Title of Invention	COMPOSITIONS CONTAINING FLOURINE SUBSTITUTED OLEFINS
Abstract	A method of transferring heat to or from a fluid or body to provide cooling of air in an automobile, said method comprising: (a) providing a heat transfer system comprising an automobile air conditioning system; (b) providing in said system a heat transfer composition comprising at least one lubricant such as herein described and at least one fluoroalkene having a total of at least four fluorine substituents, said fluoroalkene being of Formula II: where R' is (CR2)nY, Y is CF3 each R is independently For H, and n is 0 or 1, provided that there is at least one H on said unsaturated terminal carbon and wherein said fluoroalkene has no substantial toxicity.

Title of Invention

COMPOSITIONS CONTAINING FLOURINE SUBSTITUTED OLEFINS

Abstract

A method of transferring heat to or from a fluid or body to provide cooling of air in an automobile, said method comprising: (a) providing a heat transfer system comprising an automobile air conditioning system; (b) providing in said system a heat transfer composition comprising at least one lubricant such as herein described and at least one fluoroalkene having a total of at least four fluorine substituents, said fluoroalkene being of Formula II: where R' is (CR2)nY, Y is CF3 each R is independently For H, and n is 0 or 1, provided that there is at least one H on said unsaturated terminal carbon and wherein said fluoroalkene has no substantial toxicity.

