USRE37938E1

USRE37938E1 - Pentafluoropropane compositions

Info

Publication number: USRE37938E1
Application number: US09/320,440
Authority: US
Inventors: Barbara Haviland Minor; Tuneen E. C. Chisolm
Original assignee: EI Du Pont de Nemours and Co
Current assignee: EIDP Inc
Priority date: 1997-05-05
Filing date: 1999-05-26
Publication date: 2002-12-17
Anticipated expiration: 2017-05-05
Also published as: US5788886A

Abstract

The present invention relates to compositions of pentafluoropropane and a fluorinated propane having from 1 to 5 fluorine atoms; a hydrocarbon having from 1 to 5 carbon atoms; 1,1,1,4,4,4-hexafluorobutane, (CF₃)₂CHCH₃, dimethyl ether; or 1,1,1,2,3,4,4,5,5,5-decafluoropentane. The compositions, which may be azeotropic or azeotrope-like, may be used as refrigerants, 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, particular removal fluids, carrier fluids, buffing abrasive agents or displacement drying agents.

Description

FIELD OF THE INVENTION

This invention relates to compositions that include pentafluoropropane. These compositions are 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 chiorodifluoromethane (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 application. 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 one or more fluorinated hydrocarbons.

Fluorinated hydrocarbons 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 a 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 compositions of pentafluoropropane and a fluoropropane such as tetrafluoropropane, trifluoropropane, difluoropropane or fluoropropane; 1,1,1,4,4,4-hexafluorobutane; (CF₃)₂CHCH₃; 1,1,1,2,3,4,4,5,5,5-decafluoropentane; a hydrocarbon such as butane, cyclopropane, isobutane, propane, pentane; or propylene; or dimethyl ether. These compositions are useful as refrigerants, 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 pentafluoropropane and a fluoropropane such as tetrafluoropropane, trifluoropropane, difluoropropane or fluoropropane; 1,1,1,4,4,4-hexafluorobutane; (CF₃)₂CHCH₂; 1,1,1,2,3,4,4,5,5,5-decafluoropentane; a hydrocarbon such as butane, cyclopropane, isobutane, propane, pentane, or propylene; or dimethyl ether to form an azeotropic or azeotrope-like composition.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph of the vapor/liquid equilibrium curve for mixtures of HFC-245ca and HFC-245eb at 25° C.;

FIG. 2 is a graph of the vapor/liquid equilibrium curve for mixtures of HFC-245ca and HFC-263fb at 25° C.;

FIG. 3 is a graph of the vapor/liquid equilibrium curve for mixtures of HFC-245ca and HFC-272ca at 25° C.;

FIG. 4 is a graph of the vapor/liquid equilibrium curve for mixtures of HFC-245ca and HFC-272ea at 25° C.;

FIG. 5 is a graph of the vapor/liquid equilibrium curve for mixtures of HFC-245ca and HFC-356mff at 25° C.;

FIG. 6 is a graph of the vapor/liquid equilibrium curve for mixtures of HFC-245ca and HFC-356mmz at 25° C.;

FIG. 7 is a graph of the vapor/liquid equilibrium curve for mixtures of HFC-245ca and butane at 20° C.;

FIG. 8 is a graph of the vapor/liquid equilibrium curve for mixtures of HFC-245ca and cyclopropane at 25° C.;

FIG. 9 is a graph of the vapor/liquid equilibrium curve for mixtures of HFC-245ca and isobutane at 25° C.;

FIG. 10 is a graph of the vapor/liquid equilibrium curve for mixtures of HFC-245ca and propane at 25° C.;

FIG. 11 is a graph of the vapor/liquid equilibrium curve for mixtures of HFC-245cb and HFC-245eb at 25° C.;

FIG. 12 is a graph of the vapor/liquid equilibrium curve for mixtures of HFC-245cb and HFC-254ca at 25° C.;

FIG. 13 is a graph of the vapor/liquid equilibrium curve for mixtures of HFC-245cb and HFC-272ea at 25° C.;

FIG. 14 is a graph of the vapor/liquid equilibrium curve for mixtures of HFC-245cb and HFC-281 ea at 25° C.;

FIG. 15 is a graph of the vapor/liquid equilibrium curve for mixtures of HFC-245cb and HFC-281fa at 25° C.;

FIG. 16 is a graph of the vapor/liquid equilibrium curve for mixtures of HFC-245cb and butane at 25° C.;

FIG. 17 is a graph of the vapor/liquid equilibrium curve for mixtures of HFC-245cb and cyclopropane at 25° C.;

FIG. 18 is a graph of the vapor/liquid equilibrium curve for mixtures of HFC-245cb and DME at 25° C.;

FIG. 19 is a graph of the vapor/liquid equilibrium curve for mixtures of HFC-245cb and isobutane at 25° C.;

FIG. 20 is a graph of the vapor/liquid equilibrium curve for mixtures of HFC-245cb and propane at 25° C.;

FIG. 21 is a graph of the vapor/liquid equilibrium curve for mixtures of HFC-245cb and propylene at 25° C.;

FIG. 22 is a graph of the vapor/liquid equilibrium curve for mixtures of HFC-245ea and HFC-272ca at 25° C.;

FIG. 23 is a graph of the vapor/liquid equilibrium curve for mixtures of HFC-245ea and HFC-272ea at 25° C.;

FIG. 24 is a graph of the vapor/liquid equilibrium curve for mixtures of HFC-245ea and HFC-356mff at 25° C.;

FIG. 25 is a graph of the vapor/liquid equilibrium curve for mixtures of HFC-245ea and HFC-356mmz at 25° C.;

FIG. 26 is a graph of the vapor/liquid equilibrium curve for mixtures of HFC-245ea and HFC-4310mee at 25° C.;

FIG. 27 is a graph of the vapor/liquid equilibrium curve for mixtures of HFC-245ea and butane at 25° C.;

FIG. 28 is a graph of the vapor/liquid equilibrium curve for mixtures of HFC-245ea and cyclopropane at 25° C.;

FIG. 29 is a graph of the vapor/liquid equilibrium curve for mixtures of HFC-245ea and isobutane at 25° C.;

FIG. 30 is a graph of the vapor/liquid equilibrium curve for mixtures of HFC-245ea and propane at 25° C.;

FIG. 31 is a graph of the vapor/liquid equilibrium curve for mixtures of HFC-245eb and HFC-263ca at 25° C.;

FIG. 32 is a graph of the vapor/liquid equilibrium curve for mixtures of HFC-245eb and HFC-263fb at 25° C.;

FIG. 33 is a graph of the vapor/liquid equilibrium curve for mixtures of HFC-245eb and HFC-356mff at 25° C.;

FIG. 34 is a graph of the vapor/liquid equilibrium curve for mixtures of HFC-245eb and HFC-356mmz at 25° C.;

FIG. 35 is a graph of the vapor/liquid equilibrium curve for mixtures of HFC-245eb and butane at 25° C.;

FIG. 36 is a graph of the vapor/liquid equilibrium curve for mixtures of HFC-245eb and cyclopropane at 25° C.;

FIG. 37 is a graph of the vapor/liquid equilibrium curve for mixtures of HFC-245eb and isobutane at 25° C.;

FIG. 38 is a graph of the vapor/liquid equilibrium curve for mixtures of HFC-245eb and propane at 25° C.;

FIG. 39 is a graph of the vapor/liquid equilibrium curve for mixtures of HFC-245fa and HFC-263ca at 25° C.;

FIG. 40 is a graph of the vapor/liquid equilibrium curve for mixtures of HFC-245fa and HFC-272ca at 25° C.;

FIG. 41 is a graph of the vapor/liquid equilibrium curve for mixtures of HFC-245fa and HFC-272fb at 25° C.;

FIG. 42 is a graph of the vapor/liquid equilibrium curve for mixtures of HFC-245fa and butane at 25° C.;

FIG. 43 is a graph of the vapor/liquid equilibrium curve for mixtures of HFC-245fa and cyclopropane at 25° C.;

FIG. 44 is a graph of the vapor/liquid equilibrium curve for mixtures of HFC-245fa and isobutane at 25° C.;

FIG. 45 is a graph of the vapor/liquid equilibrium curve for mixtures of HFC-245fa and pentane at 25° C.;

DETAILED DESCRIPTION

The present invention relates to compositions of pentafluoropropane and a fluorinated propane having from 1 to 5 fluorine atoms; a hydrocarbon having from 1 to 5 carbon atoms; 1,1,1,4,4,4-hexafluorobutane; (CF₃)₂CHCH₃; dimethyl ether (DME); or 1,1,1,2,3,4,4,5,5,5-decafluoropentane.

