HK1141748B - Azeotropic and azeotrope-like compositions of z-1,1,1,4,4,4-hexafluoro-2-butene - Google Patents

Description

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

This patent application claims priority from the following patent applications: U.S. patent application 60/926617 filed on 27/4/2007; U.S. patent applications 60/930467, 60/930445, and 60/930383 filed on 16/5/2007; U.S. patent applications 60/931960 and 60/931875 filed on 24/5/2007; U.S. patent application 60/967874 filed on 7/9/2007; U.S. patent application 60/962203 filed on 5.10.2007; us patent application 60/999871 filed on day 22 of month 10, 2007.

Background

FIELD OF THE DISCLOSURE

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

Description of the Related Art

Over the past few decades, many industries have been working to find ozone depleting replacements for chlorofluorocarbons (CFCs) and Hydrochlorofluorocarbons (HCFCs). CFCs and HCFCs have been used 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 extinguishing agents, power cycle working fluids, polymerization media, particulate removal fluids, carrier fluids, buffing abrasive agents, and displacement drying agents. In the search for alternatives to these multi-functional compounds, many industries have turned to the use of Hydrofluorocarbons (HFCs).

HFCs are not destructive to stratospheric ozone, but are of interest because they contribute to the "greenhouse effect," i.e., they contribute to global warming. Since they contribute to global warming, HFCs have been scrutinized and their widespread use will be in the futureIs subject to limitations. Thus, there is a need for compositions that are not destructive to stratospheric ozone and also have low Global Warming Potentials (GWPs). It is believed that certain hydrofluoroolefins such as 1,1,1,4,4, 4-hexafluoro-2-butene (CF)₃CH＝CHCF₃FC-1336mzz) meet both requirements.

Summary of The Invention

This patent application includes eight different types of azeotropic or azeotrope-like mixtures.

The present 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 mixture with Z-FC-1336 mzz.

The present 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-1336 mzz.

The present 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-1336 mzz.

The present disclosure also provides compositions consisting essentially of (a) Z-FC-1336mzz and (b)1, 1,1, 3, 3-pentafluorobutane (CF)₃CH₂CF₂CH₃HFC-365 mfc); wherein said HFC-365mfc is present in an effective amount to form an azeotrope-like mixture with Z-FC-1336 mzz.

The present disclosure also provides a composition consisting 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-1336 mzz.

The present disclosure also provides compositions consisting essentially of (a) Z-FC-1336mzz and (b)1, 1,1, 3, 3-pentafluoropropane (CF)₃CH₂CF₂H, HFC-245 fa); whereinThe HFC-245fa is present in an amount effective to form an azeotrope-like mixture with Z-FC-1336 mzz.

The disclosure also provides compositions consisting essentially of (a) Z-FC-1336mzz and (b) dimethoxymethane (CH)₃OCH₂OCH₃Methylal); wherein the dimethoxymethane is present in an effective amount to form an azeotrope-like mixture with Z-FC-1336 mzz.

The disclosure also provides compositions consisting essentially of (a) Z-FC-1336mzz and (b) cyclopentane (C-C)₅H₁₀) The composition of (a); wherein the cyclopentane is present in an effective amount to form an azeotropic or azeotrope-like mixture with Z-FC-1336 mzz.

Brief description of the drawings

FIG. 1 is a schematic representation of azeotropic and azeotrope-like compositions consisting essentially of Z-FC-1336mzz and methyl formate at a temperature of about 50.1 ℃.

Figure 2 is a schematic representation of azeotropic and azeotrope-like compositions consisting essentially of Z-FC-1336mzz and pentane at a temperature of about 19.9 ℃.

Figure 3 is a schematic representation of azeotropic and azeotrope-like compositions consisting essentially of Z-FC-1336mzz and isopentane at a temperature of about 19.9 ℃.

Figure 4 is a schematic representation of an azeotrope-like composition consisting essentially of Z-FC-1336mzz and HFC-365mfc at a temperature of about 50.0 ℃.

Figure 5 is a schematic representation of azeotropic and azeotrope-like compositions consisting essentially of Z-FC-1336mzz and trans-1, 2-dichloroethylene at a temperature of about 50.1 ℃.

Figure 6 is a schematic representation of an azeotrope-like composition consisting essentially of Z-FC-1336mzz and HFC-245fa at a temperature of about 20.0 ℃.

Figure 7 is a schematic representation of an azeotrope-like composition consisting essentially of Z-FC-1336mzz and dimethoxymethane at a temperature of about 50.0 ℃.