Full Text	COMPOSITIONS CONTAINING rLUOniNE GUDOTITUTCD OUTIN3 HELD OF THE INVENTION This invention relates to compositions having utility in numerous applications, including particularly refrigeration systems, and to methods and systems utilizing such compositions. In preferred aspects, the present invention Is directed to refrigerant compositions comprising at least one multi-fluorinated olefin of the present invention. BACKGROUND OF THE INVENTION Ffuorocarbon 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 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 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 fluids, such as refrigerants, for many years in many applications. For, example, fluoroalkanes, such as chlorofluoromefriane and chtorofluoroethane 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. Concern has Increased in recent years about potential damage to the earth's atmosphere i-4 climate, and certain chlorine-based compounds have been identfaed as particularly problematic In this regard. The use of chlorine-containing compositions (such as chlorofluorocarbons (CFCs), hydrochtorofluorocarbons (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 hydrofiuorocarbon 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-flammabliity 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-chiorine-containing refrigeration fluids, including HFCs, are relatively insoluble and/or immiscible in the types of lubricants used traditionally with CFCs and HFCs, including, for example, mineral oils, alkyfbenzenes or poly(a!pha-otefins). in order for a refrigeration fluW- iubrlcant 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. Flammabilrty 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 drfluoroetharte (HFC-1S2a) and the fluoroalkene 1,1,1- trifluoropropene {HFO-1243zf) are each flammable and therefore not viable for use in many applications. Higher ffuoroalkenes, that is fluorine-substituted alkenes having at least flva carbon atoms, have been suggested for use as refrigerants. U.S. Patent Mo. 4,788,352 - Smutny Is directed to production of fluoridated Cs to Cs 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 fiuorinated 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. Bromofluoromethaneand 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 compatabifeing agents, that are potentially useful in numerous applications. Including vapor compression heating and cooling systems and methods, while avoiding one ormore of the disadvantages noted above. SUMMARY Applicants have found that the above-noted need, and other needs, can be satisfied by compositions comprising one or more C3 or C4 fluoroalkenes, preferably compounds having Formula I as follows: XCFZR^(1) where X is a C2 or a C3 unsaturated, substituted or unsubstftuted, alkyf radical, each R is Independently CI, F, Br, I or H, and z is 1 to 3. Highly preferred among the compounds of Formula I are the cis- and trans- isorners of 1,3,3,3-tetrafluoropropene (HFO-1234ze) The present Invention provides also methods and systems which utilize the compositions of the present invention, including methods and systems for heat transfer, foam blowing, solvating, flavor and fragrance extraction and/or delivery, and aerosol generation. DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS THE COMPOSITIONS The present Invention is directed to compositions comprising at least one fluoroalkene containing from 3 to 4 carbon atoms, preferably three carbon atoms, and at least one carbon-carbon double bond. The fluoroalkene compounds of the present invention 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 invention may contain two carbon - carbon double bonds, such compounds at the present time are not considered to be preferred. As mentioned above, the present compositions comprise one or more compounds in accordance with Formula I. In preferred embodiments, the compoafflons Indude compounds of Formula H below: whereeachRtsfodependentryCt,F, Br, lorH RiB(CR2)bY, YtoCRFj andnteOoM. In highly preferred embodiments, Y is CF3, n is 0 and at least one of the remaining Rs is F. AppCcants before that, In general, the compounds of the above identified Formulas I and II are generafly effective and exhfctt udBty ki refrigerant composiJons, blowing agent compositions, compatJbiftDBrs, aerosols, propeUants, fragrances, flavor formulations, and solvent compositions of the present invention. However, appfcants have surprisingly and unexpectedly found that certain of the compounds having a structure In accordance with the formulas described above exhtt a highry desirable low level of toxicity compared to other of such compounds. As can be readily appreciated, this discovery is ofpotenttaUy enormous advantage and benefit for the formulation of not only refrigerant compositions, but also any and at oomposWona, which would otherwise contain retatrveiy toxic compounds satisfying the formulas described above. More partJcubrty, appftcants believe that a relatively tow toxicity level is associated wflh compounds of Formula II, preferably wherein Y is CFj, wherein at least one R on the unsaturated terminal carbon is H, and at least one of the remaining Rs b F. Applicants beBeve abo that al structural, geometric and stereoisomers of such compounds are-effectJva and of beneficiaOy low toxicity. In highly preferred embodiments, especially embodiments comprising the low toxicity compounds described above, n is zero. In certain highly preferred embodiments the compositions of the present invention comprise one or more tetrafluoropropenes. The term "HFO- 1234" is used herein to refer to all tetrafluoropropenes. Among the tetrafluoropropenes, both cis- and trans-1,3,3,3-tetraftuoropropene (HFO-1234ze) are particularly preferred. The term HFCM234ze is used herein genetically to refer to 1,3,3,3-tetrafluoropropene, independent of whether it is the cis- or trans- form. The terms "cfeHFO-1234ze" and 1ransHF01234ze* 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 dsHFO-1234ze, transHFO-1234ze, and all combinations and mixtures of these. Although the properties of cfsHFO-1234ze and transHFO-1234ze differ in at least some respects, it is contemplated that each of these compounds is adaptable for use, either alone or together with other compounds including its stereoisomer, in connection with each of the applications, methods and systems described herein. For example, while transHFO-1234ze may be preferred for use in certain refrigeration systems because of its relatively low boiling point (-19° C), ft Is nevertheless contemplated that cisHFO-1234ze, with a boiling point of +9* C, also has utility in certain refrigeration systems of the present invention. Accordingly, it is to be understood that the terms HFO-1234ze and 1,3,3,3-tetrafiuoropropene refer to both stereo isomers, and the use of this term is intended to indicate that each of the cls-and trans- forms applies and/or is useful for the stated purpose unless otherwise indicated. HFO-1234 compounds are known materials and are listed in Chemical Abstracts databases. The production offluoropropenes such as CF3CH=CH2 by catalytic vapor phase fluorination of various saturated and unsaturated halogen-containing C3 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, discloses the preparation of 1,1,1,3-tetrafluoropropene by contacting 1.1,1,3,3-perrtafluoropropane (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 MgXOHk In addition, methods for producing compounds In accordance with the present Invention are described generally in connection with pending United States Patent Application entitled "Process for Producing FJuoropropenes" bearing attorney docket number (H0003789 {26267)), which is also incorporated herein by reference. The present compositions, particularly those comprising HFO- 1234ze, 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 fluorootefins 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 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 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 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 (OOP) of not greater than 0.06, mora preferably not greater than 0.02 arc! even nxxe preferably about zero. As used herein, "OOP* is 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 herein by reference. The amount of the Formula I compounds. pertlcUariy HFO-1234, contained in the present compositions can vary widely, depending the particular appOcation, and compositions containing more than trace amounts and less than 100% of the compound are wttNh broad the scope of the present Invention. Moreover, the compositions of the present Invention can be azeotroplc azeotrope-lfce or rwn-azeotroplc. In preferred embodiments, the present compositions comprise HFO-1234, preferably HFO-1234z», In amounts from about 5% by weight to about 09% by weight, and even more preferably from about 5% to about 95%. Many addKonal compounds may be included in the present compositions, and the presence of afl 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: DffkJoromethane (HFC-32) PentafTuoroethane (HFC-126) 1,1^-t0trafluoroethane 1,1.U-Tetrafluoroethane (HFC-134a) Dffluoroelhane (HFC-152a) 1,1,1 ^,3,3,34taptaflixxopropane (HFC-227ea) 1,1,1,3,3,3-riexafluorcorop8ne (HFC-236«a) 1,1,1,3,3-pentafhx)fopropane 1,1.1.3,3-pentaOuc^obutane (HFC-38Smfc) water CO? 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 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. HEAT TRANSFER COMPOSITIONS Although it is contemplated that Hie compositions of the present invention may include the compounds of the present invention in widely ranging amounts, it is generally preferred that refrigerant compositions of the present invention comprise compound(s) in accordance with Formula I, more preferably In accordance with Formula il, and even more preferably HFO-1234ze. in an amount tnat is at least about 60% by weight and even more preferably at least about 70 % by weight, of the composition. In many embodiments, it is preferred that the heat transfer compositions of the present invention comprise transHFO-1234ze. In certain preferred embodiments, the heat transfer compositions of the present invention comprise a combination of cisHFO-1234ze and transHF01234ze in a dsrtrans weight ratio of from about 1:99 to about 10:99, more preferably from about 1:99 to about 5:95, and even more preferably from about 1:99 to about 3:97. The compositions of the present invention may include other components for the purpose of enhancing or providing certain functionality to the composition, or tn some cases to reduce the cost of the composition. For example, refrigerant compositions according to the present invention, especially those used in vapor compression systems, Include a lubricant, generally in amounts of from about 30 to about SO percent by weight of the composition. Furthermore, the present compositions may also include a compatibDizar, such as propane, for the purpose of aiding compatibility and/or solubility of the lubricant Such cornpatibiiizers, including propane, butanes and pentanes, are preferably present in amounts of from about 0.5 to about 5 percent by weight of the composition. Combinations of surfactants and sofubilizing 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), silicone oil, mineral oil, alkyl benzenes (ABs) and poly(alpha-olefin) (PAO) that are used in refrigeration machinery with hydrofluorocarbon (HFC) refrigerants may be used with the refrigerant compositions of the present invention. Many existing refrigeration systems are currently adapted for use in connection with existing refrigerants, and the compositions of the present invention are believed to be adaptable for use in many of such systems, either with or without system modification. In many applications the compositions of the present invention may provide an advantage as a replacement In systems, which are currently based on refrigerants having a relatively high capacity. Furthermore, in embodiments where it is desired to use a lower capacity refrigerant composition of the present invention, for reasons of cost for example, to replace a refrigerant of higher capacity, such embodiments of the present compositions provide a potential advantage. Thus, K is preferred in certain embodiments to use compositions of the present invention, particularly compositions comprising a substantial proportion of, and in some embodiments consisting essentially of transHFO-1234ze, as a replacement for existing refrigerants, such as HFC-134a. In certain applications, the refrigerants of the present Invention potentially permit the beneficial use of larger displacement compressors, thereby resulting in better energy efficiency than other refrigerants, such as HFC-134a. Therefore the refrigerant compositions of the present invention, particularly compositions comprising transHFP-1234ze, provide the possibility of achieving a competitive advantage on an energy basis for refrigerant replacement applications. It is contemplated that the compositions of the present, including particularly those comprising HFO-1234ze, also have advantage (either in original systems or when used as a replacement for refrigerants such as R-12 and R-500), in chillers typically used in connection with commercial air conditioning systems. In certain of such embodiments it Is preferred to including in the present HFO-1234ze compositions from about 0.5 to about 5% of a flammabillty suppressant, such as CF3I. The present methods, systems and compositions are thus adaptable for use in connection with automotive air conditioning systems and devices, commercial refrigeration systems and devices, chillers, residential refrigerator and freezers, general air conditioning systems, heat pumps, and the like. BLOWING AGENTS, FOAMS AND FOAMABLE COMPOSITIONS Blowing agents may also comprise or constitute one or more of the present compositions. As mentioned above, the compositions of the present Invention 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 in accordance with the present Invention, compound(s) In accordance with Formula I, and-even more preferably Formula II, 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. In certain preferred embodiments, the blowing agent compositions of the present invention and Include, in addition to HFO- 1234 (preferably HFO-t234ze) one or mora of the following components as a co-blowing agent, filler, vapor pressure modifier, or for any other purpose: Difluoromethane (HFC-32) Pentafiuoroethane (HFC-125) 1,1,2,2-tetrafluoroethane (HFC-134) 1,1,1,2-Tefrafluoroethane (HFC-134a) Difluoroethane (HFC-152a) 1,1,1 A3,3,3-Heptafkjoropropane (HFC-227ea) 1,1,1,3,3,3-hexafluonopropane (HFC-236fe) 1,1,1,3,3-rjentafluoropropane 1,1,1,3,3-pentafluoiobutane (HFC-365mfc) water COz it is contemplated that the blowing agent compositions of the present Invention may comprise clsHFO-1234ze, transHF01234ze or combinations thereof. In certain preferred embodiments, the blowing agent composition of the present invention comprise his a combination of dsHFO-1234ze and transHF01234ze in a cls_-trans weight ratio of from about 1:99 to about 10:99, and even more preferably from about 1:99 to .about 5:95. in other embodiments, the invention provides foamable compositions, and preferably polyurethane, polylsocyanurate and extruded thermoplastic foam compositions, prepared using the compositions of the present Invention. In such foam embodiments, one or more of the present 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 The invention also relates to foam, and preferably closed cell foam, prepared from a polymer foam formulation containing a blowing agent comprising the compositions of the invention. In yet other embodiments, the invention provides foamable compositions comprising thermoplastic or polyolefin foams, such as polystyrene (PS), polyethylene (PE), polypropylene (PP) and poryethyleneterpthalate (PET) foams, preferably low-density foams. In certain preferred embodiments, dispersing agents, cell stabilizers, surfactants and other additives may also be incorporated into the blowing agent compositions of the present invention. Surfactants are ' optionally but preferably added to serve as cell stabilizers. Some representative materials are sold under the names of OC-193, B-8404, and L-5340 which are, generally, polysiloxane polyoxyalkyiene 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 retardants such as tri(2-chloroethyl)phosphate, tri(2- chloropropyi)phosphata, tri(2,3-dibromopropyl)-phospnate, trf(1,3- dichloropropyl) phosphate, diammonium phosphate, various haiogenated aromatic compounds, antimony oxide, aluminum trihydrate, polyvinyl chloride, and the like. PROPELLANT AND AEROSOL COMPOSITIONS in another aspect, the present invention provides propeliant compositions comprising or consisting essentially of a composition of the present invention, such propeliant composition preferably being a sprayable composition. The propeliant compositions of the present invention preferably comprise a material to be sprayed and a propeliant 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 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 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 a compound of Formula I of the present invention, preferably HFO-1234, and even more preferably HFO-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. 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 commonly used liquefied gas propellants are hydrocarbons such as butane, isobutane, and propane. Dimethyl ether and HFC-152a (1,1-dtfluoroethane) are also used, either alone or in blends with the hydrocarbon propellants. Unfortunately, ail of these liquefied gas propellants are highly flammable and their incorporation into aerosol formulations will 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 HFO-1234, and even more preferably HFO-1234ze, for use in certain industrial aerosol products, including for 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 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 othertherapeutic 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, introducing the c»mpc«JbonlntDtheM01)arritheodbcharglogtt»p«es«ntconipos«k« from the MD). The compositions of the present Invention, particularly compositions comprising or consisting essentialy of HFO-1234ZB. are capable of providing nonflammable, Dqusfod gas propesantand aerosols that do not cortrfautesubstamlafly to global vvartning. The present compositions can be used to formulate a variety of industrial aerosols or other sprayable compositions such as contact cleaners, dusters, lubricant sprays, and the Bee, and consumer aerosols such as personal car* products, household products and automotive products. HFO-1234ze Is particularly preferred for use as an important component of propeSant compoeWons for In medicinal aerosols such as metered dose Inhalers. Tha medicinal aerosol and/or propaBant and/or sprayabie oomposfbons ot the present invention h many appBcattons Include, tn addition to compound of formula (I) or (II) (preferably HF01234ze), a medicament such as a beta-agonist, a corticosteroid or other medtoarnent, and, opttonaBy. other Ingredients, such as surfactants, solvents, other propelants, flavorants and other exdpients. The compositions of the present Invention, unito many compositions previously used in these appBcattons, have good environmental properties and are not considered to be potential contributors to global warmtig. The present cornposftons therefore provide In certain preferred embodiments subetantialy rorrftonmabte, Iquefied gas propeOants having very iow Global Warming potentials. FLAVORANTS AND FRAGRANCES The compositions of the present invention also provide advantage when used as part of, and In particular as a carrier for, flavor formulations arid fragrance formulations. TtosuttabOrryof tfwpresericctrnposttionsfor this purpose Is demonstrated by a test procedure In wMch 0.38 grams of Jasmone were put Into a heavy waBed glass tube. 1.73grameofR- 1234Z8 were added to the glass tube. The tube was then frozen and sealed. Upon thawing the tube, It was found that the mixture had one liquid phase. The solution contained 20 wL % Jasome and 80 wt % R- 1234ze, thus establishing Its favorable use as a carrier or part of delivery system for flavor formulations, In aerosol and other formulations. It also establishes its potential as an extractant of fragrances, including from plant matter. METHODS AND SYSTEMS The compositions of the present invention 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 comprising or consisting of the aerosol propeltant in such systems and methods. Methods of forming foams and methods of extinguishing and suppressing fire are also included In certain aspects of the present invention. The present invention also provides in certain aspects methods of removing residue from articles in which the present compositions are used as solvent compositions in such methods and systems. HEAT TRANSFER METHODS . The preferred heat transfer methods generally comprise providing a composition of the present Invention and causing heat to be transferred to or from the composition changing the phase of the-composition, for example, the present methods 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 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, nigh pressure vapor at least a portion of the heat added by the evaporation and compression steps. The heat removal step preferably includes 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 Invention. This relatively high-pressure liquid preferably then undergoes a nominally isoenthalplc reduction In pressure to produce a relatively low temperature, low-pressure liquid, in such embodiments, it is this reduced temperature refrigerant liquid which is then vaporized by heat transferred from the body or fluid to be cor Mii. in another process embodiment of the invention, the compositions of the invention may 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, frequently are reverse cycles to the refrigeration cycle described above. ' FOAM BLOWING METHODS One embodiment of the p.esent invention relates to methods of forming foams, and preferably polyurethane and poiyfeocyarHirate foams. The methods generally comprise providing a blowing agent composition of the present inventions, 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 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 hi accordance with the foam embodiments of the present invention. In general, such preferred methods comprise preparing polyurethane or polyisocyanurate foams by combining an Isocyanate, a polyo) or mixture of polyols, a blowing agent or mixture of 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 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 polyo! mixture, surfactant catalysts, blowing agents, flame retardant and other isocyanate reactive components comprise the second component commonly referred to as the "B" component Accordingly, 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 Bke. Optionally, other ingredients such as fire retardants, colorants, auxiliary blowing agents, and even other polyols can be added as a third stream to the mix head or reaction site. Most preferably, however, they are all incorporated into one B-component as described above. It is also possible to produce thermoplastic foams using the compositions of the invention. For example, conventional polystyrene and polyethylene formulations may be combined with the compositions in a conventional manner to produce rigid foams. CLEANING METHODS The present invention also provides methods of removing containments from a product part, component, substrate, or any other article or portion thereof by applying to the article a composition of the present inventfon. 