As used herein, pentafluoropropane includes 1,1,2,2,3-pentafluoropropane (HFC-245ca), 1,1,1,2,2-pentafluoropropane (HFC-245cb), 1,1,2,3,3-pentafluoropropane (HFC-245ea), 1,1,1,2,3-pentafluoropropane (HFC-245eb) and 1,1,1,3,3-pentafluoropropane (HFC-245fa). As used herein, a fluorinated propane having from 1 to 5 fluorine atoms includes 1,1,1,2,3-pentafluoropropane (HFC-245eb), 1,2,2, 3-tetrafluoropropane (HFC-254ca), 1,2,2-trifluoropropane (HFC-263ca), 1,1,1-trifluoropropane (HFC-263fb), 2,2-difluoropropane (HFC-272ca), 1,2-difluoropropane (HFC-272ea), 1,1-difluoropropane (HFC-272fb), 2-fluoropropane (HFC-281ea) and 1-fluoropropane (HFC-281fa). As used herein, a hydrocarbon having from 1 to 5 carbon atoms includes butane, cyclopropane, isobutane, propane, pentane, and propylene.

Examples of these compositions include:

(a) HFC-245ca and HFC-245eb, HFC-263fb, HFC-272ca, HFC-272ea, 1,1,1,4,4,4-hexafluorobutane (HFC-356mff), (CF₃)₂CHCH₃(HFC-356mmz), butane, cyclopropane, isobutane or propane;

(b) HFC-245cb and HFC-245eb, HFC-254ca, HFC-272ea, HFC-281ea, HFC-281fa, butane, cyclopropane, DME, isobutane, propane or propylene;

(c) HFC-245ea and HFC-272ca, HFC-272ea, HFC-356mff, HFC-356mmz, 1,1,1,2,3,4,4,5,5,5-decafluoropentane (HFC-4310mee), butane, cyclopropane, isobutane or propane;

(d) HFC-245eb and HFC-263ca, HFC-263fb, HFC-356mff, HFC-356mmz, butane, cyclopropane, isobutane or propane; or

(e) HFC-245fa and HFC-263ca, HFC-272ca, HFC-272fb, butane, cyclopropane, isobutane, or pentane.

1-99 wt. % of each of the components of the compositions can be used as refrigerants. Further, the present invention also relates to the discovery of azeotropic or azeotrope-like compositions of effective amounts of each of the above mixtures 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. Another way to characterize an azeotrope-like composition is that the bubble point vapor pressure and the dew point vapor pressure of the composition at a particular temperature are substantially the same.

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 less than 10 percent, 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 no difference 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

(a) HFC-245ca and HFC-245eb, HFC-263fb, HFC-272ca, HFC-272ea, HFC-356mff, HFC-356mmz, butane, cyclopropane, isobutane or propane;

(b) HFC-245cb and HFC-245eb, HFC-254ca, HFC-272ea, HFC-281 ea, HFC-281fa, butane, cyclopropane, DME, isobutane, propane or propylene;

(c) HFC-245ea and HFC-272ca, HFC-272ea, HFC-356mff, HFC-356mmz, HFC-4310mee, butane, cyclopropane, isobutane or propane;

(e) HFC-245fa and HFC-263ca, HFC-272ca, HFC-272fb, butane, cyclopropane, isobutane;

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 point that, for a maximum boiling azeotrope, having boiling points at a particular pressure higher than the pure components of the composition at that pressure and have vapor pressures at a particular temperature lower 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 at a particular temperature higher 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 combination of 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 have a change in vapor pressure of less than about 10% when 50 weight percent of the composition is evaporated. 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 temperatures, are broader than the range of compositions that have a change in vapor pressure of less than about 10% when 50 weight percent of the composition 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 vapor pressure of the components at 25° C are:


Components	Psia	kPa

HPC-245ca	14.2	98
HPC-245cb	67.4	465
HPC-245ea	8.62	59
HPC-245eb	16.9	117
HPC-245fa	21.4	148
HPC-263fb	54.0	372
HPC-272ca	34.5	238
HPC-272ca	20.8	143
HPC-356mff	14.7	101
HPC-356mmz	16.6	114
butane	35.2	243
cyclopropane	105.0	724
isobutane	50.5	348
propane	137.8	950
HPC-254ca	13.7	94
HPC-281ca	47.1	325
HPC-281fa	37.7	260
DMB	85.7	591
propylene	165.9	1144
HPC-4310mee	4.36	30
HPC-263ca	18.2	125
HPC-272fb	26.5	183
pentane	10.5	71

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. %)

HPC-245ca/HPC-245cb	1-99/1-99	30-99/1-70
HPC-245ca/HPC-263fb	1-36/64-99	1-36/64-99
HPC-245ca/HPC-272ca	1-55/45-99	1-55/45-99
HPC-245ca/HPC-272ca	1-99/1-99	1-99/1-99
HPC-245ca/HPC-356mff	1-99/1-99	1-80/20-99
HPC-245ca/HPC-356mmz	1-99/1-99	1-80/20-99
HPC-245ca/butane	1-73/27-99	20-73/27-80
HPC-245ca/cyclopropane	1-55/45-99	1-55/45-99
HPC-245ca/isobutane	1-65/35-99	1-65/35-99
HPC-245ca/propane	1-57/43-99	1-57/43-99
HPC-245cb/HPC-245cb	70-99.5/0.5-30	70-99.5/0.5-30
HPC-245cb/HPC-254ca	74-99/1-26	74-99/1-26
HPC-245cb/HPC-272ca	75-99/1-25	75-99/1-25
HPC-245cb/HPC-281ca	1-99/1-99	40-99/1-60
HPC-245cb/HPC-281fa	59-99/1-41	59-99/1-41
HPC-245cb/butane	59-99/1-41	59-99/1-41
HPC-245cb/cyclopropane	1-90/10-99	30-90/10-70
HPC-245cb/DME	1-89/11-99	40-89/11-60
HPC-245cb/isobutane	40-99/1-60	40-99/1-60
HPC-245cb/propane	1-76/24-99	10-76/24-90
HPC-245cb/prypylene	1-69/31-99	10-69/31-90
HPC-245ca/HPC-272ca	1-45/55-99	1-45/55-90
HPC-245ca/HPC-272ca	1-55/45-99	1-55/45-99
HPC-245ca/HPC-356mff	1-54/46-99	1-54/46-99
HPC-245ca/HPC-356mmz	1-45/55-99	1-45/55-99
HPC-245ca/HPC-4310mme	1-56/44-99	1-56/44-99
HPC-245ca/butane	1-65/35-99	1-65/35-99
HPC-245ca/cyclopropane	1-54/46-99	1-54/46-99
HPC-245ca/isobutane	1-62/38-99	1-62/38-99
HPC-245ca/propane	1-57/43-99	1-57/43-99
HPC-245cb/HPC-263ca	1-99/1-99	10-99/1-90
HPC-245cb/HPC-263fb	-43/57-99	1-43/57-99
HPC-245cb/HPC-356mff	11-99/1-89	11-99/1-89
HPC-245cb/HPC-356mmz	1-99/1-99	1-70/30-99
HPC-245cb/butane	21-71/29-79	21-71/29-79
HPC-245cb/cyclopropane	1-56/44-99	1-56/44-99
HPC-245cb/isobutane	1-66/34-99	1-66/34-99
HPC-245cb/propane	1-57/43-99	1-57/43-99
HPC-245fa/HPC-263ca	1-99/1-99	1-80/20-99
HPC-245fa/HPC-272ca	1-99/1-99	1-99/1-99
HPC-245ca/HPC-272fb	1-99/1-99	1-99/1-99
HPC-245ca/butane	1-78/22-99	1-78/22-99
HPC-245fa/cyclopropane	1-56/44-99	1-56/44-99
HPC-245fa/isobutane	1-70/30-99	1-70/30-99
HPC-245fa/pentane	58-99/1-42	70-99/1-30

