AU2013203627B2 - Compositions containing fluorine substituted olefins - Google Patents

Abstract

3540753-1 The use to e of tetrafluoropropenes, particularly (HFO-1234) in a variety of applications, including refrigeration equipment, is disclosed. These materials are generally useful as 5 refrigerants for heating and cooling, as blowing agents, as aerosol propellants, as solvent composition, and as fire extinguishing and suppressing agents. *1/1 Figure 1 r- r-i 1~li~ I

Description

COMPOSITIONS CONTAINING FLUORINE SUBSTITUTED OLEFINS This is a divisional of Australian Patent Application No. 2012202525 which in turn is a divisional of Australian Patent Application No. 2011201225 which in turn is a further 5 divisional of Australian Patent Application No. 2005238537, the entire contents of which are incorporated herein by reference. FIELD OF THE INVENTION 10 This invention relates to compositions having utility in numerous applications, including particularly propellants. BACKGROUND OF THE INVENTION 15 Fluorocarbon based fluids have found widespread use in many commercial and industrial applications. For example, fluorocarbon based fluids are frequently used as a working fluid in systems such as air conditioning, heat pump and refrigeration applications. The vapor compression cycle is one of the most commonly used type methods to accomplish cooling or heating in a refrigeration system. The vapor 20 compression cycle usually involves the phase change of the refrigerant from the liquid to the vapor phase through heat absorption at a relatively low pressure and then from the vapor to the liquid phase through heat removal at a relatively low pressure and temperature, compressing the vapor to a relatively elevated pressure, condensing the vapor to the liquid phase through heat removal at this relatively elevated pressure and 25 temperature, and then reducing the pressure to start the cycle over again. While the primary purpose of refrigeration is to remove heat from an object or other fluid at a relatively low temperature, the primary purpose of a heat pump is to add heat at a higher temperature relative to the environment. Certain fluorocarbons have been a preferred component in many heat exchange 30 fluids, such as refrigerants, for many years in many applications. For, example, fluoroalkanes, such as chlorofluoromethane and chlorofluoroethane derivatives, have gained widespread use as 2 refrigerants in applications including air conditioning and heat pump applications owing to their unique combination of chemical and physical properties. Many of the refrigerants commonly utilized in vapor compression systems are either single components fluids or azeotropic mixtures. Concern has increased in recent years about potential damage to the earth's atmosphere and climate, and certain chlorine-based compounds have been identified as particularly problematic in this regard. The use of chlorine-containing compositions (such as chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs) and the like) as refrigerants in air-conditioning and refrigeration systems has become disfavored because of the ozone-depleting properties associated with many of such compounds. There has thus been an increasing need for new fluorocarbon and hydrofluorocarbon compounds and compositions that offer alternatives for refrigeration and heat pump applications. For example, it has become desirable to retrofit chlorine-containing refrigeration systems by replacing chlorine-containing refrigerants with non-chlorine-containing refrigerant compounds that will not deplete the ozone layer, such as hydrofluorocarbons (HFCs). It is generally considered important, however, that any potential substitute refrigerant must also possess those properties present in many of the most widely used fluids, such as excellent heat transfer properties, chemical stability, low- or no- toxicity, non-flammability and lubricant compatibility, among others. Applicants have come to appreciate that lubricant compatibility is of particular importance in many of applications. More particularly, it is highly desirably for refrigeration fluids to be compatible with the lubricant utilized in the compressor unit, used in most refrigeration systems. Unfortunately, many non-chlorine-containing refrigeration fluids, including HFCs, are relatively insoluble and/or immiscible in the types of lubricants used traditionally with CFC's and HFCs, including, for example, mineral oils, 3 alkylbenzenes or poly(alpha-olefins). In order for a refrigeration fluid lubricant combination to work at a desirable level of efficiently within a compression refrigeration, air-conditioning and/or heat pump system, the lubricant should be sufficiently soluble in the refrigeration liquid over a wide range of operating temperatures. Such solubility lowers the viscosity of the lubricant and allows it to flow more easily throughout the system. In the absence of such solubility, lubricants tend to become lodged in the coils of the evaporator of the refrigeration, air-conditioning or heat pump system, as well as other parts of the system, and thus reduce the system efficiency. With regard to efficiency in use, it is important to note that a loss in refrigerant thermodynamic performance or energy efficiency may have secondary environmental impacts through increased fossil fuel usage arising from an increased demand for electrical energy. Furthermore, it is generally considered desirably for CFC refrigerant substitutes to be effective without major engineering changes to conventional vapor compression technology currently used with CFC refrigerants. Flammability is another important property for many applications. That is, it is considered either important or essential in many applications, including particularly in heat transfer applications, to use compositions, which are non-flammable. Thus, it is frequently beneficial to use in such compositions compounds, which are nonflammable. As used herein, the term "nonflammable" refers to compounds or compositions, which are determined to be nonflammable as determined in accordance with ASTM standard E-681, dated 2002, which is incorporated herein by reference. Unfortunately, many HFCs, which might otherwise be desirable for used in refrigerant compositions are not nonflammable. For example, the fluoroalkane difluoroethane (HFC-152a) and the fluoroalkene 1,1,1 trifluoropropene (HFO-1243zf) are each flammable and therefore not viable for use in many applications.

