AU774247B2 - Hydrofluorocarbon compositions - Google Patents

Description

P/00/011 Regulation 3.2

AUSTRALIA

Patents Act 1990 COMPLETE

SPECIFICATION

FOR A DIVISIONAL

PATENT

ORIGINAL

TO BE COMPLETED BY APPLICANT Name of Applicant: E.I. DUPONT DE NEMOURS AND COMPANY Actual Inventors: FELIX, MINOR, SIEVERT,

A.C.

Address for Service: CALLINAN LAWRIE, 711 High Street, Kew, Victoria 3101, Australia Invention Title: HYDROFLUOROCARBON

COMPOSITIONS

The following statement is a full description of this invention, including the best method of performing it known to 12/03/02,SW12623cover 1

TITLE

HYDROFLUOROCARBON COMPOSITIONS FIELD OF THE INVENTION The present invention relates to the discovery of compositions which include fluoroethane, 2-fluoropropane or tert-butylfluoride. These compositions are useful as pure components or with at least one of tetrafluoroethane, difluoroethane, hexafluoropropane, a hydrocarbon or dimethylether.

These compositions are useful as aerosol propellants, refrigerants, cleaning agents, expansion agents for polyolefins and polyurethanes, 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 S 20 Fluorinated hydrocarbons have had many uses, such as aerosol propellants, S* blowing agents and refrigerants. These compounds include trichlorofluoromethane (CFC- 11), dichlorodifluoromethane (CFC-12) and chlorodifluoromethane (HCFC-22).

In recent years it has been pointed out that certain kinds offluorinated hydrocarbons 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.

There is also a demand for aerosol propellants and blowing agents which have significantly less photochemical reactivity than hydrocarbons that contribute-to the formation of ambient ozone and ground level smog. These compounds are typically referred to as low-VOC (volatile organic compound) or non-VOC.

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. 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. The change in refrigerant composition 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 20 fluorinated hydrocarbons.

Fluorinated hydrocarbons which are classified as low or non-VOC are also useful as aerosol propellants or blowing agents because they do not contribute significantly to ground level pollution.

Fluorinated hydrocarbons may also be used as cleaning agents 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.

a. 11 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 heat transfer media, gaseous dielectrics, fire extinguishing agents or power cycle working fluids such as for heat pumps.

These compositions may also be used as 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 or as buffing abrasive agents to remove buffing abrasive compounds from polished surfaces such as metal. They are also used 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 compositions which include fluoroethane, 2-fluoropropane or tert-butylfluoride. These compositions have zero ozone depletion potential (ODP), low global warming potential and are lower VOC than hydrocarbons. These compositions are also useful as pure components or with at least one oftetrafluoroethane, difluoroethane, hexafluoropropane, a hydrocarbon or 20 dimethylether. These compositions are used as aerosol propellants, refrigerants, cleaning agents, expansion agents for polyolefins and polyurethanes, 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 fluoroethane, 2fluoropropane or tert-butylfluoride and a second component oftetrafluoroethane, difluoroethane, hexafluoropropane, a hydrocarbon or dimethylether, to form an azeotropic or azeotrope-like composition. Azeotropes are highly desirable for refrigerants but not necessary for aerosol propellants.

The invention provides in one form an aerosol composition and an agent to be atomised wherein the propellant is selected from the group consisting of fluoroethane, 2fluoropropane, and tert-butylfluoride.

29/04/04.atlI 2623.specipgs,32 The compounds of the present invention include the following components: 1 fluoroethane (HFC- 161, or CH 3

CH

2 F, boiling point 8*C), 2. 1, 1,2,2-tetrafluoroethane (HFC-13 4, or CHF 2

CHF

2 boiling point 3. 1, 1, 1,2-tetrafluoroethane (HEC- I 34a, or CF 3

CH

2 F, boiling point -26-C), 4. 1, 1 -difluoroethane (HFC-1I52a, or CH 3

CHF

2 boiling point 2-fluoropropane (HIFC-28 l ea, or CH 3

CHFCH

3 boiling point -1 I C), 6. tert-butylfluoride (HFC-3 -10- 1sy, or (CH 3 3 CF, boiling point= 12-C), 7. 1,1,1,2,3,3 -hexafluoropropane (H-FC-236ea, or CF 3

CHFCHF

2 boiling point 6'CQ 8. 1,1,1,3,3,3-hexafluoropropane (HFC-236fa, or CF 3

CH

2

CF

3 boiling point 9. dimethylether (DME, or CH 3

OCH

3 boiling point butane (CH 3

CH

2

CH

2

CH

3 boiling point 11. isobutane ((CH 3 3 CH, boiling point -1 2"C), 12. propane (CH 3

CH

2

CH

3 boiling point -42*C).

BFC-161 (GAS Reg. No. 353-36-6) and BFC-281ea (isopropyl fluoride, :CAS Reg. No. 420-26-8) have been prepared by reaction of hydrogen fluoride with ethylene and propylene, respectively, as reported by Grosse and Lin in JI Org. Chem., Vol. 3, pp. 26-32 (1938).

25 2-Fluoro-2-methylpropane (t-butyl fluoride, BFC-3-10-ly, GAS Reg. No.

