 81.9 90..5 9.5 -- ----- --------- -70.Ã~ 108,6 92.7 7.3 ',~ ............... _.._,__..................~'+.............. _____...
......... ......... ....................................
._...__.,................
~. i 80.0 1:~8.6 9 5,3 AdditÃanally, azeot~ope-ikel.ompositions contaÃnEÃ~g E-FC-1336mzz and n-pentaeie niay aiso be formed. Such azeotrope-like compositions exist ar~urd azeotropic compositions. Some embodiments of azeotrope-Ã~~~
~om,,posÃtions are 1isted in Table 2: Rd-ditionaI err3~e-li~~nts of azeotrope-like compositions are listed in Table 3.
Tabl::e 2A-zeotÃ~gpe-like-22Mpositions ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~
~~~~~~~~~~~~~ ~~~~~~~~~~~~~~~~~~- T
...............................................................................
............ ...................
..................................................................!
rTiole percent nwpentarte (which form azeotropic compositions boiling at a ~emperatÃ.Ãre of from about v20 OC to about 80 "C and at a pressure of from about 4.5 pspa, (31 kPa) to about 139 psia ~'951 kPa)). ~ome embodiments of azeotropic ~ompo. ;t:ans are lÃstedr in TabIQ 1_ TabE~ I Azeotropic compositions ............. ................................................. ----- ------- -------- -------- -----------Azec~~roptc Azeotropic E-FC-1336nizz r#-Pentane Temperature Pressure (Ps,a, ,,--roa L'~} (mole %) '-------------- ~!...---------------------------- '-"-'-- ---------..................... -'--" --------- '-------- I ........-'----------------'~
~Ã~,~3 ~,~~ ~3~.~ ~'.~
................................................ .............
....................... ......... ......... ........................;
10:0 7.36 i 7;5 0.0 11.4 17.0 -------- -------- ,~ --------- ------ 17.0 --------- -------- 83.7 --------- --------1~.~
7 . _______- ______ _________ t ... _____- -------- ________- - _______- -----_- ________- I _______- ^----- ________- -20.0 24.6 84.6 1;?A
............... _......................................
_.,,........................ .................... _..._._ ......... .........
....................i 30,0 34s6 85:7 14.3 ........ ......~.} .........._ ~ ............... j{'[ i.iM,........................ 1............. y~
.)...................... ......... ...)....f..~.............. .q `"&.~ `.'l`~t .~ ~Y .L.71~.LT
50.0 63:8 88.6 11.4 60.0 81.9 90..5 9.5 -- ----- --------- -70.Ã~ 108,6 92.7 7.3 ',~ ............... _.._,__..................~'+.............. _____...
......... ......... ....................................
._...__.,................
~. i 80.0 1:~8.6 9 5,3 AdditÃanally, azeot~ope-ikel.ompositions contaÃnEÃ~g E-FC-1336mzz and n-pentaeie niay aiso be formed. Such azeotrope-like compositions exist ar~urd azeotropic compositions. Some embodiments of azeotrope-Ã~~~
~om,,posÃtions are 1isted in Table 2: Rd-ditionaI err3~e-li~~nts of azeotrope-like compositions are listed in Table 3.
Tabl::e 2A-zeotÃ~gpe-like-22Mpositions ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~
~~~~~~~~~~~~~ ~~~~~~~~~~~~~~~~~~- T
...............................................................................
............ ...................
..................................................................!
9 WO 2008/154612' PCT/US2008/066621 .....b'M~~~~~ ......... .........f~
............................................... .... ~.. '~'~ ....~l...i`~
.... P ~Ãc ..... ....~~ .... .., ~,, k~ ~ +'~ {g ... e Range ------------------------------------------------------------------------------------------- -------- --- ----------------------- - ---------------------EaFC-1 336mzzin-Pentar~e -40 88-9911-12 E-~C- I 336tanzz:/n-Pentane 0 86-99.11-14 = -- - ------- - - ------- --------- ---------; - --------- --- --FC-1336rs'n,.Pentane 20 86 99/1-14 E
............... _____________ ~-FC-1336mzz/n-~entane 40 85-9911-15 ,,,,, ,,,,,,, ,,,,,,,, ,,,,,,,, ,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, -,,,,,,,,,,,,,,,,,,, ,,,,,,, ,,,,,,,,,,,,,,,,,,,,,.
E-FC-1336rn'-7zln-Pentane 80 84-9911-16 =----- -------,~ --------- ------- -------------------------------------- ----------------- -----------------~.-FG-1,~36ra;fin..Pentane 120 83-99='1-17 :..............................................................................
............. ...................
.................................................
................:
Table 3 Azeotro2e-like compositions Weight Percentage COMPONENTS T (r,C) Range E-FC-I 336mzz/n-Pentane -40 88-95/5-12 --------------------------------------------------------------------------E-FC-~~~~nazz/n-Pentane 86-95/5-14 , E-FC-1336mz2;/Ã-i-Penrane 20 86.-9515-14 . . . . . . . . . . . . . ~
h . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . .................. ....................
........................................................
nenk~~ne 40 85-95/5-15 _ _ _ _ _ __ _ _ _ _ _ ___ _ _ _ _ _ __ _ __ _ _ _ _ __ _ _ _ _ _ _ _ _ _ _ _ __ ..................................................... ....................
.................................................. EYFC-1 336mzzln-Pentad~~ 80
............................................... .... ~.. '~'~ ....~l...i`~
.... P ~Ãc ..... ....~~ .... .., ~,, k~ ~ +'~ {g ... e Range ------------------------------------------------------------------------------------------- -------- --- ----------------------- - ---------------------EaFC-1 336mzzin-Pentar~e -40 88-9911-12 E-~C- I 336tanzz:/n-Pentane 0 86-99.11-14 = -- - ------- - - ------- --------- ---------; - --------- --- --FC-1336rs'n,.Pentane 20 86 99/1-14 E
............... _____________ ~-FC-1336mzz/n-~entane 40 85-9911-15 ,,,,, ,,,,,,, ,,,,,,,, ,,,,,,,, ,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, -,,,,,,,,,,,,,,,,,,, ,,,,,,, ,,,,,,,,,,,,,,,,,,,,,.
E-FC-1336rn'-7zln-Pentane 80 84-9911-16 =----- -------,~ --------- ------- -------------------------------------- ----------------- -----------------~.-FG-1,~36ra;fin..Pentane 120 83-99='1-17 :..............................................................................
............. ...................
.................................................
................:
Table 3 Azeotro2e-like compositions Weight Percentage COMPONENTS T (r,C) Range E-FC-I 336mzz/n-Pentane -40 88-95/5-12 --------------------------------------------------------------------------E-FC-~~~~nazz/n-Pentane 86-95/5-14 , E-FC-1336mz2;/Ã-i-Penrane 20 86.-9515-14 . . . . . . . . . . . . . ~
h . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . .................. ....................
........................................................
nenk~~ne 40 85-95/5-15 _ _ _ _ _ __ _ _ _ _ _ ___ _ _ _ _ _ __ _ __ _ _ _ _ __ _ _ _ _ _ _ _ _ _ _ _ __ ..................................................... ....................
.................................................. EYFC-1 336mzzln-Pentad~~ 80
10-90/10-90 and 84-__ _ _____ ________________________ _________ __________________________ __ ________________ _______ __________________________-ErFC-1336mzzln-Pentane 120 83-95/5-17 , = , - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -- - - - - - - - - - - - - - - - - - - = - - - - - - ............... - - - - - -- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -- - - - - - - - - - - - - - - - - - - - - - - - - =
It was found through ~~~eriments that E-FCr 1336mz~ and methyl formate form azeotrope-like compositions. To determine the relative volatÃlity of this binary pair, the PTx method descri~~~ ~~~~e was useci.
The total absolute pressure in a PTx ceI1 of known volume was measured at constant temperature, for various bic-tar~ compositions. These measurements were then reduced to equilibrium vapor ancJ liquid compositions in the cell using the NRTL equation.
The vapor pressure measured versus the compositions in the PTx cell for E-FC-1336mzz1~~~thy[ formate mixture is Shown in FIG. 1, which WO 2008/154612' PCT/US2008/066621 illustrates gÃ'aphi:;::liy the fbrmat#on of azeotrope-like compositions consisting essenii-illy of E-1, 1,1,4;4,4-hexaf Lioro-2-butene and methyl formate at 20,O rC, as indicated by mÃxt~ires of about 83 mole % to about 99 mole % E-1;1,1t4,4,4-hexafluoro-2-b~~ene and about 17 to about 1 mole % methyl ft~~~ate-Some eÃTiboditTtenks of azeatrope-lrke composÃtÃoÃas are listed in Table 4. Additional embodiments of azeotrope-1ike compositions are listed in Table S.