4 Higher fluoroalkenes, that is fluorine-substituted alkenes having at least five carbon atoms, have been suggested for use as refrigerants. U.S. Patent No. 4,788,352 - Smutny is directed to production of fluorinated C to C8 compounds having at least some degree of unsaturation. The Smutny patent identifies such higher olefins as being known to have utility as refrigerants, pesticides, dielectric fluids, heat transfer fluids, solvents, and intermediates in various chemical reactions. (See column 1, lines 11 - 22). While the fluorinated olefins described in Smutny may have some level of effectiveness in heat transfer applications, it is believed that such compounds may also have certain disadvantages. For example, some of these compounds may tend to attack substrates, particularly general purpose plastics such as acrylic resins and ABS resins. Furthermore, the higher olefinic compounds described in Smutny may also be undesirable in certain applications because of the potential level of toxicity of such compounds which may arise as a result of pesticide activity noted in Smutny. Also, such compounds may have a boiling point, which is too high to make them useful as a refrigerant in certain applications. Bromofluoromethane and bromochlorofluoromethane derivatives, particularly bromotrifluoromethane (Halon 1301) and bromochlorodifluoromethane (Halon 1211) have gained widespread use as fire extinguishing agents in enclosed areas such as airplane cabins and computer rooms. However, the use of various halons is being phased out due to their high ozone depletion. Moreover, as halons are frequently used in areas where humans are present, suitable replacements must also be safe to humans at concentrations necessary to suppress or extinguish fire. Applicants have thus come to appreciate a need for compositions, and particularly heat transfer compositions, fire extinguishing/suppression compositions, blowing agents, solvent compositions, and compatabilizing agents, that are potentially useful in numerous applications, including 3540753-1 5 vapor compression heating and cooling systems and methods, while avoiding one or more of the disadvantages noted above. SUMMARY 5 In an embodiment the present invention provides use as a propellant of a composition comprising trans-1,3,3,3-tetrafluoropropene (trans-HFO-1234ze), provided that the composition is not selected from any of: an azeotrope-like composition comprising a pentafluoropropene (HFO- 1225) and trans-1,3,3,3 -tetrafluoropropene (trans-HFO 1234ze); an azeotrope-like composition comprising trans-1,3,3,3-tetrafluoropropene (trans 10 HFO-1234ze) and CF 3 I; and an azeotrope-like composition comprising trans-1,3,3,3 tetrafluoropropene (trans-HFO-1234ze), 1,1-difluoroethane (HFC-152a), and CF 3 1. In another embodiment the present invention provides a sprayable composition comprising: (a) a propellant composition comprising trans-1,3,3,3-tetrafluoropropene (trans-HFO- 1234ze), and (b) a material to be sprayed; provided that the propellant 15 composition is not selected from any of: an azeotrope-like composition comprising a pentafluoropropene (HFO-1225) and trans-1,3,3,3-tetrafluoropropene (trans-HFO-1234ze); an azeotrope-like composition comprising trans-1,3,3,3-tetrafluoropropene (trans-HFO 1234ze) and CF 3 I; and an azeotrope-like composition comprising trans-1,3,3,3 tetrafluoropropene (trans-HFO- 1 234ze), 1,1 -difluoroethane (HFC- 1 52a), and CF 3 I. 20 In another embodiment the present invention provides use of a sprayable composition comprising: (a) a propellant composition comprising 1,3,3,3 tetrafluoropropene (HFO- 1 234ze), and (b) a material to be sprayed; as an industrial aerosol, a contact cleaner, a duster, a household product, an automotive product or a medical product which is a metered dose inhaler. 25 In another embodiment the present invention provides a sprayable composition comprising: (a) a propellant composition comprising 1,3,3,3-tetrafluoropropene (HFO 1234ze), and (b) a material to be sprayed; wherein the material to be sprayed is selected from a beta-agonist and a corticosteroid.

