CA2684290C

CA2684290C - Azeotropic and azeotrope-like compositions of e-1,1,1,4,4,4-hexafluoro-2-butene

Info

Publication number: CA2684290C
Application number: CA2684290A
Authority: CA
Inventors: Mark L. Robin
Original assignee: EI Du Pont de Nemours and Co
Current assignee: Chemours Co FC LLC
Priority date: 2007-06-12
Filing date: 2008-06-12
Publication date: 2016-09-06
Anticipated expiration: 2028-06-12
Also published as: KR20100037591A; CN106433563B; CN106433563A; CN106474649A; AU2008261695A1; MY149324A; BRPI0809736A2; MX2009013465A; BRPI0809736B1; CN110643328A; CN106634849A; US20100163776A1; CA2684290A1; US20110220832A1; CN110643328B; BR122018074407B1; EP2152833A1; CN106474649B; KR101434710B1; CN106634849B

Abstract

Azeotropic or azeotrope-like compositions are disclosed. The azeotropic or azeotrope-like compositions are mixtures of E-1,1,1,4,4,4-hexafluoro-2-butene with methyl formate, n-pentane, 2-methylbutane,, trans-1,2-dichloroethylene, 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 azeotropic or azeotrope-like compositions as blowing agents. Also disclosed is a process of producing refrigeration by using such azeotropic or azeotrope-like compositions. Also disclosed is a process of using such azeotropic or azeotrope-like compositions as solvents. Also disclosed is a process of producing an aerosol product by using such azeotropic or azeotrope-like compositions. Also disclosed is a process of using such azeotropic or azeotrope-like compositions as heat transfer media. Also disclosed is a process of extinguishing or suppressing a fire by using such azeotropic or azeotrope-like compositions. Also disclosed is a process of using such azeotropic or azeotrope-like compositions as dielectrics.

Description

2 TITLE OF INVENTION
AZEOTROPIC AND AZEOTROPE-LIKE COMPOSITIONS OF
E-1,1,1,4,4,4-HEXAFLUORO-2-BUTENE
This application claims priority of U.S. Patent Applications 60/934199 and 60/934209 filed June 12, 2007, U.S. Patent Application 60/936082 filed June 18, 2007, U.S Patent Application 60/937590 filed June 28, 2007, U.S. Patent Applications 60/970387 and 60/970384 filed September 6: 2007 and U.S. Patent Application 60/993241 filed September 11, 2007.
BACKGROUND OF THE INVENTION
Field of the Disclosure The present disclosure relates to azeotropic or azeotrope-like compositions of E-1,1,1,4,4,4-nexafluoro-2-butene, Description of Related Art Many industries have been working for the past few decades to find replacements for the ozone depleting chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs). The CFCs and HCFCs have been employed in a wide range of applications, including their use as aerosol propellants, refrigerants, cleaning agents, expansion agents for thermoplastic and thermoset foams, heat transfer media, gaseous dielectrics, fire extinguishing and suppression agents, power cycle working fluids, polymerization media, particulate removal fluids, carrier fluids, buffing abrasive agents, and displacement drying agents. In the search for replacements for these versatile compounds, many industries have turned to the use of hydrofluorocarbons (HFCs).
The HFCs do not contribute to the destruction of stratospheric ozone, but are of concern due to their contribution to the "greenhouse effect": i.e.: they contribute to global warming. As a result of their contribution to global warming, the HFCs have come under scrutiny, and WO 2008/154612*

their widespread use may also be limited in the future. Thus, there is a need for compositions that do not contribute to the destruction of stratosphenc ozone and also have low global warming potentials (GWPs).
Certain hydrofluoroolefins, such as 1,1,1,4,4,4-hexafluoro-2-butene (CF3CH=CHCF3, FC-1336mzz), are believed to meet both goals SUMMARY OF THE INVENTION
This application includes seven different types of azeotropic or azeotrope-like mixtures.
This disclosure provides a composition consisting essentially of (a) E-FC-1336nIzz and (b) methyl formate; wherein the methyl formate is present in an effective amount to form an azeotrope-like mixture with E-FC-1336nizz.
This disclosure also provides a composition consisting essentially of (a) E-FC-1336rnzz 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-1336nizz, This disclosure also provides a composition consisting essentially of (a) E-FC-1336mzz and (b) 2-methylbutane (isopentane); wherein the isopentane is present in an effective amount to form an azeotropic or azeotrope-like mixture with E-FC-1336m7.2..
This disclosure also provides a composition consisting essentially of (a) E-FC-1336rnzz and (b) trans-1 ,2-dichloroethylene; wherein the trans-1,2-dichloroethylene is present in an effective amount to form an azeotrope-like mixture with E-FC-1336mzz.
This disclosure also provides a composition consisting essentially of (a) E-FC-1336rnzz and (b) 1,1,1,3,3-pentafluoropropane (CF3CH2CF2H, HFC-245fa); wherein the HFC-245fa is present in an effective amount to form an azeotrope-like mixture with E-FC-1336mzz.
The disclosure also provides a composition consisting essentially of (a) E-FC-1336mzz and (b) n-butane; wherein the n-butane is present in an effective amount to form an azeotropic or azeotrope-like mixture with E-FC-1336mzz.