For purposes of this invention, “effective amount” is defined as the amount 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 compositions are azeotropic, all at 25° C.


	Vapor Press.

	Composition No.		psia	(kPa)

HPC-245ca/HPC-245cb	75.0/25.0	14.1	97
HPC-245ca/HPC-263fb	1.0/99.0	54.0	372
HPC-245ca/HPC-272ca	17.2/82.8	35.8	247
HPC-245ca/HPC-272ca	17.6/82.4	21.1	145
HPC-245ca/HPC-356mff	28.0/72.0	16.9	117
HPC-245ca/HPC-356mmz	21.6/78.4	18.5	128
HPC-245ca/butane	41.9/58.1	40.8	281
HPC-245ca/cyclopropane	12.1/87.9	106.9	737
HPC-245ca/isobutane	30.1/69.9	56.3	388
HPC-245ca/propane	8.8/91.2	139.0	958
HPC-245cb/HPC-245cb	99.5/0.5	67.4	465
HPC-245cb/HPC-254ca	98.6/1.4	67.5	465
HPC-245cb/HPC-272ca	96.5/3.5	68.2	470
HPC-245cb/HPC-281ca	87.7/12.3	70.5	486
HPC-245cb/HPC-281ca	93.4/6.6	68.8	474
HPC-245cb/butane	93.3/6.7	68.5	472
HPC-245cb/cyclopropane	40.8/59.2	110.7	763
HPC-245cb/DMB	68.9/31.1	107.0	738
HPC-245cb/isobutane	80.2/19.8	75.1	518
HPC-245cb/propane	24.3/75.7	139.7	963
HPC-245cb/propylene	28.2/71.8	172.9	1192
HPC-245ca/HPC-272ca	8.8/91.2	35.0	241
HPC-245ca/HPC-272ca	5.6/94.4	20.8	143
HPC-245ca/HPC-356mff	12.0/88.0	15.5	107
HPC-245ca/HPC-356mmz	9.4/50.6	17.2	119
HPC-245ca/HPC-4310mee	34.4/65.6	3.50	24
HPC-245ca/butane	28.9/71.1	39.6	273
HPC-245ca/cyclopropane	8.6/91.4	106.4	734
HPC-245ca/isobutane	21.3/78.7	54.3	374
HPC-245ca/propane	5.9/94.1	138.6	956
HPC-245cb/HPC-263ca	26.3/73.7	18.4	127
HPC-245cb/HPC-263fb	6.3/93.7	54.4	375
HPC-245cb/HPC-356mff	45.1/54.9	20.0	138
HPC-245cb/HPC-356mmz	38.5/61.5	21.4	148
HPC-245cb/butane	43.5/56.5	43.5	300
HPC-245cb/cyclopropane	13.6/86.4	107.1	738
HPC-245cb/isobutane	33.5/66.5	57.4	396
HPC-245cb/propane	9.9/90.1	139.1	959
HPC-245fa/HPC-263ca	23.2/76.8	18.0	124
HPC-245fa/HPC-272ca	10.1/89.9	34.6	239
HPC-245ca/HPC-272fb	3.5/96.5	26.5	183
HPC-245fa/butane	48.6/51.4	40.9	282
HPC-245ca/cyclopropane	2.3/97.7	105.1	725
HPC-245fa/isobutane	33.7/66.3	53.9	372
HPC-245fa/pentane	85.0/15.0	23.6	163

EXAMPLE 2 Impact of Vapor Leakage on Vapor Pressure at 25° C.

A vessel is charged with an initial composition at 25° C., and the initial vapor pressure of the composition is measured. The composition is allowed to leak from the vessel, while the temperature is held constant at 25° C., until 50 weight percent of the initial composition is removed, at which time the vapor pressure of the composition remaining in the vessel is measured. The results are summarized below.