Table 4. AzeOtro. e-Iike Compos-t3ons CO31~~~~~ENTS .~ ~~~_~... ,~feÃght ~r~, Ran~~......
.................................
ethyl formate -40 ~ ~ ~~6mzzr~~thylõ~orc~~e 0 95-99/1-5 ____ _ __________........................................................
~thyl formate ....... 40 92-99/1 8 -- --- ------- -- -- --------- ------- ----------- ~------------ -------- ----------------~
E-~C 1,~36mzz.W~thyl forrrÃate 80 86-99/1 --~-4---- -------- - - --------------- ------------------------------ ------------------------- ----------------------------------------------------------E-F; 1 33~~iizzr~~~~.y!-farmate 120 73 'i00/1-27 Table 5. Ageotro. e-li~~ ~ompositÃoÃ~~
W~~g~;t"-~ ~~~~~~
~OMP~~ENTS T
--- ---- ----- ------- ------ ~------- ----- --------E FC 1 ~~6m,zzrMethyl forriate -40 98-9911 2 ______ _________ _________ _________ _________ _________ E-FC 'I~~~rnzz/MeLh vi 11"ormate 0 : 97-9911-3 ----- - ---~ fG I3;6~~zzr~r~ei,~~.( formate 40 95 99~<'1:~
___________ _____________ E-FC ~~~6m,zz/1V1eiiyl ;formate 80 ,92-99l'~ 8 ~ ~G '133~a~`~~zzrMet~ÃvI fÃ~Ã Ã~~at~ 1 2 ... 0 8 ... 7 ------ 9 .... 9r'i 1 3 _________ It was found through experiments that E-FC-1336mzz and isopentane form azeotropic or azeotrope-i,ke;--t;~~i-.,na,,:;itions.. To determine the relative voiat:if~ty of this binary paÃt', the PTx melkhod described above was used. The total absolute pressure in a PTx cell of known volume was measured at constant temperature for various binary compositions. These measurements were then reduced to equilibrium vapor and liquid compositions in the cell using the NRTL equation.
The vapor pressure measured versus the compositions in the PTx cell for E-FG-1336mzz1 isopentane mixture is shoWrt in FIG. 3, which ~~
WO 2008/154612' PCT/US2008/066621 illustrates gÃ'aphi:;::liy the fbrrmat#on of an azeotrope aaid azeotrape-like compositions of E-1. 1 , 1,4,4;4-hexaffuoro-2-butene and ~~opentane at 20_0 tsC; as i~~icated by a mixture of about 77.2 rno(e % E-1,1,1,4,4:4-~~~afluoro-2-butiene and 22;8 mole % isopentane having the highest pressurre over tfie range of compositions at this temperature.
~~~~d upon these findings, Ãt has been ca1c>Lilated that E-FC-1336mzz and isopentane form azeotropic compositions ranging from about 75A mole percent to about 95A mole percent E-FC-1336r~~z atid ~~om about 24.9 mole percent to about 4_6 mole percent isopentane (which form azeot~opmc c~orTiposÃtÃons boiling at a temperature of from aboot 40 C
to abou~ ~ OV'C and at a pressure of from about 1.6 psia (11 kRa) to about 218 psia (1503 kPa)). Some embo(lEment~ ~~~zeot~~~~~~ compositions are listed in Table 6.
Table 6 Azeotro -~ co~~ ~~~~itsor~~
Azeotrapic Azeotropic EwFC-'~ ~~6mzz ~~~~entane Temperature Pressure (psaa) (mole %) (mole %) ________ ________ .................................................
....................................
20'0 8 75.0 250 - 10.0 7,7 75.3 24.7 }_______ _________ _________________;______________________ ;..................... ~ _.................... _ .
0.0 ~2.~ ~~ .~ ~~ ~
............................................ ____ ______________, ____________________ ___________________ ..................................
'~~.Ã~ 17.8 76.4 23.6 ----- ------- ; -------- ------- ------- ----- } - -------20.0 25.6 77.2 ~22.8 ---------- --------------------------- -----------------------------------------------------30.0 35.9 78.3 213 --------------------------------------------- --40,0 49.0 73.5 20.5 _________________________________________________n........ 50.0 65.4 81,1 18.9 60.0 85.6________________ 83.0________________ :17:0 ------ ---- ------------ --------: ------------------ ---------------------} ---------- --r0.0 1:10r3 85.2 14,8 80:0 140.0 88,0 12,0 1'75.6 91.3 87 WO
____ _________;
~~~`~
__-___ ___________ _____________~217.9 _______________ _______________~ ~~.~
_________________ ___4. 6 ----------------------------- -------------------------------------------- ----------------------------- ---------------------------~
AdditioÃia11y: azeotrope-like compositions containing E-FC-1336mzz and isopentaÃ~e may also be formed. Such azeotrope-like compositions exist around azeotropi~ ~omposifions. Some embodiments of azeotrope-WO 2008/154612' PCT/US2008/066621 kike eompositi~~~s are listed an Table 7~ Adiditiona1 err;bc;d:ments of azeotrope-iÃk~ ~omposÃtÃ~~~~ are Irsted in TabIe 8.
~aUe 7. Azeotrope(Ãke ~:rrns --- -------- ------ ------------------------COMPONENTS E-FC-" 33# mzz'~sc~erÃtan~e -40 81-94+6-19 0 80-99,'1-20 E-FC-1336mzz/isopentane 40 80-9.9t 1-20 E-FC-1336Ã~zz/is~ 79-99,'1-21 E-FC-1336mzz/isopentane 100-1 77-99/1-23 ~
Table 8. Azeotropew li~~ ~om o4 !':cns Ãg h t % Range COMPONENTS T (jC) - - -- -- - -- ------- ------ --- ----E-FC-'~ 3')6mzz,%isqp~~t-ane -46 81-95/5-19 ------------------ --------------------------------- --------------------- -------------------------------------------------------------E---FC--l a~~mzz,risoper~tane -------------- 0 80-9~~5,20 ------ +--- -- -------E-FC-,1 336mzz%isopentaÃie 40 8 09 15t 2 0 ------------------ -------------------------------- ------ ---------------------- -----------------------------------------------------------------------------------E ~ ~~~ ~ ~~~~=is~p~r taÃ~e 80 79-9' f~;~21 - - - -------- - -- ------- _ E-FC-1 336mzz%isopc:, ;tane ~ ~~ 7-7-95/5-23 It was fc id through experiments that E-FC-1 336mzz aÃid t.rans-1,2-div.hlorcaethylene form azeotropewl~~~ ~ompositions. To determÃne the relative volatility of this binary pair, the PTx method described above was used. The totai absolute pressure in a PTx cell of known voltÃme was measured at constant temperature for various binary cor~posi:<Jns. These measurements were then reduced to equilibrium vapor and !'iquid compositions in the cell using the NRTL ~quation.
The vapor pressure measured versus t~~~ compositions in the PTx cell for E-FC-1336mzz] trans- 1,2-dichioroethylene mixture is shown irt FIG. 4, which illustrates graphically the fbrmation of azeotrope-like cornposÃtions of Ex1,1,1,4,4,4-hexafluoà o-2-butene and trans-1,2-dichforoet~~~ene at 20.O `C, as indicated by mixtures comprised of about 84 mole % to about 99 mole % E-1 336mzz and from about 16 to about 1 mole % ts a.ns-I,2w,d::ichloroethy(ene:
Some embodimeri s of azeotrope-li~e compositioÃ~~ are listed in Table 9. Additponal embcdm~ents of azeotrope-i~~e compositions are listed in Table 10:.
WO 2008/154612' PCT/US2008/066621 Table 9: Azeotro wlik~ Compositions ~OMPONE f~~~ T (,~C) Weight %
~
Ran ________ E-FC 133~s~t~1Tra#~s-1 2 dÃch1~3r~aethyiene -40 ~f2-99L 1 8 E__F~ 1336rn~l~'rans ~ ichlorogt~~rl~~______ 0 94~ ~3911 T0 ErFC 1336mzz/'~~ans-1,2-dÃchl~~~~th~iene- 40 90-9~?i1 '~0 `
________ _________ _________ _______ ______ _~_;FC-1336m~iTrans 1 2 dic}~Ioroee ....................... 80 89 ~3911 '~ 1 ErFC-1336mzz+~~ans-1,2-dÃchloroethvlt r,~ 120 88-9911-12 ...........
T.abl!e 10. Azeotrc}~~ejik~ ~2Mpositi ...............................................................................
.....................~~~~~~~~~~~~~~~ ------------------- ~.. -------------------------------Weaghtaia Range, , ~,~O~~E~.NT~ ~ ~' .....:= ........ ......... ........ ....... ....... .. .. . `
..._~` . :...............