Figure 8 is a schematic representation of azeotropic and azeotrope-like compositions consisting essentially of Z-FC-1336mzz and cyclopentane at a temperature of about 50 ℃.

Detailed Description

In many applications, it is desirable to use a single pure component or an azeotropic or azeotrope-like mixture. For example, when a blowing agent composition (also referred to as a foam expansion agent or foam expansion composition) is not a single pure component or an azeotropic or azeotrope-like mixture, the composition may change during its application to the foaming process. Such compositional changes can adversely affect processing or result in poor performance in applications. Also, in refrigeration applications, refrigerant is typically lost during operation via shaft seals, hose connections, weld joints, and cracks in the fold lines. Furthermore, the refrigerant may be released into the atmosphere during maintenance procedures of the refrigeration equipment. If the refrigerant is not a single pure component or an azeotropic or azeotrope-like composition, the refrigerant composition will change when leaked from a refrigeration unit or vented to the atmosphere. The change in refrigerant composition may cause the refrigerant to become flammable or to have poor refrigeration performance. Thus, there is a need for azeotropic or azeotrope-like mixtures to be used in these and other applications, e.g., comprising Z-1,1,1,4,4, 4-hexafluoro-2-butene (Z-CF)₃CH＝CHCF₃Z-FC-1336 mzz).

Before addressing details of the embodiments described below, certain terms are defined or clarified.

FC-1336mzz may exist as one of two configurational isomers, E or Z. As used herein, FC-1336mzz refers to the isomers Z-FC-1336mzz or E-FC-1336mzz, as well as any combination or mixture 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. Furthermore, unless expressly stated to the contrary, "or" refers to an inclusive "or" and not to an exclusive "or". For example, the condition a or B is satisfied in any of the following cases: a is true (or present) and B is spurious (or absent), a is spurious (or absent) and B is true (or present), and both a and B are true (or present).

Also, the use of "a" or "an" is used to describe elements and components described herein. This is done merely for convenience and to provide a general sense of the scope of the invention. Such description should be understood to include one or at least one and the singular also includes the plural unless it is obvious that it is meant otherwise.

Unless defined otherwise, 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 also be used 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 specific passage is cited. In case of conflict, the present specification, including definitions, 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 60/926293[ FL1346 US PRV ], filed on 26.4.2007, which is incorporated herein by reference in its entirety.

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

In some embodiments of the invention, the composition consists 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 mixture with Z-FC-1336 mzz.

In some embodiments of the 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 mixture with Z-FC-1336 mzz.

In some embodiments of the 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-1336 mzz.

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

In some embodiments of the 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-1336 mzz.

In some embodiments of the invention, the composition consists essentially of (a) Z-FC-1336mzz and (b) HFC-245 fa; wherein the HFC-245fa is present in an effective amount to form an azeotrope-like mixture with the Z-FC-1336 mzz.

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

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

By effective amount is meant an amount which, when combined with Z-FC-1336mzz, results in the formation of an azeotropic or azeotrope-like mixture. This definition includes the amount of each component, which may vary depending on the pressure applied to the composition, so long as the azeotropic or azeotrope-like compositions persist at different pressures, but have possibly different boiling points. Accordingly, effective amounts include amounts, such as amounts expressed in weight percent or mole percent, of each component in the compositions of the present invention that form azeotropic or azeotrope-like compositions at temperatures or pressures different from those described herein.

As recognized in the art, an azeotropic composition is a mixture of two or more different components that, when in liquid form at a given pressure, will boil at a substantially constant temperature, which may be above or below the boiling temperature of the individual components, and will provide a vapor composition that is substantially the same as the overall liquid composition undergoing boiling. (see, e.g., "Conceptual Design of Distillation Systems", McGraw-Hill (New York) from M.F. Doherty and M.F. Malone, 2001, pages 185 to 186, 351 to 359).

Thus, the essential features of an azeotropic composition are: at a given pressure, the boiling point of the liquid composition is fixed, and the composition of the vapor above the boiling composition is essentially that of the entire boiling liquid composition (i.e., no fractionation of the liquid composition components occurs). It is also recognized in the art that the boiling point and weight percentages of each component of the azeotropic composition can vary when the azeotropic composition is subjected to boiling at different pressures. Thus, an azeotropic composition can be defined in terms of: the unique relationship that exists between the components, or the compositional ranges of the components, or the exact weight percentages of each component in the composition, the composition characterized by a fixed boiling point at a particular pressure.