	INITIAL	50% LEAK	DELTA

WT % A/WT % B	PSIA	KPA	PSIA	KPA	% P

HPC-245ca/HPC-245cb
75.0/25.0	14.1	97	14.1	97	0.0
90/10	14.2	98	14.2	98	0.0
99/1	14.2	98	14.2	98	0.0
50/50	14.5	100	14.4	99	0.7
30/70	15.3	105	15.1	104	1.3
10/90	16.3	112	16.2	112	0.6
1/99	16.9	117	16.8	116	0.6
HPC-245ca/HPC-263fb
1.0/99.0	54.0	372	54.0	372	0.0
30/70	50.7	350	47.4	327	6.5
35/65	49.7	343	45.1	311	9.3
36/64	49.5	341	44.6	308	9.9
HPC-245ca/HPC-272ca
17.2/82.8	35.8	247	35.8	247	0.0
1/99	34.7	239	34.6	239	0.3
50/50	34.0	234	31.6	218	7.1
55/45	33.4	230	30.1	208	9.9
HPC-245ca/HPC-272ca
17.6/82.4	21.1	145	21.1	145	0.0
1/99	20.8	143	20.8	143	0.0
40/60	20.7	143	20.5	141	1.0
60/40	19.6	135	19.0	131	3.1
80/20	17.6	121	16.7	115	5.1
99/1	14.4	99	14.3	99	0.7
HPC-245ca/HPC-356mff
28.0/72.0	16.9	117	16.9	117	0.0
15/85	16.7	115	16.6	114	0.6
1/99	15.1	104	14.8	102	2.0
60/40	16.2	112	16.0	110	1.2
80/20	15.3	105	15.1	104	1.3
99/1	14.2	98	14.2	98	0.0
HPC-245ca/HPC-356mmz
21.6/78.4	18.5	128	18.5	128	0.0
10/90	18.2	125	18.0	124	1.1
1/99	17.0	117	16.7	115	1.8
60/40	17.1	118	16.6	114	2.9
80/20	15.7	108	15.3	105	2.5
99/1	14.3	99	14.2	98	0.7
HPC-245ca/butane
41.9/58.1	40.8	281	40.8	281	0.0
20/80	39.9	275	38.3	264	4.0
10/90	38.5	265	36.2	250	6.0
1/99	35.7	246	35.3	243	1.1
60/40	40.4	279	39.8	274	1.5
73/27	39.7	274	35.8	247	9.8
74/26	39.6	273	35.0	241	11.6
HPC-245ca/cyclopropane
12.1/87.9	106.9	737	106.9	737	0.0
1/99	105.5	727	105.2	725	0.3
40/60	105.3	726	102.7	708	2.5
55/45	103.2	712	93.4	644	9.5
56/44	102.7	708	92.3	636	10.1
HPC-245ca/isobutane
30.1/69.9	56.3	388	56.3	388	0.0
15/85	55.9	385	54.1	373	3.2
1/99	51.4	354	50.5	348	1.8
50/50	56.0	386	55.2	381	1.4
65/35	55.0	379	49.7	343	9.6
66/34	54.9	379	48.8	336	11.1
HPC-245ca/propane
8.8/91.2	139.0	958	139.0	958	0.0
1/99	138.2	953	138.0	951	0.1
40/60	136.3	940	133.3	919	2.2
50/50	134.8	929	128.0	883	5.0
57/43	133.3	919	120.9	834	9.3
58/42	133.0	917	119.4	823	10.2
HPC-245cb/HPC-245cb
99.5/0.5	67.4	465	67.4	465	0.0
70/30	61.8	426	56.1	387	9.2
69/31	61.6	425	55.4	382	10.1
HPC-245cb/HPC-254ca
98.6/1.4	67.5	465	67.5	465	0.0
99/1	67.5	465	67.5	465	0.0
75/25	63.0	434	57.5	396	8.7
74/26	62.8	433	56.8	392	9.6
HPC-245cb/HPC-272ca
96.5/3.5	68.2	470	68.2	470	0.0
99/1	67.8	467	67.8	467	0.0
80/20	64.9	447	61.1	421	5.9
75/25	63.4	437	57.1	394	9.9
HPC-245cb/HPC-281ca
87.7/12.3	70.5	486	70.5	486	0.0
99/1	68.1	470	67.9	468	0.3
50/50	63.7	439	59.7	412	6.3
40/60	60.8	419	56.1	387	7.7
30/70	57.6	397	52.9	365	8.2
20/80	54.3	374	50.4	347	7.2
1/99	47.5	328	47.3	326	0.4
HPC-245cb/HPC-281fa
93.4/6.6	68.8	474	68.8	474	0.0
99/1	67.9	468	67.8	467	0.1
60/40	61.2	422	55.5	383	9.3
59/41	60.8	419	54.9	379	9.7
58/42	60.5	417	54.4	375	10.1
HPC-245cb/butane
93.3/6.7	68.5	472	68.5	472	0.0
99/1	67.7	467	67.7	467	0.0
70/30	64.5	445	61.6	425	4.5
60/40	62.0	427	56.2	387	9.4
59/41	61.7	425	55.6	383	9.9
HPC-245cb/cyclopropane
40.8/59.2	110.7	763	110.7	763	0.0
20/80	109.4	754	108.7	749	0.6
1/99	105.3	726	105.2	725	0.1
70/30	106.6	735	103.4	713	3.0
85/15	97.0	669	88.8	612	8.5
90/10	90.6	625	81.6	563	9.9
91/9	89.1	614	80.1	552	10.1
HPC-245cb/DME
68.9/31.1	107.0	738	107.0	738	0.0
85/15	104.4	720	100.0	689	4.2
89/11	102.1	704	92.2	636	9.7
90/10	101.3	698	89.4	616	11.7
40/60	102.4	706	98.1	676	4.2
20/80	95.2	656	90.2	622	5.3
10/90	90.7	625	87.6	604	3.4
1/99	86.2	594	85.9	592	0.5
HPC-245cb/isobutane
80.2/19.8	75.1	518	75.1	518	0.0
90/10	73.9	510	73.3	505	0.8
99/1	68.6	473	68.1	470	0.7
50/50	70.9	489	66.9	461	5.6
40/60	68.3	471	61.9	427	9.4
HPC-245cb/propane
24.3/75.7	139.7	963	139.7	963	0.0
10/90	139.0	958	138.9	958	0.1
1/99	128.0	951	137.9	951	0.1
50/50	137.3	947	135.7	936	1.2
70/30	129.9	896	122.0	841	6.1
76/24	126.8	860	113.8	785	8.8
77/23	125.6	866	112.1	773	10.7
HPC-245cb/propylene
28.2/71.8	172.9	1192	172.9	1192	0.0
10/90	170.6	1176	169.3	1167	0.8
1/99	166.6	1149	166.2	1146	0.2
60/40	167.0	1151	159.2	1098	4.7
69/31	161.5	1114	145.7	1005	9.8
70/30	160.6	1107	143.7	991	10.5
HPC-245ca/HPC-272ca
8.8/91.2	35.0	241	35.0	241	0.0
1/99	34.6	239	34.6	239	0.0
40/60	33.4	230	31.3	216	6.3
45/55	32.9	227	29.8	205	9.4
46/54	32.8	226	29.5	203	10.1
HPC-245ca/HPC-272ca
5.6/94.4	20.8	143	20.8	143	0.0
1/99	20.8	143	20.8	143	0.0
40/60	19.7	136	18.9	130	4.1
55/45	18.6	128	16.8	116	9.7
56/44	18.5	128	16.6	114	10.3
HPC-245ca/HPC-356mff
12.0/88.0	15.5	107	15.5	107	0.0
1/99	14.9	103	14.8	102	0.7
40/60	14.5	100	13.6	94	6.2
54/46	13.4	92	12.1	83	9.7
55/45	13.3	92	11.9	82	10.5
HPC-245ca/HPC-356mmz
9.4/90.6	17.2	119	17.2	119	0.0
1/99	16.8	116	16.7	115	0.6
40/60	15.8	109	14.5	100	0.2
45/55	15.3	105	13.8	95	9.8
46/54	15.2	105	13.6	94	10.5
HPC-245/HPC-4310mee
34.4/65.6	3.50	24	3.50	24	0.0
15/85	3.81	26	3.70	26	2.9
1/99	4.32	30	4.30	30	0.5
50/50	3.77	26	3.58	25	5.0
56/44	4.05	28	3.66	25	9.6
57/43	4.10	28	3.68	25	10.2
HPC-245ca/butane
28.9/71.1	39.6	273	39.6	273	0.0
10/90	39.1	270	36.0	248	7.9
1/99	36.2	250	35.2	243	2.8
60/40	39.2	270	37.3	257	4.8
65/35	38.9	268	35.2	243	9.5
66/34	38.9	268	34.6	239	11.1
HPC-245ca/cyclopropane
8.6/91.4	106.4	734	106.4	734	0.0
1/99	105.5	727	105.2	725	0.3
40/60	105.0	724	102.2	705	2.7
54/46	103.2	712	93.5	645	9.4
55/45	103.0	710	92.5	638	10.2
HPC-245ca/isobutane
21.3/78.7	54.3	374	54.3	374	0.0
10/90	54.0	372	52.7	363	2.4
1/99	51.4	354	50.5	348	1.8
40/60	54.1	373	53.7	370	0.7
62/38	53.2	367	47.9	330	10.0
HPC-245ca/propane
5.9/94.1	138.6	956	138.6	956	0.0
1/99	138.1	952	138.0	951	0.1
40/60	136.2	939	133.4	920	2.1
57/43	133.9	923	122.5	845	8.5
58/42	133.6	921	119.7	825	10.4
HPC-245ca/HPC-263ca
26.3/73.7	18.4	127	18.4	127	0.0
10/90	18.3	126	18.3	126	0.0
1/99	18.2	125	18.2	125	0.0
60/40	18.1	125	18.1	125	0.0
80/20	17.7	122	17.6	121	0.6
99/1	17.0	117	17.0	117	0.0
HPC-245cb/HPC-263fb
6.3/93.7	54.4	375	54.4	375	0.0
1/99	54.1	373	54.1	373	0.0
40/60	50.9	351	46.8	323	8.1
43.57	50.3	347	45.3	312	9.9
HPC-245nb/HPC-356mff
45.1/54.9	20.0	138	20.0	138	0.0
20/80	19.3	133	18.5	128	4.1
11/89	18.3	126	16.5	114	9.8
10/90	18.2	125	16.2	120	11.0
60/40	19.8	137	19.7	136	0.5
80/20	18.8	130	18.4	127	2.1
99/1	17.0	117	17.0	117	0.0
HPC-2455cb/HPC-356mme
38.5/61.5	212.4	148	21.4	148	0.0
20/80	20.9	144	20.4	141	2.4
1/99	17.2	119	16.7	115	2.9
70/30	20.2	139	19.6	135	3.0
85/15	18.9	130	18.2	125	3.7
99/1	17.1	118	17.0	117	0.6
HPC-245cb/butane
43.5/56.5	43.5	300	43.5	300	0.0
21/79	43.0	296	38.9	268	9.5
20/80	42.9	296	38.3	264	10.7
71/29	42.5	293	38.7	267	8.9
72/28	42.4	292	38.1	263	10.1
HPC-245cb/cyclopropane
13.6/86.4	107.1	738	107.1	738	0.0
1/99	105.5	727	105.2	725	0.3
40/60	105.6	728	103.1	711	2.4
56/44	102.8	709	92.9	641	9.6
57/43	102.5	707	91.8	633	10.4
HPC-245cb/isobutane
33.5/66.5	57.4	396	57.4	396	0.0
20/80	57.1	394	55.9	385	2.1
10/90	55.8	385	51.8	357	7.2
1/99	51.5	355	50.5	348	1.9
60/40	56.5	390	54.0	372	4.4
66/34	56.0	386	50.7	350	9.5
67/33	55.8	385	49.9	344	10.6
HPC-254cb/propane
9.9/90.1	139.1	959	139.1	959	0.0
1/99	138.1	952	138.0	951	0.1
40/80	136.5	941	133.4	920	2.3
57/43	133.1	918	120.5	831	9.5
58/42	132.8	916	119.1	821	10.3
HPC-245ca/HPC-263ca
23.2/76.8	18.0	124	18.0	124	0.0
10/90	18.1	125	18.1	125	0.0
1/99	18.2	125	18.2	125	0.0
40/60	18.2	125	18.2	125	0.0
60/40	18.8	130	18.6	128	1.1
80/20	19.9	137	19.7	136	1.0
99/1	21.3	147	21.3	147	0.0
HPC-245fa/HPC-272ca
10.1/89.9	34.6	239	34.6	239	0.0
1/99	34.5	238	34.5	238	0.0
40/60	33.8	233	33.5	231	0.9
70/30	30.7	212	29.0	200	5.5
85/15	27.4	189	25.1	173	8.4
90/10	25.8	178	23.8	164	7.8
99/1	22.0	152	21.6	149	1.8
HPC-245fa/HPC-272fb
3.5/96.5	26.5	183	26.5	183	0.0
1/99	26.5	183	26.5	183	0.0
40/60	26.0	179	26.0	179	0.0
70/30	24.7	170	24.5	169	0.8
85/15	23.5	162	23.1	159	1.7
99/1	21.6	149	21.6	149	0.0
HPC-245fa/butane
48.6/51.4	40.9	282	40.9	282	0.0
30/70	40.4	279	39.6	273	2.0
10/90	37.8	261	36.3	250	4.0
1/99	35.5	245	35.3	243	0.6
70/30	40.1	276	38.6	266	3.7
78/22	38.9	268	35.1	242	9.8
79/21	38.7	267	34.5	238	10.9
HPC-245fa/cyclopropane
2.3/97.7	105.1	725	105.1	725	0.0
1/99	105.1	725	105.1	725	0.0
40/60	101.2	698	98.0	676	3.2
56/44	97.2	670	88.0	607	9.5
57/43	96.8	667	87.0	600	10.1
HPC-245fa/isobutane
33.7/66.3	53.9	372	53.9	372	0.0
20/80	53.5	369	53.1	366	0.7
10/90	52.5	362	51.8	357	1.3
1/99	50.7	350	50.6	349	0.2
60/40	52.6	363	50.8	350	3.4
70/30	51.1	352	46.1	318	9.8
71/29	50.9	351	45.4	313	10.8
HPC-245fa/pentane
85.5/15.0	23.6	163	23.6	163	0.0
90/10	23.5	162	23.3	161	0.9
99/1	21.9	151	21.7	150	0.9
70/30	23.1	159	22.6	156	2.2
60/40	22.6	156	20.9	144	7.5
58/42	22.5	155	20.4	141	9.3

