AU2014202593B2 - Azeotropic and azeotrope-like compositions of z-1,1,1,4,4,4-hexafluoro-2-butene - Google Patents

Abstract

Azeotropic or azeotrope-like compositions are disclosed. The azeotropic or azeotrope-like compositions are mixtures of Z-1,1,1,4,4,4 hexafluoro-2-butene with methyl formate, pentane, 2-methylbutane, 5 1,1,1,3,3-pentafluorobutane, trans-1,2-dichloroethylene, 1,1,1,3,3 pentafluoropropane, dimethoxymethane, or cyclopentane. 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 10 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 15 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

2014202593 13 May 2014 P/00/011 Regulation 3.2 AUSTRALIA Patents Act 1990

COMPLETE SPECIFICATION

FOR A DIVISIONAL PATENT ORIGINAL

Name of Applicant: E. I. DU PONT DE NEMOURS AND COMPANY Actual Inventor: Mark L. ROBIN Address for Service: Houlihan2, Level 1, 70 Doncaster Road, Balwyn North, Victoria 3104, Australia Invention Title: AZEOTROPIC AND AZEOTROPE-LIKE COMPOSITIONS OF Z-1,1,1,4,4,4-HEXAFLUORO-2-BUTENE

The following statement is a full description of this invention, including the best method of performing it known to the Applicant:-1

TITLE OF INVENTION 2014202593 13 May 2014 AZEOTROPIC AND AZEOTROPE-LIKE COMPOSITIONS OF Z-1,1,1,4,4,4-HEXAFLUORO-2-BUTENE 5

The present application is a divisional application from Australian patent application number 2008246132. The entire disclosures of Australian patent application number 2008246132 and its corresponding International application, PCT/US2008/005481, are incorporated herein by 10 reference.

This application claims priority of U.S. Patent Application 60/926617 filed April 27, 2007, U.S. Patent Applications 60/930467, 60/930445 and 60/930383 filed May 16, 2007, U.S. Patent Applications 60/931960 and 60/931875 filed May 24, 2007, U.S. Patent Application 60/967874 filed 15 September 7, 2007, U.S. Patent Application 60/962203 filed October 5, 2007, U.S. Patent Application 60/999871 filed October 22, 2007.

BACKGROUND OF THE INVENTION

Field of the Disclosure 20 The present disclosure relates to azeotropic or azeotrope-like compositions of Z-1,1,1,4,4,4-hexafluoro-2-butene.

Description of Related Art

Many industries have been working for the past few decades to find 25 replacements for the ozone depleting chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs). The CFCs and FICFCs 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 30 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 2 for replacements for these versatile compounds, many industries have turned to the use of hydrofluorocarbons (HFCs). 2014202593 13 May 2014

The HFCs do not contribute to the destruction of stratospheric ozone, but are of concern due to their contribution to the "greenhouse 5 effect", i.e., they contribute to global warming. As a result of their contribution to global warming, the HFCs have come under scrutiny, and 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 stratospheric ozone and also have low global warming potentials (GWPs). 10 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 15 This application includes eight different types of azeotropic or azeotrope-like mixtures.

This disclosure provides a composition consisting essentially of (a) Z-FC-1336mzz and (b) methyl formate; wherein the methyl formate is present in an effective amount to form an azeotropic or azeotrope-like 20 mixture with Z-FC-1336mzz.

This disclosure also provides a composition consisting essentially of (a) Z-FC-1336mzz and (b) pentane; wherein the pentane is present in an effective amount to form an azeotropic or azeotrope-like mixture with Z-FC-1336mzz. 25 This disclosure also provides a composition consisting essentially of (a) Z-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 Z-FC-1336mzz.

This disclosure also provides a composition consisting essentially 30 of (a) Z-FC-1336mzz and (b) 1,1,1,3,3-pentafluorobutane (CF3CH2CF2CH3, HFC-365mfc); wherein the HFC-365mfc is present in an effective amount to form an azeotrope-like mixture with Z-FC-1336mzz.

This disclosure also provides a composition consisting essentially of (a) Z-FC-1336mzz and (b) trans-1,2-dichloroethylene; wherein the 3 trans-1,2-dichloroethylene is present in an effective amount to form an azeotropic or azeotrope-like mixture with Z-FC-1336mzz. 2014202593 13 May 2014

This disclosure also provides a composition consisting essentially of (a) Z-FC-1336mzz and (b) 1,1,1,3,3-pentafluoropropane (CF3CH2CF2H , 5 HFC-245fa); wherein the HFC-245fa is present in an effective amount to form an azeotrope-like mixture with Z-FC-1336mzz.

This disclosure also provides a composition consisting essentially of (a) Z-FC-1336mzz and (b) dimethoxymethane (CH3OCH2OCH3, methylal); wherein the dimethoxymethane is present in an effective 10 amount to form an azeotrope-like mixture with Z-FC-1336mzz.

