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`Application Data Sheet 37 CFR 1.76
`Application Number
`COMPOSITIONS CONTAINING FLUORINE SUBSTITUTED OLEFINS AND METHODS AND SYSTEMS
`USING SAME
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`Title of Invention
`
`The application data sheet is part of the provisional or nonprovisional application for which it is being submitted. The following form contains the
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`
`(9 US Residency 0 Non US Residency 0 Active US Military Service
`StateIProvince | NY
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`18 Foxfire Drive
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`StateIPr°vin<=e
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`
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`2
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`
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`T.
`
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`PHAM
`
`Residence Information (Select One) @ US Residency 0 Non US Residency 0 Active US Military Service
`S*a*°'Pr°vi"°°
`°°untrv°fRe='-idem‘
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`3
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`
`136 Larkspur Lane
`
`I 14228
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`
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`
`Family Name
`Shankland
`
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`Application Data Sheet 37 CFR 1.76
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`Title of Invention
`
`Application Number
`COMPOSITIONS CONTAINING FLUORINE SUBSTITUTED OLEFINS AND METHODS AND SYSTEMS
`USING SAME
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`City
`
`Buffalo
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`StateIProvince INY Icountry ofRe5idenceI
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`US
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`6 Horizon Court
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`Buffalo
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`Prior Application Status
`Application Number
`
`Pending
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`Continuity Type
`
`Prior Application Number
`11847192
`
`Filing Date (YYYY—MM—DD)
`2007-08-29
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`Prior Application Status
`Application
`Number
`11847192
`
`Patented
`.
`.
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`Division of
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`Application
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`10837525
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`Patented
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`Number
`10837525
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`Filing Date
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`2004-04-29
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`Patent Number
`7279451
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`(YYYY_MM_DD)
`2007-10-09
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`Number
`10694272
`
`Filing Date
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`2003-10-27
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`7230146
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`2007-06-12
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`10837525
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`2003-10-27
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`Patent Number
`7534366
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`2009-05-19
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`Expired
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`10694273
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`non provisional of
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`60421263
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`2002-10-25
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`Expired
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`Prior Application Number
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`Filing Date (YYYY-MM-DD)
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`10694273
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`non provisional of
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`60421435
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`2002-10-25
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`Number
`10837525
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`Patented
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`Continuation in part of
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`Prior Application
`Number
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`2007-06-12
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`PTO/AIAI14 (08-12)
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`PTO/AIAI14 (08-12)
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`

`
`PATENT
`
`Attorney Docket No. H0003965D|V1C
`
`COMPOSITIONS CONTAINING FLUORINE SUBSTITUTED OLEFINS AND
`
`METHODS AND SYSTEMS USING SAME
`
`RELATED APPLICATIONS
`
`The present application is a divisional of U.S. Application No. 11/847,192, filed
`
`August 29, 2007 (now pending), which in turn is a divisional of U.S. Application No.
`
`10/837,525, filed April 29, 2004 (now U.S. Patent No. 7,279,451), which in turn is a
`
`continuation in part of each of U.S. Application No. 10/694,272, filed October 27, 2003
`
`(now U.S. Patent No. 7,230,146) and U.S. Patent Application No. 10/694,273, filed
`
`October 27, 2003 (now U.S. Patent No, 7,534,366), which in turn 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. U.S. Patent Application No.
`
`10/837,525, filed April 29, 2004 is also a continuation—in—part of U.S. Patent Application
`
`No. 10/694,272, filed October 27, 2003 (now U.S. Patent No. 7,230,146). The
`
`disclosure of each of the patent applications and patents identified in the preceding
`
`sentence is incorporated herein by reference.
`
`FIELD OF THE INVENTION
`
`This invention relates to compositions having utility in numerous applications,
`
`including particularly refrigeration systems, and to methods and systems utilizing such
`
`compositions.
`
`In preferred aspects, the present invention is directed to refrigerant
`
`compositions comprising at least one mu|ti—f|uorinated 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 fluid in systems such as air conditioning, heat pump and refrigeration
`
`applications. The vapor compression cycle is one of the most commonly used type
`
`PH1 3464430v1 03/15/13
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`Page 7 of 41
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`

