MXPA06009843A - Compositions containing fluorine substituted olefins - Google Patents

Abstract

The use to e of tetrafluoropropenes, particularly (HFO-1234) in a variety of applications, including refrigeration equipment, is disclosed. These materials are generally useful as refrigerants for heating and cooling, as blowing agents, as aerosol propellants, as solvent composition, and as fire extinguishing and suppressing agents.

Description

COMPOSITIONS CONTAINING FLUID-SUBSTITUTED OLEFINS FIELD OF THE INVENTION This invention relates to compositions that have utility in numerous applications, including particularly cooling 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 It has been found that fluorocarbon fluids are widely used in many commercial and industrial applications. For example, fluorocarbon-based fluids are often used as a working fluid in systems such as air conditioning, heat pumps and refrigeration applications. The vapor compression cycle is one of the methods of this type most commonly used to achieve cooling or heating in a refrigeration system. The vapor compression cycle usually involves the phase change of the refrigerant from the liquid phase to vapor through thermal absorption at a relatively high pressure and then vapor to the liquid phase through the extraction of heat at a relatively high pressure and temperature. low, compress the steam at a relatively high pressure, condense the vapor to the liquid phase through the extraction of heat at this relatively high pressure and temperature, and then reduce the pressure to start the cycle once again. While the main purpose of refrigeration is to remove heat from an object or other fluid at a relatively low temperature, the main purpose of the heat pump is to add heat to 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 various applications. For example, fluoroalkanes, such as chlorofluoromethane and chlorofluoroethane derivatives, have gained widespread use as refrigerants in applications including air conditioning and heat pump applications due to their unique combination of chemical and physical properties. Many of the refrigerants commonly used in vapor compression systems are either individual component fluids or azeotropic mixtures. In recent years there has been increasing concern about the potential damage to the atmosphere and climate of the earth, and certain chlorine-based compounds have been identified as particularly problematic in this regard. The use of chlorine-containing compositions (such as chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs) and the like) as refrigerants in air-conditioning and refrigeration systems has become unfavorable due to the properties of the ozone layer depletion associated with many such compounds. Accordingly, there has been a growing need for new compounds and fluorocarbon and hydrofluorocarbon compositions that offer alternatives for refrigeration applications and heat pumps. For example, it has become desirable to improve the chlorine-containing refrigeration systems by replacing the chlorine-containing refrigerants with non-chlorine-containing, non-ozone-depleting refrigerant compounds, such as hydrofluorocarbons (HFCs). It is generally considered important, however, that any potential substitute refrigerant must also possess those properties present in many of the most widely used fluids, such as excellent heat transfer properties, chemical stability, low or no toxicity, non-flammability and lubricant compatibility, among others. Applicants have come to appreciate that lubricant compatibility is of particular importance in many applications. More particularly, it is highly desirable that the cooling fluids be compatible with the lubricant used in the compressor unit, used in most refrigeration systems. Unfortunately, many refrigeration fluids that do not contain chlorine, including HFCs, are relatively insoluble and / or immiscible in the types of lubricants traditionally used with CFCs and HFCs, including, for example, mineral oils, alkylbenzenes or poly (alpha-olefins). ). In order for a combination of cooling fluid-lubricant to work at a desirable level of efficiency within a compression, air conditioning and / or heat pump system, the lubricant must be sufficiently soluble in the cooling liquid above 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 lodge in the evaporator coils of the refrigeration system, air conditioning or heat pump, as well as in other parts of the system, and thus reduce the efficiency of the system. With respect to efficiency in use, it is important to note that a loss in the thermodynamic performance of the refrigerant or energy efficiency, can have environmental, secondary impacts, through the increased use of fossil fuel, originated from a demand each time greater electrical power. ' In addition, it is generally considered desirable that CFC refrigerant substitutes be effective without major engineering changes to conventional vapor compression technology, currently used with CFC refrigerants. Flammability is another important property for many applications. That is, it is considered either important or essential in many applications, including particularly heat transfer applications, for • use compositions, which are non-flammable. Accordingly, it is often beneficial to use in such compositions compounds, which are non-flammable. When used herein, the term "non-flammable" refers to compounds or compositions, which were determined to be non-flammable, as determined in accordance with the ASM standard E-681, dated 2002, which is incorporated herein as a reference. Unfortunately, many HFCs, which might otherwise be desirable for use in the refrigerant compositions, are non-flammable. For example, fluoroalkane difluoroethane (HFC-152a) and fluoroalkene 1,1,1-trifluoropropene (HFO-1234zf) are each flammable and therefore non-viable for use in many applications. The higher fluoroalkenes, ie the fluoro-substituted alkenes having at least five carbon atoms, have been suggested for use as refrigerants. U.S. Patent No. 4,788,352 - Smutny is directed to the production of fluoro compounds with C5 to C8 having at least some degree of unsaturation. The Smutny patent identifies such higher olefins which are 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). Although the fluorinated olefins described in Smutny may have some level of effectiveness in heat transfer applications, it is believed that such compounds may also have certain disadvantages. For example, some of these compounds may tend to attack substrates, particularly plastics of general application such as acrylic resins and ABS resins. In addition, higher olefinic compounds described in Smutny may also be undesirable in certain applications due to the potential level of toxicity of such compounds which may arise as a result of the pesticidal activity mentioned in Smutny. Also, such compounds may have a boiling point, which is too high to make them useful as a refrigerant in certain applications. The derivatives of bromofluoromethane and bromochlorofluoromethane, 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 several halons is being phased out due to its high ozone layer depletion. In addition, since halons are often used in areas where humans are present, adequate replacements must also be safe for humans at concentrations needed to suppress or extinguish fires. Accordingly applicants have come to appreciate the need for compositions, and particularly heat transfer compositions, fire suppression / suppression compositions, blowing agents, solvent compositions, and compatibility agents, which are potentially useful in numerous applications, including systems and methods of heating and cooling by vapor compression, while avoiding one or more of the disadvantages mentioned above.