This disclosure also provides a composition consisting essentially of (a) Z-FC-1336mzz and (b) cyclopentane (C-C5H10); wherein the cyclopentane is present in an effective amount to form an azeotropic or azeotrope-like mixture with Z-FC-1336mzz. 15 This disclosure also provides a composition consisting essentially of: (a) Z-1,1,1,4,4,4-hexafluoro-2-butene; and (b) methyl formate, pentane, 2-methylbutane, 1,1,1,3,3-pentafluorobutane, trans-1,2-dichloroethylene, 1,1,1,3,3-pentafluoropropane, dimethoxymethane or cyclopentane; wherein component (b) is present in an effective amount to form an 20 azeotropic or azeotropic-like combination with the Z-1,1,1,4,4,4- hexafluoro-2-butene; with the proviso that when component (b) is pentane or 2-methylbutane the ratio of component (a) to pentane or 2-methylbutane is not 95 to 80 weight percent: 5 to 20 weight percent. 25

BRIEF SUMMARY OF THE DRAWINGS FIG. 1 - FIG. 1 is a graphical representation of an azeotrope and azeotrope-like compositions consisting essentially of Z-FC-1336mzz and methyl formate at a temperature of about 50.1 °C. 30 FIG. 2 - FIG. 2 is a graphical representation of an azeotrope and azeotrope-like compositions consisting essentially of Z-FC-1336mzz and pentane at a temperature of about 19.9 °C. 4 FIG. 3 - FIG. 3 is a graphical representation of an azeotrope and azeotrope-like compositions consisting essentially of Z-FC-1336mzz and isopentane at a temperature of about 19.9 °C. 2014202593 13 May 2014 5 FIG. 4 - FIG. 4 is a graphical representation of azeotrope-like compositions consisting essentially of Z-FC-1336mzz and HFC-365mfc at a temperature of about 50.0 °C. FIG. 5 - FIG. 5 is a graphical representation of an azeotrope and 10 azeotrope-like compositions consisting essentially of Z-FC-1336mzz and trans-1,2-dichloroethylene at a temperature of about 50.1 °C. FIG. 6 - FIG. 6 is a graphical representation of azeotrope-like compositions consisting essentially of Z-FC-1336mzz and HFC-245fa at a 15 temperature of about 20,0 °C. FIG. 7 - FIG. 7 is a graphical representation of azeotrope-like compositions consisting essentially of Z-FC-1336mzz and dimethoxymethane at a temperature of about 50.0 °C. 20 FIG. 8 - FIG. 8 is a graphical representation of an azeotrope and azeotrope-like compositions consisting essentially of Z-FC-1336mzz and cyclopentane at a temperature of about 50 °C. 25

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 30 expansion compositions) is not a pure single component or an azeotropic or azeotrope-like mixture, the composition may change during its 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 5 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 5 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 10 and other applications, for example azeotropic or azeotrope-like mixtures containing Z-1,1,1,4,4,4-hexafluoro-2-butene (Z-CF3CH=CHCF3, Z-FC-1336mzz). 2014202593 13 May 2014

Before addressing details of embodiments described below, some 15 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-1336mzz or E-FC-1336mzz, as well as any combinations or mixtures of such isomers.

As used herein, the terms “comprises,” “comprising,” “includes,” 20 “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 25 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). 30 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 should be read to include one or at least one and the singular also includes the plural unless it is obvious that it is meant otherwise. 6

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although methods and materials similar or equivalent to those described herein can be used 5 in the practice or testing of embodiments of the present invention, suitable methods and materials are described below. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety, unless a particular passage is cited. In case of conflict, the present specification, including definitions, 2014202593 13 May 2014 10 will control. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting. Z-FC-1336mzz is a known compound, and its preparation method has been disclosed, for example, in U.S. Patent Application No. 60/926293 [FL1346 US PRV] filed April/26/2007, hereby incorporated by 15 reference in its entirety.

This application includes azeotropic or azeotrope-like compositions comprising Z-FC-1336mzz.

In some embodiments of this invention, the composition consists essentially of (a) Z-FC-1336mzz and (b) methyl formate; wherein the 20 methyl formate is present in an effective amount to form an azeotropic or azeotrope-like mixture with Z-FC-1336mzz.

In some embodiments of this invention, the composition consists essentially of (a) Z-FC-1336mzz and (b) pentane; wherein the pentane is present in an effective amount to form an azeotropic or azeotrope-like 25 mixture with Z-FC-1336mzz.

In some embodiments of this invention, the composition consists essentially of (a) Z-FC-1336mzz and (b) isopentane; wherein the isopentane is present in an effective amount to form an azeotropic or azeotrope-like mixture with Z-FC-1336mzz. 30 In some embodiments of this invention, the composition consists essentially of (a) Z-FC-1336mzz and (b) FIFC-365mfc; wherein the HFC-365mfc is present in an effective amount to form an azeotrope-like mixture with Z-FC-1336mzz. 7

In some embodiments of this invention, the composition consists essentially of (a) Z-FC-1336mzz and (b) trans-1,2-dichloroethylene; wherein the trans-1,2-dichloroethylene is present in an effective amount to form an azeotropic or azeotrope-like mixture with Z-FC-1336mzz. 2014202593 13 May 2014 5 In some embodiments of this invention, the composition consists essentially of (a) Z-FC-1336mzz and (b) HFC-245fa; wherein the HFC-245fa is present in an effective amount to form an azeotrope-like mixture with Z-FC-1336mzz.