`
`PATENT
`
`Attorney Docket No. H0O03965D|V1C
`
`methods to accomplish cooling or heating in a refrigeration system. The vapor
`
`compression cycle usually involves the phase change of the refrigerant from the liquid
`
`to the vapor phase through heat absorption at a relatively low pressure and then from
`
`the vapor to the liquid phase through heat removal at a relatively low pressure and
`
`temperature, compressing the vapor to a relatively elevated pressure, condensing the
`
`vapor to the liquid phase through heat removal at this relatively elevated pressure and
`
`temperature, and then reducing the pressure to start the cycle over again.
`
`While the primary purpose of refrigeration is to remove heat from an object or
`
`other fluid at a relatively low temperature, the primary purpose of a heat pump is to add
`
`heat at a higher temperature relative to the environment.
`
`Certain fluorocarbons have been a preferred component in many heat exchange
`
`fluids, such as refrigerants, for many years in many applications. For, example,
`
`fluoroalkanes, such as chlorofluoromethane and chlorofluoroethane derivatives, have
`
`gained widespread use as refrigerants in applications including air conditioning and heat
`
`pump applications owing to their unique combination of chemical and physical
`
`properties. Many of the refrigerants commonly utilized in vapor compression systems
`
`are either single components fluids or azeotropic mixtures.
`
`Concern has increased in recent years about potential damage to the earth's
`
`atmosphere and climate, and certain chlorine-based compounds have been identified
`
`as particularly problematic in this regard. The use of chlorine—containing compositions
`
`(such as chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs) and the like)
`
`as refrigerants in air—conditioning and refrigeration systems has become disfavored
`
`because of the ozone—depleting properties associated with many of such compounds.
`
`There has thus been an increasing need for new fluorocarbon 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—chlorine—
`
`containing refrigerant compounds that will not deplete the ozone layer, such as
`
`hydrofluorocarbons (HFCs).
`
`It is generally considered important, however, that any potential substitute
`
`refrigerant must also possess those properties present in many of the most widely used
`
`PH1 3464430v1 03/15/13
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`Page 8 of 41
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`

`
`PATENT
`
`Attorney Docket No. H0O03965D|V1 C
`
`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 particularly, it is highly desirably for
`
`refrigeration fluids to be compatible with the lubricant utilized in the compressor unit,
`
`used in most refrigeration systems. Unfortunately, many non-chlorine-containing
`
`refrigeration fluids, including HFCs, 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(a|pha-olefins).
`
`In order for a refrigeration fluid-
`
`lubricant combination to work at a desirable level of efficiently within a compression
`
`refrigeration, air-conditioning and/or heat pump system, the lubricant should be
`
`sufficiently soluble in the refrigeration liquid over a wide range of operating
`
`temperatures. Such solubility lowers the viscosity of the lubricant and allows it to flow
`
`more easily throughout the system.
`
`In the absence of such solubility, lubricants tend to
`
`become lodged in the coils of the evaporator of the refrigeration, air-conditioning or heat
`
`pump system, as well as other parts of the system, and thus reduce the system
`
`efficiency.
`
`With regard to efficiency in use, it is important to note that a loss in refrigerant
`
`thermodynamic performance or energy efficiency may have secondary environmental
`
`impacts through increased fossil fuel usage arising from an increased demand for
`
`electrical energy.
`
`Furthermore, it is generally considered desirably for CFC refrigerant substitutes
`
`to be effective without major engineering changes to conventional vapor compression
`
`technology currently used with CFC refrigerants.
`
`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—flammab|e. Thus, it is
`
`frequently beneficial to use in such compositions compounds, which are nonflammable.
`
`As used herein, the term “nonflammab|e” 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
`
`PH1 3464430v1 03/15/13
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`Page 9 of 41
`
`

`
`PATENT
`
`Attorney Docket No. H0O03965D|V1C
`
`HFCs, which might otherwise be desirable for used in refrigerant compositions are not
`
`nonflammable. For example, the fluoroalkane difluoroethane (HFC-152a) and the
`
`fluoroalkene 1 ,1,1—trifluoropropene (HFO—1243zf) are each flammable and therefore not
`
`viable for use in many applications.
`
`Higher fluoroalkenes, that is f|uorine—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 C5 to C8 compounds having at least
`
`some degree of unsaturation. The Smutny patent identifies such higher olefins as being
`
`known to have utility as refrigerants, pesticides, dielectric fluids, heat transfer fluids,
`
`solvents, and intermediates in various chemical reactions.
`
`(See column 1, lines 11 —
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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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`Page 10 of 41
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`

