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FIELD OF THE
INVENTION
This invention relates to refrigerant compositions that include at least one acyclic fluoroether. 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 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 discovery of refrigerant compositions of hexafluoro dimethyl ether and cyclopropane, dimethyl ether or propylene; bis(difluoromethyl) ether and 2,2,3,4,4-pentafluorooxetane; fluoromethyl trifluoromethyl ether
and 2,2,4,4,5,5-hexafluoro-1, 3-dioxolane, 1-trifluoromethoxy-1,2,2,2-tetrafluoroethane, dimethyl ether or tris(trifluoromethyl)amine; trifluoromethyl methyl ether and perfluorooxetane, 2,2,4,4,5,5-hexafluoro-1,3-dioxolane, perfluoromethyl ethyl ether,
perfluorodimethoxyrnethane, 1-trifluoromethoxy-1,2,2,2-tetrafluoroethane, dimethyl ether or tris(trifluoromethyl)amine; perfluoromethyl ethyl ether and dimethyl ether or propylene; perfluorodimethoxymethane and dimethyl ether or isobutane;
1-trifluoromethoxy-1,1,2,2-tetrafluoroethane and tris(trifluoromethyl)amine or dimethyl ether; difluoromethoxy pentafluoroethane and dimethyl ether, isobutane or tris(trifluoromethyl)amine; 1-trifluoromethoxy-1,2,2,2-tetrafluoroethane and dimethyl ether
or isobutane; 1-difluoromethoxy-1,1,2,2-tetrafluoroethane and N(CHF.sub.2).sub.2 (CF.sub.3); or 1,1,1,2,2,3,3-heptafluoro-3-(1,2,2,2-tetrafluoroethoxy)propane and 1,1,2,2,3-pentafluoropropane or 1,1,1,2,3-pentafluoropropane. This invention also relates
to the discovery of effective amounts of the components of these compositions to form azeotropic or azeotrope-like compositions.
These compositions are also useful as cleaning agents, expansion agents for polyolefins and polyurethanes, aerosol propellants, heat transfer media, gaseous dielectrics, fire extinguishing agents, power cycle working fluids, polymerization media,
particulate removal fluids, carrier fluids, buffing abrasive agents, and displacement drying agents.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a graph of the vapor/liquid equilibrium curve for mixtures of 116E and cyclopropane at 25.degree. C.;
FIG. 2 is a graph of the vapor/liquid equilibrium curve for mixtures of 116E and DME at 25.degree. C.;
FIG. 3 is a graph of the vapor/liquid equilibrium curve for mixtures of 116E and propylene at 25.degree. C.;
FIG. 4 is a graph of the vapor/liquid equilibrium curve for mixtures of 134E and C-225eE.alpha..beta. at 25.degree. C.;
FIG. 5 is a graph of the vapor/liquid equilibrium curve for mixtures of 134aE and C-216E2 at 25.degree. C.;
FIG. 6 is a graph of the vapor/liquid equilibrium curve for mixtures of 134aE and 227eaE at 25.degree. C.;
FIG. 7 is a graph of the vapor/liquid equilibrium curve for mixtures of 134aE and DME at 25.degree. C.;
FIG. 8 is a graph of the vapor/liquid equilibrium curve for mixtures of 134aE and N(CF.sub.3).sub.3 at 25.degree. C.;
FIG. 9 is a graph of the vapor/liquid equilibrium curve for mixtures of 143aE and C-216E at 25.degree. C.;
FIG. 10 is a graph of the vapor/liquid equilibrium curve for mixtures of 143aE and C-216E2 at 25.degree. C.;
FIG. 11 is a graph of the vapor/liquid equilibrium curve for mixtures of 143aE and 218E at 25.degree. C.;
FIG. 12 is a graph of the vapor/liquid equilibrium curve for mixtures of 143aE and 218E2 at 25.degree. C.;
FIG. 13 is a graph of the vapor/liquid equilibrium curve for mixtures of 143aE and 227eaE at 25.degree. C.;