6 DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS THE COMPOSITIONS The present invention relates to composition comprising trans-1,3,3,3 tetrafluoropropene, otherwise known as transHFO-1234ze. 5 Applicants believe that transHFO-1234ze is generally effective and exhibits utility in aerosols and propellants. Applicants have surprisingly and unexpectedly found that transHFO-1234ze exhibits a highly desirable low level of toxicity. As can be readily appreciated, this discovery is of potentially enormous advantage and benefit for the formulation of compositions. 10 The term HFO-1234ze is used herein generically to refer to 1,3,3,3-tetrafluoropropene, independent of whether it is the cis- or trans- form. The terms "cisHFO-1 234ze" and "transHFO-1234ze" are used herein to describe the cis- and trans- forms of 1, 3,3,3 tetrafluoropropene respectively. The term "HFO-1234ze" therefore includes within its scope cisHFO-1234ze, transHFO-1234ze, and all combinations and mixtures of these. 15 HFO-1234 compounds are known materials and are listed in Chemical Abstracts databases. The production of fluoropropenes such as CF 3

CH=CH

2 by catalytic vapor phase fluorination of various saturated and unsaturated halogen-containing C 3 compounds is described in U.S. Patent Nos. 2,889,379; 4,798,818 and 4,465,786, each of which is incorporated herein by reference. EP 974,571, also incorporated herein by reference, 20 discloses the preparation of 1,1,1,3-tetrafluoropropene by contacting 1,1,1,3,3 pentafluoropropane (HFC-245fa) in the vapor phase with a chromium-based catalyst at elevated temperature, or in the liquid phase with an alcoholic solution of KOH, NaOH, Ca(OH) 2 or Mg(OH) 2 . In addition, methods for producing compounds in accordance with the present invention are described generally in connection with pending United States 25 Patent Application entitled "Process for Producing Fluoropropenes" bearing attorney docket number (H0003789 (26267)), which is also incorporated herein by reference. The present compositions, particularly those comprising transHFO1234ze, are believed to possess properties that are advantageous for a number of important reasons. For example, applicants believe, based at least in part on mathematical modeling, that the 30 fluoroolefins of the present invention will not have a substantial negative affect on atmospheric chemistry, being negligible contributors to ozone depletion in comparison to some other halogenated species. The preferred compositions of the present invention thus 3540753-1 7 have the advantage of not contributing substantially to ozone depletion. The preferred compositions also do not contribute substantially to global warming compared to many of the hydrofluoroalkanes presently in use. In certain preferred forms, compositions of the present invention have a Global 5 Warming Potential (GWP) of not greater than about 1000, more preferably not greater than about 500, and even more preferably not greater than about 150. In certain embodiments, the GWP of the present compositions is not greater than about 100 and even more preferably not greater than about 75. As used herein, "GWP" is measured relative to that of carbon dioxide and over a 100-year time horizon, as defined in "The Scientific Assessment 10 of Ozone Depletion, 2002, a report of the World Meteorological Association's Global Ozone Research and Monitoring Project," which is incorporated herein by reference. In certain preferred forms, the present compositions also preferably have an Ozone Depletion Potential (ODP) of not greater than 0.05, more preferably not greater than 0.02 and even more preferably about zero. As used herein, "ODP" is as defined in "The 15 Scientific Assessment of Ozone Depletion, 2002, A report of the World Meteorological Association's Global Ozone Research and Monitoring Project," which is incorporated herein by reference. The amount of the transHFO-1234ze, contained in the present compositions can vary widely, depending the particular application, and compositions containing more than 20 trace amounts and less than 100% of the compound are within broad the scope of the present invention. Moreover, the compositions of the present invention can be azeotropic, azeotrope-like or non-azeotropic. In preferred embodiments, the present compositions comprise transHFO-1234ze, in amounts from about 5% by weight to about 99% by weight, and even more preferably from about 5% to about 95%. Many additional compounds may 25 be included in the present compositions, and the presence of all such compounds is within the broad scope of the invention. In certain preferred embodiments, the present compositions include, in addition to HFO- 1234ze one or more of the following: Difluoromethane (HFC-32) Pentafluoroethane (HFC- 125) 30 1,1,2,2-tetrafluoroethane (HFC-134) 1,1,1,2-Tetrafluoroethane (HFC- 1 34a) Difluoroethane (HFC-152a) 8 1,1,1,2,3,3,3-Heptafluoropropane (HFC-227ea) 1,1,1,3,3,3-hexafluoropropane (HFC-236fa) 1,1,1,3,3-pentafluoropropane (HFC-245fa) 1,1,1,3,3-pentafluorobutane (HFC-365mfc) 5 water