In some embodiments of this invention, the composition consists 10 essentially of (a) Z-FC-1336mzz and (b) dimethoxymethane; wherein the dimethoxymethane is present in an effective amount to form an azeotropelike mixture with Z-FC-1336mzz.

In some embodiments of this invention, the composition consists essentially of (a) Z-FC-1336mzz and (b) cyclopentane; wherein the 15 cyclopentane is present in an effective amount to form an azeotropic or azeotrope-like mixture with Z-FC-1336mzz.

By effective amount is meant an amount, which, when combined with Z-FC-1336mzz, results in the formation of an azeotropic or azeotropelike mixture. This definition includes the amounts of each component, 20 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 25 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 30 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. 8 (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 5 that the composition of the vapor above the boiling composition is 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 10 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 15 fixed boiling point at a specified pressure. 2014202593 13 May 2014

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 20 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 25 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 30 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 9 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. 2014202593 13 May 2014

To determine the relative volatility of any two compounds, a method known as the PTx method can be used. In this procedure, the total 5 absolute pressure in a cell of known volume is measured at a constant temperature for various compositions of the two compounds. Use of the PTx Method is described in detail in "Phase Equilibrium in Process Design", Wiley-lnterscience Publisher, 1970, written by Harold R. Null, on pages 124 to 126; hereby incorporated by reference. 10 These measurements can be converted into equilibrium vapor and liquid compositions in the PTx cell by using an activity coefficient equation model, such as the Non-Random, Two-Liquid (NRTL) equation, to represent liquid phase nonidealities. Use of an activity coefficient equation, such as the NRTL equation is described in detail in "The Properties of 15 Gases and Liquids," 4th edition, published by McGraw Hill, written by

Reid, Prausnitz and Poling, on pages 241 to 387, and in "Phase Equilibria in Chemical Engineering," published by Butterworth Publishers, 1985, written by Stanley M. Walas, pages 165 to 244. Both aforementioned references are hereby incorporated by reference. Without wishing to be 20 bound by any theory or explanation, it is believed that the NRTL equation, together with the PTx cell data, can sufficiently predict the relative volatilities of the Z-1,1,1,4,4,4-hexafluoro-2-butene-containing compositions of the present invention and can therefore predict the behavior of these mixtures in multi-stage separation equipment such as 25 distillation columns.

It was found through experiments that Z-FC-1336mzz and methyl formate 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 30 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. 10

The vapor pressure measured versus the compositions in the PTx cell for Z-FC-1336mzz/methyl formate mixture is shown in FIG. 1, which graphically illustrates the formation of an azeotropic and azeotrope-like composition consisting essentially of Z-FC-1336mzz and methyl formate 5 as indicated by a mixture of about 20.4 mole % Z-1,1,1,4,4,4-hexafluoro-2-butene and 79.6 mole % methyl formate having the highest pressure over the range of compositions at this temperature. Based upon these findings, it has been calculated that Z-FC-1336mzz and methyl formate form azeotropic compositions ranging from about 25.4 mole percent to 10 about 15.6 mole percent Z-FC-1336mzz and from about 74.6 mole percent to about 84.4 mole percent methyl formate (which form azeotropic compositions boiling at a temperature of from about -20 °C to about 100 °C and at a pressure of from about 1.4 psia (10 kPa) to about 113 psia (779 kPa)). Some embodiments of azeotropic compositions are listed in 15 Table 1.

Table 1 Azeotropic compositions

Azeotropic Temperature (°C) Azeotropic Pressure (psia) Z-FC-1336mzz (mole %) Methyl formate (mole %) -20.0 1.38 25.4 74.6 - 10.0 2.40 25.2 74.8 0.0 3.97 24.8 75.2 10.0 6.30 24.3 75.7 20.0 9.64 23.7 76.3 30.0 14.3 22.9 77.1 40.0 20.5 22.1 77.9 50.0 28.7 21.2 78.8 60.0 39.2 20.2 79.8 70.0 52.4 19.1 80.9 80.0 68.9 18.0 82.0 90.0 89.0 16.8 83.2 100.0 113.3 15.6 84.4 2014202593 13 May 2014 11

Additionally, azeotrope-like compositions containing Z-FC-1336mzz and methyl formate may also be formed. Such azeotrope-like compositions exist around azeotropic compositions. Some embodiments of azeotropelike compositions are listed in Table 2. Additional embodiments of 5 azeotrope-like compositions are listed in Table 3

Table 2 Azeotrope-like compositions COMPONENTS T(°C) Weight Percentage Range Z-FC-1336mzz/Methyl formate -40 1-99/1-99 Z-FC-1336mzz/Methyl formate 0 1-99/1-99 Z-FC-1336mzz/Methyl formate 20 1-99/1-99 Z-FC-1336mzz/Methyl formate 40 1-99/1-99 Z-FC-1336mzz/Methyl formate 80 1-99/1-99 Z-FC-1336mzz/Methyl formate 120 1-99/1-99