For the purposes of this invention, azeotrope-like compositions refer to compositions that behave like azeotropic compositions (i.e., have constant boiling characteristics or no tendency to fractionate upon boiling or evaporation). Thus, during boiling or evaporation, if the vapor and liquid compositions change, only a minimal or negligible change occurs. This is in contrast to non-azeotrope-like compositions in which the vapor and liquid compositions change to a significant extent during boiling or evaporation.

In addition, azeotrope-like compositions exhibit dew point pressure and bubble point pressure with little pressure differential. That is, the difference between dew point pressure and bubble point pressure at a given temperature is a small value. In the present invention, compositions having a difference between dew point pressure and bubble point pressure of less than or equal to 5% (based on bubble point pressure) are considered azeotrope-like.

It is recognized in the art that when the relative volatility of a system approaches 1.0, the system is defined as forming an azeotropic or azeotrope-like composition. The relative volatility is the ratio of the volatility of component 1 to the volatility of component 2. The molar fraction ratio of the component in the vapor state to the component in the liquid state is the volatility of the component.

The relative volatility of any two compounds can be defined using a method known as the PTx method. In this method, the total absolute pressure in a cell of known volume at a constant temperature is determined for different compositions of two compounds. The use of the PTx method is described in more detail in "Phase Equilibrium in Process Design" (Wiley-Interscience distributor, 1970) by Harold r.null at pages 124 to 126; said document is incorporated herein by reference.

These measurements can be converted to equilibrium vapor and Liquid compositions in the PTx cell by expressing Liquid phase Non-idealities using an activity coefficient equation model such as the Non-Random, Two-Liquid (NRTL) equation. The application of activity coefficient equations such as The NRTL equation is described in more detail in pages 241 to 387, 4 th edition, written by Reid, Prausnitz and Poling, "The Properties of Gases and Liquids," published by McGraw Hill, and pages 165 to 244, written by Stanley M.Wals, "Phase Equiribria in Chemical Engineering," published by Butterworth Publishers (1985). Both of these documents are incorporated herein by reference. Without being bound by any theory or explanation, it is believed that the NRTL equation, together with the PTx cell data, may be sufficient to predict the relative volatility of the compositions of the present invention comprising Z-1,1,1,4,4, 4-hexafluoro-2-butene, and thus the behavior of these mixtures in a multi-stage separation apparatus such as a distillation column.

It was found by experiment that Z-FC-1336mzz forms an azeotropic or azeotrope-like composition with methyl formate.

The relative volatility of the binary pair was determined using the PTx method described above. The total absolute pressure in a PTx cell of known volume at constant temperature was determined for each binary composition. These measurements were then reduced to the equilibrium vapor and liquid compositions in the cell using the NRTL equation.

The relationship of the measured vapor pressure of the Z-FC-1336 mzz/methyl formate mixture in the PTx unit versus composition is shown in figure 1, which shows the formation of an azeotropic and azeotrope-like composition consisting essentially of Z-FC-1336mzz and methyl formate, as shown by a mixture of about 20.4 mole% Z-1,1,1,4,4, 4-hexafluoro-2-butene with 79.6 mole% methyl formate having the highest pressure in the compositional range at that temperature. Based on these findings, it has been calculated that Z-FC-1336mzz and methyl formate form an azeotropic composition in the range of about 25.4 mole% to about 15.6 mole% Z-FC-1336mzz and about 74.6 mole% to about 84.4 mole% methyl formate (which forms an azeotropic composition that boils at a temperature of about-20 ℃ to about 100 ℃ and at a pressure of about 1.4psia (10kPa) to about 113psia (779 kPa)). Some embodiments of azeotropic compositions are listed in table 1.

Table 1: azeotropic composition

Azeotropic temperature (. degree.C.)	Azeotropic pressure (psia)	Z-FC-1336mzz (mol%)	Methyl formate (mol%)
				-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

In addition, azeotrope-like compositions comprising Z-FC-1336mzz and methyl formate may also be formed. Such azeotrope-like compositions exist in the vicinity of azeotropic compositions. Some embodiments of azeotrope-like compositions are listed in table 2. Other embodiments of azeotrope-like compositions are listed in table 3.

