AU2015200222B2 - Compositions containing flourine substituted olefins - Google Patents

Abstract

4266756-1 The use of pentafluoropropene (HFO-1225) and tetrafluoropropene (HFO-1234) in refrigeration equipment is disclosed. These materials are generally useful as refrigerants for heating and cooling, as blowing agents, as aerosol propellants, as solvent composition, and as fire extinguishing and suppressing agents.

Description

COMPOSITIONS CONTAINING FLUORINE SUBSTITUTED OLEFINS This is a divisional of Australian Patent Application No. 2013203604, which in turn is divisional of Australian Patent Application No. 2012202305, which in turn is a divisional of Australian Patent Application No. 2011202712, the entire contents of which are incorporated 5 herein by reference. RELATED APPLICATIONS The present application is related to and claims the priority benefit of U.S. Provisional Application Nos. 60/421,263, and 60/421,435, each of which was filed on October 25, 2002, 10 and each of which is incorporated herein by reference. The present application is also related to and incorporates by reference each of the following concurrently filed United States Patent Applications: Number H0004412 (26269) entitled "Fluorinated Alkene Refrigerant Composition," by Raymond Thomas and Attorney Docket Number H0003789 (26267) entitled "Process For Producing Fluoropropenes," by Hsueh Sung Tung et al. 15 FIELD OF THE INVENTION This invention relates to compositions having utility in numerous applications, including particularly refrigeration systems, and to methods and systems which utilize such compositions. In preferred aspects, the present invention is directed to refrigerant 20 compositions which comprise at least one multi-fluorinated olefin of the present invention. BACKGROUND OF THE INVENTION 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 25 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 vapour 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 30 relatively low pressure and temperature, compressing the vapor to a relatively 1 elevated pressure, condensing the vapor to the liquid phase through heat removal at this relatively elevated pressure and 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 5 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 fluids, such as refrigerants, for many years in many applications. For, example, fluoroalkanes, such as chlorofluoromethane and chiorofluoroethane 10 derivatives, have gained widespread use as 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. 15 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 (CFC's), hydrochiorofluorocarbons (HCF's) and the like) as refrigerants in air-conditioning and refrigeration systems has 20 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 25 refrigerants with non-chlorine-containing refrigerant compounds that will not deplete the ozone layer, such as hydrofluorocarbons (HFC's). 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 30 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 2 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 HFC's, are relatively insoluble and/or immiscible in the types of lubricants used traditionally with CFC's and HFC's, including, for example, 5 mineral oils, 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 10 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 15 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 20 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 25 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 HFC's which might otherwise be desirable for used in refrigerant compositions are not nonflammable. For example, the fluoroalkane 30 difluoroethane (HFC-1 52a) and the fluoroalkene 1,1,1 -trifluorpropene (HFO-1243zf) are each flammable and therefore not viable for use in many applications. Higher fluoroalkenes, that is fluorine-substituted alkenes having at least five 3 carbon atoms, have been suggested for use as refrigerants. U.S. Patent No. 4,788,352 - Smutny is directed to production of fluorinated Cs to Ca 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 5 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 10 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 15 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 20 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, 25 blowing agents, solvent compositions, and compatabilizing agents, that are potentially useful in numerous applications, including vapor compression heating and cooling systems and methods, while avoiding one or more of the disadvantages noted above. 4 SUMMARY The present invention provides use of a composition comprising 1,3,3,3 tetrafluoropropene (HFO-1234ze) as a propellant. 5 The present invention also provides a sprayable composition comprising: a propellant comprising HFO 1234ze, and a material to be sprayed. The present invention also provides a sprayable composition for use in medicine, said sprayable composition comprising a propellant comprising HFO-1234ze, and a material to be sprayed, wherein said material to be sprayed is a medicinal 10 material. The present invention also provides a sprayable composition for use in treating asthma, said sprayable composition comprising a propellant comprising HFO-1234ze, and a material to be sprayed, wherein said material to be sprayed comprises an anti asthma medication. 