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Description  |
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FIELD OF THE INVENTION
This invention relates to compositions that include
1,1,1,2,3,4,4,5,5,5-decafluoropentane. 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.
BACKGROUND OF THE INVENTION
Fluorinated hydrocarbons have many uses, one of which is as a refrigerant.
Such refrigerants include trichlorofluoromethane (CFC-11)
dichlorodifluoromethane (CFC-12) and chlorodifluoromethane (HCFC-22).
In recent years it has been pointed out that certain kinds of fluorinated
hydrocarbon refrigerants released into the atmosphere may adversely affect
the stratospheric ozone layer. Although this proposition has not yet been
completely established, there is a movement toward the control of the use
and the production of certain chlorofluorocarbons (CFCs) and
hydrochlorofluorocarbons (HCFCs) under an international agreement.
Accordingly, there is a demand for the development of refrigerants that
have a lower ozone depletion potential than existing refrigerants while
still achieving an acceptable performance in refrigeration applications.
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, if possible, to use as a refrigerant a single
compound or an azeotropic or azeotrope-like composition of more than one
compound.
It is also desirable to find replacements for CFCs and HCFCs for use as a
cleaning agent or solvent to clean, for example, electronic circuit
boards. It is preferred 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.
Replacements for CFCs and HCFCs may also useful as blowing agents in the
manufacture of closed-cell polyurethane, phenolic and thermoplastic foams,
as propellants in aerosols, as heat transfer media, gaseous dielectrics,
fire extinguishing agents, power cycle working fluids such as for heat
pumps, inert media for polymerization reactions, fluids for removing
particulates from metal surfaces, as carrier fluids that may be used, for
example, to place a fine film of lubricant on metal parts, as buffing
abrasive agents to remove buffing abrasive compounds from polished
surfaces such as metal, as displacement drying agents for removing water,
such as from jewelry or metal parts, as resist developers in conventional
circuit manufacturing techniques including chlorine-type developing
agents, or as strippers for photoresists when used with, for example, a
chlorohydrocarbon such as 1,1,1-trichloroethane or trichloroethylene.
SUMMARY OF THE INVENTION
The present invention relates to the following compositions:
1,1,1,2,3,4,4,5,5,5-decafluoropentane and bis(fluoromethyl) ether,
2,2,4,4-tetrafluorooxetane, 2,2,3,3-tetrafluorooxetane,
1,1,1,2-tetrafluoro-2-(fluoromethoxy)ethane,
1-(difluoromethoxy)-1,2,2-trifluoroethane,
1-(difluoromethoxy)-1,1,2-trifluoroethane, acetone, cyclopentane, ethyl
acetate, ethyl formate, methyl tert-butyl ether, methyl acetate, methyl
formate, propylene oxide, 2,2-dimethylbutane, n-pentane or n-propanol.
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 these
components 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
4310mee and 152E at 25.degree. C.;
FIG. 2 is a graph of the vapor/liquid equilibrium curve for mixtures of
4310mee and 245eaE at 25.degree. C.;
FIG. 3 is a graph of the vapor/liquid equilibrium curve for mixtures of
4310mee and acetone at 25.degree. C.;
FIG. 4 is a graph of the vapor/liquid equilibrium curve for mixtures of
4310mee and cyclopropane at 25.degree. C.;
FIG. 5 is a graph of the vapor/liquid equilibrium curve for mixtures of
4310mee and ethyl acetate at 25.degree. C.;
FIG. 6 is a graph of the vapor/liquid equilibrium curve for mixtures of
4310mee and ethyl formate at 25.degree. C.;
FIG. 7 is a graph of the vapor/liquid equilibrium curve for mixtures of
4310mee and methyl acetate at 25.degree. C.;
FIG. 8 is a graph of the vapor/liquid equilibrium curve for mixtures of
4310mee and methyl formate at 25.degree. C.;
FIG. 9 is a graph of the vapor/liquid equilibrium curve for mixtures of
4310mee and propylene oxide at 25.degree. C.;
FIG. 10 is a graph of the vapor/liquid equilibrium curve for mixtures of
4310mee and 2,2-dimethylbutane at 25.degree. C.;
FIG. 11 is a graph of the vapor/liquid equilibrium curve for mixtures of
4310mee and n-pentane at 25.degree. C.;
FIG. 12 is a graph of the vapor/liquid equilibrium curve for mixtures of
4310mee and n-propanol at 25.degree. C.; and
FIG. 13 is a graph of the vapor/liquid equilibrium curve for mixtures of
4310mee and MTBE at 18.46.degree. C.
