MX2007016127A

MX2007016127A - Compositions containing fluorine substituted olefins

Info

Publication number: MX2007016127A
Application number: MXMX/A/2007/016127A
Authority: MX
Inventors: T Pham Hang; R Singh Rajiv; P Wilson David; H Thomas Raymond; W Spatz Mark; A Metcalf David
Original assignee: Honeywell International Inc; A Metcalf David; T Pham Hang; R Singh Rajiv; W Spatz Mark; H Thomas Raymond; P Wilson David
Priority date: 2005-06-24
Filing date: 2007-12-17
Publication date: 2008-10-03

Abstract

Various uses of tetrafluoropropenes, particularly (HFO-1234) in a variety of applications, including refrigeration equipment, are 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 REPLACED OLEFINS FIELD OF THE INVENTION This invention relates to compositions, methods and systems that have utility in numerous applications, including particularly heat transfer systems such as refrigeration systems. 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 Fluorocarbon-based fluids have found widespread use in many industrial and commercial applications, including as the working fluid in systems such as air conditioning systems, heat pump and refrigeration, as aerosol propellants, as agents of blowing, as heat transfer media, and as gaseous dielectrics. Due to certain suspect environmental problems, including relatively high global warming potentials, associated with the use of some of the compositions that have hitherto been used in these applications, it has become increasingly desirable to use fluids having a potential of low or even zero ozone removal, such as hydrofluorocarbons ("HFCs"). Thus, the use of fluids not containing chlorofluorocarbons ("CFCs") or hydrochlorofluorocarbons ("HCFCs") is desirable. In addition, some HFC fluids may have associated relatively high global warming potentials, and it is desirable to use hydrofluorocarbons or other fluorinated fluids having as low global warming potentials as possible while maintaining the desired performance in the properties of use. Additionally, the use of single component fluids or azeotrope-like mixtures, which do not substantially fractionate on boiling and evaporation, is desirable in certain circumstances. 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 the 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 single-component fluids or azeotropic mixtures. As suggested above, the concern in recent years 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 (HCFs) and the like) as the working fluid in heat transfer systems, such as in refrigeration and air conditioning systems, has become disadvantaged due to the ozone removal properties associated with many such compounds. Thus, there has been an increasing need for novel compounds and compositions of hydrofluorocarbons and fluorocarbons that are attractive alternatives to the compositions hitherto used in these and other applications. For example, it has become desirable to rebuild 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). The industry in general and the heat transfer industry in particular are continually looking for new mixtures based on fluorocarbons that offer alternatives to, and that are considered environmentally safer substitutes for, CFCs and HCFCs. That is generally considered important, however, at least with With respect to heat transfer fluids, any potential substitute 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 / or 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 for the cooling fluids to 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 efficiency level within a compression cooling, air conditioning and / or heat pump system, the lubricant should be sufficiently soluble in the cooling liquid over a wide temperature range of operation. Such solubility reduces 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 cooling system, air conditioning or heat pump, as well as in other parts of the system, and thus reduce system efficiency. Regarding efficiency in use, it is important to note that a loss in the thermodynamic performance of the refrigerant or in the energy efficiency can have secondary environmental impacts through the increased use of fossil fuel that arises from an increased demand of electrical energy. In addition, it is generally considered desirable that CFC refrigerant substitutes be effective without major design changes to the conventional vapor compression technology currently used with CFC refrigerants. Flammability is another important property for many applications. That is, it is considered either important or essential in many applications, including particularly in heat transfer applications, to use compositions that are non-flammable. Thus, it is often beneficial to use in such compositions, compounds that are non- flammable As used herein, the term "non-flammable" refers to compounds or compositions that are determined to be non-flammable as determined in accordance with the ASTM E-681 standard, dated 2002, which is incorporated herein by 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-1243zf) are each flammable and therefore are not viable for use in many applications. The higher fluoroalkenes, which are alkenes substituted with fluorine 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 fluorinated C5 to C8 compounds having at least some degree of unsaturation. The Smutny patent identifies such higher olefins as known to have utility as refrigerants, pesticides, dielectric fluids, heat transfer fluids, solvents, and intermediates in various chemical reactions. (See column 1, lines 11 - 22). While the fluorinated olefins described in Smutny may have some level of effectiveness in heat transfer applications, it is believed that such compounds also They may 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. In addition, the 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 rise as a result of the pesticidal 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. The bromofluoromethane and bromochlorofluoromethane derivatives, particularly bromotrifluoromethane (Halon 1301) and bromochlorodifluoromethane (Halon 1211) have gained widespread use as fire extinguishing agents in enclosed areas such as aircraft cabins and computer rooms. However, the use of several halons is being phased out due to its high ozone removal. In addition, since halons are frequently used in areas where humans are present, adequate replacements must also be safe for humans at concentrations necessary to suppress or extinguish fire. Applicants have consequently come to appreciate a need for compositions, and particularly heat transfer compositions, extinguishing / fire suppression compositions, blowing agents, solvent compositions, and compatibilizing agents, which are potentially useful in numerous applications, including systems and methods of cooling and heating by vapor compression, avoiding or more of the disadvantages previously noted. BRIEF DESCRIPTION OF THE INVENTION Applicants have found that the need noted above, and other needs, can be met by the compositions, preferably heat transfer compositions, comprising one or more fluoroalkenes C3 to C6, and more preferably one or more fluoroalkenes C3 , C4, or C5, preferably compounds having the Formula I as follows: XCFZR3-Z (I) where X is a C2, C3, C4 or C5 unsaturated, substituted or unsubstituted radical, each R is independently Cl, F, Br , I or H, and z is 1 to 3. In certain preferred embodiments, the fluoroalkene of the present invention has at least four (4) halogen substituents, at least three of which is F and even more preferably none of which is Br In certain preferred embodiments, the compound of formula one comprises a compound, and preferably a compound of three. carbons, in which each unsaturated, non-terminal carbon has a fluorine substituent. For embodiments in which at least one Br substituent is present, it is preferred that the compound does not include hydrogen. In such embodiments it is also generally preferred that the Br substituent be on an unsaturated carbon, and even more preferably the Br substituent be on an unsaturated, non-terminal carbon. A particularly preferred embodiment in this class is CF3CBr = CF2, including all its isomers. In certain embodiments it is highly preferred that the compounds of Formula I comprise propenes, butenes, pentanes and hexanes having from 3 to 5 fluorine substituents, with other substituents being present or not. In certain preferred embodiments, no R is Br, and preferably the unsaturated radical does not contain substituents Br. Among the propenes, tetrafluoropropenes (HFO-1234) and fluorochloropropenes (such as trifluoromonorochloropropenes (HFCO-1233), and even more preferably CF3CC1 = CH2 (HFO-1233xf) and CF3CH = CHC1 (HFO-1233zd)) are especially preferred in certain modalities.

In certain embodiments, pentafluoropropenes are preferred, particularly including those pentafluoropropenes in which there is a hydrogen substituent on the terminal unsaturated carbon, such as CF3CF = CFH (HFO-1225yez and / or yz), particularly because the applicants have discovered that such compounds have a relatively low degree of toxicity compared to at least the compound CF3CH = CF2 (HFO-1225zc). Among the butenes, Fluorochlorobutenes are especially preferred in certain embodiments. The term "HFO-1234" is used herein to refer to all tetrafluoropropenes. Tetrafluoropropenes include 1, 1, 1, 2 -tetrafluoropropene (HFO-1234yf) and both cis- and trans-1,1,1,3-tetrafluoropropene (HFO-1234ze). The term HFO-1234ze is used herein generically to refer to 1,1,1,3-tetrafluoropropene, regardless of whether it is the cis- or trans- form. The terms "cisHFO-1234ze" and "transHFO-1234ze" are used herein to describe the cis- and trans- forms of 1,1,1,3-tetrafluoropropene respectively. The term "HFO-1234ze" accordingly includes within its scope cisHFO-1234ze, transHFO-1234ze, and all combinations and mixtures thereof. The term "HFO-1233" is used herein to refer to all trifluoromonorochloropropenes. Trifluoromonochloropropenes include 1,1,1-trifluoro-2-chloro-propene (HFCO-1233xf), both cis- and trans- 1,1,1-trifluo-3-chloro-propene (HFCO-1233 zd). The term HFCO-1233zd is used here generically to refer to 1, 1, 1-trifluorinated 3-chloro-propene, independent if it is the cis- or trans- form. The terms "cisHFCO-1233zd" and "transHFCO-1233 zd" are used herein to describe the cis- and trans- forms of 1,1,1-trifluo-3-chloro-propene, respectively. The term "HFCO-1233 zd" therefore includes within its scope cisHFCO-1233zd, transHFCO-1233zd, and all combinations and mixtures thereof. The term "HFO-1225" is used herein to refer to all pentafluoropropenes. Among such molecules are 1, 1, 1, 2, 3 -pentafluoropropene (HFO-1225yez), both cis- and trans- forms thereof. The term HFO-1225yez is therefore generically used herein to refer to 1, 1, 1, 2, 3 -pentafluoropropene, whether it is the cis- or trans- form. The term "HFO-1225yez" therefore includes within its scope cisHFO-1225yez, transHFO-1225yez, and all combinations and mixtures thereof. In certain preferred embodiments, the present compositions comprise a combination of two or more compounds of Formula I. In such a preferred embodiment the composition comprises at least one tetrafluoropropene and at least one pentafluoropropene compound, preferably with each compound being present in the composition in a amount of about 20% by weight to about 80% by weight, more preferably about 30% by weight to about 70% by weight, and even more preferably from about 40% by weight to about 60% by weight. In certain such embodiments, the tetrafluoropropene comprises, and preferably consists essentially of HFO-1234 (more preferably HFO-1234yf) and HF01225 (more preferably HFO-1225yez). The present invention also provides methods and systems utilizing the compositions of the present invention, including systems and methods for heat transfer, for reconstructing existing heat transfer equipment, to replace existing heat transfer fluids in a heat transfer system. Existing heat transfer. In certain cases, the present compositions may also be used in connection with foam blowing, solvation, extraction and / or supply of flavor and fragrance, aerosol generation, non-aerosol propellants and as blowing agents. DETAILED DESCRIPTION OF THE PREFERRED MODALITIES THE COMPOSITIONS Preferred embodiments of the present invention are directed to compositions comprising at least one fluoroalkene containing from 3 to 6 carbon atoms, preferably 3 to five carbon atoms, and in certain highly preferred embodiments three carbon atoms, and to the minus 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 are currently not considered to be preferred. For HFOs that also contain at least one chlorine atom, the designation HFCO is sometimes used herein. 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, 1, 2 or 3, preferably 0 or 1, however it is generally preferred that when Br is present in the compound there is no hydrogen in the compound. In certain embodiments, Br is not present in the compound.