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 performed on compositions of HFC-245ca and HFC-272ca, at the temperature of 0° C. The results are summarized below.


WT % A/WT %B	INITIAL	50% LEAK

HPC-245ca/HPC-272ca	PSIA	KPA	PSIA	KPA	DELTA % P

15.2/84.8	15.4	106	15.4	106	0.0
1/99	15.0	103	15.0	103	0.0
40/60	15.0	103	14.4	99	4.0
52/48	14.4	99	13.0	90	9.7
53.47	14.4	99	12.8	88	11.1

These results show that compositions of HFC-245ca and HFC-272ca are azeotropic or azeotrope-like at different temperatures, but that the weight percents of the components vary as the temperature is changed.

EXAMPLE 4 Refrigerant Performance

The following table shows the performance of various refrigerants. The data are based on the following conditions.


	Evaporator temperature	45.0° F. (7.2° C.)
	Condenser temperature	130.0° F. (54.5° C.)
	Subcooled	15.0° F. (8.3° C.)
	Return gas	65.0° 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.	Comp.	Capacity
Refrig.	Press.	Press.	Dis. Temp.	BTU/min

Comp.	Psia	(kPa)	Psia	(kPa)	° F.	(° C.)	COP	(kw)

HPC-245ca/HPC-245cb

1.0/99.0	8	55	43	296	157	69	3.72	46	0.3
99.0/1.0	7	48	37	255	158	70	3.74	39	0.7

HPC-245ca/HPC-263fb

1.0/99.0	30	207	119	820	155	68	3.53	1.28	2.3
99.0/1.0	7	48	37	255	158	70	3.76	40	0.7

HPC-245ca/HPC-272ca

1.0/99.0	19	131	78	538	161	72	3.70	89	1.6
99.0/1.0	7	48	37	255	158	70	3.75	40	0.7

HPC-245ca/HPC-272ca

1.0/99.0	11	76	51	352	171	77	3.80	58	1.0
99.0/1.0	7	48	37	255	158	70	3.75	39	0.7

HPC-245ca/HPC-356mff

1.0/99.0	7	48	38	262	138	59	3.54	38	0.7
99.0/1.0	7	48	37	255	158	70	3.74	39	0.7

HPC-245ca/HPC-356mmz

1.0/99.0	8	55	42	290	137	58	3.53	42	0.7
99.0/1.0	7	48	37	255	158	70	3.74	39	0.7

HPC-245ca/butane

1.0/99.0	20	138	81	558	155	68.3	3.66	91	1.6
99.0/1.0	8	55	40	276	155	68.3	3.99	46	0.8

HPC-245ca/cyclopropane

1.0/99.0	62	427	214	1475	200	93	3.67	258	4.5
99.0/1.0	8	55	40	276	157	69	3.93	46	0.8

HPC-245ca/isobutane

1.0/99.0	29	200	110	758	152	67	3.56	120	2.1
99.0/1.0	7	48	38	262	158	70	3.77	41	0.7

HPC-245ca-propane

1.0/99.0	83	572	270	1862	167	75	3.31	280	4.9
99.0/1.0	8	55	40	276	156	69	3.96	46	0.8

