Title of Invention

HEAT TRANSFER COMPOSITION FOR AN AIR CONDITIONING SYSTEM

Abstract

The invention discloses a heat transfer composition for use in an air conditioning system comprising: (a) at least about 50% by weight of 1,1,1,2- tetrafluoropropene (HFO-1234yf) having no substantial acute toxicity; and (b) at least one poly alkylene glycol lubricant in the form of a homopolymer or copolymer consisting of 2 or more oxypropylene groups and having a viscosity of from about 10 to about 200 centistokes at about 37°C .

Full Text

HEAT TRANSFER COMPOSITION FOR AN AIR CONDITIONING SYSTEM RELATED APPUCATIONS The present application is related to and claims the priority benefit of U.S. Provisional Application Nos. 60/421.263. and 60/421.435. each of which was filed on October 25. 2002. and each of which is incorporated herein by reference. The present application is also related to and incorporates by reference each of the following concurrently filed United States Patent Applications: Attorney Docket Number H0004412 (26269) entitled "Fluorinated Aikene Refrigerant Composition,' by Raymond Thomas and Attorney Docket Number H0003789 (26267) entitled 'Process For Producing Fluoropropenes, by Hsuch Sung Tung et al. FIELD OF THE INVENTION This invention relates to compositions having utility in nurnerous applications, including particularly refrigeration systems, and to methods and systems which utilize such compositions. In preferred aspects, the present invention is directed to refrigerant compositions which comprise at least one multi-fluortnated olefin of the present invention. BACKGROUND OF THE INVENTION Fluorocarbon based fluids have found widespread use in many commercial and industrial applications. For example, fluorocarbon based fluids are frequently used as a working flud in systems such as air conditioning, heat pump and refrigeration appHcalions. The vapor compression cycle is one of the most commonly used type methods to aocomplish cooGng or heating in a refrigeration system. The vapor compression cycle usually involves the phase change of the refrigerant from the liquid to the vapor phase through heat absorption at a relatively low pressure and then from the vapor to the liquid phase through heat removal at a relatively low pressure and temperature, compressing the vapor to a relatively elevated pressure, condensing the vapor to the liquid phase through heat removal at this relatively elevated pressure and temperature, and then reducing the pressure to start the cyde over again. While the primary purpose of refrigeration is to remove heat from an object or otfier fluid at a relatively low temperabjre, the primary purpose of a heat pump is to add heat at a higher temperature relatfve to the environment. Certain fluorocarbons have t)een a preferred component in many heat exdiange fluids, such as refrigerants, for many years in many appfications. For, example, fluoroalkanes, such as chlOFofluoromethane and chkxofluoroethane derivatives, have gained widespread use as refrigerants in applications including air conditioning and heat pump applications owing to their unique combination of chemical and physical properties. Many of the refrigerants commonly utilized in vapor compression systems are either single components fluids or azeotropic mixUires. Concern has increased in recent years about potential damage to the earth's atmosi^lere and climate, and certain chlorine-based compounds have l)een identifled as particulariy problematic in this regard. The use of chlorine-containing compositions (such as chlorofluorocartx>ns (CFC's), hydrochlorofluoinocarbons (HCFs) arxi the like) as refrigerants in air-conditioning and refrigeration systems has t)ecome disfavored because of the ozone-depleting properties associated with many of such Compounds. There has thus |}een an increasing need for new fluorocart>on and hydrofluorocarbon compounds and compositions that offer alternatives for refrigeration and heat pump applications. For example, it has become desirable to retrofit chlorine-containing refrigeration systems by replacing chlorine-containing refrigerants with non-chtorine-containing refrigerant compounds that will not deplete the ozone layer, such as hydrofluorocartx}ns (HFC's). It is generally considered important, however, that any potential substitute refrigerant must also possess those properties present in many of the most widely used fluids, such as excellent heat transfer properties, chemical stability, low- or no- toxicity, non-flammability and lubricant compatibility, among others. Applicants have come to appreciate that lubricant compatibility is of particular importance in many of applications. More particulariy, it is highly desirably for refrigeration fluids to be compatible with the tubricant utilized in the compressor unit, used in most refrigeration systems. Unfortunately, many non-chlorine-containing refrigeration fluids, including HFC's, are relatively insoluble and/or immiscible in the types of lubricants used traditionally with CFC's and HFCs, including, for example, mineral oils, alkylbenzenes or poly(alpha-ol6fins). In order for a refrigeration fluid- lubricant comlMnation to work at a desirat>ie level of efRdently within a compression refrigeration, air-conditioning and/or heat pump system, the lubricant should be sufndentfy soluble in the refrigeration liquid over a wide range of operating temperatures. Such solubility lowers the viscosity of the lubricant and aHows it to flow more easily ttiroughout the system, in ttie absence of such solubHity, lubricants tend to become lodged in the coils of the evaporator of the refrigeration, air- conditioning or heat pump system, as well as other parts of the system, and thus reduce the system efficiency. With regard to efficiency in use, it is important to note that a loss in refrigerant thermodynamic performance or energy efficiency may have secondary envronmental impacts through increased fossil fuel usage arisirig from an increased demand for electrical energy. Furthermore, it is generally considered desirably for CFC refrigerant substitutes to be effective without major engineering changes to conventional vapor compression technology currently used with CFC refrigerants. Fiammability is another important property for many applications. That is, it is considered either important or essential in many