[353-61-7]) may be prepared by the reaction of t-butyl alcohol with aqueous hydrogen fluoride as discussed on page 689 of "Chemistry of Organic Fluorine Compounds" by Milos Hudlicky, 2nd. ed., 1976.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a graph of the vapor/liquid equilibrium curve for mixtures of HFC-161/HFC-134a at -14.15 0

C;

Figure 2 is a graph of the vapor/liquid equilibrium curve for mixtures of HFC-161/HFC-152a at -0.05 0

C;

Figure 3 is a graph of the vapor/liquid equilibrium curve for mixtures of HFC-161/HFC-281ea at -10 0

C;

Figure 4 is a graph of the vapor/liquid equilibrium curve for mixtures of HFC-161/HFC-3-10-1sy at -20 0

C;

Figure 5 is a graph of the vapor/liquid equilibrium curve for mixtures of HFC-161/butane at -20 0

C;

Figure 6 is a graph of the vapor/liquid equilibrium curve for mixtures of HFC-161/isobutane at -10 0

C;

Figure 7 is a graph of the vapor/liquid equilibrium curve for mixtures of HFC-161/DME at 0C; Figure 8 is a graph of the vapor/liquid equilibrium curve for mixtures of HFC-281ea/HFC-134a at -10 0

C;

Figure 9 is a graph of the vapor/liquid equilibrium curve for mixtures of HFC-28lea/HFC-152a at -10.01 0

C;

20 Figure 10 is a graph of the vapor/liquid equilibrium curve for mxitures of HFC-281ea/HFC-3-10-lsy-at 0OC; Figure 11 is a graph of the vapor/liquid equilibrium curve for mixtures of HFC-28lea/propane at -10 0

C;

Figure 12 is a graph of the vapor/liquid equilibrium curve for mixtures of HFC-28lea/DME at -9.95 0

C;

Figure 13 is a graph of the vapor/liquid equilibrium curve for mixtures of HFC-3-10-lsy/HFC-134 at -21.7 0

C;

Figure 14 is a graph of the vapor/liquid equilibrium curve for mixtures of HFC-3-10-lsy/HFC-134a at 0°C; Figure 15 is a graph of the vapor/liquid equilibrium curve for mixtures of HFC-3-10- I1sy/IFC- 15 2a at 0 0

C;

Figure 16 is a graph of the vapor/liquid equilibrium curve for mixtures of HFC-3-10-lsy/HC-236ea at -1.7'C; Figure 17 is a graph of the vapor/liquid equilibrium curve for mixtures of HIFC-3-10-lsyWIC-236fa at Figure 18 is a graph of the vapor/liquid equilibrium curve for mixtures of HFC-3-10-Isy/butane at 0 0

C;

Figure 19 is a graph of the vapor/liquid equilibrium curve for mixtures of HFC-3-10-lsy/isobutane at 0 0

C;

Figure 20 is a graph of the vapor/liquid equilibrium curve for mixtures of HFC-3- 10- 1sy/propane, at Figure 21 is a graph of the vapor/liquid equilibrium curve for mixtures of HFC-3-10-lsy/DME at -10 0

C.

DETAILED DESCRIPTION The present invention relates to the following compositions: fluoroethane (HFC- 16 1); 2-fluoropropane (HFC-28 l ea);- 20 tert-butylfluoride (HIFC-3 -10-1sy);- HFC- 161 and 1, 1, 1,2-tetrafluoroethane (HIFC-lI34a); HFC- 161 and 1-difluoroethane (HFC-1I52a); HIFC- 161 and 2-fluoropropane (HFC- :28 1ea); HFC- 161 and tert-butylfluoride (EFC-3- 10-l1sy); HFC- 161 and butane; HFC- 161 and isobutane; or HFC- 161 and dimethylether

(DME);

BFC-28 l ea and HFC-1I34a; HFC-28 l ea and HFC- I52a; BFC-28 l ea :and HFC-3- 10-1sy;- BFC-28 l ea and propane; orHBFC-281 ea and DME; or HFC-3-10-1sy and 1,1,2,2-tetrafluoroethane (HFC-134); HFC-3- 1 0 -lsy and HFC-134a; HFC-3-10-lsy and HFC-152a; and 1,1,1,2,3,3-hexafluoropropane (HFC-236ea); HFC-3-10-1sy and 1,1,1,3,3,3-hexafluoropropane (HFC-236fa); HFC-3-10-lsy and butane; HFC-3-10-lsy and isobutane; HFC-3-10-Isy and propane; or HFC-3-10-lsy and DME.

1-99 wt.% of each of the components of the compositions are useful as aerosol propellants, refrigerants, cleaning agents, expansion agents for polyolefins and polyurethanes, 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. 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 S" 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 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 about 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: HFC-161 and 1,1,1,2-tetrafluoroethane (HFC-134a); HFC-161 and 1,1-difluoroethane (HFC-152a); HFC-161 and 2-fluoropropane (HFC- 281ea); HFC-161 and tert-butylfluoride (HFC-3-10-1sy); HFC-161 and 20 butane; HFC-161 and isobutane; or HFC-161 and dimethylether *o

*(DME);

HFC-281ea and HFC-134a; HFC-281ea and HFC-152a; HFC-281ea and HFC-3-10-lsy; HFC-281ea and propane; or HFC-281ea and DME; or HFC-3-10-1sy and 1,1,2,2-tetrafluoroethane (HFC-134); HFC-3-10- Isy and HFC-134a; HFC-3-l0-lsy and HFC-152a; HFC-3-10-lsy and 1,1,1,2,3,3-hexafluoropropane (HFC-236ea); HFC-3-10-lsy and 1,1,1,3,3,3-hexafluoropropane (HFC-236fa); HFC-3-10-lsy and butane; HFC-3-10-1sy and isobutane; HFC-3-10-1sy and propane; or HFC-3-10-1 sy and DME; 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 20 change in vapor pressure of less than about 10% when 50 weight percent of the o• 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.