15 The present invention also provides a sprayable composition for use in treating halitosis, said sprayable composition comprising a propellant comprising HFO-1234ze, and a material to be sprayed, wherein said material to be sprayed comprises an anti halitosis medication. The present invention also provides as a propellant of a composition comprising 20 HFO-1 234ze, in a composition comprising a medicinal material. Also described are one or more C3 or C4 fluoroalkenes, preferably compounds having Formula I as follows: XCFzR 3 -z (1) 25 where X is a C2 or a C3 unsaturated, substituted or unsubstituted, alkyl radical, each R is independently Cl, F, Br, I or H, and z is 1 to 3. There are further disclosed methods and systems which utilize the compositions of the present disclosure, including methods and systems for heat transfer, foam blowing, solvating, and aerosol generation. 30 5 DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS THE COMPOSITIONS There are disclosed compositions comprising at least one fluoroalkene 5 containing from 3 to 4 carbon atoms and at least one carbon-carbon double bond. The fluoroalkene compounds of the present disclosure are sometimes referred to herein for the purpose of convenience as hydrofluoro-olefins or "HFOs" if they contain at least one hydrogen Although it is contemplated that the HFOs of the present disclosure may contain two carbon -- carbon double bonds, such compounds at the present time are 10 not considered to be preferred. As mentioned above, the present compositions comprise one or compounds in accordance with Formula 1. The compositions may include compounds of Formula Il below: 15 where each R is independently Cl, F, Br, I or H R' is (CR 2 ),Y, Y is CRF 2 20 and n is0or1. In highly preferred embodiments, Y is CF 3 , n is 0 and at least one of the remaining Rs is F. Applicants believe that, in general, the compounds of the above identified Formulas I and || are generally effective and exhibit utility in refrigerant compositions, 25 blowing agent compositions, compatibilizers, and solvent compositions of the present invention. However, applicants have surprisingly and unexpectedly found that certain of the compounds having a structure in accordance with the formulas described above exhibit a highly desirable low level of toxicity compared to other of such compounds. As can be readily appreciated, this discovery is of potentially enormous advantage and 30 benefit for the formulation of not only refrigerant compositions, but also any and all compositions which would otherwise contain relatively toxic compounds satisfying the formulas described above. More particularly, applicants believe that a relatively low toxicity level is associated with compounds of Formula 1l, preferably wherein Y is CF3, 6 wherein at least one R on the unsaturated terminal carbon is H, and at least one of the remaining Rs is F. Applicants believe also that all structural, geometric and stereoisomers of such compounds are effective and of beneficially low toxicity. In the low toxicity compounds described above, n is zero. Thus, the 5 compositions of the present disclosure may comprise one or more compounds selected from the group consisting of tetrafluoropropenes (HFO-1 234), pentafluoropropenes (HFO-1225) and combinations of these. There are specifically described tetrafluoropropene and pentafluoropropene compounds In which the unsaturated terminal carbon has not more than one F 10 substituent, specifically: 1,3,3,3-tetrafluoropropene (HFO-1 234ze); 2,3,3,3 tetrafluoropropene (HFO-1 234yf); and 1,2,3,3,3-pentafluoropropene (HFO-1 225ye), and any and all stereoisomers of each of these. In particular, the present invention relates to HFO-1234ze. Applicant has discovered that such compounds have a very low acute toxicity level, as measured by inhalation exposure to mice and rats. On the 15 other hand, applicants have found that a relatively high degree of toxicity may be associated with certain compounds adaptable for use with the present compositions, namely, those compounds which have more than one F on the terminal unsaturated carbon, or which do not have at least one H on the terminal unsaturated carbon. For example, applicants have discovered that 1, 1,3,3,3-pentafluoropropene (HFO-1225zc) 20 exhibits an unacceptably high degree of toxicity, as measured by inhalation exposure to mice and rats. HFO-1 225 and HFO-1 234 are known materials and are listed in Chemical Abstracts databases. HFO-1 225 is commercially available, from example from Syntex Chemical Co. Futhermore, methods are described generally in the patent literature for 25 producing fluoroalkenes. For example, 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. U.S. Patent No. 5,532,419, which is also incorporated herein by reference, discloses a 30 vapor phase catalytic process for the preparation of fluoroalkene using a chloro- or bromo-halofluorocarbon and HF. EP 974,571, also incorporated herein by reference, 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, 35 NaOH, Ca(OH) 2 or Mg(OH) 2 . In addition, methods for producing compounds in 7 accordance with the present disclosure are described generally in connection with concurrently filed United States Patent Application entitled "Process for Producing Fluorpropenes" bearing attorney docket number (H0003789 (26267)), which is also incorporated herein by reference. 