FIG. 14 is a graph of the vapor/liquid equilibrium curve for mixtures of 143aE and DME at 25.degree. C.;
FIG. 15 is a graph of the vapor/liquid equilibrium curve for mixtures of 143aE and N(CF.sub.3).sub.3 at 25.degree. C.;
FIG. 16 is a graph of the vapor/liquid equilibrium curve for mixtures of 218E and DME at 25.degree. C.;
FIG. 17 is a graph of the vapor/liquid equilibrium curve for mixtures of 218E and propylene at 25.degree. C.;
FIG. 18 is a graph of the vapor/liquid equilibrium curve for mixtures of 218E2 and DME at 25.degree. C.;
FIG. 19 is a graph of the vapor/liquid equilibrium curve for mixtures of 218E2 and isobutane at 25.degree. C.;
FIG. 20 is a graph of the vapor/liquid equilibrium curve for mixtures of 227caE.alpha..beta. and N(CF.sub.3).sub.3 at 25.degree. C.;
FIG. 21 is a graph of the vapor/liquid equilibrium curve for mixtures of 227caE.alpha..beta. and DME at 25.degree. C.;
FIG. 22 is a graph of the vapor/liquid equilibrium curve for mixtures of 227caE.beta..gamma. and DME at 25.degree. C.;
FIG. 23 is a graph of the vapor/liquid equilibrium curve for mixtures of 227caE.beta..gamma. and isobutane at 25.degree. C.;
FIG. 24 is a graph of the vapor/liquid equilibrium curve for mixtures of 227caE.beta..gamma. and N(CF.sub.3).sub.3 at 25.degree. C.;
FIG. 25 is a graph of the vapor/liquid equilibrium curve for mixtures of 227eaE and DME at 25.degree. C.;
FIG. 26 is a graph of the vapor/liquid equilibrium curve for mixtures of 227eaE and isobutane at 25.degree. C.;
FIG. 27 is a graph of the vapor/liquid equilibrium curve for mixtures of 236caE and N(CHF.sub.2).sub.2 (CF.sub.3) at 25.degree. C.;
FIG. 28 is a graph of the vapor/liquid equilibrium curve for mixtures of E-42-11meE.gamma..delta. and HFC-245ca at 19.05.degree. C.; and
FIG. 29 is a graph of the vapor/liquid equilibrium curve for mixtures of E-42-11meE.gamma..delta. and HFC-245eb at 14.14.degree. C.
DETAILED DESCRIPTION
The present invention relates to the following compositions: hexafluorodimethyl ether and cyclopropane, dimethyl ether or propylene; bis(difluoromethyl) ether and 2,2,3,4,4-pentafluorooxetane; fluoromethyl trifluoromethyl ether and
2,2,4,4,5,5-hexafluoro-1,3-dioxolane, 1-trifluoromethoxy-1,2,2,2-tetrafluoroethane, dimethyl ether or tris(trifluoromethyl)amine; trifluoromethyl methyl ether and perfluorooxetane, 2,2,4,4,5,5-hexafluoro-1,3-dioxolane, perfluoromethyl ethyl ether,
perfluorodimethoxymethane, 1-trifluoromethoxy-1,2,2,2-tetrafluoroethane, dimethyl ether or tris(trifluoromethyl)amine; perfluoromethyl ethyl ether and dimethyl ether or propylene; perfluorodimethoxymethane and dimethyl ether or isobutane;
1-trifluoromethoxy-1,1,2,2-tetrafluoroethane and tris(trifluoromethyl)amine or dimethyl ether; difluoromethoxy pentafluoroethane and dimethyl ether, isobutane or tris(trifluoromethyl)amine; 1-trifluoromethoxy-1,2,2,2-tetrafluoroethane and dimethyl ether
or isobutane; 1-difluoromethoxy-1,1,2,2-tetrafluoroethane and N(CHF.sub.2).sub.2 (CF.sub.3); or 1,1,1,2,2,3,3-heptafluoro-3-(1,2,2,2-tetrafluoroethoxy)propane and 1,1,2,2,3-pentafluoropropane or 1,1,1,2,3-pentafluoropropane. This invention also relates
to the discovery of effective amounts of the components of these compositions to form azeotropic or azeotrope-like compositions.
1-99 wt. % of each of the above components can be used as refrigerants.
The components of the refrigerants in this invention include the following.