BRIEF DESCRIPTION OF THE INVENTION Applicants have found that the aforementioned need, and other needs, can be met by compositions comprising one or more fluoroalkenes with C3 or C4, preferably compounds having Formula I as follows: XCFZR3_Z (I) where X is a substituted or unsubstituted radical, unsaturated with C2 or C3, each R is independently Cl, F, Br, I or H, and z is 1 to 3. Extremely preferred among the compounds of Formula I are cis- and trans -isomers of 1,3,3,3-tetrafluoropropene (HFO-1234ze). The present invention also provides methods and systems which use the compositions of the present invention, including methods and systems for heat transfer, foam blowing, solvation or dissolution, extraction and / or supply of flavors and fragrances, and aerosol generation. DETAILED DESCRIPTION OF THE PREFERRED MODALITIES COMPOSITIONS The present invention is directed to compositions comprising at least one fluoroalkene containing 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 convenience purposes 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 are currently not considered to be preferred. As mentioned above, the present compositions comprise one or more compounds according to Formula I. In preferred embodiments, the compositions include compounds of Formula II below: where each R is independently Cl, F, Br, I or HR 'is (CR2) nY, Y is CRF2 and n is 0 or 1. In highly preferred embodiments, Y is CF3, n is 0 and at least one of the remaining Rs is F. Applicants believe that, in general, the compounds of Formulas I and II identified above, are generally effective and exhibit utility in refrigerant compositions, blowing agent compositions, compatibility agents, aerosols, propellants, fragrances, formulations of flavor, and solvent compositions of the present invention. However, applicants have surprisingly and unexpectedly found that some of the compounds having a structure in accordance with the formulas described above, exhibit a very desirable low level of toxicity compared to another such compound. As can be readily appreciated, this discovery is of potentially enormous benefit and benefit for the formulation not only of refrigerant compositions, but also of any and all of the compositions, which could otherwise contain relatively toxic compounds that satisfy the formulas described. previously. More particularly, applicants believe that a relatively low level of toxicity is associated with the compounds of Formula II, preferably wherein Y is CF3, wherein at least one R at the terminal, unsaturated carbon is H, and at least one of the remaining Rs is F. Applicants believe that all structures, geometry and stereoisomers of such compounds are effective and of beneficially low toxicity. In the highly preferred embodiments, especially the 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 tetrafluoropropenes, cis- and trans-1,3,3,3-tetrafluoropropene (HFO-1234ze) are particularly preferred. The term HFO-1234ze is used herein generically to refer to 1,3,3,3-tetrafluoropropene, regardless of whether it is in the cis or trans form. The terms "cisHFO-1234ze" and "transHFO-1234ze" are used herein to describe the cis and trans forms of 1, 3, 3, 3-tetrafluoropropene, respectively. The term "HFO-1234ze" therefore includes within its scope cisHFO-1234ze, transHFO-1234ze, and all combinations and mixtures thereof. Although the properties of cisHFO-1234ze and transHFO-1234ze differ in at least some respects, it is contemplated that each of these compounds be adaptable for use, either alone or together with other compounds that include their 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 due to its relatively low boiling point (-19 ° C), nevertheless it is contemplated that cisHFO-1234ze, with a boiling point of + 9 ° C, also has utility in certain cooling systems of the present invention. Accordingly, it is understood that the terms "HFO-1234ze" and 1,3,3,3-tetrafluoropropene refer to both stereoisomers, and that it is intended that the use of this term indicates that each of the cis and trans applies and / or is useful for the stated purpose unless otherwise indicated. The HFO-1234 compounds are known materials and are listed in the Chemical Abstracts databases. The production of fluoropropenes such as CF3CH = CH2 by catalytic vapor phase fluorination of various halogen-containing saturated and unsaturated C3 compounds is described in US Pat. Nos. 2,889,379; 4,798,818 and 4,465,786, each of which is incorporated by reference. EP 974, 571 also incorporated herein by reference, describes the preparation of 1,1,1,3-tetrafluoropropene by contacting 1,1,1,3,3-pentafluoropropene (HFO-245fa) in the vapor phase with a catalyst based on chromium at elevated temperature, or in the liquid phase with an alcoholic solution of KOH, NaOH, Ca (OH) 2 or Mg (OH) 2. In addition, methods for producing compounds in accordance with the present invention are generally described in connection with the pending U.S. Patent Application, entitled "Process for Producing Fluoropropenes" which bears the attorney's registration number (H0. 003789 (26267)), which is also incorporated herein by reference. It is believed that the present compositions, particularly those comprising HFO-1234ze, possess properties that are advantageous for a number of reasons. For example, applicants believe, based at least in part on a mathematical model, that the fluoroolefins of the present invention will not have a substantial negative effect on atmospheric chemistry, which are insignificant contributors to the depletion of the ozone layer. in comparison with some other halogenated species. The preferred compositions of the present invention therefore have the advantage of not contributing substantially to the depletion of the ozone layer. Preferred compositions also do not contribute substantially to global warming, compared to many of the hydrofluoroalkanes currently in use. In certain preferred forms, the compositions of the present invention have a Global Warming Potential (GWP) not greater than about 1000, more preferably not more than about 500, and still more preferably not more than about 150. In certain embodiments, the GWP of the present compositions is not greater than about 100 and still most preferably no greater than about 75. When used herein, "GWP" is measured relative to that of carbon dioxide and above a 100-year time horizon, as defined in "The Scientific Assessment of Ozone Depletion, 2002, a report of the Global Ozone Monitoring and Research Project of the World Meteorological Association, "which is incorporated herein by reference. In certain preferred forms, the present compositions preferably also have an Ozone Depletion Potential (ODP) of not greater than 0.05, preferably not greater than 0.02 and still more preferably of approximately zero. When used herein, "ODP" is as defined in "The Scientific Assessment of Ozone Depletion, 2002, A Report of the Global Ozone Monitoring and Research Project of the World Meteorological Association", which is incorporated herein as reference.

