# Patent

## Title
Hydrofluorocarbon compositions

## Abstract

Refrigerant compositions include mixtures of difluoromethane and isobutane, butane, propylene or cyclopropane; pentafluoroethane and propylene or cyclopropane; 1,1,2,2-tetrafluoroethane and propane; 1,1,1,2-tetrafluoroethane and cyclopropane; 1,1,1-trifluoroethane and DME or propylene; 1,1-difluoroethane and propane, isobutane, butane or cyclopropane; fluoroethane and propane or cyclopropane; 1,1,1,2,2,3,3-heptafluoropropane and butane, cyclopropane, DME, isobutane or propane; or 1,1,1,2,3,3,3-heptafluoropropane and butane, cyclopropane, isobutane or propane.

## Background
This application is a divisional of U.S. application Ser. No. 09/384,599 filed Aug. 27, 1999, now U.S. Pat. No. 6,531,441 which is a divisional of U.S. application Ser. No. 09/014,449 filed Jan. 28, 1998, now U.S. Pat. No. 6,001,273, which is a divisional of U.S. application Ser. No. 08/842,164 filed Apr. 23, 1997, now U.S. Pat. No. 5,785,883, which is a divisional of U.S. application Ser. No. 08,435,108 filed May 4, 1995, now U.S. Pat. No. 5,672,293, which is a divisional of U.S. application Ser. No. 08/208,777 filed Mar. 11, 1994, now U.S. Pat. No. 5,417,871.


FIELD OF THE INVENTION
This invention relates to refrigerant compositions that include a hydrofluorocarbon as a component. These compositions are also useful as cleaning agents, expansion agents for polyolefins and polyurethanes, aerosol propellants, refrigerants, heat transfer media, gaseous dielectrics, fire extinguishing agents, power cycle working fluids, polymerization media, particulate removal fluids, carrier fluids, buffing abrasive agents, and displacement drying agents.
BACKGROUND OF THE INVENTION
Fluorinated hydrocarbons have many uses, one of which is as a refrigerant. Such refrigerants include dichlorodifluoromethane (CFC-12) and chlorodifluoromethane (HCFC-22).
In recent years it has been pointed out that certain kinds of fluorinated hydrocarbon refrigerants released into the atmosphere may adversely affect the stratospheric ozone layer. Although this proposition has not yet been completely established, there is a movement toward the control of the use and the production of certain chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) under an international agreement.
Accordingly, there is a demand for the development of refrigerants that have a lower ozone depletion potential than existing refrigerants while still achieving an acceptable performance in refrigeration applications. Hydrofluorocarbons (HFCs) have been suggested as replacements for CFCs and HCFCs since HFCs have no chlorine and therefore have zero ozone depletion potential.
In refrigeration applications, a refrigerant is often lost during operation through leaks in shaft seals, hose connections, soldered joints and broken lines. In addition, the refrigerant may be released to the atmosphere during maintenance procedures on refrigeration equipment. If the refrigerant is not a pure component or an azeotropic or azeotrope-like composition, the refrigerant composition may change when leaked or discharged to the atmosphere from the refrigeration equipment, which may cause the refrigerant to become flammable or to have poor refrigeration performance.
Accordingly, it is desirable to use as a refrigerant a single fluorinated hydrocarbon or an azeotropic or azeotrope-like composition that includes at least one fluorinated hydrocarbon.
Mixtures that include a fluorinated hydrocarbon may also be used as a cleaning agent or solvent to clean, for example, electronic circuit boards. It is desirable that the cleaning agents be azeotropic or azeotrope-like because in vapor degreasing operations the cleaning agent is generally redistilled and reused for final rinse cleaning.
Azeotropic or azeotrope-like compositions that include a fluorinated hydrocarbon are also useful as blowing agents in the manufacture of closed-cell polyurethane, phenolic and thermoplastic foams, as propellants in aerosols, as heat transfer media, gaseous dielectrics, fire extinguishing agents, power cycle working fluids such as for heat pumps, inert media for polymerization reactions, fluids for removing particulates from metal surfaces, as carrier fluids that may be used, for example, to place a fine film of lubricant on metal parts, as buffing abrasive agents to remove buffing abrasive compounds from polished surfaces such as metal, as displacement drying agents for removing water, such as from jewelry or metal parts, as resist developers in conventional circuit manufacturing techniques including chlorine-type developing agents, or as strippers for photoresists when used with, for example, a chlorohydrocarbon such as 1,1,1-trichloroethane or trichloroethylene.