1. Hexafluorodimethyl ether (116E, or CF.sub.3 OCF.sub.3, boiling point=-59.0.degree. C.),
2. bis(difluoromethyl) ether (134E, or CHF.sub.2 OCHF.sub.2, boiling point=5.degree. C.),
3. Fluoromethyl trifluoromethyl ether (134aE, or CH.sub.2 FOCF.sub.3, boiling point=-20.0.degree. C.),
4. Trifluoromethyl methyl ether (143aE, or CH.sub.3 OCF.sub.3, boiling point=-24.2.degree. C.),
5. Perfluorooxetane (C-216E or ##STR1## boiling point=-29.2.degree. C.),
6. 2,2,4,4,5,5-hexafluoro-1,3-dioxolane (C-216E2 or C.sub.3 F.sub.6 O.sub.2, having a structure of ##STR2## boiling point=-22.1.degree. C.),
7. Perfluoromethyl ethyl ether (218E, or CF.sub.3 OCF.sub.2 CF.sub.3, boiling point=23.3.degree. C.),
8. Perfluorodimethoxymethane (218E2, or CF.sub.3 OCF.sub.2 OCF.sub.3, boiling point =-10.2.degree. C.),
9. 1-trifluoromethoxy-1,1,2,2-tetrafluoroethane (227caE.alpha..beta., or CF.sub.3 OCF.sub.2 CHF.sub.2, boiling point=about -3.degree. C.),
10. Difluoromethoxy pentafluoroethane (227caE.beta..gamma., or CHF.sub.2 OCF.sub.2 CF.sub.3, boiling point=-8.0.degree. C.),
11. 1-trifluoromethoxy-1,2,2,2-tetrafluoroethane (227eaE, or CF.sub.3 OCHFCF.sub.3, boiling point=-9.4.degree. C.
12. 1,1,1,2,2,3,3-heptafluoro-3-(1,2,2,2-tetrafluoroethoxy)propane (E42-11meE.gamma..delta., or CF.sub.3 CF.sub.2 CF.sub.2 OCHFCF.sub.3, boiling point=40.8.degree. C.),
13. dimethyl ether (DME, or CH.sub.3 OCH.sub.3)
14. 2,2,3,4,4-pentafluorooxetane (C-225eE.alpha..beta., or C.sub.3 HF.sub.5 O, having a structure of ##STR3## boiling point=3.4.degree. C.)
15. tris(trifluoromethyl)amine, (CF.sub.3).sub.3 N, boiling point=-6.5.degree. C.),
16. 1-difluoromethoxy-1,1,2,2-tetrafluoroethane (236caE, or CHF.sub.2 OCF.sub.2 CHF.sub.2, boiling point=28.5.degree. C.),
17. 1,1,2,2,3-pentafluoropropane (HFC-245ca, or CHF.sub.2 CF.sub.2 CH.sub.2 F, boiling point=25.13.degree. C.), and
18. 1,1,1,2,3-pentafluoropropane (HFC-245eb, or CF.sub.3 CHFCH.sub.2 F, boiling point=22.46.degree. C.).
116E (CAS Reg. No. 1479-49-8) has been prepared by electrochemical fluorination of dimethyl ether as disclosed by Simons in U.S. Pat. No. 2,519,983.
134aE (CAS Reg. No. 2261-01-0) has been made by the electrochemical fluorination of methyl 2-methoxypropionate as reported by Berenblit, et. al. Zh. Org. Khim., Vol. 12, pp. 767-770 (1976).
143aE (CAS Reg. No. 421-14-7) has been made by the reaction of methyl fluoroformate with sulfur tetrafluoride as reported by Aldrich and Sheppard, J. Am. Chem. Soc., Vol. 29, 11-15 (1964).
C-216E (CAS Reg. No. 425-82-1) can be made by electrochemical fluorination of trimethylene oxide (oxetane) in anhydrous hydrogen fluoride as disclosed by Kauck and Simons in U.S. Pat. No. 2,594,272.
C-216E2 (CAS Reg. No. 21297-65-4) has been prepared by UV irradiation of perfluoro-b-oxa-d-valerolactone in the vapor or liquid phase as reported by Throckmorton in J. Org. Chem., Vol. 34, pp. 3438-3440 (1969). The lactone was prepared by the
reaction of KF with perfluorooxydiacetyl chloride.