5 The present compositions 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 fluoroolefins of the present disclosure will not have a substantial negative affect on atmospheric chemistry, being negligible contributors to ozone depletion in comparison to some other halogenated 10 species. The compositions of the present invention thus have the advantage of not contributing substantially to ozone depletion. The compositions also do not contribute substantially to global warming compared to many of the hydrofluoroalkanes presently in use. Preferably, the compositions of the present invention have a Global Warming 15 Potential (GWP) of not greater than 150, more preferably not greater than 100 and even more preferably not greater than 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 of Ozone Depletion, 2002, a report of the World Meteorological Association's Global Ozone Research and Monitoring Project," which is incorporated 20 herein by reference. 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 Scientific Assessment of Ozone Depletion, 2002, A report of the World Meteorological 25 Association's Global Ozone Research and Monitoring Project," which is incorporated herein by reference. HEAT TRANSFER COMPOSITIONS 30 Although it is contemplated that the compositions of the present disclosure may include the compounds disclosed herein in widely ranging amounts, there are described refrigerant compositions that comprise compound(s) in accordance with Formula I, and even more preferably Formula 1l, in an amount that is at least about 50% by weight, and even more preferably at least about 70 % by weight, of the 35 composition. 8 The compositions of the present invention may include other components for the purpose of enhancing or providing certain functionality to the composition, or in some cases to reduce the cost of the composition. For example, refrigerant compositions according to the present disclosure, especially those used in vapor 5 compression systems, include a lubricant, generally in amounts of from about 30 to about 50 percent by weight of the composition. Furthermore, the present compositions may also include a compatibilizer, such as propane, for the purpose of aiding compatibility and/or solubility of the lubricant. Such compatibilizers, including propane, butanes and pentanes, are preferably present in amounts of from about 0.5 to about 5 10 percent by weight of the composition. Combinations of surfactants and solubilizing agents may also be added to the present compositions to aid oil solubility, as disclosed by U.S. Patent No. 6,516,837, the disclosure of which is incorporated by reference. Commonly used refrigeration lubricants such as Polyol Esters (POEs) and Poly Alkylene Glycols (PAGs) that are used in refrigeration machinery with 15 hydrofluorocarbon (HFC) refrigerants may be used with the refrigerant compositions of the present disclosure. BLOWING AGENTS, FOAMS AND FOAMABLE COMPOSITIONS 20 Blowing agents may also comprise or constitute one or more of the compositions disclosed herein. As mentioned above, the compositions of the present disclosure may include the compounds of the present invention in widely ranging amounts. It is generally preferred, however, that for preferred compositions for use as blowing agents, compound(s) in accordance with Formula I, and even more preferably 25 Formula 1l, are present in an amount that is at least about 5 % by weight; and even more preferably at least about 15 % by weight, of the composition. There are also described foamable compositions, and preferably polyurethane, polyisocyanurate and extruded thermoplastic foam compositions, prepared using the compositions described herein. In such foams, one or more of the present 30 compositions are included as or part of a blowing agent in a foamable composition, which composition preferably includes one or more additional components capable of reacting and/or foaming under the proper conditions to form a foam or cellular structure, as is well known in the art. Also described is foam, and preferably closed cell foam, prepared from a polymer foam formulation containing a blowing agent 35 comprising the compositions disclosed herein. There is also described a foamable 9 composition comprising thermoplastic foams, such as polystyrene and polyethylene (PE), preferably low density PE. Dispersing agents, cell stabilizers, surfactants and other additives may also be incorporated into the blowing agent compositions. Surfactants are optionally but 5 preferably added to serve as cell stabilizers. Some representative materials are sold under the names of DC-1 93, B-8404, and L-5340 which are, generally, polysiloxane polyoxyalkylene block co-polymers such as those disclosed in U.S. Patent Nos. 2,834,748, 2,917,480, and 2,846,458, each of which is incorporated herein by reference. Other optional additives for the blowing agent mixture may include flame 10 retardants such as tri(2-chloroethyl)phosphate, tri(2-chloropropyl)phosphate, tri(2,3 dibromopropyl)-phosphate, tri(1,3-dichloropropyl)phosphate, diammonium phosphate, various halogenated aromatic compounds, antimony oxide, aluminium trihydrate, polyvinyl chloride, and the like. 15 PROPELLANT COMPOSITIONS In another aspect, the present invention provides propellant compositions comprising or consisting essentially of a composition of the present invention, such propellant composition preferably being a sprayable composition. The propellant 20 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 also be present in the sprayable mixture. Preferably, the sprayable composition is an aerosol. Suitable materials to be sprayed include, without limitation, cosmetic 25 materials such as deodorants, perfumes, hair sprays, cleansers, and polishing agents as well as medicinal materials such as anti-asthma and anti-halitosis medications. METHODS AND SYSTEMS 30 The compositions of the present invention and disclosure are useful in connection with numerous methods and systems, including as heat transfer fluids in methods and systems for transferring heat, such as refrigerants used in refrigeration, air conditioning and heat pump systems. The present compositions are also advantageous for in use in systems and methods of generating aerosols, preferably 35 comprising or consisting of the aerosol propellant in such systems and methods. 