Table 3 Azeotrope-like compositions COMPONENTS T(°C) Weight Percentage Range Z-FC-1336mzz/Methyl formate -40 10-90/10-90 Z-FC-1336mzz/Methyl formate 0 10-90/10-90 Z-FC-1336mzz/Methyl formate 20 10-90/10-90 Z-FC-1336mzz/Methyl formate 40 10-90/10-90 Z-FC-1336mzz/Methyl formate 80 10-90/10-90 Z-FC-1336mzz/Methyl formate 120 10-90/10-90 2014202593 13 May 2014 12

It was found through experiments that Z-FC-1336mzz and pentane 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 5 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. 2014202593 13 May 2014

The vapor pressure measured versus the compositions in the PTx cell for Z-FC-1336mzz/pentane mixture is shown in FIG. 2, which 10 illustrates graphically the formation of an azeotropic and azeotrope-like composition consisting essentially of Z-1,1,1,4,4,4-hexafluoro-2-butene and pentane at 19.9 °C, as indicated by a mixture of about 50.0 mole % Z-1,1,1,4,4,4-hexafluoro-2-butene and 50.0 mole % pentane having the highest pressure over the range of compositions at this temperature. 15

Based upon these findings, it has been calculated that Z-FC-1336mzz and pentane form azeotropic compositions ranging from about 48.2 mole percent to about 58.7 mole percent Z-FC-1336mzz and from about 51.8 mole percent to about 41.3 mole percent pentane (which form 20 azeotropic compositions boiling at a temperature of from about -20 °C to about 120 °C and at a pressure of from about 2.2 psia (15 kPa) to about 182 psia (1255 kPa)). Some embodiments of azeotropic compositions are listed in Table 4. 25 13 2014202593 13 May 2014

Table 4 Azeotropic compositions Azeotropic Temperature (°C) Azeotropic Pressure (psia) Z-FC-1336mzz (mole %) Pentane (mole %) -20.0 2.20 48.2 51.8 - 10.0 3.70 48.9 51.1 0.0 5.91 49.5 50.5 10.0 9.07 50.1 49.9 20.0 13.4 50.7 49.3 30.0 19.2 51.2 48.8 40.0 26.7 51.8 48.2 50.0 36.2 52.3 47.7 60.0 48.0 52.9 47.1 70.0 62.4 53.6 46.4 80.0 79.6 54.3 45.7 90.0 100 55.1 44.9 100.0 124 56.0 44.0 110.0 151 57.2 42.8 120.0 182 58.7 41.3

Additionally, azeotrope-like compositions containing Z-FC-1336mzz and pentane may also be formed. Such azeotrope-like compositions exist 5 around azeotropic compositions. Some embodiments of azeotrope-like compositions are listed in Table 5. Additional embodiments of azeotropelike compositions are listed in Table 6. 14

Table 6 Azeotrope-like compositions COMPONENTS T(°C) Weight Percentage Range Z-FC-1336mzz/Pentane -40 62-70/30-38 Z-FC-1336mzz/Pentane 0 64-74/26-36 Z-FC-1336mzz/Pentane 20 64-76/24-36 Z-FC-1336mzz/Pentane 40 64-78/22-36 Z-FC-1336mzz/Pentane 80 62-84/16-38 Z-FC-1336mzz/Pentane 120 57-99/1 -43 2014202593 13 May 2014

Table 5 Azeotrope-like compositions COMPONENTS T(°C) Weight Percentage Range Z-FC-1336mzz/Pentane -40 60-75/25-40 Z-FC-1336mzz/Pentane 0 60-80/20-40 Z-FC-1336mzz/Pentane 20 60-82/28-40 Z-FC-1336mzz/Pentane 40 60-85/15-40 Z-FC-1336mzz/Pentane 80 55-90/10-45 Z-FC-1336mzz/Pentane 120 45-99/1-55 5 It was found through experiments that Z-FC-1336mzz 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 10 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 Z-FC-1336mzz/ isopentane mixture is shown in FIG. 3, which illustrates graphically the formation of an azeotrope and azeotrope-like 15 compositions of Z-1,1,1,4,4,4-hexafluoro-2-butene and isopentane at 19.9 °C, as indicated by a mixture of about 40.0 mole % Z-1,1,1,4,4,4- 15 hexafluoro-2-butene and 60.0 mole % isopentane having the highest pressure over the range of compositions at this temperature. 2014202593 13 May 2014

Based upon these findings, it has been calculated that Z-FC-1336mzz and isopentane form azeotropic compositions ranging from 5 about 37.1 mole percent to about 48.6 mole percent Z-FC-1336mzz and from about 62.9 mole percent to about 51.4 mole percent isopentane (which form azeotropic compositions boiling at a temperature of from about -20 °C to about 120 °C and at a pressure of from about 2.7 psia (19 kPa) to about 199 psia (1372 kPa)). Some embodiments of azeotropic 10 compositions are listed in Table 7.