218E (CAS Reg. No. 665-16-7) has been made by direct fluorination of CF.sub.3 OCH.sub.2 CF.sub.3 (prepared by reaction of CF.sub.3 OF with vinylidene fluoride) as reported by Sekiya and Ueda in Chemistry Letters, pp. 609-612 (1990).
218E2 (CAS Reg. No. 53772-78-4) was made in the electrochemical fluorination of methyl 2-methoxypropionate as reported by Berenblit, et. al. Zh. Org. Khim., Vol. 12, pp. 767-770 (1976).
227caE.alpha..beta. (CAS Reg. No. 2356-61-8) has been prepared by reacting difluoroacetyl fluoride with cesium fluoride and carbonyl fluoride followed by treatment with sulfur tetrafluoride as disclosed by Eisemann in U.S. Pat. No. 3,362,190.
227caE.beta..gamma. (CAS Reg. No. 53997-64-1) has been made by electrochemical fluorination of CHCl.sub.2 OCF.sub.2 CHClF as reported by Okazaki, et. al. J. Fluorine Chem., Vol. 4, pp. 387-397 (1974).
227eaE (CAS Reg. No. 2356-62-9) was prepared by reacting 2-trifluoromethoxy-tetrafluoropropionyl fluoride (CF.sub.3 CF(OCF.sub.3)COF) with aqueous potassium hydroxide at 230.degree. C. as disclosed by Eisemann in U.S. Pat. No. 3,362,190.
236caE (CAS Reg. No. 32778-11-3) has been prepared by fluorination of CHCl.sub.2 OCF.sub.2 CHF.sub.2 (prepared in turn by chlorination of CH.sub.3 OCF.sub.2 CHF.sub.2) using anhydrous hydrogen fluoride with antimony pentachloride catalyst as
reported by Terrell, et. al. in J. Medicinal Chem., Vol. 15, pp. 604-606 (1972).
E42-11meE.gamma..delta. (CAS Reg. No. 3330-15-2) has been prepared by heating CF.sub.3 CF.sub.2 CF.sub.2 OCF(CF.sub.3)CO.sub.2 --Na+ in ethylene glycol as disclosed by Selman and Smith in French Patent No. 1,373,014 (Chemical Abstracts
62:13047g).
C-225eE.alpha..beta. (CAS Reg. No. 144109-03-5) 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. Re., 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 recovered by fractional
distillation.
(CF.sub.3).sub.3 N (CAS Reg. No. 432-03-1) has been made by electrochemical fluorination of trimethyl amine in anhydrous hydrogen fluoride as disclosed by Kauck and Simons in U.S. Pat. No. 2,616,927.
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, tort,
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 116E and cyclopropane, DME or propylene; 134E and C-225eE.alpha..beta.; 134aE and C-216E2, 227eaE, DME or N(CF.sub.3).sub.3 ; 143aE and C-216E, C-216E2, 218E, 218E2,
227eaE, DME or N(CF.sub.3).sub.3 ; 218E and DME or propylene; 218E2 and DME or isobutane; 227ca.alpha..beta. and N(CF.sub.3).sub.3 or DME; 227caE.beta..gamma. and DME, isobutane or N(CF.sub.3).sub.3 ; 227eaE and DME or isobutane; 236caE and
N(CHF.sub.2).sub.2 (CF.sub.3); or E-42-11meE.gamma..delta. and HFC-245ca or HFC-245eb, 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.
______________________________________ Components Psia kPa ______________________________________ 116E 292.2 2015 134E 30.4 210 134aE 73.8 509 143aE 83.8 578 218E 83.8 578 218E2 52.3 361 227caE.alpha..beta. 41.3 285 227caE.beta..gamma.