SUMMARY OF THE INVENTION
The present invention relates to the discovery of refrigerant compositions of difluoromethane (HFC-32) and isobutane, butane, propylene or cyclopropane; pentafluoroethane (HFC-125) and propylene or cyclopropane; 1,1,2,2-tetrafluoroethane (HFC-134) and propane; 1,1,1,2-tetrafluoroethane (HFC-134a) and cyclopropane; 1,1,1-trifluoroethane (HFC-143a) and dimethyl ether (DME) or propylene; 1,1-difluoroethane (HFC-152a) and propane, isobutane, butane or cyclopropane; fluoroethane (HFC-161) and propane or cyclopropane; 1,1,1,2,2,3,3-heptafluoropropane (HFC-227ca) and butane, cyclopropane, DME, isobutane or propane; or 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea) and butane, cyclopropane, isobutane or propane. These compositions are also useful as cleaning agents, expansion agents for polyolefins and polyurethanes, aerosol propellants, heat transfer media, gaseous dielectrics, fire extinguishing agents, power cycle working fluids, polymerization media, particulate removal fluids, carrier fluids, buffing abrasive agents, and displacement drying agents.
Further, the invention relates to the discovery of binary azeotropic or azeotrope-like compositions comprising effective amounts of difluoromethane (HFC-32) and isobutane, butane, propylene or cyclopropane; pentafluoroethane (HFC-125) and propylene or cyclopropane; 1,1,2,2-tetrafluoroethane (HFC-134) and propane; 1,1,1,2-tetrafluoroethane (HFC-134a) and cyclopropane; 1,1,1-trifluoroethane (HFC-143a) and propylene; 1,1-difluoroethane (HFC-152a) and propane, isobutane, butane and cyclopropane; fluoroethane (HFC-161) and propane or cyclopropane; 1,1,1,2,2,3,3-heptafluoropropane (HFC-227ca) and butane, cyclopropane, DME, isobutane or propane; or 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea) and butane, cyclopropane, isobutane or propane to form an azeotropic or azeotrope-like composition.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a graph of the vapor pressure of liquid mixtures of HFC-32 and isobutane at 25′C;
FIG. 2 is a graph of the vapor pressure of liquid mixtures of HFC-32 and butane at 25′C;
FIG. 3 is a graph of the vapor pressure of liquid mixtures of HFC-32 and propylene at 25′C;
FIG. 4 is a graph of the vapor pressure of liquid mixtures of HFC-32 and cyclopropane at 0′C;
FIG. 5 is a graph of the vapor pressure of liquid mixtures of HFC-125 and propylene at 25′C;
FIG. 6 is a graph of the vapor pressure of liquid mixtures of HFC-125 and cyclopropane at 0′C;
FIG. 7 is a graph of the vapor pressure of liquid mixtures of HFC-134 and propane at 15′C;
FIG. 8 is a graph of the vapor pressure of liquid mixtures of HFC-134 a and cyclopropane at 0.01′C;
FIG. 9 is a graph of the vapor pressure of liquid mixtures of HFC-143a and propylene at 25′C;
FIG. 10 is a graph of the vapor pressure of liquid mixtures of HFC-152a and propane at 25′C;
FIG. 11 is a graph of the vapor pressure of liquid mixtures of HFC-152a and isobutane at 25′C;
FIG. 12 is a graph of the vapor pressure of liquid mixtures of HFC-152a and butane at 25′C;
FIG. 13 is a graph of the vapor pressure of liquid mixtures of HFC-152a and cyclopropane at 25′C;
FIG. 14 is a graph of the vapor pressure of liquid mixtures of HFC-161 and propane at 25′C;
FIG. 15 is a graph of the vapor pressure of liquid mixtures of HFC-161 and cyclopropane at 25′C;
FIG. 16 is a graph of the vapor pressure of liquid mixtures of HFC-227ca and butane at 25′C;
FIG. 17 is a graph of the vapor pressure of liquid mixtures of HFC-227ca and cyclopropane at 25′C;
FIG. 18 is a graph of the vapor pressure of liquid mixtures of HFC-227ca and DME at 25′C;
FIG. 19 is a graph of the vapor pressure of liquid mixtures of HFC-227ca and isobutane at 25′C;
FIG. 20 is a graph of the vapor pressure of liquid mixtures of HFC-227ca and propane at 25′C;
FIG. 21 is a graph of the vapor pressure of liquid mixtures of HFC-227ea and butane at 25′C;
FIG. 22 is a graph of the vapor pressure of liquid mixtures of HFC-227ea and cyclopropane at 25′C;
FIG. 23 is a graph of the vapor pressure of liquid mixtures of HFC-227ea and isobutane at 25′C; and
FIG. 24 is a graph of the vapor pressure of liquid mixtures of HFC-227ea and propane at 25′C