WO 2008/154612*

The disclosure also provides a composition consisting essentially of (a) E-FC-1336mzz and (b) 2-methyl-propane (isobutane); wherein the 2-methylpropane is present in an effective amount to form an azeotropic or azeotrope-like mixture with E-FC-1336mzz.
BRIEF SUMMARY OF THE DRAWINGS
FIG. 1 - FIG. 1 is a graphical representation of azeotrope-like compositions consisting essentially of E-FC-1336nizz and methyl formate at a temperature of about 20.0 C.
FIG. 2 - FIG. 2 is a graphical representation of an azeotrope and azeotrope-like compositions consisting essentially of E-FC-1336mzz and n-pentane at a temperature of about 20.0 C
FIG, 3 - FIG. 3 is a graphical representation of an azeotrope and azeotrope-like compositions consisting essentially of E-FC-1336rnzz and isopentane at a temperature of about 20.0 C.
FIG. 4 - FIG. 4 is a graphical representation of azeotrope-like compositions consisting essentially of E-FC-1336mzz and trans-1,2-dichloroethylene at a temperature of about 20.0 "C.
FIG. 5 - FIG. 5 is a graphical representation of azeotrope-like compositions consisting essentially of E-FC-1336mzz and HFC-245fa at a temperature of about 20.0 C.
FIG. 6 - FIG. 6 is a graphical representation of an azeotrope and azeotrope-like compositions consisting essentially of E-FC-1336rnzz and n-butane at a temperature of about 20.0 C.
FiG. 7 - FIG. 7 is a graphical representation of an azeotrope and azeotrope-like compositions consisting essentially of E-FC-1336mzz and isobutane at a temperature of about 20.0 C.
DETAILED DESCRIPTION OF THE INVENTION
In many applications, the use of a pure single component or an azeotropic or azeotrope-like mixture is desirable. For example, when a blowing agent composition (also known as foam expansion agents or foam expansion compositions) is not a pure single component or an azeotropic or azeotrope-like mixture, the composition may change during its

3 WO 2008/154612*

application 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 during maintenance procedures on refrigeration equipment. If the refrigerant is not a pure single component or an azeotropic or azeotrope-like composition, the refrigerant composition may change when leaked or discharged to the atmosphere from the refrigeration equipment.
The change in refrigerant composition may cause the refrigerant to become flammable or to have poor refrigeration performance. Accordingly, there is a need for using azeotropic or azeotrope-like mixtures in these and other applications, for example azeotropic or azeotrope-like mixtures containing E-1,1,1,4,4,4-hexafluoro-2-butene (E-CF3CH=CHCF3, E-FC-1336mzz), Before addressing details of embodiments described below, some terms are defined or clarified, FC-1336mzz may exist as one of two configurational isomers, E or Z. FC-1336mzz as used herein refers to the isomers, Z-FC-1336nizz or E-FC-1336mzz, as well as any combinations or mixtures of such isomers.
As used herein, the terms "comprises," "comprising," Includes,"
"including," "has,' "having" or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Further, unless expressly stated to the contrary, -or" refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following.. A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present), Also, use of "a" or "an" are employed to describe elements and components described herein. This is done merely for convenience and to give a general sense of the scope of the invention. This description