DETAILED DESCRIPTION
The present invention relates to the discovery of compositions of
1,1,1,2,3,4,4,5,5,5-decafluoropentane (HFC-4310mee) and bis(fluoromethyl)
ether (152E), 2,2,4,4-tetrafluorooxetane (c234fE.alpha..beta.),
2,2,3,3-tetrafluorooxetane (c234fE.beta..gamma.),
1,1,1,2-tetrafluoro-2-(fluoromethoxy)ethane (245ebE.beta..gamma.),
1-(difluoromethoxy)-1,2,2-trifluoroethane (245eaE),
1-(difluoromethoxy)-1,1,2-trifluoroethane (245caE.alpha..beta.), acetone,
cyclopentane, ethyl acetate, ethyl formate, methyl tert-butyl ether
(MTBE), methyl acetate, methyl formate, propylene oxide,
2,2-dimethylbutane, n-pentane or n-propanol. 1-99 wt. % of each of the
components in the above compositions can be used as refrigerants.
The present invention also relates to the discovery of azeotropic or
azeotrope-like compositions of effective amounts of 4310mee and 152E,
c234fE.alpha..beta., c234fE.beta..gamma., 245ebE.beta..gamma., 245eaE,
245caE.alpha..beta., acetone, cyclopentane, ethyl acetate, ethyl formate,
MTBE, methyl acetate, methyl formate, propylene oxide, 2,2-dimethylbutane,
n-pentane, or n-propanol to form an azeotropic or azeotrope-like
composition.
The components of the compositions of this invention include the following.
1. 1,1,1,2,3,4,4,5,5,5-decafluoropentane (HFC-4310mee, or CF.sub.3
CFHCFHCF.sub.2 CF.sub.3) boiling point=50.0C,
2. Bis(fluoromethyl)ether (152E, CH.sub.2 FOCH.sub.2 F), having a boiling
point=33C,
3. 2,2,4,4-tetrafluorooxetane (c234fE.alpha..beta., or C.sub.3 H.sub.2
F.sub.4 O, having a structure of
##STR1##
boiling point=21.2.degree. C.),
4. 2,2,3,3-tetrafluorooxetane (c234fE.beta..gamma., or C.sub.3 H.sub.2
F.sub.4 O, having a structure of
##STR2##
boiling point=28.degree. C.),
5. 1,1,1,2-tetrafluoro-2-(fluoromethoxy)ethane, (245ebE.beta..gamma., or
CH.sub.2 FOCHFCF.sub.3, boiling point=43.degree. C.)
6. 1-(difluoromethoxy)-1,2,2-trifluoroethane (245eaE, or CHF.sub.2
OCHFCHF.sub.2, boiling point=53.degree. C.),
7. 1-(difluoromethoxy)-1,1,2-trifluoroethane (245caE.alpha..beta., or
CHF.sub.2 OCF.sub.2 CH.sub.2 F, boiling point=40.degree. C.),
8. acetone, CH.sub.3 COCH.sub.3, boiling point=56.2C,
9. cyclopentane, C.sub.5 H.sub.10, boiling point=49.2C,
10. ethyl acetate, CH.sub.3 COOC.sub.2 H.sub.5, boiling point=77C,
11. ethyl formate, HCOOC.sub.2 H.sub.5, boiling point=53-54C,
12. methyl tert-butyl ether, (CH.sub.3).sub.3 C(OCH.sub.3), or MTBE,
boiling point=55.2C,
13. methyl acetate, CH.sub.3 COOCH.sub.3, boiling point=56.9C,
14. methyl formate, HCOOCH.sub.3, boiling point=31.5C,
15. propylene oxide, C3H6O, boiling point=34.23C,
16. 2,2-dimethylbutane, CH.sub.3 CH.sub.2 C(CH.sub.3).sub.3, boiling
point=49.74C,
17. n-pentane, CH.sub.3 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3, boiling
point=35.07C,
18. n-propanol, CH.sub.3 CH.sub.2 CH.sub.2 OH, boiling point=97.2C.
152E, CAS Reg. No. [462-51-1], has been prepared by reacting
poly(oxymethylene) with sulfur tetrafluoride as reported by Hasek, et. al.
in J. Am. Chem. Soc. Vol. 82, pages 543-551 (1960).
c234fE.alpha..beta. may be prepared by direct fluorination of trimethylene
oxide (cyclo-CH.sub.2 CH.sub.2 CH.sub.2 O--) using techniques described by
Lagow and Margrave in Progress in Inorganic Chemistry, Vol. 26, pp.