applications, including parb'culariy in heat transfer applications, to use compositions which are rKMvflammable. Thus, it is frequently beneficial to use in such compositions compounds which are nonflammable. As used herein, the term "nonflammable" refers to compounds or compositions which are determined to be nonflammable as determined in accordance with ASTM standard E-681, dated 2002, which is incorporated herein by reference. Unfortunately, many HFC's which might othenvise be desirable for used in refrigerant compositions arie not nonflammable. For example, the fluoroalkane difluoroethane (HFC-152a) and the fluoroalkene 1,1.1-trifluorpropene (HFO-1243zO are each flammable and therefore not viable for use in many appfications. Higher fluoroalkenes, that is fluorine-substituted alkenes having at least five carbon atoms, have been suggested for use as refrigerants. U.S. Patent No. 4,788,352 - Smutny is directed to production of fluorinated Cs to C« compounds having at least some degree of unsaturation. The Smutny patent identifies such higher olefins as being known to have utility as refrigerants, pestiddes, dielectric fluids, heat transfer fluids, solvents, and intennediates in various dnemical reactions. (See column 1, lines 11 - 22). Whfle the fluorinated olefins described in Smutny may have some level of effectiveness in heat transfer applications, it is believed that such compounds may also have certain disadvantages. For example, some of these compourKis may tend to attack substrates, partkxilariy generaH>u(pose plastics such as acryik: resins and ABS resins. Furthermore, the higher olefink; compounds described in Smutny may also be undesirable in certain applk^tions because of the potential level of toxk:ity of such compounds which may arise as a result of pesticide activity noted in Smutny. Also, such compounds may have a t>oiNng point which is too high to make them useful as a refrigerant in certain applk^ations. Bromofkioromethane and t>romochiorofluoromethane derivatives, partk:uiariy bromotrifluoromethane (Halon 1301) and bromochlorodifluoromethane (Hak>n 1211) have gained widespread use as fire extinguishing agents in enclosed areas such as airplane cabins and computer rooms. However, the use of various hatons is being phased out due to their high ozone depletion. Moreover, as halons are frequently used in areas where humans are present, suitable replacements must also be safe to humans at concentrations necessary to suppress or extir)guish fire. Applicants have thus come to appreciate a need for compositions, and particuiariy heat transfer compositions, fire extinguishing/suppression compositions, blowing agents, solvent compositions, and compatabilizing agents, that are potentially useful in numerous applications, irKluding vapor compression heating and cooling systems and methods, while avoiding one or more of the disadvantages noted above. SUMMARY Applicants have found that the at>ove-noted need, and other needs, can be satisfied t}y compositions comprising one or more C3 or C4 fluoroalkenes, preferably compounds having Fomiula I as follows: XCFJRi-z (I) where X is a C2 or a C3 unsaturated, substituted or unsubstituted, alkyi radical, each R is independently a, F, Br, I or H, and z is 1 to 3. The present invention provides also methods and systems which utilize the compositons of the present invention, including methods and systems for heat transfer, foam blowing, soivating, and aerosol generation. DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS THE COMPOSITIONS The present invention is directed to compositions comprising at least one fluoroalkene containing from 3 to 4 carbon atoms and at least one carbon-carbon double iKxid. 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 ttiat the HFOs of the president mentioned mdy contain two cart>on ~ carbon double l)onds. such compounds at the present time are not considered to be preferred. As mentioned atxjve, the present compositions comprise one or compounds in accordance with Formula I. In ^refemed embodiments, the compositions include compounds of Formula 11 below. where each R Is independently CI. F. Br, I or H R' is (CR2)„Y, Y is CRF2 andnisOorl. In highly prftferred embodiments, Y Is CF3. n is 0 and at least one of the remaining Rsis F. Applicants t)elieve that, in general, the compounds of the above identified Fomnuias I and II are generally effective and exhibit utility in refrigerant compositions, blowing agent compositions, compatibflzers, and solvent compositions of the present invention. However, applicants Mive surprisingly and unexpectedly found that certain of the compounds having a staicture in accordance with the formulas described above exhitMt a highly desvabie low level of toxicity compared to other of such compounds. As can be readily appreciated, this discovery is of potentially enormous advantage arid tjenefit for the formulation of not only refrigerant compositions, but also any and all compositions which would othenn/ise contain relatively toxic compounds satisfying the formulas described above. More particulariy, applicants believe that a relatively low toxidty level is associated with compounds of Formula II. preferably wherein Y is CF3. wherein at least one R on the unsaturated tenminal carton is H. and at least one of the remaining Rs is F. Applicants believe also that all structural, geometric and stereoisomers of such compounds are effective and of beneficially low toxicity. In highly preferred embodiments, especially embodiments which comprise the low toxicity compounds descrit}ed above, n is zero. Thus, in certain preferred embodiments the compositions of the present invention comprise one or more compounds selected firom the group consisting of tetrafluoropropenes (HFO-1234), pentafluoropropenes (HFO-1225) and combinations of these. It is even more preferred that the compounds of the present invention are the tetrafluoroprpoene and pentafluoropropene compounds in which the unsaturated terminal carbon has not more tiian one F substituent, specifically: 1, 3, 3, 3- tetrafluoropropene (HFO-1234ze); 2, 3, 3, 3-tetrafluoropropene (HFO-1234yf); and 1,2,3.3,3-pentafluoropropene (HF01225ye), and any and all stereoisomers of each of these. Applicant has discovered that such compounds have a very low acute toxicity level, as measured by inhalation exposure to mice