4 Should be read to Include one or at least one and the.singular also includes tile plural unless iris obviOus that it is meant otherwise Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by of Ordinary skill in the art to Which this invention belongs. Attflopoh Methods and niaterials Similar or equivalent to those described herein ca rj be used in the practice or testing of embodiments of the present invention, suitable methods and. materials are desoribed below. All publications, patent appfications. Patents, and other referent** mentioned herein ate incorporated by referenciti4nlheteenti.46,. unless a p4rtioular pssage is dted. In csee of .conftt, the presentitpacift=etion,:inOluding defirfitions will controi, In addition, the material, methods, and examples are illustrative only and not intended to be limiting.
E-FC-1336inzz is a known compound, and its preparation method has been disclosed; for example, in Dawciedi, et. al,, Journal of the Chemical Society, Chemical Communications (1982), (12) ,696-8.
'This application includes azeotropic or azeotrope-iikecompo,ttions compdsing E-FC-133errizz.
In some embodiments of this invention, the composition consists essentially 'of (0) E-FC-1336mzz and (b) methyl formate, wherein the methyl formate is present in an effective arriok.trtto font an azeotrope-like rnixt(ire'with E-FC-/336mz.z.
In some embodiments of this invention, the composition consists essentially of (a) E-FC-1336rrizz and (b) n-pernarie; wherein the n--pentene is present in an effective amount to form an azeotrooic or azeotrope-like mixture vyitts E-FC-1336m72..
In some embodiments of this invention, the composition consists essentially of (a) E-FC-1336mzz and (0) isopentane, wherein the isopentane is present in an effective amount tolorm an azaotropic azeotrope-like mixture with E-FC.-1336n=.
In some embodiments of this invention, the composition consists essentially of (a) E-FC-1338enzz and (b) trane-1.2-dichioroethylene;

5 WO 2008/154612*

wherein the trans-1,2-dichloroethylene is present in an effective amount to form an azeotrope-like mixture with E-FC-1336mzz.
In some embodiments of this invention, the composition consists essentially of (a) E-FC-1336mzz and (b) HFC-245fa; wherein the HFC-245fa is present in an effective amount to form an azeotrope-like mixture with E-FC-1336mzz, In some embodiments of this invention, the composition consists essentially of (a) E-FC-1336nizz and (b) n-butane, wherein the n-butane is present in an effective amount to form an azeotropic or azeotrope-like mixture with E-FC-1336mzz.
In some embodiments of this invention, the composition consists essentially of (a) E-FC-1336mzz and (b) 2-methyl-propane (isobutane):
wherein the 2-methylpropane is present in an effective amount to form an azeotropic or azeotrope-like mixture with E-FC-1336mzz.
By effective amount is meant an amount, which, when combined with E-FC-1336mzz, results in the formation of an azeotropic or azeotrope-like mixture. 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 azeotrope-like compositions continue to exist at the different pressures, but with possible different boiling points. Therefore, effective amount includes the amounts, such as may be expressed in weight or mole percentages, of each component of the compositions of the instant invention which form azeotropic or azeotrope-like compositions at temperatures or pressures other than as described herein.
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 than the boiling temperatures of the individual components, and which will provide a vapor composition essentially identical to the overall liquid composition undergoing boiling, (see, e.g., M. F. Doherty and M.F. Malone, Conceptual Design of Distillation Systems, McGraw-Hill (New York), 2001, 185-186, 351-359).
Accordingly, the essential features of an azeotropic composition are that at a given pressure, the boiling point of the liquid composition is fixed and that the composition of the vapor above the boiling composition is

6 WO 2008/154612*

essentially that of the overall boiling liquid composition (i.e., no fractionation 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 azeotropic composition may change when the azeotropic composition is subjected to boiling at different pressures. Thus, an azeotropic composition may be defined in terms of the unique relationship that 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 by a fixed boiling point at a specified pressure.
For the purpose of this invention, an azeotrope-like composition means a composition that behaves like an azeotropic composition (i.e., has constant boiling characteristics or a tendency not to fractionate upon boiling or evaporation). Hence, during boiling or evaporation, the vapor and liquid compositions, if they change at all, change only to a minimal or negligible extent. This is to be contrasted with non-azeotrope-like compositions in which during boiling or evaporation, the vapor and liquid compositions change to a substantial degree.
Additionally, azeotrope-like compositions exhibit dew point pressure and bubble point pressure with virtually no pressure differential. That is to say that the difference in the dew point pressure and bubble point pressure at a given temperature will be a small value. In this invention, compositions with a difference in dew point pressure and bubble point pressure of less than or equal to 5 percent (based upon the bubble point pressure) is considered to be azeotrope-like.
It is recognized in this field that when the relative volatility of a system approaches 1.0, the system is defined as forming an azeotropic or azeotrope-like composition. Relative volatility is the ratio of the volatility of component 1 to the volatility of component 2. The ratio of the mole fraction of a component in vapor to that in liquid is the volatility of the component.
To determine the relative volatility of any two compounds, a method known as the PTx method can be used. In this procedure, the total absolute pressure in a cell of known volume is measured at a constant

