(12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT)
`
`(19) World Intellectual Property Organization
`International Bureau
`
`(43) International Publication Date
`4 January 2007 (04.01.2007)
`
`(51) International Patent Classification:
`C09K 5/04 (2006.01)
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`(21) International Application Number:
`PCT/US2006/024886
`
`(22) International Filing Date:
`
`26 June 2006 (26.06.2006)
`
`(25) Filing Language:
`
`(26) Publication Language:
`
`English
`
`English
`
`(30) Priority Data:
`60/693,853
`
`24 June 2005 (24.06.2005)
`
`US
`
`(71) Applicant (for all designated States except US): HONEY-
`WELL INTERNATIONAL INC. [US/US]; 101 Colum-
`bia Road, Law Department, PO. Box 2245, Morristown,
`New Jersey 07962-2245 (US).
`
`(72) Inventors; and
`(75) Inventors/Applicants (for US only): SINGH, Rajiv,
`R.
`[US/US]; 18 Foxfire Drive, Getzville, NY 14068
`(US). PHAM, Hang, T. [US/US]; 136 Larkspur Lane,
`Amherst, NY 14228 (US). WILSON, David, P. [US/US];
`118 Waxwing Court, East Amherst, NY 14094 (US).
`THOIVIAS, Raymond, H.
`[US/US]; 5990 Hopi Ct.,
`Pendleton, NY 14051 (US). SPATZ, Mark, W. [US/US];
`56 Britannia Drive, East Amherst, 14051 (US). MET-
`CALF, David, A. [US/US]; 20 Harriet Drive, Whippany,
`NJ 07981 (US).
`
`(10) International Publication Number
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`WO 2007/002625 A2
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`(74) Agent: SZUCH, Colleen; Honeywell International Inc.,
`101 ColumbiaRoad, PO. Box 2245, Morristown, NJ 07962
`(US).
`
`(81) Designated States (unless otherwise indicated, for every
`kind of national protection available): AE, AG, AL, AM,
`AT, AU, AZ, BA, BB, BG, BR, BW, BY, BZ, CA, CH, CN,
`CO, CR, CU, CZ, DE, DK, DM, DZ, EC, EE, EG, ES, FI,
`GB, GD, GE, GH, GM, HN, HR, HU, ID, IL, IN, IS, JP,
`KE, KG, KM, KN, KP, KR, KZ, LA, LC, LK, LR, LS, LT,
`LU, LV, LY, MA, MD, MG, MK, MN, MW, MX, MZ, NA,
`NG, NI, NO, NZ, OM, PG, PH, PL, PT, RO, RS, RU, SC,
`SD, SE, SG, SK, SL, SM, SY, TJ, TM, TN, TR, TT, TZ,
`UA, UG, US, UZ, VC, VN, ZA, ZM, ZW.
`
`Designated States (unless otherwise indicated, for every
`kind of regional protection available): ARIPO (BW, GH,
`GM, KE, LS, MW, MZ, NA, SD, SL, SZ, TZ, UG, ZM,
`ZW), Eurasian (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM),
`European (AT, BE, BG, CH, CY, CZ, DE, DK, EE, ES, FI,
`FR, GB, GR, HU, IE, IS, IT, LT, LU, LV, MC, NL, PL, PT,
`RO, SE, SI, SK, TR), OAPI (BF, BJ, CF, CG, CI, CM, GA,
`GN, GQ, GW, ML, MR, NE, SN, TD, TG).
`
`Published:
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`without international search report and to be republished
`upon receipt of that report
`
`For two—letter codes and other abbreviations, refer to the ”Guid—
`ance Notes on Codes and Abbreviations ” appearing at the begin-
`ning of each regular issue of the PCT Gazette.
`
`(54) Title: COMPOSITIONS CONTAINING FLUORINE SUBSTITUTED OLEFINS
`
`(57) Abstract: Various uses of tetrafluoropropenes, particularly (HFO—l234) 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.
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`Arkema Exhibit 1011
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`N 4 I
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`nNeNecE l
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`\ceN
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`Arkema Exhibit 1011
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`COMPOSITIONS CONTAINING FLUORINE SUBSTITUTED OLEFINS
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`FIELD OF THE INVENTION
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`This invention relates to compositions, methods and systems having utility in
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`numerous applications, including particularly heat transfer systems such as refrigeration
`
`systems.