161-210 (1979) or by Adcock and Cherry in Ind. Eng. Chem. Res., Vol. 26,
pp. 208-215 (1987). The direct fluorination is carried out to the desired
level of fluorine incorporation into the starting material, and products
receovered by fractional distillation.
c234fE.beta..gamma. (CAS Reg. No. 765-63-9) has been prepared by Weinmayr
(J. Org. Chem., Vol. 28, pp. 492-494 (1963)) as a by-product from the
reaction of TFE with formaldehyde in HF.
245caE.alpha..beta. (CAS Reg. No. 69948-24-9), HFOC-245caE.alpha..beta.,
has been prepared by hydrogenation of 2-chloro-1,1,2-trifluoroethyl
difluoromethyl ether at 200.degree. C. over a palladium catalyst as
reported by Bagnall, et. al. in J. Fluorine Chem. Vol. 13, pages 123-140
(1979).
245eaE (CAS Reg. No. 60113-74-8), HFOC-245eaE, has been prepared by
hydrogenation of 1,2-dichloro-1,2,2-trifluoroethyl difluoromethyl ether at
a temperature range of 200-250C using a palladium on charcoal catalyst as
disclosed by Bell, et. al. U.S. Pat. No. 4,149,018.
245ebE.beta..gamma. (CAS Reg. No. 56885-27-9), HFOC-245ebE.beta..gamma. has
been prepared by fluorination of
1,1,1,2-tetrafluoro-2-(chloromethoxy)ethane using HF and a chromium
oxyfluoride catalyst as disclosed by Siegemund, et. al. in Ger. Offen.
2,520,962.
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 4310mee and 152E, c234fE.alpha..beta., c234fE.beta..gamma.,
245ebE.beta..gamma., 245eaE, 245caE.alpha..beta., acetone, cyclopentane,
ethyl acetate, ethyl formate, MTBE, methyl acetate, methyl formate,
propylene oxide, 2,2-dimethylbutane, n-pentane or n-propanol, 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, have 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 temperature, 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 components of the compositions of this invention have the following
vapor pressures at 25.degree. C.
______________________________________
Component Psia kPa
______________________________________
4310mee 4.36 30
152E 11.00 76
c234fE.alpha..beta.
16.75 115
c234fF.beta..gamma.
13.26 91
245ebE.beta..gamma.
7.63 53
245eaE 5.22 36
245caE.alpha..beta.
8.51 59
acetone 4.45 31
cyclopentane 6.14 42
ethyl acetate 1.87 13
ethyl formate 4.69 32
MTBE 4.59 32
methyl acetate 4.18 29
methyl formate 10.68 74
propylene oxide 10.43 72
2,2-dimethylbutane 6.17 43
n-pentane 10.29 71
n-propanol 0.403 2.8
______________________________________
Substantially constant boiling, azeotropic or azeotrope-like compositions
of this invention comprise the following (all compositions are measured at
25.degree. C.):
______________________________________
WEIGHT
RANGES PREFERRED
COMPONENTS (wt. %/wt/%) (wt. %/wt. %)
______________________________________
4310mee/152E 1-70/30-99 40-70/30-60
4310mee/c234fE.alpha..beta.
1-41/59-99 1-41/59-99
4310mee/c234fE.beta..gamma.
1-49/51-99 1-49/51-99
4310mee/245ebE.beta..gamma.
1-99/1-99 15-99/1-85
4310mee/245eaE 1-99/1-99 40-99/1-60
4310mee/245caE.alpha..beta.
1-99/1-99 10-80/20-90
4310mee/acetone 1-99/1-99 40-99/1-60
4310mee/cyclopentane
39-83/17-61 39-83/17-61
4310mee/ethyl acetate
65-99/1-35 65-99/1-35
4310mee/ethyl formate
53-89/11-47 53-89/11-47
4310mee/MTBE 1-99/1-99 40-99/1-60
4310mee/methyl acetate
50-89/11-50 50-89/11-50
4310mee/methyl formate
36-82/18-64 50-82/18-50
4310mee/propylene oxide
28-79/21-72 50-79/21-50
4310mee/2,2-dimethylbutane
39-82/18-61 50-82/18-50
4310mee/n-pentane
29-77/23-71 40-77/23-60
4310mee/n-propanol
85-99.3/0.7-15
85-99.3/0.7-15
______________________________________
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.degree. C.
______________________________________
Vapor Press.