.... ....... ..........
E Ft~ ~ ~~~~zz/T#'arts-- i ,2 d#ch9oCoeth,y-ien-e ~--6 ----E-F;" , 336mzz/Trans1 2-d#chl:oroeth ~= =_ne ---- ======_~========:============_~~ ~~r ~ 7 ===== ======== ========= ======= ======= ======= <=
======= == ===;
E-FC-'~336mzz/Trans-1,2dichi~oroetii~ ,~r~e 40 --- --EuFC-'1336mzz/Trans-1 2-dichl:oroethviene 80 1 8 ----- ------ ----- - ------- -- ------- -E-FC 1 336mzz!Trans-1 2-dichloroethylene 1 20 93 -99<1 7 Ã
------- -------- -------- --------- ------- ---------- - -------- --------------~
~t was found through experiments that E-FC-1336mzz and 'HFC-245fa form: azootrope-Iik~ compositions. To deterryiine the relative volatility of this binary pair, the PTx method described, above was used:
The tota.I absolute pressure in a PTx cell of known volume was measured at constant temperattire for various binary compositions. These measurements were then reduced to eqÃaiIibrium vapor and iiqLiici Compositians i~ the cell using the NRTL ~quation:
The vapor pressure measured versus the compositi~~~~ ~~ the PTx cell for E-FCw1336,-# izzf HFC-245fa rtiixtLire is s;-,own in: FIG.. 5, which illustrates grap:iicaliy the formation of azee~rope-sike compositions of E-1,1,1,4,44-hexafi~oro-2-but~~~ and HDC-245fa at 20.0 C. as indicated by mixtures of about I to 99 mole % E--'j,1,1.4>4,4-hexafluoro-2-~atene atid about 99 to 1 mole % HFC-245fa.
Some embodiments of azeotrope-like compositions are listed in Table 11. Additional embodiments of ~zeotrope-1ike compositions are listed in Table 12.
WO 2008/154612' PCT/US2008/066621 ~~~~~.' ~. ~ ~'C}~fC? ~ ~1'=+:~ i~C?2~?t+t~"~ Ãt3Ãi~a CO~''~~~i~~~ ~ ~ifeÃght % Range E-FC-1 336mzz/HFC-2466~ 1 9911 99 -- ---- ------ --- -------- ---------- - ---------E-FC-'~ ~~~~z7YNFC-24u?fa o -------------- -- --- ---------E-FC-1336mzz/~FC 245fa 40 1r99111-99 _________ _____________________________ .. =___________________ ___;
~-FCr 1336m7-zjHFC-24,5a -- --- ------ ------- -------- --- - --- ---------E FC ~ ~36mzz'HFC-245fa I20 t ~~+ 1 99 _____. _______ _________________________ _________ Table 12. Azeotrope-I~~~ Compositions . , WeÃcÃht % Range ~~~iP~~ENTS T
c) E.-FCr1336m7-zlHFC145fa -40 10w90110-9Ã3 -------, -- -------- ---- -- --------- -E--FG- j1-)36mzz,FHFC-245fa ( o 1 0p90110.-90 _______ _________ ________________ ___;__ ________ __________________ E-FC-1336r~z~'H~'C-2~~6 4~ 1 0w90110-90 E-FC-1:~36Ã~?~`~~FC-24, 80 1~]-901'[Ã~~-~Ã~
............................................... _; ________________ _____ ________ __________________ E-FC-1336mz~HFC-245fa _______ 1,2 10-90f 10-90 ~________________ ___<_____ _________ ___________________.
It was found through expenment~ that E-FC-1336mzz and n-butanp-forÃ~~ azeotropBc or azeotrope-like cor~~~~~~ions. To determine the relative volatiiity of this binary pair, the PTxmetliod described above was used.
The total absolute pr~~sureÃn a PTx cell of known volume was r~~~stir~~
at constant temperature for varioÃ.xs binary compc~~ttions. These measurements were then reduced to equilibrium vapor and liquid ~ompositioris in the cell using the NRTL eqciatÃor).
The vapor Pr~~sure measured versus the compositions in the PTx:
cell for E-FC-1336,mzz~n-butane mixture is ~~owz-a in FIG, 6, which illustrates gr~~~~ÃicalAy the formation of anazeotropic composition of E-1<1,,1.4,4,4-hexafiuoro-2-~~~ef)e atid cycl'opentane at 20.0 wC, as indicated by a mixtu re of about 38. ~ mole % E- 1, 1;1 A4;4-hexafiuoro-2-butene a nd 61.9 moIe% n-butane having the highest pressure over the range of compositions ~t. this temperature.
Based upon these findirigs, it has been calculated that E-FC-1336mzz and n-butane form azeotrolpÃc comrpositions ranging from about 29.5 mole percent to about 47 2 mole percent ~~~~- 1;336mzz and from aboLit 70.5 mole percent to about 52.8 mole percent n-butane (whÃ~~ form azeotropic compositions boÃli~ng at a ternperature of from about -40 "C to WO 2008/154612' PCT/US2008/066621 about 100 "C and at a. pressure of from about 3.0 psia (21 kPa) to about 277 ps#~ (1910 kPa)). Some embodiments c~~ azeotropic compositions are listed in Table 13, Table 13. AgeoÃropic GgMposifions Azeotropic Azeotropic E-FC-1336ÃTazz n-butane Temperature ('$C) Pressur~ (psia) (mole %) (mole %) --40 10 29.5% 70.5%
-30 5A 313% 68,7%
-20 8.2 33.0% 67.0%
-10 12,7 34.5% 65,5%
0 19:0 35_8% 64:2%
27.4 37.0% 63.0%
38.3 38.1% 61.9~'~~
523 39.2% 60,6%
697 40.2% 59.8%
91,1 41,2% 58.8~~~
116.$ 4 2.'2 % 57.8~'r~
1'47.6 433`,-% 56:7%
183.9 44,4`=;~ 55.6%
226.5 457% 543~'~`~
100 276.6 472% 52.8%
~
Additionally, azeotrope-like compositÃons containing E-FG_,1336Ãrzz and n-butane may also be formed. Such azeotrope-like compositions exis~ arouiid azeotropic compositions. Some embodiments of azeotrope-like compositions are listed in Table 14. Additional embodiments of 10 azeotrope-like compositions are listed in Table 15, Tabfe 14. Az~~~e* IÃke Cs?msitions --------------------------------------------------------------------------- ------- -----------------------------------------------------------------------------COMPONENTS T ( C) ~~~ % R~~~ ~e E-FC-1 336mzz/n-butane -40 38-64/36_62 E-FC-1336r-qz /n-~~AaÃ~~ 0 44-72/28-56 E-FC- I 336r~zz/n" butane 40 1-13~87-99 and 43-80/20-57 - ------ ----- ----- ------- - -- ------ ------- -- ------- an-d-----~87 -~9i1 E-FG-!.-36rnzz/r~~butane 80 1-91/9-99 and 94-99/1-6 -- --- --- ---- --- --- ------- ----- --- -------E FCr i 336mzz1n-butane 1 00 1-99/1-99 Tabfe 15. ,:~eotro. eNlike CorrDosit~ons , We:ghf A, Ratige COMPONENTS ;T ('G) E FC-1336mxzln-butane -40 50. 64136-50 ......... .. ....................................................
.........
WO 2008/154612' PCT/US2008/066621 E-FC--1336mzz1n-butane0,,,,,,,, 50-72f'28-50 E-FC-1 336mzz/Ã~-butane 40 10;13/87-90 and 43-80.+20-57 E-FC-1 336m~71n-butane 80 10-90/10-90 ___ E~-~'C-`à a36r~it~-Ã~utar~e 1 0~] 1 Ã~~.-90110-90 It was found through exÃaerimenks that E-FCw 1~~6mzz. and isobutane form azeotropic or azeotrope-i'ike compositions. To determine the reÃatiAre uoÃatÃ(ity of this Ã~~~~ry paÃr, the PTx maAhod described above was Lased. The tofiaà absolute pressure iÃ) a PTx cell of known vo1tÃme was ~~~~sureÃ.~ at constant ~emper"+i;~-efor various binary corn!)osiiEons. These measurements were then reduced to ~quilsbriurn vapor and liquid compositions in the cell using ffie NRTr L eqLmtion, The vapor pressur~ measured versi.,s tt~~ compositions ifi the PTx cell for EaF~~~ 336, r~lizzlisobutane mixture is showri in FlG. 7, which iÃIusfirates grap'sIicaÃ'y the formation of an ~~eotropÃc composition of E-'à <1,.1.4.4,4-hexafluorow2-bu#~~~~ and cy;;;opentane at 20.0 "C, as Ãndicated by a mixture of about 24.9 mole % E-1>1;1 AAA-hexafluorci-2-butene artd 75.1 mole ~~~.~ isobutane having the highest pressure over the range of compositions at this temperature.