HPC-245cb/HPC-245cb

1.0/99.0	8	55	44	303	156	69	3.73	47	0.8
99.5/0.5	36	248	136	938	139	59	3.31	135	2.4

HPC-245cb/HPC-254ca

1.0/99.0	7	48	36	248	161	72	3.79	39	0.7
98.6/1.4	35	241	134	924	140	60	3.31	133	2.3

HPC-245cb/HPC-272ca

1.0/99.0	11	76	51	352	171	77	3.81	58	1.0
99.0/1.0	36	248	136	938	139	59	3.32	135	2.4

HPC-245cb/HPC-281ca

1.0/99.0	27	186	105	724	168	76	3.69	121	2.1
99.0/1.0	36	248	137	945	139	59	3.31	136	2.4

HPC-245cb/HPC-281fa

1.0/99.0	21	145	87	600	169	76	3.72	100	1.8
99.0/1.0	36	248	137	945	139	59	3.31	136	2.4

HPC-245cb/butane

1.0/99.0	20	138	81	558	155	58	3.65	90	1.6
99.0/1.0	36	248	136	938	139	59	3.31	135	2.4

HPC-245cb/cyclopropane

1.0/99.0	63	434	215	1483	200	93	3.67	259	4.6
99.0/1.0	37	255	141	972	140	60	3.33	141	2.5

HPC-245cb/DME

1.0/99.0	48	331	182	1255	193	89	3.67	21.4	3.8
99.0/1.0	37	255	141	972	140	60	3.32	141	2.5

HPC-245cb/isobutane

1.0/99.0	29	200	110	758	152	67	3.56	1.21	2.1
99.0/1.0	36	248	136	938	139	59	3.31	136	2.4

HPC-245cb/propane

1.0/99.0	84	579	271	1868	166	74	3.32	282	5.0
99.0/1.0	37	255	140	965	140	60	3.32	140	2.5

HPC-245cb/propylene

1.0/99.0	104	717	331	2282	184	84	3.30	351	6.2
99.0/1.0	38	262	142	979	140	60	3.35	143	2.5

HPC-245ca/HPC-272ca

1.0/99.0	19	131	78	538	161	72	3.70	88	1.5
99.0/1.0	4	28	24	165	168	76	3.86	26	0.5

HPC-245ea/HPC-272ca

1.0/99.0	11	76	51	352	171	77	3.80	57	1.0
99.0/1.0	4	28	24	165	168	76	3.83	25	0.4

HPC-245ca/HPC-356mff

1.0/99.0	7	48	38	262	138	59	3.54	38	0.7
99.0/1.0	4	28	24	165	168	76	3.83	25	0.4

HPC-245ca/HPC-356mmz

1.0/99.0	8	55	42	290	1.37	58	3.53	42	0.7
99.0/1.0	4	28	24	165	168	76	3.83	25	0.4

HPC-245ca/HPC-4310mee

1.0/	2	14	16	110	133	56	3.46	13	0.2
99.0*
99.0/1.0	4	28	23	159	167	75	3.82	25	0.4

HPC-245ca/butane

1.0/99.0	19	131	80	552	155	68	3.66	89	1.6
99.0/1.0	4	28	24	165	167	75	3.86	26	0.5

HPC-245ca/cyclopropane

1.0/99.0	61	421	213	1469	201	94	3.65	256	4.5
99.0/1.0	5	34	27	186	165	74	4.14	31	0.5

HPC-245ca/isobutane

1.0/99.0	29	200	109	752	152	67	3.55	120	2.1
99.0/1.0	4	28	25	172	167	75	3.92	27	0.5

HPC-245ca/propane

1.0/99.0	82	565	269	1855	166	74	3.31	279	4.9
99.0/1.0	5	34	27	186	163	73	4.25	33	0.6

HPC-245cb/HPC-263ca

1.0/99.0	9	62	45	310	162	72	3.77	50	0.9
99.0/1.0	8	55	43	296	157	69	3.72	46	0.8

HPC-245cb/HPC-263fb

1.0/99.0	30	207	199	1372	155	68	3.53	128	2.3
99.0/1.0	9	62	44	303	157	69	3.72	47	0.8

HPC-245cb/HPC-356mff

1.0/99.0	7	48	38	262	138	59	3.54	38	0.7
99.0/1.0	8	55	43	296	156	69	3.72	46	0.8

HPC-245cb/HPC-356mmz

1.0/99.0	8	55	43	390	137	58	3.53	42	0.7
99.0/1.0	8	55	43	296	156	69	3.71	46	0.8

HPC-245eb/butane

1.0/99.0	19	131	80	552	155	68	3.65	90	1.6
99.0/1.0	9	62	44	303	157	69	3.72	47	0.8

HPC-245cb/cyclopropane

1.0/99.0	62	427	214	1475	200	93	3.66	258	4.5
99.0/1.0	9	62	47	324	156	69	3.87	53	0.9

HPC-245cb/isobutane

1.0/99.0	29	200	110	758	152	67	3.56	120	2.1
99.0/1.0	9	62	44	303	156	69	3.74	47	0.8

HPC-245cb/propane

1.0/99.0	83	572	270	1862	166	74	3.32	281	4.9
99.0/1.0	10	60	47	324	144	68	3.88	53	0.9

HPC-245fa/HPC-263ca

1.0/99.0	9	62	45	310	162	72	3.77	50	0.9
99.0/1.0	11	76	54	372	155	68	3.67	57	1.0

HPC-246fa/HFC-272ca

1.0/99.0	19	131	78	538	161	72	3.70	89	1.6
99.0/1.0	11	76	54	372	155	68	3.67	58	1.0

HPC-245fa/HCF-272fb

1.0/99.0	14	97	63	434	169	76	3.76	72	1.3
99.0/1.0	11	76	54	372	155	68	3.67	58	1.0

HPC-245fu/butane

1.0/99.0	19	131	80	552	155	68	3.66	90	1.6
99.0/1.0	11	76	54	372	155	68	3.67	58	1.0

HPC-245fa/cyclopropane

1.0/99.0	62	427	214	1475	200	93	3.67	258	4.5
99.0/1.0	12	83	58	400	155	68	3.79	64	1.1

HPC-245fa/isobutane

1.0/99.0	29	200	110	758	152	67	3.56	120	2.1
99.0/1.0	11	76	55	379	155	68	3.68	59	1.0

HPC-245fa/pentane

1.0/99.0	5	34	26	179	150	66	3.74	28	0.5
99.0/1.0	11	76	53	365	155	68	3.68	57	1.0

*70° F. Return Gas

EXAMPLE 5

This Example is directed to measurements of the liquid/vapor equilibrium curves for the mixtures in FIGS. 1-6 and 8-45.

Turning to FIG. 1, the upper curve represents the composition of the liquid, and the lower curve represents the composition of the vapor.

The data for the compositions of the liquid in FIG. 1 are obtained as follows. A stainless steel cylinder is evacuated, and a weighed amount of HFC-245ca is added to the cylinder. The cylinder is cooled to reduce the vapor pressure of HFC-245ca, and then a weighed amount of HFC-245eb is added to the cylinder. The cylinder is agitated to mix the HFC-245ca and HFC-245eb, and then the cylinder is placed in a constant temperature bath until the temperature comes to equilibrium at 25° C., at which time the vapor pressure of the HC-245ca and HFC-245eb in the cylinder is measured. Additional samples of liquid are measured the same way, and the results are plotted in FIG. 1.

The curve which shows the composition of the vapor is calculated using an ideal gas equation of state.