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`In preferred aspects, the present invention is directed to refrigerant
`
`compositions which comprise at least one multi-fluorinated olefin of the present
`
`invention.
`
`BACKGROUND
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`Fluorocarbon based fluids have found widespread use in many commercial and
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`industrial applications, including as the working fluid in systems such as air conditioning,
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`heat pump and refrigeration systems, as aerosol propellants, as blowing agents, as heat
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`transfer media, and as gaseous dielectrics. Because of certain suspected
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`environmental problems, including the relatively high global warming potentials,
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`associated with the use of some of the compositions that have heretofore been used in
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`these applications, it has become increasingly desirable to use fluids having low or even
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`zero ozone depletion potential, such as hydrofluorocarbons (“HFCs”). Thus, the use of
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`fluids that do not contain chlorofluorocarbons (“CFCS”) or hydrochlorofluorocarbons
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`(“HCFCs") is desirable. Furthermore, some HFC fluids may have relatively high global
`
`warming potentials associated therewith, and it is desirable to use hydrofluorocarbon or
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`other fluorinated fluids having as low global warming potentials as possible while
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`maintaining the desired performance in use properties. Additionally, the use of single
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`component fluids or azeotrope—like mixtures, which do not substantially fractionate on
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`boiling and evaporation, is desirable in certain circumstances.
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`Certain fluorocarbons have been a preferred component in many heat exchange
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`fluids, such as refrigerants, for many years in many applications. For, example,
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`fluoroalkanes, such as chlorofluoromethane and chlorofluoroethane derivatives, have
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`gained widespread use as refrigerants in applications including air conditioning and heat
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`pump applications owing to their unique combination of chemical and physical
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`properties. Many of the refrigerants commonly utilized in vapor compression systems
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`are either single components fluids or azeotropic mixtures.
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`As suggested above, concern has been increasing in recent years about
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`potential damage to the earth’s atmosphere and climate, and certain chlorine-based
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`compounds have been identified as particularly problematic in this regard. The use of
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`chlorine-containing compositions (such as chlorofluorocarbons (CFC’s),
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`hydrochlorofluorocarbons (HCF’s) and the like) as the working fluid in heat transfer
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`systems, such as in refrigeration and air-conditioning systems, has become disfavored
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`because of the ozone-depleting properties associated with many of such compounds.
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`There has thus been an increasing need for new fluorocarbon and hydrofluorocarbon
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`compounds and compositions that are attractive alternatives to the compositions
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`heretofore used in these and other applications. For example, it has become desirable
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`to retrofit chlorine-containing refrigeration systems by replacing chlorine-containing
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`refrigerants with non—chlorine—containing refrigerant compounds that will not deplete the
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`ozone layer, such as hydrofluorocarbons (HFC’s).
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`industry in general and the heat
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`transfer industry in particular are continually seeking new fluorocarbon based mixtures
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`that offer alternatives to, and are considered environmentally safer substitutes for, CFCs
`
`and HCFCs.
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`it is generally considered important, however, at least with respect to heat
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`transfer fluids, that any potential substitute must also possess those properties present
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`in many of the most widely used fluids, such as excellent heat transfer properties,
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`chemical stability, low- or no- toxicity, non-flammability and/or lubricant compatibility,
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`among others.
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`Applicants have come to appreciate that lubricant compatibility is of particular
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`importance in many of applications. More particularly, it is highly desirably for
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`refrigeration fluids to be compatible with the lubricant utilized in the compressor unit,
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`used in most refrigeration systems. Unfortunately, many non-chlorine-containing
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`refrigeration fluids, including HFC’s, are relatively insoluble and/or immiscible in the
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`types of lubricants used traditionally with CFC’s and HFC’s, including, for example,
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`mineral oils, alkylbenzenes or poly(alpha-olefins).
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`in order for a refrigeration fluid-
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`lubricant combination to work at a desirable level of efficiently within a compression
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`refrigeration, air-conditioning and/or heat pump system, the lubricant should be
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`sufficiently soluble in the refrigeration liquid over a wide range of operating
`
`temperatures. Such solubility lowers the viscosity of the lubricant and allows it to flow
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`more easily throughout the system.