Based upon these findingss it has been calculated that ~~~C-'Ã 336mzz and isobutane form azeotropic compositions ranging from about 19.4 mole percent to abotrt 32.4 mole per-ent E-F:, 1 336mzz and from aboL,t 80.6 mole percent to about 67.6 mole percent isobutane (which form azeotropic compositions boiling at a temperature of from about -40 "C to about 80 C and at a pressure of from about 4.5 psÃa {31 kPa) to about 218 psia (1503 kPa)). Some embodiments of azeotropic compositions are listed -n Table 16.
Table 16. Azeotropic Compositions Azeotropic Azeotropic E-FC'-1 336mzz isobutane Temperature ( C) Pr~~sure (mole %) (mole %) (psia) -40 4.5 'k 9:4% 80.6%
-30 7:3 20:3% 797%
-20 11.5 21:2% 78.8~'~~~
-10 17.2 22A% 77.9%
0 25.0 23.0% 77:0%
10 35:2 24.0% 76.0%
WO 2008/154612' PCT/US2008/066621 20 48.4 249% 75.:1 %
30 64.9 25.9% 74: ~ ~~~
40 8.~.~,? 27.0% 73,0%
50 1t~: A 28A% 71:9%
60 ' 4 0;0 29,3% 70 7%
70 175,7 30_7%69 010`
80 218.2 32;4~~"~ 67 6%
AdditionaIly, azeotrope-like ~ompositions containing E-FC-1336.rr~~~~
and isobutane may also be formed. ~~~~~ azeotrope-like ~ompositions exist around azeotropic compositions. Sc~~~ ~~boc#i~~~nts of azeotrope-l#ke compositions are fssted in TabIe 17 Additionaà embod3merits of azeotrope-like ~omposÃtions are 1Ãsted in TabIe 1 8..
TabIe 17. Azeotrope-like Cogra ositions COMPONENTS T (C) W-eiaht R-a-nae --------------~ FC-1 336mzzJ~~~butane -40 1 - 48:8151.2 - 99 --- -- --- ---- --- -------- ---- ------- --E-FC 1 ~~~mzzJ~~~butane 0 1 ~~ ~ ~0,7 99 _ E FC-1336rnzz/~~~~~~~~~ 40 1 68 8/31.2- 99 ---------------------------------------------------------------------------- --------------------- ------------------------------- -- -------------------------------E-FC 1 336rnzzAsc~butane 80 1 78,7121 3 - 99 lsob~3. .Ã~e ~~.~<1 t.~ ~~
1 E-FC-1336m~F ~
'--- --------- -------- .. ..... --------- ............................. -------- -------- --------- --------' Tab1e 18. Azeotrope-like Compositions ___ ____ ____ ------------i1'~etgt~t ~~~16~.
COMPONENTS Preff Ett~=~:,-'~336Ãt~.~ll~~~~~an~ ~40 i, n - 47.4/5Z6 - 90 - - --- -- --- ------------- --- ------ ------E FC 1 336Ã~~zzIlsok~ufiane 0 ;~6'9143 1 4Ã~ --- ----- - -- -- ---- - --- ------- --- --EHFC-1336mzzl1so~~~~~~ 40 i, n - 65.3/34:7 - 90 --L E-FC-1 336mzzIlsobufiane 80 74,3125 ? go - -- - - - -------- -- - ------- ---- ------------E-FC-1336Ãt~11sobufane 95 10-- 77.7;22:3 - 90 - -------------------------------------------------------------------------------------------- --------------------------------------------------------------The azeotropic c~r azeotrope-like compositions of the present in: enhon canbe prepared by any convenient method including mixing or combining the desired amounts. In one embodÃment of this invention, an azeotropic or azeotrope-like composition can be prepared by weighing the desired c~~~~nemt amounts and thereafter combining them ir~ ~~~
appropriate coÃitaineÃ'.
The azeotropic or azeotrope-like compositions of the present invention can be used in a wide range of applications, including their use as, aerosol ~~~opellants, r~~~~~erants,. solvents, cleaning agents, ~~owa~~
agents (#oam expans:on agents) for thermoplastic and thermoset foams, WO 2008/154612' PCT/US2008/066621 heat transfer media, gaseous dielec¾r:cs; fire oxt,n;uÃshing and suppression agents: power cycle working fluids, polymerÃzation media, paÃ~icLiIate removal fluids, carner flLiÃds, buffing abrasive agenis,and displ~~ement drying agents.
C3rie, en-t~~~'In ent of this invention provides a process for preparing a thermoplastic oi thermoset foam. The process comprises using an azeotropÃc or azeotrope-like composition as a blowing agent, wherein said azeotropic or azeotrope-like composition consists essentially of E.
It was found through ~~~eriments that E-FCr 1336mz~ and methyl formate form azeotrope-like compositions. To determine the relative volatÃlity of this binary pair, the PTx method descri~~~ ~~~~e was useci.
The total absolute pressure in a PTx ceI1 of known volume was measured at constant temperature, for various bic-tar~ compositions. These measurements were then reduced to equilibrium vapor ancJ liquid compositions in the cell using the NRTL equation.
The vapor pressure measured versus the compositions in the PTx cell for E-FC-1336mzz1~~~thy[ formate mixture is Shown in FIG. 1, which WO 2008/154612' PCT/US2008/066621 illustrates gÃ'aphi:;::liy the fbrmat#on of azeotrope-like compositions consisting essenii-illy of E-1, 1,1,4;4,4-hexaf Lioro-2-butene and methyl formate at 20,O rC, as indicated by mÃxt~ires of about 83 mole % to about 99 mole % E-1;1,1t4,4,4-hexafluoro-2-b~~ene and about 17 to about 1 mole % methyl ft~~~ate-Some eÃTiboditTtenks of azeatrope-lrke composÃtÃoÃas are listed in Table 4. Additional embodiments of azeotrope-1ike compositions are listed in Table S.
Table 4. AzeOtro. e-Iike Compos-t3ons CO31~~~~~ENTS .~ ~~~_~... ,~feÃght ~r~, Ran~~......
.................................
ethyl formate -40 ~ ~ ~~6mzzr~~thylõ~orc~~e 0 95-99/1-5 ____ _ __________........................................................
~thyl formate ....... 40 92-99/1 8 -- --- ------- -- -- --------- ------- ----------- ~------------ -------- ----------------~
E-~C 1,~36mzz.W~thyl forrrÃate 80 86-99/1 --~-4---- -------- - - --------------- ------------------------------ ------------------------- ----------------------------------------------------------E-F; 1 33~~iizzr~~~~.y!-farmate 120 73 'i00/1-27 Table 5. Ageotro. e-li~~ ~ompositÃoÃ~~
W~~g~;t"-~ ~~~~~~
~OMP~~ENTS T
--- ---- ----- ------- ------ ~------- ----- --------E FC 1 ~~6m,zzrMethyl forriate -40 98-9911 2 ______ _________ _________ _________ _________ _________ E-FC 'I~~~rnzz/MeLh vi 11"ormate 0 : 97-9911-3 ----- - ---~ fG I3;6~~zzr~r~ei,~~.( formate 40 95 99~<'1:~
___________ _____________ E-FC ~~~6m,zz/1V1eiiyl ;formate 80 ,92-99l'~ 8 ~ ~G '133~a~`~~zzrMet~ÃvI fÃ~Ã Ã~~at~ 1 2 ... 0 8 ... 7 ------ 9 .... 9r'i 1 3 _________ It was found through experiments that E-FC-1336mzz and isopentane form azeotropic or azeotrope-i,ke;--t;~~i-.,na,,:;itions.. To determine the relative voiat:if~ty of this binary paÃt', the PTx melkhod described above was used. The total absolute pressure in a PTx cell of known volume was measured at constant temperature for various binary compositions. These measurements were then reduced to equilibrium vapor and liquid compositions in the cell using the NRTL equation.
The vapor pressure measured versus the compositions in the PTx cell for E-FG-1336mzz1 isopentane mixture is shoWrt in FIG. 3, which ~~
WO 2008/154612' PCT/US2008/066621 illustrates gÃ'aphi:;::liy the fbrrmat#on of an azeotrope aaid azeotrape-like compositions of E-1. 1 , 1,4,4;4-hexaffuoro-2-butene and ~~opentane at 20_0 tsC; as i~~icated by a mixture of about 77.2 rno(e % E-1,1,1,4,4:4-~~~afluoro-2-butiene and 22;8 mole % isopentane having the highest pressurre over tfie range of compositions at this temperature.