and rats. On the other hand, applicants have found that a relatively high degree of toxicity may be associated with certain compounds adaptable for use with the present compositions, namely, those compounds which have more than one F on the terminal unsaturated carton, or which do not have at least one H on the terminal unsaturated carbon. For example, applicants have discovered that 1,1,3,3,3-pentafluoropropene (HFO- i22Sze> ex^its an unacceptably high degree of toxicity, as measured by inhalation e)q}osure to mice and rats. The prefsn^ compounds of the present invention, namely, HFO-1225 and HFO-1234 are known materials and are listed in Chemical Abstracts databases. {^01225 is commerdaiiy available, from example firom Syntex Chemical Co. Futiiermore, methods are described generatty in the patent literature for producing fluoroatKenes. For example, the production of fluoropropenes such as CF3CH=CH2 by catialytiG vapor phase fiuorination of various saturated and unsaturated halogen- containing C3 compounds is described in U.S. Patent Nos. 2,889,379; 4,798,818 and 4,465,786, each of which is incorporated herein by reference. U.S. Patent No. 5,532,419. which is also incorporated herein by reference, discloses a vapor phase catalytic process for the preparation of fluoroaikene using a chloro- or bromo- haiofluoroGartx>n and HF. EP 974,571, also incorporated herein by reference, discloses the preparation of 1,1,1,3-tetraf)uoroproper)e by contacting 1,1,1,3,3- pentafluoropropane (HFC-245fa) in the vapor phase with a chromium-based catalyst at elevated temperature, or in the liquid phase with an alcoholic solution of KOH, NaOH, Ca(OH)2 or Mg(0H)2. In addition, methods for producing compounds in accordance with the present invention are described generally in connection with concurrently filed United States Patent Application entitled "Process for Producing Fluorpropenes" bearing attorney docket number (H0003789 (26267)), which is also incorporated herein by reference. The present compositions are lielieved to possess properties that are advantageous for a number of important reasons. For example, applicants believe, based at least in part on mathematical modefing. that the fluoroolefins of the present invention wiH not have a substantial negative affect on atmospheric chemistry, being negligible contributors to ozone depletkin in comparison to some other hatogenated species. The preferred compositions of the present invention thus have the advantage of not contributing substantially to ozone depletion. The preferred compositions also do not contribute substantially to global warming compared to many of the hydrofluoroalkanes presently in use. Preferably, the compositions of the present invention have a Global Warming Potential (GWP) of not greater than 150, more preferably not greater than 100 and even more preferably not greater than 75. As used herein, 'GWP" is measured relative to that of carbon dioxide and over a 100 year time horizon, as defined in "The Scientific Assessment of Ozone Depletion, 2002. a report of the World Meteorological Association's Global Ozone Research and Monitoring Project," which is incorporated herein by reference. The present compositions also preferably have an Ozone Depletion Potential (ODP) of fK}t greater than 0.05. more preferat)ly not greater than 0.02 and even more preferably about zero. As used herein, "ODP" is as defined in "The Scientific Assessment of Ozone Depletion. 2002, A report of the Worid Meteorological Assodation's GJdt>al Ozone Research and Monitoring Project," which is incorporated herein by reference. HEAT TRANSFER COMPOSITIONS AMv>ugh it is contemplated that the compositions of the present invention may include the compounds of the present invention in widely ranging amounts, it is generally preferred that refrigerant compositions of the present invention comprise compound(s) in accordance with Formula I, and even more preferably Formula II, in an amount that is at least about 50% by weight, and even more preferably at least about 70 % by weight, of the composition. The compositions of the present invention may Include other components for the purpose of enhancing or providing certain functionality to the composition, or in some cases to reduce the cost of the composition. For example, refrigerant compositions according to ttie present invention, especially ttiose used in vapor compression systems, include a lubricant, generally in amounts of from atxiut 30 to about 50 percent by weight of the composition. Furthermore, ttie present compositions may also include a compatibilzer, such as propane, for the purpose of aiding compatibility and/or solubility of the lubricant Such compatibilizers, including propane, butanes and pentanes, are preferably present in amounts of from about 0.5 to about 5 percent by weight of the composition. Combinations of surfactants and solut>ilizing agents may also be added to the present compositions to aid oil solubility, as disclosed by U.S. Patent No. 6,516,837, the disclosure of which is incorporated by reference. Commonly used refrigeration lubricants such as Polyol Esters (fOEs) and Poly Alkylene Glycols (PAGs) that are used in refrigeration machinery with hydrofluorocartx>n (HFC) refrigerants may be used with the refrigerant compositions of the present invention. BLOWING AGENTS, FOAMS AND FOAMABLE COMPOSITIONS Blowing agents may also comprise or constitute one or more of the present composttions. As mentioned above, the compositions of the present invention may include the compounds of the present invention in widely ranging amounts,. It is generally preferred, however, that for preferred compositions for use as blowing agents in accordance with the present invention, compound(s) in accordance with Formula I, and even more preferably Fonnula II, are present in an amount that is at least at>out 5 % by weight, and even more preferably at least about 15 % by weight, of the composition. In other embodiments, the invention provides foamable compositions, and preferably polyurethane. polyisocyanurate and extruded thermoplastic foam compositions, prepared using the compositions of the present invention. In such foam embodiments, one or more of the present compositions are included as or part of a blowing agent in a foamable composition, which composition preferably includes one or more