DETAILED DESCRIPTION
The present invention relates to compositions of difluoromethane (HFC-32) and isobutane, butane, propylene or cyclopropane; pentafluoroethane (HFC-125) and propylene and cyclopropane; 1,1,2,2-tetrafluoroethane (HFC-134) and propane; 1,1,1,2-tetrafluoroethane (HFC-134a) and cyclopropane; 1,1,1-trifluoroethane (HFC-143a) and dimethyl ether (DME) or propylene; 1,1-difluoroethane (HFC-152a) and propane, isobutane, butane and cyclopropane; fluoroethane (HFC-161) and propane or cyclopropane; 1,1,1,2,2,3,3-heptafluoropropane (HFC-227ca) and butane, cyclopropane, DME, isobutane or propane; or 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea) and butane, cyclopropane, isobutane or propane.
The present invention also relates to the discovery of azeotropic or azeotrope-like compositions of effective amounts of difluoromethane (HFC-32) and isobutane, butane, propylene or cyclopropane; pentafluoroethane (HFC-125) and propylene or cyclopropane; 1,1,2,2-tetrafluoroethane (HFC-134) and propane; 1,1,1,2-tetrafluoroethane (HFC-134a) and cyclopropane; 1,1,1-trifluoroethane (HFC-143a) propylene; 1,1-difluoroethane (HFC-152a and propane, isobutane, butane and cyclopropane; fluoroethane (HFC-161) and propane or cyclopropane; 1,1,1,2,2,3,3-heptafluoropropane (HFC-227ca) and butane, cyclopropane, DME, isobutane or propane; or 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea) and butane, cyclopropane, isobutane or propane to form an azeotropic or azeotrope-like composition.
By “azeotropic” composition is meant a constant boiling liquid admixture of two or more substances that behaves as a single substance. One way to characterize an azeotropic composition is that the vapor produced by partial evaporation or distillation of the liquid has the same composition as the liquid from which it was evaporated or distilled, that is, the admixture distills/refluxes without compositional change. Constant boiling compositions are characterized as azeotropic because they exhibit either a maximum or minimum boiling point, as compared with that of the non-azeotropic mixtures of the same components.
By “azeotrope-like” composition is meant a constant boiling, or substantially constant boiling, liquid admixture of two or more substances that behaves as a single substance. One way to characterize an azeotrope-like composition is that the vapor produced by partial evaporation or distillation of the liquid has substantially the same composition as the liquid from which it was evaporated or distilled, that is, the admixture distills/refluxes without substantial composition change.
It is recognized in the art that a composition is azeotrope-like if, after 50 weight percent of the composition is removed such as by evaporation or boiling off, the difference in vapor pressure between the original composition and the composition remaining after 50 weight percent of the original composition has been removed is about 10 percent or less, when measured in absolute units. By absolute units, it is meant measurements of pressure and, for example, psia, atmospheres, bars, torr, dynes per square centimeter, millimeters of mercury, inches of water and other equivalent terms well known in the art. If an azeotrope is present, there is nodifference in vapor pressure between the original composition and the composition remaining after 50 weight percent of the original composition has been removed.
Therefore, included in this invention are compositions of effective amounts of difluoromethane (HFC-32) and isobutane, butane, propylene or cyclopropane; pentafluoroethane (HFC-125) and propylene or cyclopropane; 1,1,2,2-tetrafluoroethane (HFC-134) and propane; 1,1,1,2-tetrafluoroethane (HFC-134a) and cyclopropane; 1,1,1-trifluoroethane (HFC-143a) and propylene; 1,1-difluoroethane (HFC-152a) and propane, isobutane, butane and cyclopropane; fluoroethane (HFC-161) and propane or cyclopropane; 1,1,1,2,2,3,3-heptafluoropropane (HFC-227ca) and butane, cyclopropane, DME, isobutane or propane; or 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea) and butane, cyclopropane, isobutane or propane such that after 50 weight percent of an original composition is evaporated or boiled off to produce a remaining composition, the difference in the vapor pressure between the original composition and the remaining composition is 10 percent or less.
For compositions that are azeotropic, there is usually some range of compositions around the azeotrope that, for a maximum boiling azeotrope, have boiling points at a particular pressure higher than the pure components of the composition at that pressure and have vapor pressures lower at a particular temperature than the pure components of the composition at that temperature, and that, for a minimum boiling azeotrope, have boiling points at a particular pressure lower than the pure components of the composition at that pressure and have vapor pressures higher at a particular temperature than the pure components of the composition at that temperature. Boiling temperatures and vapor pressures above or below that of the pure components are caused by unexpected intermolecular forces between and among the molecules of the compositions, which can be a combinationof repulsive and attractive forces such as van der Waals forces and hydrogen bonding.
The range of compositions that have a maximum or minimum boiling point at a particular pressure, or a maximum or minimum vapor pressure at a particular temperature, may or may not be coextensive with the range of compositions that are substantially constant boiling. In those cases where the range of compositions that have maximum or minimum boiling temperatures at a particular pressure, or maximum or minimum vapor pressures at a particular temperature, are broader than the range of compositions that are substantially constant boiling according to the change in vapor pressure of the composition when 50 weight percent is evaporated, the unexpected intermolecular forces are nonetheless believed important in that the refrigerant compositions having those forces that are not substantially constant boiling may exhibit unexpected increases in the capacity or efficiency versus the components of the refrigerant composition.
The components of the compositions of this invention have the following vapor pressures at 25′C.