In the highly preferred embodiments, Y is CF3, n is 0 or 1 (more preferably 0) and at least one of the remaining Rs is F, and preferably no R is Br or when Br is present, there is no hydrogen in the compound. Applicants believe that, in general, the compounds of Formulas I and II identified above are generally effective and exhibit utility in the heat transfer compositions generally and in the refrigerant compositions particularly. The compositions of the present invention also find use as blowing agent compositions, compatibilizers, aerosols, propellants, fragrances, flavor formulations, solvent compositions and composition of the inflation agent. However, applicants have surprisingly and unexpectedly found that certain of the compounds having a structure according to the formulas described above exhibit a highly 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 compositions that would otherwise contain relatively toxic compounds that satisfy the formulas described above. More particularly, the applicants believe that a relatively low level of toxicity is associated with the compounds of Formula II, preferably wherein Y is CF3, n is 0 or 1, wherein at least one R at the unsaturated terminal carbon is H, and at least one of the Rs remaining is F or Cl. Applicants also believe that all the structural and geometric stereoisomers of such compounds are effective and of beneficially low toxicity. In certain preferred embodiments the compounds of the present invention comprise one or more of which comprises an HFO of C3 or C4, preferably a HFO of C3, and preferably a compound according to Formula I wherein X is a C3 alkylene substituted with halogen and z is 3. In certain such embodiments X is C3 alkylene substituted with fluorine and / or chlorine, with the following C3 alkylene radicals being preferred in certain embodiments: -CH = CF-CH3 -CF = CH-CH3 -CH2-CH = CFH Such modalities therefore comprise the following preferred compounds: CF3-CH = CF-CH3; CF3-CF = CH-CH3; CF3-CH2-CF = CH2; CF3-CH2-CH = CFH; and combinations of these with each other and / or with other compounds according to Formula I In certain preferred embodiments, the compound of the present invention comprises a HFCO C3 or C4, preferably an HFCO C3, and more preferably a compound according to Formula II in which Y is CF3, n is 0, at least one R at the unsaturated terminal carbon is H, and at least one of the remaining Rs is Cl. HFCO-1233 is an example of such a preferred compound. 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, including HFO-1234yf, (cis) HFO-1234ze and (trans) HFO-1234ze, with HFO-1234ze being generally preferred. Although the properties of (cis) HFO-1234ze and (trans) HFO-1234ze differ in at least some respects, it is contemplated that each of these compounds is adaptable for use, either alone or in combination with other compounds including their stereoisomer, in connection with each of the applications, methods and systems described here. For example, (trans) HFO-1234ze may be preferred for use in certain systems due to its relatively low boiling point (-19 ° C), while the (cis) HFO-1234ze, with a boiling point of +9 ° C, may be preferred in other applications. Of course, combinations of the cis- and trans-isomers are likely to be acceptable and / or preferred in many embodiments.

