Information
-
Patent Grant
-
RE37938
-
Patent Number
RE37,938
-
Date Filed
Wednesday, May 26, 199925 years ago
-
Date Issued
Tuesday, December 17, 200221 years ago
-
Inventors
-
Original Assignees
-
Examiners
Agents
-
-
US Classifications
Field of Search
US
- 252 67
- 252 364
- 510 108
- 510 177
- 510 408
- 510 411
- 510 415
- 134 40
- 134 42
-
International Classifications
- B01F100
- C09K500
- C11D730
- C11D750
- C23G5024
-
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)
Divisions (1)
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