Substantially constant boiling, azeotropic or azeotrope-like compositions of this invention comprise the following: COMPONENTS T C HFC-161/HFC-134a HFC-161/HFC-152a HFC-161/HFC-281ea HFC-161/HFC-3-10-1sy HFC-161/butane HFC-161/isobutane HFC-161/DME HFC-281ea/HFC-134a HFC-281 ea/HFC-152a HFC-281ea/HFC-3-10-lsy HFC-281ea/propane HFC-281ea/DME HFC-3-10-lsy/HFC-134 HFC-3-10-lsy/HFC-134a HFC-3-10-lsy/HFC-152a HFC-3-10-1 sy/HFC-236ea HFC-3-10-1 sy/HFC-236fa HFC-3-10- lsy/butane HFC-3-10- Isy/isobutane HFC-3-10-1 sy/propane HFC-3-10-1sy/DME -20 -30 -10 -20 -20 -20 -30 -10 -20 0 -10 -9.95 -21.7 0 0 -1.7 -2.5 0 0 -20 -10 WEIGHT RANGES 1-99/1-99 1-99/1-99 73-99/1-27 75-99/1-25 67-99/1-33 52-99/1-48 1-99/1-99 1-99/1-99 1-99/1-99 41-99/1-59 1-41/59-99 1-99/1-99 1-44/56-99 1-32/68-99 1-30/70-99 11-60/40-89 and 1-3/97-99 1-52/48-99 1-99/1-99 1-45/55-99 and 89-99/1-11 1-19/81-99 1-42/58-99

PREFERRED

10-90/10-90 10-90/10-90 73-99/1-27 75-99/1-25 67-99/1-33 52-99/1-48 10-90/10-90 10-90/10/90 10-90/10-90 41-99/1-59 1-41/59-99 10-90/10-90 1-44/56-99 1-32/68-99 1-30/70-99 11-60/40-89 and 1-3/97-99 1-52/48-99 10-90/10-90 1-45/55-99 and 89-99/1-11 1-19/81-99 1-42/58-99 a. a a.

S30 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.

a *a o 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 ofA, 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 for this unique composition of matter which is a constant boiling composition.

20 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 25 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 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 I: A phase study shows the following compositions are azeotropic, all at the 20 temperature specified.

Vapor Press.

Components ToC Weight Ranges psia (kPa) HFC-3-10-1sy/HFC-134 -21.7 13.9/86.1 14.7 101 HFC-3-10-1sy/HFC-236ea -1.7 33.6/66.4 14.7 101 25 HFC-3-10-lsy/HFC-236fa -2.5 12.7/87.3 14.7 101

S

EXAMPLE 2 Impact of Vapor Leakage A vessel is charged with an initial composition at a specified temperature, 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, 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/WT%B INITIAL 50% LEAK PSIA KPA PSIA KPA DELTA %P HFC-161/HFC-134a (-20 0

C)

1/99 19.6 135 19.5 134 10/90 22.0 152 21.2 146 3.6 20/80 24.1 166 22.9 158 30/70 25.8 178 24.6 170 4.7 40/60 27.2 188 26.1 180 50/50 28.3 195 27.5 190 2.8 60/40 29.2 201 28.6 197 2.1 70/30 29.9 206 29.5 203 1.3 80/20 30.5 210 30.3 209 0.7 90/10 30.9 213 30.8 212 0.3 99/1 31.2 215 31.2 215 0.0 25 HFC-161/HFC-152a (-30 0

C)

S 1/99 11.7 80.7 11.7 80.7 0.0 S* 10/90 12.7 87.6 12.3 84.8 3.1 20/80 13.8 95.1 13.1 90.3 5.1 30/70 14.9 103 14.0 96.5 40/60 15.9 110 14.9 103 6.3 50/50 16.9 117 15.9 110 5.9 S" 60/40 17.8 123 16.9 117 5.1 70/30 18.7 129 18.0 124 3.7 80/20 19.5 134 19.0 131 2.6 35 90/10 20.3 140 20.0 138 99/1 20.9 144 20.9 144 0.0 4 oo it HFC- 161/IFC-28 Iea (-1I0 0

C)

99/1 44.9 310 44.8 309 0.2 90/10 42.7 294 41.1 283 3.7 80/20 40.0 276 37.1 256 7.2 73/27 38.1 263 34.3 236 10.0 HFC-161/HFC-3-10-lsy 99/1 31.1 214 31.0 214 0.3 90/10 29.7 205 28.6 197 3.7 80/20 28.1 194 25.9 179 7.8 75/25 27.2 188 24.6 170 9.6 74/26 27.1 187 24.3 168 10.3 HFC- 16 1/butane 99/1 31.1 214 31.0 214 0.3 90/10 29.8 205 29.1 201 2.3 80/20 28.4 196 26.9 185 5.3 70/30 26.9 185 24.6 170 8.6 67/33 26.5 183 23.9 165 9.8 66/34 26.3 181 23.6 163 10.3 HIFC- 16 1/isobutane 99/1 31.2 215 31.2 215 0.0 90/10 30.5 210 30.3 209 0.7 80/20 29.6 204 29.0 200 70/30 28.6 197 27.5 190 3.8 60/40 27.4 189 25.6 177 6.6 **e52/48 26.4 182 23.9 165 *51/49 26.3 181 23.6 163 10.3 HC-161IDME (-30 0

C)

*1/99 11.6 80.0 11.6 80.0 0.0 S10/90 12.4 85.5 12.1 83.4 2.4 20/80 13.2 91.0 12.7 87.6 3.8 35 30/70 14.1 97.2 13.3 91.7 5.7 @5540/60 15.0 103 14.1 97.2 50/50 16.0 110 15.0 103 6.3 60/40 17.0 117 16.0 110 5.9 S70/30 17.9 123 17.1 118 80/20 18.9 130 18.3 126 3.2 .50:90/10 19.9 137 19.6 135 99/120.8 143 20.81430.0 BFC-281Iea/HFC-1I34a (I10 0

C)

1/99 29.1 201 29.0 200 0.3 10/90 26.7 184 25.6 177 4.1 20/80 24.4 168 22.7 157 30/70 22.4 154 20.4 141 8.9 40/60 20.6 142 18.8 130 8.7 50/50 19.1 132 17.5 121 8.4 60/40 17.8 123 16.5 114 7.3 70/30 16.7 115 15.8 109 5.4 80/20 15.7 108 15.1 104 3.8 90/10 14.9 103 14.6 101 99/1 14.2 97.9 14.2 97.9 0.0 BFC-28 1 ea/HFC- I 52a (-201C) 1/99 17.8 123 17.8 123 0.0 10/90 17.0 117 16.6 114 2.4 20/80 16.0 110 15.3 105 4.4 30/70 15.1 104 14.2 97.9 40/60 14.2 97.9 13.2 91.0 50/50 13.3 91.7 12.3 84.8 60/40 12.4 85.5 11.6 80.0 70/30 11L6 80.0 10.9 75.2 80/20 10.8 74.5 10.2 70.3 5.6 90/10 10.0 68.9 9.68 66.7 3.2 99/1 9.28 64.0 9.23 63.6 HFC-28 IeaIHFC-3-10-lsy (0 0