Table 2: azeotrope-like compositions

Components	T(℃)	Weight percentage range
			Z-FC-1336 mzz/methyl formate	-40	1-99/1-99
Z-FC-1336 mzz/methyl formate	0	1-99/1-99
			Z-FC-1336 mzz/methyl formate	20	1-99/1-99
Z-FC-1336 mzz/methyl formate	40	1-99/1-99
			Z-FC-1336 mzz/methyl formate	80	1-99/1-99
Z-FC-1336 mzz/methyl formate	120	1-99/1-99

Table 3: azeotrope-like compositions

Components	T(℃)	Weight percentage range
			Z-FC-1336 mzz/methyl formate	-40	10-90/10-90
Z-FC-1336 mzz/methyl formate	0	10-90/10-90
			Z-FC-1336 mzz/methyl formate	20	10-90/10-90
Z-FC-1336 mzz/methyl formate	40	10-90/10-90
			Z-FC-1336 mzz/methyl formate	80	10-90/10-90
Z-FC-1336 mzz/methyl formate	120	10-90/10-90

It was found by experiment that Z-FC-1336mzz forms an azeotropic or azeotrope-like composition with pentane. The relative volatility of the binary pair was determined using the PTx method described above. The total absolute pressure in a PTx cell of known volume at constant temperature was determined for each binary composition. These measurements were then reduced to the equilibrium vapor and liquid compositions in the cell using the NRTL equation.

The relationship of the measured vapor pressure of the Z-FC-1336 mzz/pentane mixture in the PTx unit versus composition is shown in figure 2, which shows 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 ℃, as shown 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 compositional range at that temperature.

Based on these findings, it has been calculated that Z-FC-1336mzz and pentane form an azeotropic composition in the range of about 48.2 mole% to about 58.7 mole% Z-FC-1336mzz and about 51.8 mole% to about 41.3 mole% pentane (which forms an azeotropic composition that boils at a temperature of about-20 ℃ to about 120 ℃ and at a pressure of about 2.2psia (15kPa) to about 182psia (1255 kPa)). Some embodiments of azeotropic compositions are listed in table 4.

Table 4: azeotropic composition

Azeotropic temperature (. degree.C.)	Azeotropic pressure (psia)	Z-FC-1336mzz (mol%)	Pentane (mol%)
				-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

In addition, azeotrope-like compositions comprising Z-FC-1336mzz and pentane may also be formed. Such azeotrope-like compositions exist in the vicinity of azeotropic compositions. Some embodiments of azeotrope-like compositions are listed in table 5. Other embodiments of azeotrope-like compositions are listed in table 6.

Table 5: azeotrope-like compositions

Components	T(℃)	Weight percentage range
			Z-FC-1336 mzz/pentane	-40	60-75/25-40
Z-FC-1336 mzz/pentane	0	60-80/20-40
			Z-FC-1336 mzz/pentane	20	60-82/28-40
Z-FC-1336 mzz/pentane	40	60-85/15-40
			Z-FC-1336 mzz/pentane	80	55-90/10-45
Z-FC-1336 mzz/pentane	120	45-99/1-55

Table 6: azeotrope-like compositions

Components	T(℃)	Weight percentage range
			Z-FC-1336 mzz/pentane	-40	62-70/30-38
Z-FC-1336 mzz/pentane	0	64-74/26-36
			Z-FC-1336 mzz/pentane	20	64-76/24-36
Z-FC-1336 mzz/pentane	40	64-78/22-36
			Z-FC-1336 mzz/pentane	80	62-84/16-38
Z-FC-1336 mzz/pentane	120	57-99/1-43

It was found by experiment that Z-FC-1336mzz forms an azeotropic or azeotrope-like composition with isopentane. The relative volatility of the binary pair was determined using the PTx method described above. The total absolute pressure in a PTx cell of known volume at constant temperature was determined for each binary composition. These measurements were then reduced to the equilibrium vapor and liquid compositions in the cell using the NRTL equation.

The relationship of the measured vapor pressure of the Z-FC-1336 mzz/isopentane mixture in the PTx unit versus composition is shown in figure 3, which shows the formation of an azeotropic and azeotrope-like composition consisting of Z-1,1,1,4,4, 4-hexafluoro-2-butene and isopentane at 19.9 ℃, as shown by a mixture of about 40.0 mole% Z-1,1,1,4,4, 4-hexafluoro-2-butene and 60.0 mole% isopentane with the highest pressure in the composition range at that temperature.

Based on these findings, it has been calculated that Z-FC-1336mzz and isopentane form an azeotropic composition in the range of about 37.1 mole% to about 48.6 mole% Z-FC-1336mzz and about 62.9 mole% to about 51.4 mole% isopentane (which forms an azeotropic composition that boils at a temperature of about-20 ℃ to about 120 ℃ and at a pressure of about 2.7psia (19kPa) to about 199psia (1372 kPa)). Some embodiments of azeotropic compositions are listed in table 7.