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`in the absence of such solubility, lubricants tend to
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`become lodged in the coils of the evaporator of the refrigeration, air-conditioning or heat
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`pump system, as well as other parts of the system, and thus reduce the system
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`efficiency.
`
`With regard to efficiency in use, it is important to note that a loss in refrigerant
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`thermodynamic performance or energy efficiency may have secondary environmental
`
`impacts through increased fossil fuel usage arising from an increased demand for
`
`electrical energy.
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`Furthermore, it is generally considered desirably for CFC refrigerant substitutes
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`to be effective without major engineering changes to conventional vapor compression
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`technology currently used with CFC refrigerants.
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`Flammability is another important property for many applications. That is, it is
`
`considered either important or essential in many applications, including particularly in
`
`heat transfer applications, to use compositions which are non-flammable. Thus, it is
`
`frequently beneficial to use in such compositions compounds which are 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
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`HFC’s which might otherwise be desirable for used in refrigerant compositions are not
`
`nonflammable. For example, the fluoroalkane difluoroethane (HFC-152a) and the
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`fluoroalkene 1,1 ,1—trif|uorpropene (HFO-1243zf) are each flammable and therefore not
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`viable for use in many applications.
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`Higher fluoroalkenes, that is f|uorine—substituted alkenes having at least five
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`carbon atoms, have been suggested for use as refrigerants. U.S. Patent No. 4,788,352
`
`— Smutny is directed to production of fluorinated C5 to C3 compounds having at least
`
`some degree of unsaturation. The Smutny patent identifies such higher olefins as being
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`known to have utility as refrigerants, pesticides, dielectric fluids, heat transfer fluids,
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`solvents, and intermediates in various chemical reactions.
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`(See column 1, lines 11 —
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`22).
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`While the fluorinated olefins described in Smutny may have some level of
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`effectiveness in heat transfer applications, it is believed that such compounds may also
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`have certain disadvantages. For example, some of these compounds may tend to
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`attack substrates, particularly general-purpose plastics such as acrylic resins and ABS
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`resins. Furthermore, the higher olefinic compounds described in Smutny may also be
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`undesirable in certain applications because of the potential level of toxicity of such
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`compounds which may arise as a result of pesticide activity noted in Smutny. Also,
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`such compounds may have a boiling point which is too high to make them useful as a
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`refrigerant in certain applications.
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`Bromofluoromethane and bromochlorofluoromethane derivatives, particularly
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`bromotrifluoromethane (Halon 1301) and bromochlorodifluoromethane (Halon 1211)
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`have gained widespread use as fire extinguishing agents in enclosed areas such as
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`airplane cabins and computer rooms. However, the use of various halons is being
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`phased out due to their high ozone depletion. Moreover, as halons are frequently used
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`in areas where humans are present, suitable replacements must also be safe to
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`humans at concentrations necessary to suppress or extinguish fire.
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`Applicants have thus come to appreciate a need for compositions, and
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`particularly heat transfer compositions, fire extinguishing/suppression compositions,
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`blowing agents, solvent compositions, and compatabilizing agents, that are potentially
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`useful in numerous applications, including vapor compression heating and cooling
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`systems and methods, while avoiding one or more of the disadvantages noted above.
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`SUMMARY
`
`Applicants have found that the above-noted need, and other needs, can be
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`satisfied by compositions, preferably heat transfer compositions, comprising one or
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`more C3 to C6 fluorakenes, and more preferably one or more C3, C4, or C5
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`fluoroalkenes, preferably compounds having Formula l as follows:
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`XCFzR3-z (D
`
`where X is a C2, C3, C4 or C5 unsaturated, substituted or unsubstituted, radical, each R
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`is independently Cl, F, Br, l or H, and z is 1 to 3.
`
`in certain preferred embodiments, the
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`fluoroalkene of the present invention has at least four (4) halogen substituents, at least
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`three of which are F and even more preferably none of which are Br.
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`in certain
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`preferred embodiments, the compound of formula one comprises a compound, and
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`preferably a three carbon compound, in which each non-terminal unsaturated carbon
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`has a fluorine substituent.
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`For embodiments in which at least one Br substituent is present, it is preferred
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`that the compound includes no hydrogen.