Consequently, it should be understood that the terms "HFO-1234ze" and 1, 3, 3, 3 -tetrafluoropropene refer to both stereoisomers, and that the use of this term is intended to indicate that each of the cis- and trans forms applies and / or is useful for the stated purpose unless otherwise indicated. The HFO-1234 compounds are known materials and are listed in the databases of the Chemical Compendiums. The production of fluoropropenes such as CF3CH = CH2 by the catalytic vapor phase fluorination of various saturated and unsaturated halogen-containing C3 compounds is disclosed in U.S. Patent Nos. 2,889,379; 4,798,818 and 4,465,786, each of which are incorporated herein by reference. EP 974,571, also incorporated herein by reference, describes the preparation of 1,1,1,3-tetrafluoropropene, contacting 1,1,1,3,3-pentafluoropropane (HFC-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, the methods for producing the compounds according to the present invention are described generally in connection with the pending North American Patent Application entitled "Process for Producing Fluorpropenes" which houses the lawyer's reference number (H0003789 (26267)), which is incorporated herein by reference. Other preferred compounds for use in accordance with the present invention include pentafluoropropenes, including all isomers thereof (e.g., HFO-1225), tetra- and penta-fluorobutenes, including all isomers thereof (e.g., HFO- 1354 and HFO-1345). Of course, the present compositions may comprise combinations of any two or more compounds within the broad scope of the invention or within any preferred scope of the invention. It is believed that the present compositions, particularly those comprising HFO-1234 (including HFO-1234ze and HFO-1234yf), possess properties that are advantageous for several important reasons. For example, applicants believe, based at least in part on mathematical modeling, that the fluoroolefins of the present invention will not have a substantial negative affect on atmospheric chemistry, being negligible contributors to the removal of ozone compared to some other halogenated species . The preferred compositions of the present invention therefore have the advantage of not contributing substantially to the removal of ozone. Preferred compositions also do not contribute substantially to the global warming compared to many of the hydrofluoroalkanes currently in use. Of course other compounds and / or components that modulate a particular property of the compositions (such as cost for example) can also be included in the present compositions, and the presence of all such compounds and such components is within the broad scope of the invention. . In certain preferred forms, the 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 (ODP) of not greater than 0.05, more preferably no greater 0.02 and even more preferably approximately zero. As used herein, "ODP" is as defined in "The Scientific Assessment of Ozone Depletion, 2002, A report of the World Meteorological Association 1 s Global Ozone Research and Monitoring Project", which is incorporated herein by reference. The amount of the compounds of Formula I, particularly HFO-1234, and even more preferably HFO-1234yf, contained in the present compositions can vary widely, depending on the particular application, and the compositions containing more than trace amounts and less than 100% of the compound are within the broad scope of the present invention. In addition, the compositions of the present invention can be azeotropic, azeotrope-like or non-azeotropic. In preferred embodiments, the present compositions comprise compounds of Formula I, preferably HFO-1234 and more preferably HFO-1234ze and / or HFO-1234yf, preferably HFO-1234ze and / or HFO-1234yf, in amounts of about 5% by weight to about 99% by weight, and even more preferably from about 5% to about 95%. Many additional compounds or components, including lubricants, stabilizers, metal passivators, corrosion inhibitors, flammability suppressive agents, and other compounds and / or components that modulate a particular property of the Compositions (such as cost for example) can be included in the present compositions, and the presence of all such compounds and such components is within the broad scope of the invention. In certain preferred embodiments, the present compositions include, in addition to the compounds of formula I (including particularly HFO-1234ze and / or HFO-1234yf), one or more of the following: Trichlorofluoromethane (CFC-11) Dichlorodifluoromethane (CFC-12) ) Difluoromethane (HFC-32) Pentafluoroethane (HFC-125) 1,1,2,2 -tetrafluoroethane (HFC-134) 1,1,1- 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 above-noted compounds of the present invention, 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 according to the particular application for the composition, and all such relative amounts are considered to be within the scope thereof. Consequently, Applicants have recognized that certain compositions of the present invention can be used to great advantage in various applications. For example, included in the present invention are methods and compositions that relate to heat transfer applications, blowing agent and foam applications, propellant applications, sprayable composition applications, sterilization applications, aerosol applications , compatibilizer application, fragrance and flavor applications, solvent applications, cleaning applications, inflation agent applications and others. It is believed that those skilled in the art will readily be able to adapt the present compositions for use in any and all such applications without undue experimentation. The present compositions are generally useful as replacements for CFCs, such as dichlorodifluoromethane (CFC-12), HCFCs, such as chlorodifluoromethane (HCFC-22), HFCs, such as tetrafluoroethane (HFC-134a), and combinations of HFCs and CFCs, such as the combination ofCFC-12 and 1,1-difluoroethane (HFC-152a) (the combination CFC-12: HFC-152a in a mass ratio of 73.8: 26.2 which is known as R-500) in refrigerant, aerosol, and other applications Applications. HEAT TRANSFER COMPOSITIONS The compositions of the present invention are generally adaptable for use in heat transfer applications, that is, as a cooling and / or heating medium, including as evaporative cooling agents. In connection with evaporative cooling applications, the compositions of the present invention are contacted, either directly or indirectly, with a body to be cooled and then allowed to evaporate or boil while in such contact, with the preferred result that the boiling gas according to the present composition absorbs the heat of the body to be cooled. In such applications it may be preferred to use the compositions of the present invention, preferably in liquid form, by spraying or otherwise applying the liquid to the body to be cooled. In other evaporative cooling applications, it may be preferred to allow a liquid composition according to the present intention to escape from a relatively high pressure container to a environment of relatively lower pressure wherein the body to be cooled is in contact, either directly or indirectly, with the container enclosing the liquid composition of the present invention, preferably without recovering or re-compressing the escaped gas. A particular application for this type of modality is the cooling of a beverage, food item, novelty element or similar. Prior to the invention described herein, the above compositions, such as HFC-152a and HFC-134a were used for such applications. However, such compositions have recently been viewed negatively in such application due to the negative environmental impact caused by the release of these materials into the atmosphere. For example, the US EPA has determined that the use of such prior chemicals in this application is unacceptable because of the high global warming nature of these chemicals and the resulting detrimental effect on the environment that may result from their use. The compositions of the present invention should have a distinct advantage in this regard due to their low global warming potential and low ozone removal potential, as described herein. Additionally, it is expected that the present compositions also find substantial utility in connection with the cooling of electrical components or electronics, either during manufacturing or during the accelerated life-time test. In an accelerated life-time test, the component is heated and cooled sequentially in rapid succession to simulate the use of the component. Such uses would therefore be of particular advantage in the computer board and semiconductor manufacturing industry. Another advantage of the present compositions in this regard is that they are expected to be exhibited as contagious electrical properties when used in connection with such applications. Another application of evaporative cooling comprises methods for temporarily causing a discontinuation of fluid flow through a conduit. Preferably, such methods would include contacting the conduit, such as a water pipe through which the water flows, with a liquid composition according to the present invention and allowing the liquid composition of the present invention to evaporate while in water. contact with the conduit to freeze the liquid contained therein and thereby temporarily stopping the flow of fluid through the conduit. Such methods have a distinct advantage in connection with providing the service or other work that is to be performed in such conduits, or systems connected to such conduits, at a location downstream from the location at which the conduit is located. applies the present composition. 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 the compound (s) according to the Formula I, more preferably according to Formula II, and even more preferably HFO-1234 (including HFO-1234ze and HFO-1234yf), in an amount that is at least about 50% by weight, and even more preferably at least about 70 % by weight, of the composition. In certain embodiments, it is preferred that the heat transfer compositions of the present invention comprise transHFO-1234ze. In certain preferred embodiments, it is preferred that the heat transfer compositions of the present invention comprise at least about 80%, and even more preferably at least about 90% by weight of HFO-1234, and even more preferably HFO-1234yf and / or HFO-1234ze. The heat transfer compositions of the present invention comprise in certain embodiments a combination of cisHFO-1234ze and transHF01234ze, preferably in a cis: trans weight ratio of from about 1:99 to about 10:99, more preferably about 1: 99 to approximately 5:95, and even more preferably from about 1:99 to about 3: 97. The relative amount of the hydrofluoroolefin used according to the present invention is preferably selected to produce a heat transfer fluid having the required heat transfer capacity, particularly the capacity of cooling, and preferably it is at the same time non-flammable. As used herein, the term "non-flammable" refers to a fluid that is non-flammable in all proportions in air as measured by ASTM E-681. The compositions of the present invention can include other components for the purpose of improving or providing certain functionality to the composition, or in some cases to reduce the cost of the composition. For example, the refrigerant compositions according to the present invention, especially those used in vapor compression systems, include a lubricant, generally in amounts of about 30 to about 50 weight percent of the composition. In addition, the present compositions may also include a co-coolant, or compatibilizer, such as propane, for the purpose of aiding the compatibility and / or solubility of the lubricant. Such compatibilizers, including propane, butanes and pentanes, are preferably present in amounts of from about 0.5 to about 5 weight percent of the composition. Combinations of surfactants and solubilizing agents may also be added to the present compositions to aid oil solubility, as described by US 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), PAG oils, silicone oil, mineral oil, alkyl benzenes (ABs) and poly (alpha-olefin) (PAO) that are used in the refrigeration machinery with hydrofluorocarbon (HFC) refrigerants can be used with the refrigerant compositions of the present invention. Commercially available mineral oils include Witco LP 250 (registered trademark) from Witco, Zerol 300 (registered trademark) from Shrieve Chemical, Sunisco 3GS from Witco, and Calumet R015 from Calumet. Commercially available alkylbenzene lubricants include Zerol 150 (registered trademark). Commercially available esters include neopentyl glycol dipelargonate, which is available as Emery 2917 (registered trademark) and Hatcol 2370 (registered trademark). Other useful esters include phosphate esters, acid esters dibasic, and fluoroesters. In some cases, hydrocarbon-based oils have sufficient solubility with the coolant that is comprised of an iodocarbide, the combination of iodocarbide and hydrocarbon oil may be more stable than other types of lubricants. Such a combination can therefore be advantageous. Preferred lubricants include polyalkylene glycols and esters. Polyalkylene glycols are highly preferred in certain embodiments because they are currently in use in particular applications such as mobile air conditioning. Of course, different mixtures of different types of lubricants can be used. In certain preferred embodiments, the heat transfer composition comprises from about 10% to about 95% by weight of a compound of Formula I, more preferably a compound of Formula II, and even more preferably one or more compounds HFO-1234, and from about 5% to about 90% by weight of an adjuvant, particularly in certain embodiments a co-coolant (such as HFC-152, HFC-125 and / or CF3I). The use of the term co-refrigerant is not intended for use herein in a limiting sense with respect to the relative performance of the compound of the compounds of Formula I, but is used instead of being used to identify other components of the invention.

Coolant composition that generally contributes to the desirable heat transfer characteristics of the composition for a desired application. In certain such embodiments the co-coolant comprises, and preferably consists essentially of, one or more HFCs and / or one or more fluoro-Io C3 compounds, such as trifluoroiodomethane, and combinations of these with each other and with other components. In preferred embodiments in which the co-coolant comprises HFC, preferably HFC 125, the composition comprises HFC in an amount of about 50% by weight to about 95% by weight of the total heat transfer composition, more preferably about 60% by weight. % by weight to about 90% by weight, and even more preferably from about 70% to about 90% by weight of the composition. In such embodiments the compound of the present invention preferably comprises, and still more preferably consists essentially of, HFO-1234, and even more preferably HFO-1234yf and / or HFO-1234ze in an amount of from about 5% by weight to about 50. % by weight of the total heat transfer composition, more preferably from about 10% by weight to about 40% by weight, and even more preferably from about 10% to about 30% by weight of the composition.