The amount of the compounds of Formula I, particularly HFO-1234, contained in the present compositions, can vary widely, depending on the particular application, and compositions containing more than trace and less than 100% of the compound, are within the broad scope of the present invention. In addition, the compositions of the present invention may be azeotropic, azeotrope-like or non-azeotropic. In preferred embodiments, the present compositions comprise HFO-1234, preferably HFO-1234ze, in amounts of from about 5% by weight to about 99% by weight, and even more preferably from about 5% to about 95%. Many additional compounds can be included in the present compositions, and the presence of such compounds is within the broad scope of the invention. In certain preferred embodiments, the present compositions include, in addition to HFO-1234ze, one or more of the following: Difluoromethane (HFC-32) Pentafluoroethane (HFC-125) 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 C02 The relative amount of any of the components before mentioned, as well as any additional components that may be included in the present compositions, may vary widely within the broad general scope of the present invention in accordance with the particular application for the composition, and it is considered that all such relative amounts are within the scope of the invention. scope of it. HEAT TRANSFER COMPOSITIONS Although it is contemplated that the compositions of the present invention may include the compounds of the present invention in widely varying amounts, it is generally preferred that the refrigerant compositions of the present invention comprise a compliant composition (s). with Formula I, more preferably in accordance with Formula II, and even more preferably HFO-1234ze, in an amount which is at least about 50% 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 transHFO-1234ze in a cis: trans weight ratio 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 can include other components in order to improve or provide certain functionality to the composition, or in some cases to reduce the cost of the composition. For example, the refrigerant compositions in accordance with the present invention, especially those used in vapor compression systems, include a lubricant, usually in amounts of from about 30 to about 50 percent by weight of the composition. In addition, the present compositions may also include a compatibility agent, such as propane, for the purpose of aiding the compatibility and / or solubility of the lubricant. Such compatibility agents, including propane, butanes and pentanes, are preferably present in amounts of from about 0.5 to about 5 weight percent of the composition. Surface combinations or agents and solubility agents may also be added, as described in US Patent No. 6,516,837, the disclosure of which is incorporated by reference. Commonly used refrigeration lubricants such as Polyol Esters (POEs) and Polyalkylene glycols (PAGs) silicone oil, mineral oil, alkyl benzenes (ABs) and. Poly (alpha-olefin) (PAO) which are used in the refrigeration machinery with hydrofluorocarbon refrigerants (HFC), can be used with the refrigerant compositions of the present invention. Many of the existing refrigeration systems are currently adapted to be used in connection with existing refrigerants, and it is believed that the compositions of the present invention are adaptable, for use in many such systems, either with or without system modification. In many applications the compositions of the present invention can provide an advantage as a replacement in systems, which are currently based on refrigerants having a relatively high capacity. In addition, in embodiments where it is desired to use a low capacity refrigerant composition of the present invention, for cost reasons for example, to replace a high capacity refrigerant, such embodiments of the present compositions provide a potential advantage. Accordingly, it 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 transHF0-1234ze, as a replacement to existing refrigerants, such as HFC-134a. In certain applications, the refrigerants of the present invention potentially allow the beneficial use of large displacement compressors, thereby resulting in better energy efficiency than other refrigerants, such as HFC-134a. Therefore, the refrigerant compositions of the present invention, particularly the compositions comprising transHFO-1234ze, provide the possibility of achieving a competitive advantage in an energy base for refrigerant replacement applications. It is contemplated that the compositions herein, including particularly those comprising HFO-1234ze, also have an advantage (either in original systems or when used as a replacement for refrigerants such as R-12 and R-500), Chillers typically used in connection with commercial air conditioning systems. In certain embodiments it is preferred to include in the present HFO-1234ze compositions from about 0.5 to about 5% of a flammability suppressant, such as CF31. The present methods, systems and compositions are therefore adaptable for use in connection with air conditioning systems and devices, automotive, commercial refrigeration systems and systems, residential chillers, refrigerators and freezers, general air conditioning systems, heat pumps, and similar.

SUGGESTING AGENTS, FOAMS AND COMPOSITIONS THAT CAN FORM FOAMS Blowing agents can 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 varying amounts. However, it is generally preferred that preferred compositions for use as blowing agents in accordance with the present invention, the compound (s) in accordance with Formula 1, and even more preferably Formula II, are present in an amount that is at least about % by weight, and still 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-1234ze) one or more of the following components as co-blowing agent, filler, vapor pressure modifier or for any other purpose: 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-pentafluorobutane (HFC-365mfc) ) water C02 it is contemplated that the blowing agent compositions of the present invention may comprise cisHF0-1234ze, transHFO-1234ze or combinations thereof. In certain preferred embodiments, the blowing agent composition of the present invention comprises a combination of cisHFO-1234ze and transHFO-1234ze in a cis: trans weight ratio 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, and preferably polyurethane, polyisocyanurate 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 molten and expandable composition, which composition preferably includes one or more additional components capable of reacting and / or foaming under appropriate 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 still other embodiments, the invention provides fused and expandable compositions comprising thermoplastic or polyolefin foams, such as polystyrene (PS), polyethylene (PE), polypropylene (PP) and polyethylene-polyethalate (PET) foams, preferably low density foams. . In certain embodiments, dispersing agents, cell stabilizers, surface agents and other additives may also be incorporated into the blowing agent compositions of the present invention. Surface agents can be optionally added but preferably added to serve as cell stabilizers. Some representative materials are sold under the names of DC-193, B-8404, and L-5340 which, generally, are polyoxyalkylene polysiloxane block copolymers such as those described in US Pat. Nos. 2,834,748, 2,917,480, and 2,846,458 , each of which is incorporated as a reference. Other optional additives for the blowing agent mixture may include flame retardants such as tri (2-chloroethyl) phosphate, tri (2-chloropropyl) phosphate, tri (2,3-dibromopropyl) phosphate, tri (1,3-dichloropropyl) phosphate, diammonium phosphate, various aromatic compounds, halogenated, antimony oxide, aluminum trihydrate, polyvinyl chloride, and the like. PROPELLANT AND AEROSOL COMPOSITIONS In another aspect, the present invention provides propellant compositions comprising or consisting essentially of a composition of the present invention, such a propellant composition preferably being a sprayable composition. The propellant compositions of the present invention preferably comprise a material that is sprayed and a propellant comprising, consisting essentially, 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 linting agents as well as medicinal materials such as anti-asthma components, anti-halitosis components and any other medication or the like. , which preferably include any other medication 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 residue 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, personal or medical use typically contain one or more propellants together with one or more active ingredients, inert ingredients or solvents. The propellant provides the force that expels the product in the form of an aerosol. While some aerosol products are propelled with compressed gases such as carbon dioxide, nitrogen, nitrous oxide and even air, most commercial aerosols use liquefied gas propellants. The liquefied gas propellants, most commonly used, are hydrocarbons such as butane, isobutane, and propane. Dimethyl ether and HFC-152a (1,1-difluoroethane) are also used, either alone or in mixtures with the hydrocarbon propellants. Unfortunately, all of these liquefied gas propellants are highly flammable and their incorporation into aerosol formulations frequently results in flammable aerosol products.