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`In such embodiments it also generally
`
`preferred that the Br substituent is on an unsaturated carbon, and even more preferably
`
`the Br substituent is on an non-terminal unsaturated carbon. One particularly preferred
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`embodiment in this class is CF3CBr=CF2, including all of its isomers.
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`In certain embodiments it is highly preferred that the compounds of Formula I
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`comprise propenes, butenes, pentanes and hexanes having from 3 to 5 fluorine
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`substituents, with other substituents being either present or not present.
`
`in certain
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`preferred embodiments, no R is Br, and preferably the unsaturated radical contains no
`
`Br substituents. Among the propenes, tetrafluoropropenes (HFO-1234) and
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`fluorochloroporpenes (such as trifluoro,monochloropropenes (HFCO—1233), and even
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`more preferably CF3CCl=CH2 (HFO-1233xf) and CF3CH=CHCl (HFO-1233zd)) are
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`especially preferred in certain embodiments.
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`In certain embodiments, pentafluoropropenes are preferred, including particularly
`
`those pentafluoropropenes in which there is a hydrogen substituent on the terminal
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`unsaturated carbon, such as CF3CF=CFH (HFO—1225yez and/or yz), particularly since
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`applicants have discovered that such compounds have a relatively low degree of toxicity
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`in comparison to at least the compound CF3CH=CF2 (HFO-1225zc).
`
`Among the butenes, fluorochlorobutenes are especially preferred in certain
`
`embodiments.
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`The term “HFO-1234” is used herein to refer to all tetrafluoropropenes. Among
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`the tetrafluoropropenes are included 1,1,1 ,2-tetrafluoropropene (HFO-1234yf) and both
`
`cis- and trans-1, 1, 1, 3-tetrafluoropropene (HFO-1234ze). The term HFO-1234ze is
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`used herein generically to refer to 1, 1,1, 3-tetrafluoropropene, independent of whether
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`it is the cis- or trans- form. The terms “cisHFO-1234ze” and “transHFO—1234ze" are
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`used herein to describe the cis- and trans- forms of 1, 1, 1, 3-tetrafluoropropene
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`respectively. The term "HFO-1234ze” therefore includes within its scope cisHFO-
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`1234ze, transHFO-1234ze, and all combinations and mixtures of these.
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`The term “HFO—1233" is used herein to refer to all trifluoro,monochloropropenes.
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`Among the trifluoro,monochloropropenes are included 1,1,1,trifluoro-2,chloro—propene
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`(HFCO-1233xf), both cis- and trans-1,1,1-trifluo-3,chlororopropene (HFCO-1233zd).
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`The term HFCO-1233zd is used herein generically to refer to 1,1,1-trifluo-3,chloro-
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`propene, independent of whether it is the cis- or trans- form. The terms “cisHFCO-
`
`1233zd” and “transHFCO-1233zd” are used herein to describe the cis- and trans- forms
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`of 1, 1, 1-trifluo,3-chlororopropene, respectively. The term “HFCO—1233zd” therefore
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`includes within its scope cisHFCO-1233zd, transHFCO-1233zd, and all combinations
`
`and mixtures of these.
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`The term “HFO-1225" is used herein to refer to all pentafluoropropenes. Among
`
`such molecules are included 1,1,1,2,3 pentafluoropropene (HFO—1225yez), both cis-
`
`and trans- forms thereof. The term HFO-1225yez is thus used herein generically to
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`refer to 1,1,1,2,3 pentafluoropropene, independent of 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 of these.
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`In certain preferred embodiments, the present compositions comprise a
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`combination of two or more compounds of Formula l.
`
`in one such preferred
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`embodiment the composition comprises at least one tetrafluoropropene and at least one
`
`pentafluoropropene compound, preferably with each compound being present in the
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`composition in an amount of from about 20% by weight to about 80% by weight, more
`
`preferably from about 30% by weight to about 70% by weight, and even more preferably
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`from about 40% by weight to about 60% by weight.
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`In certain of such embodiments,
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`the tetrafluoropropene comprises, and preferably consists essentially of HFO-1234
`
`(most preferably HFO-1234yf) and HFO1225 (most preferably HFO-1225yez).
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`The present invention provides also methods and systems which utilize the
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`compositions of the present invention, including methods and systems for heat transfer,
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`for retrofitting existing heat transfer equipment, for replacing the existing heat transfer
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`fluids in an existing heat transfer system.