CO

2 The relative amount of any of the above noted components, as well as any additional components which may be included in present compositions, can vary widely within the 10 general broad scope of the present invention according to the particular application for the composition, and all such relative amounts are considered to be within the scope hereof PROPELLANT AND AEROSOL COMPOSITIONS In another aspect, the present invention provides propellant compositions 15 comprising or consisting essentially of a composition of the present invention, such propellant composition preferably being a sprayable composition. The propellant compositions of the present invention preferably comprise a material to be sprayed and a propellant comprising, consisting essentially of, or consisting of a composition in accordance with the present invention. Inert ingredients, solvents, and other materials may 20 also be present in the sprayable mixture. Preferably, the sprayable composition is an aerosol. Suitable materials to be sprayed include, without limitation, cosmetic materials such as deodorants, perfumes, hair sprays, cleansers, and polishing agents as well as medicinal materials such as anti-asthma components, anti-halitosis components and any other medication or the like, including preferably any other medicament or agent intended 25 to be inhaled. The medicament or other therapeutic agent is preferably present in the composition in a therapeutic amount, with a substantial portion of the balance of the composition comprising transHFO-1234ze. Aerosol products for industrial, consumer or medical use typically contain one or more propellants along with one or more active ingredients, inert ingredients or solvents. 30 The propellant provides the force that expels the product in aerosolized form. While some aerosol products are propelled with compressed gases like carbon dioxide, nitrogen, nitrous oxide and even air, most commercial aerosols use liquefied gas propellants. The most 9 commonly used liquefied gas propellants are hydrocarbons such as butane, isobutane, and propane. Dimethyl ether and HFC-152a (1, 1-difluoroethane) are also used, either alone or in blends with the hydrocarbon propellants. Unfortunately, all of these liquefied gas propellants are highly flammable and their incorporation into aerosol formulations will 5 often result in flammable aerosol products. Applicants have come to appreciate the continuing need for nonflammable, liquefied gas propellants with which to formulate aerosol products. The present invention provides compositions of the present invention, particularly and preferably compositions comprising transHFO-1234ze, for use in certain industrial aerosol products, including for 10 example spray cleaners, lubricants, and the like, and in medicinal aerosols, including for example to deliver medications to the lungs or mucosal membranes. Examples of this includes metered dose inhalers (MDIs) for the treatment of asthma and other chronic obstructive pulmonary diseases and for delivery of medicaments to accessible mucous membranes or intranasally. The present invention thus includes methods for treating 15 ailments, diseases and similar health related problems of an organism (such as a human or animal) comprising applying a composition of the present invention containing a medicament or other therapeutic component to the organism in need of treatment. In certain preferred embodiments, the step of applying the present composition comprises providing a MDI containing the composition of the present invention (for example, 20 introducing the composition into the MDI) and then discharging the present composition from the MDI. The compositions of the present invention comprising or consisting essentially of, transHFO-1234ze, are capable of providing nonflammable, liquefied gas propellant and aerosols that do not contribute substantially to global warming. The present compositions 25 can be used to formulate a variety of industrial aerosols or other sprayable compositions such as contact cleaners, dusters, lubricant sprays, and the like, and consumer aerosols such as personal care products, household products and automotive products. TransHFO 1234ze is particularly preferred for use as an important component of propellant compositions for in medicinal aerosols such as metered dose inhalers. The medicinal 30 aerosol and/or propellant and/or sprayable compositions of the present invention in many applications include, in addition to transHFO- 123 4ze, a medicament such as a beta agonist, a corticosteroid or other medicament, and, optionally, other ingredients, such as 10 surfactants, solvents, other propellants, flavorants and other excipients. The compositions of the present invention, unlike many compositions previously used in these applications, have good environmental properties and are not considered to be potential contributors to global warming. The present compositions therefore provide in certain preferred 5 embodiments substantially nonflammable, liquefied gas propellants having very low Global Warming potentials. METHODS AND SYSTEMS The present compositions are advantageous for in use in systems and methods of 10 generating aerosols, preferably comprising or consisting of the aerosol propellant in such systems and methods. Throughout this specification and the claims which follow, unless the context requires otherwise, the word "comprise", and variations such as "comprises" and 15 "comprising", will be understood to imply the inclusion of a stated integer or step or group of integers or steps but not the exclusion of any other integer or step or group of integers or steps. The reference in this specification to any prior publication (or information derived from it), or to any matter which is known, is not, and should not be taken as an 20 acknowledgment or admission or any form of suggestion that that prior publication (or information derived from it) or known matter forms part of the common general knowledge in the field of endeavour to which this specification relates.