COMPONENTS
PSIA
KPA




















HFC-32
246.7
1701 



HFC-125
199.1
1373 



HFC-134
76.1
525



HFC-134a
98.3
677



HFC-143a
180.6
1245 



HFC-152a
85.8
591



HFC-161
130.2
898



HFC-227ca
63.8
440



HFC-227ea
66.6
459



butane
35.2
243



cyclopropane
105.0
724



DME
85.7
591



isobutane
50.5
348



propane
137.8
950



propylene
165.9
1144 










Substantially constant boiling, azeotropic or azeotrope-like compositions of this invention comprise the following (all compositions are measured at 25′C):













WEIGHT RANGES
PREFERRED


COMPONENTS
(wt. %/wt/%)
(wt. %/wt. %)







HFC-32/isobutane
61-99/1-39
70-99/1-30


HFC-32/butane
65-99/1-35
70-99/1-30


HFC-32/propylene
26-99/1-74
70-99/1-30


HFC-32/cyclopropane
54-99/1-46
54-99/1-46


HFC-125/propylene
 1-99/1-99
60-99/1-40


HFC-125/cyclopropane
66-99/1-34
66-99/1-34


HFC-134/propane
 1-75/25-99
 30-75/25-70


HFC-134a/cyclopropane
 1-99/1-99
50-99/1-50


HFC-143a/propylene
 1-99/1-99
70-99/1-30


HFC-152a/propane
 1-78/22-99
 30-78/22-70


HFC-152a/isobutane
44-99/1-56
60-99/1-40


HFC-152a/butane
54-99/1-46
70-99/1-30


HFC-152a/cyclopropane
 1-99/1-99
20-99/1-80


HFC-161/propane
 1-99/1-99
20-99/1-80


HFC-161/cyclopropane
 1-99/1-99
40-99/1-60


HFC-227ca/butane
61-99/1-39
70-99/1-30


HFC-227ca/cyclopropane
 27-82/18-73
 40-82/18-60


HFC-227ca/DME
 1-92/8-99
60-92/8-40


HFC-227ca/isobutane
53-92/8-47
60-92/8-40


HFC-227ca/propane
 1-79/21-99
 30-79/21-70


HFC-227ea/butane
61-99/1-39
70-99/1-30


HFC-227ea/cyclopropane
 24-83/17-76
 40-83/17-60


HFC-227ea/isobutane
52-99/1-48
60-99/1-40


HFC-227ea/propane
 1-79/21-99
 40-79/21-60









For purposes of this invention, “effective amount” is defined as theamount of each component of the inventive compositions which, when combined, results in the formation of an azeotropic or azeotrope-like composition. This definition includes the amounts of each component, which amounts may vary depending on the pressure applied to the composition so long as the azeotropic or azeotrope-like compositions continue to exist at the different pressures, but with possible different boiling points.
Therefore, effective amount includes the amounts, such as may be expressed in weight percentages, of each component of the compositions of the instant invention which form azeotropic or azeotrope-like compositions at temperatures or pressures other than as described herein.
For the purposes of this discussion, azeotropic or constant-boiling is intended to mean also essentially azeotropic or essentially-constant boiling. In other words, included within the meaning of these terms are not only the true azeotropes described above, but also other compositions containing the same components in different proportions, which are true azeotropes at other temperatures and pressures, as well as those equivalent compositions which are part of the same azeotropic system and are azeotrope-like in their properties. As is well recognized in this art, there is a range of compositions which contain the same components as the azeotrope, which will not only exhibit essentially equivalent properties for refrigeration and other applications, but which will also exhibit essentially equivalent properties to the true azeotropic composition in terms of constant boiling characteristics or tendency not to segregate or fractionate on boiling.
It is possible to characterize, in effect, a constant boiling admixture which may appear under many guises, depending upon the conditions chosen, by any of several criteria:

    
    
        The composition can be defined as an azeotrope of A, B, C (and D . . . ) since the very term “azeotrope” is at once both definitive and limitative, and requires that effective amounts of A, B, C (and D . . . ) for this unique composition of matter which is a constant boiling composition.
        It is well known by those skilled in the art, that, at different pressures, the composition of a given azeotrope will vary at least to some degree, and changes in pressure will also change, at least to some degree, the boiling point temperature. Thus, an azeotrope of A, B, C (and D . . . ) represents a unique type of relationship but with a variable composition which depends on temperature and/or pressure. Therefore, compositional ranges, rather than fixed compositions, are often used to define azeotropes.
        The composition can be defined as a particular weight percent relationship or mole percent relationship of A, B, C (and D . . . ), while recognizing that such specific values point out only one particular relationship and that in actuality, a series of such relationships, represented by A, B, C (and D . . . ) actually exist for a given azeotrope, varied by the influence of pressure.
        An azeotrope of A, B, C (and D . . . ) can be characterized by defining the compositions as an azeotrope characterized by a boiling point at a given pressure, thus giving identifying characteristics without unduly limiting the scope of the invention by a specific numerical composition, which is limited by and is only as accurate as the analytical equipment available.
    
    


The azeotrope or azeotrope-like compositions of the present invention can be prepared by any convenient method including mixing or combining the desired amounts. A preferred method is to weigh the desired component amounts and thereafter combine them in an appropriate container.
Specific examples illustrating the invention are given below. Unless otherwise stated therein, all percentages are by weight. It is to be understood that these examples are merely illustrative and in no way are to be interpreted as limiting the scope of the invention.
EXAMPLE 1
Phase Study
A phase study shows the following composition is azeotropic. The temperature is 25′C.














Vapor Press.













Composition
Weight Percents
psia
kPa
















HFC-32/isobutane
93.8/6.2 
249.6
1721



HFC-32/butane
99.0/1.0 
246.8
1702



HFC-32/propylene
81.0/19.0
261.5
1803



HFC-32/cyclopropane
85.2/14.8
260.6
1797



HFC-125/propylene
79.5/20.5
229.1
1580



HFC-125/cyclopropane
91.3/8.7 
209.6
1445



HFC-134/propane
52.3/47.7
164.3
1132



HFC-134a/cyclopropane
65.5/34.5
137.5
 948



HFC-143a/propylene
89.6/10.4
181.2
1249



HFC-152a/propane
45.9/54.1
155.1
1069



HFC-152a/isobutane
75.5/24.5
97.0
 669



HFC-152a/butane
85.0/15.0
90.5
 624



HFC-152a/cyclopropane
44.3/55.7
117.8
 812



HFC-161/propane
44.5/55.5
161.2
1111



HFC-161/cyclopropane
63.4/36.6
140.8
 971



HFC-227ca/butane
84.4/15.6
77.5
 534



HFC-227ca/cyclopropane
55.8/44.2
126.5
 872



HFC-227ca/DME
75.6/24.4
101.0
 696



HFC-227ca/isobutane
76.8/23.2
90.0
 621



HFC-227ca/propane
51.6/48.4
159.8
1102



HFC-227ca/butane
85.8/14.2
76.8
 530



HFC-227ea/cyclopropane
55.2/44.8
125.1
 863



HFC-227ea/isobutane
77.6/22.4
88.8
 612



HFC-227ea/propane
50.4/49.6
157.4
1085










EXAMPLE 2
Impact of Vapor Leakage on Vapor Pressure at 25′C
A vessel is charged with an initial liquid composition at 25′C. The liquid, and the vapor above the liquid, are allowed to come to equilibrium, and the vapor pressure in the vessel is measured. Vapor is allowed to leak from the vessel, while the temperature is held constant at 25′C, until 50 weight percent of the initial charge is removed, at which time the vapor pressure of the composition remaining in the vessel is measured. The results are summarized below.