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`In certain cases, the present compositions
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`may also be used in connection with foam blowing, solvating, flavor and fragrance
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`extraction and/or delivery, aerosol generation, non-aerosol propellants and as inflating
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`agents.
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`DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
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`THE COMPOSITIONS
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`The preferred embodiments of the present invention are directed to compositions
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`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 at least one carbon-carbon double bond. The fluoroalkene compounds of the
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`present invention are sometimes referred to herein forthe purpose of convenience as
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`hydrofluoro-olefins or “H FOs” if they contain at least one hydrogen. Although it is
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`contemplated that the HFOs of the present invention may contain two carbon -- carbon
`
`double bonds, such compounds at the present time are not considered to be preferred.
`
`For HFOs which also contain at least one chlorine atom, the designation HFCO is
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`sometimes used herein
`
`As mentioned above, the present compositions comprise one or more
`
`compounds in accordance with Formula l.
`
`in preferred embodiments, the compositions
`
`include compounds of Formula ll below:
`R
`I
`=c—-—R'
`
`R\
`R/C
`
`(ll)
`
`where each R is independently Cl, F, Br, I or H,
`
`R’ is (CR2)nY,
`
`Y is CRF2
`
`and n is O, 1, 2 or 3, preferably 0 or 1, it being generally preferred however 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.
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`In highly preferred embodiments, Y is CF3, n is O or 1 (most preferably 0) and at
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`least one of the remaining Rs is F, and preferably no R is Br or when Br is present,
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`there is no hydrogen in the compound.
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`Applicants believe that, in general, the compounds of the above identified
`
`Formulas I and ll are generally effective and exhibit utility in heat transfer compositions
`
`generally and in refrigerant compositions particularly. The compositions of the present
`
`invention also find use as blowing agent compositions, compatibilzers, aerosols,
`
`propellants, fragrances, flavor formulations, solvent compositions and inflating agent
`
`composition. However, applicants have surprisingly and unexpectedly found that
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`certain of the compounds having a structure in accordance with the formulas described
`
`above exhibit a highly desirable low level of toxicity compared to other of such
`
`compounds. As can be readily appreciated, this discovery is of potentially enormous
`
`advantage and benefit for the formulation of not only refrigerant compositions, but also
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`any and all compositions which would otherwise contain relatively toxic compounds
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`satisfying the formulas described above. More particularly, applicants believe that a
`
`relatively low toxicity level is associated with compounds of Formula II, preferably
`
`wherein Y is CF3, n is O or 1, wherein at least one R on the unsaturated terminal carbon
`
`is H, and at least one of the remaining Rs is F or Cl. Applicants believe also that all
`
`structural, geometric and 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 comprises a C3 or C4 HFO, preferably a C3 HFO, and preferably
`
`a compound accordance with Formula I in which X is a halogen substituted C3 alkylene
`
`and z is 3.
`
`In certain of such embodiments X is fluorine and/or chlorine substituted C3
`
`alkylene, with the following C3 alkylene radicals being preferred in certain embodiments:
`
`—CH=CF-CH3
`
`-CF=CH-CH3
`
`-CH2-CF=CH2
`
`-CH2-CH=CFH,
`
`Such embodiments therefore comprise the following preferred compounds: CF3-
`
`CH=CF-CH3; CF3—CF=CH-CH3; CF3-CH2-CF=CH2; CF3-CH2-CH=CFH; and
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`combinations of these with one another and/or with other compounds in accordance
`
`with Formula l,
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`In certain preferred embodiments, the compound of the present invention
`
`comprises a C3 or C4 HFCO, preferably a C3 HFCO, and more preferably a compound
`
`in accordance with Formula ll in which Y is CF3, n is O, at least one R on 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 highly preferred embodiments, especially embodiments which comprise 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 together with other
`
`compounds including its stereo isomer, in connection with each of the applications,
`
`methods and systems described herein. For example, (trans)HFO—1234ze may be
`
`preferred for use in certain systems because of its relatively low boiling point (-19° C),
`
`while (cis)HFO—1234ze, with a boiling point of +9° C, may be preferred in other
`
`applications. Of course, it is likely that combinations of the cis— and trans- isomers will
`
`be acceptable and/or preferred in many embodiments. Accordingly, it is to be
`
`understood that the terms “HFO-1234ze" and 1, 3, 3, 3—tetrafluoropropene refer to both
`
`stereo isomers, and 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 othenNise indicated.