Table 7: azeotropic composition

Azeotropic temperature (. degree.C.)	Azeotropic pressure (psia)	Z-FC-1336mzz (mol%)	Isopentane (mol%)
				-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

In addition, azeotrope-like compositions comprising Z-FC-1336mzz and isopentane can also be formed. Such azeotrope-like compositions exist in the vicinity of azeotropic compositions. Some embodiments of azeotrope-like compositions are listed in table 8. Other embodiments of azeotrope-like compositions are listed in table 9.

Table 8: azeotrope-like compositions

Components	T(℃)	Weight percentage range
			Z-FC-1336 mzz/isopentane	-40	40-65/35-60
Z-FC-1336 mzz/isopentane	0	45-70/30-55
			Z-FC-1336 mzz/isopentane	20	45-75/25-55
Z-FC-1336 mzz/isopentane	40	45-75/25-55
			Z-FC-1336 mzz/isopentane	80	40-85/15-60
Z-FC-1336 mzz/isopentane	120	1-99/1-99

Table 9: azeotrope-like compositions

Components	T(℃)	Weight percentage range
			Z-FC-1336 mzz/isopentane	-40	49-58/42-51
Z-FC-1336 mzz/isopentane	0	53-65/35-47
			Z-FC-1336 mzz/isopentane	20	53-68/32-47
Z-FC-1336 mzz/isopentane	40	53-71/29-47
			Z-FC-1336 mzz/isopentane	80	52-77/23-48
Z-FC-1336 mzz/isopentane	120	43-89/11-57

It was found by experiment that Z-FC-1336mzz forms azeotrope-like compositions with HFC-365 mfc. The relative volatility of the binary pair was determined using the PTx method described above. The total absolute pressure in a PTx cell of known volume at constant temperature was determined for each binary composition. These measurements were then reduced to the equilibrium vapor and liquid compositions in the cell using the NRTL equation.

The relationship of measured vapor pressure versus composition of the Z-FC-1336mzz/HFC-365mfc mixture in the PTx unit is shown in fig. 4, which shows the formation of an azeotrope-like composition consisting essentially of Z-1,1,1,4,4, 4-hexafluoro-2-butene and HFC-365mfc at 50.1 ℃, such as shown by a mixture of about 1 to 99 mole% Z-1,1,1,4,4, 4-hexafluoro-2-butene and about 1 to 99 mole% HFC-365 mfc.

Some embodiments of azeotrope-like compositions are listed in table 10. Other embodiments of azeotrope-like compositions are listed in table 11.

Table 10: azeotrope-like compositions

Components	T(℃)	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

Table 11: azeotrope-like compositions

Components	T(℃)	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	-90/10
			Z-FC-1336mzz/HFC-365mfc	120	-90/10
Z-FC-1336mzz/HFC-365mfc	160	-90/10

It was found by experiment that Z-FC-1336mzz forms an azeotropic or azeotrope-like composition with trans-1, 2-dichloroethylene. The relative volatility of the binary pair was determined using the PTx method described above. The total absolute pressure in a PTx cell of known volume at constant temperature was determined for each binary composition. These measurements were then reduced to the equilibrium vapor and liquid compositions in the cell using the NRTL equation.

The measured vapor pressure versus composition of the Z-FC-1336 mzz/trans-1, 2-dichloroethylene mixture in the PTx unit is shown in figure 5, which shows the formation of an azeotropic composition consisting of Z-1,1,1,4,4, 4-hexafluoro-2-butene and trans-1, 2-dichloroethylene at 50.1 ℃ as shown by the mixture of about 64.8 mole% Z-1,1,1,4,4, 4-hexafluoro-2-butene and 35.2 mole% trans-1, 2-dichloroethylene with the highest pressure in the composition range at that temperature.

Based on these findings, it has been calculated that Z-FC-1336mzz and trans-1, 2-dichloroethylene form azeotropic compositions in the range of about 62.4 mole% to about 71.0 mole% Z-FC-1336mzz and about 37.6 mole% to about 29.0 mole% trans-1, 2-dichloroethylene (which form azeotropic compositions that boil at a temperature of about-20 ℃ to about 120 ℃ and at a pressure of about 1.6psia (11kPa) to about 170psia (1172 kPa)). Some embodiments of azeotropic compositions are listed in table 12.