10 Methods of forming foams and methods of extinguishing and suppressing fire are also described. Further described are methods of removing residue from articles in which the present compositions are used as solvent compositions in such methods and systems. 5 HEAT TRANSFER METHODS The preferred heat transfer methods generally comprise providing a composition as described herein and causing heat to be transferred to or from the composition changing the phase of the composition. For example, the methods 10 described herein provide cooling by absorbing heat from a fluid or article, preferably by evaporating the present refrigerant composition in the vicinity of the body or fluid to be cooled to produce vapor comprising the present composition. Preferably the methods include the further step of compressing the refrigerant vapor, usually with a compressor or similar equipment to produce vapor of the present composition at a relatively 15 elevated pressure. Generally, the step of compressing the vapor results in the addition of heat to the vapor, thus causing an increase in the temperature of the relatively high pressure vapor. Preferably, the present methods include removing from this relatively high temperature, high pressure vapor at least a portion of the heat added by the evaporation and compression steps. The heat removal step preferably includes 20 condensing the high temperature, high pressure vapor while the vapor is in a relatively high pressure condition to produce a relatively high pressure liquid comprising a composition of the present disclosure. This relatively high pressure liquid preferably then undergoes a nominally isoenthalpic reduction in pressure to produce a relatively low temperature, low pressure liquid. In such embodiments, it is this reduced 25 temperature refrigerant liquid which is then vaporized by heat transferred from the body or fluid to be cooled. The compositions of the invention may also be used in a method for producing heating which comprises condensing a refrigerant comprising the compositions in the vicinity of a liquid or body to be heated. Such methods, as mentioned hereinbefore, 30 frequently are reverse cycles to the refrigeration cycle described above. FOAM BLOWING METHODS There are described methods of forming foams, and preferably polyurethane 35 and polyisocyanurate foams. The methods generally comprise providing a blowing 11 agent composition disclosed herein, adding (directly or indirectly) the blowing agent composition to a foamable composition, and reacting the foamable composition under the conditions effective to form a foam or cellular structure, as is well known in the art. Any of the methods well known in the art, such as those described in "Polyurethanes 5 Chemistry and Technology," Volumes I and II, Saunders and Frisch, 1962, John Wiley and Sons, New York, NY, which is incorporated herein by reference, may be used or adapted for use in accordance with the foam disclosed herein. In general, such preferred methods comprise preparing polyurethane or polyisocyanurate foams by combining an isocyanate, a polyol or mixture of polyols, a blowing agent or mixture of 10 blowing agents comprising one or more of the present compositions, and other materials such as catalysts, surfactants, and optionally, flame retardants, colorants, or other additives. It is convenient in many applications to provide the components for polyurethane or polyisocyanurate foams in pre-blended formulations. Most typically, the 15 foam formulation is pre-blended into two components. The isocyanate and optionally certain surfactants and blowing agents comprise the first component, commonly referred to as the "A" component. The polyol or polyol mixture, surfactant, catalysts, blowing agents, flame retardant, and other isocyanate reactive components comprise the second component, commonly referred to as the "B" component. Accordingly, 20 polyurethane or polyisocyanurate foams are readily prepared by bringing together the A and B side components either by hand mix for small preparations and, preferably, machine mix techniques to form blocks, slabs, laminates, pour-in-place panels and other items, spray applied foams, froths, and the like. Optionally, other ingredients such as fire retardants, colorants, auxiliary blowing agents, and even other polyols can be 25 added as a third stream to the mix head or reaction site. Most preferably, however, they are an incorporated into one B-component as described above. It is also possible to produce thermoplastic foams using the compositions of the present disclosure. For example, conventional polystyrene and polyethylene formulations may be combined with the compositions in a conventional manner to 30 produce rigid foams. CLEANING METHODS There