`
`HFO-1234 compounds are known materials and are listed in Chemical Abstracts
`
`databases. The production of fluoropropenes such as CF3CH=CH2 by catalytic vapor
`
`phase fluorination of various saturated and unsaturated halogen-containing C3
`
`compounds is described in U.S. Patent Nos. 2,889,379; 4,798,818 and 4,465,786, each
`
`of which is incorporated herein by reference. EP 974,571, also incorporated herein by
`
`reference, discloses the preparation of 1,1,1,3-tetrafluoropropene by contacting
`
`1,1,1,3,3-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(OH)2_ In addition, methods for producing compounds in
`
`accordance with the present invention are described generally in connection with
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`pending United States Patent Application entitled “Process for Producing
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`Fluorpropenes” bearing attorney docket number (H0003789 (26267)), which is also
`
`incorporated herein by reference.
`
`Other preferred compounds for use in accordance with the present invention
`
`include pentafluoropropenes, including all isomers thereof (eg., HFO-1225), tetra- and
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`penta—fluorobutenes, including all isomers thereof (eg., HFO-1354 and HFO-1345). Of
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`course, the present compositions may comprise combinations of any two or more
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`compounds within the broad scope of the invention or within any preferred scope of the
`invention.
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`The present compositions, particularly those comprising HFO-1234 (including
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`HFO-1234ze and HFO-1234yf), are believed to possess properties that are
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`advantageous for a number of important reasons. For example, applicants believe,
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`based at least in part on mathematical modeling, that the fluoroolefins of the present
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`invention will not have a substantial negative affect on atmospheric chemistry, being
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`negligible contributors to ozone depletion in comparison to some other halogenated
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`species. The preferred compositions of the present invention thus have the advantage
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`of not contributing substantially to ozone depletion. The preferred compositions also do
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`not contribute substantially to global warming compared to many of the
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`hydrofluoroalkanes presently in use.
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`Of course other compounds and/or components that modulate a particular
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`property of the compositions (such as cost for example) may also be included in the
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`present compositions, and the presence of all such compounds and components is
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`within the broad scope of the invention.
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`In certain preferred forms, compositions of the present invention have a Global
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`Warming Potential (GWP) of not greater than about 1000, more preferably not greater
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`than about 500, and even more preferably not greaterthan about 150.
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`In certain
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`embodiments, the GWP of the present compositions is not greater than about 100 and
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`even more preferably not greater than about 75. As used herein, “GWP” is measured
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`relative to that of carbon dioxide and over a 100 year time horizon, as defined in “The
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`Scientific Assessment of Ozone Depletion, 2002, a report of the World Meteorological
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`Association's Global Ozone Research and Monitoring Project,” which is incorporated
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`herein by reference.
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`In certain preferred forms, the present compositions also preferably have an
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`Ozone Depletion Potential (ODP) of not greater than 0.05, more preferably not greater
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`than 0.02 and even more preferably about zero. As used herein, “ODP" is as defined in
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`“The Scientific Assessment of Ozone Depletion, 2002, A report of the World
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`Meteorological Association's Global Ozone Research and Monitoring Project,” which is
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`incorporated herein by reference.
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`The amount of the Formula I compounds, particularly HFO—1234, and even more
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`preferably HFO—1234yf, contained in the present compositions can vary widely,
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`depending the particular application, and compositions containing more than trace
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`amounts and less than 100% of the compound are within broad the scope of the
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`present invention. Moreover, the compositions of the present invention can be
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`azeotropic, azeotrope-like or non-azeotropic.
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`In preferred embodiments, the present
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`compositions comprise Formula I compounds, preferably HFO—1234 and more
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`preferably HFO-1234ze and/or HFO—1234yf, preferably HFO-1234ze and/or HFO-
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`1234yf, in amounts from about 5% by weight to about 99% by weight, and even more
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`preferably from about 5% to about 95%. Many additional compounds or components,
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`including lubricants, stabilizers, metal passivators, corrosion inhibitors, flammability
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`suppressants, and other compounds and/or components that modulate a particular
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`property of the compositions (such as cost for example) may be included in the present
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`compositions, and the presence of all such compounds and components is within the
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`broad scope of the invention.