7 temperature for various C.,0111positwe of the two (x)impounds. Use of the PTx Method is described in detail in Phase EquilibriUrn in Process Design", Wiley,interecience Publisher, 1970, written by Harold R, Nuii, on pages 124, to 126' hereby incorpOrated by reference.
These measurements can be oonverted into equilibrium vapor and liquid compositions in the PT x coil by using an activity coefficient equation model, such as the Non-Random, Tveso-Liquid (NR71...) equation, to represent liquid phase nonidealities. Use of an activity coeifficient equation, such as the NEZTL equation is described in detail in The Properties of 1C Gases and Liquids," 4th edition, published by McGraw Hill, written by Reid, Prausnitz and Poling, on pages 241 to..187, and in 'Phase Equilibria in Chemical Erigineeting,s published by Butterworth Publishers, 1986, written by Stanley M. Was, pages 165 to 244.
Without wishing to be bound by any 'theory or explanation,. it is believed that the NRTL. equation, together with the FT$ cell data, can sufficiently predict the relative volatiiities of the B.1,1,1,4;4A-hexefluoro-2-butene-containin9 e.,:ompositions of the present invention and can therefore predict the behavior of these mixtures In =m,41ti-stage separation equipment such as distillation columns.
It was found through experiments that E-FC-1336mzz and n-pentane form azeotropio or azeotropelike compositions.
To determine the relative volatility of this binary pair, the PTx method described above was used. The total abeolute pressure in a PTIc cell of known volume was measured at constant temperature for various binary compositions. These ineasunements were then reduced to equilibrium vapor and liqtAid composons in the cell 1.4sing the NRIL
equation.
The vapor pressure measured versus the coMpositions in the PTx cell for -F01336zin-rientane rra*Ures is shown in FIG, 2, which graphically iltustrates the formatiOn of 8fT azeotropic and azectrope4ike composition consisting eSiiientially of E.-FC-1õ:33nizz and n-pentarte as indicated by a mixture of about 84.6 mole El ,1 ,1 A4,4-nexafluoro-2-WO 2008/154612*

butene and 15.4 mole % n-pentane having the highest pressure over the range of compositions at this temperature. Based upon these findings, it has been calculated that E-FC-1336mzz and n-pentane form azeotropic compositions ranging from about 82.2 mole percent to about 95,3 mole percent E-FC-1336rnzz and from about 17 8 mole percent to about 4.7 mole percent n-pentane (which form azeotropic compositions boiling at a temperature of from about -20 C to about 80 C and at a pressure of from about 4.5 psia (31 kPa) to about 139 psia (951 kPa)). Some embodiments of azeotropic compositions are listed in Table 1.
Table 1 Azeotropic compositions Azeotropic Azeotropic E-FC-1336tnzz n-Pentane Temperature Pressure (psia) (mole %) (mole %) ( C) -20.0 4.55 82.2 17.8 - 10.0 7.36 82.5 17.5 0.0 11.4 83.0 17.0 10.0 17.0 83.7 16.3 20.0 24.6 84.6 154 30.0 34.6 85.7 14.3 40.0 47.5 87.0 13,0 50.0 63,8 88.6 11.4 60.0 83.9 90.5 9.5 70,0 108.6 92.7 7.3 80.0 138.6 95.3 4.7 Additionally, azeotrope-like compositions containing E-FC-1336mzz and n-pentane may also be formed. Such azeotrope-like compositions exist around azeotropic compositions. Some embodiments of azeotrope-like compositions are listed in Table 2, Additional embodiments of azeotrope-like compositions are listed in Table 3.
Table 2 Azeotrope-like compositions W9 2008/.154612 COMPONENTS T (DC) Weight Percentag0 Range E-FC-1336mzzin-Pentane 40 88-99/1-12 E:µ7F.C.7.1336M4in-Pentane. 0 86-99/1-14 E-FC-1336rnzzin -Pentane 20 86-99/144 E-F04:335rnzzin-Pentane 40 $5,9911-15 E-FC-1336mzzin-Pentane 80 84-99/1-16 E-FC-1336men -Pentane 120 83-99/141 Table 3 Azeotrope-like compositions Weight Percentage COMPONENTS 1 (C)i Range E-FC-1336M4h1,PentOn0 -40: 88-95/5,12 E-FC-1336mzzin-Pentane 0 86-95/5-14 E-FC-1336mzzln-Pentane 20 86-95/5-14 E-FC-1336rnzzin-Pentane 40 85-95/5-15 E-FC-1336mzzin-Pentane 80 10-90/10-90 and 84-EFQ-13,36mzz/n-Pentane 120 83,9.5/5.-17 it was found through experiments that E-FC-1336mzz and methyl formate form azeotrope-like compositions. To determine the relative volatility of this binary pair, the PTx method 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 NRTI.. equation.
The vapor pressure measured versus the compositions in the PTx cell for E-FC-1336mzzimethyl formate mixture is shown in FIG. 1 which W9 .2008/.154612= PCT/US2008/066621 illustrates graphically the formation of azeotrope-like compositions consisting essentially of .E-1.1,1.4A4-hexafluoro-2-butene and methyl formate at 20..e.C, as indicated by mixtures of about. 83 mole % to about 99 mole % E-1,11,4,4,4-hexafTuoro-..2-butene.and about 17 to about 1 mole.% .methyl formate.
Some embodiments of azeotrope-like compositions are listed in Table 4. Additional embodiments of azeotrope-like Compositions are listed in Table 5.
Table 4.. Azeotrope-like Compositions COMPONENTS T CC) + .Weight .%
Range E-FC-1336mzz/Methyl formate . -40 i 96-99/1-4 E-FC-1336mzz/Methyl formate .0 i 95-99/1-5.
i E-FC-1336mzz/Methyl formate 40 i 92-99/1-8 +
E-FC-1835m2z/Methyl formate 80 i 85-99/1-14 +
, E-FC-1.336mzz/Methyl formate , 120 i 7.-100/1-27 .
Table 5. Azeotrope-like Compositions ..
'Wei** %Range COMPONENTS 'T (9C:).
; E-FC-1.336mzziMethyl forma-40 ..................... 98-9911-2 -I
E-FC-1336mzz/Methyl formate 0 . 97-99/1-3 , I E-FC-1336mzziMethyl formate 40 .i 95-9911-5 r E-FC-1336mzz/Methyl formate T 80 I 92 -99/1-8 [ E7FQ-1336mzz/Methyl formate I 124) L 87-99043: , it was found through experiments that E-FC-4336mzz and isopentane form azeotropic or .aZeotrope-like compositions. To determine the relative volatility of this binary pair, the PTx method 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 WTI_ equation.
The vapor pressure measured versus the compositions in the PTx cell for EFC-1336mzz/ isopentane mixture is shown in FIG .3i which W9 2008/.154612 PCT/US2008/066621 illustrates graphically the formation of an azeotrope and azeotrope-like compositions of E-1,1,1,4,4,4-hexafluoro-2-butene and isopentane at 20.0 T, as indicated by a mixture of about 77.2 mole %