additional components capable of reacting and/or foaming under the proper conditions to forni a foam or cellular structure, as is weH known in the art. The invention also relates to foam, and preferably closed cell foam, prepared from a polymer foam formulation containing a blowing agent comprising the compositions of the invention. In yet anotiier embodiments, the invention provides a foamable composition comprising thermoplastic foams, such as polystyrene and polyethylene (PE), preferably low density PE. In certain preferred embodiments, dispersing agents, cell stabilizers, surfactants and other additives may also be incorporated into the blowing agent compositions of the present invention. Surfactants are optionally but preferably added to serve as cell stabilizers. Some representative materials are sold under the names of DC-193. B-8404, and L-5340 which are. generally, polysiloxane potyoxyallcylene block co-polymers such as those disclosed in U.S. Patent Nos. 2,834,748. 2,917,480, and 2,846,458, each of which is incorporated herein by reference. Other optional additives for the blowing agent mixture may include flame retardants such as tri(2-chloroethyl)phosphate, tri(2-chloropropyl)phosphate, tri(2,3^ dtbromopropyt)-phosphate, tri(1,3-dichloropropyi) phosphate, diammonium phosphate, various halogenated aromatic compounds, antimony oxide, aluminum trihydrate. polyvinyl chloride, and the like. PROPELLANT COMPOSITIONS in anottier aspect the present inventkm provkled propellant compositkins comprising or consisting essentially of a composition of ttie present invention, such propellant composition preferat}ly being a sprayiabie composition. The propellant compositions of the present invention preferably comprise a material to be sprayed and a propellant comprising, consisting essentially of, or consisting of a composition in accordance with the present inventk>n. inert ingredients, solvents, and other materials may also be present in the sprayable mixture. Preferably, the sprayable composition is an aerosol. Suitable materials to t>e sprayed include, without limitation, cosmetic materials such as deodorants, perfumes, hair sprays, cleansers, and polishing agents as well as medicinal materials such as anti-asthma and anti- halitosis medicatk>ns. METHODS AND SYSTEMS The compositions of the present invention are useful in connection with numerous methods and systems, including as heat transfer fluids in mettiods and systems for transferring heat, such as refrigerants used in refrigeration, air conditioning and heat pump systems. The present compositions are also advantageous for in use in systems and metiiods of generating aerosols, preferably comprising or consisting of the aerosol propellant in such systems and methods. Methods of forming foams and methods of extinguishing and suppressing fire are also included in certain aspects of the present invention. The present invention also provides in certain aspects methods of removing residue from articles in which the present compositions are used as solvent compositions in such methods and systems. HEAT TRANSFER METHODS The preferred heat transfer methods generally comprise providing a composition of the present invention and causing heat to be transfen'ed to or from the composition changing the phase of the composition. For example, the present methods provide cooling by absortM'ng heat from a fluid or article, preferably by evaporating the present refrigerant composition in the vicinity of the t>ody or fluid to be cooled to produce vapor comprising the present composition. Preferably the methods indude the further step of compressing the refrigerant vapor, usually with a compressor or similar equipment to produce vapor of the present composition at a relatively elevated pressure. Generally, ttie step of compressing the vapor results in the addition of heat to the vapor, thus causing an increase in the temperature of the relatively high pressure vapor. Prefenrably, the present methods include removing from this relatively high temperature, high pressure vapor at least a portion of the heat added by the evaporation and compression steps. The heat removal step preferably includes condensing the high temperature, high pressure vapor while the vapor is in a relatively high pressure condition to produce a relatively high pressure liquid comprising a composition of the present invention. This relatively high pressure liquid preferably then undergoes a nominally isoenthalpic reduction in pressure to produce a relatively low temperature, low pressure liquid. In such embodiments, it is this reduced temperature refrigerant liquid which is then vaporized by heat transferred from the body or fluid to be cooled. In another process embodiment of the invention, the compositions of the invention may be used in a method for producing heating which comprises condensing a refrigerant comprising the compositions in the vicinity of a liquid or body to t>e heated.. Such methods, as mentioned hereinbefore, frequently are reverse cycles to the refrigeration cycle described above. FOAM BLOWING METHODS One embodiment of the present invention relates to methods of fonning foams, and preferably polyurethane and polyisocyanurate foams. The methods generally comprise providing a blowing agent composition of the present inventions, adding (Meetly or indirectly) the blowing agent composition to a foamable composition, and reacting the foamable composition under the conditions effective to form a foam or cellular structure, as is weH known in the art Any of the methods well known in the art such as those described in Tdlyurethanes Chemistry and Technoksgy." Volumes I and II. Saunders and Frisch, 1962, John Wiley and Sons, New York, NY, which is incorporated herein by reference, may t>e 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 iso btowing agent or mixture of blowing agents comprising one or more of the present compositions, and other materials such as catalysts, surfactants, and optionally, flame retardants, colorants, or other additives. It is convenient in many applk:ations to provide the components for polyuretiiane or polyisocyanurate foams in pre-blended formulations. Most typically, ttie foam formulation is pre-blended into two components. The isocyanate and optionally certain surfactants and bk>wing agents comprise the first