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`in certain preferred embodiments, the present
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`compositions include, in addition to the compounds of formula I (including particularly
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`HFO-1234ze and/or HFO—1234yf), one or more of the following:
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`Trichlorofluoromethane (CFC-1 1)
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`Dichlorodifluoromethane (CFC-12)
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`Difluoromethane (HFC-32)
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`Pentafluoroethane (HFC—125)
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`1 ,1,2,2-tetrafluoroethane (HFC—134)
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`1,1,1,2-Tetrafluoroethane (HFC—134a)
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`Difluoroethane (H FC—1 52a)
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`1,1,1,2,3,3,3-Heptafluoropropane (HFC—227ea)
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`1,1,1,3,3,3-hexafluoropropane (HFC—236fa)
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`1,1,1,3,3—pentafluoropropane (HFC-245fa)
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`1,1,1,3,3—pentafluorobutane (HFC—365mfc)
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`water
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`C02
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`The relative amount of any of the above noted compounds of the present
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`invention, as well as any additional components which may be included in present
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`compositions, can vary widely within the general broad scope of the present invention
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`according to the particular application for the composition, and all such relative amounts
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`are considered to be within the scope hereof.
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`Accordingly, applicants have recognized that certain compositions of the present
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`invention can be used to great advantage in a number of applications. For example,
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`included in the present invention are methods and compositions relating to heat transfer
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`applications, foam and blowing agent applications, propellant applications, sprayable
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`composition applications, sterilization applications, aerosol applications, compatibilizer
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`application, fragrance and flavor applications, solvent applications, cleaning
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`applications, inflating agent applications and others.
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`it is believed that those of skill in
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`the art will be readily able to adapt the present compositions for use in any and all such
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`applications without undue experimentation.
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`The present compositions are generally useful as replacements for CFCs, such
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`as dichlorodifluormethane (CFC-12), HCFCs, such as chlorodifluoromethane (HCFC-
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`22), HFCs, such as tetrafluoroethane (HFC-134a), and combinations of HFCs and
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`CFCs, such as the combination of CFC-12 and 1,1-difluorethane (HFC-152a) (the
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`combination CFC-12:HFC—152a in a 73.82262 mass ratio being known as R-500) in
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`refrigerant, aerosol, and other applications.
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`HEAT TRANSFER COMPOSITIONS
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`The compositions of the present invention are generally adaptable for use in heat
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`transfer applications, that is, as a heating and/or cooling medium, including as
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`evaporative cooling agents.
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`in connection with evaporative cooling applications, the compositions of the
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`present invention are brought in contact, either directly or indirectly, with a body to be
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`cooled and thereafter permitted to evaporate or boil while in such contact, with the
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`preferred result that the boiling gas in accordance with the present composition absorbs
`heat from the body‘ to be cooled.
`In such applications it may be preferred to utilize the
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`compositions of the present invention, preferably in liquid form, by spraying or otherwise
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`applying the liquid to the body to be cooled.
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`In other evaporative cooling applications, it
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`may be preferred to permit a liquid composition in accordance with the present intention
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`to escape from a relatively high pressure container into a relatively lower pressure
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`environment wherein the body to be cooled is in contact, either directly or indirectly, with
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`the container enclosing the liquid composition of the present invention, preferably
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`without recovering or recompressing the escaped gas. One particular application for
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`this type of embodiment is the self cooling of a beverage, food item, novelty item or the
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`like. Previous to the invention described herein, prior compositions, such as HFC-152a
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`and HFC-134a were used for such applications. However, such compositions have
`recently been looked upon negatively in such application because of the negative
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`environmental impact caused by release of these materials into the atmosphere. For
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`example, the United States EPA has determined that the use of such prior chemicals in
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`this application is unacceptable due to the high global warming nature of these
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`chemicals and the resulting detrimental effect on the environment that may result from
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`their use. The compositions of the present invention should have a distinct advantage
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`in this regard clue to their low global warming potential and low ozone depletion
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`potential, as described herein. Additionally, the present compositions are expected to
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`also find substantial utility in connection with the cooling of electrical or electronic
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`components, either during manufacture or during accelerated lifetime testing.
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`In a
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`accelerated lifetime testing, the component is sequentially heated and cooled in rapid
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`succession to si