48.7 336 227eaE 51.3 354 236caE 12.9 89 E-42-11meE.gamma..delta. 8.1 56 Cyclopropane 105.0 724 DME 85.7 591 Propylene 165.9 1144 C-225eE.alpha..beta. 31.1 214 C-216E2 76.7 529 N(CF.sub.3).sub.3 45.8 316 C-216E 100.3 692 isobutane 50.5 348
N(CHF.sub.2).sub.2 (CF.sub.3) 13.9 96 HFC-245ca 14.2 98 HFC-245eb 16.3 112 ______________________________________
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. %) ______________________________________ 116E/cyclopropane 72-99/1-28 72-99/1-28 116E/DME 68-99/1-32 68-99/1-32 116E/propylene 60-99/1-40
60-99/1-40 134E/C-225eE.alpha..beta. 1-99/1-99 1-80/20-99 134aE/C-216E2 1-99/1-99 20-99/1-80 134aE/227eaE 1-99/1-99 20-99/1-80 134aE/DME 1-99/1-99 20-99/1-80 134aE/N(CF.sub.3).sub.3 20-99/1-80 40-99/1-60 143aE/C-216E 1-99/1-99 1-80/20-99
143aE/C-216E2 1-99/1-99 1-80/20-99 143aE/218E 1-99/1-99 1-80/20-99 143aE/218E2 1-99/1-99 1-99/1-99 143aE/227eaE 1-99/1-99 1-99/1-99 143aE/DME 1-99/1-99 10-90/10-90 143aE/N(CF.sub.3).sub.3 27-99/1-73 27-99/1-73 218E/DME 50-92/8-50 50-92/8-50
218E/propylene 1-82/18-99 20-82/18-80 218E2/DME 1-86/14-99 30-86/14-70 218E2/isobutane 1-99/1-99 20-99/1-80 227caE.alpha..beta./N(CF.sub.3).sub.3 1-99/1-99 1-80/20-99 227caE.alpha..beta./DME 1-80/20-99 10-80/20- 90 227caE.beta..gamma./DME
1-83/17-99 20-83/17-80 227caE.beta..gamma./isobutane 1-99/1-99 20-99/1-80 227caE.beta..gamma./N(CF.sub.3).sub.3 1-99/1-99 20-99/1-80 227eaE/DME 1-84/16-99 20-84/16-80 227eaE/isobutane 1-99/1-99 20-99/1-80 236caE/N(CHF.sub.2).sub.2 (CF.sub.3)
1-99/1-99 1-80/20-99 E-42-11meE.gamma..delta./ 1-72/18-99 1-50/50-99 HFC-245ca E-42-11meE.gamma..delta./ 98-99/1-2 -- HFC-245eb E-42-11meE.gamma..delta./ 1-70/30-99 1-50/50-99 HFC-245eb ______________________________________
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.
______________________________________ Weight percent of Vapor Press. Composition No. the components psia (kPa) ______________________________________ 116E/cyclopropane 96.9/3.1 295.1 2035 116E/DME 93.9/6.1 308.6 2128 116E/propylene
89.3/10.7 312.7 2156 134E/C-225eE.alpha..beta. 35.6/64.4 31.8 219 134aE/C-216E2 27.8/72.2 77.9 537 134aE/227eaE 94.0/6.0 73.9 510 134aE/DME 36.7/63.3 86.7 598 134aE/N(CF.sub.3).sub.3 71.8/28.2 76.9 530 143aE/C-216E 3.8/96.2 100.4 692
143aE/C-216E2 60.3/39.7 85.4 589 143aE/218E 39.3/60.7 105.6 728 143aE/218E2 73.8/26.2 85.7 591 143aE/227eaE 92.9/7.1 83.9 578 143aE/DME 51.4/48.6 92.6 638 143aE/N(CF.sub.3).sub.3 71.0/29.0 87.6 604 218E/DME 75.5/24.5 126.6 873 218E/propylene
40.1/59.9 171.9 1185 218E2/DME 60.9/39.1 100.2 691 218E2/isobutane 83.6/16.4 53.5 369 227caE.alpha..beta./N(CF.sub.3).sub.3 35.1/64.9 48.0 331 227caE.alpha..beta./DME 4.7/95.3 85.7 591 227caE.beta..gamma./DME 49.5/50.5 93.2 643
227caE.beta..gamma./isobutane 39.1/60.9 50.6 349 227caE.beta..gamma./N(CF.sub.3).sub.3 80.0/20.0 48.9 337 227eaE/DME 52.9/47.1 95.1 656 227eaE/isobutane 80.9/19.1 51.8 357 236caE/N(CHF.sub.2).sub.2 (CF.sub.3) 16.2/83.8 14.0 97
E-42-11meE.gamma..delta./ 26.0/74.0 15.2 105 HFC-245ca E-42-11meE.gamma..delta./ 15.7/84.3 16.4 113 HFC-245eb ______________________________________
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.