are also described methods of removing contaminants from a product, 35 part, component, substrate, or any other article or portion thereof by applying to the 12 article a composition of the present disclosure. For the purposes of convenience, the term "article" is used herein to refer to all such products, parts, components, substrates, and the like and is further intended to refer to any surface or portion thereof. Furthermore, the term "contaminant" is intended to refer to any unwanted 5 material or substance present on the article, even if such substance is placed on the article intentionally. For example, in the manufacture of semiconductor devices it is common to deposit a photoresist material onto a substrate to form a mask for the etching operation and to subsequently remove the photoresist material from the substrate. The term "contaminant" as used herein is intended to cover and encompass 10 such a photo resist material. Preferred methods described herein comprise applying the present composition to the article, with vapor degreasing and solvent cleaning methods being particularly preferred for certain applications, especially those intricate parts and difficult to remove soils. Preferred vapor degreasing and solvent cleaning methods consist of exposing an 15 article, preferably at room-temperature, to the vapors of a boiling solvent. Vapors condensing on the object have the advantage of providing a relatively clean, distilled solvent to wash away grease or other contamination. Such processes thus have an additional advantage in that final evaporation of the present solvent composition from the object leaves behind relatively little residue as compared to the case where the 20 object is simply washed in liquid solvent. For applications in which the article includes contaminants that are difficult to remove, it is preferred that the present methods involve raising the temperature of the solvent composition of the present invention above ambient or to any other temperature that is effective in such application to substantially improve the cleaning 25 action of the solvent. Such processes are also generally preferred for large volume assembly line operations where the cleaning of the article, particularly metal parts and assemblies, must be done efficiently and quickly. The cleaning methods may comprise immersing the article to be cleaned in liquid solvent at an elevated temperature, and even more preferably at about the 30 boiling point of the solvent. In such operations, this step preferably removes a substantial amount, and even more preferably a major portion, of the target contaminant from the article. This step is then preferably followed by immersing the article in solvent, preferably freshly distilled solvent, which is at a temperature below the temperature of the liquid solvent in the preceding immersion step, preferably at 35 about ambient or room temperature. The preferred methods also include the step of 13 then contacting the article with relatively hot vapor of the present solvent composition, preferably by exposing the article to solvent vapors rising from the hot/boiling solvent associated with the first mentioned immersion step. This preferably results in condensation of the solvent vapor on the article. The article may also be sprayed with 5 distilled solvent before final rinsing. It is contemplated that numerous varieties and types of vapor degreasing equipment are adaptable for use in connection with the present methods. One example of such equipment and its operation is disclosed by Sherliker et al. in U.S. Pat. No. 3,085,918, which is incorporated herein by reference. The equipment disclosed in 10 Sherliker et al includes a boiling sump for containing a solvent composition, a clean sump for containing distilled solvent, a water separator, and other ancillary equipment. The present cleaning methods may also comprise cold cleaning in which the contaminated article is either immersed in the fluid composition of the present disclosure under ambient or room temperature conditions or wiped under such 15 conditions with rags or similar objects soaked in solvents. FLAMMABILITY REDUCTION METHODS There are further described methods for reducing the flammability of fluids, said 20 methods comprising adding a compound or composition of the present disclosure to said fluid. The flammability associated with any of a wide range of otherwise flammable fluids may be reduced. For example, the flammability associated with fluids such as ethylene oxide, flammable hydrofluorocarbons and hydrocarbons, including: HFC 152a, 1, 1, 1-trifluoroethane (HFC-143a), difluoromethane (HFC-32), propane, hexane, 25 octane, and the like can be reduced. For the purposes of the present disclosure, a flammable fluid may be any fluid exhibiting flammability ranges in air as measured via any standard conventional test method, such as ASTM E-681, and the like. Any suitable amounts of the present compounds or compositions may be added to reduce flammability of a fluid. As will be recognized by those of skill in the art, the 30 amount added will depend, at least in part, on the degree to which the subject fluid is flammable and the degree to which it is desired to reduce the flammability thereof. The amount of compound or composition added to the flammable fluid can be effective to render the resulting fluid substantially non-flammable. 