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`PATENT
`
`Attorney Docket No. H0O03965D|V1C
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`systems and methods, while avoiding one or more of the disadvantages noted above.
`
`SUMMARY
`
`Applicants have found that the above-noted need, and other needs, can be
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`satisfied by compositions comprising one or more C3 or C4 fluoroalkenes, preferably
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`compounds having Formula I as follows:
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`XCFZR3.Z (I)
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`where X is a C2 or a C3 unsaturated, substituted or unsubstituted, alkyl radical, each R
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`is independently CI, F, Br,
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`I or H, and z is 1 to 3. Highly preferred among the
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`compounds of Formula I are the cis- and trans- isomers of 1, 3, 3, 3-tetrafluoropropene
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`(H FO-1 234ze)
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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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`foam blowing, solvating, flavor and fragrance extraction and/or delivery, and aerosol
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`generation.
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`DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
`
`THE COMPOSITIONS
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`The present invention is directed to compositions comprising at least one
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`fluoroalkene containing from 3 to 4 carbon atoms, preferably three carbon atoms, and at
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`least one carbon—carbon double bond. The fluoroalkene compounds of the present
`
`invention are sometimes referred to herein for the purpose of convenience as
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`hydrofluoro-olefins or “HFOs” 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
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`double bonds, such compounds at the present time are not considered to be preferred.
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`As mentioned above, the present compositions comprise one or more
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`compounds in accordance with Formula I.
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`In preferred embodiments, the compositions
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`include compounds of Formula II below:
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`Page 11 of 41
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`

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`PATENT
`
`Attorney Docket No. H0O03965D|V1C
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`R
`l=c—R'
`
`R\
`R/C
`
`(H)
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`where each R is independently Cl, F, Br,
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`I or H
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`R’ is (CR2),,Y,
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`Y is CRF2
`
`and n is 0 or 1.
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`In highly preferred embodiments, Y is CF3, n is O and at least one of the remaining Rs is
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`F.
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`Applicants believe that, in general, the compounds of the above identified
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`Formulas I and II are generally effective and exhibit utility in refrigerant compositions,
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`blowing agent compositions, compatibilizers, aerosols, propellants, fragrances, flavor
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`formulations, and solvent compositions of the present invention. However, applicants
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`have surprisingly and unexpectedly found that certain of the compounds having a
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`structure in accordance with the formulas described above exhibit a highly desirable low
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`level of toxicity compared to other of such compounds. As can be readily appreciated,
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`this discovery is of potentially enormous advantage and benefit for the formulation of not
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`only refrigerant compositions, but also any and all compositions, which would otherwise
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`contain relatively toxic compounds satisfying the formulas described above. More
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`particularly, applicants believe that a relatively low toxicity level is associated with
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`compounds of Formula II, preferably wherein Y is CF3, wherein at least one R on the
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`unsaturated terminal carbon 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
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`effective and of beneficially low toxicity.
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`In highly preferred embodiments, especially embodiments comprising the low
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`toxicity compounds described above, n is zero.
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`In certain highly preferred embodiments
`
`the compositions of the present invention comprise one or more tetrafluoropropenes.
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`The term “HFO-1234” is used herein to refer to all tetrafluoropropenes. Among the
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`tetrafluoropropenes, both cis— and trans—1, 3, 3, 3—tetraf|uoropropene (HFO—1234ze) are
`
`particularly preferred. The term HFO—1234ze is used herein generically to refer to 1, 3,
`
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`Page 12 of 41
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`

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`PATENT
`
`Attorney Docket No. H0O03965D|V1 C
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`3, 3-tetrafluoropropene, independent of whether it is the cis- or trans— form. The terms
`
`“cisHFO-1234ze” and “transHFO-1234ze” are used herein to describe the cis- and
`
`trans— forms of 1, 3, 3, 3-tetrafluoropropene respectively. The term “HFO—1234ze”
`
`therefore includes within its scope cisHFO-1234ze, transHFO-1234ze, and all
`
`combinations and mixtures of these.
`
`Although the properties of cisHFO-1234ze and transHFO-1234ze differ in at least
`
`some respects, it is contemplated that each of these compounds is adaptable for use,
`
`either alone or together with other compounds including its stereoisomer, in connection
`
`with each of the applications, methods and systems described herein. For example,
`
`while transHFO-1234ze may be preferred for use in certain refrigeration systems
`
`because of its relatively low boiling point (-19° C), it is nevertheless contemplated that
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`cisHFO-1234ze, with a boiling point of +9° C, also has utility in certain refrigeration
`
`systems of the present invention. Accordingly, it is to be understood that the terms
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`“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 otherwise 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
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`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
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`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
`
`pending United States Patent Application entitled “Process for Producing
`
`Fluoropropenes” bearing attorney docket number (H0003789 (26267)), which is also
`
`incorporated herein by referen