______________________________________ WT % A/ INITIAL 50% LEAK WT % B PSIA KPA PSIA KPA DELTA % P ______________________________________ 116E/ cyclopropane 96.9/3.1 295.1 2035 295.1 2035 0.0 99/1 293.9 2026 293.8 2026 0.0 60/40 255.9 1764
133.6 921 47.8 80/20 276.4 1906 262.7 1811 5. 75/25 270.6 1866 250.4 1726 7.5 72/28 267.4 1844 241.7 1666 9.6 71/29 266.4 1837 238.2 1642 10.6 116E/DME 93.9/6.1 308.6 2128 308.6 2128 0.0 99/1 299.0 2062 296.8 2046 0.7 70/30 292.7 2018 275.8 1902
5.8 68/32 291.6 2011 267.6 1845 8.2 67/33 291.1 2007 257.7 1777 11.5 116E/propylene 89.3/10.7 312.7 2156 312.7 2156 0.0 99/1 297.2 2049 295.9 2040 0.4 60/40 292.1 2014 263.3 1815 9.9 59/41 291.2 2008 259.5 1789 10.9 134E/ C-225eE.alpha..beta.
35.6/64.4 31.8 219 31.8 219 0.0 20/80 31.6 218 31.6 218 0.0 1/99 31.1 214 31.1 214 0.0 80/20 31.1 214 31.1 214 0.0 99/1 30.5 210 30.5 210 0.0 134aE/C-216E2 27.8/72.2 77.9 537 77.9 537 0.0 15/85 77.7 536 77.7 536 0.0 1/99 76.8 530 76.8 530 0.0
60/40 76.9 530 76.8 530 0.1 80/20 75.6 521 75.5 521 0.1 99/1 73.9 510 73.9 510 0.0 134aE/227eaE 94.0/6.0 73.9 510 73.9 510 0.0 99/1 73.8 509 73.8 509 0.0 60/40 71.9 496 71.3 492 0.8 40/60 68.4 472 66.8 461 2.3 20/80 62.3 430 59.6 411 4.3 10/90
57.6 397 55.4 382 3.8 1/99 52. 359 51.7 356 0.6 134aE/DME 36.7/63.3 86.7 598 86.7 598 0.0 20/80 86.5 596 86.5 596 0.0 1/99 85.8 592 85.8 592 0.0 60/40 86.0 593 85.8 592 0.2 80/20 83.0 572 82.4 568 0.7 99/1 74.6 514 74.4 513 0.3
134aE/N(CF.sub.3).sub.3 71.8/28.2 76.9 530 76.9 530 0.0 85/15 76.3 526 76.1 525 0.3 99/1 74.1 511 74. 510 0.1 40/60 73.6 507 71.2 491 3.3 20/80 65.9 454 59.3 409 10. 19/81 65.3 450 58.6 404 10.3 143aE/C-216E 3.8/96.2 100.4 692 100.4 692 0.0 1/99
100.4 692 100.4 692 0.0 20/80 99.5 686 99.4 685 0.1 40/60 96.9 668 96.4 665 0.5 60/40 93.3 643 92.3 636 1.1 80/20 88.9 613 87.9 606 1.1 90/10 86.4 596 85.8 592 0.7 99/1 84.1 580 84. 579 0.1 143aE/C-216E2 60.3/39.7 85.4 589 85.4 589 0.0 80/20 85.