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 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 such a photo resist material. Preferred methods of the present invention comprise applying the present composition to the article. Although It is contemplated that numerous and varied cleaning techniques can employ the compositions of the present invention to good advantage, it is considered to be particularly advantageous to use the present compositions In connection with supercritical cleaning techniques. Supercritical cleaning is disclosed in US Patent No. 6,589,355, which is assigned to the assignee of the present invention and incorporated herein by reference. For supercritical cleaning applications, Is preferred in certain embodiments to Include in the present cleaning compositions, in addition to the HFO-1234 (preferably HFO- 1234ze), one or more additional components, such as C02 and other additional components known for use In connection with supercritical cleaning applications. It may also be possible and desirable in certain embodiments to use the present cleaning compositions in connection with particular vapor degreasing and solvent cleaning methods. FLAMMAB1LITY REDUCTION METHODS According to certain other preferred embodiments, the present invention provides methods for reducing the flammabiiity of fluids, said methods comprising adding a compound or composition of the present invention to said fluid. The flammabiiity associated with any of a wide range of otherwise flammable fluids may be reduced aocording to the present invention. For example, the flammabiiity associated with fluids such as ethylene oxide, flammable hydrofluorocarbons and hydrocarbons, including: HFC-1S2a, 1,1,1^nTiuoroetrane(HFC-143a),ditluorornethane (HFC-32), propane, hexane. octane, and the like can be reduced according to the present Invention. For the purposes of the present invention, a flammable fluid may be any fluid exhibiting flammabiiity 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 flammabiiity of a fluid according to the present invention. As will be recognized by those of skill in the art, the amount added will depend, at least In part, on the degree to which the subject fluid Is flammable and the degree to which ft is desired to reduce the flammabiiity thereof. In certain preferred embodiments, the amount of compound or composition added to the flammable fluid Is effective to render the resulting fluid substantially non-flammable. FLAME SUPPRESSION METHODS The present invention further provides methods of suppressing a flame, said methods comprising contacting a flame with a fluid .comprising a compound or composition of the present invention. Any suitable methods for contacting the flame with the present composition may tie used. For example, a composition of the present invention may be sprayed, poured, and the like onto the flame, or at toast 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 the present invention. 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 safety of patients and hospital staff. The present Invention provides methods of sterilizing comprising contacting the articles, devices or material to be sterilized with a compound or composition of the present invention comprising a compound of Formula I, preferably HFO-1234, and even more preferably HFO-1234ze, in combination with one or more sterilizing agents. While many sterilizing agents are known in the art and are considered to be adaptable for use in connection with the present invention, In certain preferred embodiments sterilizing agent comprises ethylene oxide, formaldehyde, hydrogen peroxide, chlorine dioxide, ozone and combinations of these. In certain embodiments, ethylene oxide is the preferred sterilizing agent Those skilled in the art, in view of the teachings contained herein, will be able to readily determine the relative proportions of sterilizing agent and the present compound(s) to be used In connection with the present sterilizing compositions and methods, and all such ranges are within the broad scope hereof. As is known to those skilled in the art, certain sterilizing agents, such as ethylene oxide, are relatively flammable components, and the compound(s) in accordance with the present invention are included hi the present compositions in amounts effective, together with other components present in the composition, to reduce the flammability of the sterilizing composition to acceptable levels. The sterilization methods of the present invention may be either high or low-temperature sterilization of the present invention involves the use of a compound or composition of the present Invention at a temperature of from about 250°F to about?270,>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. In low temperature sterilization methods, the article to be sterilised is exposed to a fluid comprising a composition of Hie present invention at a temperature of from about room temperature to about 200°F, more preferably at a temperature of from about room temperature to about 100°F. The low-temperature sterilization of the present invention 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. In certain embodiments, ft is preferable to inject steam into the chamber to achieve a relative humidity that ranges 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 ts 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 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 invention are used. Typical aeration 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 unfit the desired removal of sterilant Is achieved. Continuous aeration typically involves 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 ate combined. For example, a common approach involves performing air washes and then an aeration cycle. EXAMPLES The following examples are provided for the purpose of illustrating the present Invention but without limiting the scope thereof. 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 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 specific compressor, a refrigerant with a higher capacity will deliver more cooling or heating power. One means tor 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, RUOROCARBON REFRIGERANTS HANDBOOK, Chapter 3, Prentice- Hall, 1988). 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 feentropic compression with a compressor inlet temperature of about 50°F. COP is determined for several compositions of the present invention over a range of condenser and evaporator temperatures and reported in Table I below, based upon HFC- 134a having a COP value of 1.00, a capacity value of 1.00 and a discharge temperature of 175 °F. 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 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 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) on {Goodwrench Refrigeration OH for 134a systems), and a poWalpha-olefin) oil{CP«005-100). For-each refrigerantfoll combination, throe compositions are tested, namely 5,20 and 50 weight percent of lubricant, with the balance of each being the 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 added, and the tubes are then sealed; The tubes are then put into an air br, i environmental chamber, the temperature of which is varied from about-SO'C to 70C. At roughly 10C intervals, visual observations of the tube contents are r-ade for the existence of one or more liquid phases. In a case where more than one liquid 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 of) lubricants were judged to be miscible In all tested proportions over the entire temperature range, except that for the HKM225ye mixtures with polyalkylene glycol, the refrigerant mixture was found to be immiscible over the temperature range of -SO'C to-30'C and to be partially miscible over from-20 to 50C. At 50 weight percent concentration of the PAG in refrigerant and at 60, the refrigerant/PAG mixture was miscible. At 70°C, ft was miscible from 5 weight percent lubricant In refrigerant to 50 weight percent lubricant in refrigerant EXAMPLES The compatibility of the refrigerant compounds and compositions of the present invention with PAG lubricating oHs while in contact with metals used in refrigeration and air conditioning systems is tested at 350° 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 ofoil are added to the tubes. The tubes are then evacuated and one 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: a) HFO-1234ze and GM Goodwrench PAG oil b) HF01243zf and GM Goodwrench oB PAG oil c) HFO-1234zeandMOPAR-56PAGoll d) HFO-1243zfandMOPAR-56PAGoil e) HFO-1225yeandMOPAR-56PAGoil. 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 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. 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 350°C, as in Example 3. At the em) of file exposure period, the tube is removed and visual observations are made. The liquid contents are observed to turn black, indicating there is severe decomposition of the contents of the tube. CFC-12 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 commonly used lubricating oils than the widely used prior art refrigerant-lubricating oil combination. EXAMPLE 4 - POLYOL FOAM This example illustrates the use of blowing agent in accordance with one of the preferred embodiments of the present invention, namely the use of HF0-I234ze, and the production of polyol foams in accordance with the present Invention. The components of a polyol foam formulation are prepared in accordance with the following table: Polvol Component* PBW Voranol 490 50 Voranol391 50 Water 0.5 B-8462 (surfactant) 2.0 Polycat 8 0.3 Polycat41 3.0 HFO-1234ze 35 Total 140.8 lsocvanate M-20S 123.8 Index 1.10 Voranoi 490 is a sucrose-based polyol and Voranol 391 is a toluene diamine based polvol, and each are from Dow Chemical. B-8462 Is a surfactant available from Degussa-Goldschmidt Polycat catalysts are tertiary amine based and are available from Air Products. Isocyanate M-20S Is a product of Bayer LLC. The foam is prepared by first mixing the ingredients thereof, but without the addition of blowing agent. Two Fisher-Porter tubes are each filled with about 52.6 grams of the polyol mixture (without blowing agent) and sealed and placed in a refrigerator to cool and form a slight vacuum. Using gas burets, about 17.4 grams of HFO-1234ze are added to each tube, and the tubes are then placed in an ultrasound bath in warm water and allowed to sit for 30 minutes. The solution produced is hazy, a vapor pressure measurement at room temperature indicates a vapor pressure of about 70 psig, indicating that the blowing agent is not in solution. The tubes are then placed in a freezer at 27" F for 2 hours. The vapor pressure was again measured and found to be 14-psig. The isocyanate mixture, about 87.9 grams, is placed into a metal container and placed In a refrigerator and allowed to cool to about 508F. The polyol tubes were then opened and weighed into a metal mixing container^about 100 grams of polyol blend are used). The Isocyanate from the cooled metal container is then Immediately poured into the polyol and mixed with an air mixer with double propellers at 3000 RPMs for 10 seconds. The blend Immediately begins to froth with the agitation and Is then poured into an 8x8x4 inch box and allowed to foam. Because of the froth, a cream time cannot be measured. The foam has a 4-minute gel time and a 5-mFnute tack free time. The foam Is then allowed to cure for two days at room temperature. The foam is then cut to samples suitable for measuring physical properties and is found to have a density of 2.14 pcf. K-factors are measured and found to be as follows: Temperature K, BTU In / Ft2 h "F 40°F .1464 75°F .1640 110" .1808 EXAMPLE 5 - POLYSTYRENE FOAM This example illustrates the use of blowing agent in accordance with two preferred embodiments of the present invention, namely the use of HFO-1234ze and HFO-1234-yf, and the production of polystyrene foam. A testing apparatus and protocol has been-established as an aid to determining whether a specific blowing agent and polymer are capable of producing a foam and the quality of the foam. Ground polymer (Dow Polystyrene 68SD) and blowing agent consisting essentially of HFO- 1234ze are combined in a vessel A sketch of the vessel Is illustrated below. The vessel volume is 200 cm3 and it is made from two pipe flanges and a section of 2-inch diameter schedule 40 stainless steel pipe 4 inches long (see Figure 1). The vessel is placed in an oven, with temperature set at from about 190°F to about 285°F, preferably for polystyrene at 266°F, and remains there until temperature equilibrium is reached. The pressure in the vessel is then released, quickly producing a foamed polymer. The btowing agent plastldzes the polymer as it dissolves into it The resulting density of the two foams thus produced using this method are given in Table 1 and graphed in Figure 1 as the density of the foams produced using trans-HFO-1234ze and HFO-1234yf. The data show that foam polystyrene is obtainable in accordance with the present invention. The die temperature for R1234ze with polystyrene is about 250'P. i WE CLAIM: 1. A method of transferring heat to or from a fluid or body to provide cooling of air in an automobile, said method comprising: (a) providing a heat transfer system comprising an automobile air conditioning system; (b) providing in said system a heat transfer composition comprising at least one lubricant such as herein described and at least one fluoroalkene having a total of at least four fluorine substituents, said fluoroalkene being of Formula II: where R' is (CR2)nY, Y is CF3 each R is independently For H, and n is 0 or 1, provided that there is at least one H on said unsaturated terminal carbon and wherein said fluoroalkene has no substantial toxicity. 2. The method as claimed in claim 1 wherein said composition has a Global Warming Potential (GWP) of not greater than 500. 3. The method as claimed in claim 2 wherein said fluoroalkene of Formula II comprises 1,1,1,2-tetrafluoropropene (HFO-1234yf). 4. The method as claimed in claim 1 wherein said providing step comprises circulating said composition in said automobile air conditioning system. 5. The method as claimed in claim 1 wherein said unsaturated terminal carbon has one F substituent. 6. The method as claimed in claim 1 wherein n is 0. 7. The method as claimed in claim 4 wherein said unsaturated terminal carbon has no F substituent. 8. The method as claimed in claim 1 wherein each substituent on the unsaturated terminal carbon is H. 9. The method as claimed in claim 1 wherein n is 1. 10. The method as claimed in claim 1 wherein said fluoroalkene of Formula II consists essentially of 1,1,1,2-tetrafluoropropene (HFO-1234yf). 11. The method as claimed in claim 1 wherein said fluoroalkene of Formula II comprises 1,1,1,3-tetrafluoropropene (HFO-1234ze). 12. The method as claimed in claim 1 wherein said fluoroalkene of Formula II comprises trans 1,1,1,3-tetrafluoropropene (HFO-1234ze). 13. The method as claimed in claim 1 comprising conditioning the air in an automobile comprising: (a) providing a vapor compression air conditioning system having at least one compressor, at least one condenser and a heat transfer fluid in said system, said heat transfer fluid comprising 1,1,1,2-tetrafluoropropene (HFO-1234y£) in an amount of from 5 % by weight to 99 % by weight of the heat transfer fluid; and (b) operating said condenser in a temperature range that includes 150°F. 14. The method as claimed in claim 11 wherein said heat transfer composition comprises from 5 % by weight to 95 % by weight of 1,1,1.2-tetrafluoropropene (HFO-1234yf). 15. The method as claimed in claim 13 wherein said lubricant is present in the composition in an amount of from 30% to 50% by weight of the heat transfer composition based on the total weight of said lubricant and said compound(s) of Formula II. 16. The method as claimed in claim 1 wherein said lubricant is selected from the group consisting of polyol esters, polyalkylene glycols, polyalkylene silicon oils, mineral oils, alkyl benzenes, poly(alpha-olefins) and combinations of these. 17. The method as claimed in claim 11 wherein said lubricant comprises at least one polyalkylene glycol. 18. The method as claimed in claim 1 wherein said lubricant comprises polyalkylene glycol ester. 19. The method as claimed in claim 1 wherein said heat transfer composition has a Global Warming Potential (GWP) of not greater than 150. 20. The method as claimed in claim 1 wherein said heat transfer composition has a Global Wanning Potential (GWP) of not greater than 75. 21. The method as claimed in claim 1 wherein said heat transfer composition has an ozone depletion potential (ODP) of not greater than 0.05. 22. The method as claimed in claim 1 wherein said heat transfer composition has an ozone depletion potential (ODP) of not greater than 0.02. 23. The method as claimed in claim 1 wherein said heat transfer composition has an ozone depletion potential (ODP) of not greater than zero 24. The method as claimed in claim 1 wherein said compound of Formula II is present in the composition in an amount of from 5 % by weight to 95 % by weight. 25. The method as claimed in claim 1 wherein said compound of Formula II is present in the composition in an amount of at least 50 % by weight. 26. The method as claimed in claim 1 wherein said compound of Formula II is present in the composition in an amount of at least 70 % by weight. 27. The method as claimed in claim 1 wherein said heat transfer composition comprises one or more of the following: difluoromethane (HFC-32); pentafluoroethane (HFC-125); 1,1,2,2-tetrafluoroethane (HFC-134); 1,1,1,2- tetrafluoroethane (HFC-134a); difluoroethane (HFC-152a); 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); water; and CO2. 28. The method as claimed in claim 1 wherein said heat transfer composition comprises a flammability suppressant. 29. The method as claimed in claim 28 wherein said flammability suppressant comprises CF3I. 30. The method as claimed in claim 1 wherein said lubricant comprises an alkyl benzene. 31. The method as claimed in claim 1 wherein said lubricant comprises an ester oil. 32. The method as claimed in claim 1 wherein said lubricant comprises a poly(alpha- olefin) oil. 33. The method as claimed in claim 1 wherein said heat transfer composition has one liquid phase at at least one temperature between -50°C and +70°C. 34. The method as claimed in claim 1 wherein said heat transfer composition is stable when in contact with aluminum, steel and copper under the conditions of use in said air conditioning systems. 35. The method as claimed in claim 1 wherein said automobile air conditioning system comprises a vapor compression air conditioning system having at least one compressor and at least one condenser operable in a temperature range that includes 150°F. 36. The method as claimed in claim 1 wherein said automobile air conditioning system includes at least one compressor and at least one evaporator, said method comprising: (a) utilizing in said system a heat transfer fluid comprising 1,1,1,2- tetrafluoropropene (HFO-1234yf) in an amount of from 5 % by weight to 99 % by weight of the heat transfer fluid; and (b) using said heat transfer fluid to absorb heat from the air in the automobile by evaporating in said evaporator said heat transfer fluid to produce a vapor comprising said HFO-1234yf; (c) compressing at least a portion of said vapor from said step (b) in said at least one compressor to produce a relatively elevated pressure vapor comprising HFO- 1234yf; and (d) removing heat from said relatively elevated pressure vapor by condensing said vapor. 37. The method as claimed in claim 5 wherein said lubricant is selected from the group consisting of polyol esters, polyalklene glycols, polyalkylene silicon oils, mineral oils, alkyl benzenes, poly(alpha-olefins) and combinations of these. 38. The method as claimed in claim 5 wherein said at least one lubricant comprises at least one polyalkylene glycol. 39. The method as claimed in claim 5 wherein said at least one lubricant comprises polyalkylene glycol ester. 40. The method as claimed in claim 5 wherein said heat transfer fluid has a capacity relative to HFC-134a of 1 and a Coefficient of Performance (COP) relative to HFC-134aof 1. 41. The method as claimed in claim 39 wherein said heat transfer composition has one liquid phase at at least one temperature between -50°C and +70°C and wherein said heat transfer composition has a capacity relative to HFC-134a of 1 and a Coefficient of Performance (COP) relative to HFC-134a of 1. 42. The method as claimed in claim 41 wherein said fluoroalkene of Formula II comprises 1,1,1,2-tetrafluoropropene (HFO-1234yf) present in the composition in an amount of at least 70 % by weight. 43. The method as claimed in claim 40 wherein said heat transfer composition comprises one or more of the following: difluoromethane (HFC-32); pentafluoroethane (HFC-125); 1,1,2,2-tetrafluoroethane (HFC-134); 1,1,1,2- tetrafluoroethane (HFC-134a); difluoroethane (HFC-152a); 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); water; and CO2. 44. The method as claimed in claim 36 wherein said heat transfer fluid comprises at least one lubricant selected from the group consisting of polyol esters, polyalkylene glycols, polyalkylene silicon oils, mineral oils, alky] benzenes, poy(alpha-olefins) and combinations of these. 45. The method as claimed in claim 44 wherein said system comprises a condenser operated in a temperature range that includes 150°F. 46. The method as claimed in claim 45 wherein said heat transfer fluid has a Global Warming Potential (GWP) of not greater than 75. 47. The method as claimed in claim 14 wherein said at least one lubricant comprises a poly alkylene glycol. 48. The method as claimed in claim 47 wherein said heat transfer composition has one liquid phase at at least one temperature between -50°C and +70°C and wherein said heat transfer composition has a capacity relative to HFC-134a of 1, a Coefficient of Performance (COP) relative to HFC-134a of 1 and a Global Warming Potential (GWP) of not greater than 75. A method of transferring heat to or from a fluid or body to provide cooling of air in an automobile, said method comprising: (a) providing a heat transfer system comprising an automobile air conditioning system; (b) providing in said system a heat transfer composition comprising at least one lubricant such as herein described and at least one fluoroalkene having a total of at least four fluorine substituents, said fluoroalkene being of Formula II: where R' is (CR2)nY, Y is CF3 each R is independently For H, and n is 0 or 1, provided that there is at least one H on said unsaturated terminal carbon and wherein said fluoroalkene has no substantial toxicity.