35 14 FLAME SUPPRESSION METHODS There are also described methods of suppressing a flame, said methods comprising contacting a flame with a fluid comprising a compound or composition of the present disclosure. Any suitable methods for contacting the flame with the present 5 composition may be used. For example, a composition described herein may be sprayed, poured, and the like onto the flame, or at least a portion of the flame may be immersed in the composition. In light of the teachings herein, those of skill in the art will be readily able to adapt a variety of conventional apparatus and methods of flame suppression for use in accordance with this disclosure. 10 STERILIZATION METHODS Many articles, devices and materials, particularly for use in the medical field, must be sterilized prior to use for the health and safety reasons, such as the health and 15 safety of patients and hospital staff. There are therefore described methods of sterilizing comprising contacting the articles, devices or material to be sterilized with a compound or composition described herein. Such methods may be either high or low temperature sterilization methods. High-temperature sterilization can comprise exposing the articles, device or material to be sterilized to a hot fluid comprising a 20 compound or composition of the present disclosure at a temperature of from about 250OF to about 270 0 F, preferably in a substantially sealed chamber. The process can be completed usually in less than about 2 hours. However, some articles, such as plastic articles and electrical components, cannot withstand such high temperatures and require low-temperature sterilization. 25 Low-temperature sterilization may involve the use of a compound or composition of the present disclosure at a temperature of from about 100 to about 200 0 F. The compounds of the present disclosure may be combined with other common chemical sterilants, including, for example, ethylene oxide (EO), formaldehyde, hydrogen peroxide, chlorine dioxide, and ozone to form a sterilant composition. 30 The low-temperature sterilization of the present disclosure is preferably at least a two-step process performed in a substantially sealed, preferably air tight, chamber. In the first step (the sterilization step), the articles having been cleaned and wrapped in gas permeable bags are placed in the chamber. Air is then evacuated from the chamber by pulling a vacuum and perhaps by displacing the air with steam. It is 35 preferable to inject steam into the chamber to achieve a relative humidity that ranges 15 preferably from about 30% to about 70%. Such humidities may maximize the sterilizing effectiveness of the sterilant which is introduced into the chamber after the desired relative humidity is achieved. After a period of time sufficient for the sterilant to permeate the wrapping and reach the interstices of the article, the sterilant and steam 5 are evacuated from the chamber. In the preferred second step of the process (the aeration step), the articles are aerated to remove sterilant residues. Removing such residues is particularly important in the case of toxic sterilants, although it is optional in those cases in which the substantially non-toxic compounds of the present disclosure are used. Typical aeration 10 processes include air washes, continuous aeration, and a combination of the two. An air wash is a batch process and usually comprises evacuating the chamber for a relatively short period, for example, 12 minutes, and then introducing air at atmospheric pressure or higher into the chamber. This cycle is repeated any number of times until the desired removal of sterilant is achieved. Continuous aeration typically involves 15 introducing air through an inlet at one side of the chamber and then drawing it out through an outlet on the other side of the chamber by applying a slight vacuum to the outlet. Frequently, the two approaches are combined. For example, a common approach involves performing air washes and then an aeration cycle. 20 EXAMPLES The following examples are provided for the purpose of illustrating the present invention but without limiting the scope thereof. 25 EXAMPLE 1 The coefficient of performance (COP) is a universally accepted measure of refrigerant performance, especially useful in representing the relative thermodynamic efficiency of a refrigerant in a specific heating or cooling cycle involving evaporation or 30 condensation of the refrigerant. In refrigeration engineering, this term expresses the ratio of useful refrigeration to the energy applied by the compressor in compressing the vapor. The capacity of a refrigerant represents the amount of cooling or heating it provides and provides some measure of the capability of a compressor to pump quantities of heat for a given volumetric flow rate of refrigerant. In other words, given a 35 specific compressor, a refrigerant with a higher capacity will deliver more cooling or 16 heating power. One means for estimating COP of a refrigerant at specific operating conditions is from the thermodynamic properties of the refrigerant using standard refrigeration cycle analysis techniques (see for example, R.C. Downing, FLUOROCARBON REFRIGERANTS HANDBOOK, Chapter 3, Prentice-Hall, 1988). 