C)

99/1 21.0 145 20.9 144 30 90/10 20.3 140 20.1 139 80/20 19.6 135 19.1 132 2.6 70/30 18.8 130 18.0 124 4.3 60/40 17.9 123 16.9 117 5.6 50/50 17.0 117 15.7 108 7.6 *41/59 16.1 111 14.5 100 9.9 40/60 16.0 110 14.3 98.6 10.6 HFC-28lIealpropane 0 0

C)

1/99 35.3 344 49.8 343 0.2 10/90 48.6 335 48.1 332 20/80 47.1 325 45.7 315 30/70 45.4 313 42.9 296 *40/60 43.4 299 39.3 271 9.4 415.32 28 89281.

H-FC-28 1 ea!DME 1/99 10/90 20/80 30/70 40/60 0/50 60/40 70/30 80/20 90/10 99/1 26.7 25.8 24.8 23.7 22.5 21.3 20.0 18.7 17.3 15.9 14.4 184 26.7 HFC-3-10-lsy/HFC-134 13.9/86.1 14.7 7/93 14.5 1/99 13.7 0/100 13.4 20/80 14.6 30/70 14.5 40/60 14.3 44/56 14.2 45/55 14.2 100/0 3.89 HFC-3-1O-lsy/HIFC-134a (0 0

C)

1/99 42.9 5/95 42.3 10/90 41.5 15/85 40.6 20/80 39.7 25/75 38.9 30/70 38.0 32/68 37.7 33/67 37.5 178 171 163 155 147 138 129 119 110 99.3 101.4 100.0 94.5 92.4 100.7 100.0 98.6 97.9 97.9 26.8 296 292 286 280 274 268 262 260 259 265 254 241 229 228 25.4 24.1 22.7 21.3 20.0 18.7 17.5 16.3 15.2 14.3 14.7 14.3 13.5 13.4 14.6 14.2 13.5 12.8 12.6 3.89 42.9 42.1 40.8 39.4 38.0 36.4 34.7 34.0 33.6 38.4 36.0 33.1 30.0 29.6 184 175 166 157 147 138 129 121 112 105 98.6 101.4 98.6 93.1 92.4 100.7 97.9 93.1 88.3 86.9 26.8 296 290 281 272 262 251 239 234 232 265 248 228 207 204 0.0 2.8 4.2 5.3 6.1 6.4 5.8 4.4 0.7 :0 0.

0 0.0 1.4 0.0 0.0 2.1 5.6 9.9 11.3 0.0 0.0 1.7 4.3 6.4 8.7 9.8 10.4 0.0 2.2 5.4 9.6 10.3 FC-3 -10- 1 sy/HFC- 15 2a (0 0

C)

1/99 38.4 10/90 36.8 40 20/80 35.0 30/70 33.2 *31/69 33.0 HFC-3- 10-1 sy/HFC-23 6ea 7*C) 33.6/66.4 14.7 101 14.7 101 0.0- 20/80 14.5 100 14.1 97.0- 2.9 11/89 13.8 94.9 12.4 85.5 9.9 50/50 14.6 100 14.3 98.5 1.9 60/40 14.4 99.3 13.2 90.7 8.7 61/39 14.4 99.3 12.9 88.9 10. 4 100/0 8.91 61.4 8.91 61.4 0.0 0/100 10.4 71.7 10.4 71.7 0.0 1/99 11.0 75.6 10.5 72.3 4.4 3/97 11.9 81.8 10.7 73.9 9.7 HFC-3 -10-1 sy/HFC-23 6fa 00) 12.7/87.3 14.7 101 14.7 101 0.0 1/99 14.2 98.0 14.2 97.8 0.2 0/100 14.1 97.2 14.1 97.2 0.0 40/60 13.9 95.6 13.2 91.1 4.7 50/50 13.4 92.1 12.2 84.0 8.8 2/48 13.2 91.3 12.0 82.5 9.7 53/47 13.2 90.9 11.8 81.6 10.2 100/0 8.64 59.6 8.64 59.6 0.0 HFC-3- 10-1 sy/butane (0 0

C)

1/99 14.9 103 14.9 103 0.0 10/90 14.6 101 14.5 99.8 0.7 20/80 14.2 97.7 14.0 96.4 1.3 30/70 13.7 94.7 13.5 92.7 40/60 13.3 91.4 12.9 88.9 2.7 ***50/50 12.8 87.9 12.3 85.1 3.2 60/40 12.2 84.1 11.8 81.1 3.6 :*:70/30 11.6 80.0 11.2 77.1 3.7 80/20 11.0 75.6 10.6 73.1 3.4 *90/10 10.3 70.8 10.0 69.2 2.2 9.59 66.1 9.56 65.9 0.3 1 HFC-3-10O-1sy/isobutane (0°C) 1/99 22.6 156 22.6 156 0.0 10/90 21.7 150 21.3 147 2. r 20/80 20.7 143 19.8 136 4.3 30/70 19.6 135 18.3 126 40/60 18.4 127 16.8 116 8.8 45/55 17.8 123 16.0 111 9.9 46/54 17.7 122 15.9 110 10.1 88/12 11.6 80.2 10.5 72.1 10.1 89/11 11.5 79.0 10.4 71.5 99/1 9.69 66.8 9.57 66.0 1.2 HFC-3-10-1 sy/propane (-20 0

C)

1/99 35.2 243 35.0 241 0.6 10/90 33.5 231 31.9 220 4.8 19/81 31.6 218 28.6 197 20/80 31.4 216 28.2 194 10.2 HFC-3-10-lsy/DME (-10 0

C)

1/99 26.7 184 26.7 184 0.0 10/90 26.0 179 25.7 177 1.2 20/80 25.1 173 24.4 168 2.8 30/70 24.2 167 22.9 158 5.4 40/60 23.2 160 21.1 145 9.1 42/58 23.0 159 20.7 143 10.0 43/57 22.8 157 20.5 141 10.1 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 30 pressure of the remaining composition is within about 10% of the vapor pressure of the S: original composition, at a temperature of 25 0

C.