0 wt %
50 wt %



Refrigerant
evaporated
evaporated
0% change in












Composition
psia
kPa
psia
kPa
vapor pressure















HFC-32/isobutane







93.8/6.2
249.6
1721
249.6
1721
0.0


99/1
247.8
1709
247.5
1706
0.1


70/30
240.8
1660
230.3
1588
4.4


60/40
234.8
1619
209.6
1445
10.7


61/39
235.5
1624
212.3
1464
9.9


HFC-32/butane


99.0/1.0
246.8
1702
246.8
1702
0.0


70/30
232.3
1602
217.4
1499
6.4


65/35
229.1
1580
206.6
1424
9.8


HFC-32/propylene


81.0/19.0
261.5
1803
261.5
1803
0.0


99/1
248.8
1715
248.0
1710
0.3


70/30
259.3
1788
257.7
1777
0.6


60/40
254.3
1753
248.8
1715
2.2


50/50
246.7
1701
235.7
1625
4.5


40/60
236.6
1631
219.6
1514
7.2


30/70
223.8
1543
202.6
1397
9.5


29/71
222.3
1533
200.9
1385
9.6


27/73
219.3
1512
197.6
1362
9.9


26/74
217.8
1502
196.0
1351
10.0


HFC-32/cyclopropane


85.2/14.8
260.6
1797
260.6
1797
0.0


99/1
249.3
1719
248.2
1711
0.4


60/40
250.5
1727
236.5
1631
5.6


54/46
246.0
1696
222.5
1534
9.6


53/47
245.2
1691
219.7
1515
10.4


HFC-125/propylene


79.5/20.5
229.1
1580
229.1
1580
0.0


90/10
224.8
1550
222.4
1533
1.1


99/1
203.9
1406
201.8
1391
1.0


70/30
227.4
1568
225.9
1558
0.7


50/50
217.2
1498
206.5
1424
4.9


40/60
209.9
1447
194.1
1338
7.5


30/70
201.2
1387
183.1
1262
9.0


20/80
191.1
1318
174.8
1205
8.5


10/90
179.3
1236
169.3
1167
5.6


1/99
167.4
1154
166.2
1146
0.7


HFC-125/cyclopropane


91.3/8.7
209.6
1445
209.6
1445
0.0


99/1
202.2
1394
201.3
1388
0.4


66/34
194.9
1344
176.5
1217
9.4


65/35
194.1
1338
174.2
1201
10.3


HFC-134/propane


90/10
140.0
965
83.6
576
40.3


75.6/24.4
158.9
1095
143.0
986
10.0


52.3/47.7
164.3
1132
164.3
1132
0.0


25/75
157.3
1085
152.1
1049
3.3


1/99
138.5
955
137.8
950
0.5


HFC-134a/cyclopropane


65.5/34.5
137.5
948
137.5
948
0.0


90/10
126.8
874
116.8
805
7.9


95/5
117.1
807
106.2
732
9.3


99/1
103.2
712
99.5
686
3.6


30/70
129.4
892
119.4
823
7.7


15/85
120.2
829
109.5
755
8.9


10/90
115.9
799
107.5
741
7.2


1/99
106.3
733
105.2
725
1.0


HFC-143a/propylene


89.6/10.4
181.2
1249
181.2
1249
0.0


99/1
180.7
1246
180.7
1246
0.0


60/40
178.4
1230
178.1
1228
0.2


40/60
174.7
1205
174.2
1201
0.3


20/80
170.5
1176
170.0
1172
0.3


1/99
166.2
1146
166.1
1145
0.1


HFC-152a/propane


45.9/54.1
155.1
1069
155.1
1069
0.0


60/40
153.7
1060
152.2
1049
1.0


70/30
151.0
1041
146.1
1007
3.2


78/22
147.5
1017
134.5
927
8.8


79/21
147.0
1014
131.9
909
10.3


30/70
153.2
1056
152.0
1048
0.8


20/80
149.9
1034
147.6
1018
1.5


10/90
144.8
998
142.6
983
1.5


1/99
138.6
956
138.2
953
0.3


HFC-152a/isobutane


75.5/24.5
97.0
669
97.0
669
0.0


90/10
94.7
653
92.5
638
2.3


99/1
87.3
602
86.3
595
1.1


60/40
95.7
660
93.9
647
1.9


40/60
90.4
623
79.2
546
12.4


43/57
91.5
631
82.3
567
10.1


44/56
91.8
633
83.3
574
9.3


HFC-152a/butane


85.0/15.0
90.5
624
90.5
624
0.0


95/5
88.9
613
88.2
608
0.8


99/1
86.6
597
86.2
594
0.5


70/30
89.0
614
87.4
603
1.8


60/40
87.1
601
82.4
568
5.4


53/47
85.3
588
76.7
529
10.1


54/46
85.6
590
77.6
535
9.3


HFC-152a/cyclopropane


44.3/55.7
117.8
812
117.8
812
0.0


70/30
113.8
785
110.9
765
2.5


90/10
100.4
692
94.3
650
6.1


99/1
87.6
604
86.5
596
1.3


20/80
114.6
790
113.0
779
1.4


1/99
105.8
729
105.4
727
0.4


HFC-161/propane


44.5/55.5
161.2
1111
161.2
1111
0.0


70/30
156.0
1076
153.2
1056
1.8


90/10
142.2
980
137.9
951
3.0


99/1
131.6
907
130.9
903
0.5


20/80
156.0
1076
153.2
1056
1.8


1/99
139.3
960
138.5
955
0.6


HFC-161/cyclopropane


63.4/36.6
140.8
971
140.8
971
0.0


80/20
138.9
958
138.4
954
0.4


99/1
130.8
902
130.7
901
0.1


30/70
134.2
925
129.8
895
3.3


15/85
125.2
863
116.3
802
7.1


10/90
120.4
830
111.6
769
7.3


1/99
107.1
738
105.5
727
1.5


HFC-227ca/butane


84.4/15.6
77.5
534
77.5
534
0.0


92/8
76.4
527
74.5
514
2.5


99/1
67.3
464
64.8
447
3.7


60/40
75.4
520
67.8
467
10.1


61/39
75.5
521
69.0
476
8.6


HFC-227ca/cyclopropane


55.8/44.2
126.5
872
126.5
872
0.0


80/20
121.4
837