Table 12: azeotropic composition

Azeotropic temperature (. degree.C.)	Azeotropic pressure (psia)	Z-FC-1336mzz (mol%)	Trans-1, 2-dichloroethylene (mol%)
				-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

In addition, azeotrope-like compositions comprising Z-FC-1336mzz and trans-1, 2-dichloroethylene may also be formed. Such azeotrope-like compositions exist in the vicinity of azeotropic compositions. Some embodiments of azeotrope-like compositions are listed in table 13. Other embodiments of azeotrope-like compositions are listed in table 14.

Table 13: azeotrope-like compositions

Components	T(℃)	Weight percentage range
			Z-FC-1336 mzz/trans-1, 2-dichloroethylene	-40	71-82/18-29
Z-FC-1336 mzz/trans-1, 2-dichloroethylene	0	67-86/14-33
			Z-FC-1336 mzz/trans-1, 2-dichloroethylene	20	65-93/7-35
Z-FC-1336 mzz/trans-1, 2-dichloroethylene	40	65-99/1-35
			Z-FC-1336 mzz/trans-1, 2-dichloroethylene	80	63-99/1-37
Z-FC-1336 mzz/trans-1, 2-dichloroethylene	120	61-99/1-39
			Z-FC-1336 mzz/trans-1, 2-dichloroethylene	160	58-99/1-42

Table 14: azeotrope-like compositions

Components	T(℃)	Weight percentage range
			Z-FC-1336 mzz/trans-1, 2-dichloroethylene	-40	72-80/20-38
Z-FC-1336 mzz/trans-1, 2-dichloroethylene	0	69-83/17-31
			Z-FC-1336 mzz/trans-1, 2-dichloroethylene	20	68-86/14-32
Z-FC-1336 mzz/trans-1, 2-dichloroethylene	40	68-90/10-32
			Z-FC-1336 mzz/trans-1, 2-dichloroethylene	80	66-99/1-34
Z-FC-1336 mzz/trans-1, 2-dichloroethylene	120	65-99/1-35
			Z-FC-1336 mzz/trans-1, 2-dichloroethylene	160	65-99/1-35

It was found by experimentation that Z-FC-1336mzz forms azeotrope-like compositions with HFC-245 fa. The relative volatility of the binary pair was determined using the PTx method described above. The total absolute pressure in a PTx cell of known volume at constant temperature was determined for each binary composition. These measurements were then reduced to the equilibrium vapor and liquid compositions in the cell using the NRTL equation.

The measured vapor pressure versus composition of the Z-FC-1336mzz/HFC-245fa mixture in the PTx unit is shown in figure 6, which shows the formation of azeotrope-like compositions consisting essentially of Z-1,1,1,4,4, 4-hexafluoro-2-butene and HFC-245fa at 19.9 c, as shown 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 having a vapor pressure of about 17psia (117kPa), and as shown by mixtures of about 94 to 99 mole% Z-1,1,1,4,4, 4-hexafluoro-2-butene and 1 to 6 mole% HFC-245fa having a vapor pressure of about 9psia (62 kPa).

Some embodiments of azeotrope-like compositions are listed in table 15. Other embodiments of azeotrope-like compositions are listed in table 16.

Table 15: azeotrope-like compositions

Components	T(℃)	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(℃)	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 by experiment that Z-FC-1336mzz forms azeotrope-like compositions with dimethoxymethane. The relative volatility of the binary pair was determined using the PTx method described above. The total absolute pressure in a PTx cell of known volume at constant temperature was determined for each binary composition. These measurements were then reduced to the equilibrium vapor and liquid compositions in the cell using the NRTL equation.

The relationship of the measured vapor pressure of the Z-FC-1336 mzz/dimethoxymethane mixture versus composition in the PTx unit is shown in figure 7, which shows the formation of an azeotrope-like composition consisting of Z-1,1,1,4,4, 4-hexafluoro-2-butene and dimethoxymethane, such as a mixture of about 1 to 99 mole% Z-1,1,1,4,4, 4-hexafluoro-2-butene and about 1 to 99 mole% dimethoxymethane, at 49.99 ℃ and about 22.5psia (155 kPa).

Some embodiments of azeotrope-like compositions are listed in table 17. Other embodiments of azeotrope-like compositions are listed in table 18.