~~~~d upon these findings, Ãt has been ca1c>Lilated that E-FC-1336mzz and isopentane form azeotropic compositions ranging from about 75A mole percent to about 95A mole percent E-FC-1336r~~z atid ~~om about 24.9 mole percent to about 4_6 mole percent isopentane (which form azeot~opmc c~orTiposÃtÃons boiling at a temperature of from aboot 40 C
to abou~ ~ OV'C and at a pressure of from about 1.6 psia (11 kRa) to about 218 psia (1503 kPa)). Some embo(lEment~ ~~~zeot~~~~~~ compositions are listed in Table 6.
Table 6 Azeotro -~ co~~ ~~~~itsor~~
Azeotrapic Azeotropic EwFC-'~ ~~6mzz ~~~~entane Temperature Pressure (psaa) (mole %) (mole %) ________ ________ .................................................
....................................
20'0 8 75.0 250 - 10.0 7,7 75.3 24.7 }_______ _________ _________________;______________________ ;..................... ~ _.................... _ .
0.0 ~2.~ ~~ .~ ~~ ~
............................................ ____ ______________, ____________________ ___________________ ..................................
'~~.Ã~ 17.8 76.4 23.6 ----- ------- ; -------- ------- ------- ----- } - -------20.0 25.6 77.2 ~22.8 ---------- --------------------------- -----------------------------------------------------30.0 35.9 78.3 213 --------------------------------------------- --40,0 49.0 73.5 20.5 _________________________________________________n........ 50.0 65.4 81,1 18.9 60.0 85.6________________ 83.0________________ :17:0 ------ ---- ------------ --------: ------------------ ---------------------} ---------- --r0.0 1:10r3 85.2 14,8 80:0 140.0 88,0 12,0 1'75.6 91.3 87 WO
____ _________;
~~~`~
__-___ ___________ _____________~217.9 _______________ _______________~ ~~.~
_________________ ___4. 6 ----------------------------- -------------------------------------------- ----------------------------- ---------------------------~
AdditioÃia11y: azeotrope-like compositions containing E-FC-1336mzz and isopentaÃ~e may also be formed. Such azeotrope-like compositions exist around azeotropi~ ~omposifions. Some embodiments of azeotrope-WO 2008/154612' PCT/US2008/066621 kike eompositi~~~s are listed an Table 7~ Adiditiona1 err;bc;d:ments of azeotrope-iÃk~ ~omposÃtÃ~~~~ are Irsted in TabIe 8.
~aUe 7. Azeotrope(Ãke ~:rrns --- -------- ------ ------------------------COMPONENTS E-FC-" 33# mzz'~sc~erÃtan~e -40 81-94+6-19 0 80-99,'1-20 E-FC-1336mzz/isopentane 40 80-9.9t 1-20 E-FC-1336Ã~zz/is~ 79-99,'1-21 E-FC-1336mzz/isopentane 100-1 77-99/1-23 ~
Table 8. Azeotropew li~~ ~om o4 !':cns Ãg h t % Range COMPONENTS T (jC) - - -- -- - -- ------- ------ --- ----E-FC-'~ 3')6mzz,%isqp~~t-ane -46 81-95/5-19 ------------------ --------------------------------- --------------------- -------------------------------------------------------------E---FC--l a~~mzz,risoper~tane -------------- 0 80-9~~5,20 ------ +--- -- -------E-FC-,1 336mzz%isopentaÃie 40 8 09 15t 2 0 ------------------ -------------------------------- ------ ---------------------- -----------------------------------------------------------------------------------E ~ ~~~ ~ ~~~~=is~p~r taÃ~e 80 79-9' f~;~21 - - - -------- - -- ------- _ E-FC-1 336mzz%isopc:, ;tane ~ ~~ 7-7-95/5-23 It was fc id through experiments that E-FC-1 336mzz aÃid t.rans-1,2-div.hlorcaethylene form azeotropewl~~~ ~ompositions. To determÃne the relative volatility of this binary pair, the PTx method described above was used. The totai absolute pressure in a PTx cell of known voltÃme was measured at constant temperature for various binary cor~posi:<Jns. These measurements were then reduced to equilibrium vapor and !'iquid compositions in the cell using the NRTL ~quation.
The vapor pressure measured versus t~~~ compositions in the PTx cell for E-FC-1336mzz] trans- 1,2-dichioroethylene mixture is shown irt FIG. 4, which illustrates graphically the fbrmation of azeotrope-like cornposÃtions of Ex1,1,1,4,4,4-hexafluoà o-2-butene and trans-1,2-dichforoet~~~ene at 20.O `C, as indicated by mixtures comprised of about 84 mole % to about 99 mole % E-1 336mzz and from about 16 to about 1 mole % ts a.ns-I,2w,d::ichloroethy(ene:
Some embodimeri s of azeotrope-li~e compositioÃ~~ are listed in Table 9. Additponal embcdm~ents of azeotrope-i~~e compositions are listed in Table 10:.
WO 2008/154612' PCT/US2008/066621 Table 9: Azeotro wlik~ Compositions ~OMPONE f~~~ T (,~C) Weight %
~
Ran ________ E-FC 133~s~t~1Tra#~s-1 2 dÃch1~3r~aethyiene -40 ~f2-99L 1 8 E__F~ 1336rn~l~'rans ~ ichlorogt~~rl~~______ 0 94~ ~3911 T0 ErFC 1336mzz/'~~ans-1,2-dÃchl~~~~th~iene- 40 90-9~?i1 '~0 `
________ _________ _________ _______ ______ _~_;FC-1336m~iTrans 1 2 dic}~Ioroee ....................... 80 89 ~3911 '~ 1 ErFC-1336mzz+~~ans-1,2-dÃchloroethvlt r,~ 120 88-9911-12 ...........
T.abl!e 10. Azeotrc}~~ejik~ ~2Mpositi ...............................................................................
.....................~~~~~~~~~~~~~~~ ------------------- ~.. -------------------------------Weaghtaia Range, , ~,~O~~E~.NT~ ~ ~' .....:= ........ ......... ........ ....... ....... .. .. . `
..._~` . :...............
.... ....... ..........
E Ft~ ~ ~~~~zz/T#'arts-- i ,2 d#ch9oCoeth,y-ien-e ~--6 ----E-F;" , 336mzz/Trans1 2-d#chl:oroeth ~= =_ne ---- ======_~========:============_~~ ~~r ~ 7 ===== ======== ========= ======= ======= ======= <=
======= == ===;
E-FC-'~336mzz/Trans-1,2dichi~oroetii~ ,~r~e 40 --- --EuFC-'1336mzz/Trans-1 2-dichl:oroethviene 80 1 8 ----- ------ ----- - ------- -- ------- -E-FC 1 336mzz!Trans-1 2-dichloroethylene 1 20 93 -99<1 7 Ã
------- -------- -------- --------- ------- ---------- - -------- --------------~
~t was found through experiments that E-FC-1336mzz and 'HFC-245fa form: azootrope-Iik~ compositions. To deterryiine the relative volatility of this binary pair, the PTx method described, above was used:
The tota.I absolute pressure in a PTx cell of known volume was measured at constant temperattire for various binary compositions. These measurements were then reduced to eqÃaiIibrium vapor and iiqLiici Compositians i~ the cell using the NRTL ~quation:
The vapor pressure measured versus the compositi~~~~ ~~ the PTx cell for E-FCw1336,-# izzf HFC-245fa rtiixtLire is s;-,own in: FIG.. 5, which illustrates grap:iicaliy the formation of azee~rope-sike compositions of E-1,1,1,4,44-hexafi~oro-2-but~~~ and HDC-245fa at 20.0 C. as indicated by mixtures of about I to 99 mole % E--'j,1,1.4>4,4-hexafluoro-2-~atene atid about 99 to 1 mole % HFC-245fa.
Some embodiments of azeotrope-like compositions are listed in Table 11. Additional embodiments of ~zeotrope-1ike compositions are listed in Table 12.
WO 2008/154612' PCT/US2008/066621 ~~~~~.' ~. ~ ~'C}~fC? ~ ~1'=+:~ i~C?2~?t+t~"~ Ãt3Ãi~a CO~''~~~i~~~ ~ ~ifeÃght % Range E-FC-1 336mzz/HFC-2466~ 1 9911 99 -- ---- ------ --- -------- ---------- - ---------E-FC-'~ ~~~~z7YNFC-24u?fa o -------------- -- --- ---------E-FC-1336mzz/~FC 245fa 40 1r99111-99 _________ _____________________________ .. =___________________ ___;
~-FCr 1336m7-zjHFC-24,5a -- --- ------ ------- -------- --- - --- ---------E FC ~ ~36mzz'HFC-245fa I20 t ~~+ 1 99 _____. _______ _________________________ _________ Table 12. Azeotrope-I~~~ Compositions . , WeÃcÃht % Range ~~~iP~~ENTS T
c) E.-FCr1336m7-zlHFC145fa -40 10w90110-9Ã3 -------, -- -------- ---- -- --------- -E--FG- j1-)36mzz,FHFC-245fa ( o 1 0p90110.-90 _______ _________ ________________ ___;__ ________ __________________ E-FC-1336r~z~'H~'C-2~~6 4~ 1 0w90110-90 E-FC-1:~36Ã~?~`~~FC-24, 80 1~]-901'[Ã~~-~Ã~
............................................... _; ________________ _____ ________ __________________ E-FC-1336mz~HFC-245fa _______ 1,2 10-90f 10-90 ~________________ ___<_____ _________ ___________________.