Applicants have come to appreciate the continued need for liquefied gas propellants, non-flammable, with which to formulate aerosol products. The present invention provides compositions of the present invention, in particular and preferably compositions comprising HFO-1234, and even more preferably HF0-1234ze, for use in certain industrial aerosol products, including for example aerosol cleaners, lubricants and the like , and in medicinal sprays, which include for example administering medications to the lungs or mucous membranes. Examples of this include metered dose inhalers (MDIs) for the treatment of asthma and other pulmonary, obstructive, chronic conditions and for the delivery of drugs that are accessible to the mucous membranes or intranasally. The present invention therefore includes methods for 'treating food, ailments and similar problems related to the health of an organism (such as a human or animal) which comprises applying a composition of the present invention containing a medicament or other therapeutic component to the organism in need of such treatment. In certain preferred embodiments, the step of applying the present composition comprises providing an MDI containing the composition of the present invention (for example, introducing the composition into the MDI) and then discharging the present composition from the MDI). The compositions of the present invention, particularly compositions comprising or consisting essentially of HF0-1234ze, are capable of providing liquefied, non-flammable gas propellant, and aerosols that do not contribute substantially to global warming. The present compositions can be used to formulate a variety of industrial aerosols or other compositions may be sprayed such as cleaning contact, cloths dust, lubricants aerosols, and the like, and aerosols for the consumer such as personal care products, household products and automotive products. HFO-1234ze is particularly preferred for use as an important component of propellant compositions for medicinal aerosols such as metered dose inhalers. The medicinal and / or propellent and / or sprayable aerosol compositions of the present invention in many applications include, in addition to a compound of the formula (I) or (II) (preferably HF0-1234ze), a medicament such as a beta-agonist, a corticosteroid or another medicament, and, optionally, other ingredients, such as surface agents, solvents and other propellants, flavorings and other excipients. The compositions of the present invention, unlike many compositions previously used in these applications, have good environmental properties and are not considered potential contributors to global warming. The present compositions therefore provide in certain preferred embodiments liquefied gas propellants, substantially non-flammable, which have very low Global Warming potentials. SAVORIZERS AND FRAGRANCES The compositions of the present invention also provide advantages when used as part of, and in particular as a carrier for, flavor formulations and fragrance formulations. The suitability of the present compositions for this purpose is demonstrated by a test procedure in which 0.39 grams of Jasmone was introduced into a thick-walled glass tube. 1.73 grams of R-1234ze were added to the glass tube. The tube was then frozen and sealed. Upon thawing the tube, it was found that the mixture had a liquid phase. The solution contained 20% by weight of Jasóme and 80% by weight of R-1234ze, thus establishing its favorable use as a carrier or part of the supply system for flavor, aerosol and other formulations. It also establishes its potential as a fragrance extractant, which includes plant material.

METHODS AND SYSTEMS The compositions of the present invention are useful in connection with numerous methods and systems, including heat transfer fluids in methods and systems for transferring heat, such as refrigerants used in refrigeration, air conditioning systems and heat pump. The present compositions are also advantageous for use in systems and methods for generating aerosols, which preferably comprise or consist of the aerosol propellant in such systems and methods. Methods for forming foams and methods of extinguishing and suppressing fires are also included in certain aspects of the present invention. The present invention also provides in certain aspects methods for removing waste from articles in which the present compositions are used as solvent compositions in such methods and systems. HEAT TRANSFER METHODS Preferred methods of heat transfer generally comprise providing a composition of the present invention and causing the heat to be transferred to or from the composition that changes the phase of the composition. For example, the present methods provide cooling by absorbing heat from a fluid or article, preferably evaporating the present refrigerant composition in the vicinity of the body or fluid to be cooled to produce steam comprising the present composition. Preferably the methods include the additional step of compressing the refrigerant vapor, usually with a compressor or the like to produce steam of the present composition at a relatively high pressure. Generally, the step of compressing the vapor results in the addition of heat to the vapor, thereby causing an increase in the temperature of the relatively high pressure steam. Preferably, the present methods include removing from this relatively high temperature, high pressure vapor at least a portion of the added heat by evaporation and compression steps. The heat removal step preferably includes condensing the high pressure steam at a high temperature, while the steam is in a relatively high pressure condition to produce a relatively high pressure liquid comprising a composition of the present invention. The relatively high pressure liquid preferably then undergoes a nominally isenthalpic reduction in its pressure to produce a low pressure, relatively low temperature liquid. In such embodiments, this is a refrigerant liquid at reduced temperature which is then vaporized by the heat transferred from the body or fluid to be cooled.