hexafluoro-2-butene and 22.8 mole % isopentane having the highest pressure over the range of compositions at this temperature.
Based upon these findings, it has been calculated that E-FC-1336mzz and isopentane form azeotropic compositions ranging from about 75.1 mole percent to about 95.4 mole percent E-FC-1336mzz and from about 24.9 mole percent to about 4.6 mole percent isopentane (which form azeotropic compositions boiling at a temperature of from about -40 C
to about 100 f't and at a pressure of from about 1.6 psia (11 kPa) to about 218 psia (1503 kPa)). Some embodiments of azeotropic compositions are listed in Table 6.
Table 6 Azeotropic compositions Azeotropic Azectropic E-FC-1336rnzz lsopentane Temperature Pressure (psia) (mole %) (mole %) ----(C-- 20.0 4.8 75.0 25.0 - 10.0 7.7 75.3 24.7 0.0 12.0 75.7 24.3 10.0 17.8 76.4 23.6 20.0 25.6 772 22.8 30.0 35.9 78.3 21.7 40.0 49.0 79.5 20.5 50.0 65.4 81.1 18.9 60,0 85.6 83.0 17.0 70.0 110,3 85.2 14.8 80.0 140.0 88,0 12,0 90.0 176,6 91.3 8.7 100.0 217.9 96.4 4.6 Additionally, azeotrope-like compositions containing E-FC-1336mzz and isopentane may also be formed. Such azeotrope-like compositions exist around azeotropic compositions. Some embodiments of azeotrope-W9 2008/.154612 like compositions are listed in Table 7. Additional embodiments of azeotrope-like compositions are listed in Table 8, Tabie 7. Azeotrobe-like Compositions COMPONENTST.C. We.ht% Ranse E-FC-1336mzzlisopentahe -40 81-94/6-19 E-FC-1336mzzfiso entane 0 80-99/1-20 E-FC-1336mzzlisopentane 40 80-99/1-2Q
1 E-FC-1336mzzliso*entane 80 79-99/1-21 LE-FG-1336mzzlisopentane 100 77-99/1-23 Table 8. Azeotrope-like Compositions Weight Range COMPONENTS T (cc) ________________________________________ E-FC-1336mzzlisopentane -40 81-95/5-19 E-FC-1336mzzlisopentane _____________ 0 _____ 80-95/5-20 ..õõA
E-FC-1336mthisopentane 40 80-95/5-20 E-FC-1336mzziisopentane ____________ 80 _____ 79-95/5-21 E-FC-1336mzzlisopentane 100 77-95/5,23 It was found through experiments that E-FC-1336mzz and trans-1,2-dithloroethylene form azeotrope-like compositions. To determine the relative volatility of this binary pair, the PT.x method 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, 1.5 The vapor pressure measured versus the compositions in the PTx cell for E-FC-1336mzz1 trans-1 ,2-dichlaroethylene mixture is shown in FIG. 4, which illustrates graphically the formation of azeotrope-like compositions of E-1,1,1,4,4,4-hexafluoro-2-butene and trans-12-dichloroethylene at 20.0 C, as indicated by mixtures comprised of about 84 mole % to about 99 mole % E-1336mzz and from about 16 to about 1 mole % trans-1,2-dichloroethylene.
Some embodiments of azeotrope-like compositions are listed in Table 9, Additional embodiments of azeotrope-like compositions are listed in Table 10, W9 2008/.154612 Table 9. Azeotrope-like Compositions COMPONENTS T CC) Weight %
_____________________________________________________ Range __ E-FC-1836m77/Trans-1 ,2-dichloroethylene -40 92-9911-8 E-FC-1336mzzarans-1,2-dichloroethylene 0 90-99/1-10 E-FC-1336mzzarans-1,2-dichloroethylene 40 90-99/1 -10 E-FC-1336mzzarans-1,2-dichloroethylene 80 89-99/141 E-FC-1336mzz/Trans4,2-clichloroethylene 120 88-99/14 Table 10. Azeotrope-like Compositions Weight % Range, COMPONENTS T (CC) E-FC-1336mzz/Trans-1,2-clichforoethytene ........... 94-99/1-6 E-FC-1336mzz/Trans-1,2-dichloroethylene 0 93-99/1-7 E-FC-1336rnzz/Trans-1,2-dichloroethylene 40 92-99/1-8 E-FC-1336mzz/Trans-12-dichloroethylene 80 92-99/1-8 E-FC-1336mzz/Trans-1,2-clichloroethylene 120 93-99/1-7 It was found through experiments that E-FC-1336mzz and HFC-245fa form azeotrope-like compositions. To determine the relative volatility of this binary pair, the PTx method described above was used.
The total absolute pressure in a PIx 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-FC-1336rnzz/ HFC-2451a mixture is shown in FIG. 5, which illustrates graphically the formation of azeotrope-like compositions of E-1,1,1,4,44-hexafluoro-2-butene and HFC-245fa at 20,0 '5C, as indicated by mixtures of about 1 to 99 mole % E-1,1,1,4,4,4-hexafluor0-2-butene and about 99 to 1 mole % HFC-245fa, Some embodiments of azeotrope-like compositions are listed in Table 11. Additional embodiments of azeotrope-like compositions are listed in Table 12.