Full Text

COMPOSITIONS CONTAINING rLUOniNE GUDOTITUTCD OUTIN3 HELD OF THE INVENTION
This invention relates to compositions having utility in numerous
applications, including particularly refrigeration systems, and to methods
and systems utilizing such compositions. In preferred aspects, the present
invention Is directed to refrigerant compositions comprising at least one
multi-fluorinated olefin of the present invention.
BACKGROUND OF THE INVENTION
Ffuorocarbon 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
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
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 fluids, such as refrigerants, for many years in many
applications. For, example, fluoroalkanes, such as chlorofluoromefriane
and chtorofluoroethane 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.
Concern has Increased in recent years about potential damage to
the earth's atmosphere i-4 climate, and certain chlorine-based
compounds have been identfaed as particularly problematic In this regard.
The use of chlorine-containing compositions (such as chlorofluorocarbons
(CFCs), hydrochtorofluorocarbons (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 hydrofiuorocarbon 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-flammabliity 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-chiorine-containing refrigeration fluids, including HFCs, are
relatively insoluble and/or immiscible in the types of lubricants used
traditionally with CFCs and HFCs, including, for example, mineral oils,

alkyfbenzenes or poly(a!pha-otefins). in order for a refrigeration fluW-
iubrlcant 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.
Flammabilrty 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 drfluoroetharte (HFC-1S2a) and the fluoroalkene 1,1,1-
trifluoropropene {HFO-1243zf) are each flammable and therefore not
viable for use in many applications.