'J EXAMPLE 3 Impact of Vapor Leakage at -20 0

C

A leak test is performed on compositions of HFC-3-10-lsy and SHFC-236fa, at the temperature of-20 0 C. The results are summarized below. "A" represents HFC-3-10-lsy and represents HFC-236fa.

INITIAL 50% LEAK WT%A/WTB PSIA KPA PSIA KPA DELTA %P HFC-3-10-1sy/HFC-236fa 16.3/83.7 6.86 47.3 6.86 47.3 0.0 10/90 6.82 47.0 6.80 46.9 0.3 1/99 6.49 44.7 6.47 44.6 0.3 30/70 6.75 46.5 6.66 45.9 1.3 40/60 6.59 45.4 6.34 43.7 3.8 50/50 6.37 43.9 5.90 40.7 7.4 55/45 6.25 43.1 5.63 38.8 9.9 56/44 6.22 42.9 5.58 38.5 10.3 These results show that compositions of HFC-3-10-lsy and HFC-236fa are azeotropic or azeotrope-like at different temperatures, but that the weight percents of the components vary as the temperature is changed.

EXAMPLE 4 Vapor Pressures and Kauri-butanol Values Vapor pressures of the compounds of the present invention are given below. The data indicate these compounds are useful replacements for hydrocarbons widely used in aerosol formulations today. IFC-281ea and isobutane as well as HFC-161 and propane have nearly identical vapor pressures. Kauri-butanol values for the compounds of the present invention are also higher than each respective hydrocarbon.

25 This indicates these compounds have better solvent capability as well as compatibility with aerosol resins and other active ingredients.

Vapor Pressure (Psig) Kauri-Butanol 70°F 130 0 F Value 30 HFC-161 106 264 16.3 HFC-281ea 31 99 20.3 HFC-3-10-sy 5 38 Propane 108 262 Isobutane 31 97 18 35 Butane 17 65 EXAMPLE VOC (Volatile Organic Compound) Predictions Kinetic rate measurements were measured experimentally (Jet Propulsion Laboratories) or predicted for compounds of the present invention using group reactivity methodology ofR. Atkinson (ref: Kwok, and R. Atkinson, "Estimation of Hydroxyl Radical Reaction Rate Constants for Gas-Phase Organic Compounds using a Structure-Reactivity Relationship: An Update", Final Report to CMA Contract No. ARC- 1994). A compound can be considered a potential non-VOC if its kinetic rate at 298 degrees K relative to ethane is less than 1.0. Results are shown in the Table below.

TABLE

k at 298K cm'/molecule-sec for OH radical k relative Measured Compound reaction to ethane or predicted Ethane 2.4 X 10'" 1.0 Measured Propane 1.1 X 10-1 2 4.6 Measured Butane 2.54 X 10' 1 2 10.5 Predicted Isobutane 2.33 X 10-1 2 9.7 Predicted HFC-161 1.7 X 10 3 0.7 Measured HFC-281ea 4.6 X 10 1 3 1.9 Measured HFC-3-l0-1sy 7.7 X 10-14 0.3 Predicted The compounds of the present invention have significantly reduced 25 photochemical (hydroxyl radical) reactivity compared to hydrocarbons propane, butane and isobutane widely used in aerosols today. Using the compounds of the present invention in aerosols can significantly reduce ground level smog. HFC-161 and could be classified as non-VOCs because their reactivity is less than ethane.

And HFC-281 ea is significantly less reactive than its hydrocarbon analogue isobutane.

EXAMPLE 6 VOC HAIR SPRAY Prototvne A 55% VOC (volatile organic compound) hair spray in accordance with the present invention is formulated as follows:

TABLE

Octylacrylanmide/acrlyates/butylami noethyI methacrylate copolymer (National Starch) AMPv (2-amino-2-methyl-1I-propanol, Kodak) Dimethicone silylate (Hydrolabs) Water Wt% 5.00 0.96 0.50 3.54 To this mixture is added ethanol and propellants of the present inven'ion to yield a 55% VOC formulation: HFC- 161 LIFC-3 -10- 1sy HIFC-161IHFC-134a HFC-161JHC-152a HFC-16 1f.HFC-28 lea HFC-161/HFC-3-10-Isy HIFC-28l1ea/HFC-1I34a HFC-281ea/HFC- 152a HFC-28 1eaIHFC-3 -10- 1sy HFC-3-10-IsyIHFC-134 HFC-3 -10-l1syfHFC- 13 4a HFC-3 -10-1sy/HFC- I52a Wt%/Wt% 35.00 35.00 5.00/3 0.00 5.00/30.00 35.00/7.00 28.00/7.00 7.00/3 5.00 7.00/3 5.00 7.00/35.00 5.00/30.00 5.00/30.00 7.00/28.00 Wt% Ethanol 55.00 55.00 55.00 55.00 48.00 55.00 48.00 48.00 48.00 55.00 55.00 55.00 The vapor pressure of each mixture may vary with formulation. This example is illustrative and does not reflect an optimized system.

EXAMPLE 7 VOC HAIR SPRAY PROTOTYPE Two 55% VOC hair sprays in accordance with the present invention are formulated as follows: A B Component Wt% Wt% PVM/MA Copolymer 6.00 6.00 AMP 0.35 0.35 SWater 29.05 38.65 Ethanol 40-1 34.60 25.00 To these mixtures are added 30.00 weight percent of one of the following compositions of the present invention to yield a 55% VOC formulation:

TABLE

Formulation Component HFC-161/DME HFC-161/butane HFC-161/isobutane HFC-281 ea/propane HFC-281ea/DME HFC-3-10-lsy/butane HFC-3-10- sy/isobutane 25 HFC-3-10-1sy/propane HFC-3-10-1sy/DME

A

Wt% 9.60/20.40 9.60/20.40 9.60/20.40 9.60/20.40 9.60/20.40 9.60/20.40 9.60/20.40

B

Wt% 9.60/20.40 9.60/20.40 The vapor pressure of each mixture may vary with formulation. This example is illustrative and does not reflect an optimized system. The formulations 30 containing HFC-281ea will have less impact on ground level smog than those containing hydrocarbons because HFC-281ea has less significantly less photochemical reactivity.