component, comirionly referred to as the "A" component. The polyol or poiyd mixture, surfactant, catalysts, blowing agents, flame retardant. and other isocyanate reactive components comprise the second component, commonly referred to as the "6" component. Accordingly, polyurethane or polyisocyanurate foams are readily prepared by bringing together the A and B side components either by hand mix for small preparations and, preferably, machine mix techniques to fonn blocks, slabs, laminates, pour-in-place panels and other items, spray applied foams, froths, and the like. Optionally, other ingredients such as fire retardants, cokirants, auxiliary blowing agents, and even other poiyols can be added as a third stream to ttie mix head or reaction site. Most preferably, however, they are all incorporated into one B-component as described above. it is also possit}le to produce thermoplastic foams using the compositions of the invention. For example, conventional polystyrene and polyethylene formulations may be combined with the compositions in a conventional manner to produce rigid foams. CLEANING METHODS The present invention also provides methods of removing containments from a product, part, component, substrate, or any other article or portion thereof by applying to the article a (imposition of the present invention. For the purposes of converiience, the term "article" is used herein to refer to all such products, parts, components, substrates, and the like and is further intended to refer to any surface or portion thereof. Furthermore, the term "contaminant" is intended to refer to any unwauited material or substance present on the article, even if such substance is placed on the article intentionally. For example, in the manufacture of semicorKluctor devices K is common to deposit a photoresist material onto a substrate to form a mask for the etching operation and to subsequently remove the photoresist material from the substrate. The term "contaminant" as used herein is intended to cover and encompass such a photo resist material. Preferred methods of the present invention comprise applying the present composition to the article, with vapor degreasing and solvent cleaning methods t>erng partkxiiariy preferred for certain applications, especially those intricate parts and diffkxilt to remove soils. Preferred vapor degreasing and solvent cleaning methods consist of exposing an artk:le, preferably at room-temperature, to the vapors of a t>oiHng solvent. Vapors condensing on the object have the advantage of providing a relatively clean, distilled solvent to wash away grease or other contamination. Such processes thus have an additional advantage in that final evaporation of the present solvent composition from the object leaves behind relatively NtUe residue as compared to the case where the ot)ject is simply washed in liquid solvent. For applications in which the article includes contaminants that are difficult to remove, it is preferred that the present methods involve raising the temperature of the solvent composition of Vne present invention above ambient or to any otiier temperature that is effective in such application to substantially improve the cleaning action of the solvent Such processes are also generally preferred for large volume assembly line operations where the cleaning of the article, particularly metal parts and assemblies, must be done efficiently and quickly. In preferred emtx>diments, the cleaning methods of the present invention comprise immersing the article to be cleaned in liquid solvent at an elevated tempersrture. and even more preferably at about the boiling point of the solvent. In such operations, this step preferably removes a substantial amount, and even more preferdbiy a major portion, of the target contaminant from the article. This step is then preferably followed by immersing the article in solvent, preferably freshly distilled solvent, which is at a temperature below the temperature of the liquid solvent in the preceding immersion step, preferably at atx)ut ambient or room temperature. The preferred methods also include the step of then contacting the article with relatively hot vapor of the present solvent composition. preferat>ly by exposing the article to solvent vapors rising from the hot/boiling solvent assodated with the first mentioned immersion step. This preferably results in condensation of the solvent vapor on the article. In certain preferred embodiments, the article may be sprayed with distitted solvent before final rinsing. It is contemplated that numerous varieties and types of vapor degreasing equipment are adaptable for use in connection with the present methods. One example of such equipment and its operation is disclosed by Sheriiker et al. in U.S. Pat No. 3,085,918, which is incorporated herein by reference. The equipment disdosed in Sheriiker et al includes a boiling sump for containing a solvent composition, a clean sump for containing distilled solvent, a water separator, and other ancillary equipment. The present cleaning methods may also comprise cold cleaning in whk;h the contaminated article is either immersed in the fluid composition of the present invention under ambient or room temperature conditions or wiped under such conditions with rags or similar objects soaked in solvents. 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 otherwise flammable fluids may be reduced according to the present invention. For example, Oie flammabiiity associated with fluids such as ethylene oxide, flammable hydrofluorocarbons and hydrocaibons, including: HFC-152a, 1.1.1-trifluoroethane (HFC-143a), difluoromeDiane (HFC-32), propane, hexane, octane, and the like can be reduced according to the present invention. For the purposes of the present invention, a flammable fluid may t>e any fluid exhibiting flammabiiity ranges in air as measured via any standaMI eonventionai test method, such as ASTM E-681, and ttie like. Any suitable amounts of the present compounds or compositions may be added to reduce flammabiiity of a fluid according to the present invention. As will be recognized by tttose of skill in ttie art the amount added will depend, at least in part on the degree to whk:h the subject fluid is flammable and the degree to which it is desired to reduce the flammat}iiity tiiereof. In certain preferred embodiments, the amount