Table 7 Azeotropic compositions

Azeotropic Temperature (°C) Azeotropic Pressure (psia) Z-FC-1336mzz (mole %) Isopentane (mole %) -20.0 2.72 37.1 62.9 - 10.0 4.47 38.3 61.7 0.0 7.01 39.4 60.6 10.0 10.6 40.4 59.6 20.0 15.4 41.2 58.8 30.0 21.9 42.0 58.0 40.0 30.1 42.8 57.2 50.0 40.5 43.5 56.5 60.0 53.4 44.2 55.8 70.0 69.0 44.8 55.2 80.0 87.6 45.5 54.5 90.0 110 46.2 53.8 100.0 135 46.9 53.1 110.0 165 47.7 52.3 120.0 199 48.6 51.4

Additionally, azeotrope-like compositions containing Z-FC-1336mzz 15 and isopentane may also be formed. Such azeotrope-like compositions exist around azeotropic compositions. Some embodiments of azeotrope- 16

Table 9 Azeotrope-like compositions COMPONENTS T(°C) Weight Percentage Range Z-FC-1336mzz/lsopentane -40 49-58/42-51 Z-FC-1336mzz/lsopentane 0 53-65/35-47 Z-FC-1336mzz/lsopentane 20 53-68/32-47 Z-FC-1336mzz/lsopentane 40 53-71/29-47 Z-FC-1336mzz/lsopentane 80 52-77/23-48 Z-FC-1336mzz/lsopentane 120 43-89/11-57 2014202593 13 May 2014 like compositions are listed in Table 8. Additional embodiments of azeotrope-like compositions are listed in Table 9.

Table 8 Azeotrope-like compositions COMPONENTS T(°C) Weight Percentage Range Z-FC-1336mzz/lsopentane -40 40-65/35-60 Z-FC-1336mzz/lsopentane 0 45-70/30-55 Z-FC-1336mzz/lsopentane 20 45-75/25-55 Z-FC-1336mzz/lsopentane 40 45-75/25-55 Z-FC-1336mzz/lsopentane 80 40-85/15-60 Z-FC-1336mzz/lsopentane 120 1-99/1-99 5

It was found through experiments that Z-FC-1336mzz and HFC-365mfc form azeotrope-like compositions. To determine the relative 10 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 17 measurements were then reduced to equilibrium vapor and liquid compositions in the cell using the NRTL equation. 2014202593 13 May 2014

The vapor pressure measured versus the compositions in the PTx cell for Z-FC-1336mzz/ HFC-365mfc mixture is shown in FIG. 4, which 5 illustrates graphically the formation of azeotrope-like compositions of Z- 1,1,1,4,4,4-hexafluoro-2-butene and FIFC-365mfc at 50.1 °C, as indicated by a mixtures of about 1 to 99 mole % Z-1,1,1,4,4,4-hexafluoro-2-butene and about 1 to 99 mole % FIFC-365mfc.

Some embodiments of azeotrope-like compositions are listed in 10 Table 10. Additional embodiments of azeotrope-like compositions are listed in Table 11.

Table 10 Azeotrope-like compositions COMPONENTS T(°C) Weight Percentage Range Z-FC-1336mzz/HFC-365mfc -40 1-99/1-99 Z-FC-1336mzz/HFC-365mfc 0 1-99/1-99 Z-FC-1336mzz/HFC-365mfc 40 1-99/1-99 Z-FC-1336mzz/HFC-365mfc 80 1-99/1-99 Z-FC-1336mzz/HFC-365mfc 120 1-99/1-99 Z-FC-1336mzz/HFC-365mfc 160 1-99/1-99 18 2014202593 13 May 2014

Table 11 Azeotrope-like compositions COMPONENTS T(°C) Weight Percentage Range Z-FC-1336mzz/HFC-365mfc -40 10-99/10-90 Z-FC-1336mzz/HFC-365mfc 0 10-99/10-90 Z-FC-1336mzz/HFC-365mfc 40 10-99/10-90 Z-FC-1336mzz/HFC-365mfc 80 10-90 Z-FC-1336mzz/HFC-365mfc 120 10-90 Z-FC-1336mzz/HFC-365mfc 160 10-90

It was found through experiments that Z-FC-1336mzz and trans-1,2-dichloroethylene form azeotropic or azeotrope-like compositions. To 5 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. 10 The vapor pressure measured versus the compositions in the PTx cell for Z-FC-1336mzz/ trans-1,2-dichloroethylene mixture is shown in FIG. 5, which illustrates graphically the formation of an azeotropic composition of Z-1,1,1,4,4,4-hexafluoro-2-butene and trans-1,2-dichloroethylene at 50.1 °C, as indicated by a mixture of about 64.8 mole % Z-1,1,1,4,4,4-15 hexafluoro-2-butene and 35.2 mole % trans-1,2-dichloroethylene having the highest pressure over the range of compositions at this temperature.

Based upon these findings, it has been calculated that Z-FC-1336mzz and trans-1,2-dichloroethylene form azeotropic compositions ranging from about 62.4 mole percent to about 71.0 mole percent Z-FC-20 1336mzz and from about 37.6 mole percent to about 29.0 mole percent trans-1,2-dichloroethylene (which form azeotropic compositions boiling at a temperature of from about -20 °C to about 120 °C and at a pressure of 19 from about 1.6 psia (11 kPa) to about 170 psia (1172 kPa)). Some embodiments of azeotropic compositions are listed in Table 12.