In preferred embodiments in which the co-coolant comprises fluorocarbon, preferably CF3I, the composition comprises fluorocarbon in an amount from about 15% by weight to about 50% by weight of the total heat transfer composition, more preferably about 20% by weight to about 40% by weight, and even more preferably from about 25% to about 35% by weight of the composition. In such embodiments the compound of the present invention preferably comprises, and still more preferably consists essentially of, HFO-1234, and even more preferably HFO-1234yf in an amount of about 50% by weight to about 90% by weight of the total composition heat transfer, more preferably from about 60% by weight to about 80% by weight, and even more preferably from about 65% to about 75% by weight of the composition. The present methods, systems and compositions are therefore adaptable for use in connection with a wide variety of heat transfer systems in general and refrigeration systems in particular, such as air conditioning systems (including both systems; of stationary and mobile air), cooling, of heat pumps, and the like. In certain Preferred embodiments, the compositions of the present invention are used in refrigeration systems originally designed for use with an HFC refrigerant, such as, for example, HFC-134a, or an HCFC refrigerant, such as, for example, HCFC-22 . Preferred compositions of the present invention tend to exhibit many of the desirable characteristics of HFC-134a and other HFC refrigerants, including a GWP that is as low, or lower than that of conventional HFC refrigerants and a capacity that is as high or higher. that such refrigerants and a capacity that is substantially similar to or substantially equal, and preferably is as high or greater than such refrigerants. In particular, applicants have recognized that certain preferred embodiments of the present compositions tend to exhibit relatively low global warming potentials ("GWPs"), preferably less than about 1000, more preferably less than about 500, and even more preferably less than about 150. In addition, the relatively constant boiling nature of certain of the present compositions, including the azeotrope-like compositions described in the co-pending patent applications incorporated herein by reference, makes them even more desirable than certain conventional HFCs, such as R - 404A or combinations of HFC-32, HFC-125 and HFC-134a (the combination HFC-32: HFC-125: HFC134a in approximate weight ratio of 23:25:52 is referred to as R-407C), for use as refrigerants in many applications. The heat transfer compositions of the present invention are particularly preferred as replacements for HFC-134, HFC-152a, HFC-22, R-12 and R-500. In certain other preferred embodiments, the present compositions are used in refrigeration systems originally designed for use with a CFC refrigerant. Preferred cooling compositions of the present invention can be used in refrigeration systems containing a lubricant conventionally used with CFC refrigerants, such as mineral oils, polyalkylbenzene, polyalkylene glycol oils, and the like, or can be used with other traditionally used lubricants with HFC refrigerants. As used herein the term "cooling system" generally refers to any system or apparatus, or any part or portion of such a system or apparatus, that employs a refrigerant to provide cooling. Such refrigeration systems include, for example, air conditioners, electric refrigerators, chillers (including chillers using centrifugal compressors), transport refrigeration, commercial refrigeration systems and the like. Many existing refrigeration systems are currently adapted for use 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. Many applications of the compositions of the present invention can provide an advantage as a replacement in smaller systems currently based on certain refrigerants, for example, those that require a small cooling capacity and therefore dictate a need for relatively small displacements of the compressor . In addition, in embodiments where it is desirable to use a cooler composition of lower capacity of the present invention, for efficiency reasons eg to replace a higher capacity coolant, such embodiments of the present compositions provide a potential advantage. Thus, it is preferred in certain embodiments to use compositions of the present invention, particularly compositions comprising a substantial proportion of, and in some embodiments essentially consisting of the present compositions, as a replacement for existing refrigerants, such as: HFC-134a; CFC-12; HCFC-22; HFC-152a; combinations of pentafluoroethane (HFC-125), trifluoroethane (HFC-143a) and tetrafluoroethane (HFC-134a) (the combination HFC-125: HFC-143a: HFC134a in approximate weight ratio of 44: 52: 4 is referred to as R- 404A); the combinations of HFC-32, HFC-125 and HFC-134a (the combination HFC-32: HFC-125: HFC134a in approximate weight ratio of 23:25:52 is referred to as R-407C); the combinations of methylene fluoride (HFC-32) and pentafluoroethane (HFC-125) (the combination HFC-32: HFC-125 in weight ratio of approximately 50:50 is referred to as R-410A); the combination of CFC-12 and 1,1-difluoroethane (HFC-152a) (the combination CFC-12: HFC-152a in a weight ratio of 73.8: 26.2 refers to R-500); and the combinations of HFC-125 and HFC-143a (the combination HFC-125: HFC143a in weight ratio of approximately 50:50 is referred to as R-507A). In certain embodiments it may also be beneficial to use the present compositions in connection with the replacement of refrigerants formed from the combination HFC-32: HFC-125: HFC134a in approximate weight ratio of 20:40:40, which is referred to as R-407A, or in approximate weight ratio of 15:15:70, which is referred to as R-407D. It is also believed that the present compositions are suitable as replacements for the compositions previously noted in other applications, such as aerosols, agents of blown and the like, as explained elsewhere here. 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. Accordingly, the refrigerant compositions of the present invention provide the possibility of achieving a competitive advantage in an energy base for refrigerant replacement applications, including automotive air conditioning systems and devices, commercial refrigeration systems and devices, coolers, freezers and residential refrigerators, general air conditioning systems, heat pumps and the like. Many existing refrigeration systems are currently adapted for use 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 the systems currently based on refrigerants having a relatively high capacity. In addition, in the modalities where it is desirable to use a refrigerant composition of Lower capacity of the present invention, for cost reasons for example, to replace a higher capacity refrigerant, such embodiments of the present compositions provide a potential advantage. Thus, 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, HFO-1234 (preferably HFO-1234ze and / or HFO-1234yf) as a replacement for 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. Accordingly, the refrigerant compositions of the present invention, particularly compositions comprising HFO-1234yf and / or HFO-1234ze (preferably HFO-1234ze), provide the possibility of achieving a competitive advantage in an energy base for replacement applications. of the refrigerant. It is contemplated that the compositions herein, including particularly those comprising HFO-1234yf and / or HFO-1234ze, also have an advantage (either in the original systems or when used as a replacement for refrigerants such as CFC-11, CFC-12, HCFC-22, HFC-134a, HFC-152a, R-500 and R-507A), in coolers typically used in connection with commercial air conditioning systems. In certain such embodiments it is preferred to include in the present compositions, particularly those comprising HFO-1234yf and / or HFO-1234ze, from about 0.5 to about 30% of a supplemental suppressant of flammability, and in certain cases more preferably 0.5% to about 15% by weight and even more preferably from about 0.5 to about 10% on a weight basis. In this regard it is noteworthy that certain of the HFO-1234 and / or HFO-1225 components of the present compositions can, in certain embodiments, act as flammability-suppressing agents with respect to other components in the composition. Thus, components other than HFO-1234 and HFO-1225 which have flammability suppressing agent functionality in the composition will sometimes be referred to herein as a supplemental suppressive agent of flammability. In certain preferred embodiments, the present compositions include, in addition to the compounds of formula I, particularly HFO-1234 (including HFO-1234ze and HFO-1234yf), one or more of the following additional compounds that may be included primarily for their impact on the characteristics of heat transfer, costs and the like. The following components can accordingly be included in the compositions as heat transfer co-fluids (or co-coolants in the case of cooling operations): Trichlorofluoromethane (CFC-11) Dichlorodifluoromethane (CFC-12) 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 BLOWING AGENTS, FOAM AND FOAM COMPOSITIONS The 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 varying amounts. It is generally preferred, however, that for the compositions Preferred for use as blowing agents according to the present invention, the compound (s) according to Formula I, and even more preferably with 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 comprises at least about 50% by weight of the present compositions, and in certain embodiments the blowing agent consists essentially of the present compositions. In certain preferred embodiments, the blowing agent compositions of the present invention include, in addition to HFO-1234 (preferably HFO-1234ze and / or HFO-1234yf) one or more blowing coagents, fillers, vapor pressure modifiers, flame arresting agents, stabilizers and similar adjuvants. By way of example, one or more of the following components may be included in certain preferred blowing agents of the present invention in widely varying amounts: 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 It is contemplated that the blowing agent compositions of the present invention may comprise, preferably in amounts of at least about 15% by weight of the composition, HFO-1234yf, cisHFO-1234ze, transHF01234ze or combinations of two or more of these. In certain preferred embodiments, the blowing agent compositions of the present invention comprise a combination of cisHFO-1234 ze and transHF01234ze in a cis: 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. The foamable compositions of the present invention generally include one or more foamable components having a generally cellular structure and a blowing agent in accordance with the present invention. In certain embodiments, the one or more components comprise a thermosetting composition capable of of foaming and / or foamable compositions. Examples of thermosetting compositions include polyurethane and polyisocyanurate foam compositions, and also phenolic foam compositions. In such thermosetting foam embodiments, one or more of the present compositions are included as either part of a blowing agent in a foamable composition, or as a part of a two or more part foamable composition, which preferably includes one or more of the components capable of reacting and / or foaming under the appropriate conditions to form a foam or cellular structure. In certain other embodiments, the one or more components comprise thermoplastic materials, particularly thermoplastic polymers and / or resins. Examples of thermoplastic foam components include polyolefins, such as polystyrene (PS), polyethylene (PE), polypropylene (PP) and polyethylene terephthalate (PET), and foams formed therefrom, preferably low density foams. In certain embodiments, the thermoplastic foamable composition is a composition that can be extruded. The invention also relates to foams, and preferably to 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 foamable compositions comprising polyolefin or thermoplastic foams, such as foams of polystyrene (PS), polyethylene (PE), polypropylene (PP) and polyethylene terephthalate (PET), preferably low density foams. It will be appreciated by those skilled in the art, especially in view of the description contained herein, that the order and manner in which the blowing agent of the present invention is formed and / or added to the foamable composition generally does not affect the operability of the present invention. For example, in the case of foams that can be extruded, it is possible that several components of the blowing agent, and even the components of the present composition, are not mixed prior to introduction to the extrusion equipment, or even that the components do not are added to the same location on the extrusion equipment. Thus, in certain embodiments it may be desirable to introduce one or more components of the blowing agent into a first location in the extrusion machine, which is upstream of the addition site of one or more other components of the blowing agent, with the expectation that the components will join in the extrusion machine and / or operate more effectively in this way. However, in certain embodiments, two or more components of the blowing agent are combined before and introduced together in the foamable composition, either directly or as part of the premix which is subsequently added further to other parts of the foamable composition. In certain preferred embodiments, dispersing agents, cellular stabilizers, surfactants and other additives may also be incorporated into the blowing agent compositions of the present invention. The surfactants are optionally but preferably aggregated to serve as cellular stabilizers. Some representative materials are sold under the names of DC-193, B-8404, and L-5340 which are, generally, polyoxyalkylene polysiloxane block copolymers such as those described 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-chloropropyl) phosphate, tri (2,3-dibromopropyl) -phosphate, tri (3 ', 3) -dichloropropyl) phosphate, diammonium phosphate, various halogenated aromatic compounds, antimony oxide, aluminum trihydrate, polyvinyl chloride, and the like. 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 iley and Sons, New York, NY, which is incorporated herein by reference, may be used or adapted for use in accordance with the foam embodiments of the present invention. AEROSOL COMPOSITIONS AND PROPELLERS In another aspect, the present invention provides propellant compositions comprising or consisting essentially of a composition of the present invention. In certain preferred embodiments, such propellant composition is preferably a sprayable composition, either alone or in combination with other known propellants. In one aspect, the present compositions can be used to propel objects, including solid and / or liquid objects and / or gaseous objects, by applying to such objects a force generated by the present composition, such as would occur through the expansion of the compositions of the present invention. For example, such force may be preferably provided, at least in part, by the phase change of the compositions of the present invention from liquid to gas, and / or by the force released as a result of a substantial reduction in pressure as the The composition of the present invention leaves a pressurized container. In this way, the compositions of the present invention can be used to apply a force burst, or a sustained force to an object that is going to be propelled. Accordingly, the present invention comprises systems, containers and devices that include the compositions of the present invention and that are configured to propel or move an object, whether a liquid object or a solid object or a gaseous object, with the amount of force desired . Examples of such uses include containers (such as pressurized cans and similar devices) that can be used, through propellant force, to unblock drains, pipes or obstructions in ducts, channels or nozzles. Another application includes the use of the present composition to propel solid objects through the environment, particularly ambient air, such as bullets, pellets, grenades, nets, baskets, grain bags, electrodes or other individual projectiles in captivity or not in captivity. In other embodiments, the present compositions can be used to impart movement, such as a sizzling motion, to gyroscopes, centrifuges, toys or other bodies to be rotated, or to impart a propellant force to solid objects, such as fireworks, confetti, pellets, ammunition and other solid objects. In other applications, the force provided by the compositions of the present invention it can be used to push or direct moving objects, including rockets or other projectiles. The propellant compositions of the present invention preferably comprise a material to be sprayed and a propellant comprising, consisting essentially of, or consisting of a composition according to the present invention. Inert ingredients, solvents, and other materials may also be present in the spray mixture. Preferably, the sprayable composition is an aerosol. Suitable materials to be sprayed include, without limitation, cosmetic materials such as deodorants, perfumes, hair sprays, cleaning solvents, and lubricants, as well as medicinal materials such as anti-asthma medications. The term "medicinal materials" is used herein in its broadest sense to include any and all materials that are, or at least are believed to be, effective in connection with therapeutic treatments, diagnostic methods, pain relief, and similar treatments, and as such would include for example drugs and biologically active substances. The medicinal material in certain preferred embodiments is adapted 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 and / or HFO-1234yf. Aerosol products for industrial, consumer 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. Most of the most commonly used liquefied gas propellants are hydrocarbons such as butane, isobutane, and propane. Dimethyl ether and HFC-152a (1,1-difluoroethane) are also used, either alone or in mixtures with the hydrocarbon propellants. Unfortunately, all these liquefied gas propellants are highly flammable and their incorporation into aerosol formulations will often result in flammable aerosol products. The applicants have come to appreciate the permanent need for non-flammable liquefied gas propellants, with which to formulate the 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 lubricants, spray cleaners, and the like, and in medicinal aerosols, including for example deliver medications to the lungs or mucous membranes. Examples of this include metered dose inhalers (MDIs) for the treatment of asthma and other chronic obstructive pulmonary diseases and for delivery of the drugs to accessible mucous membranes or intranasally. The present invention accordingly includes methods for treating ailments, ailments and similar problems related to the health of an organism (such as a human or animal) comprising applying a composition of the present invention containing a medicament or other therapeutic component to the organism in need for treatment In certain preferred embodiments, the step of applying the present composition comprises providing an MDI containing the composition of the present invention (e.g., introducing the composition into the MDI) and subsequently downloading the present MDI composition. The compositions of the present invention, particularly compositions comprising or consisting essentially of HF0-1234ze, are capable of provide non-flammable liquefied gas aerosols and propellants, which do not contribute substantially to global warming. The present compositions can be used to formulate a variety of industrial aerosols or other sprayable compositions such as contact cleansers, dust covers, lubricant sprays, and the like, and aerosols for consumption 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 sprayable and / or medicinal spray and / or aerosol compositions of the present invention in many applications include, in addition to the compound of formula (I) or (II) (preferably HFO-1234ze), a medicament such as a beta-agonist. , a corticosteroid or other medicine, and, optionally, other ingredients, such as surfactants, solvents, 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 of substantially nonflammable liquefied gas propellants, which have very low Global Warming potentials. SAVORIZERS 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 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 placed in a thick walled glass tube. 1.73 grams of R-1234ze was added to the glass tube. Subsequently, the tube was 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 the favorable use of a carrier for the flavor and fragrance formulations. It also establishes its potential as an extract of biologically active compounds (such as Biomass) and fragrances, including plant material. In certain embodiments, it may be preferred to use the present composition for extraction applications with the present fluid in its supercritical state. This and other applications of involved use of the present compositions in the supercritical or near supercritical state are described hereinafter.