of compound or composition added to the flammable fluid is effective to render the resutting fluid substantially norvflammable. FLAME SUPPRESSION METHODS The present invention further provides methods of suppressing a flame, said methods comprisirig contacting a flame witii a fluid comprising a compound or composition of tiie present invention. Any suitable methods for contacting the flame with the present composition may be used. For example, a composition of the present invention may be sprayed, poured, and the like onto the flame, or at least a portion of the flame may be immersed in the composition. In light of the teachings herein, tiiose of skill in tiie art will be readily able to adapt a variety of conventional apparatus and methods of flame suppression for use in the present invention. STERiUZATION METHODS Many articles, devices and materials, particularly for use In tiie medical field, must be sterilized prior to use for tiie health and safety reasons, such as tiie health and safety of patients and hospital staff. The present invention provides methods of stenHzing comprising contacting the articies, devices or material to be sterilized with a compound or composition of the present invention. Such methods may be either high or lowMemperature sterilization met)ods. In certain embodiments, high- temperature sterilization comprises exposing the articles, device or material to be stsf^eed to a hot fluid comprising a con^xMind or composition of the present inventim at a temperature of from about 25(yF to about 270'F. preferably in a subj^antiafly sealed chamber. The process can be completed usually in less than stoout 2 hours. However, some articies, such as plastic articles and electrical components, cannot withstand such high temperatures and require low-temperature steriisation. Low-temperature sterilization of the present invention involves tfie use of a compound or oNTiposition of the present invention at a temperature of from about 100 to about 200 "F. The compounds of the present invention may be combined wiVn otiier common chemical sterilants, including, for example, etiiytene oxide (EO), formaldehyde, hydrogen peroxide, chlorine dioxide, and ozone to form a sterilant composition of the present invention. The low^temperature sterilization of tiie present invention is preferably at least a two-step process performed in a substantially sealed, preferably air tight, chamber, in the first step (ttie sterilization step), the articles having been cleaned and wrapped in gas pemneable bags are placed in Vne chamber. Air is ttien evacuated from the chamber by puUing a vacuum and periiaps by displacing the air with steam. In certain embodiments, it is preferable to Inject steam Into ttie chamber to achieve a relative humidity tttat ranges preferably from about 30% to afcwut 70%. Such humidities may maximize ttie sterilizing effectiveness of the sterilant which is introduced into tiie chamber after the desired relative humidity is achieved. After a period of time sufficient for the sterilant to permeate the wrapping and reach tiie interstices of tile article, ihe sterilant and steam are evacuated from the chamt>er. In tiie prefenred second step of the process (tiie aeration step), the articles are aerate to remove sterilant residues. Removing such residues Is partlcularty important in the case of toxic sterilants. although It is optional in those cases in which the substantiatty non-toxic compounds of the present invention are used. Typical aeration processes include air washes, continuous aeration, and a combination of the two. An air wash is a batch process and usually comprises evacuating the chamber for a relatively short period, for example, 12 minutes, and then introducing air at atmospheric pressure or higher into ttie chamt)er. This cycle is repeated any number of times until the desired removal of sterilant is achieved. Continuous aeration fypicaHy involves introducing air ttrough an inlet at one side of the chamber arKi then drawing it out through an outlet on ttie other side of the chamt>er by applying a slight vacuum to ttie outlet Frequently, the two approaches are combirted. For example, a common approach involves performing air washes and then an a^ation cyde. EXAMPLES The foltowing examples are provided for the purpose of illustrating the present invention but without limiting the scope thereof. EXAMPLE 1 The coefficient of performance (COP) is a universally accepted measure of refrigerant performance, especially useful in representing the relative thermodynamic efficiency of a refrigerant in a specific heating or cooling cycle involving evaporation or condensation of the refrigerant In refrigeration engineering, this term expresses the ratio of use&il refrigeration to the energy applied by the compressor in compressing ttie vapor. The capacity of a refrigerant represents the amount of cooling or heating it provides and provides some measure of the capability of a compressor to pump quantities of heat for a given volumetric flow rate of refrigerant. In other words, given a specific compressor, a refrigerant with a higher capacity vmII deliver more cooling or heating power. One means for estimating COP of a refrigerant at specific operating conditions is from the thermodynamic properties of the refrigerant using standard refrigeration cyde analysis techniques (see for example, R C. Downing, FLUOROCARBON REFRIGERANTS HANDBOOK, Chapters, Prentice-Hall, 1988). A refrigeration /air conditioning cycle system is provided where ttie condenser temperature is about ISO'F and the evaporator temperature is at}out -SS'F under nominally isentropic compression with a compressor inlet temperature of at>out SO'F. COP Is determined for several compositions of ttie present invention over a range of condenser and evaporator temperatures and reported in Table I below, based upon HFC-134a having a COP value of 1.00, a capacity value of 1.00 and a discharge temperature of 175 'F. TABLE i 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 ttie present refrigerant compositions will produce discharge temperatures (158,165 and 155 compared to 175), whidi is advantageous since such result will likely leading to reduced maintenance problems. EXAMPLE 2 The misdbility of HFO-1225ye and HFO-1234ze with various refrigeration lubricants is tested. The lubricants tested are mineral