Table 12 Azeotropic compositions

Azeotropic Temperature (°C) Azeotropic Pressure (psia) Z-FC-1336mzz (mole %) trans-1,2-dichloroethylene (mole %) -20.0 1.60 62.4 37.6 - 10.0 2.74 62.4 37.6 0.0 4.47 62.5 37.5 10.0 6.98 62.8 37.2 20.0 10.5 63.1 36.9 30.0 15.3 63.6 36.4 40.0 21.7 64.2 35.8 50.0 29.9 64.8 35.2 60.0 40.3 65.5 34.5 70.0 53.2 66.3 33.7 80.0 69.0 67.2 32.8 90.0 88.2 68.1 31.9 100.0 111 69.0 31.0 110.0 138 70.0 30.0 120.0 170 71.0 29.0 2014202593 13 May 2014 5

Additionally, azeotrope-like compositions containing Z-FC-1336mzz and trans-1,2-dichloroethylene may also be formed. Such azeotrope-like compositions exist around azeotropic compositions. Some embodiments of azeotrope-like compositions are listed in Table 13. Additional 10 embodiments of azeotrope-like compositions are listed in Table 14. 20

Table 14 Azeotrope-like compositions COMPONENTS T (°C) Weight Percentage Range Z-FC-1336mzz/trans-1,2-dichloroethylene -40 72-80/20-38 Z-FC-1336mzz/trans-1,2-dichloroethylene 0 69-83/17-31 Z-FC-1336mzz/trans-1,2-dichloroethylene 20 68-86/14-32 Z-FC-1336mzz/trans-1,2-dichloroethylene 40 68-90/10-32 Z-FC-1336mzz/trans-1,2-dichloroethylene 80 66-99/1-34 Z-FC-1336mzz/trans-1,2-dichloroethylene 120 65-99/1-35 Z-FC-1336mzz/trans-1,2-dichloroethylene 160 65-99/1-35 2014202593 13 May 2014

Table 13 Azeotrope-like compositions COMPONENTS T (°C) Weight Percentage Range Z-FC-1336mzz/trans-1,2-dichloroethylene -40 71-82/18-29 Z-FC-1336mzz/trans-1,2-dichloroethylene 0 67-86/14-33 Z-FC-1336mzz/trans-1,2-dichloroethylene 20 65-93/7-35 Z-FC-1336mzz/trans-1,2-dichloroethylene 40 65-99/1-35 Z-FC-1336mzz/trans-1,2-dichloroethylene 80 63-99/1-37 Z-FC-1336mzz/trans-1,2-dichloroethylene 120 61-99/1-39 Z-FC-1336mzz/trans-1,2-dichloroethylene 160 58-99/1 -42 5 It was found through experiments that Z-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 PTx cell of known volume was measured at constant temperature for various binary compositions. These 10 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 Z-FC-1336mzz/ FIFC-245fa mixture is shown in FIG. 6, which illustrates graphically the formation of azeotrope-like compositions of Z-15 1,1,1,4,4,4-hexafluoro-2-butene and FIFC-245fa at 19.9 °C, as indicated 21 by mixtures of about 1 to 21 mole % Z-1,1,1,4,4,4-hexafluoro-2-butene and about 79 to 99 mole % HFC-245fa with vapor pressure of approximately 17 psia (117 kPa), and by mixtures of about 94 to 99 mole percent Z-1,1,1,4,4,4-hexafluoro-2-butene and 1 to 6 mole % HFC-245fa 5 with vapor pressure of approximately 9 psia (62 kPa). 2014202593 13 May 2014

Some embodiments of azeotrope-like compositions are listed in Table 15. Additional embodiments of azeotrope-like compositions are listed in Table 16. 10 Table 15 Azeotrope-like compositions COMPONENTS T(°C) Weight Percentage Range Z-FC-1336mzz/HFC-245fa -40 1-19/81-99 and 97-99/1-3 Z-FC-1336mzz/HFC-245fa 0 1-22/78-99 and 95-99/1-5 Z-FC-1336mzz/HFC-245fa 40 1-26/74-99 and 94-99/1-6 Z-FC-1336mzz/HFC-245fa 80 1-35/65-99 and 90-99/1-10 Z-FC-1336mzz/HFC-245fa 120 1-58/42-99 and 76-99/1-24

Table 16 Azeotrope-like compositions COMPONENTS T(°C) Weight Percentage Range Z-FC-1336mzz/HFC-245fa -40 10-13/87-90 and 98-99/1-2 Z-FC-1336mzz/HFC-245fa 0 10-14/86-90 and 97-99/1-3 Z-FC-1336mzz/HFC-245fa 40 10-17/83-90 and 96-99/1-4 Z-FC-1336mzz/HFC-245fa 80 10-22/78-90 and 95-99/1-5 Z-FC-1336mzz/HFC-245fa 120 10-33/67-90 and 90-99/1 -10

It was found through experiments that Z-FC-1336mzz and 15 dimethoxymethane 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 22 measurements were then reduced to equilibrium vapor and liquid compositions in the cell using the NRTL equation. 2014202593 13 May 2014