Table 17: azeotrope-like compositions

Components	T(℃)	Weight percentage range
			Z-FC-1336 mzz/dimethoxymethane	-40	1-99/1-99
Z-FC-1336 mzz/dimethoxymethane	0	1-99/1-99
			Z-FC-1336 mzz/dimethoxymethane	40	1-99/1-99
Z-FC-1336 mzz/dimethoxymethane	80	1-99/1-99
			Z-FC-1336 mzz/dimethoxymethane	120	1-99/1-99
Z-FC-1336 mzz/dimethoxymethane	160	1-99/1-99

Table 18: azeotrope-like compositions

Components	T(℃)	Weight percentage range
			Z-FC-1336 mzz/dimethoxymethane	-40	5-95/5-95
Z-FC-1336 mzz/dimethoxymethane	0	5-95/5-95
			Z-FC-1336 mzz/dimethoxymethane	40	5-95/5-95
Z-FC-1336 mzz/dimethoxymethane	80	5-95/5-95
			Z-FC-1336 mzz/dimethoxymethane	120	5-95/5-95
Z-FC-1336 mzz/dimethoxymethane	160	5-95/5-95

It was found by experiment that Z-FC-1336mzz forms an azeotropic or azeotrope-like composition with cyclopentane. The relative volatility of the binary pair was determined using the PTx method described above. The total absolute pressure in a PTx cell of known volume at constant temperature was determined for each binary composition. These measurements were then reduced to the equilibrium vapor and liquid compositions in the cell using the NRTL equation.

The relationship of the measured vapor pressure of the Z-FC-1336 mzz/cyclopentane mixture in the PTx unit versus composition is shown in figure 8, which shows the formation of an azeotropic composition consisting of Z-1,1,1,4,4, 4-hexafluoro-2-butene and cyclopentane as shown 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 in the compositional range at this temperature.

Based on these findings, it has been calculated that Z-FC-1336mzz and cyclopentane form an azeotropic composition in the range of about 64.2 mole% to about 74.4 mole% Z-FC-1336mzz and about 35.8 mole% to about 25.6 mole% cyclopentane (which forms an azeotropic composition that boils at a temperature of about-20 ℃ to about 150 ℃ and at a pressure of about 1.7psia (12kPa) to about 302psia (2082 kPa)). Some embodiments of azeotropic compositions are listed in table 18.

Table 18: azeotropic composition

Azeotropic temperature (. degree.C.)	Azeotropic pressure (psia)	Z-FC-1336mzz (mol%)	Cyclopentane (mol%)
				-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

In addition, azeotrope-like compositions comprising Z-FC-1336mzz and cyclopentane may also be formed. Such azeotrope-like compositions exist in the vicinity of azeotropic compositions. Some embodiments of azeotrope-like compositions are listed in table 19. Other embodiments of azeotrope-like compositions are listed in table 20.

Table 19: azeotrope-like compositions

Components	T(℃)	Weight percentage range
			Z-FC-1336 mzz/cyclopentane	-20	77-86/14-23
Z-FC-1336 mzz/cyclopentane	0	76-87/13-24
			Z-FC-1336 mzz/cyclopentane	40	74-90/10-26
Z-FC-1336 mzz/cyclopentane	80	72-99/1-28
			Z-FC-1336 mzz/cyclopentane	120	70-99/1-30
Z-FC-1336 mzz/cyclopentane	150	68-99/1-32

Table 20: azeotrope-like compositions

Components	T(℃)	Weight of hundredRange of ratio
			Z-FC-1336 mzz/cyclopentane	-20	80-86/14-20
Z-FC-1336 mzz/cyclopentane	0	80-87/13-20
			Z-FC-1336 mzz/cyclopentane	40	80-90/10-206
Z-FC-1336 mzz/cyclopentane	80	80-95/5-20
			Z-FC-1336 mzz/cyclopentane	120	80-95/5-20
Z-FC-1336 mzz/cyclopentane	150	80-99/5-20

The azeotropic or azeotrope-like compositions of the present invention may be prepared by any convenient method, including mixing or combining the desired amounts. In one embodiment of the invention, an azeotropic or azeotrope-like composition is prepared by weighing the desired amounts of the components and then combining them in a suitable container.

The azeotropic or azeotrope-like compositions of the present invention are useful in a wide range of applications, including their use as aerosol propellants, refrigerants, solvents, cleaning agents, blowing agents for thermoplastic and thermoset foams (foam expansion agents), heat transfer media, gaseous dielectrics, fire extinguishing and flame retarding agents, power cycle working fluids, polymerization media, particle removal fluids, carrier fluids, buffing abrasive agents, and displacement drying agents.

One embodiment of the present 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 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.

Another embodiment of the present invention provides a method 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 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.

Another embodiment of the present 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, 3-pentafluorobutane, trans-1, 2-dichloroethylene, 1,1,1, 3, 3-pentafluoropropane, dimethoxymethane and cyclopentane.