oil (C3), alkyl benzene (Zerol 150), ester oil (Mobil EAL 22 cc and Solest 120), polyailkylene glycol (PAG) oil (Goodwrench Refrigeration Oil for 134a systems), and a poly(alpha-oiefin) oil (CP- 6005-100). For each refrigerant/oil comtMnation, three compositions are tested, namely 5,20 and 50 weight percent of lubrk:ant, with the balance of each being ttie compound of ttie present invention being tested The kibricant compositions are placed in heavy^walled glass tubes. The tubes are evacuated, the refrigerant compound in accordance with the present invention is added^ and the tubes are then sealed. The tubes are then put into an air bath environmental chamber, the temperature of which is varied from at>out -50'C to 70*C. At roughly 10'C mtervais, visual observations of the tube contents are made for the exigence of one or more liquid phases. In a case where more than one liquid phase is ofosen/ed, the mixture is reported to be immiscible. In a case where there is only one Kquid phase observed, the mixfaire is reported to he misdbie. In those cases vAmre two liquid phases were observed, but with one of the liquid phases occupyin§ only a very small volume, the mixture is reported to be partially misdbie. The pot^l^ene glycol and ester oH iut)ricants were judged to t>e miscible in aN tested proportons over the entire temperature range, except that for the HFO- 1225ye mixtures with polyalkyl^® SIfycol, ttie refrigerant mixture was found to be immisdble over the temperature range of--50*C to -30*C and to be partially misdbie over tram -20 to 50*C. At 50 weight percent concentration of the PAG in refrigerant and at 60*. the refrigerant/PAG mixture was misdbie. At yO'C, it was misdbie from 5 weight percent lubricant in refngerant to 50 weight percent lutxicant in refrigerant. EXAMPLE 3 The compatibility of the refrigerant compounds and compositions of the present invention with PAG lutxlcating oils while in contact with metals used in refrigeratidn and air conditioning systems is tested at 350* C, representing conditions much more severe than are found in many refrigeration and air conditioning applications. Aluminum, copper and steel coupons are added to heavy walled glass tubes. Two grams of oil are added to the tubes. The tubes are ttien evacuated and one gram of refrigerant is added. The tubes are put into an oven at SSO'F for one week and visual observations are made. At the end of the exposure period, the tubes are removed. This procedure was done for the following combinations of oil and the compound of the present invention: a) HF01234ze and GM Goodwrench PAG oil b) HFC1243 zf and GM Goodwrench oil PAG oil c) HFC-1234ze and MOPAR-56 PAG oil d) HFC-1243 zf and MOPAR-56 PAG oil e) HFC-1225 ye and MOPAR-56 PAG oil. In aH cases, there is minimal change in the appearance of the contents of the tut>e. This indicates that the refrigerant compounds and compositions of the present invention are stable in contact with aluminum, steel and copper fourul in refirigeration and air conditioning systems, and the types of lubricating oils that are likely to be included in such compositions or used with such compositions in these types of systems. COMPARATIVE EXAMPLE Aluminum, copper and steel coupons are added to a heavy walled glass tube with mineral oil and CFC-12 and heated for one week at 350*C, as in Example 3. At ttie end of ttie exposure period, ttie tut>e is removed and visual ot>servations are made. The liquid contents are ot>served to turn black, indicating there is severe decomposifion of the contents of tiie tube. CFC-12 and mineral oil have heretofore been the combination of choice in many refrigerant systems and methods. Thus, the refrigerant compounds and compositions of the present inventton possess signifk:antiy t>etter statMlity with many commonly used lubricating oils than the widely-used prior art refrigerant-lubricating oil combination. We claim : 1. A heat transfer composition for use in an air conditioning system comprising; (a) at least 50% by weight of 2,3,3,3-tetrafluoropropene (HFO-1234yf) having no substantial acute toxicity; and (b) at least one poly alkylene glycol lubricant. 2. The composition of claim 1 having a Global Wamning Potential (GWP) of not greater than 150. 3. The heat transfer composition of claim 1 optionally comprising at least one compatablizer. 4. The heat transfer composition of claim 1 wherein said lubricant is present in an amount of at least 30% by weight. 5. The composition of claim 1 wherein said lubricant is present in an amount of 50% by weight of the composition 6. The composition of claim 1 wherein said composition is non-flammable. 7. The composition of claim 1 having a Global Warming Potential (GWP) of not greater than 100. 8. The composition of claim 1 having a Global Warming Potential (GWP) of not greater than 75. 9. The composition of claim 1 having an Ozone Depletion Potential (ODP) of not greater than 0.02. 10. The composition of claim 1 wherein said HFO-1234yf comprises at least 70 % by weight of the composition. 11. The composition of claim 10 wherein said compatablizer is selected from the group consisting of propane, butane, pentane, and combinations of these. 12. The composition of claim 10 comprising compatablizer in amounts of from 0.5 to 5 percent by weight of the composition. 13. The composition of claim 1 having a capacity relative to HFC-134a of 1. 14. The composition of claim 1 having a Coefficient of Performance (COP) relative to HFC- 134a of 1. 15. The composition of claim 1 further comprising a surfactant and a solubilizing agent. 16. The composition of claim 1 wherein said lubricant optionally comprises at least one polyol ester. 17. The composition of claim 1 wherein said composition has one liquid phase at at least one temperature between -50°C and +70°C. 18. The composition of claim 1 wherein said fluorinated propene consists essentially of HFO-1234yf and lubricant. The invention discloses a heat transfer composition for use in an air conditioning system comprising: (a) at least about 50% by weight of 1,1,1,2- tetrafluoropropene (HFO-1234yf) having no substantial acute toxicity; and (b) at least one poly alkylene glycol lubricant in the form of a homopolymer or copolymer consisting of 2 or more oxypropylene groups and having a viscosity of from about 10 to about 200 centistokes at about 37°C .