Claims (52)

1. Use as a propellant of a composition comprising trans-1,3,3,3 -tetrafluoropropene (trans-HFO-1234ze), provided that the composition is not selected from any of: an azeotrope-like composition comprising a pentafluoropropene (HFO-1225) and trans-1,3,3,3-tetrafluoropropene (trans-HFO-1234ze); an azeotrope-like composition comprising trans-1,3,3,3-tetrafluoropropene (trans HFO-1234ze) and CF 3 I; and an azeotrope-like composition comprising trans- 1,3,3,3-tetrafluoropropene (trans HFO-1234ze), 1,1-difluoroethane (HFC-152a), and CF 3 I.

2. Use according to claim 1, wherein said composition comprises trans-1,3,3,3 tetrafluoropropene (trans-HFO-1234ze) in amounts of from 5% by weight to 99% by weight.

3. Use according to any preceding claim, wherein said composition comprises cis 1,3,3,3-tetrafluoropropene (cis HFO-1234ze).

4. Use according to claim 1, wherein said composition consists essentially of trans 1,3,3,3-tetrafluoropropene (trans-HFO-1234ze).

5. Use according to claim 1, wherein said composition consists of trans-1,3,3,3 tetrafluoropropene (trans-HFO-1234ze).

6. Use according to any preceding claim, wherein said composition is a sprayable composition.

7. Use according to claim 6, wherein the sprayable composition is an aerosol.

8. Use according to any preceding claim, wherein said composition has a Global Warming Potential (GWP) of not greater than 150. n1-IneRCVOVCflUNWODIULA.vIVNo\D40~14JaLoC-JUfUVf4UI. 12

9. Use according to claim 7, wherein the aerosol is a medicinal aerosol.

10. Use according to claim 9, wherein the medicinal aerosol is a metered dose inhaler (MDI).

11. Use according to claim 7, wherein the aerosol is an industrial aerosol.

12. Use according to claim 11, wherein the industrial aerosol is a contact cleaner, a spray cleaner, a duster, a lubricant spray or an automotive aerosol.

13. Use according to claim 11, wherein the industrial aerosol is a duster and the composition consists essentially of trans-HFO-1234ze.

14. Use according to claim 7, wherein the aerosol is a personal care aerosol.

15. Use according to claim 14, wherein the personal care aerosol comprises a perfume, a hair spray, a cleanser or a polishing agent.

16. Use according to any of claims 1 to 3, 6 to 12 or 14 to 15, wherein the composition further comprises an inert ingredient, a solvent, a flavorant, a surfactant, a further propellant or an excipient.

17. Use according to any of claims I to 3, 6 to 12 or 14 to 15, wherein the composition further comprises a solvent.

18. A sprayable composition comprising: (a) a propellant composition comprising trans-1,3,3,3-tetrafluoropropene (trans HFO-1234ze), and (b) a material to be sprayed; provided that the propellant composition is not selected from any of: an azeotrope-like composition comprising a pentafluoropropene (HFO-1225) and trans-1,3,3,3 -tetrafluoropropene (trans-HFO-1234ze); n-1.MVKuIl~nVUVw~.tuNI-ULlu/...UVNoiVA4 f4l_.(OV-JwU,UtU 13 an azeotrope-like composition comprising trans- 1,3,3,3-tetrafluoropropene (trans HFO-1234ze) and CF 3 I; and an azeotrope-like composition comprising trans- 1,3,3,3-tetrafluoropropene (trans HFO-1234ze), 1,1-difluoroethane (HFC-152a), and CF 3 1.