17 A refrigeration /air conditioning cycle system is provided where the condenser temperature is about 150"F and the evaporator temperature is about -35*F under nominally isentropic compression with a compressor inlet temperature of about 50"F. COP is determined for several compositions of the present invention over a range of 5 condenser and evaporator temperatures and reported in Table I below, based upon HFC-1 34a having a COP value of 1.00, a capacity value of 1.00 and a discharge temperature of 175 "F. TABLE I REFRIGERANT Relative COP Relative DISCHARGE COMPOSTION CAPACITY TEMPERATURE ("F) HFO 1225ye 1.02 06 158 HFO trans-1234ze 1.04 0.70 165 HFOcis-1234ze 1.13 0.36 155 HFO 1234f 0.98 110 168 10 This example shows that certain of the preferred compounds for use with the present compositions each have a better energy efficiency than HFC-134a (1.02, 1.04 and 1.13 compared to 1.00) and the compressor using the present refrigerant compositions will produce discharge temperatures (158, 165 and 155 compared to 15 175), which is advantageous since such result will likely leading to reduced maintenance problems. EXAMPLE 2 The miscibility of HFO-1225ye and HFO-1234ze with various refrigeration 20 lubricants is tested. The lubricants tested are mineral oil (C3), alkyl benzene (Zerol 150), ester oil (Mobil EAL 22 cc and Solest 120), polyalkylene glycol (PAG) oil (Goodwrench Refrigeration Oil for 134a systems), and a poly(alpha-olefin) oil (CP 6005-100). For each refrigerant/oil combination, three compositions are tested, namely 5, 20 and 50 weight percent of lubricant, with the balance of each being the 25 compound of the present invention being tested The lubricant compositions are placed in heavy-walled glass tubes. The tubes are evacuated, the refrigerant compound in accordance with the present invention is 18 added, and the tubes are then sealed. The tubes are then put into an air bath environmental chamber, the temperature of which is varied from about -50"C to 700C. At roughly 10"C intervals, visual observations of the tube contents are made for the existence of one or more liquid phases. In a case where more than one liquid 5 phase is observed, the mixture is reported to be immiscible. In a case where there is only one liquid phase observed, the mixture is reported to be miscible. In those cases where two liquid phases were observed, but with one of the liquid phases occupying only a very small volume, the mixture is reported to be partially miscible. The polyalkylene glycol and ester oil lubricants were judged to be miscible in 10 all tested proportions over the entire temperature range, except that for the HFO 1225ye mixtures with polyalkylene glycol, the refrigerant mixture was found to be immiscible over the temperature range of -50"C to -30"C and to be partially miscible over from -20 to 50'C. At 50 weight percent concentration of the PAG in refrigerant and at 60", the refrigerant/PAG mixture was miscible. At 70C, it was miscible from 5 15 weight percent lubricant in refrigerant to 50 weight percent lubricant in refrigerant. EXAMPLE 3 The compatibility of the refrigerant compounds and compositions of the present invention with PAG lubricating oils while in contact with metals used in 20 refrigeration and air conditioning systems is tested at 35 0 " C, representing conditions much more severe than are found in many refrigeration and air conditioning applications. Aluminum, copper and steel coupons are added to heavy walled glass tubes. Two grams of oil are added to the tubes. The tubes are then evacuated and one 25 gram of refrigerant is added. The tubes are put into an oven at 350"F for one week and visual observations are made. At the end of the exposure period, the tubes are removed. This procedure was done for the following combinations of oil and the compound of the present invention: 30 a) HFC-1234ze and GM Goodwrench PAG oil b) HFC1243 zf and GM Goodwrench oil PAG oil c) HFC-1234ze and MOPAR-56 PAG oil 19 d) HFC-1 243 zf and MOPAR-56 PAG oil e) HFC-1 225 ye and MOPAR-56 PAG oil. In all cases, there is minimal change in the appearance of the contents of the tube. This indicates that the refrigerant compounds and compositions of the present 5 invention are stable in contact with aluminum, steel and copper found in refrigeration and air conditioning systems, and the types of lubricating oils that are likely to be included in such compositions or used with such compositions in these types of systems. 10 COMPARATIVE EXAMPLE Aluminum, copper and steel coupons are added to a heavy walled glass tube with mineral oil and CFC-12 and heated for one week at 350C, as in Example 3. At the end of the exposure period, the tube is removed and visual observations are made. 15 The liquid contents are observed to turn black, indicating there is severe decomposition of the contents of the tube. CFC-1 2 and mineral oil have heretofore been the combination of choice in many refrigerant systems and methods. Thus, the refrigerant compounds and compositions of the present invention possess significantly better stability with many 20 commonly used lubricating oils than the widely-used prior art refrigerant-lubricating oil combination. Throughout this specification and the claims which follow, unless the context requires otherwise, the word "comprise", and variations such as "comprises" and "comprising", will be understood to imply the inclusion of a stated integer or step or 25 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 acknowledgment or admission or any form of suggestion that that prior publication (or 30 information derived from it) or known matter forms part of the common general knowledge in the field of endeavour to which this specification relates. 20