586 84.9 585 0.1 99/1 83.9 578 83.9 578 0.0 30/70 83.9 578 83.7 577 0.2 1/99 77.1 532 77.1 532 0.0 143aE/218E 39.3/60.7 105.6 728 105.6 728 0.0 20/80 102.6 707 100.7 694 1.9 10/90 96.7 667 93.1 642 3.7 1/99 85.6 590 84.7 584 1.1 60/40 103.6 714
101.7 701 1.8 70/30 101.4 699 97. 669 4.3 80/20 97.9 675 91.3 629 6.7 90/10 92.5 638 86.5 596 6.5 99/1 84.9 585 84. 579 1.1 143aE/218E2 73.8/26.2 85.7 591 85.7 591 0.0 85/15 85.4 589 85.3 588 0.1 99/1 84. 579 83.9 578 0.1 60/40 85.2 587 85. 586
0.2 40/60 82.3 567 80.2 553 2.6 20/80 74.4 513 68.5 472 7.9 15/85 70.8 488 64.3 443 9.2 13/87 69.2 477 62.5 431 9.7 12/88 68.2 470 61.7 425 9.5 10/90 66.3 457 59.9 413 9.7 9/91 65.2 450 59.1 407 9.4 5/95 60.2 415 55.8 385 7.3 1/99 54.1 373 52.9
365 2.2 143aE/227eaE 92.9/7.1 83.9 578 83.9 578 0.0 99/1 83.9 578 83.9 578 0.0 60/40 81.6 563 80.7 556 1.1 40/60 77.3 533 74.4 513 3.8 20/80 68.8 474 63.6 439 7.6 15/85 65.5 452 60.4 416 7.8 10/90 61.6 425 57.1 394 7.3 1/99 52.5 362 51.8 357 1.3 143aE/DME 58.9/41.1 88.2 608 88.2 608 0.0 80/20 87.5 603 87.4 603 0.1 99/1 84.1 580 84.1 580 0.0 40/60 87.9 606 87.8 605 0.1 20/80 86.9 599 86.9 599 0.0 1/99 85.8 592 85.8 592 0.0 143aE/N(CF.sub.3).sub.3 71.0/29.0 87.6 604 87.6 604 0.0 85/15
86.9 599 86.5 596 0.5 99/1 84.1 580 84. 579 0.1 40/60 84.2 581 80.9 558 3.9 20/80 74.9 516 64.4 444 14. 25/75 78.2 539 69.7 481 10.9 27/73 79.3 547 71.6 494 9.7 218E/DME 75.5/24.5 126.6 873 126.6 873 0.0 90/10 121.7 839 114.0 786 6.3 92/8 119.0
820 108.3 747 9.0 93/7 117.2 808 105.0 724 10.4 50/50 124.1 856 111.8 771 9.9 49/51 124.0 855 109.3 754 11.9 218E/propylene 40.1/59.9 171.9 1185 171.9 1185 0.0 20/80 170.4 1175 169.7 1170 0.4 1/99 166.2 1146 166.1 1145 0.1 60/40 169.9 1171 168.2
1160 1. 80/20 158.8 1095 146.2 1008 7.9 85/15 151.7 1046 133.5 920 12. 82/18 156.4 1078 141.6 976 9.5 218E2/DME 60.9/39.1 100.2 691 100.2 691 0.0 80/20 97.7 674 93.8 647 4.0 86/14 94.3 650 85.1 587 9.8 87/13 93.4 644 83.1 573 11.0 40/60 99.0 683
96.3 664 2.7 30/70 97.5 672 92.0 634 5.6 15/85 93.5 645 87.2 601 6.7 1/99 86.4 596 85.8 592 0.7 218E2/ isobutane 83.6/16.4 53.5 369 53.5 369 0.0 90/10 53.3 367 53.3 367 0.0 99/1 52.5 362 52.5 362 0.0 60/40 52.8 364 52.8 364 0.0 40/60 52. 359
51.9 358 0.2 20/80 51.2 353 51.1 352 0.2 1/99 50.5 348 50.5 348 0.0 227caE.alpha..beta./ N(CF.sub.3).sub.3 35.1/64.9 48. 331 48. 331 0.0 15/85 47.3 326 47.2 325 0.2 1/99 46. 317 45.9 316 0.2 60/40 47.1 325 46.9 323 0.4 80/20 45.1 311 44.5 307
1.3 99/1 41.6 287 41.5 286 0.2 227caE.alpha..beta./ DME 4.7/95.3 85.7 591 85.7 591 0.0 1/99 85.7 591 85.7 591 0.0 40/60 84.4 582 83.9 578 0.6 60/40 81.5 562 79.4 547 2.6 80/20 73.8 509 66.7 460 9.6 81/19 73.1 504 65.6 452 10.3