The vapor pressure measured versus the compositions in the PTx cell for Z-FC-1336mzz/dimethoxymethane mixture is shown in FIG. 7, 5 which illustrates graphically the formation of azeotrope-like compositions of Z-1,1,1,4,4,4-hexafluoro-2-butene and dimethoxymethane at 49.99 °C and about 22.5 psia (155 kPa), as indicated by mixtures of about 1 to 99 mole % Z-1,1,1,4,4,4-hexafluoro-2-butene and about 1 to 99 mole % dimethoxymethane. 10 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 (°C) Weight Percentage Range Z-FC-1336mzz/Dimethoxymethane -40 1-99/1-99 Z-FC-1336mzz/Dimethoxymethane 0 1-99/1-99 Z-FC-1336mzz/Dimethoxymethane 40 1-99/1-99 Z-FC-1336mzz/Dimethoxymethane 80 1-99/1-99 Z-FC-1336mzz/Dimethoxymethane 120 1-99/1-99 Z-FC-1336mzz/Dimethoxymethane 160 1-99/1-99 15

Table 18 Azeotrope-like compositions COMPONENTS T (°C) Weight Percentage Range Z-FC-1336mzz/Dimethoxymethane -40 5-95/5-95 Z-FC-1336mzz/Dimethoxymethane 0 5-95/5-95 Z-FC-1336mzz/Dimethoxymethane 40 5-95/5-95 Z-FC-1336mzz/Dimethoxymethane 80 5-95/5-95 Z-FC-1336mzz/Dimethoxymethane 120 5-95/5-95 Z-FC-1336mzz/Dimethoxymethane 160 5-95/5-95 23

It was found through experiments that Z-FC-1336mzz and cyclopentane 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 5 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. 2014202593 13 May 2014

The vapor pressure measured versus the compositions in the PTx cell for Z-FC-1336mzz/cyclopentane mixture is shown in FIG. 8, which 10 illustrates graphically the formation of an azeotropic composition of Z- 1,1,1,4,4,4-hexafluoro-2-butene and cyclopentane at 49.97 °C, as indicated by a mixture of about 63.9 mole % Z-1,1,1,4,4,4-hexafluoro-2-butene and 36.1 mole % cyclopentane having the highest pressure over the range of compositions at this temperature. 15 Based upon these findings, it has been calculated that Z-FC- 1336mzz and cyclopentane form azeotropic compositions ranging from about 64.2 mole percent to about 74.4 mole percent Z-FC-1336mzz and from about 35.8 mole percent to about 25.6 mole percent cyclopentane (which form azeotropic compositions boiling at a temperature of from 20 about -20 °C to about 150 °C and at a pressure of from about 1.7 psia (12 kPa) to about 302 psia (2082 kPa)). Some embodiments of azeotropic compositions are listed in Table 18. 24 2014202593 13 May 2014

Table 18 Azeotropic compositions Azeotropic Temperature (°C) Azeotropic Pressure (psia) Z-FC-1336mzz (mole %) Cyclopentane (mole %) -20.0 1.74 64.2 35.8 -10.0 2.98 63.9 36.1 0.0 4.86 63.7 36.3 10.0 7.59 63.6 36.4 20.0 11.4 63.5 36.5 30.0 16.6 63.6 36.4 40.0 23.4 63.7 36.3 49.97 32.1 63.9 36.1 50.0 32.1 63.9 36.1 60.0 43.1 64.2 35.8 70.0 56.7 64.6 35.4 80.0 73.2 65.1 34.9 90.0 92.9 65.8 34.2 100.0 116 66.6 33.4 110.0 144 67.6 32.4 120.0 175 68.9 31.1 130.0 211 70.4 29.6 140.0 254 72.3 27.7 150.0 302 74.4 25.6

Additionally, azeotrope-like compositions containing Z-FC-1336mzz and cyclopentane may also be formed. Such azeotrope-like compositions 5 exist around azeotropic compositions. Some embodiments of azeotropelike compositions are listed in Table 19. Additional embodiments of azeotrope-like compositions are listed in Table 20. 25 2014202593 13 May 2014

Table 19 Azeotrope-like compositions COMPONENTS T(°C) Weight Percentage Range Z-FC-1336mzz/cyclopentane -20 77-86/14-23 Z-FC-1336mzz/cyclopentane 0 76 -87/13 - 24 Z-FC-1336mzz/cyclopentane 40 74-90/10-26 Z-FC-1336mzz/cyclopentane 80 72 - 99/1 - 28 Z-FC-1336mzz/cyclopentane 120 70 - 99/1 - 30 Z-FC-1336mzz/cyclopentane 150 68 - 99/1 - 32