In another embodiment of the process of the invention, the compositions of the invention can 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, which are mentioned above, are often cycles inverse to the refrigeration cycle described above. FOAM STIMATE METHODS One embodiment of the present invention relates to methods for forming foams, and preferably polyurethane and polyisocyanurate foams. The methods generally comprise providing a blowing agent composition of the present invention, adding (directly or indirectly) the blowing agent composition to a foamable composition, and reacting the foamable composition under the effective conditions 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 as a reference, it may be used or adapted to be used in accordance with the foam embodiments of the present invention. In general, such preferred methods comprise preparing polyurethane foams or polyisocyanurates by combining an isocyanate, a polyol or mixture of polyols, a blowing agent or blowing agent mixture comprising one or more of the present compositions, and other materials such as catalysts, surface agents , and optionally, flame retardants, colorants, and other additives. It is convenient in many applications to provide the components for polyurethane or polyisocyanurate foams in pre-mixed formulations. More typically, the foam formulation is pre-mixed into two components. The isocyanate and optionally certain surface agents and blowing agents comprise the first component, commonly referred to as the "A" component. The polyol or polyol mixture, surface agent, catalysts, blowing agents, fire retardants, and other isocyanate reactive components, comprising the second component, are commonly referred to as the "B" component. Accordingly, polyurethane or polyisocyanurate foams are easily prepared by putting together the side components A and B either with manual mixing for small preparations or, preferably, with machine mixing techniques to form blocks, slabs, laminates, poured panels on the site, and other articles, foams applied with spray, foams, and the like. Optionally, other ingredients such as fire retardants, colorants, blowing agents, auxiliaries, and even other polyols can be added as a third stream at the mixing head or reaction site. More preferably, however, they are fully incorporated into a component B as described above. It is also possible to produce thermoplastic foams using the compositions of the invention. For example, conventional polystyrene and polyethylene formulations can be combined with the compositions in conventional manner to produce rigid foams. CLEANING METHODS The present invention also provides methods for removing deposits from a product, part, component, substrate, or any other article or portion thereof by applying a composition of the present invention to the article. For purposes of convenience, the term "article" is used herein to refer to all such products, parts, components, substrates, and the like and is also intended to refer to any surface or portion thereof. In addition, the term "contaminant" is intended to refer to any undesirable material or substance present in the article, even if such substance is intentionally placed in the article. For example, in the manufacture of semiconductor devices it is common to deposit a photoresist material on a substrate to form a mask for the etching operation and to subsequently remove the photo-protective material from the substrate. It is intended that the term "contaminant" when used herein, cover and encompass such photo-protective material. Preferred methods of the present invention comprise applying the present composition to the article. Although it is contemplated that the numerous and various cleaning techniques may employ the compositions of the present invention with good advantage, it is considered particularly advantageous to use the present compositions in connection with supercritical cleaning techniques. Supercritical cleaning is described in U.S. Patent No. 6,589,355, which is assigned to the assignee of the present invention and is incorporated herein by reference. Supercritical cleaning applications are preferred in certain embodiments to include in the present cleaning compositions, in addition to HFO-1234 (preferably HF0-1234ze), one or more additional components, such as C02 and other additional components known for use in connection with supercritical cleaning applications. It is also possible and desirable in certain embodiments to use the present cleaning compositions in connection with vapor degreasing and solvent cleaning methods. METHODS OF REDUCING FLAMMABILITY In accordance with certain other preferred modalities, the present invention provides methods for reducing the flammability of fluids, said methods comprising adding a compound or composition of the present invention to said fluid. The flammability associated with any of a wide range of otherwise flammable fluids can be reduced in accordance with the present invention. For example, the flammability associated with fluids such as ethylene oxide, flammable hydrofluorocarbons and hydrocarbons, including: HFC-152a, 1,1,1-trifluoroethane (HFC-143a), difluoromethane (HFC-32), propane, hexane, octane, and the like, may be reduced in accordance with the present invention. For the purposes of the present invention, a flammable fluid can be any fluid that exhibits flammability ranges in air when measured by any conventional, standard analytical method, such as ASTM E-681, and the like. Any suitable amount of the present compounds or compositions can be added to reduce the flammability of a fluid in accordance with the present invention. As will be recognized by those skilled in the art, the aggregate amount will depend, at least in part, on the degree to which the fluid subjected is flammable and the degree to which it is desired to reduce the flammability thereof. In certain preferred embodiments, the amount of compound or composition added to the flammable fluid is effective to give the resultant substantially non-flammable fluid. FIRE SUPPRESSION METHODS The present invention further provides methods for suppressing a flame, said methods comprising contacting a flame with a fluid comprising a compound or composition of the present invention. Any suitable method can be used to contact the flame with the present composition. For example, a composition of the present invention can be sprayed, poured, etc. onto the flame, or at least a portion of the flame can be immersed in the composition. In view of those taught herein, those skilled in the art will be able to adapt a variety of conventional flame suppression apparatuses and methods for use in the present invention. STERILIZATION METHODS Many items, devices and materials, particularly for use in the medical field, must be sterilized before use for health and safety reasons, such as the health and safety of patients and hospital staff. The present invention provides methods for sterilization, comprising contacting 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 most preferably HF0 -1234ze, in combination with one or more sterilizing agents. While many sterilizing agents are known in the art and are considered adaptable for use in connection with the present invention, in certain preferred embodiments the sterilizing agent comprises ethylene oxide, formaldehyde, hydrogen peroxide, chlorine dioxide, ozone and combinations thereof. . 