W9 2008/.154612 Table 11. Azeotrope-like Compositions COMPONENTS I Weight '1:4 Range E-F04336mzziNFCL245fa -40 1-99/1-99 E-FC-1336mzzlHFC-245fa f 0 1-9911-99 E-FC-1336mzz/HFC-245fa 40 1-9911-99 E-FO-1336mzzil-IFC-245fa 80 1-99/1-99 E-FC-18.36mzz/HFQ-245fa 120 1-99/1-99 Table 12. Azeotrope-like Compositions = Weight % Range COMPONENTS I
E-FC-1336rnzzifirCi245fa 1-40 10-90/10-90 E-FC-1336mzziFIFC-245fa 1 0 10-90/10-90 E-FC-1336mzz/HFC-245fa 40 10-90/10-90 -E:rel-1-3-36inzzil-IFC-245fa 80 10-90/10-90 E-FC7,1836mzzil-iFC-245fa f120: 10-90/10-90 It was found through experiments that E-FC-1336mzz and n-butane form azeotropic or azeotrope-like compositions. To determine the relative volatility of this binary pair, the PTx method 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-FC-1336mzzin-butane mixture is shown in FIG. 6, which illustrates graphically the formation of an azeotropic composition of E-1,1 ,1,4,4,4-hexafluorobutene and cyclopentane at 20.0 C, as indicated by a mixture of about 38.1 mole % E-1,1,1,4,4.4-hexafluoro-2-butene and 61,9 mole % n-butane having the highest pressure over the range of compositions at this temperature.
Based upon these findings, it has been calculated that E-FC-1336mzz and n-butane form azeotropic compositions ranging from about 29.5 mole percent to about 472 mole percent E-FC-1336mzz and from about 70.5 mole percent to about 52.8 mole percent n-butane (which form azeotropic compositions boiling at a temperature of from about -40 C to W9 20080,54612 PCT/US2008/066621 about 100 C and at a pressure of from about 3,0 psia (21 kPa) to about 277 psia (1910 kPa)). Some embodiments of azeotropic composons are listed in Table 13, Table 13. Azeotropic Compositions Azeotropic Azeotropic E-FC-1336mzz n-butane Temperature (C) Pressure (psia) (mole %) (mole ,43) -40 3.0 29,5% 70.5%
-30 5,1 31.3% 681%
-20 8.2 33.0%
-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%
52,3 39,2%
69,7 40,2% 59.8%
91.1 41.2%
116,8 42.2% 57,8%
147.6 43.3% 56.7%
183.9 44,4% 55.6%
226.5 45.7% 54.3%
100 276,6 47.2% 52,8%