It was found through expenment~ that E-FC-1336mzz and n-butanp-forÃ~~ azeotropBc or azeotrope-like cor~~~~~~ions. To determine the relative volatiiity of this binary pair, the PTxmetliod described above was used.
The total absolute pr~~sureÃn a PTx cell of known volume was r~~~stir~~
at constant temperature for varioÃ.xs binary compc~~ttions. These measurements were then reduced to equilibrium vapor and liquid ~ompositioris in the cell using the NRTL eqciatÃor).
The vapor Pr~~sure measured versus the compositions in the PTx:
cell for E-FC-1336,mzz~n-butane mixture is ~~owz-a in FIG, 6, which illustrates gr~~~~ÃicalAy the formation of anazeotropic composition of E-1<1,,1.4,4,4-hexafiuoro-2-~~~ef)e atid cycl'opentane at 20.0 wC, as indicated by a mixtu re of about 38. ~ mole % E- 1, 1;1 A4;4-hexafiuoro-2-butene a nd 61.9 moIe% n-butane having the highest pressure over the range of compositions ~t. this temperature.
Based upon these findirigs, it has been calculated that E-FC-1336mzz and n-butane form azeotrolpÃc comrpositions ranging from about 29.5 mole percent to about 47 2 mole percent ~~~~- 1;336mzz and from aboLit 70.5 mole percent to about 52.8 mole percent n-butane (whÃ~~ form azeotropic compositions boÃli~ng at a ternperature of from about -40 "C to WO 2008/154612' PCT/US2008/066621 about 100 "C and at a. pressure of from about 3.0 psia (21 kPa) to about 277 ps#~ (1910 kPa)). Some embodiments c~~ azeotropic compositions are listed in Table 13, Table 13. AgeoÃropic GgMposifions Azeotropic Azeotropic E-FC-1336ÃTazz n-butane Temperature ('$C) Pressur~ (psia) (mole %) (mole %) --40 10 29.5% 70.5%
-30 5A 313% 68,7%
-20 8.2 33.0% 67.0%
-10 12,7 34.5% 65,5%
0 19:0 35_8% 64:2%
27.4 37.0% 63.0%
38.3 38.1% 61.9~'~~
523 39.2% 60,6%
697 40.2% 59.8%
91,1 41,2% 58.8~~~
116.$ 4 2.'2 % 57.8~'r~
1'47.6 433`,-% 56:7%
183.9 44,4`=;~ 55.6%
226.5 457% 543~'~`~
100 276.6 472% 52.8%
~
Additionally, azeotrope-like compositÃons containing E-FG_,1336Ãrzz and n-butane may also be formed. Such azeotrope-like compositions exis~ arouiid azeotropic compositions. Some embodiments of azeotrope-like compositions are listed in Table 14. Additional embodiments of 10 azeotrope-like compositions are listed in Table 15, Tabfe 14. Az~~~e* IÃke Cs?msitions --------------------------------------------------------------------------- ------- -----------------------------------------------------------------------------COMPONENTS T ( C) ~~~ % R~~~ ~e E-FC-1 336mzz/n-butane -40 38-64/36_62 E-FC-1336r-qz /n-~~AaÃ~~ 0 44-72/28-56 E-FC- I 336r~zz/n" butane 40 1-13~87-99 and 43-80/20-57 - ------ ----- ----- ------- - -- ------ ------- -- ------- an-d-----~87 -~9i1 E-FG-!.-36rnzz/r~~butane 80 1-91/9-99 and 94-99/1-6 -- --- --- ---- --- --- ------- ----- --- -------E FCr i 336mzz1n-butane 1 00 1-99/1-99 Tabfe 15. ,:~eotro. eNlike CorrDosit~ons , We:ghf A, Ratige COMPONENTS ;T ('G) E FC-1336mxzln-butane -40 50. 64136-50 ......... .. ....................................................
.........
WO 2008/154612' PCT/US2008/066621 E-FC--1336mzz1n-butane0,,,,,,,, 50-72f'28-50 E-FC-1 336mzz/Ã~-butane 40 10;13/87-90 and 43-80.+20-57 E-FC-1 336m~71n-butane 80 10-90/10-90 ___ E~-~'C-`à a36r~it~-Ã~utar~e 1 0~] 1 Ã~~.-90110-90 It was found through exÃaerimenks that E-FCw 1~~6mzz. and isobutane form azeotropic or azeotrope-i'ike compositions. To determine the reÃatiAre uoÃatÃ(ity of this Ã~~~~ry paÃr, the PTx maAhod described above was Lased. The tofiaà absolute pressure iÃ) a PTx cell of known vo1tÃme was ~~~~sureÃ.~ at constant ~emper"+i;~-efor various binary corn!)osiiEons. These measurements were then reduced to ~quilsbriurn vapor and liquid compositions in the cell using ffie NRTr L eqLmtion, The vapor pressur~ measured versi.,s tt~~ compositions ifi the PTx cell for EaF~~~ 336, r~lizzlisobutane mixture is showri in FlG. 7, which iÃIusfirates grap'sIicaÃ'y the formation of an ~~eotropÃc composition of E-'à <1,.1.4.4,4-hexafluorow2-bu#~~~~ and cy;;;opentane at 20.0 "C, as Ãndicated by a mixture of about 24.9 mole % E-1>1;1 AAA-hexafluorci-2-butene artd 75.1 mole ~~~.~ isobutane having the highest pressure over the range of compositions at this temperature.
Based upon these findingss it has been calculated that ~~~C-'Ã 336mzz and isobutane form azeotropic compositions ranging from about 19.4 mole percent to abotrt 32.4 mole per-ent E-F:, 1 336mzz and from aboL,t 80.6 mole percent to about 67.6 mole percent isobutane (which form azeotropic compositions boiling at a temperature of from about -40 "C to about 80 C and at a pressure of from about 4.5 psÃa {31 kPa) to about 218 psia (1503 kPa)). Some embodiments of azeotropic compositions are listed -n Table 16.
Table 16. Azeotropic Compositions Azeotropic Azeotropic E-FC'-1 336mzz isobutane Temperature ( C) Pr~~sure (mole %) (mole %) (psia) -40 4.5 'k 9:4% 80.6%
-30 7:3 20:3% 797%
-20 11.5 21:2% 78.8~'~~~
-10 17.2 22A% 77.9%
0 25.0 23.0% 77:0%
10 35:2 24.0% 76.0%
WO 2008/154612' PCT/US2008/066621 20 48.4 249% 75.:1 %
30 64.9 25.9% 74: ~ ~~~
40 8.~.~,? 27.0% 73,0%
50 1t~: A 28A% 71:9%
60 ' 4 0;0 29,3% 70 7%
70 175,7 30_7%69 010`
80 218.2 32;4~~"~ 67 6%
AdditionaIly, azeotrope-like ~ompositions containing E-FC-1336.rr~~~~
and isobutane may also be formed. ~~~~~ azeotrope-like ~ompositions exist around azeotropic compositions. Sc~~~ ~~boc#i~~~nts of azeotrope-l#ke compositions are fssted in TabIe 17 Additionaà embod3merits of azeotrope-like ~omposÃtions are 1Ãsted in TabIe 1 8..
TabIe 17. Azeotrope-like Cogra ositions COMPONENTS T (C) W-eiaht R-a-nae --------------~ FC-1 336mzzJ~~~butane -40 1 - 48:8151.2 - 99 --- -- --- ---- --- -------- ---- ------- --E-FC 1 ~~~mzzJ~~~butane 0 1 ~~ ~ ~0,7 99 _ E FC-1336rnzz/~~~~~~~~~ 40 1 68 8/31.2- 99 ---------------------------------------------------------------------------- --------------------- ------------------------------- -- -------------------------------E-FC 1 336rnzzAsc~butane 80 1 78,7121 3 - 99 lsob~3. .Ã~e ~~.~<1 t.~ ~~
1 E-FC-1336m~F ~
'--- --------- -------- .. ..... --------- ............................. -------- -------- --------- --------' Tab1e 18. Azeotrope-like Compositions ___ ____ ____ ------------i1'~etgt~t ~~~16~.