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 the sterilizing agent and the present compound (s) to be used in connection with the present sterilizing compositions and methods, and all of such ranges are within the broad scope thereof. As is known to those skilled in the art, certain sterilizing agents, such as ethylene oxide, are relatively flammable components, and the compound (s) according to the present invention are included in the present compositions in effective amounts. , 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 can be sterilization at either high or low temperature, of the present invention involves the use of a compound or composition of the present invention at a temperature from about 121.11 ° C (250 ° F) to about 132.22 ° C (270 ° F), preferably in a substantially sealed chamber. The process can usually be completed in less than about 2 hours. However, some items such as plastic articles and electrical components can not withstand such high temperatures and require low temperature sterilization. In low temperature sterilization methods, the article to be sterilized is exposed to a fluid comprising a composition of the present invention at a temperature from about room temperature to about 93.33 ° C (200 ° F), more preferably to a temperature from about room temperature to about 37.78 ° C (100 ° F). The low-temperature sterilization of the present invention is preferably at least a two-step process, performed in a substantially air-tight, substantially sealed chamber. In the first step (the sterilization step), the items that have been cleaned and wrapped in gas permeable bags are placed in the chamber. The air is then evacuated from the chamber by extracting a vacuum and perhaps displacing the air with steam. In certain embodiments, it is preferable to inject steam into the chamber to achieve a relative humidity that preferably ranges from about 30% to about 70%. Such humidities can maximize the sterilizing effectiveness of the sterilizing agent, which is introduced into the chamber after the desired relative humidity is achieved. After a period of time sufficient for the sterilizing agent to permeate the envelope and reach the interstices of the article, the sterilizing agent and the vapor are evacuated from the chamber. In the second preferred step of the process (the aeration step), the articles are aerated to remove residues of the sterilizing agent. Removing such residues is particularly important in the case of toxic sterilizing agents, 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 involves evacuating the chamber for a relatively short period, for example, 12 minutes, and then introducing air at atmospheric pressure or higher into the chamber. This cycle is repeated any number of times until the desired removal of the sterilizing agent is achieved. Continuous aeration typically involves entering the air through an inlet on one side of the chamber and then pulling it out through the outlet on the other side of the chamber by applying a slight vacuum to the outlet. Frequently, the two methodologies are combined. For example, a methodology 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 performance coefficient (COP) is a universally accepted measure of refrigerant performance, especially useful for representing the thermodynamic, relative efficiency of a refrigerant in a specific heating or cooling cycle that involves the evaporation or condensation of the refrigerant. In refrigeration engineering, this term expresses the ratio of useful cooling to the energy applied by the compressor when compressing the vapor. The capacity of a refrigerant represents the amount of cooling or heating that is provided or provides some measure of the capacity of a compressor, for the quantities of the heat pump for a given volumetric flow ratio of the refrigerant. In other words, given a specific compression, a refrigerant with high capacity will supply more cooling or heating power. A means to estimate the COP of a refrigerant under specific operating conditions is from the thermodynamic properties of the refrigerant using standard refrigeration cycle analysis techniques (see, for example, RC Downing, FLUOROCARBON REFRIGERANTS HANDBOOK, Chapter 3, Prentice-Hall , 1988). A system of refrigeration / air conditioning cycles is provided where the temperature of the condenser is. approximately 65.56 ° C (150 ° F) and the evaporator temperature is approximately -37.22 ° C (-35 ° F) under nominally isentropic compression with an inlet temperature of the compressor of approximately 10.00 ° C (50 ° F). The COP is determined for various compositions of the present invention over a range of condenser temperatures and evaporated, and was reported in Table 1 below, based on HFC-134a having a COP value of 1.00, a capacity value of 1.00 and a discharge temperature of 79.44 ° C (175 ° F). TABLE 1 This example shows that certain 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 a result will likely lead to reduced maintenance problems. EXAMPLE 2 The miscibility of HFO-1225ye and HFO-1234ze with various refrigeration lubricants was tested. The lubricants tested are mineral oil (C3), alkyl benzene (Zerol 150), ester oil (Mobil EAL 22 ce and Solest 120), polyalkylene glycol oil (PAG) (Goodwrench Refrigeration Oil for 134a systems), and an oil of poly (alpha-olefin) (CP-6005-100). For each refrigerant / oil combination, three compositions were tested particularly 5, 20 and 50 weight percent lubricant, with the residue of each which is the compound of the present invention being tested. The lubricant compositions were placed in thick-walled glass tubes. The tubes are evacuated, the refrigerant compound according to the present invention is added, and the tubes are then sealed. The tubes are then introduced into an ambient air bath chamber, the temperature of which is varied from about -50 ° C to 70 ° C. At intervals of just 10 ° C, visual observations were made of the contents of the tube for the existence of one or more liquid phases. In a case where more than one liquid phase is observed, the mixture is reported as immiscible. In a case where there was only one observed liquid phase, the mixture was reported as miscible. In those cases where two liquid phases were observed, but with one of the liquid phases occupying only a very small volume, the mixture is reported to be partially miscible. The polyalkylene glycol and ester oil lubricants were considered to be miscible in all the proportions tested above the full temperature range, except that for HFO-1225ye mixtures with polyalkylene glycol, it was found that the refrigerant mixture is immiscible over the temperature range of -50 ° C to -30 ° C and which is partially miscible above -20 to 50 ° C. At a concentration of 50 percent by weight of the PAG in the refrigerant and at 60 °, the refrigerant / PAG mixture was miscible. At 70 ° C, it was miscible - from 5 weight percent of the lubricant in refrigerant to 50 weight percent of the lubricant in refrigerant. EXAMPLE 3 The compatibility of the refrigerant compositions and compositions of the present invention with PAG lubrication oils while in contact with metals used in refrigeration and air conditioning systems was tested at 350 ° C, representing much more severe conditions found in Many applications of refrigeration and air conditioning. Coupons or samples of aluminum, copper and steel are added to the thick-walled glass tubes. Two grams of oil are added to the tubes. The tubes are then evacuated and one gram of refrigerant is added. The tubes were placed in an oven at 350 ° F for one week and visual observations were made. At the end of the exposure period, the tubes are removed.

This procedure was done for the following oil combinations and the compound of the present invention: a) HFO-1234ze and GM Goodwrench PAG oil b) HF01243 zf and GM Goodwrench oil PAG oil c) HFO-1234ze and MOPAR-56 oil PAG d) HFO-1243 zf and MOPAR-56 PAG oil e) HFO-1225 e and MOPAR-56 PAG oil In all cases, there is a minimal change in the appearance of the contents of the tube. This indicates that the refrigerant compositions 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 will be used with such compositions. compositions in these types of systems. COMPARATIVE EXAMPLE Coupons or aluminum samples are added, copper and steel to a thick-walled glass tube with mineral oil and CFC-12 and heated for one week at 350 ° C, as in Example 3. At the end of the exposure period, the tube was removed and made visual observations. It is observed that the liquid contents turn black, indicating that there is severe decomposition of the contents of the tube.