INFLATING AGENTS A potential advantage of the compositions of the present invention is that the preferred compositions are in a gaseous state under most environmental conditions. This feature allows them to fill the space while they are not significantly added to the weight of the space to which they are being poured. In addition, the compositions of the present invention can be compressed or liquefied for relatively easy storage and transportation. Thus, for example, the compositions of the present invention can be included, preferably but not necessarily in liquid form, in a closed container, such as a pressurized can, having a nozzle adapted therein to release the composition in another environment in the which will exist, at least for a period of time, as a pressurized gas. For example, such an application may include containing the present compositions in a can adapted to be connected to the tires such that it can be used in transport vehicles (including cars, trucks and aircraft). Other examples according to this embodiment include the use of the present compositions, in a similar arrangement, for inflating air pockets or other air chambers (including other protective air chambers) adapted to contain, at least for a period of time, a gaseous material under pressure. Alternatively for the use of a fixed container, such as a can, the present compositions may be applied in accordance with this aspect of the invention through a hose or other system containing the present composition, either in liquid or gaseous form, and through from which a pressurized environment may be introduced in such a manner as is required for the particular application. METHODS AND SYSTEMS The compositions of the present invention are useful in connection with numerous systems and methods, including as heat transfer fluids in methods and systems for transferring heat, such as refrigerants used in refrigeration, air conditioning and pump systems. of heat. 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 for extinguishing and suppressing fire 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.