Additionally, azeotrope-like compositions containing E-FC=i336mzz and n-butane may also be formed. Such azeotrope-like compositions exist around 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, Table 14. Azeotropezlike Cornpo itions COMPONENTS T re Wei ht% Ranie E-FC-1336mzzin-butane -40 38-64/36-62 E-FC-1336m771n-butane 0 44-72/28-56 E-FC-1336inzzin-butane 40 143/87-99 and and 98-99/1-2 E-FC-1336mzzin-butane 80 1-91/9-99 and 94-[ E -FC- 1336 mzz/n-buta ne 100 1-99/1-99 Table 15. Azeotrope-like Compositions Weight % Range COMPONENTS T ____________________ E-FC-1336mz2ln-butane -40 j 50-64136-50 WO 2008/154612* PCT/US2008/066621 E-FC-1336rnzzin-butane 0 50-72/28-50 E-FC-1336mzz/n-butane 40 10-13/87-90 and 43-80/20-57 E-FC-1336mzz/n-butane 80 10-90/10-90 E-FC-1336mzzin-butane 100 10-90/10-90 It was found through experiments that E-FC-1336mzz and isobutane form azeotropic or azeotrope-like compositions. To determine the relative volatility of this binary pair, the PTx method 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-FC-1336mzziisobutane mixture is shown in FIG, 7, which illustrates graphically the formation of an azeotropic composition of E-1,1,1,4,4,4-hexafluoro-2-butene and cyclopentane at 20.0 C, as indicated by a mixture of about 24,9 mole % E-1,1 ,1,4,4,4-hexafluoro-2-butene and 75,1 mole % isobutane having the highest pressure over the range of compositions at this temperature.
Based upon these findings, it has been calculated that E-FC-1336mzz and isobutane form azeotropic compositions ranging from about 19.4 mole percent to about 32 4 mole percent E-FC-1336mzz and from about 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 psia (31 kPa) to about 218 psia (1503 kPa)). Some embodiments of azeotropic compositions are listed in Table 16.
Table 16, Azeotropic Compositions Azeotropic Azeotropic E-FC-1336mzz isobutane Temperature ( C) Pressure (mole %) (mole %) (psia) -40 4.5 19.4% 80.6%
-30 7.3 20.3% 79.7%
-20 11.5 21.2% 78.8%
-10 17.2 22.1% 77.9%
0 25.0 23.0% 77.0%
10 35,2 24.0% 76.0%

W9 2008/.154612 PCT/US2008/066621 20 48.4 249% 75.1%
30 64.9 25,9% 74.1%
40 85,3 27.0% 73.0%
50 110.1 28.1% 71,9%
60 140,0 29,3% 70_7%
70 175,7 30.7% 69.3%
80 218,2 32.4%
Additionally, azeotrope-like compositions containing E-FC-1336rnzz and isobutane may also be formed. Such azeotrope-like compositions exist around azeotropic compositions. Some embodiments of azeotrope-like compositions are listed in Table 17_ Additional embodiments of azeotrope-like compositions are listed in Table 18, Table 17. Azeotrope-like Compositions COMPONENTS T CC) Weight Range E-FC-1336rnzzilsobutane -40 1 - 48.8/51.2 - 99 E-FC-1336mzz/lsobutane 0 1 - 59.3/40.7 - 99 E-FC-1336mzzilsobutane 40 1 - 68.8/31.2- 99 E-FC-1336mzzilsobuta.ne 80 1 - 78.7/21.3 - 99 __ E-FC-1336mzzilsobutane 95 1 - 82.6/17,4-99 Table 18, Azeotrope-like Compositions Weight Range, COMPONENTS T CC) Preferred E-FC-1336mzzilsobutane -40 __ 10 - 47,4/52.6 - 90 E-FC-1336mzzilsobutane 0 10 - 56,9/43.1 - 90 E-FC-1336mz7/Isobutane 40 ___ 10 - 65,3/34.7 - 90 E-FC-1336mzzilsobutane 80 10 - 74,3/25.7 - 90 E-FC-1336m77/Isobutane 95 10- 773/223 - 90 The azeotropic or azeotrope-like compositions of the present invention can be prepared by any convenient method including mixing or combining the desired amounts. In one embodiment of this invention, an azeotropic or azeotrope-like composition can be prepared by weighing the desired component amounts and thereafter combining them in an appropriate container.
The azeotropic or azeotrope-like compositions of the present invention can be used in a wide range of applications, including their use as aerosol propellants, refrigerants, solvents, cleaning agents, blowing agents (foam expansion agents) fot thermoplastic and thermoset foams, WO 2008/154612*