CFC-12 and mineral oil have so far been the preferred combination in many refrigerant systems and methods. Accordingly, the refrigerant compositions and compositions of the present invention possess significantly better stability with many commonly used lubricating oils than the prior art, widely used lubricant-coolant 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, particularly the use of HFO-1234ze, and the production of polyol foams in accordance with the present invention. The components of a polyol foam formulation are prepared according to the following table: Polyol component * Parts by weight Voranol 490 50 Voranol 391 50 Water 0.5 'B-8462 (surface agent) 2.0 Polycat 8 0.3 Polycat 41 3.0 HFO-1234ze 35 Total 140.8 Isocyanate M-20S 123.8 index 1.10 * E1 Voranol 490 is a polyol based on sucrose and Voranol 391 is a polyol based on toluene diamine, and each is from Dow Chemical. B-8462 is a surfactant or surface agent available from Degussa-Goldschmidt. The Polycat catalysts are based on tertiary amine 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. Each of the two Fisher-Porter tubes is filled with approximately 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 burettes, approximately 17.4 grams of HFO-1234ze is added to each tube, and the tubes are then placed in an ultrasonic bath in hot water and allowed to settle for 30 minutes. The solution produced is hazy, a measurement of vapor pressure at room temperature indicates a vapor pressure of about 4,921 kg / cm2 (70 psig), which indicates that the blowing agent is not in the solution. The tubes are then placed in a freezer at -2.78 ° C (27 ° F) for 2 hours. The vapor pressure of new * was measured and found to be 14 psig. The isocyanate mixture, approximately 87.9 grams, is placed in a metal container and placed in a refrigerator and allowed to cool to approximately 10.0 ° C (50 ° F). The polyol tubes are then opened and weighed in a metal mixing container (approximately 100 grams of the polyol mixture are used). The isocyanate from the cooled metal container is then immediately seen in the polyol and mixed with an air mixer with double propellant at 3000 RPM's for 10 seconds. The mixture immediately begins to foam with the agitation and is then placed in a 20.32 x 20.32 x 10.16 cm (8 x 8 x 4 inches) box and allowed to foam. Due to the foam, you can not measure a time in creamy state. The foam has a time in the gel state of 4 minutes and an adhesive-free time of 5 minutes. The foam is then allowed to cure for two days at room temperature. The foam is then cut into suitable samples to measure its physical properties and found to have a density of 2.14 pcf. The K factors are measured and found to be as follows: Temperature K, BTU In. / Pie2 h ° F 40 ° F .1464 75 ° F .1640 110 °. 1808 EXAMPLE 5 - POLYSTYRENE FOAM This example illustrates the use of the blowing agent in accordance with two preferred embodiments of the present invention, particularly the use of HF0- 1234ze and HFO-1234-yf, and the production of polystyrene foam. An analytical and protocol apparatus has been established as an aid to determine if a specific blowing agent and polymer are capable of producing foam and foam quality. The ground polymer (Dow Polystyrene 685D) and blowing agent consisting essentially of HFO-1234ze, they are combined in a container. A sketch of the container is illustrated below. The volume of the container is 200 cm3 and is made of two tube flanges and a stainless steel tube section of 4-inch stainless steel tube of Schedule 40 of 5.08 cm (2 inches) in diameter (see Figure 1). The container is placed in an oven, with temperature setting from approximately 87.78 ° C (190 ° F) to approximately 140.56 ° C (285 ° F), preferably for polystyrene at 129.44 ° C (265 ° F), and remains there until that a balance in the temperature is reached. The pressure in the container is then released, rapidly producing a foamed polymer. The blowing agent plasticizes the polymer when it dissolves therein. The resulting density of the two foams thus produced using this method are given in Table 1 and plotted in Figure 1 as the density of the foams produced using transHFO-1234ze 'and HFO-1234yf. The data shows that polystyrene foam is obtainable in accordance with the present invention. The melt temperature for R1234ze with polystyrene is approximately 121.11 ° C (250 ° F). Table 1

Claims (1)

1. CLAIMS 1.- A heat transfer composition, characterized in that it comprises: (a) at least one fluoroalkene having at least four halogen substituents and no bromine substituent, at least three of said halogen substituents are F, said compound is of Formula I: XCFZR3-Z (I) wherein X is an unsaturated radical, unsubstituted, with C or C3, having at least one fluoro substituent, and each R is independently Cl, F, I or H, yz is 1 to 3, as long as a terminal carbon, unsaturated, is present, then there is not more than one F in the terminal carbon, unsaturated, and also provided that said compound contains four F substituents and has at least one terminal carbon, unsaturated, then there is no F at the terminal, unsaturated carbon. 2. - The heat transfer composition of claim 1, characterized in that it has a Global Warming Potential (GWP) no greater than about 1000. 3. - The heat transfer composition of claim 1, characterized in that said at least a fluoroalkene is a compound of Formula II: wherein each R is independently Cl, F, Br, I or HR 'is (CR2) nY, Y is CRF2 and n is 0 or 1. 4.- The heat transfer composition of claim 3, characterized in that said at least one HFO-1234 comprises HFO-1234yf. 5. The heat transfer composition of claim 2, characterized in that it comprises at least about 50% by weight of said composition of the Formula II. 6. - The heat transfer composition of claim 1, characterized in that it comprises from about 5% to about 99% by weight of HFO-1234yf. 7. - The heat transfer composition of claim 1, characterized in that it comprises from more than about traces to less than about 100% by weight of said composition of Formula I. 8. - The heat transfer composition of claim 7, characterized in that it comprises from about 5% to about 95% by weight of HFO-1234yf. 9. The heat transfer composition of claim 1, characterized in that it further comprises one or more compounds selected from the group consisting of 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), 1,1,3,3-pentafluorobutane (HFC- 365mfc), water, C02 and combinations of two or more of these. 10. The heat transfer composition of claim 1, characterized in that it further comprises one or more lubricants in an amount from about 30 to about 50 weight percent of the heat transfer composition. 11. The heat transfer composition of claim Y, characterized in that it also comprises one or more flame suppressors or reducers. 