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00962-kolnp-2005-abstract.pdf

00962-kolnp-2005-claims.pdf

00962-kolnp-2005-description complete.pdf

00962-kolnp-2005-form 1.pdf

00962-kolnp-2005-form 3.pdf

00962-kolnp-2005-form 5.pdf

00962-kolnp-2005-international publication.pdf

962-KOLNP-2005-(13-10-2011)-OTHER PATENT DOCUMENTS.pdf

962-kolnp-2005-abstract.pdf

962-kolnp-2005-cancelled docoment.pdf

962-kolnp-2005-claims.pdf

962-kolnp-2005-description complate.pdf

962-kolnp-2005-form 1.pdf

962-kolnp-2005-form 13.pdf

962-kolnp-2005-form 3.pdf

962-KOLNP-2005-FORM-27.pdf

962-kolnp-2005-granted-abstract.pdf

962-kolnp-2005-granted-assignment.pdf

962-kolnp-2005-granted-claims.pdf

962-kolnp-2005-granted-correspondence.pdf

962-kolnp-2005-granted-description (complete).pdf

962-kolnp-2005-granted-examination report.pdf

962-kolnp-2005-granted-form 1.pdf

962-kolnp-2005-granted-form 13.pdf

962-kolnp-2005-granted-form 18.pdf

962-kolnp-2005-granted-form 3.pdf

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962-kolnp-2005-others.pdf

962-kolnp-2005-pct priority document notification.pdf

962-kolnp-2005-petition under rule 137.pdf

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