COMPONENTS Preff Ett~=~:,-'~336Ãt~.~ll~~~~~an~ ~40 i, n - 47.4/5Z6 - 90 - - --- -- --- ------------- --- ------ ------E FC 1 336Ã~~zzIlsok~ufiane 0 ;~6'9143 1 4Ã~ --- ----- - -- -- ---- - --- ------- --- --EHFC-1336mzzl1so~~~~~~ 40 i, n - 65.3/34:7 - 90 --L E-FC-1 336mzzIlsobufiane 80 74,3125 ? go - -- - - - -------- -- - ------- ---- ------------E-FC-1336Ãt~11sobufane 95 10-- 77.7;22:3 - 90 - -------------------------------------------------------------------------------------------- --------------------------------------------------------------The azeotropic c~r azeotrope-like compositions of the present in: enhon canbe prepared by any convenient method including mixing or combining the desired amounts. In one embodÃment of this invention, an azeotropic or azeotrope-like composition can be prepared by weighing the desired c~~~~nemt amounts and thereafter combining them ir~ ~~~
appropriate coÃitaineÃ'.
The azeotropic or azeotrope-like compositions of the present invention can be used in a wide range of applications, including their use as, aerosol ~~~opellants, r~~~~~erants,. solvents, cleaning agents, ~~owa~~
agents (#oam expans:on agents) for thermoplastic and thermoset foams, WO 2008/154612' PCT/US2008/066621 heat transfer media, gaseous dielec¾r:cs; fire oxt,n;uÃshing and suppression agents: power cycle working fluids, polymerÃzation media, paÃ~icLiIate removal fluids, carner flLiÃds, buffing abrasive agenis,and displ~~ement drying agents.
C3rie, en-t~~~'In ent of this invention provides a process for preparing a thermoplastic oi thermoset foam. The process comprises using an azeotropÃc or azeotrope-like composition as a blowing agent, wherein said azeotropic or azeotrope-like composition consists essentially of E.
11>1AAA-hex~fiuoro-2-butene and acomponeÃit selected from the group consisting of rTiethyl formate,. n-pentar1e, 2-methylbutane, , firans-1,2-dich3aroethylene, 1,1,11;3,3-pen#.aflÃ,Ãoropropane, n-butane and isobutane.
Another embodiment of this invention provides a process for ~~~~dLFcing refrigeration. The process comprises condensing an azeotropic or azeotrope-like composition and thereafter evaporating said azeotropic or azeotrope..iike composition in the vicinity of the body to be cooled, wherein said azeotropic or azeotrope-like composition consists essentially of E-1,1, 1:4,44-hexafluoro-2-butene and a componen:t selected from ttie group consisting of methyl formate, r}-pergtar}e, 2-methyIbutane;, trans-1,2-dichlaroethylene; 1, 1T 1,3,3-pent~~~~orapropane, n-butane and isobutane.
Another en-ibodin-ient of this Ãnv~nttor# provides, a process using an azeotropic or azeotrope-like cornpos;fion as a solvent, wherein said azeotropic or azeotrope-like. cornpos;t~or? consists essentially of E-1,1, 1,4,4,~~~ex~fluoroY2-bÃ.Ãtene and a component ~~~ected. from the groÃ.ip consisting of methyl formate, ii-pee~~ane, 2-methyibutane, , trans-1,2-dsch1oroethylene, 1,1,1,3,3-pentafluoÃ'opropane, nYbutar~~ and isobutane.
Anr-it~~~~ embodiiment of this invention provides a process for producing an aerosol product. The process comprises using an azeotropic or azeotrope-like composition as a propellant, wherein said azeotropic or azeotropew iike composition consists essentially of EN1, 1, 1,4.4,4..
hexafluoro-2-butene and a component selected from the group consisting of methyl formate, nr~entane, 2-methylbutane, trans-1,2-diGhioroet~~~ene; 1,1,1,3,3-pentafluoÃ'opropane; nYbutar~~ and isobutane-
Another embodiment of this invention provides a process for ~~~~dLFcing refrigeration. The process comprises condensing an azeotropic or azeotrope-like composition and thereafter evaporating said azeotropic or azeotrope..iike composition in the vicinity of the body to be cooled, wherein said azeotropic or azeotrope-like composition consists essentially of E-1,1, 1:4,44-hexafluoro-2-butene and a componen:t selected from ttie group consisting of methyl formate, r}-pergtar}e, 2-methyIbutane;, trans-1,2-dichlaroethylene; 1, 1T 1,3,3-pent~~~~orapropane, n-butane and isobutane.
Another en-ibodin-ient of this Ãnv~nttor# provides, a process using an azeotropic or azeotrope-like cornpos;fion as a solvent, wherein said azeotropic or azeotrope-like. cornpos;t~or? consists essentially of E-1,1, 1,4,4,~~~ex~fluoroY2-bÃ.Ãtene and a component ~~~ected. from the groÃ.ip consisting of methyl formate, ii-pee~~ane, 2-methyibutane, , trans-1,2-dsch1oroethylene, 1,1,1,3,3-pentafluoÃ'opropane, nYbutar~~ and isobutane.
Anr-it~~~~ embodiiment of this invention provides a process for producing an aerosol product. The process comprises using an azeotropic or azeotrope-like composition as a propellant, wherein said azeotropic or azeotropew iike composition consists essentially of EN1, 1, 1,4.4,4..
hexafluoro-2-butene and a component selected from the group consisting of methyl formate, nr~entane, 2-methylbutane, trans-1,2-diGhioroet~~~ene; 1,1,1,3,3-pentafluoÃ'opropane; nYbutar~~ and isobutane-
12' PCT/US2008/066621 Another ei~~~~~i:ment of this ir,~~nttorà provides a process using an azeotropic or a~.~ofrope-li~ce coÃ~posQ on as a heat transfer media, wherein said azeotropic or azeotrope-like composition consists essentially ofE-1,1,1,4t4,4-t~exafluoro-:~-butene and a component selected from the group consistirig of methyl formate, n-pentane, 2-methyfbtitane, 1, traÃis_ 1,2-dich#oroethvlene, 1.1, 1, 3,3--pent~fluoropropane, n-butane and isobutane.
Another embodiment of this invention provides a process for extingtiishÃÃig or suppressing a fire. The process comprises usirig an azeotropic or azeotrope-like composition as a fire extinguishÃÃjig or suppression agent, wherein said azeotropic or azeotr~pe--like composition consists esseÃitialfy of E-1,1,1;4r4:4-hexafluoro-2-btitene and a CoÃ~~onent seIected from the grotip conssstiÃ~~ of methy# ~rmate< n-pentane, 2w Ã~~~hylbutaa~e., tÃans-1,2-dich iaÃoethyIene; 1.1,1,3>3-pen~afluoÃopropane, n-butane aÃid isobutane, Another embodiment of fhis invention provides a process usirig an azeotropic or azeofropeml{ke composition as dBeÃectrics, wherein said ~~eotropic or azeotrope..like composition consists essentially of E-1<1õ1.4,4,4-hexafiuoro-2-butene aÃid a component selected from the group coÃ~~~~~ing: of methyl formate, n-perÃtane; 2-methyIbÃatarie: , tÃans-1,2-dich&ornethylenea 1,1,1,3:3-pent~~uoÃoprc~~ane1 n-butane and isobutane.
Another embodiment of this invention provides a process for extingtiishÃÃig or suppressing a fire. The process comprises usirig an azeotropic or azeotrope-like composition as a fire extinguishÃÃjig or suppression agent, wherein said azeotropic or azeotr~pe--like composition consists esseÃitialfy of E-1,1,1;4r4:4-hexafluoro-2-btitene and a CoÃ~~onent seIected from the grotip conssstiÃ~~ of methy# ~rmate< n-pentane, 2w Ã~~~hylbutaa~e., tÃans-1,2-dich iaÃoethyIene; 1.1,1,3>3-pen~afluoÃopropane, n-butane aÃid isobutane, Another embodiment of fhis invention provides a process usirig an azeotropic or azeofropeml{ke composition as dBeÃectrics, wherein said ~~eotropic or azeotrope..like composition consists essentially of E-1<1õ1.4,4,4-hexafiuoro-2-butene aÃid a component selected from the group coÃ~~~~~ing: of methyl formate, n-perÃtane; 2-methyIbÃatarie: , tÃans-1,2-dich&ornethylenea 1,1,1,3:3-pent~~uoÃoprc~~ane1 n-butane and isobutane.
Claims (18)
1. A composition consisting essentially of:
(a) E-1.1,1,4,4,4-hexafluoro-2-butene; and (b) methyl formate; wherein the methyl formate is present in an effective amount to form an azeotrope-like combination with the E-1,1,1,4,4,4-hexafluoro-2-tautene.