12. - The heat transfer composition of claim 11, characterized in that said flame suppressor comprises CF3I. 13. - A method for replacing an existing refrigerant, contained in a refrigerant system, characterized in that it removes at least a portion of said existing refrigerant from said system and replaces at least a portion of said existing refrigerant introducing in said system a refrigerant composition comprising at least a fluoroalkene having a total of at least four halogen substituents and no bromine substituent, at least three of said halogen substituents is F, said compound of Formula I: XCFZR3-Z (I) wherein X is an unsaturated radical, not substituted with C2 or C3, which has at least one fluoro substituent, and each R is independently Cl, F, I or H, and z is 3, as long as a terminal carbon, unsaturated, is present, then there is no more than one F in the terminal carbon, unsaturated, and as long as said compound contains four substituents F and has at least one terminal carbon, unsaturated, then there is no F in the terminal carbon, unsaturated 14. The method of claim 15, characterized in that said existing refrigerant comprises HFC-134a. 15. The method of claim 15, characterized in that said existing refrigerant comprises R-12. 16. - The method of claim 15, characterized in that said existing refrigerant comprises R-500. 17. The method of claim 15, characterized in that said existing cooling system is a cooling system used in a commercial air conditioning system. 18. The method of claim 15, characterized in that said existing cooling system is a cooling system used in a residential air conditioning system. 19. The method of claim 15, characterized in that said refrigerant comprises from about 5% to about 95% by weight of HF0-1234ze. 20. The method of claim 15, characterized in that said refrigerant comprises from about 5% to about 95% by weight of HFO-1234yf. 21. A method for transferring heat to or from a fluid or body, characterized in that it comprises contacting the fluid or body with a composition comprising at least one fluoroalkene having a total of at least four halogen substituents and no bromine substituents , at least three of said halogen substituents are F and at least one of said halogen substituent is located on a non-terminal, unsaturated carbon atom, said compound is of Formula I: XCFZR3.Z (I) wherein X is a substituted radical, unsaturated, with C2 or C3, having at least one fluoro substituent, and each R is independently Cl, F, I or H, provided that a terminal, unsaturated carbon is present, then said terminal carbon, unsaturated, has at least one substituent which is not F, and z is 1 to 3. 22. The method of claim 21, characterized in that said composition has a GWP no greater than about 500. 23.- The method of in accordance with claim 21, characterized in that said fluoroalkene of the Formula I comprises HFO-1234yf. 24. The method of claim 21, characterized in that said step of contacting comprises circulating said composition in an air conditioning system for automobiles. 25. The method of claim 21, characterized in that said step of contacting comprises circulating said composition in a commercial refrigeration system. 26. - The method of claim 21, characterized in that said step of contacting comprises circulating said composition in a cooler. 27. The method of claim 21, characterized in that said step of contacting comprises circulating said composition in a residential refrigerator and freezer. 28. The method of claim 21, characterized in that said step of contacting comprises circulating said composition in a heat pump. 29. A foamable or foamable composition, characterized in that it comprises a polymer or prepolymer that can foam, and a blowing agent comprising at least one fluoroalkene of Formula I: XCFZR3.Z (I) where X is a radical unsubstituted or substituted alkyl, unsaturated, with C2 or C3, R is independently Cl, F, Br, I or H, and z is 1 to 3, said blowing agent has a Global Warming Potential (GWP) not greater than about 1000 30. A foam made of the foamable or foamable composition of claim 29. 31.- A foam premix composition, characterized in that it comprises a polymer or a prepolymer and a blowing agent comprising at least one fluoroalkene of Formula I: XCFZR3.Z (I) wherein X is unsubstituted or unsubstituted alkyl radical, with C2 or C3, each R is independently Cl, F, Br, I or H and z is 3, said foam premix It has a Heating Potential or Global (GWP) not greater than about 1000. 32.- The foam premix of claim 31, characterized in that it also comprises a flame suppressor. 33. A composition characterized in that it comprises: (a) at least one fluoroalkene of Formula I: XCFZR3_Z (I) wherein X is an unsaturated, substituted or unsubstituted alkyl radical, with C2 or C3, each R is independently Cl, F , Br, I or H and z is 3; and (b) at least one adjuvant selected from the group consisting of polyol premix components, flavors, fragrances and combinations of two or more of these. 34.- The composition of claim 33, characterized in that it has a Global Warming Potential (GWP) of no greater than about 1000. 35.- A propellant composition characterized in that it comprises at least one fluoroalkene of the Formula I: XCFZR3.Z (I) where X is unsaturated, substituted or unsubstituted alkyl radical, with C2 or C3, R is independently Cl, F, Br, I or H and z is 1 to 3, which has a Global Warming Potential (GWP) of no greater than about 1000. 36.- A method for extracting a vegetable flavor or fragrance compound, characterized in that it comprises contacting said plant material with an extraction agent comprising at least one fluoroalkene of Formula I: XCFZR3-Z (I) wherein X is unsubstituted or unsubstituted alkyl radical, with C2 or C3, R is independently Cl, F, Br, I or H and z is 1 to 3. 37.- The method of claim 55, characterized in that said extraction agent comprises HFO-1234. 38.- A supercritical cleaning method characterized in that it comprises contacting the article to be cleaned with a composition according to claim 1. 39. The supercritical cleaning method of claim 38, characterized in that said composition in accordance with the claim 1, further comprises C02. 40.- A composition characterized in that it comprises: (a) a fluoroalkene having at least 3 halogens (not Br), of Formula I XCFZR3_Z where X is an unsaturated radical, substituted with C2 or C3, and each R is independently Cl , F, I or H and z is 3, provided that said compound has at least one terminal, unsaturated carbon, then there is not more than one F in the terminal carbon, unsaturated, said compound is present in an amount to produce a GWP < 150. 41. A composition characterized in that it comprises: (a) a fluoroalkene having at least 3 halogens (without Br), of Formula 1 XCFZR3_Z where X is an unsaturated radical, substituted with C2 or C3, and each R is independently Cl, F, I or H and z is 3, provided that said compound has at least one terminal, unsaturated carbon, then there is not more than one F in the terminal carbon, unsaturated, said compound is present in an amount to produce an ODP < 0.05. 42. A composition characterized in that it comprises: (a) a fluoroalkene having at least 3 halogens (not Br), of Formula I XCFZR3_Z where X is an unsaturated radical, substituted with C2 or C3, and each R is independently Cl, F, I or H and z is 3, said composition has no acute, substantial toxicity.