Another embodiment of the present invention provides a method of 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 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.

Another embodiment of this invention provides a process for using an azeotropic or azeotrope-like composition as 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 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.

Another embodiment of the present invention provides a method for extinguishing or retarding a fire. The process comprises using an azeotropic or azeotrope-like composition as a fire extinguishing or flame retardant, 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.

Another embodiment of the present invention provides a process for 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 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.

Claims (16)

1. A composition consisting essentially of:

(a) z-1,1,1,4,4, 4-hexafluoro-2-butene; and

(b) methyl formate; wherein said methyl formate is present in an effective amount to form an azeotropic combination with said Z-1,1,1,4,4, 4-hexafluoro-2-butene.

2. A composition consisting essentially of:

(a) z-1,1,1,4,4, 4-hexafluoro-2-butene; and

(b) methyl formate; wherein said methyl formate is present in an effective amount to form an azeotrope-like combination with said Z-1,1,1,4,4, 4-hexafluoro-2-butene.

3. A composition consisting essentially of:

(a) z-1,1,1,4,4, 4-hexafluoro-2-butene; and

(b)1, 1,1, 3, 3-pentafluorobutane; wherein said 1,1,1, 3, 3-pentafluorobutane is present in an effective amount to form an azeotrope-like combination with said Z-1,1,1,4,4, 4-hexafluoro-2-butene.

4. A composition consisting essentially of:

(a) z-1,1,1,4,4, 4-hexafluoro-2-butene; and

(b) trans-1, 2-dichloroethylene; wherein said trans-1, 2-dichloroethylene is present in an effective amount to form an azeotropic combination with said Z-1,1,1,4,4, 4-hexafluoro-2-butene.

5. A composition consisting essentially of:

(a) z-1,1,1,4,4, 4-hexafluoro-2-butene; and

(b) trans-1, 2-dichloroethylene; wherein said trans-1, 2-dichloroethylene is present in an effective amount to form an azeotrope-like combination with said Z-1,1,1,4,4, 4-hexafluoro-2-butene.

6. A composition consisting essentially of:

(a) z-1,1,1,4,4, 4-hexafluoro-2-butene; and

(b)1, 1,1, 3, 3-pentafluoropropane; wherein said 1,1,1, 3, 3-pentafluoropropane is present in an effective amount to form an azeotrope-like combination with said Z-1,1,1,4,4, 4-hexafluoro-2-butene.

7. A composition consisting essentially of:

(a) z-1,1,1,4,4, 4-hexafluoro-2-butene; and

(b) dimethoxymethane; wherein said dimethoxymethane is present in an effective amount to form an azeotrope-like combination with said Z-1,1,1,4,4, 4-hexafluoro-2-butene.

8. A composition consisting essentially of:

(a) z-1,1,1,4,4, 4-hexafluoro-2-butene; and

(b) cyclopentane; wherein said cyclopentane is present in an effective amount to form an azeotropic combination with said Z-1,1,1,4,4, 4-hexafluoro-2-butene.

9. A composition consisting essentially of:

(a) z-1,1,1,4,4, 4-hexafluoro-2-butene; and

(b) cyclopentane; wherein said cyclopentane is present in an effective amount to form an azeotrope-like combination with said Z-1,1,1,4,4, 4-hexafluoro-2-butene.

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

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

12. A process comprising 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, 1,1,1, 3, 3-pentafluorobutane, trans-1, 2-dichloroethylene, 1,1,1, 3, 3-pentafluoropropane, dimethoxymethane and cyclopentane.

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

14. A process comprising using an azeotropic or azeotrope-like composition as a heat transfer medium, 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, 1,1,1, 3, 3-pentafluorobutane, trans-1, 2-dichloroethylene, 1,1,1, 3, 3-pentafluoropropane, dimethoxymethane and cyclopentane.

15. A process for extinguishing or retarding a fire comprising using an azeotropic or azeotrope-like composition as a fire extinguishing or retarding 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, 1,1,1, 3, 3-pentafluorobutane, trans-1, 2-difluoroethylene, 1,1,1, 3, 3-pentafluoropropane, dimethoxymethane and cyclopentane.

16. A process comprising using an azeotropic or azeotrope-like composition as a dielectric, 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, 1,1,1, 3, 3-pentafluorobutane, trans-1, 2-dichloroethylene, 1,1,1, 3, 3-pentafluoropropane, dimethoxymethane and cyclopentane.