EXAMPLE 8 FRAGRANCE PROTOTYPE A fragrance in accordance with the present invention is formulated as follows:

TABLE

Wt% Fragrance Ethanol 40-1 70.0 Water 15.0 To this mixture is added 12.0 weight percent of one of the following mixtures of the present invention: Wt% VOC HFC- 161 12.0 BFC-28 Iea 12.0 82 HFC-3-10-Isy 12.0 HFC-161/HFC-134a 3.0/9.0 HFC-161f.HFC-152a 3.0/9.0 HFC-161/HFC-281ea 9.0/3.0 73 IHFC- 16 1 /BF-3 -10- 1sy 9.0/3.0 IHFC-161/butane 9.0/3.0 73 HFC-161/isobutane 9.0/3.0 73 BHFC-161/DMiE 6.0/6.0 76 HFC-28lea/jFC-134a 3.0/9.0 73 BHFC-281IeaIHFC-1I52a 3.0/9.0 73 HFC-281eaIHFC-3-10-Isy 3.0/9.0 73 HFC-28lealpropane 3.0/9.0 82 BI: FC-28 IeaIDME 3.0/9.0 82 B FC-3-1O-lsy/B-FC-134 2.0/10.0 HFC-3-IO-lsy/HFC-134a 3.0/9.0 HFC-3 -10-l1sy/HFC- 152a 3.0/9.0 HFC-3 -10-l1sy/butane 5.0/4.0 74 FC-3- 10-l1sy/isobutane 4.0/5.0 HFC~~~B -3 -10-1Isy/propane 2./008 HFC-3 -10-l1sy/DME 3.0/9.0 79 35 The vapor pressure of each midxture may vary with formulation. This example is illustrative and does not reflect an optimized system. The formulations containing BFC-28 l ea will have less impact on ground level smog than those containing hydrocarbons because HFC-28 l ea has less significantly less photochemical reactivity.

EXAMPLE 9 AEROSOL ANTIPERSPIRANT PROTOTYPE A 60% VOC aerosol antiperspirant in accordance with the present invention is formulated as follows:

TABLE

Wt% Aluminum chlorohydrate 10.0 Isopropyl myristate Silicone fluid DC-344 (Dow Coming) Talc Quatemium-18 hectorite Ethanol 40-1 To this mixture is added 75.0 weight percent of one of the following mixtures of the present invention to yield a 60% VOC formulation: HFC-161/DME 17.0/58.0 HFC-161/butane 17.0/58.0 HFC-161/isobutane 17.0/58.0 HFC-3-10-llsy/butane 17.0/58.0 HFC-3-10-1 sy/isobutane 17.0/58.0 HFC-3-10-1sy/propane 17.0/58.0 HFC-3-10-1sy/DME 17.0/58.0 25 Similar formulations can also be developed for air fresheners, household disinfectants, insect foggers and spray paints using the compositions of the present invention.

oo EXAMPLE HAIR SPRAY PERFORMANCE The following example demonstrates efficacy of the patent invention in hair sprays, compared to a widely used hydrofluorocarbon propellant HFC-152a (CH 3

CHF

2 as shown in the table below. The formulations were one phase indicating complete miscibility. Tack and dry times, curl droop, and flame extension tests were used to evaluate performance. Curl droop measures the percent lengthening of a curl five minutes after spraying. Flame extension was measured to determine the flammability of each formulation. Results show each formulation achieved 80% or higher curl retention, good tack and dry times, and acceptable flame extensions despite the fact that the formulations were not optimized.

Component A Resin* 25 Ethanol 43 Additives 2 HFC-161 20 HFC-281ea HFC-152a 30 Butane Water

DME

Total Wt% 100

TABLE

Formulation C D 25 25 43 43 2 2 18

F

19.5 35.0 1.7 10.0

G

19.5 35.0 1.7 10.0

H

19.5 35.0 1.7 10.0 12 18 13.8 20.0 100 100 100 100 100 13.8 20.0 100 13.8 20.0 100 Vapor Pressure 60 95 31 79 52 47 40 64 70 0 F (psig).

%VOC 43 43 73 55 55 55 65 Curl droop 9 21 11 17 16 18 11 17 Tack Time (sec) 10 14 4 7 11 8 14 58 Dry Time (sec) 24 28 17 46 54 21 39 73 Flame Extension 4 6 9 4 13 4 12 16 (inches) t-butylacrylate/ethylacrylate/methacrylic acid copolymer resin EXAMPLE 11 AIR FRESHENER PERFORMANCE To test air freshener flammability and miscibility, compositions of the present invention were formulated into air fresheners as shown in the table below. The formulations were one phase indicating complete miscibility. Flame extensions were measured which were less than 18 inches, the desirable maximum. The formulations showed good spray patterns and delivery.

*9*e 20 TABLE Formulation A B Component Wt% Wt% Fragrance 1 1 25 Water 4 4 Ethanol 30 HFC-161 65 HFC-281ea Total Wt% 100 100 Vapor Pressure 70F 106 33 (psig) Flame Extension (in) 13 16 EXAMPLE 12 FRAGRANCE PERFORMANCE To test fragrance flammability and miscibility, compositions of the present invention were formulated into fragrances as shown in the table below. The formulations were one phase indicating complete miscibility. Flame extensions were then measured which were less than 18 inches, the desirable maximum. The formulations showed good spray patterns and delivery.