112.6
776
7.2


85/15
117.0
807
102.1
704
12.7


83/17
119.1
821
106.8
736
10.3


82/18
119.9
827
108.9
751
9.2


30/70
124.8
860
116.5
803
6.7


25/75
123.9
854
110.4
761
10.9


26/74
124.1
856
111.5
769
10.2


27/73
124.3
857
112.7
777
9.3


HFC-227ca/DME


75.6/24.4
101.0
696
101.0
696
0.0


90/10
98.1
676
94.3
650
3.9


92/8
96.9
668
90.0
621
7.1


93/7
96.1
663
86.1
594
10.4


40/60
95.1
656
92.7
639
2.5


20/80
90.3
623
88.5
610
2.1


1/99
85.9
592
85.8
592
0.1


HFC-227ca/isobutane


76.8/23.2
90.0
621
90.0
621
0.0


90/10
87.5
603
81.8
564
6.5


95/5
82.0
565
70.6
487
13.9


93/7
85.0
586
75.3
519
11.4


92/8
86.0
593
77.6
535
9.8


50/50
88.0
607
75.2
518
14.5


55/45
88.6
611
83.0
572
6.3


53/47
88.4
610
80.5
555
8.9


52/48
88.3
609
79.0
545
10.5


HFC-227ca/propane


51.6/48.4
159.8
1102
159.8
1102
0.0


30/70
157.9
1089
152.1
1049
3.7


20/80
155.0
1069
143.8
991
7.2


15/85
152.6
1052
140.9
971
7.7


10/90
149.3
1029
139.2
960
6.8


1/99
139.4
961
137.9
951
1.1


80/20
153.6
1059
136.8
943
10.9


78/22
154.9
1068
142.2
980
8.2


79/21
154.3
1064
139.7
963
9.5


HFC-227ea/butane


85.8/14.2
76.8
530
76.8
530
0.0


92/8
76.0
524
75.1
518
1.2


99/1
69.0
476
67.7
467
1.9


60/40
73.8
509
66.1
456
10.4


61/39
74.0
510
67.2
463
9.2


HFC-227ea/cyclopropane


55.2/44.8
125.1
863
125.1
863
0.0


80/20
119.7
825
111.8
771
6.6


90/10
107.4
741
89.5
617
16.7


85/15
115.2
794
102.3
705
11.2


83/17
117.3
809
106.5
734
9.2


84/16
116.3
802
104.5
721
10.1


30/70
123.3
850
116.7
805
5.4


25/75
122.4
844
111.5
769
8.9


23/77
122.0
841
109.7
756
10.1


24/76
122.2
843
110.6
763
9.5


HFC-227ea/isobutane


77.6/22.4
88.8
612
88.8
612
0.0


85/15
88.2
608
87.1
601
1.2


99/1
71.0
490
67.6
466
4.8


50/50
86.3
595
74.9
516
13.2


55/45
87.0
600
81.5
562
6.3


53/47
86.8
598
79.4
547
8.5


52/48
86.6
597
78.1
538
9.8


HFC-227ea/propane


50.4/49.6
157.4
1085
157.4
1085
0.0


70/30
155.2
1070
150.8
1040
2.8


90/10
133.7
922
91.5
631
31.6


80/20
150.0
1034
133.6
921
10.9


79/21
150.8
1040
136.3
940
9.6


30/70
155.7
1074
151.4
1044
2.8


20/80
153.0
1055
144.3
995
5.7


10/90
147.8
1019
139.6
963
5.5


1/99
139.1
959
137.9
951
0.9









The results of this Example show that these compositions are azeotropic or azeotrope-like because when 50 wt. % of an original composition is removed, the vapor pressure of the remaining composition is within about 10% of the vapor pressure of the original composition, at a temperature of 25′C.
EXAMPLE 3
Impact of Vapor Leakage at 0′C
A leak test is perfromed on compositions of HFC-32 and cyclopropane, at the temperature of 0′C. The results are summarized below.














0 wt %
50 wt %



Refrigerant
evaporated
evaporated
0% change in












Composition
psia
kPa
psia
kPa
vapor pressure















HFC-32/cyclopropane







83.7/16.3
126.6
873
126.6
873
0.0


99/1
119.7
825
118.9
820
0.7


60/40
122.5
845
116.4
803
5.0


53/47
120.2
829
108.5
748
9.7


52/48
119.8
826
107.1
738
10.6









EXAMPLE 4
Refrigerant Performance
The following table shows the performance of various refrigerants in an ideal vapor compression cycle. The data are based on the following conditions.
















Evaporator temperature
48.0° F. (8.9° C.)



Condenser temperature
115.0° F. (46.1° C.)



Liquid subcooled to
120° F. (6.7° C.)



Return Gas
65° F. (18.3° C.)



Compressor efficiency is 75%.










The refrigeration capacity is based on a compressor with a fixed displacement of 3.5 cubic feet per minute and 75% volumetric efficiency. Capacity is intended to mean the change in enthalpy of the refrigerant in the evaporator per pound of refrigerant circulated, i.e. the heat removed by the refrigerant in the evaporator per time. Coefficient of performance (COP) is intended to mean the ratio of the capacity to compressor work. It is a measure of refrigerant energy efficiency.

















Evap.
Cond.


Capacity



Refrig.
Press.
Press.
Comp. Dis.