Higher ffuoroalkenes, that is fluorine-substituted alkenes having at
least flva carbon atoms, have been suggested for use as refrigerants.
U.S. Patent Mo. 4,788,352 - Smutny Is directed to production of
fluoridated Cs to Cs 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 fiuorinated 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.
Bromofluoromethaneand 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 compatabifeing
agents, that are potentially useful in numerous applications. Including

vapor compression heating and cooling systems and methods, while
avoiding one ormore of the disadvantages noted above.
SUMMARY
Applicants have found that the above-noted need, and other needs,
can be satisfied by compositions comprising one or more C3 or C4
fluoroalkenes, preferably compounds having Formula I as follows:
XCFZR^(1)
where X is a C2 or a C3 unsaturated, substituted or unsubstftuted, alkyf
radical, each R is Independently CI, F, Br, I or H, and z is 1 to 3. Highly
preferred among the compounds of Formula I are the cis- and trans-
isorners of 1,3,3,3-tetrafluoropropene (HFO-1234ze)
The present Invention provides also methods and systems which
utilize the compositions of the present invention, including methods and
systems for heat transfer, foam blowing, solvating, flavor and fragrance
extraction and/or delivery, and aerosol generation.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
THE COMPOSITIONS
The present Invention is directed to compositions comprising at
least one fluoroalkene containing from 3 to 4 carbon atoms, preferably
three carbon atoms, and at least one carbon-carbon double bond. The
fluoroalkene compounds of the present invention 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 invention may contain two carbon - carbon double
bonds, such compounds at the present time are not considered to be
preferred.
As mentioned above, the present compositions comprise one or
more compounds in accordance with Formula I. In preferred

embodiments, the compoafflons Indude compounds of Formula H below:

whereeachRtsfodependentryCt,F, Br, lorH
R*iB(CR2)bY,
YtoCRFj
andnteOoM.
In highly preferred embodiments, Y is CF3, n is 0 and at least one of the
remaining Rs is F.
AppCcants before that, In general, the compounds of the above
identified Formulas I and II are generafly effective and exhfctt udBty ki
refrigerant composiJons, blowing agent compositions, compatJbiftDBrs,
aerosols, propeUants, fragrances, flavor formulations, and solvent
compositions of the present invention. However, appfcants have
surprisingly and unexpectedly found that certain of the compounds having
a structure In accordance with the formulas described above exhtt* a
highry desirable low level of toxicity compared to other of such
compounds. As can be readily appreciated, this discovery is ofpotenttaUy
enormous advantage and benefit for the formulation of not only refrigerant
compositions, but also any and at oomposWona, which would otherwise
contain retatrveiy toxic compounds satisfying the formulas described
above. More partJcubrty, appftcants believe that a relatively tow toxicity
level is associated wflh compounds of Formula II, preferably wherein Y is
CFj, wherein at least one R on the unsaturated terminal carbon is H, and
at least one of the remaining Rs b F. Applicants beBeve abo that al
structural, geometric and stereoisomers of such compounds are-effectJva
and of beneficiaOy low toxicity.

In highly preferred embodiments, especially embodiments
comprising the low toxicity compounds described above, n is zero. In
certain highly preferred embodiments the compositions of the present
invention comprise one or more tetrafluoropropenes. The term "HFO-
1234" is used herein to refer to all tetrafluoropropenes. Among the
tetrafluoropropenes, both cis- and trans-1,3,3,3-tetraftuoropropene
(HFO-1234ze) are particularly preferred. The term HFCM234ze is used
herein genetically to refer to 1,3,3,3-tetrafluoropropene, independent of
whether it is the cis- or trans- form. The terms "cfeHFO-1234ze" and
1ransHF01234ze* 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 dsHFO-1234ze, transHFO-1234ze, and
all combinations and mixtures of these.
Although the properties of cfsHFO-1234ze and transHFO-1234ze
differ in at least some respects, it is contemplated that each of these
compounds is adaptable for use, either alone or together with other
compounds including its stereoisomer, in connection with each of the
applications, methods and systems described herein. For example, while
transHFO-1234ze may be preferred for use in certain refrigeration
systems because of its relatively low boiling point (-19° C), ft Is
nevertheless contemplated that cisHFO-1234ze, with a boiling point of
+9* C, also has utility in certain refrigeration systems of the present
invention. Accordingly, it is to be understood that the terms *HFO-1234ze*
and 1,3,3,3-tetrafiuoropropene refer to both stereo isomers, and the use
of this term is intended to indicate that each of the cls-and trans- forms
applies and/or is useful for the stated purpose unless otherwise indicated.
HFO-1234 compounds are known materials and are listed in
Chemical Abstracts databases. The production offluoropropenes such as
CF3CH=CH2 by catalytic vapor phase fluorination of various saturated and
unsaturated halogen-containing C3 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,
discloses the preparation of 1,1,1,3-tetrafluoropropene by contacting
1.1,1,3,3-perrtafluoropropane (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 MgXOHk In
addition, methods for producing compounds In accordance with the
present Invention are described generally in connection with pending
United States Patent Application entitled "Process for Producing
FJuoropropenes" bearing attorney docket number (H0003789 {26267)),
which is also incorporated herein by reference.
The present compositions, particularly those comprising HFO-
1234ze, 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 fluorootefins 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 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 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 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 (OOP) of not greater than 0.06, mora
preferably not greater than 0.02 arc! even nxxe preferably about zero. As
used herein, "OOP* is 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 herein by
reference.
The amount of the Formula I compounds. pertlcUariy HFO-1234,
contained in the present compositions can vary widely, depending the
particular appOcation, and compositions containing more than trace
amounts and less than 100% of the compound are wttNh broad the scope
of the present Invention. Moreover, the compositions of the present
Invention can be azeotroplc azeotrope-lfce or rwn-azeotroplc. In
preferred embodiments, the present compositions comprise HFO-1234,
preferably HFO-1234z», In amounts from about 5% by weight to about
09% by weight, and even more preferably from about 5% to about 95%.
Many addKonal compounds may be included in the present compositions,
and the presence of afl 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:
DffkJoromethane (HFC-32)
PentafTuoroethane (HFC-126)
1,1^-t0trafluoroethane 1,1.U-Tetrafluoroethane (HFC-134a)
Dffluoroelhane (HFC-152a)
1,1,1 ^,3,3,34taptaflixxopropane (HFC-227ea)
1,1,1,3,3,3-riexafluorcorop8ne (HFC-236«a)
1,1,1,3,3-pentafhx)fopropane 1,1.1.3,3-pentaOuc^obutane (HFC-38Smfc)
water
CO?

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 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.
HEAT TRANSFER COMPOSITIONS
Although it is contemplated that Hie compositions of the present
invention may include the compounds of the present invention in widely
ranging amounts, it is generally preferred that refrigerant compositions of
the present invention comprise compound(s) in accordance with Formula
I, more preferably In accordance with Formula il, and even more
preferably HFO-1234ze. in an amount tnat is at least about 60% by
weight and even more preferably at least about 70 % by weight, of the
composition. In many embodiments, it is preferred that the heat transfer
compositions of the present invention comprise transHFO-1234ze. In
certain preferred embodiments, the heat transfer compositions of the
present invention comprise a combination of cisHFO-1234ze and
transHF01234ze in a dsrtrans weight ratio of from about 1:99 to about
10:99, more preferably from about 1:99 to about 5:95, and even more
preferably from about 1:99 to about 3:97.
The compositions of the present invention may include other
components for the purpose of enhancing or providing certain functionality
to the composition, or tn some cases to reduce the cost of the
composition. For example, refrigerant compositions according to the
present invention, especially those used in vapor compression systems,
Include a lubricant, generally in amounts of from about 30 to about SO
percent by weight of the composition. Furthermore, the present
compositions may also include a compatibDizar, such as propane, for the
purpose of aiding compatibility and/or solubility of the lubricant Such
cornpatibiiizers, including propane, butanes and pentanes, are preferably

present in amounts of from about 0.5 to about 5 percent by weight of the
composition. Combinations of surfactants and sofubilizing 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), silicone oil, mineral oil, alkyl
benzenes (ABs) and poly(alpha-olefin) (PAO) that are used in refrigeration
machinery with hydrofluorocarbon (HFC) refrigerants may be used with
the refrigerant compositions of the present invention.
Many existing refrigeration systems are currently adapted for use in
connection with existing refrigerants, and the compositions of the present
invention are believed to be adaptable for use in many of such systems,
either with or without system modification. In many applications the
compositions of the present invention may provide an advantage as a
replacement In systems, which are currently based on refrigerants having
a relatively high capacity. Furthermore, in embodiments where it is
desired to use a lower capacity refrigerant composition of the present
invention, for reasons of cost for example, to replace a refrigerant of
higher capacity, such embodiments of the present compositions provide a
potential advantage. Thus, K is preferred in certain embodiments to use
compositions of the present invention, particularly compositions
comprising a substantial proportion of, and in some embodiments
consisting essentially of transHFO-1234ze, as a replacement for existing
refrigerants, such as HFC-134a. In certain applications, the refrigerants of
the present Invention potentially permit the beneficial use of larger
displacement compressors, thereby resulting in better energy efficiency
than other refrigerants, such as HFC-134a. Therefore the refrigerant
compositions of the present invention, particularly compositions
comprising transHFP-1234ze, provide the possibility of achieving a
competitive advantage on an energy basis for refrigerant replacement
applications.