19. A sprayable composition according to claim 18, wherein the propellant comprises trans-1,3,3,3-tetrafluoropropene (trans-HFO-1234ze) in amounts of from 5% by weight to 99% by weight.

20. A sprayable composition according to claims 18 or 19, wherein the material to be sprayed comprises a cosmetic material, or a medicinal material.

21. A sprayable composition according to any of claims 18 to 20, which further comprises an inert ingredient, a solvent, a flavorant, a surfactant or an excipient.

22. A sprayable composition according to any of claims 18 to 20, which further comprises a solvent.

23. A sprayable composition according to claim 20, wherein the cosmetic material is selected from deodorants, perfumes, hair sprays, cleansers and polishing agents.

24. A sprayable composition according to claim 20, wherein the medicinal material is selected from a beta-agonist, a corticosteroid, anti-asthma and anti-halitosis medications.

25. A sprayable composition according to any of claims 18 to 24, which is an aerosol.

26. A sprayable composition according to any of claims 18 to 25, in the form of a product selected from spray cleaners, dusters, lubricant spray, medical aerosols, industrial aerosols, contact cleaners, dusters, personal care products, household products and automotive products.

27. A sprayable composition according to claim 26, wherein the medical aerosol is a 14 metered dose inhaler.

28. A sprayable composition according to vlaim 26, wherein the personal care product comprises a perfume, a hair spray, a cleanser or a polishing agent.

29. A sprayable composition according to any of claims 18 to 28, wherein said composition has a Global Warming Potential (GWP) of not greater than 150.

30. A sprayable composition according to claim 29, wherein said composition has a Global Warming Potential (GWP) of not greater than 100.

31. A sprayable composition according to claim 30, wherein said composition has a Global Warming Potential (GWP) of not greater than 75.

32. A sprayable composition according to any of claims 18 or 20 to 31, wherein the propellant consists essentially of trans-HFO-1234ze.

33. A sprayable composition according to any of claims 18 or 20 to 31, wherein the propellant consists of trans-HFO-1234ze.

34. Use of a sprayable composition comprising: (a) a propellant composition comprising 1,3,3,3-tetrafluoropropene (HFO-1 234ze), and (b) a material to be sprayed; as an industrial aerosol, a contact cleaner, a duster, a household product, an automotive product or a medical product which is a metered dose inhaler.

35. Use according to claim 34, as an industrial aerosol.

36. Use according to claim 34, as a household product.

37. Use according to claim 34, as an automotive product. 15

38. Use according to claim 34, as a contact cleaner.

39. Use according to claim 34, as a medical product which is a metered dose inhaler.

40. Use of a propellant composition comprising 1,3,3,3-tetrafluoropropene (HFO 1234ze) as a duster.

41. Use according to any of claims 34 to 40, wherein said HFO-1234ze is trans-HFO 1234ze.

42. Use according to any of claims 34 to 41, wherein the propellant composition comprises HFO-1234ze in amounts of from 5% by weight to 99% by weight.

43. Use according to any of claims 34 to 41, wherein the propellant composition consists essentially of trans-HFO- 1234ze.

44. Use according to any of claims 34 to 41, wherein the propellant composition consists of trans-HFO-1234ze.

45. Use according to any of claims 34 to 43, wherein the propellant composition further comprises an inert ingredient, a solvent, a flavorant, a surfactant or an excipient.

46. A sprayable composition comprising: (a) a propellant composition comprising 1,3,3,3-tetrafluoropropene (HFO-1234ze), and (b) a material to be sprayed; wherein the material to be sprayed is selected from a beta-agonist and a corticosteroid.

47. The sprayable composition according to claim 46, wherein said tetrafluoropropene is trans-HFO-1234ze. 16

48. The sprayable composition according to claim 46 or 47, wherein the propellant composition comprises HFO-1234ze in amounts of from 5% by weight to 99% by weight.

49. The sprayable composition according to claim 46 or 47, wherein the propellant composition consists essentially of trans-HFO-1234ze.

50. The sprayable composition according to any of claims 46 or 47, wherein the propellant composition consists of trans-HFO-1234ze.

51. The sprayable composition according to any of claims 46 to 50, which further comprises an inert ingredient, a solvent, a flavorant, a surfactant or an excipient.

52. The use according to claim 1, claim 34 or claim 40, the sprayable composition according to claim 18 or claim 46, substantially as hereinbefore described.