Component Fragrance Ethanol Water HFC-161 HFC-281ea Vapor Pressure 70F (psig) Flame Extension (in)

TABLE

Formulation A B Wt% Wt% 3 3 70 15 12 12 100 100 46 14 6*

I

S

S. r S I EXAMPLE 13 Shelf Life Stability Compositions shown in the table below were prepared and loaded into tinplate aerosol cans. Cans were placed in an oven at 120°F or held at room temperature (21-23 0 C) for several months.

Composition HFC-161/Ethanol (30/70 wt%) Temperature 120 0

F

TABLE

Time 2 months 6 months Can Interior No corrosion Slight detinning No corrosion Medium detinning FC-161/Ethanol Room 24 months No corrosion (30/70 wt%) Slight detinning HFC-281ea/Ethanol 120 0 F 1 month No corrosion (60/40 wt%) or detinning 3 months No corrosion or detinning HFC-281ea/Ethanol/ 120°F 1 month No corrosion Water (40/54/6 wt%) or detinning As shown in the table, the propellant compositions demonstrated good stability in formulation solvents, even without corrosion inhibitors.

EXAMPLE 14 The following table shows the performance of various refrigerants. The data is based on the following conditions.

Evaporator temperature 45.0 0 F (7.2 0

C)

Condenser temperature 130.0°F (54.4 0

C)

Subcooled 15.0F (8.3 0

C)

Return gas 65.0 F (18.3 0

C)

Compressor efficiency is The refrigeration capacity is based on a compressor with a fixed 20 displacement of3.5 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 Capacity Refrig Press Press Comp. Dis BTU/min Comp. Psia (kPa) Psia (kPa) Temp. F COP (kW 30 HFC-161/HFC-134a 1/99 55 379 215 1482 171 77 3.43 225 99/1 80 552 279 1924 201 94 3.49 316 5.6 HIFC- 16 l/.FC- 152a 1/99 99/1 51 352 194 1338 204 90 552 278 1917 200 HIFC-161/HFC-281ea 1/99 99/1 27 186 106 731 168 79 545 278 1917 201 HIFC-161/HFC-3-10-Isy.

1/99 13 90 55 379 148 99/1 79 545 277 1910 201 HIFC- 16 1/butane 1/99 99/1 20 138 79 545 HIFC- 161 /isobutane 1/99 30 207 99/1 79 545 82 565 155 277 1910 201 65 448 12 279 1924 201 HFC- 16 1/DME 1/99 99/1 49 338 183 1262 194 79 545 279 1924 201 3.60 224 1.55-- 318 3.71 123 3.49 314 3.75 63 3.50 314 3..68 93 3.49 314 3.57 123 3.49 315 3.67 215 3.49 315 3.43 222 3.70 121 3.61 222 3.70 122 3.68 59 3.70 120 3.32 282 3.71 123 3.68 213 3.70 122 HFC-218eaIHFC-134a 1/99 99/1 54 372 27 186 212 1462 171 105 724 168 BFC-281eaIHFC-152a 30 1/99 99/1 50 345 192 1324 204 27 186 105 724 168 BFC-28 1 eaIHFC-3 -10-1 sy 1/99 12 83 54 372 148 99/1 26 179 104 717 168 HFC-28 1 ea/propane 1/99 99/1 83 572 27 186 48 331 27 186 270 1862 166 107 738 168 181 1248 193 106 731 168 BFC-28 1 eaIDM[E 1/99 99/1 HFC-3-10-sy/HFC-134a 1/99 42 290 99/1 12 83 HFC-3-10-1sy/HFC-134a 1/99 54 372 99/1 12 83 HFC-3-10-1sy/HFC-152a 1/99 50 345 99/1 13 90 HFC3-10-1sy/HFC-236ea 1/99 15 103 99/1 12 83 HFC-3-10-1sy/HFC-236fa 1/99 20 138 99/1 12 83 167 1151 182 83 3.60 54 372 148 64 3.69 187 66 210 1448 54 372 191 1317 54 372 171 148 3.44 221 3.69 203 95 148 64 3.60 3.70 3.50 3.67 221 483 143 62 365 148 64 593 141 60 365 148 64 552 155 68 365 148 64 3.42 86 3.67 59 HFC-3-10-1sy/butane 1/99 19 99/1 12 HFC-3-10-1 sy/isobutane 1/99 29 200 99/1 12 83 HFC-3-10-sy/propane 1/99 83 572 30 99/1 13 90 110 758 152 67 54 372 148 64 3.65 3.67 3.56 3.68 3.33 3.74 3.67 3.73 269 1855 55 379 181 1248 55 379 166 74 147 64 193 89 148 64 120 2.1 59 281 4.9 62 1.1 213 3.7 62 1.1 HFC-3-10-1sy/DME 1/99 48 99/1 13 331 90 ADDITIONAL COMPOUNDS Other components, such as aliphatic hydrocarbons having a boiling point of to +60 0 C, hydrofluorocarbonalkanes having a boiling point of-60 to +60 0

C,

hydrofluoropropanes having a boiling point of between -60 to +60 0 C, hydrocarbon esters having a boiling point between -60 to +60 0 C, hydrochlorofluorocarbons having a boiling point between -60 to +60 0 C, hydrofluorocarbons having a boiling point of-60 to +60 0

C,

hydrochlorocarbons having a boiling point between -60 to +60 0 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.

Where the terms "comprise", "comprises", "comprised" or "comprising" are used in this specification, they are to be interpreted as specifying the presence of the stated features, integers, steps or components referred to, but not to preclude the presence or addition of one or more other feature, integer, step, component or group thereof.

This is a divisional application of AU51606/98 the disclosure of which is incorporated herein by way of reference.

e e e *f

Claims (17)

1. An aerosol composition and an agent to be atomised wherein the propellant is selected from the group consisting of fluoroethane, 2-fluoropropane, and tert-butylfluoride.