Claims (25)

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

2. Use according to claim 1, wherein the composition is a sprayable composition.

3. Use according to claim 1 or claim 2, wherein the sprayable composition is an aerosol.

4. Use according to any one of the preceding claims, wherein the composition consists essentially of HFO-1 234ze.

5. A sprayable composition comprising: a propellant comprising HFO-1 234ze, and a material to be sprayed.

6. A composition according to claim 5, wherein the propellant consists essentially of HFO-1234ze.

7. A composition according to claim 5 or 6, wherein the material to be sprayed comprises a cosmetic material or a medicinal material.

8. A composition according to claim 7, wherein the cosmetic material is selected from the group consisting of deodorants, perfumes, hair sprays, cleansers and polishing agents.

9. A composition according to claim 7, wherein the medicinal material is selected from the group consisting of anti-asthma and anti-halitosis medications.

10. A composition according to any one of claims 5 to 9, wherein the composition is an aerosol.

11. A sprayable composition for use in medicine, said sprayable composition comprising a propellant comprising HFO-1 234ze, and a material to be sprayed, wherein said material to be sprayed is a medicinal material.

12. A sprayable composition for use in treating asthma, said sprayable composition comprising a propellant comprising HFO-1234ze, and a material to be sprayed, wherein said material to be sprayed comprises an anti-asthma medication. 21

13. A sprayable composition for use in treating halitosis, said sprayable composition comprising a propellant comprising HFO-1234ze, and a material to be sprayed, wherein said material to be sprayed comprises an anti-halitosis medication.

14. The composition for use according to any one of claims 11 to 13, wherein the propellant consists essentially of HFO-1234ze.

15. The composition for use according to any one of claims 11 to 14, wherein the composition is an aerosol.

16. Use as a propellant of a composition comprising HFO-1 234ze, in a composition comprising a medicinal material.

17. Use according to claim 16, wherein the propellant consists essentially of HFO 1234ze.

18. Use according to claim 16 or 17, wherein said medicinal material comprises anti asthma or anti-halitosis medications.

19. Use according to any one of claims 16 to 18, wherein the composition is an aerosol.

20. The use or composition according to any one of claims 1 to 19, wherein the composition has a Global Warming Potential (GWP) of not greater than about 150.

21. The use or composition according to any one of claims 1 to 20, wherein the composition has a Global Warming Potential (GWP) of not greater than about 100.

22. The use or composition according to any one of claims 1 to 21, wherein the composition has a Global Warming Potential (GWP) of not greater than about 75.

23. The use or composition according to any one of claims 1 to 22, wherein the composition has an Ozone Depletion Potential (ODP) of not greater than about 0.05.

24. The use or composition according to any one of claims 1 to 23, wherein the composition has an Ozone Depletion Potential (ODP) of not greater than about 0.02.

25. The use or composition according to any one of claims 1 to 24, wherein the composition has an Ozone Depletion Potential (ODP) of about zero. 22