Table 20 Azeotrope-like compositions COMPONENTS T (°C) Weight Percentage Range Z-FC-1336mzz/cyclopentane -20 80 -86/14- 20 Z-FC-1336mzz/cyclopentane 0 80 -87/13 - 20 Z-FC-1336mzz/cyclopentane 40 80- 90/10 - 206 Z-FC-1336mzz/cyclopentane 80 80 - 95/5 - 20 Z-FC-1336mzz/cyclopentane 120 80 - 95/5 - 20 Z-FC-1336mzz/cyclopentane 150 80 - 99/5 - 20 5 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 10 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) for thermoplastic and thermoset foams, 15 heat transfer media, gaseous dielectrics, fire extinguishing and suppression agents, power cycle working fluids, polymerization media, 26 particulate removal fluids, carrier fluids, buffing abrasive agents, and displacement drying agents. 2014202593 13 May 2014

One embodiment of this invention provides a process for preparing a thermoplastic or thermoset foam. The process comprises using an 5 azeotropic or azeotrope-like composition as a blowing agent, wherein said azeotropic or azeotrope-like composition consists essentially of Z- 1.1.1.4.4.4- hexafluoro-2-butene and a component selected from the group consisting of methyl formate, pentane, 2-methylbutane, 1,1,1,3,3-pentafluorobutane, trans-1,2-dichloroethylene, 1,1,1,3,310 pentafluoropropane, dimethoxymethane and cyclopentane.

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, 15 wherein said azeotropic or azeotrope-like composition consists essentially of Z-1,1,1,4,4,4-hexafluoro-2-butene and a component selected from the group consisting of methyl formate, pentane, 2-methylbutane, 1,1,1,3,3-pentafluorobutane, trans-1,2-dichloroethylene, 1,1,1,3,3-pentafluoropropane, dimethoxymethane and cyclopentane. 20 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 Z- 1.1.1.4.4.4- hexafluoro-2-butene and a component selected from the group consisting of methyl formate, pentane, 2-methylbutane, 1,1,1,3,325 pentafluorobutane, trans-1,2-dichloroethylene, 1,1,1,3,3- pentafluoropropane, dimethoxymethane and cyclopentane.

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 30 azeotrope-like composition consists essentially of Z-1,1,1,4,4,4- hexafluoro-2-butene and a component selected from the group consisting of methyl formate, pentane, 2-methylbutane, 1,1,1,3,3-pentafluorobutane, trans-1,2-dichloroethylene, 1,1,1,3,3-pentafluoropropane, dimethoxymethane and cyclopentane. 27

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 Z-1,1,1,4,4,4-hexafluoro-2-butene and a component selected from the 5 group consisting of methyl formate, pentane, 2-methylbutane, 1,1,1,3,3-pentafluorobutane, trans-1,2-dichloroethylene, 1,1,1,3,3-pentafluoropropane, dimethoxymethane and cyclopentane. 2014202593 13 May 2014

Another embodiment of this invention provides a process for extinguishing or suppressing a fire. The process comprises using an 10 azeotropic or azeotrope-like composition as a fire extinguishing or suppression agent, wherein said azeotropic or azeotrope-like composition consists essentially of Z-1,1,1,4,4,4-hexafluoro-2-butene and a component selected from the group consisting of methyl formate, pentane, 2-methylbutane, 1,1,1,3,3-pentafluorobutane, trans-1,2-dichloroethylene, 15 1,1,1,3,3-pentafluoropropane, dimethoxymethane and cyclopentane.

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 Z- 1,1,1,4,4,4-hexafluoro-2-butene and a component selected from the group 20 consisting of methyl formate, pentane, 2-methylbutane, 1,1,1,3,3-pentafluorobutane, trans-1,2-dichloroethylene, 1,1,1,3,3-pentafluoropropane, dimethoxymethane and cyclopentane.

Where the terms “comprise”, “comprises”, “comprised” or “comprising” are used in this specification, they are to be interpreted as 25 specifying the presence of the stated features, integers, steps or components referred to, but not to preclude the presence or addition of one or more other feature, integer, step, component or group thereof.

Further, any prior art reference or statement provided in the specification is not to be taken as an admission that such art constitutes, 30 or is to be understood as constituting, part of the common general knowledge in Australia. 28

Claims (5)

1. The Claims defining the invention are as follows:

   1. A composition consisting essentially of: (a) Z-1,1,1,4,4,4-hexafluoro-2-butene; and (b) methyl formate; wherein component (b) is present in an effective amount to form an azeotropic or azeotropic-like combination with the Z- 1.1.1.4.4.4- hexafluoro-2-butene.
2. 2. The composition of claim 1 consisting essentially of from 1 to 99 weight percent Z-1,1,1,4,4,4-hexafluoro-2-butene and from 99 to 1 weight percent methyl formate, characterized by: at a temperature of from -40° C. to 120° C., said composition having a difference in dew point pressure and bubble point pressure of less than or equal to 5 percent based upon the bubble point pressure.
3. 3. The composition of claim 1 or claim 2 consisting essentially of from about 25.4 mole percent to about 15.6 mole percent Z- 1.1.1.4.4.4- hexafluoro-2-butene and from about 74.6 mole percent to about 84.4 mole percent methyl formate, which has boiling point temperature of from about -20° C. to about 100° C. at a pressure of from about 1.4 psia to about 113 psia.
4. 4. A process comprising using the composition of any one of claims 1 to 3.
5. 5. Use of the composition of any one of claims 1 to 3.