It is contemplated that the compositions of the present, including
particularly those comprising HFO-1234ze, also have advantage (either in
original systems or when used as a replacement for refrigerants such as
R-12 and R-500), in chillers typically used in connection with commercial
air conditioning systems. In certain of such embodiments it Is preferred to
including in the present HFO-1234ze compositions from about 0.5 to about
5% of a flammabillty suppressant, such as CF3I.
The present methods, systems and compositions are thus
adaptable for use in connection with automotive air conditioning systems
and devices, commercial refrigeration systems and devices, chillers,
residential refrigerator and freezers, general air conditioning systems, heat
pumps, and the like.
BLOWING AGENTS, FOAMS AND FOAMABLE COMPOSITIONS
Blowing agents may also comprise or constitute one or more of the
present compositions. As mentioned above, the compositions of the
present Invention 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 in accordance with the
present Invention, compound(s) In accordance with Formula I, and-even
more preferably Formula II, 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. In certain preferred embodiments, the blowing agent
compositions of the present invention and Include, in addition to HFO-
1234 (preferably HFO-t234ze) one or mora of the following components
as a co-blowing agent, filler, vapor pressure modifier, or for any other
purpose:
Difluoromethane (HFC-32)
Pentafiuoroethane (HFC-125)
1,1,2,2-tetrafluoroethane (HFC-134)
1,1,1,2-Tefrafluoroethane (HFC-134a)

Difluoroethane (HFC-152a)
1,1,1 A3,3,3-Heptafkjoropropane (HFC-227ea)
1,1,1,3,3,3-hexafluonopropane (HFC-236fe)
1,1,1,3,3-rjentafluoropropane 1,1,1,3,3-pentafluoiobutane (HFC-365mfc)
water
COz
it is contemplated that the blowing agent compositions of the present
Invention may comprise clsHFO-1234ze, transHF01234ze or
combinations thereof. In certain preferred embodiments, the blowing
agent composition of the present invention comprise his a combination of
dsHFO-1234ze and transHF01234ze in a cls_-trans weight ratio of from
about 1:99 to about 10:99, and even more preferably from about 1:99 to
.about 5:95.
in other embodiments, the invention provides foamable
compositions, and preferably polyurethane, polylsocyanurate and extruded
thermoplastic foam compositions, prepared using the compositions of the
present Invention. In such foam embodiments, one or more of the
present 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 The invention also relates to foam, and preferably closed cell
foam, prepared from a polymer foam formulation containing a blowing
agent comprising the compositions of the invention. In yet other
embodiments, the invention provides foamable compositions comprising
thermoplastic or polyolefin foams, such as polystyrene (PS), polyethylene
(PE), polypropylene (PP) and poryethyleneterpthalate (PET) foams,
preferably low-density foams.
In certain preferred embodiments, dispersing agents, cell
stabilizers, surfactants and other additives may also be incorporated into

the blowing agent compositions of the present invention. Surfactants are
' optionally but preferably added to serve as cell stabilizers. Some
representative materials are sold under the names of OC-193, B-8404,
and L-5340 which are, generally, polysiloxane polyoxyalkyiene 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 retardants such as tri(2-chloroethyl)phosphate, tri(2-
chloropropyi)phosphata, tri(2,3-dibromopropyl)-phospnate, trf(1,3-
dichloropropyl) phosphate, diammonium phosphate, various haiogenated
aromatic compounds, antimony oxide, aluminum trihydrate, polyvinyl
chloride, and the like.
PROPELLANT AND AEROSOL COMPOSITIONS
in another aspect, the present invention provides propeliant
compositions comprising or consisting essentially of a composition of the
present invention, such propeliant composition preferably being a
sprayable composition. The propeliant compositions of the present
invention preferably comprise a material to be sprayed and a propeliant
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 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 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 a compound of Formula I of the present invention,

preferably HFO-1234, and even more preferably HFO-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. 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 commonly used liquefied gas propellants are
hydrocarbons such as butane, isobutane, and propane. Dimethyl ether
and HFC-152a (1,1-dtfluoroethane) are also used, either alone or in
blends with the hydrocarbon propellants. Unfortunately, ail of these
liquefied gas propellants are highly flammable and their incorporation into
aerosol formulations will 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 HFO-1234,
and even more preferably HFO-1234ze, for use in certain industrial
aerosol products, including for 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 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 othertherapeutic 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, introducing the

c»mpc«JbonlntDtheM01)arritheodbcharglogtt»p«es«ntconipos«k«
from the MD).
The compositions of the present Invention, particularly compositions
comprising or consisting essentialy of HFO-1234ZB. are capable of
providing nonflammable, Dqusfod gas propesantand aerosols that do not
cortrfautesubstamlafly to global vvartning. The present compositions can
be used to formulate a variety of industrial aerosols or other sprayable
compositions such as contact cleaners, dusters, lubricant sprays, and the
Bee, and consumer aerosols such as personal car* products, household
products and automotive products. HFO-1234ze Is particularly preferred
for use as an important component of propeSant compoeWons for In
medicinal aerosols such as metered dose Inhalers. Tha medicinal aerosol
and/or propaBant and/or sprayabie oomposfbons ot the present invention
h many appBcattons Include, tn addition to compound of formula (I) or (II)
(preferably HF01234ze), a medicament such as a beta-agonist, a
corticosteroid or other medtoarnent, and, opttonaBy. other Ingredients,
such as surfactants, solvents, other propelants, flavorants and other
exdpients. The compositions of the present Invention, unito many
compositions previously used in these appBcattons, have good
environmental properties and are not considered to be potential
contributors to global warmtig. The present cornposftons therefore
provide In certain preferred embodiments subetantialy rorrftonmabte,
Iquefied gas propeOants having very iow Global Warming potentials.
FLAVORANTS AND FRAGRANCES
The compositions of the present invention also provide advantage
when used as part of, and In particular as a carrier for, flavor formulations
arid fragrance formulations. TtosuttabOrryof tfwpresericctrnposttionsfor
this purpose Is demonstrated by a test procedure In wMch 0.38 grams of
Jasmone were put Into a heavy waBed glass tube. 1.73grameofR-

1234Z8 were added to the glass tube. The tube was then frozen and
sealed. Upon thawing the tube, It was found that the mixture had one
liquid phase. The solution contained 20 wL % Jasome and 80 wt % R-
1234ze, thus establishing Its favorable use as a carrier or part of delivery
system for flavor formulations, In aerosol and other formulations. It also
establishes its potential as an extractant of fragrances, including from
plant matter.
METHODS AND SYSTEMS
The compositions of the present invention 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 comprising or consisting of the aerosol
propeltant in such systems and methods. Methods of forming foams and
methods of extinguishing and suppressing fire are also included In certain
aspects of the present invention. The present invention also provides in
certain aspects methods of removing residue from articles in which the
present compositions are used as solvent compositions in such methods
and systems.
HEAT TRANSFER METHODS
. The preferred heat transfer methods generally comprise providing a
composition of the present Invention and causing heat to be transferred to
or from the composition changing the phase of the-composition, for
example, the present methods 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 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, nigh pressure vapor at least a portion of the
heat added by the evaporation and compression steps. The heat removal
step preferably includes 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
Invention. This relatively high-pressure liquid preferably then undergoes a
nominally isoenthalplc reduction In pressure to produce a relatively low
temperature, low-pressure liquid, in such embodiments, it is this reduced
temperature refrigerant liquid which is then vaporized by heat transferred
from the body or fluid to be cor Mii.
in another process embodiment of the invention, the compositions
of the invention may 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, frequently are reverse cycles to the refrigeration cycle
described above.
' FOAM BLOWING METHODS
One embodiment of the p.esent invention relates to methods of
forming foams, and preferably polyurethane and poiyfeocyarHirate foams.
The methods generally comprise providing a blowing agent composition of
the present inventions, 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 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 hi accordance with the foam embodiments of
the present invention. In general, such preferred methods comprise
preparing polyurethane or polyisocyanurate foams by combining an
Isocyanate, a polyo) or mixture of polyols, a blowing agent or mixture of
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 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 polyo! mixture, surfactant catalysts, blowing agents, flame
retardant and other isocyanate reactive components comprise the second
component commonly referred to as the "B" component Accordingly,
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 Bke. Optionally, other ingredients such as fire
retardants, colorants, auxiliary blowing agents, and even other polyols can
be added as a third stream to the mix head or reaction site. Most
preferably, however, they are all incorporated into one B-component as
described above.
It is also possible to produce thermoplastic foams using the
compositions of the invention. For example, conventional polystyrene and
polyethylene formulations may be combined with the compositions in a
conventional manner to produce rigid foams.

CLEANING METHODS
The present invention also provides methods of removing
containments from a product part, component, substrate, or any other
article or portion thereof by applying to the article a composition of the
present inventfon. 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 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 such a photo resist material.
Preferred methods of the present invention comprise applying the
present composition to the article. Although It is contemplated that
numerous and varied cleaning techniques can employ the compositions of
the present invention to good advantage, it is considered to be particularly
advantageous to use the present compositions In connection with
supercritical cleaning techniques. Supercritical cleaning is disclosed in US
Patent No. 6,589,355, which is assigned to the assignee of the present
invention and incorporated herein by reference. For supercritical cleaning
applications, Is preferred in certain embodiments to Include in the present
cleaning compositions, in addition to the HFO-1234 (preferably HFO-
1234ze), one or more additional components, such as C02 and other
additional components known for use In connection with supercritical
cleaning applications. It may also be possible and desirable in certain
embodiments to use the present cleaning compositions in connection with
particular vapor degreasing and solvent cleaning methods.

FLAMMAB1LITY REDUCTION METHODS
According to certain other preferred embodiments, the present
invention provides methods for reducing the flammabiiity of fluids, said
methods comprising adding a compound or composition of the present
invention to said fluid. The flammabiiity associated with any of a wide
range of otherwise flammable fluids may be reduced aocording to the
present invention. For example, the flammabiiity associated with fluids
such as ethylene oxide, flammable hydrofluorocarbons and hydrocarbons,
including: HFC-1S2a, 1,1,1^nTiuoroetrane(HFC-143a),ditluorornethane
(HFC-32), propane, hexane. octane, and the like can be reduced
according to the present Invention. For the purposes of the present
invention, a flammable fluid may be any fluid exhibiting flammabiiity
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 flammabiiity of a fluid according to the present
invention. As will be recognized by those of skill in the art, the amount
added will depend, at least In part, on the degree to which the subject fluid
Is flammable and the degree to which ft is desired to reduce the
flammabiiity thereof. In certain preferred embodiments, the amount of
compound or composition added to the flammable fluid Is effective to
render the resulting fluid substantially non-flammable.
FLAME SUPPRESSION METHODS
The present invention further provides methods of suppressing a
flame, said methods comprising contacting a flame with a fluid .comprising
a compound or composition of the present invention. Any suitable
methods for contacting the flame with the present composition may tie
used. For example, a composition of the present invention may be
sprayed, poured, and the like onto the flame, or at toast 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 the
present invention.
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 safety of patients and hospital staff. The
present Invention provides methods of sterilizing comprising contacting the
articles, devices or material to be sterilized with a compound or
composition of the present invention comprising a compound of Formula I,
preferably HFO-1234, and even more preferably HFO-1234ze, in
combination with one or more sterilizing agents. While many sterilizing
agents are known in the art and are considered to be adaptable for use in
connection with the present invention, In certain preferred embodiments
sterilizing agent comprises ethylene oxide, formaldehyde, hydrogen
peroxide, chlorine dioxide, ozone and combinations of these. In certain
embodiments, ethylene oxide is the preferred sterilizing agent Those
skilled in the art, in view of the teachings contained herein, will be able to
readily determine the relative proportions of sterilizing agent and the
present compound(s) to be used In connection with the present sterilizing
compositions and methods, and all such ranges are within the broad
scope hereof. As is known to those skilled in the art, certain sterilizing
agents, such as ethylene oxide, are relatively flammable components, and
the compound(s) in accordance with the present invention are included hi
the present compositions in amounts effective, together with other
components present in the composition, to reduce the flammability of the
sterilizing composition to acceptable levels.
The sterilization methods of the present invention may be either
high or low-temperature sterilization of the present invention involves the