(a) E-1.1,1,4,4,4-hexafluoro-2-butene; and (b) methyl formate; wherein the methyl formate is present in an effective amount to form an azeotrope-like combination with the E-1,1,1,4,4,4-hexafluoro-2-tautene.
2. A composition consisting essentially of:
(a) E-1,1,1,4,4,4- hexafluoro-2-butene; and (b) n-pentane; wherein the n-pentane is present in an effective amount to form an azeotropic combination with the E-1,1,1,4,4,4-hexafluoro-2-butene.
(a) E-1,1,1,4,4,4- hexafluoro-2-butene; and (b) n-pentane; wherein the n-pentane is present in an effective amount to form an azeotropic combination with the E-1,1,1,4,4,4-hexafluoro-2-butene.
3. A composition consisting essentially of:
(a) E-1,1,1,4,4,4-hexafluoro-2-butene; and (b) n-pentane; wherein the n-pentane is present in an effective amount to form an azeotrope-like combination with the E-1,1,1,4,4,4-hexafluoro-2-butene.
(a) E-1,1,1,4,4,4-hexafluoro-2-butene; and (b) n-pentane; wherein the n-pentane is present in an effective amount to form an azeotrope-like combination with the E-1,1,1,4,4,4-hexafluoro-2-butene.
4. A composition consisting essentially of:
(a) E-1,1,1,4,4,4-hexafluoro-2-butene; and (b) 2-methylbutane; wherein the 2-methylbutane is present in an effective amount to form an azeotropic combination with the E-1,1,1,4,4,4-hexafluoro-2-butene.
(a) E-1,1,1,4,4,4-hexafluoro-2-butene; and (b) 2-methylbutane; wherein the 2-methylbutane is present in an effective amount to form an azeotropic combination with the E-1,1,1,4,4,4-hexafluoro-2-butene.
5. A composition consisting essentially of:
(a) E-1,1,1,4,4,4-hexafluoro-2-butene; and (b) 2-methylbutane: wherein the 2-methylbutane is present in an effective amount to form an azeotrope-like combination with the E-1,1,1,4,4,4-hexafluoro-2-butene.
(a) E-1,1,1,4,4,4-hexafluoro-2-butene; and (b) 2-methylbutane: wherein the 2-methylbutane is present in an effective amount to form an azeotrope-like combination with the E-1,1,1,4,4,4-hexafluoro-2-butene.
6. A composition consisting essentially of:
(a) E-1,1,1,4,4,4-hexafluoro-2-butene; and (b) trans-1,2-dichloroethylene; wherein the trans-1,2-dichloroethylene is present in an effective amount to form an azeotrope-like combination with the E-1,1,1,4,4,4-hexafluoro-2-butene,
(a) E-1,1,1,4,4,4-hexafluoro-2-butene; and (b) trans-1,2-dichloroethylene; wherein the trans-1,2-dichloroethylene is present in an effective amount to form an azeotrope-like combination with the E-1,1,1,4,4,4-hexafluoro-2-butene,
7. A composition consisting essentially of:
(a) E-1,1,1,4,4,4-hexafluoro-2-butene; and (b) 1,1,1,3,3-pentafluoropropane; wherein the 1,1,1,3,3-pentafluoropropane is present in an effective amount to form an azeotrope-like combination with the E-1,1,1,4,4,4-hexafluoro-2-butene.
(a) E-1,1,1,4,4,4-hexafluoro-2-butene; and (b) 1,1,1,3,3-pentafluoropropane; wherein the 1,1,1,3,3-pentafluoropropane is present in an effective amount to form an azeotrope-like combination with the E-1,1,1,4,4,4-hexafluoro-2-butene.
8. A composition consisting essentially of:
(a) E-1,1,1,4,4,4-hexafluoro-2-butene; and (b) n-butane; wherein the n-butane is present in an effective amount to form an azeotropic combination with the E-1,1,1,4,4,4-hexafluoro-2-butene.
(a) E-1,1,1,4,4,4-hexafluoro-2-butene; and (b) n-butane; wherein the n-butane is present in an effective amount to form an azeotropic combination with the E-1,1,1,4,4,4-hexafluoro-2-butene.
9. A composition consisting essentially of:
(a) E-1,1,1,4,4,4-hexafluoro-2-butene; and (b) n-butane; wherein the n-butane is present in an effective amount to form an azeotrope-like combination with the E-1,1,1,4,4,4-hexafluoro-2-butene.
(a) E-1,1,1,4,4,4-hexafluoro-2-butene; and (b) n-butane; wherein the n-butane is present in an effective amount to form an azeotrope-like combination with the E-1,1,1,4,4,4-hexafluoro-2-butene.
10. A composition consisting essentially of:
(a) E-1,1,1,4,4,4-hexafluoro-2-butene; and (b) isobutane; wherein the isobutane is present in an effective amount to form an azeotropic combination with the E-1,1,1,4,4,4-hexafluoro-2-butene.
(a) E-1,1,1,4,4,4-hexafluoro-2-butene; and (b) isobutane; wherein the isobutane is present in an effective amount to form an azeotropic combination with the E-1,1,1,4,4,4-hexafluoro-2-butene.
11.A composition consisting essentially of:
(a) E-1,1,1,4,4,4-hexafluoro-2-butene; and (b) isobutane; wherein the isobutane is present in an effective amount to form an azeotrope-like combination with the E-1,1,1,4,4,4-hexafluoro-2-butene.
(a) E-1,1,1,4,4,4-hexafluoro-2-butene; and (b) isobutane; wherein the isobutane is present in an effective amount to form an azeotrope-like combination with the E-1,1,1,4,4,4-hexafluoro-2-butene.
12. A process for preparing a thermoplastic or thermoset foam comprising using an azeotropic or azeotrope-like composition as a blowing agent, wherein said azeotropic or azeotrope-like composition consists essentially of E-1,1,1,4,4,4-hexafluoro-2-butene and a component selected from the group consisting of methyl formate, n-pentane, 2-methylbutane, trans-1,2-dichloroethylene, 1,1,1,3,3-pentafluoropropane, n-butane and isobutane.
13. A process for producing refrigeration comprising condensing an azeotropic or azeotrope-like composition and thereafter evaporating said azeotropic or azeotrope-like composition in the vicinity of the body to be cooled, wherein said azeotropic or azeotrope-like composition consists essentially of E-1,1,1,4,4,4-hexafluoro-2-butene and a component selected from the group consisting of methyl formate, n-pentane, 2-methylbutane, trans-1,2-dichloroethylene, 1,1,1,3,3-pentafluoropropane, n-butane and isobutane.
14. A process comprising using an azeotropic or azeotrope-like composition as a solvent, wherein said azeotropic or azeotrope-like composition consists essentially of E-1,1,1,4,4,4-hexafluoro-2-butene and a component selected from the group consisting of methyl formate, n-pentane, 2-methylbutane, trans-1,2-dichloroethylene, 1,1,1,3,3-pentafluoropropane, n-butane and isobutane.
15.A process for producing an aerosol product comprising using an azeotropic or azeotrope-like composition as a propellant, wherein said azeotropic or azeotrope-like composition consists essentially of E-1,1,1,4,4,4-hexafluoro-2-butene and a component selected from the group consisting of methyl formate, n-pentane, 2-methylbutane, trans-1,2-dichloroethylene, 1,1,1,3,3-pentafluoropropane, n-butane and isobutane.
16.A process comprising using an azeotropic or azeotrope-like composition as a heat transfer media, wherein said azeotropic or azeotrope-like composition consists essentially of E-1,1,1,4,4,4-hexafluoro-2-butene and a component selected from the group consisting of methyl formate, n-pentane, 2-methylbutane, trans-1,2-dichloroethylene, 1,1,1,3,3-pentafluoropropane, n-butane and isobutane.
17.A process for extinguishing or suppressing a fire comprising using an azeotropic or azeotrope-like composition as a fire extinguishing or suppression agent, wherein said azeotropic or azeotrope-like composition consists essentially of E-1,1,1,4,4,4-hexafluoro-2-butene and a component selected from the group consisting of methyl formate, n-pentane, 2-methylbutane, trans-1,2-dichloroethylene, 1,1,1,3,3-pentafluoropropane, n-butane and isobutane.
18. A process comprising using an azeotropic or azeotrope-like composition as dielectrics, wherein said azeotropic or azeotrope-like composition consists essentially of E-1,1,1,4,4,4-hexafluoro-2-butene and a component selected from the group consisting of methyl formate, n-pentane, 2-methylbutane, trans-1,2-dichloroethylene, 1,1,1,3,3-pentafluoropropane, n-butane and isobutane.
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