Composition Weight percents
psia kPa
______________________________________
4310mee/152E 36.3/63.7 12.07 83
4310mee/245eaE 33.6/66.4 5.38 37
4310mee/acetone 73.3/26.7 3.15 22
4310mee/cyclopentane
62.3/37.7 8.60 59
4310mee/ethyl acetate
90.3/9.7 4.67 32
4310mee/ethyl formate
70.6/29.4 7.34 51
4310mee/methyl acetate
73.8/26.2 7.04 49
4310mee/methyl formate
56.8/43.2 13.90 96
4310mee/propylene oxide
52.4/47.6 12.43 86
4310mee/2,2-dimethylbutane
62.1/37.9 9.24 64
4310mee/n-pentane
50.5/49.5 12.80 88
4310mee/n-propanol
99.3/0.7 4.38 30
______________________________________
EXAMPLE 2
Impact of Vapor Leakage on Vapor Pressure at 25.degree. C.
A vessel is charged with an initial composition at 25.degree. C., and the
vapor pressure of the composition is measured. The composition is allowed
to leak from the vessel, while the temperature is held constant at
25.degree. 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.
______________________________________
0 %
0 wt % 50 wt % change
Refrigerant evaporated
evaporated
in vapor
Composition psia kPa psia kPa pressure
______________________________________
4310mee/152E
36.3/63.7 12.07 83 12.07
83 0.0
20/80 11.97 83 11.75
81 1.8
10/90 11.72 81 11.25
78 4.0
1/99 11.11 77 11.01
76 0.9
60/40 11.87 82 11.48
79 3.3
70/30 11.56 80 10.45
72 9.6
71/29 11.51 79 10.29
71 10.6
4310mee/c234fE.alpha..beta.
1/99 16.71 115 16.69
115 0.1
20/80 15.86 109 15.39
106 3.0
41/59 14.60 101 13.17
91 9.8
42/58 14.53 100 13.03
90 10.3
4310mee/c234fE.beta..gamma.
1/99 13.25 91 13.25
91 0.0
20/80 12.88 89 12.72
88 1.2
40/60 12.21 84 11.50
79 5.8
50/50 11.71 81 10.53
73 10.1
49/51 11.76 81 10.64
73 9.5
4310mee/245ebE.beta..gamma.
1/99 7.61 52 7.61 52 0.0
20/80 7.37 51 7.30 50 0.9
40/60 6.99 48 6.81 47 2.6
60/40 6.45 44 6.12 42 5.1
80/20 5.64 39 5.24 36 7.1
90/10 5.08 35 4.78 33 5.9
99/1 4.44 31 4.40 30 0.9
4310mee/245eaE
33.6/66.4 5.38 37 5.38 37 0.0
20/80 5.36 37 5.35 37 0.2
1/99 5.23 36 5.23 36 0.0
60/40 5.27 36 5.24 36 0.6
80/20 5.00 34 4.89 34 2.2
99/1 4.40 30 4.39 30 0.2
4310mee/245caE.alpha..beta.
1/99 8.49 59 8.48 58 0.1
20/80 8.11 56 7.98 55 1.6
40/60 7.59 52 7.29 50 4.0
60/40 6.88 47 6.38 44 7.3
80/20 5.87 40 5.32 37 9.4
85/15 5.55 38 5.05 35 9.0
99/1 4.45 31 4.40 30 1.1
4310mee/acetone
73.3/26.7 3.15 22 3.15 22 0.0
90/10 3.55 24 3.40 23 4.2
99/1 4.25 29 4.20 29 1.2
40/60 3.82 26 3.49 24 8.6
30/70 4.08 28 3.74 26 8.3
20/80 4.28 30 4.04 28 5.6
1/99 4.45 31 4.45 31 0.0
4310mee/cyclopentane
62.3/37.7 8.60 59 8.60 59 0.0
80/20 8.44 58 8.01 55 5.1
83/17 8.34 58 7.62 53 8.6
84/16 8.30 57 7.44 51 10.4
39/61 8.55 59 8.09 56 5.4
38/62 8.54 59 7.58 52 11.2
4310mee/ethyl acetate
90.3/9.7 4.67 32 4.67 32 0.0
99/1 4.45 31 4.42 30 0.7
65/35 4.42 30 4.03 28 8.8
64/36 4.41 30 3.96 27 10.2
4310mee/ethyl formate
70.6/29.4 7.34 51 7.34 51 0.0
87/13 7.14 49 6.55 45 8.3
88/12 7.09 49 6.37 44 10.2
47/53 7.23 50 6.70 46 7.3
46/54 7.26 50 6.51 45 10.3
4310mee/MTBE
1/99 4.59 32 4.59 32 0.0
20/80 4.57 32 4.56 31 0.2
40/60 4.53 31 4.53 31 0.0
60/40 4.47 31 4.47 31 0.0
80/20 4.39 30 4.39 30 0.0
99/1 4.28 30 4.28 30 0.0
4310mee/methyl acetate