BTU/min
















Comp.
Psia
kPa
Psia
kPa
Temp. ° F.
° C.
COP
kw



















HFC-32/isobutane











1.0/99.0
32
221
93
641
135
57
4.91
148
2.6


93.8/6.2
154
1062
409
2820
205
96
4.32
605
10.7


99.0/1.0
155
1069
416
2868
214
101
4.33
623
11.0


HFC-32/butane


1.0/99.0
22
152
68
469
137
58
5.03
110
1.9


99.0/1.0
154
1062
413
2848
214
101
4.34
621
10.9


HFC-32/propylene


1.0/99.0
110
758
276
1903
162
72
4.50
403
7.1


81.0/19.0
163
1124
422
2910
197
92
4.25
609
10.7


99.0/1.0
156
1076
418
2882
215
102
4.32
626
11.0


HFC-32/cyclopropane


1/99
68
469
183
1262
175
79
4.89
299
5.3


85.2/14.8
163
1124
425
2930
203
95
4.28
622
11.0


99/1
156
1076
419
2889
215
102
4.32
628
11.1


HFC-125/propylene


1.0/99.0
109
752
275
1896
161
72
4.49
400
7.0


79.5/20.5
124
855
318
2193
149
65
4.12
413
7.3


99.0/1.0
128
883
337
2324
144
62
3.84
401
7.1


HFC-125/cyclopropane


1/99
67
462
180
1241
175
79
4.85
293
5.2


91.3/8.7
133
917
343
2365
147
64
3.92
421
7.4


99/1
129
889
340
2344
144
62
3.83
402
7.1


HFC-134/propane


1.0/99.0
90
621
232
1586
150
66
4.52
336
5.9


52.3/47.7
107
738
270
1862
148
64
4.37
375
6.6


99.0/1.0
50
345
149
1020
150
66
5.04
243
4.3


HFC-134a/cyclopropane


1/99
66
455
180
1241
175
79
4.85
292
5.1


65.5/34.5
86
593
229
1579
159
71
4.61
344
6.1


99/1
60
414
177
1220
151
66
4.69
269
4.7


HFC-143a/DME


1.0/99.0
52
357
150
1034
168
75
4.91
243
4.3


90.9/9.1
116
801
302
2084
183
84
4.29
429
7.6


99.0/1.0
118
813
322
2221
194
90
3.93
422
7.4


HFC-143a/propylene


1.0/99.0
109
752
274
1889
161
72
4.50
400
7.0


89.6/10.4
115
793
298
2055
155
68
4.28
408
7.2


99.0/1.0
115
793
301
2075
155
68
4.24
406
7.1


HFC-152a/propane


1.0/99.0
89
614
229
1579
150
66
4.54
333
5.9


45.9/54.1
79
545
211
1455
156
69
4.63
317
5.6


99.0/1.0
52
359
156
1076
168
76
4.82
248
4.4


HFC-152a/isobutane


1.0/99.0
31
214
91
627
135
57
4.78
139
2.4


75.5/24.5
49
338
142
979
156
69
4.80
222
3.9


99.0/1.0
52
359
154
1062
167
75
4.81
245
4.3


HFC-152a/butane


1.0/99.0
21
145
65
448
138
59
4.89
103
1.8


85.0/15.0
45
310
135
931
162
72
4.87
215
3.8


99.0/1.0
51
352
153
1055
168
76
4.82
243
4.3


HFC-152a/cyclopropane


1.0/99.0
66
455
179
1234
175
79
4.84
290
5.1


44.3/55.7
60
414
169
1165
173
78
4.83
272
4.8


99.0/1.0
52
359
155
1069
168
76
4.82
246
4.3


HFC-161/propane


1.0/99.0
90
621
229
1579
150
66
4.53
334
5.9


44.5/55.5
94
648
244
1682
159
71
4.56
361
6.4


99.0/1.0
83
572
229
1579
175
79
4.69
356
6.3


HFC-161/cyclopropane


1.0/99.0
66
455
178
1227
174
79
4.87
289
5.1


63.4/36.6
75
517
206
1420
174
79
4.79
328
5.8


99.0/1.0
84
579
230
1586
174
79
4.70
357
6.3


HFC-227ca/butane


1.0/99.0
21
145
65
448
137
58
4.89
103
1.8


84.4/15.6
34
234
103
710
129
54
4.61
149
2.6


99.0/1.0
38
262
115
793
127
53
4.45
160
2.8


HFC-227ca/cyclopropane


1.0/99.0
66
455
177
1220
174
79
4.88
289
5.1


55.8/44.2
76
524
202
1393
154
68
4.65
303
5.3


99.0/1.0
40
276
124
855
130
54
4.24
164
2.9


HFC-227ca/DME


1.0/99.0
52
359
149
1027
167
75
4.90
242
4.3


75.6/24.4
66
455
184
1267
142
61
4.48
260
4.6


99.0/1.0
41
283
122
841
128
53
4.49
170
3.0


HFC-227ca/isobutane


1.0/99.0
31
214
90
621
135
57
4.79
138
2.4


76.8/23.2
36
248
106
731
130
54
4.61
155
2.7


99.0/1.0
38
262
115
793
127
53
4.45
160
2.8


HFC-227ca/propane


1.0/99.0
88
607
226
1558
145
63
4.53
326
5.7


51.6/48.4
76
524
205
1413
141
61
4.46
288
5.1


99.0/1.0
40
276
120
827
127
53
4.47
167
2.9


HFC-227ea/butane


1.0/99.0
21
145
65
448
137
58
4.90
103
1.8


85.8/14.2
34
234
102
703
129
54
4.60
148
2.6


99.0/1.0
37
255
113
779
127
53
4.46
157
2.8


HFC-227ea/cyclopropane


1.0/99.0
66
455
179
1234
175
79
4.85
291
5.1


55.2/44.8
75
517
201
1386
154
68
4.61
300
5.3


99.0/1.0
42
290
125
862
128
53
4.45
173
3.0


HFC-227ea/isobutane


1.0/99.0
31
214
89
614
135
57
4.79
138
2.4


77.6/22.4
36
248
105
724
130
54
4.60
153
2.7


99.0/1.0
38
262
113
779
127
53
4.46
157
2.8


HFC-227ea/propane


1.0/99.0
88
607
226
1558
145
63
4.53
326
5.7


50.4/49.6
76
524
204
1407
141
61
4.47
288
5.1


99.0/1.0
39
269
119
820
129
54
4.35
160
2.8









EXAMPLE 5
This Example is directed to measurements of the vapor pressure of the following liquid mixtures of this invention at 25′C: HFC-32/isobutane; HFC-32/butane;HFC-32/propylene; HFC-125/propylene; HFC-143a/propylene; HFC-152a/propane;HFC-152a/isobutane; HFC-152a/butane; HFC-152a/cyclopropane; HFC-161/propane; HFC-161/cyclopropane; HFC-227ca/butane; HFC-227ca/cyclopropane; HFC-227ca/DME; HFC-227ca/isobutane; HFC-227ca/propane; HFC-227ea/butane; HFC-227ea/cyclopropane; HFC-227ea/isobutane; and HFC-227ea/propane. The vapor pressures for these mixtures are shown in FIGS. 1-3, 5 and 9-24.
The vapor pressure data for the graph in FIG. 1 are obtained as follows. A stainless steel cylinder is evacuated, and a weighed amount of HFC-32 is added to the cylinder. The cylinder is cooled to reduce the vapor pressure of HFC-32, and then a weighed amount of isobutane is added to the cylinder. The cylinder is agitated to mix the HFC-32 and isobutane, and then the cylinder is placed in a constant temperature bath until the temperature comes to equilibrium, at which time the vapor pressure of the HFC-32 and isobutane in the cylinder is measured. This procedure is repeated at the same temperature with different weight percents of the components, and the results are plotted in FIG. 1.