use of a compound or composition of the present Invention at a
temperature of from about 250°F to about?270,>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. In low temperature sterilization
methods, the article to be sterilised is exposed to a fluid comprising a
composition of Hie present invention at a temperature of from about room
temperature to about 200°F, more preferably at a temperature of from
about room temperature to about 100°F.
The low-temperature sterilization of the present invention 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. In certain
embodiments, ft is preferable to inject steam into the chamber to achieve a
relative humidity that ranges 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 ts
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
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 invention are used. Typical aeration 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 unfit the desired removal of sterilant Is achieved.
Continuous aeration typically involves 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 ate combined. For example, a common
approach involves performing air washes and then an aeration cycle.
EXAMPLES
The following examples are provided for the purpose of illustrating
the present Invention but without limiting the scope thereof.
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 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 specific compressor, a refrigerant with
a higher capacity will deliver more cooling or heating power. One means
tor 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,
RUOROCARBON REFRIGERANTS HANDBOOK, Chapter 3, Prentice-
Hall, 1988).

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 feentropic compression with a compressor
inlet temperature of about 50°F. COP is determined for several
compositions of the present invention over a range of condenser and
evaporator temperatures and reported in Table I below, based upon HFC-
134a having a COP value of 1.00, a capacity value of 1.00 and a
discharge temperature of 175 °F.

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 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 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) on {Goodwrench Refrigeration OH for 134a
systems), and a poWalpha-olefin) oil{CP«005-100). For-each
refrigerantfoll combination, throe compositions are tested, namely 5,20

and 50 weight percent of lubricant, with the balance of each being the
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 added, and the tubes are then sealed; The tubes are
then put into an air br, i environmental chamber, the temperature of which
is varied from about-SO'C to 70*C. At roughly 10*C intervals, visual
observations of the tube contents are r-ade for the existence of one or
more liquid phases. In a case where more than one liquid 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 of) lubricants were judged to be
miscible In all tested proportions over the entire temperature range, except
that for the HKM225ye mixtures with polyalkylene glycol, the refrigerant
mixture was found to be immiscible over the temperature range of -SO'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 70°C, ft was miscible from 5
weight percent lubricant In refrigerant to 50 weight percent lubricant in
refrigerant
EXAMPLES
The compatibility of the refrigerant compounds and compositions of
the present invention with PAG lubricating oHs while in contact with metals
used in refrigeration and air conditioning systems is tested at 350° 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 ofoil are added to the tubes. The tubes are then evacuated and one 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:
a) HFO-1234ze and GM Goodwrench PAG oil
b) HF01243zf and GM Goodwrench oB PAG oil
c) HFO-1234zeandMOPAR-56PAGoll
d) HFO-1243zfandMOPAR-56PAGoil
e) HFO-1225yeandMOPAR-56PAGoil.
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 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.
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 350°C,
as in Example 3. At the em) of file exposure period, the tube is removed
and visual observations are made. The liquid contents are observed to
turn black, indicating there is severe decomposition of the contents of the
tube.
CFC-12 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 commonly used lubricating oils than
the widely used prior art refrigerant-lubricating oil combination.

EXAMPLE 4 - POLYOL FOAM
This example illustrates the use of blowing agent in accordance
with one of the preferred embodiments of the present invention, namely
the use of HF0-I234ze, and the production of polyol foams in accordance
with the present Invention. The components of a polyol foam formulation
are prepared in accordance with the following table:
Polvol Component* PBW
Voranol 490 50
Voranol391 50
Water 0.5
B-8462 (surfactant) 2.0
Polycat 8 0.3
Polycat41 3.0
HFO-1234ze 35
Total 140.8
lsocvanate
M-20S 123.8 Index 1.10
*Voranoi 490 is a sucrose-based polyol and Voranol 391
is a toluene diamine based polvol, and each are from
Dow Chemical. B-8462 Is a surfactant available from
Degussa-Goldschmidt Polycat catalysts are tertiary
amine based and are available from Air Products.
Isocyanate M-20S Is a product of Bayer LLC.
The foam is prepared by first mixing the ingredients thereof, but without
the addition of blowing agent. Two Fisher-Porter tubes are each filled with
about 52.6 grams of the polyol mixture (without blowing agent) and sealed
and placed in a refrigerator to cool and form a slight vacuum. Using gas
burets, about 17.4 grams of HFO-1234ze are added to each tube, and the
tubes are then placed in an ultrasound bath in warm water and allowed to
sit for 30 minutes. The solution produced is hazy, a vapor pressure
measurement at room temperature indicates a vapor pressure of about 70
psig, indicating that the blowing agent is not in solution. The tubes are

then placed in a freezer at 27" F for 2 hours. The vapor pressure was
again measured and found to be 14-psig. The isocyanate mixture, about
87.9 grams, is placed into a metal container and placed In a refrigerator
and allowed to cool to about 508F. The polyol tubes were then opened
and weighed into a metal mixing container^about 100 grams of polyol
blend are used). The Isocyanate from the cooled metal container is then
Immediately poured into the polyol and mixed with an air mixer with double
propellers at 3000 RPM*s for 10 seconds. The blend Immediately begins to
froth with the agitation and Is then poured into an 8x8x4 inch box and
allowed to foam. Because of the froth, a cream time cannot be measured.
The foam has a 4-minute gel time and a 5-mFnute tack free time. The foam
Is then allowed to cure for two days at room temperature.
The foam is then cut to samples suitable for measuring physical properties
and is found to have a density of 2.14 pcf. K-factors are measured and
found to be as follows:
Temperature K, BTU In / Ft2 h "F
40°F .1464
75°F .1640
110" .1808
EXAMPLE 5 - POLYSTYRENE FOAM
This example illustrates the use of blowing agent in accordance
with two preferred embodiments of the present invention, namely the use
of HFO-1234ze and HFO-1234-yf, and the production of polystyrene foam.
A testing apparatus and protocol has been-established as an aid to
determining whether a specific blowing agent and polymer are capable of
producing a foam and the quality of the foam. Ground polymer (Dow
Polystyrene 68SD) and blowing agent consisting essentially of HFO-
1234ze are combined in a vessel A sketch of the vessel Is illustrated
below. The vessel volume is 200 cm3 and it is made from two pipe flanges

and a section of 2-inch diameter schedule 40 stainless steel pipe 4 inches
long (see Figure 1). The vessel is placed in an oven, with temperature set
at from about 190°F to about 285°F, preferably for polystyrene at 266°F,
and remains there until temperature equilibrium is reached.
The pressure in the vessel is then released, quickly producing a
foamed polymer. The btowing agent plastldzes the polymer as it
dissolves into it The resulting density of the two foams thus produced
using this method are given in Table 1 and graphed in Figure 1 as the
density of the foams produced using trans-HFO-1234ze and HFO-1234yf.
The data show that foam polystyrene is obtainable in accordance with the
present invention. The die temperature for R1234ze with polystyrene is
about 250'P.

i

WE CLAIM:
1. A method of transferring heat to or from a fluid or body to provide cooling of air
in an automobile, said method comprising:
(a) providing a heat transfer system comprising an automobile air conditioning system;
(b) providing in said system a heat transfer composition comprising at least one
lubricant such as herein described and at least one fluoroalkene having a total of
at least four fluorine substituents, said fluoroalkene being of Formula II:

where
R' is (CR2)nY,
Y is CF3
each R is independently For H,
and n is 0 or 1,
provided that there is at least one H on said unsaturated terminal carbon and wherein said
fluoroalkene has no substantial toxicity.
2. The method as claimed in claim 1 wherein said composition has a Global
Warming Potential (GWP) of not greater than 500.
3. The method as claimed in claim 2 wherein said fluoroalkene of Formula II
comprises 1,1,1,2-tetrafluoropropene (HFO-1234yf).
4. The method as claimed in claim 1 wherein said providing step comprises
circulating said composition in said automobile air conditioning system.
5. The method as claimed in claim 1 wherein said unsaturated terminal carbon has
one F substituent.
6. The method as claimed in claim 1 wherein n is 0.

7. The method as claimed in claim 4 wherein said unsaturated terminal carbon has
no F substituent.
8. The method as claimed in claim 1 wherein each substituent on the unsaturated
terminal carbon is H.
9. The method as claimed in claim 1 wherein n is 1.
10. The method as claimed in claim 1 wherein said fluoroalkene of Formula II
consists essentially of 1,1,1,2-tetrafluoropropene (HFO-1234yf).
11. The method as claimed in claim 1 wherein said fluoroalkene of Formula II
comprises 1,1,1,3-tetrafluoropropene (HFO-1234ze).
12. The method as claimed in claim 1 wherein said fluoroalkene of Formula II
comprises trans 1,1,1,3-tetrafluoropropene (HFO-1234ze).
13. The method as claimed in claim 1 comprising conditioning the air in an
automobile comprising:

(a) providing a vapor compression air conditioning system having at least one
compressor, at least one condenser and a heat transfer fluid in said system, said
heat transfer fluid comprising 1,1,1,2-tetrafluoropropene (HFO-1234y£) in an
amount of from 5 % by weight to 99 % by weight of the heat transfer fluid; and
(b) operating said condenser in a temperature range that includes 150°F.