METHODS AND HEAT TRANSFER SYSTEMS Preferred heat transfer methods generally comprise providing a composition of the present invention and causing heat to be transferred to or from the composition, either by sensible heat transfer, heat exchange transfer of phase, or a combination of these. For example, in certain preferred embodiments the present methods provide cooling systems comprising a refrigerant of the present invention and methods for producing heating or cooling by condensing and / or evaporating a composition of the present invention. In certain preferred embodiments, methods for cooling, including cooling of another fluid either directly or indirectly or of a body directly or indirectly, comprises condensing a refrigerant composition comprising a composition of the present invention and subsequently evaporating said refrigerant composition. in the vicinity of the item to be cooled. As used herein, the term "body" is intended to refer not only to inanimate objects but also to living tissue, including animal tissue in general and human tissue in particular. For example, certain aspects of the present invention involve the application of the present composition to human tissue for one or more therapeutic purposes, such as as a pain elimination technique, as a preparative anesthetic, or as part of a therapy that involves reducing the temperature of the body being treated. In certain embodiments, the application to the body comprises providing the present compositions in liquid form under pressure, preferably in a pressurized container having a valve and / or one-way discharge nozzle, and releasing the liquid from the pressurized container by spraying or otherwise. applying the composition to the body. As the liquid evaporates from the sprayed surface, the surface cools. Certain preferred methods for heating a fluid or body comprise condensing a refrigerant composition comprising a composition of the present invention in the vicinity of the fluid or body to be heated and subsequently evaporating said refrigerant composition. In view of the description at this point, those skilled in the art will readily be able to heat and cool articles according to the present inventions without undue experimentation. Applicants have found that in the systems and methods of the present invention many of the important performance parameters of the cooling system are relatively close to the parameters for R-134a. Because many existing refrigeration systems have been designed for R-134a, or for other refrigerants with properties similar to R-134a, those skilled in the art will appreciate the substantial advantage of a low GWP refrigerant and / or low ozone removal that can be used as a replacement for R-134a or similar refrigerants with relatively minimal modifications to the system. It is contemplated that in certain embodiments, the present invention provides reconstruction methods that comprise replacing the heat transfer fluid (such as a refrigerant) in an existing system with a composition of the present invention, without substantial modification of the system. In certain preferred embodiments the replacement step is a drop-by-drop replacement in the sense that no substantial redesign of the system is required and no major element of the equipment needs to be replaced to accommodate the composition of the present invention as the heat transfer fluid. . In certain preferred embodiments, the methods comprise a drop-by-drop replacement in which the capacity of the system is at least about 70%, preferably at least about 85%, and even more preferably at least about 90% of the capacity of the system before the replacement. In certain preferred embodiments, the methods comprise a drop-by-drop replacement in which the suction pressure and / or the discharge pressure of the system, and even more preferably both, is / are at least about 70%, more preferably at least about 90% and even more preferably at least about 95% of the suction pressure and / or discharge pressure before replacement. In certain preferred embodiments, the methods comprise a drop-by-drop replacement in which the mass flow of the system is at least about 80%, and even more preferably at least 90% of the mass flow before replacement. In certain embodiments, the present invention provides cooling by absorbing heat from a fluid or body, preferably evaporating the present coolant 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 similar equipment 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 in such embodiments the present methods include removing from this relatively high temperature high pressure steam at least a portion of the heat added by the evaporation and compression stages. The heat removal step preferably includes condensing the high temperature high pressure steam, while the steam 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 subsequently undergoes a nominally isenthalpic reduction in pressure to produce a relatively low temperature low pressure liquid. In such embodiments, this is the coolant liquid of reduced temperature which is subsequently 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, as mentioned above, are often cycles inverse to the refrigeration cycle described above. FOAM BLOWMET METHODS One embodiment of the present invention relates to methods of forming foams, and preferably polyurethane and polyisocyanurate foams. The usual methods comprise provg a blowing agent composition of the present inventions, adding (directly or indirectly) the composition of the blowing agent to a foamable composition, and reacting the foamable composition under the effective conditions to form a foam or cellular structure, as is known in 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 in 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 polyol or a mixture of polyols, a blowing agent or blowing agent mixture 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 premixed formulations. More typically, the foam formulation is premixed into two components. The isocyanate and optionally certain surfactants and blowing agents they comprise the first component, commonly called the "A" component. The polyol or mixture of polyols, surfactant, catalysts, blowing agents, flame retardant, and other reactive isocyanate components comprise the second component, commonly referred to as component "B". Accordingly, the polyurethane or polyisocyanurate foams are easily prepared by putting together the side components A and B either by manual mixing for small preparations and, preferably, by machine mixing techniques to form blocks, slabs, laminates, pouring panels in the place and other articles, foams applied with spray, foams and the like. Optionally, other ingredients such as fire retardants, colorants, auxiliary blowing agents, and even other polyols can be added as a third stream to the mixing head or reaction site. More preferably, however, all of them are 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 a conventional manner to produce rigid foams. CLEANING METHODS The present invention also provides methods for removing contaminants from a product, part, component, substrate, or any other article or portion thereof by applying to the article a composition of the present invention. For purposes of convenience, the term "article" is used herein to refer to all such products, parts, components, substrates, and the like and is intended to further refer to any surface or portion thereof. In addition, the term "contaminant" is intended to refer to any unwanted material or any substance present on the article, even if such substance is intentionally placed on the article. For example, in the manufacture of semiconductor devices it is common to deposit a photoprotective material on 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 photoresist material. Preferred methods of the present invention comprise applying the present composition to the article. While it is contemplated that numerous and varied cleaning techniques may employ the compositions of the present invention favorably, it is considered particularly advantageous to utilize the present compositions in connection with the supercritical cleaning techniques. Supercritical cleaning is described in US Patent No. 6, 589, 355, which is assigned to the assignee of the present invention and is incorporated herein by reference. For supercritical cleaning applications, it is preferred in certain embodiments to include in the present cleaning compositions, in addition to 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 the particular methods of solvent cleaning and steam degreasing. FLAMMABILITY REDUCTION METHODS According to certain other preferred embodiments, 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 different flammable fluids can be reduced according to the present invention. For example, the flammability associated with fluids such as ethylene oxide, hydrocarbons and flammable hydrofluorocarbons, including: HFC-152a, 1,1,1-trifluoroethane (HFC-143a), difluoromethane (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 can be any fluid that exhibits flammability ranges in air as measured by any standard conventional test 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 according to the present invention. As will be recognized by those of skill in the art, the aggregate amount will depend, at least in part, on the degree to which the target fluid 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. FLAME 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 for contacting the flame with the present composition can be used. For example, a composition of the present invention can be sprayed, poured, and the like on the flame, or at least one portion of the flame can be submerged in the composition. In view of the teachings at this point, those skilled in the art will readily be able to adapt a variety of conventional flame suppression apparatuses and methods for use in the present invention. STERILION METHODS Many articles, devices and materials, particularly for use in the medical field, must be sterilized before being used for health and safety reasons, such as the health and safety of patients and hospital staff. The present invention provides methods of sterilion 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 further preferably HFO-1234ze, in combination with one or more sterilion agents. While many sterilion 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 experts in the In view of the teachings contained herein, the art will be able to easily determine the relative proportions of the sterilizing agent and the present compound (s) to be used in connection with the present compositions and methods of sterilion, and all such ranges are within the broad scope of them. As is known to those skilled in the art, certain sterilion 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 amounts effective, together with other components present in the composition, to reduce the flammability of the sterilion composition to acceptable levels. The sterilion methods of the present invention can be any high or low temperature sterilion of the present invention, which involves the use of a compound or composition of the present invention at a temperature of from about 121.11 ° C (250 ° F) at approximately 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 sterilion.

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 at a temperature of from about room temperature to about 37.77 ° C (100 ° F). The low temperature sterilization of the present invention is preferably at least a two stage process performed in a substantially sealed chamber, preferably air tight. In the first stage (sterilization stage), items having been cleaned and wrapped in gas permeable bags are placed in the chamber. The air is then evacuated from the chamber to attract 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 ranges preferably from about 30% to about 70%. Such humidities can maximize the sterilizing effectiveness of the sterilant that is introduced into the chamber after the desired relative humidity is achieved. After a period of time sufficient for the sterilant to permeate the envelope and reach the interstices of the article, the sterilant and the vapor are evacuated from the chamber.

In the second stage of the preferred process (aeration step), the articles are aerated to remove the waste from the sterilant. 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 subsequently introducing air at atmospheric or higher pressure into the chamber. This cycle is repeated several times until the desired sterilant removal is achieved. Continuous aeration typically involves introducing air through an inlet on one side of the chamber and then extracting it through an outlet on the other side of the chamber by applying a slight vacuum to the outlet. Frequently, the two methods are combined. For example, a common method involves performing air washes and then an aeration cycle. SUPERCRITICAL METHODS It is contemplated that in general many of the uses and methods described herein may be effected with the present compositions in the supercritical or near supercritical state.

For example, the present compositions can be used in solvent and solvent extraction applications mentioned herein, particularly for use in connection with materials such as alkaloids (which are commonly derived from plant sources), for example caffeine, codeine and papaverine , for organometallic materials such as metallocenes, which are generally useful as catalysts, and for fragrances and flavors such as Jasmone. The present compositions, preferably in their supercritical or near supercritical state, can be used in connection with methods involving the deposition of catalysts, particularly organometallic catalysts, on solid supports. In a preferred embodiment, these methods include the step of generating finely divided catalyst particles, preferably by precipitating such catalyst particles of the present compositions in the supercritical or near supercritical state. It is expected that in certain preferred embodiments the catalysts prepared according to the present methods exhibit excellent activity. It is also contemplated that certain of the MDI methods and devices described herein may use drugs in finely divided form, and in such situations it is contemplated that the present invention provides methods that they include the step of incorporating such finely divided medicament particles, such as albuterol, in the present fluids, preferably by dissolving such particles, in the present composition, preferably in the supercritical or near supercritical state. In cases where the solubility of the materials is relatively low when the present fluids are in the supercritical or near supercritical state, it may be preferable to use separating agents such as alcohols. It is also contemplated that the present compositions in the supercritical or near supercritical state can be used to clean circuit boards and other electronic articles and materials. Certain materials may have very limited solubility in the present compositions, particularly when they are in the supercritical or near supercritical state. For such situations, the present compositions can be used as anti-solvents for the precipitation of such solutes of low solubility from the solution in another supercritical or near supercritical solvent, such as carbon dioxide. For example, supercritical carbon dioxide is frequently used in the extrusion process of thermoplastic foams, and the present compositions can used for the precipitation of certain materials contained within them. It is also contemplated that in certain embodiments it may be desirable to use the present compositions when they are in the supercritical or near supercritical state as a blowing agent. 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 measure of universally accepted refrigerant performance, especially useful in representing the relative thermodynamic 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 proportion 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 it provides, and provides some measure of the capacity of a compressor to pump quantities of heat for a given volumetric flow rate of refrigerant. In other words, Given a specific compressor, a coolant with a higher capacity will deliver more cooling or more power calorific. A means to estimate the COP of a refrigerant under specific operating conditions is based on the thermodynamic properties of the refrigerant using standard refrigeration cycle analysis techniques (see for example, R.C. Downing, FLUOROCARBON REFRIGERANTS HANDBOOK, Chapter 3, Prentice-Hall, 1988).

A refrigeration cycle system is provided / air conditioning where the temperature of the The condenser is approximately 65.55 ° C (150 ° F) and the evaporator temperature is approximately -37.22 ° C (-35 ° F) under isentropic compression nominally with a Compressor inlet temperature of approximately 10 ° C (50 ° F). The COP is determined for several compositions of the present invention over a range of temperatures of condenser and evaporator and is reported in Table 1 below, based on HFC-134a which has a COP value of 1. 00, a capacity value of 1.00 and a temperature of discharge of 79.44 ° C (175 ° F). TABLE 1 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 because such result will likely lead to reduced maintenance problems. further, it is evident from the above table that one embodiment of the present invention, namely, one in which the reerant composition comprises, and preferably comprises at least about 70% by weight of HFO-1234yf, has a dramatically superior performance in terms of relative capacity compared not only to R-134a, but also to modes in which the reerant consists essentially of HFO-1234ze. In certain preferred embodiments, therefore, the present invention provides methods for heating or cooling an article or a fluid comprising using a composition comprising at least about 80% by weight of HFO-1234yf, and even more preferably at least about 90% by weight, and in which the capacity of the reeration system is at least about 100%, more preferably at least about 105%, of the capacity of the same system with R-134a used as the reerant.