Vapor/liquid equilibrium data are obtained in the same way for the mixtures shown in FIGS. 2-6 and 8-45.

The data in FIGS. 2-6, 8-25, 27-38 and 40-45 show that at 25° C., there are ranges of compositions that have vapor pressures as high as or higher than the vapor pressures of the pure components of the composition at that same temperature. As stated earlier, the higher than expected pressures of these compositions may result in an unexpected increase in the refrigeration capacity and efficiency for these compositions versus the pure components of the compositions.

The data in FIGS. 1, 26 and 39 show that at 25° C., there are ranges of compositions that have vapor pressures below the vapor pressures of the pure components of the composition at that same temperature. These minimum boiling compositions are useful in refrigeration, and may show an improved efficiency when compared to the pure components of the composition.

EXAMPLE 6

This Example is directed to measurements of the liquid/vapor equilibrium curve for mixtures of HFC-245ca and butane. The liquid/vapor equilibrium data for these mixtures are shown in FIG. 7. The upper curve represents the liquid composition, and the lower curve represents the vapor composition.

The procedure for measuring the composition of the liquid for mixtures of HFC-245ca and butane in FIG. 7 was as follows. A stainless steel cylinder was evacuated, and a weighed amount of HFC-245ca was added to the cylinder. The cylinder was cooled to reduce the vapor pressure of HFC-245ca, and then a weighed amount of butane was added to the cylinder. The cylinder was agitated to mix the HFC-245ca and butane, and then the cylinder was placed in a constant temperature bath until the temperature came to equilibrium at 20.0° C., at which time the vapor pressure of the content of the cylinder was measured. Samples of the liquid in the cylinder were taken and analyzed, and the results are plotted in FIG. 7 as asterisks, with a best fit curve having been drawn through the asterisks.

This procedure was repeated for various mixtures of HFC-245ca and butane as indicated in FIG. 7.

The data in FIG. 7 show that at 20.0° 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 novel compositions of this invention, including the azeotropic or azeotrope-like compositions, may be used to produce refrigeration by condensing the compositions and thereafter evaporating the condensate in the vicinity of a body to be cooled. The novel compositions may also be used to produce heat by condensing the refrigerant in the vicinity of the body to be heated and thereafter evaporating the refrigerant.

The compositions of the present inventions are useful as blowing agents in the production of thermoset foams, which include polyurethane and phenolic foams, and thermoplastic foams, which include polystyrene or polyolefin foams.

A polyurethane foam may be made by combining a composition of the present invention, which functions as a blowing agent, together with an isocyanate, a polyol, and appropriate catalysts or surfactants to form a polyurethane or polyisocyanurate reaction formulation. Water may be added to the formulation reaction to modify the foam polymer as well as to generate carbon dioxide as an in-situ blowing agent.

A phenolic foam may be produced by combining a phenolic resin or resole, acid catalysts, a blowing agent of the present invention and appropriate surfactants to form a phenolic reaction formulation. The formulation may be chosen such that either an open cell or closed cell phenolic foam is produced.

Polystyrene or polyolefin foams may be made by extruding a molten mixture of a polymer, such as polystyrene, polyethylene or polypropylene), a nucleating agent and a blowing agent of the present invention through an extrusion die that yields the desired foam product profile.

The novel compositions of this invention, including the azeotropic or azeotrope-like compositions, may be used as cleaning agents to clean, for example, electronic circuit boards. Electronic components are soldered to circuit boards by coating the entire circuit side of the board with flux and thereafter passing the flux-coated board over preheaters and through molten solder. The flux cleans the conductive metal parts and promotes solder fusion, but leave residues on the circuit boards that must be removed with a cleaning agent. This is conventionally done by suspending a circuit board to be cleaned in a boiling sump which contains the azeotropic or azeotrope-like composition, then suspending the circuit board in a rinse sump, which contains the same azeotropic or azeotrope-like composition, and finally, for one minute in the solvent vapor above the boiling sump.

As a further example, the azeotropic mixtures of this invention can be used in cleaning processes such as described in U.S. Pat. No. 3,881,949, or as a buffing abrasive detergent.

It is desirable that the cleaning agents by azeotropic or azeotrope-like so that they do not tend to fractionate upon boiling or evaporation. This behavior is desirable because if the cleaning agent were not azeotropic or azeotrope-like, the more volatile components of the cleaning agent would preferentially evaporate, and would result in a cleaning agent with a changed composition that may become flammable and that may have less-desirable solvency properties, such as lower rosin flux solvency and lower inertness toward the electrical components being cleaned. The azeotropic character is also desirable in vapor degreasing operations because the cleaning agent is generally redistilled and employed for final rinse cleaning.

The novel compositions of this invention are also useful as fire extinguishing agents, heat transfer media, gaseous dielectrics, and power cycle working fluids.

ADDITIONAL COMPOUNDS

Other components, such as aliphatic hydrocarbons having a boiling point of −60° to +100° C., hydrofluorocarbonalkanes having a boiling point of −60° to +100° C., hydrofluoropropanes having a boiling point of between −60° to +100° C., hydrocarbon esters having a boiling point between −60° to +100° C., hydrochlorofluorocarbons having a boiling point between −60° to +100° C., hydrofluorocarbons having a boiling point of −60° to +100° C., hydrochlorocarbons having a boiling point between −60° to +100° C., chlorocarbons and perfluorinated compounds, can be added to the azeotropic or azeotrope-like compositions described above without substantially changing the properties thereof, including the constant boiling behavior, of the compositions.

Additives such as lubricants, corrosion inhibitors, surfactants, 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

What is claimed is:

1. An azeotropic or azeotrope-like composition consisting essentially of: 1-99 weight percent 1,1,2,2,3-pentafluoropropane and 1-99 weight percent 1,1,1,2,3-pentafluoropropane; 1-36 weight percent 1,1,2,2,3-pentafluoropropane and 64-99 weight percent 1,1,1-trifluoropropane; 1-55 weight percent 1,1,2,2,3-pentafluoropropane and 45-99 weight percent 2,2-difluoropropane; 1-99 weight percent 1,1,2,2,3-pentafluoropropane and 1-99 weight percent 1,2-difluoropropane; 1-73 weight percent 1,1,2,2,3-pentafluoropropane and 27-99 weight percent butane; 1-55 weight percent 1,1,2,2,3-pentafluoropropane and 45-99 weight percent and cyclopropane; 1-65 weight percent 1,1,2,2,3-pentafluoropropane and 35-99 weight percent isobutane; 1-57 weight percent 1,1,2,2,3-pentafluoropropane and 43-99 weight percent propane; 79-99.5 weight percent 1,1,1,2,2-pentafluoropropane and 0.5-30 weight percent 1,1,1,3,4-pentafluoropropane; 74-99 weight percent 1,1,1,2,2-pentafluoropropane and 1-26 weight percent 1,2,2,3-tetrafluoropropane; 75-99 weight percent 1,1,1,2,2-pentafluoropropane and 1-25 weight percent 1,2-difluoropropane; 1-99 weight percent 1,1,1,2,2-pentafluoropropane and 1-99 weight percent 2-fluoropropane; 59-99 weight percent 1,1,1,2,2-pentafluoropropane and 1-41 weight percent 1-fluoropropane; 59-99 weight percent 1,1,1,2,2-pentafluoropropane and 1-41 weight percent butane; 1-90 weight percent 1,1,1,2,2-pentafluoropropane and 10-99 weight percent cyclopropane; 1-89 weight percent 1,1,1,2, 2-pentafluoropropane and 11-99 weight percent dimethyl ether; 40-99 weight percent 1,1,1,2,2-pentafluoropropane and 1-60 weight percent isobutane; 1-76 weight percent 1,1,1,2,2-pentafluoropropane and 24-99 weight percent propane; 1-69 weight percent 1,1,1,2,2-pentafluoropropane and 31-99 weight percent propylene; 1-45 weight percent 1,1, 2,3,3-pentafluoropropane and 55-99 weight percent 2,2-difluoropropane; 1-55 weight percent 1,1,2,3,3-pentafluoropropane and 45-99 weight percent 1,2-difluoropropane; 1-54 weight percent 1,1,2,3,3-pentafluoropropane and 46-99 weight percent 1,1,1,4,4,4-hexafluorobutane; 1-56 weight percent 1,1,2,3,3-pentafluoropropane and 44-99 weight percent 1,1,1,2,3,4,4, 5,5,5-decafluoropentane; 1-65 weight percent 1,1,2,3,3-pentafluoropropane and 35-99 weight percent butane; 1-54 weight percent 1,1,2,3,3-pentafluoropropane and 46-99 weight percent cyclopropane; 1-62 weight percent 1,1,2,3, 3-pentafluoropropane and 38-99 weight percent isobutane; 1-57 weight percent 1,1,2,3,3-pentafluoropropane and 43-99 weight percent propane; 1-99 weight percent 1,1,1, 2,3-pentafluoropropane and 1-99 weight percent 1,2,2-trifluoropropane; 1-43 weight percent 1,1,1,2,3-pentafluoropropane and 57-99 percent 1,1,1-trifluoropropane; 11-99 weight percent 1,1,1,2,3-pentafluoropropane and 1-89 weight percent 1,1,1,4,4,4-hexafluorobutane; 21-71 weight p and 29-79 weight percent butane; 1-56 weight percent 1,1,1,2,3-pentafluoropropane and 44-99 weight percent cyclopropane; 1-66 weight percent 1,1,1,2,3-pentafluoropropane and 34-99 weight percent isobutane; 1-57 weight percent 1,1,1,2,3-pentafluoropropane and 43-99 weight percent propane; 1-78 weight percent 1,1,1,3,3-pentafluoropropane and 22-99 weight percent butane; 1-60 weight percent 1,1,1,3, 3-pentafluoropropane and 40-99 weight percent isobutane; or 58-99 weight percent 1,1,1,3,3-pentafluoropropane and 1-42 weight percent pentane.

2. A binary composition of claim 1 which has a maximum or minimum vapor pressure at 25° C. when compared to the vapor pressures at 25° C. of the individual components of the binary composition.

3. A process for producing refrigeration, comprising condensing a composition of claim 1 and thereafter evaporating said composition in the vicinity of a body to be cooled.

4. A process for producing heat comprising condensing a composition of claim 1 in the vicinity of a body to be heated, and thereafter evaporating said composition.

5. A process for preparing a polymer foam, comprising using a composition of claim 1 as a blowing agent.

6. A process for cleaning a solid surface comprising treating said surface with a composition of claim 1.

7. An azeotropic or azeotrope-like composition consisting essentially of: 1-99 weight percent 1,1,2,2,3 -pentafluoropropane and 1-99 weight percent 1,1,1,2,3 -pentafluoropropane; 1-36 weight percent 1,1,2,2,3 -pentafluoropropane and 64-99 weight percent 1,1,1 -trifluoropropane; 1-55 weight percent 1,1,2,2,3 -pentafluoropropane and 45-99 weight percent 2,2 -difluoropropane; 1-99 weight percent 1,1,2,2,3 -pentafluoropropane and 1-99 weight percent 1,2 -difluoropropane; 1-73 weight percent 1,1,2,2,3 -pentafluoropropane and 27-99 weight percent butane; 1-55 weight percent 1,1,2,2,3 -pentafluoropropane and 45-99 weight percent and cyclopropane; 1-65 weight percent 1,1,2,2,3 -pentafluoropropane and 35-99 weight percent isobutane; 1-57 weight percent 1,1,2,2,3 -pentafluoropropane and 43-99 weight percent propane; 70-99.5 weight percent 1,1,1,2,2 -pentafluoropropane and 0.5-30 weight percent 1,1,1,2,3 -pentafluoropropane; 74-99 weight percent 1,1,1,2,2 -pentafluoropropane and 1-26 weight percent 1,2,2,3 -tetrafluoropropane; 75-99 weight percent 1,1,1,2,2 -pentafluoropropane and 1-25 weight percent 1,2 -difluoropropane; 1-99 weight percent 1,1,1,2,2 -pentafluoropropane and 1-99 weight percent 2 -fluoropropane; 59-99 weight percent 1,1,1,2,2 -pentafluoropropane and 1-41 weight percent 1 -fluoropropane; 59-99 weight percent 1,1,1,2,2 -pentafluoropropane and 1-41 weight percent butane; 1-90 weight percent 1,1,1,2,2 -pentafluoropropane and 10-99 weight percent cyclopropane; 1-89 weight percent 1,1,1,2,2 -pentafluoropropane and 11-99 weight percent dimethyl ether; 40-99 weight percent 1,1,1,2,2 -pentafluoropropane and 1-60 weight percent isobutane; 1-76 weight percent 1,1,1,2,2 -pentafluoropropane and 24-99 weight percent propane; 1-69 weight percent 1,1,1,2,2 -pentafluoropropane and 31-99 weight percent propylene; 1-45 weight percent 1,1,2,3,3 -pentafluoropropane and 55-99 weight percent 2,2 -difluoropropane; 1-55 weight percent 1,1,2,3,3 -pentafluoropropane and 45-99 weight percent 1,2 -difluoropropane; 1-56 weight percent 1,1,2,3,3 -pentafluoropropane and 44-99 weight percent 1,1,1,2,3,4,4,5,5,5 -decafluoropentane; 1-65 weight percent 1,1,2,3,3 -pentafluoropropane and 35-99 weight percent butane; 1-54 weight percent 1,1,2,3,3 -pentafluoropropane and 46-99 weight percent cyclopropane; 1-62 weight percent 1,1,2,3,3 -pentafluoropropane and 38-99 weight percent isobutane; 1-57 weight percent 1,1,2,3,3 -pentafluoropropane and 43-99 weight percent propane; 1-99 weight percent 1,1,1,2,3 -pentafluoropropane and 1-99 weight percent 1,2,2 -trifluoropropane; 1-43 weight percent 1,1,1,2,3 -pentafluoropropane and 57-99 percent 1,1,1 -trifluoropropane; 21-71 weight percent 1,1,1,2,3 -pentafluoropropane and 29-79 weight percent butane; 1-56 weight percent 1,1,1,2,3 -pentafluoropropane and 44-99 weight percent cyclopropane; 1-66 weight percent 1,1,1,2,3 -pentafluoropropane and 34-99 weight percent isobutane; 1-57 weight percent 1,1,1,2,3 -pentafluoropropane and 43-99 weight percent propane; 1-78 weight percent 1,1,1,3,3 -pentafluoropropane and 22-99 weight percent butane; 1-60 weight percent 1,1,1,3,3 -pentafluoropropane and 40-99 weight percent isobutane.

8. A binary composition of claim 7 which has a maximum or minimum vapor pressure at 25° C. when compared to the vapor pressures at 25° C. of the individual components of the binary composition.

9. A process for producing refrigeration, comprising condensing a composition of claim 7 and thereafter evaporating said composition in the vicinity of a body to be cooled.

10. A process for producing heat comprising condensing a composition of claim 7 in the vicinity of a body to be heated, and thereafter evaporating said composition.

11. A process for preparing a polymer foam, comprising using a composition of claim 7 as a blowing agent.

12. A process for cleaning a solid surface comprising treating said surface with a composition of claim 7.