14. The method as claimed in claim 11 wherein said heat transfer composition
comprises from 5 % by weight to 95 % by weight of 1,1,1.2-tetrafluoropropene
(HFO-1234yf).
15. The method as claimed in claim 13 wherein said lubricant is present in the
composition in an amount of from 30% to 50% by weight of the heat transfer

composition based on the total weight of said lubricant and said compound(s) of
Formula II.
16. The method as claimed in claim 1 wherein said lubricant is selected from the
group consisting of polyol esters, polyalkylene glycols, polyalkylene silicon oils,
mineral oils, alkyl benzenes, poly(alpha-olefins) and combinations of these.
17. The method as claimed in claim 11 wherein said lubricant comprises at least one
polyalkylene glycol.
18. The method as claimed in claim 1 wherein said lubricant comprises polyalkylene
glycol ester.
19. The method as claimed in claim 1 wherein said heat transfer composition has a
Global Warming Potential (GWP) of not greater than 150.
20. The method as claimed in claim 1 wherein said heat transfer composition has a
Global Wanning Potential (GWP) of not greater than 75.
21. The method as claimed in claim 1 wherein said heat transfer composition has an
ozone depletion potential (ODP) of not greater than 0.05.
22. The method as claimed in claim 1 wherein said heat transfer composition has an
ozone depletion potential (ODP) of not greater than 0.02.
23. The method as claimed in claim 1 wherein said heat transfer composition has an
ozone depletion potential (ODP) of not greater than zero
24. The method as claimed in claim 1 wherein said compound of Formula II is
present in the composition in an amount of from 5 % by weight to 95 % by
weight.
25. The method as claimed in claim 1 wherein said compound of Formula II is
present in the composition in an amount of at least 50 % by weight.
26. The method as claimed in claim 1 wherein said compound of Formula II is
present in the composition in an amount of at least 70 % by weight.
27. The method as claimed in claim 1 wherein said heat transfer composition
comprises one or more of the following: difluoromethane (HFC-32);

pentafluoroethane (HFC-125); 1,1,2,2-tetrafluoroethane (HFC-134); 1,1,1,2-
tetrafluoroethane (HFC-134a); difluoroethane (HFC-152a); 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); water; and CO2.
28. The method as claimed in claim 1 wherein said heat transfer composition
comprises a flammability suppressant.
29. The method as claimed in claim 28 wherein said flammability suppressant
comprises CF3I.
30. The method as claimed in claim 1 wherein said lubricant comprises an alkyl
benzene.
31. The method as claimed in claim 1 wherein said lubricant comprises an ester oil.
32. The method as claimed in claim 1 wherein said lubricant comprises a poly(alpha-
olefin) oil.
33. The method as claimed in claim 1 wherein said heat transfer composition has one
liquid phase at at least one temperature between -50°C and +70°C.
34. The method as claimed in claim 1 wherein said heat transfer composition is stable
when in contact with aluminum, steel and copper under the conditions of use in
said air conditioning systems.
35. The method as claimed in claim 1 wherein said automobile air conditioning
system comprises a vapor compression air conditioning system having at least one
compressor and at least one condenser operable in a temperature range that
includes 150°F.
36. The method as claimed in claim 1 wherein said automobile air conditioning
system includes at least one compressor and at least one evaporator, said method
comprising:
(a) utilizing in said system a heat transfer fluid comprising 1,1,1,2-

tetrafluoropropene (HFO-1234yf) in an amount of from 5 % by weight to 99 %
by weight of the heat transfer fluid; and
(b) using said heat transfer fluid to absorb heat from the air in the automobile by
evaporating in said evaporator said heat transfer fluid to produce a vapor
comprising said HFO-1234yf;
(c) compressing at least a portion of said vapor from said step (b) in said at least
one compressor to produce a relatively elevated pressure vapor comprising HFO-
1234yf; and
(d) removing heat from said relatively elevated pressure vapor by condensing said
vapor.

37. The method as claimed in claim 5 wherein said lubricant is selected from the
group consisting of polyol esters, polyalklene glycols, polyalkylene silicon oils,
mineral oils, alkyl benzenes, poly(alpha-olefins) and combinations of these.
38. The method as claimed in claim 5 wherein said at least one lubricant comprises at
least one polyalkylene glycol.
39. The method as claimed in claim 5 wherein said at least one lubricant comprises
polyalkylene glycol ester.
40. The method as claimed in claim 5 wherein said heat transfer fluid has a capacity
relative to HFC-134a of 1 and a Coefficient of Performance (COP) relative to
HFC-134aof 1.
41. The method as claimed in claim 39 wherein said heat transfer composition has
one liquid phase at at least one temperature between -50°C and +70°C and
wherein said heat transfer composition has a capacity relative to HFC-134a of 1
and a Coefficient of Performance (COP) relative to HFC-134a of 1.
42. The method as claimed in claim 41 wherein said fluoroalkene of Formula II
comprises 1,1,1,2-tetrafluoropropene (HFO-1234yf) present in the composition
in an amount of at least 70 % by weight.
43. The method as claimed in claim 40 wherein said heat transfer composition
comprises one or more of the following: difluoromethane (HFC-32);
pentafluoroethane (HFC-125); 1,1,2,2-tetrafluoroethane (HFC-134); 1,1,1,2-

tetrafluoroethane (HFC-134a); difluoroethane (HFC-152a); 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); water; and CO2.
44. The method as claimed in claim 36 wherein said heat transfer fluid comprises at
least one lubricant selected from the group consisting of polyol esters,
polyalkylene glycols, polyalkylene silicon oils, mineral oils, alky] benzenes,
poy(alpha-olefins) and combinations of these.
45. The method as claimed in claim 44 wherein said system comprises a condenser
operated in a temperature range that includes 150°F.
46. The method as claimed in claim 45 wherein said heat transfer fluid has a Global
Warming Potential (GWP) of not greater than 75.
47. The method as claimed in claim 14 wherein said at least one lubricant comprises a
poly alkylene glycol.
48. The method as claimed in claim 47 wherein said heat transfer composition has
one liquid phase at at least one temperature between -50°C and +70°C and
wherein said heat transfer composition has a capacity relative to HFC-134a of 1, a
Coefficient of Performance (COP) relative to HFC-134a of 1 and a Global
Warming Potential (GWP) of not greater than 75.

A method of transferring heat to or from a fluid or body to provide cooling of air in
an automobile, said method comprising:
(a) providing a heat transfer system comprising an automobile air conditioning
system;
(b) providing in said system a heat transfer composition comprising at least one
lubricant such as herein described and at least one fluoroalkene having a
total of at least four fluorine substituents, said fluoroalkene being of
Formula II:

where
R' is (CR2)nY,
Y is CF3
each R is independently For H,
and n is 0 or 1,
provided that there is at least one H on said unsaturated terminal carbon and
wherein said fluoroalkene has no substantial toxicity.

Documents:

02458-kolnp-2006-abstract.pdf

02458-kolnp-2006-asignment.pdf

02458-kolnp-2006-claims.pdf

02458-kolnp-2006-correspondence others.pdf

02458-kolnp-2006-description(complete).pdf

02458-kolnp-2006-drawings.pdf

02458-kolnp-2006-form-1.pdf

02458-kolnp-2006-form-13.pdf

02458-kolnp-2006-form-3.pdf

02458-kolnp-2006-form-5.pdf

02458-kolnp-2006-international publication.pdf

02458-kolnp-2006-international search authority report.pdf

02458-kolnp-2006-pct form.pdf

02458-kolnp-2006-priority document.pdf

2458-KOLNP-2006-ABSTRACT.pdf

2458-KOLNP-2006-AMANDED CLAIMS.pdf

2458-KOLNP-2006-ASSIGNMENT.1.2.pdf

2458-KOLNP-2006-CORRESPONDENCE.1.2.pdf

2458-KOLNP-2006-DESCRIPTION (COMPLETE).pdf

2458-KOLNP-2006-EXAMINATION REPORT REPLY RECIEVED.pdf

2458-KOLNP-2006-EXAMINATION REPORT.1.2.pdf

2458-KOLNP-2006-FORM 1.pdf

2458-KOLNP-2006-FORM 13.1.2.pdf

2458-KOLNP-2006-FORM 13.pdf

2458-KOLNP-2006-FORM 18.1.2.pdf

2458-kolnp-2006-form 18.pdf

2458-KOLNP-2006-FORM 2.pdf

2458-KOLNP-2006-FORM 3.1.2.pdf

2458-KOLNP-2006-FORM 3.pdf

2458-KOLNP-2006-FORM 5.1.2.pdf

2458-KOLNP-2006-GPA.1.2.pdf

2458-KOLNP-2006-GRANTED-ABSTRACT.pdf

2458-KOLNP-2006-GRANTED-CLAIMS.pdf

2458-KOLNP-2006-GRANTED-DESCRIPTION (COMPLETE).pdf

2458-KOLNP-2006-GRANTED-DRAWINGS.pdf

2458-KOLNP-2006-GRANTED-FORM 1.pdf

2458-KOLNP-2006-GRANTED-FORM 2.pdf

2458-KOLNP-2006-GRANTED-SPECIFICATION.pdf

2458-KOLNP-2006-OTHERS.1.2.pdf

2458-kolnp-2006-others.pdf

2458-KOLNP-2006-PETITION UNDER RULR 137.pdf

2458-KOLNP-2006-REPLY TO EXAMINATION REPORT.1.2.pdf

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Patent Number

250569

Indian Patent Application Number

2458/KOLNP/2006

PG Journal Number

02/2012

Publication Date

13-Jan-2012

Grant Date

10-Jan-2012

Date of Filing

29-Aug-2006

Name of Patentee

HONEYWELL INTERNATIONAL, INC.

Applicant Address

101 COLUMBIA ROAD, LAW DEPARTMENT, P.O. BOX 2245, MORRISTOWN, NJ 07962-2245

Inventors:

#	Inventor's Name	Inventor's Address
1	SINGH RAJIV R	18 FOXFIRE DRIVE, GETZVILLE, NY 14068
2	WILSON DAVID P	118 WAXWING COURT, EAST AMHERST, NY 14051
3	THOMAS RAYMOND H	5990 HOPI COURT, PENDLETON, NY 14094
4	PHAM HANG T	136 LARKSPUR LANE, AMHERST, NY 14228

PCT International Classification Number

C09K 5/04

PCT International Application Number

PCT/US2005/014873

PCT International Filing date

2005-04-29

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	10/837,525	2004-04-29	U.S.A.