Data are obtained in the same way for the mixtures plotted in FIGS. 2, 3, 5 and 9-24.
The data in FIGS. 1-3, 5 and 9-24 show that at 25′C, there are ranges of compositions that have vapor pressures higher than the vapor pressures of the pure components of the composition at that same temperature.
EXAMPLE 6
This Example is directed to the measurements of the vapor pressure of the following liquid mixtures of this invention: HFC-32/cyclopropane; HFC-125/cyclopropane; HFC-134/propane; and HFC-134a/cyclopropane. The vapor pressures of these mixtures were measured at particular compositions as shown by the asterisks in FIGS. 4 and 6-8, and a best fit curve was drawn through the asterisks.
The procedure for measuring the vapor pressures for mixtures of HFC-32 and cyclopropane was as follows. A stainless steel cylinder was evacuated, and a weighed amount of HFC-32 was added to the cylinder. The cylinder was cooled to reduce the vapor pressure of HFC-32, and then a weighed amount of cyclopropane was added to the cylinder. The cylinder was agitated to mix the HFC-32 and cyclopropane, and then the cylinder was placed in a constant temperature bath until the temperature came to equilibrium at 0′C, at which time the vapor pressure of the content of the cylinder was measured. This procedure was repeated for various mixtures of HFC-32 and cyclopropane as indicated in FIG. 4.
The data in FIG. 4 show that at 0′C, there are ranges of compositions that have vapor pressures higher than the vapor pressures of the pure components of the composition at that same temperature.
The procedure for measuring the vapor pressure of mixtures of HFC-32/cyclopropane was carried out in the same way for mixtures of HFC-125/cyclopropane, HFC-134/propane and HFC-134a/cyclopropane, except that the measurements of the vapor pressure of mixtures of HFC-134/propane were taken at 15′C and the measuements of the vapor pressure of mixtures of HFC-134a/cyclopropane were taken at 0.01′C.
ADDITIONAL COMPOUNDS
Other components, such as aliphatic hydrocarbons having a boiling point of −60 to +60′C, hydrofluorocarbonalkanes having a boiling point of −60 to +60′C, hydrofluoropropanes having a boiling point of between −60 to +60′C, hydrocarbon ethers having a boiling point between −60 to +60′C, hydrochlorofluorocarbons having a boiling point between −60 to +60′C, hydrofluorocarbons having a boiling point of −60 to +60′C, hydrochlorocarbons having a boiling point between −60 to +60′C, chlorocarbons and perfluorinated compounds, can be added to the azeotropic or azeotrope-like compositions described above.
Additives such as lubricants, surfactants, corrosion inhibitors, stabilizers, dyes and other appropriate materials may be added to the novel compositions of the invention for a variety of purposes provides they do not have an adverse influence on the composition for its intended application. Preferred lubricants include esters having a molecular weight greater than 250.

## Claims

1. An azeotropic or azeotrope-like composition consisting essentially of:
1 to 59 weight percent of 1,1,1,2,2-pentafluoroethane (HFC-125) and about 99-41 weight percent of propylene or 81 to 99 weihht percent of 1,1,1,2,2-pentafluoroethane (HFC-125) and 19 to 1 weight percent of propylene, said composition having a vapor pressure of about 167.4 psia to about 229.1 psia when the temperature is adjusted to about 25 degrees C.; or 
about 1 to 99 weight percent of 1,1,1-trifluoroethane (HFC-143a) and about 1 to 99 weight percent of propylene said composition having a vapor pressure of about 166.2 psia to about 181.2 psia when the temperature is adjusted to about 25 degrees C.

2. An azeotropic or azeotrope-like composition consisting essentially of:
about 81 to 99 weight percent of 1,1,1,2,2-pentafluoroethane (HFC-1 25) and about 19 to 1 weight percent of propylene said composition having a vapor pressure of about 203.9 psia to about 229.1 psia when the temperature is adjusted to about 25 degrees C.; or 
about 60 to 99 weight percent of 1,1,1-trifluoroethane (HFC-143a) and about 1 to 40 weight percent of propylene said composition having a vapor pressure of about 178.4 psia to about 181.2 psia when the temperature is adjusted to about 25 degrees C.

3. An azeotropic composition consisting essentially of:
about 79.5 weight percent 1,1,1,2,2-pentafluoroethane (HFC-125) and about 20.5 weight percent of propylene having a vapor pressure of about 229.1 psia when the temperature is adjusted to about 25 degrees C.; or 
about 89.6 weight percent 1,1,1-trifluoroethane (HFC-143a) and about 10.4 weight percent of propylene having a vapor pressure of about 181.2 psia when the temperature is adjusted to about 25 degrees C.

4. A process for producing refrigeration comprising evaporating a composition of any of claims 1 through 3 in the vicinity of a body to be cooled.

5. A process for producing heat comprising condensing a composition of any of claims 1 through 3 in the vicinity of a body to be heated.