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 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 are tested, namely, 5, 20 and 50 weight percent lubricant, with the balance of each being the compound of the present invention being tested. Lubricating compositions are placed in thick-walled glass tubes. The tubes are evacuated, the refrigerant compound according to the present invention is added, and the tubes are subsequently sealed. The tubes are then placed in an ambient air bath chamber, the temperature of which is varied from about -50 ° C to 70 ° C. At approximately 10 ° C intervals, visual observations of the contents of the tube are made 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 observed liquid phase, the mixture is miscible. In those cases where two liquid phases are observed, but with one of the liquid phases occupying only a very small volume, the mixture is reported partially miscible. The polyalkylene glycol and ester oil lubricants were considered to be miscible in all the proportions tested over the entire temperature range, except that for mixtures of HFO-1225 and polyalkylene glycol, the mixture of the coolant was found to be immiscible over the temperature range of - 50 ° C to -30 ° C and partially miscible above -20 ° C to 50 ° C. At 50 weight percent concentration of PAG in refrigerant and at 60 °, the PAG / refrigerant mixture was miscible. At 70 ° C, it was miscible from 5 weight percent lubricant in coolant to 50 weight percent lubricant in coolant. EXAMPLE 3 Compatibility of the compounds and compositions of refrigerants of the present invention with PAG lubricating oils while in contact with the metals used in refrigeration and air conditioning systems is tested at 350 ° C, which represent much more severe than those found in many applications of refrigeration and air conditioning. Aluminum, copper and steel samples are added to thick-walled glass tubes. Two grams of oil to the tubes. Subsequently the tubes are evacuated and one gram of refrigerant is added. The tubes are placed in an oven at 176.67 ° C (350 ° F) for one week and visual observations are made. At the end of the exposure period, the tubes are removed. This procedure was carried out for the following combinations of oil and the compound of the present invention: a) HFC-1234ze and GM Goodwrench PAG oil b) HFC1243 zf and oil PAG oil GM Goodwrench c) HFC-1234ze and MOPAR PAG oil -56 d) HFC-1243 zf and PAG oil MOPAR-56 e) HFC-1225 and PAG oil MOPAR-56. In all cases, there is a minimal change in the appearance of the contents of the tube. This indicates that the compounds and refrigerant compositions of the present invention are stable on contact with aluminum, steel and copper found in refrigeration and air conditioning systems, and with the types of lubricating oils that are likely to be included in such compositions. or that will be used with such compositions in these types of systems. COMPARATIVE EXAMPLE Samples of aluminum, copper and steel are added to a tube of thick-walled glass 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 is removed and visual observations made. It is observed that the liquid contents turn black, indicating that there is a severe decomposition of the contents of the tube. So far CFC-12 and mineral oil have been the combination of choice 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 lubricant / coolant combination widely used. EXAMPLE 4 - POLYOL FOAM This example illustrates the use of the blowing agent according to one of the preferred embodiments of the present invention, namely, the use of HFO-1234ze, and the production of polyol foams according to the present invention. invention. The components of a polyol foam formulation are prepared according to the following Table 2: TABLE 2 Component of Polyol PBW (parts by weight) Voranol 490 50 Voranol 391 50 Water 0.5 B-8462 (surfactant) 2.0 Polycat 8 0.3 Polycat 41 3.0 HFO-1234ze 35 Total 140.8 Isocyanate M-20S 123.8 index 1.10 * Voranol 490 is a polyol based in sucrose and Voranol 391 is a polyol based on toluene diamine, and each is available from Dow Chemical. B-8462 is a surfactant available from Degussa-Goldschmidt. Polycat catalysts are based on tertiary amines and are available from Air Products. Isocyanate M-20S is a product of Bayer LLC.

The foam is prepared first by mixing the ingredients of it, but without the addition of the blowing agent. Two Fisher-Porter tubes are each filled with approximately 52. 6 grams of the polyol mixture (without blowing agent) and They are sealed and placed in a refrigerator to cool and form a slight vacuum. Using gas burettes, they are added approximately 17.4 grams of HFO-1234ze to each tube, and The tubes are then placed in an ultrasound bath in hot water and let them sit for 30 minutes. The solution produced is hazy, and a pressure measurement of steam at room temperature indicates a vapor pressure of approximately 4,935 kg / cm2 (70 psig) indicating that the agent Blowing is not in the solution. Subsequently place the tubes in a freezer at -2.77 ° C (27 ° F) for 2 hours. The vapor pressure was measured again and found to be 0.987 kg / cm2 (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 ° C (50 ° F). Subsequently, the polyol tubes are opened and weighed in a metal mixing container (approximately 100 grams of mixed polyol are used). The isocyanate from the cooled metal container is then immediately poured into the polyol and mixed with an air mixer with double helices at 3000 RPM for 10 seconds. The mixture immediately begins to foam with the stirring and is then poured into a 20.32x20.32x10.16 cm (8x8x4 inches) box and allowed to foam. Due to the foam, a creamy consistency formation time can not be measured. The foam has a gel formation time of 4 minutes and a viscosity time of 5 minutes. The foam is then allowed to cure for two days at room temperature. Subsequently the foam is cut into suitable samples to measure the physical properties and is found to have a density of 2.14 pcf. The K factors are measured and found as indicated in the following Table 3: TABLE 3 Temperature K, BTU Inch / Pie2 4.44 ° C (40 ° F) 0.1464 23.89 ° C (75 ° F) 0.1640 43.33 ° C (110 ° F) 0.1808 EXAMPLE 5 - POLYSTYRENE FOAM This example illustrates the use of the blowing agent of according to two preferred embodiments of the present invention, namely, the use of HFO-1234ze and HFO-1234yf, and the production of polystyrene foam. Have settled an apparatus and a test protocol as an aid to Determine if a specific blowing agent and a polymer are capable of producing foam and foam quality.

The ground polymer (Polystyrene Dow 685D) and the agent of Blowing consisting essentially of HFO-1234ze are combined in a recipient. A sketch of the container is illustrated continuation. The volume of the container is 200 cm3 and it is made of two tube flanges and a section of 5.08 cm in diameter of a 10.16 cm long stainless steel tube Schedule 40. The container is placed in an oven, with a fixed temperature of approximately 87.77 ° C (190 ° F) a approximately 140.55 ° C (285 ° F), preferably for the polystyrene at 129.44 ° C (265 ° F), and it stays there until the temperature balance is reached.

The pressure in the container is released then, producing quickly a foamed polymer. The blowing agent plasticizes the polymer while it dissolves in it. The resulting density of the two foams produced in this manner using this method is presented in Table 4 and is plotted in Figure 1 as the density of the foams produced using trans-HFO-1234ze and HFO-1234yf. The data shows that polystyrene foam is obtainable according to the present invention. The stamping temperature for R1234ze with polystyrene is approximately 121.11 ° C (250 ° F). TABLE 4 EXAMPLE 6 This example illustrates the performance of an embodiment of the present invention in which a refrigerant composition comprises HFO-1234 wherein a large proportion, and preferably at least about 75% by weight and even more preferably at least about 90% by weight weight, of HFO-1234 is HF0-1234yf. More particularly, such a composition is used as a replacement for HFC-134a in four z, refrigerant systems. The first system is one having an evaporator temperature (ET) of about -6.66 ° C (20 ° F) and a condenser temperature (CT) of about 54.44 ° C (130 ° F) (Example 6A). For the purposes of convenience, such heat transfer systems, that is, systems having an ET of about 0 to about 35 and a CT of about 26.66 ° C (80 ° F) to about 54.44 ° C (130 ° F) , are referred to here as "medium temperature" systems. The second system is one that has an ET of about -23.33 ° C (-10 ° F) and a CT of about 43.33 ° C (110 ° F) (Example 6B). For purposes of convenience, such heat transfer systems, that is, systems that have an evaporator temperature of about -28.89 ° C (-20 ° F) to about -6.66 ° C (20 ° F) and a CT of approximately 26.66 ° C (80 ° F) to approximately 54.44 ° C (130 ° F), are referred to herein as "refrigerant / freeze" systems. The third system is one that has an ET of approximately 1.66 ° C (35 ° F) and a CT of approximately 65.55 ° C (150 ° F) (Example 6C). For convenience purposes, such heat transfer systems, that is, systems having an evaporator temperature of about -1.11 ° C (30 ° F) to about 15.55 ° C (60 ° F) and a CT of about 32.22 ° C (90 ° F) to approximately 93.33 ° C (200 ° F), are referred to herein as "automotive AC" systems. The fourth system is one that has an ET of approximately 4.44 ° C (40 ° F) and a CT of approximately 15.55 ° C (60 ° F) (Example 6D). For convenience purposes, such heat transfer systems, that is, systems having an evaporator temperature of about 1.66 ° C (35 ° F) to about 10 ° C (50 ° F) and a CT of about 26.66 ° C (80 ° F) at approximately 48.89 ° C (120 ° F), are referred to herein as "cooler" systems or "AC chillers". The operation of each such system using R-134a and a refrigeration composition comprising at least about 90% by weight of HFO-1234yf is reported in Tables 6A-D below: TABLE 6A - Average Temperature Conditions ET 20 ° F and CT 130 ° F * Capacity per CFM of the displacement of the compressor (Volumetric Capacity) TABLE 6B - Refrigerant / Freezing Temperature Conditions ET 10 ° F and CT 110 ° F * Capacity per CFM of the displacement of the compressor (Volumetric Capacity) TABLE 6C - Temperature conditions Auto AC ET 1.67 ° C and CT 65.56 ° C * Capacity per CFM of the displacement of the compressor (Volumetric Capacity) TABLE 6D - Coolant Temperature Conditions ET 40 ° F and CT 95 ° F ^ Capacity per CFM of compressor displacement (Volumetric Capacity) As can be discerned from the above Tables, many of the important performance parameters of the cooling system are relatively close to the parameters for R-134a. Because many existing refrigeration systems have been designed for R-134a, or for other refrigerants with properties similar to R-134a, those skilled in the art will appreciate the substantial advantage of a low GWP refrigerant and / or low-GWP refrigerant. ozone that can be used as a replacement for R-134a or similar refrigerants with relatively minimal modifications to the system. It is contemplated that in certain embodiments, the present invention provides reconstruction methods that comprise replacing the refrigerant in an existing system with a composition of the present invention., preferably a composition comprising at least about 90% by weight and / or consisting essentially of HFO-1234 and even more preferably HFO-1234yf, without substantial modification of the system. In certain preferred embodiments the replacement step is a drop-by-drop replacement in the sense that no substantial redesign of the system is required and no major element of the equipment needs to be replaced to accommodate the refrigerant of the present invention.