heat transfer media, gaseous dielectrics, fire extinguishing and suppression agents, power cycle working fluids, polymerization media, particulate removal fluids, carrier fluids, buffing abrasive agents, and displacement drying agents.
One embodiment of this invention provides a process for preparing a thermoplastic or thermoset foam. The process comprises 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-hexafiuoro-2-butene and a component selected from the group consisting of methyl formate, n-pentane, 2-methylbutaneõ trans-1,2-dichloroethylene, 1,1 ,1,3,3-pentafluoropmpane, n-butane and isobutane.
Another embodiment of this invention provides a process for producing refrigeration. The process comprises 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-methylbutaneõ trans-1,2-dichloroethylene, 1,1,1,3,3-pentafluoropropane, n-butane and isobutane.
Another embodiment of this invention provides a process using an azeotropic or azeotrope-like composition as a solvent, wherein said azeotropic or azeotrope-like composition consists essentially of E-ll ,1,4,4,4-hexafluoro-2-butene and a component selected from the group consisting of methyl formate, n-pentane, 2-methylbutaneõ trans-1,2-dichloroethylene, 1,1,1,3,3-pentatluoropropane, n-butane and isobutane.
Another embodiment 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 azeotrope-like composition consists essentially of E-1,1,14,4,4-hexafluoro-2-butene and a component selected from the group consisting of methyl formate, n-pentane, 2-methylbutaneõ trans-1,2-diohloroethylene, 1,1,1,3,3-pentatluoropropane, n-butane and isobutane.

W9 2008/154612*

Another embodiment of this invention provides a process 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, 1, trans-,2-dichloroethylene, 1,1 :1 ,3,3-pentafluoropropane, n-butane and isobutane.
Another embodiment of this invention provides a process for extinguishing or suppressing a fire. The process comprises 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-rnethytbutane, trans-1,2-dichloroethylene, 1,1,1,3,3-pentafluoropropane, n-.. butane and isobutane.
Another embodiment of this invention provides a process 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-methylbutaneõ trans-1,2-dichloroethylene, 1,1,1,3,3-pentafluoropropane, n-butane and isobutane.

Claims

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-butene.

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 azeotrope-like 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) 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.

4. 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.

5. 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.

6. 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.

7. 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.

8. 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.

9. 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.

10. 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.

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 azeotropic 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 (a) E-1,1,1,4,4,4.-hexafluoro-2-butene; and (b) any one of methyl formate, n-pentane, 2-methylbutane, trans-1,2-dichloroethylene, 1,1,1,3,3-pentafluoropropane, n-butane or 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 (a) E-1,1,1,4,4,4-hexafluoro-2-butene; and (b) any one of methyl formate, n-pentane, 2-methylbutane, trans-1,2-dichloroethylene, 1,1,1,3,3-pentafluoropropane, n-butane or 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 (a) E-1,1,1,4,4,4-hexafluoro-butene; and (b) any one of methyl formate, n-pentane, 2-methylbutane, trans-1,2-dichloroethylene, 1,1,1,3,3-pentafluoropropane, n-butane or 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 (a) E-1,1,1,4,4,4-hexafluoro-2-butene; and (b) any one of methyl formate, n-pentane, 2-methylbutane, trans-1,2-dichloroethylene, 1,1,1,3,3-pentafluoropropane, n-butane or 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 (a) E-1,1,1,4,4,4-hexafluoro-2-butene; and (b) any one of methyl formate, n-pentane, 2-methylbutane, trans-1,2-dichloroethylene, 1,1,1,3,3-pentafluoropropane, n-butane or 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 (a) E-1,1,1,4,4,4-hexafluoro-2-butene; and (b) any one of methyl formate, n-pentane. 2-methylbutane, trans-1,2-dichloroethylene, 1,1,1,3,3-pentafluoropropane, n-butane or isobutane.

18. A process comprising using an azeotropic or azeotrope-like .composition as dielectrics, wherein said azeotropic or azeotrope-like composition consists essentially of (a) E-1,1,1,4,4,4-hexafluoro-2-butene; and (b) any one of methyl formate, n-pentane, 2-methylbutane, trans-1,2-dichloroethylene, 1,1,1,3,3-pentafluoropropane, n-butane or isobutane.