73.8/26.2 7.04 49 7.04 49 0.0
89/11 6.83 47 6.20 43 9.2
90/10 6.78 47 6.00 41 11.5
50/50 6.97 48 6.43 44 7.7
49/51 6.97 48 6.19 43 11.2
4310mee/methyl formate
56.8/43.2 13.90 96 13.90
96 0.0
80/20 13.77 95 12.96
89 5.9
82/18 13.72 95 12.42
86 9.5
83/17 13.69 94 12.02
83 12.2
36/64 13.88 96 12.79
88 7.9
35/65 13.88 96 10.75
74 22.6
4310mee/propylene oxide
52.4/47.6 12.43 86 12.43
86 0.0
80/20 12.05 83 10.77
74 10.6
79/21 12.10 83 10.99
76 9.2
28/72 12.33 85 11.18
77 9.3
27/73 12.32 85 11.02
76 10.6
4310mee/2,2-dimethylbutane
62.1/37.9 9.24 64 9.24 64 0.0
82/18 9.09 63 8.29 57 8.8
83/17 9.06 62 8.07 56 10.9
39/61 9.20 63 8.38 58 8.9
38/62 9.20 63 7.84 54 14.8
4310mee/n-pentane
50.5/49.5 12.80 88 12.80
88 0.0
70/30 12.70 88 12.36
85 2.7
77/23 12.55 87 11.44
79 8.8
78/22 12.52 86 11.20
77 10.5
29/71 12.75 88 11.57
80 9.3
28/72 12.74 88 11.21
77 12.0
4310mee/n-propanol
99.3/0.7 4.38 30 4.38 30 0.0
85/15 4.16 29 3.82 26 8.2
84/16 4.15 29 3.70 26 10.8
______________________________________
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.degree. C.
EXAMPLE 3
Impact of Vapor Leakage at 0.degree. C.
A leak test is performed on compositions of 4310mee and 152E, at the
temperature of 0.degree. C. The results are summarized below.
______________________________________
0 %
0 wt % 50 wt % change
Refrigerant
evaporated evaporated in vapor
Composition
psia kPa psia kPa pressure
______________________________________
4310mee/152E
30.0/70.0 4.28 30 4.28 30 0.0
20/80 4.26 29 4.24 29 0.5
10/90 4.20 29 4.09 28 2.6
1/99 4.02 28 3.99 28 0.7
60/40 4.18 29 3.96 27 5.3
66/34 4.12 28 3.73 26 9.5
67/33 4.10 28 3.67 25 10.5
______________________________________
These results show that compositions of 4310mee and 152E 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
40.0.degree. F. (4.4.degree. C.)
Condenser temperature
130.0.degree. F. (54.4.degree. C.)
Subcool 5.0.degree. F. (2.8.degree. C.)
Return gas temperature
60.0.degree. F. (15.6.degree. C.)
Compressor efficiency is
70%.
______________________________________
The refrigeration capacity is based on a compressor with a fixed
displacement of 3.5 cubic feet per minute and 70% volumetric efficiency.
Capacity is intended to mean the change in enthalpy of the refrigerant in
the evaporator per pound of refrigerant circulated, i.e. the heat removed
by the refrigerant in the evaporator per time. Coefficient of performance
(COP) is intended to mean the ratio of the capacity to compressor work. It
is a measure of refrigerant energy efficiency.
__________________________________________________________________________
Evap. Cond. Capacity
Refrig. Press.
Press.
Comp. Dis.
BTU/min
Comp. Psia
kPa
Psia
kPa
Temp. .degree.F. .degree.C.
COP
kw
__________________________________________________________________________
4310mee/152E
1.0/99.0 4.5
31 30.0
207
211.2
99.6
3.28
28.3
0.5
36.3/63.7 5.5
38 35.5
245
183.4
84.1
3.15
31.9
0.6
99.0/1.0 2.2
15 16.8
116
131.8
55.4
2.89
12.2
0.2
4310mee/c234fE.alpha..beta.
1.0/99.0 7.6
52 41.5
286
158.6
70.3
3.06
38.2
0.7
41.0/59.0 6.0
41 37.0
255
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