Pentafluoropropane compositions

Information

  • Patent Grant
  • RE37938
  • Patent Number
    RE37,938
  • Date Filed
    Wednesday, May 26, 1999
    25 years ago
  • Date Issued
    Tuesday, December 17, 2002
    21 years ago
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; (CF


3


)


2


CHCH


3


; 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; (CF


3


)


2


CHCH


2


; 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; (CF


3


)


2


CHCH


3


; 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), (CF


3


)


2


CHCH


3


(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;




(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;




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




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
  • 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.
US Referenced Citations (8)
Number Name Date Kind
5538659 Chisolm et al. Jul 1996 A
5558810 Minor et al. Sep 1996 A
5562857 Werner et al. Oct 1996 A
5605882 Klug et al. Feb 1997 A
5650089 Gage et al. Jul 1997 A
5672294 Lund et al. Sep 1997 A
5677358 Lund et al. Oct 1997 A
5866029 Lund et al. Feb 1999 A
Divisions (1)
Number Date Country
Parent 08/850970 May 1997 US
Child 09/320440 US
Reissues (1)
Number Date Country
Parent 08/850970 May 1997 US
Child 09/320440 US