227caE.beta..gamma./ DME 49.5/50.5 93.2 643 93.2 643 0.0 80/20 87.9 606 81.7 563 7.1 83/17 86.0 593 77.8 536 9.5 84/16 85.3 588 76.3 526 10.6 20/80 90.8 626 89.1 614 1.9 1/99 86.1 594 85.8 592 0.3 227caE.beta..gamma./ isobutane 39.1/60.9 50.6
349 50.6 349 0.0 60/40 50.5 348 50.5 348 0.0 80/20 50.1 345 50.1 345 0.0 90/10 49.6 342 49.6 342 0.0 99/1 48.8 336 48.8 336 0.0 20/80 50.6 349 50.6 349 0.0 10/90 50.5 348 50.5 348 0.0 1/99 50.5 348 50.5 348 0.0 227caE.beta..gamma./
N(CF.sub.3).sub.3 80.0/20.0 48.9 337 48.9 337 0.0 90/10 48.8 336 48.8 336 0.0 99/1 48.7 336 48.7 336 0.0 60/40 48.7 336 48.7 336 0.0 40/60 48.2 332 48.2 332 0.0 20/80 47.3 326 47.2 325 0.2 1/99 45.9 316 45.9 316 0.0 227eaE/DME 52.9/47.1 95.1 656
95.1 656 0.0 20/80 92.0 634 89.3 616 2.9 1/99 86.2 594 85.8 592 0.5 80/20 90.6 625 85.0 586 6.2 84/16 88.1 607 79.8 550 9.4 85/15 87.3 602 78.2 539 10.4 227eaE/ isobutane 80.9/19.1 51.8 357 51.8 357 0.0 99/1 51.3 354 51.3 354 0.0 60/40 51.5 355
51.5 355 0.0 40/60 51.2 353 51.2 353 0.0 20/80 50.8 350 50.8 350 0.0 1/99 50.5 348 50.5 348 0.0 236caE/ N(CHF.sub.2).sub.2 (CF.sub.3) 16.2/83.8 14. 97 14. 97 0.0 1/99 13.9 96 13.9 96 0.0 40/60 13.9 96 13.9 96 0.0 70/30 13.5 93 13.5 93 0.0 90/10
13.2 91 13.1 90 0.8 99/1 13. 90 12.9 89 0.8 E42-11meE.gamma..delta./ HFC-245ca 1/99 14.7 101 14.7 101 0.2 10/90 15.0 104 14.9 103 0.5 20/80 15.2 105 15.2 105 0.1 26.0/74.0 15.2 105 15.2 105 0.0 30/70 15.2 105 15.2 105 0.1 40/60 15.1 104 15.0 103
0.6 50/50 14.9 102 14.6 100 2.0 60/40 14.5 100 13.8 95 4.6 70/30 13.8 95 12.6 87 8.6 E42-11meE.gamma..delta./ HFC-245eb 99/1 8.5 59 8.2 56 4.4 98/2 9.0 61.8 8.3 56.9 7.9 73/27 14.3 99 12.7 88 11.1 70/30 14.6 101 13.2 91 9.5 50/50 15.8 109 15.4
106 2.5 30/70 16.3 112 16.2 112 0.3 15.7/84.3 16.4 113 16.4 113 0 1/99 16.3 112 16.3 112 0 ______________________________________
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 218E2 and DME at the temperature of 0.degree. C. The results are summarized below.
______________________________________ WT % A/ INITIAL 50% LEAK WT % B PSIA KPA PSIA KPA DELTA % P ______________________________________ 218E2/DME 59.9/40.1 45.4 313 45.4 313 0.0 70/30 45.2 312 44.8 309 0.9 84/16 43.3 299 39.5 272 8.8
85/15 43.0 296 38.6 266 10.2 40/60 44.9 310 43.7 301 2.7 20/80 43.2 298 39.7 274 8.1 15/85 42.5 293 39.2 270 7.8 1/99 39.0 269 38.7 267 0.8 ______________________________________
These results show that compositions of 218E2 and DME 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 48.0.degree. F. (8.9.degree. C.)
Condenser temperature 115.0.degree. F. (46.1.degree. C.)
Subcooled 12.0.degree. F. (6.7.degree. C.)
Return gas temperature 65.0.degree. F. (18.3.degree. C.)
Compressor efficiency is 75%.
The ref | | |