2. A composition as defined in claim 1 comprising 1-99 weight percent fluoroethane and 1-99 weight percent of at least one of 1,1,1,2-tetrafluoroethane, 1,1-difluoroethane, 2- fluoropropane, tert-butylfluoride, butane, isobutane or dimethylether; 1 to 99 weight percent 2-fluoropropane and 1 to 99 weight percent of at least one of 1,1,1,2- tetrafluoroethane, 1,1 -difluoroethane, tert-butylfluoride, propane, dimethylether; or 1 to 99 weight percent tert-butylfluoride and 1 to 99 weight percent of at least one of 1,1,2,2- tetrafluoroethane, 1,1,1,2-tetrafluoroethane, 1,1-difluoroethane, 1,1,1,2,3,3- hexafluoropropane, 1,1,1,3,3,3-hexafluoropropane, butane, isobutane, propane or dimethylether.

3. Effective amounts of the following compounds to form an azeotropic or azeotrope- like composition: comprising fluoroethane and 1,1,1 ,2-tetrafluoroethane, 1,1- difluoroethane, 2-fluoropropane, tert-butylfluoride, butane, isobutane or dimethylether; 2- fluoropropane and 1,1,1 ,2-tetrafluoroethane, 1,1 -difluoroethane, tert-butylfluoride, propane, dimethylether; or tert-butylfluoride and 1,1,2,2-tetrafluoroethane, 1,1,1,2- tetrafluoroethane, 1,1-difluoroethane, 1,1,1,2,3,3 -hexafluoropropane, 1,1,1,3,3,3- hexafluoropropane, butane, isobutane, propane or dimethylether.

4. The azeotropic or azeotrope-like composition of claim 3, said composition consisting essentially of: 1-99 weight percent fluoroethane and 1-99 weight percent 1,1,1 ,2-tetrafluoroethane; 1-99 weight percent fluoroethane and 1-99 weight percent 1,1- .i difluoroethane; 73-99 weight percent fluoroethane and 1-27 weight percent 2- fluoropropane; 75-99 weight percent fluoroethane and 1-25 weight percent tert- butylfluoride; 67-99 weight percent fluoroethane and 1-33 weight percent butane; 52-99 S 30 weight percent fluoroethane and 1-48 weight percent isobutane; 1-99 weight percent 0 fluoroethane and 1-99 weight percent dimethylether; 1-99 weight percent 2-fluoropropane and 1-99 weight percent 1,1,1,2-tetrafluoroethane; 1-99 weight percent 2-fluoropropane and 1-99 weight percent 1,1-difluoroethane; 11-99 weight percent 2-fluoropropane and 1- 29/04/04atl 2623.specipgs,32 59 weight percent tert-butylfluoride; 1-41 weight percent 2-fluoropropane and 59-99 weight percent propane; 1-99 weight percent 2-fluoropropane and 1-99 weight percent dimethylether; 1-44 weight percent tertbutylfluoride and 56-99 weight percent 1,1,2,2- tetrafluoroethane; 1-32 weight percent tert-butylfluoride and 68-99 weight percent 1,1,1,2- tetrafluoroethane; 1-30 weight percent tert-butylfluoride and 70-99 weight percent 1,1- difluoroethane; 11-60 weight percent tert-butylfluoride and 40-89 weight percent 1,1,1,2,3,3-hexafluoropropane; 1-3 weight percent tert-butylfluoride and 97-99 weight percent 1,1,1,2,3,3-hexafluoropropane 1-52 weight percent tert-butylfluoride and 48-99 weight percent 1,1,1,3,3,3-hexafluoropropane; 1-99 weight percent tert-butylfluoride and 1-99 weight percent butane; 1-45 weight percent tert-butylfluoride and 55-99 weight percent isobutane; 89-99 weight percent tert-butylfluoride and 1-11 weight percent isobutane; 1-19 weight percent tert-butylfluoride and 81-99 weight percent propane; or 1- 42 weight percent tert-butylfluoride and 58-99 weight percent dimethylether.

5. Effective amounts of tert-butylfluoride and a compound selected from the group consisting of 1,1,2,2-tetrafluoroethane, 1,1,1,2,3,3-hexafluoropropane or 1,1,1,3,3,3- hexafluoropropane to form binary compositions having a vapor pressure higher than that of the components of the binary composition.

6. A process for producing an aerosol comprising using a composition of claim 2.

7. A process for producing an aerosol comprising using a composition of claim 3.

8. A process for producing an aerosol comprising using a composition of claim 4.

9. A process for producing an aerosol comprising using a composition of claim A process for producing refrigeration, comprising condensing a composition of claim 2, and thereafter evaporating said composition in the vicinity of the body to be 30 cooled.

11. A process for producing refrigeration, comprising condensing a composition of claim 3, and thereafter evaporating said composition in the vicinity of the body to be .cooled. 29/04/04,atl 2623.specipgs,33

12. A process for producing refrigeration, comprising condensing a composition of claim 4, and thereafter evaporating said composition in the vicinity of the body to be cooled.

13. A process for producing refrigeration, comprising condensing a composition of claim 5, and thereafter evaporating said composition in the vicinity of the body to be cooled.

14. A process for preparing a thermoset or thermoplastic foam, comprising using a composition of claim 2 as a blowing agent. A process for preparing a thermoset or thermoplastic foam, comprising using a composition of claim 5 as a blowing agent.

16. A process for preparing a thermoset or thermoplastic foam comprising using a composition of claim 6 as a blowing agent.

17. A process for preparing a thermoset or thermoplastic foam, comprising using a composition of claim 5 as a blowing agent.

18. An aerosol propellant of claim 1, substantially as herein described with reference to any one of the Examples and/or accompanying Figures.

19. A composition of any one of claims 2 to 5, substantially as herein described with 25 reference to any one of the Examples and/or accompanying Figures. o• C A process of any one of claims 6 to 17, which process is substantially as herein described with reference to any one of the Examples and/or accompanying Figures. DATED this 2 9 th day of April, 2004 E.I. DU PONT DE NEMOURS AND COMPANY IBy their Patent Attorneys: 35 CALL AN LAW R!E 29/04/04,atl 2623.specipgs.34