Claims

CLAIMS: 1. A composition characterized in that it comprises: (a) at least one fluoroalkene of Formula I: XCF2R3-Z (I) wherein X is a Ci, C2, C3, C4 or C5 unsaturated, substituted or unsubstituted radical, each R is independently Cl, F, Br, I or H, and z is 1 to 3, provided that if Br is present in the compound then the compound does not include hydrogen and further provided that the compound has at least four (4) halogen substituents; and (b) at least one additional component selected from the group consisting of lubricants, stabilizers, metal passivators, corrosion inhibitors, flammability suppressing agents, trichlorofluoromethane (CFC-11), dichlorodifluoromethane (CFC-12), difluoromethane (HFC- 32), pentafluoroethane (HFC-125), 1, 1, 2, 2-tetrafluoroethane (HFC-134), 1,1,1-tetrafluoroethane (HFC-134a), difluoroethane (HFC-152a), 1, 1 , 1, 2, 3, 3, 3 -heptafluoropropane (HFC-227ea), I, 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.
2. A heat transfer fluid, characterized in that it comprises the composition of claim 1.
3. The heat transfer fluid of claim 2, characterized in that it has a Global Warming Potential (GWP) of not greater than about 1000..
The composition of claim 1, characterized in that said at least one fluoroalkene is a compound of Formula II: where each R is independently Cl, F, Br, I or H R 'is (CR2) nY, Y is CRF2 and n is 0 or 1.
5. The composition of claim 4, characterized in that Y is CF3.
6. The composition of claim 5, characterized in that at least one R in the unsaturated terminal carbon is H.
7. The composition of claim 6, characterized in that n is 0.
The composition of claim 4, characterized in that n is 0.
9. The composition of claim 3, characterized in that Y is CF3 and n is 0.
10. The composition of claim 1, characterized in that at least one fluoroalkene comprises at least one tetrafluoropropene (HFO-1234).
The composition of claim 10, characterized in that said at least one tetrafluoropropene is HFO-1234ze.
12. A heat transfer fluid, characterized in that it comprises the composition of claim 1 wherein said composition comprises at least about 50% by weight of the compound (s) according to Formula I.
13. A transfer fluid of heat, characterized in that it comprises the composition of claim 1 wherein said composition comprises at least about 70% by weight of the compound (s) according to Formula I.
14. A heat transfer fluid comprising the composition of the claim 13, characterized in that said compound (s) according to Formula I are selected from the group consisting essentially of HFO-1234ze, HFO-1234yf and combinations thereof.
15. A heat transfer fluid, characterized in that it comprises the composition of claim 14 wherein said compound (s) according to Formula I consist essentially of transHFO-1234ze.
16. A heat transfer fluid, characterized in that it comprises the composition of claim 14 wherein said compound (s) according to Formula I consist essentially of HFO-1234yf.
17. A method for replacing an existing heat transfer fluid contained in the heat transfer system, characterized in that it comprises removing at least a portion of said existing heat transfer fluid from said system, said existing heat transfer fluid. being selected from the group consisting of HFCs, HCFCs, CFCs and combinations thereof; and replacing at least a portion of said existing heat transfer fluid by introducing into said system a heat transfer composition comprising at least one fluoroalkene of Formula I: XCF2R3-Z (I) wherein X is an unsaturated C2 or C3 radical, substituted or unsubstituted, R is independently Cl, F, Br, I or H, and z is 1 to 3.
The method of claim 17, characterized in that said heat transfer composition comprises at least one fluoroalkene of Formula I having a heat transfer capacity of not substantially less than the heat transfer capacity of said existing refrigerant.
19. The method of claim 17, characterized in that said heat transfer composition comprises at least one fluoroalkene of Formula I having a GWP not substantially greater than the GWP of said existing refrigerant.
The method of claim 17, characterized in that said existing heat transfer composition comprises HFC-134a.
The method of claim 17, characterized in that said existing heat transfer composition comprises HCFC-12.
22. The method of claim 17, characterized in that said existing heat transfer composition comprises HFC-22.
23. The method of claim 17, characterized in that said existing heat transfer composition comprises R-404A.
The method of claim 17, characterized in that said existing heat transfer composition comprises R-407C.
25. The method of claim 17, characterized in that said existing heat transfer composition comprises HFC-134.
26. The method of claim 17, characterized in that said existing heat transfer composition. comprises HFC-152a.
27. The method of claim 17, characterized in that said existing heat transfer composition comprises HFC-134.
The method of claim 17, characterized in that said existing heat transfer composition comprises R-500.
29. The method of claim 17, characterized in that said existing heat transfer composition comprises HFC-125.
30. The method of claim 17, characterized in that said existing heat transfer composition comprises HFC-32.
31. The method of claim 17, characterized in that said existing heat transfer composition comprises R-410C.
32. The method of claim 17, characterized in that said existing heat transfer composition comprises R-410A.
33. The method of claim 17, characterized in that said existing heat transfer composition comprises R-507A.
34. The method of claim 17, characterized in that said existing heat transfer composition. comprises R-407A.
35. The method of claim 17, characterized in that said existing heat transfer composition comprises R-407D.
36. The method of claim 17, characterized in that said existing heat transfer system comprises an electric cooler.
37. The method of claim 17, characterized in that said existing heat transfer system is a cooler system comprising at least one centrifugal compressor.
38. The method of claim 17, characterized in that said existing heat transfer system is a transport cooling system.
39. The method of claim 17, characterized in that said replacement step is not associated with any substantial modification of said existing heat transfer system.
40. The method of claim 17, characterized in that said replacement step is not associated with any substantial redesign of said existing heat transfer system.
41. The method of claim 39, characterized in that the capacity of the system after said replacement is at less about 70% of the capacity of the system before replacement.
42. The method of claim 39, characterized in that the capacity of the system after said replacement is at least about 85% of the capacity of the system before replacement.
43. The method of claim 39, characterized in that the capacity of the system after said replacement is at least about 90% of the capacity of the system before replacement.
44. The method of claim 39, characterized in that the suction pressure and / or the discharge pressure of said system after said replacement is at least about 90% of the suction pressure and / or discharge pressure., respectively, before replacement.
45. The method of claim 39, characterized in that the mass flow of said system after said replacement is at least about 80% of the mass flow of said system before replacement.
46. The method of claim 17, characterized in that said existing heat transfer system is a medium temperature system.
47. The method of claim 17, characterized in that said existing heat transfer system is a refrigerant / freezer system.
48. The method of claim 17, characterized in that said existing heat transfer system is an automotive system AC.
49. The method of claim 17, characterized in that said existing heat transfer system is an AC chiller system.
50. A solvent extraction method, characterized in that it comprises extracting the solvent from a material by contacting said material with a compound of formula I in a supercritical or quasi-supercritical state: Formula I: XCF2R3-Z (I) wherein X is a C2 or C3 unsaturated, substituted or unsubstituted radical, R is independently Cl, F, Br, I or H, and z is 1 to 3.
51. The method of claim 50, characterized in that said material comprises at least one alkaloid .
52. The method of claim 51, characterized in that said at least one alkaloid is derived from at least one plant source.
53. The method of claim 52, characterized in that said at least one alkaloid is selected from the group consisting of caffeine, codeine and papaverine.
54. The method of claim 50, characterized in that said material comprises at least one organometallic material.
55. The method of claim 54, characterized in that said organometallic material comprises metallocene.
56. A method for depositing the catalyst on a solid support, characterized in that it comprises precipitating the particles of said catalyst from a compound of formula I in a supercritical or quasi-supercritical state: Formula I: XCF2R3-Z (I) wherein X is a C2 or C3 radical unsaturated, substituted or unsubstituted, R is independently Cl, F, Br, I or H, and z is 1 to 3.