PATENT
`
`Attorney Docket No. H0003965D|V1A
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`COMPOSITIONS CONTAINING FLUORINE SUBSTITUTED OLEFINS AND
`
`METHODS AND SYSTEMS USING SAME
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`Invented by: Rajiv R. Singh
`18 Foxfire Drive
`
`Getzville, NY 14068
`Citizen of the United States
`
`Hang T. Pham
`136 Larkspur Lane
`Amherst, NY 14228
`Citizen of the United States
`
`David P. Wilson
`
`118 Waxwing Court
`East Amherst, NY 14051
`Citizen of the United States
`
`Raymond H. Thomas
`5990 Hopi Court
`Pendleton, NY 14094
`Citizen of the United States
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`1 of 47
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`Arkema Exhibit 1043
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`Arkema Exhibit 1043
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`1 of 47
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`PATENT
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`Attorney Docket No. H0003965DlV1 A
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`COMPOSITIONS CONTAINING FLUORINE SUBSTITUTED OLEFINS AND
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`METHODS AND SYSTEMS USING SAME
`
`RELATED APPLICATIONS
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`The present application is related to and claims the priority benefit of each of the
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`following pending United States Patent Applications: U.S. Application No. 10/837,525,
`
`filed April 29, 2004 (now pending), which in turn is a continuation in part of each of U.S.
`
`Application Nos. 10/694,273 (now pending) and 10/694,272 ( now U.S. Patent No.
`
`7,230,1463), each of which was filed 10/27/2003, and each of which in turn is related to
`
`and claims the priority benefit of U.S. Provisional Applications 60/421,263 and
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`60/421,435, each of which was filed on October 25, 2002. The disclosure of each of the
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`patent applications and patents identified in the preceding sentence is incorporated
`
`herein by reference.
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`FIELD OF THE INVENTION
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`This invention relates to compositions having utility in numerous applications,
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`including particularly refrigeration systems, and to methods and systems utilizing such
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`compositions.
`
`In preferred aspects, the present invention is directed to refrigerant
`
`compositions comprising at least one multi-fluorinated olefin of the present invention.
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`BACKGROUND OF THE INVENTION
`
`Fluorocarbon based fluids have found widespread use in many commercial and
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`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
`
`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
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`the vapor to the liquid phase through heat removal at a relatively low pressure and
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`PATENT
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`Attorney Docket No. HOOO3965DlV1 A
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`temperature, compressing the vapor to a relatively elevated pressure, condensing the
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`vapor to the liquid phase through heat removal at this relatively elevated pressure and
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`temperature, and then reducing the pressure to start the cycle over again.
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`While the primary purpose of refrigeration is to remove heat from an object or
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`other fluid at a relatively low temperature, the primary purpose of a heat pump is to add
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`heat at a higher temperature relative to the environment.
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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
`
`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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`Concern has increased in recent years about potential damage to the earth’s
`
`atmosphere and climate, and certain chlorine-based compounds have been identified
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`as particularly problematic in this regard. The use of chlorine-containing compositions
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`(such as chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs) and the like)
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`as refrigerants in air-conditioning and refrigeration systems has become disfavored
`
`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
`
`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-
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`containing refrigerant compounds that will not deplete the ozone layer, such as
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`hydrofluorocarbons (HFCs).
`
`It is generally considered important, however, that any potential substitute
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`refrigerant must also possess those properties present in many of the most widely used
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`fluids, such as excellent heat transfer properties, chemical stability, low- or no- toxicity,
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`non-flammability and lubricant compatibility, 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 HFCs, are relatively insoluble and/or immiscible in the
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`types of lubricants used traditionally with CFC’s and HFCs, including, for example,
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`mineral oils, alkylbenzenes or poly(alpha—olefins).
`
`In order for a refrigeration fluid-
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`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
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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
`
`pump system, as well as other parts of the system, and thus reduce the system
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`efficiency.
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`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.
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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
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`are determined to be nonflammable as determined in accordance with ASTM standard
`
`E-681, dated 2002, which is incorporated herein by reference. Unfortunately, many
`
`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 (H FO-1 243zf) are each flammable and therefore not
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`viable for use in many applications.
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`PATENT
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`Attorney Docket No. HOOO3965DlV1 A
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`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 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).
`
`While the fluorinated olefins described in Smutny may have some level of
`
`effectiveness in heat transfer applications, it is believed that such compounds may also
`
`have certain disadvantages. For example, some of these compounds may tend to
`
`attack substrates, particularly general—purpose plastics such as acrylic resins and ABS
`
`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
`
`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.
`
`Bromofluoromethane and bromochlorofluoromethane derivatives, particularly
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`bromotrifluoromethane (Halon 1301) and bromochlorodifluoromethane (Halon 1211)
`
`have gained widespread use as fire extinguishing agents in enclosed areas such as
`
`airplane cabins and computer rooms. However, the use of various halons 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
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`humans at concentrations necessary to suppress or extinguish fire.
`
`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
`
`systems and methods, while avoiding one or more of the disadvantages noted above.
`
`Applicants have found that the above-noted need, and other needs, can be
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`SUMMARY
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`Attorney Docket No. HOOO3965DIV1 A
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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)
`
`where X is a C2 or a C3 unsaturated, substituted or unsubstituted, alkyl radical, each R
`
`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—1234ze)
`
`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
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`THE COMPOSITIONS
`
`The present invention is directed to compositions comprising at least one
`
`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
`
`double bonds, such compounds at the present time are not considered to be preferred.
`
`As mentioned above, the present compositions comprise one or more
`
`compounds in accordance with Formula I.
`
`In preferred embodiments, the compositions
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`include compounds of Formula II below:
`
`I
`>c=c—R'
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`R
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`R
`
`(H)
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`where each R is independently CI, F, Br,
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`I or H
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`Attorney Docket No. HOOO3965DlV1 A
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`R’ is (CFi2),,Y,
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`Y is CRF2
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`and n is 0 or 1.
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`in highly preferred embodiments, Y is CF3, n is 0 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
`
`Formulas l 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
`
`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,
`
`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
`
`compounds of Formula II, preferably wherein Y is CF3, wherein at least one R on the
`
`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.
`
`in highly preferred embodiments, especially embodiments comprising the low
`
`toxicity compounds described above, n is zero.
`
`In certain highly preferred embodiments
`
`the compositions of the present invention comprise one or more tetrafluoropropenes.
`
`The term “HFO—1234” is used herein to refer to all tetrafluoropropenes. Among the
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`tetrafluoropropenes, both cis- and trans-1, 3, 3, 3-tetrafluoropropene (HFO-1234ze) are
`
`particularly preferred. The term HFO-1234ze is used herein generically to refer to 1, 3,
`
`3, 3-tetrafluoropropene, 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”
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`therefore includes within its scope cisHFO-1234ze, transHFO-1234ze, and all
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`combinations and mixtures of these.
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`Attorney Docket No. HOOO3965DlV1 A
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`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,
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`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
`
`“HFO-1234ze” and 1, 3, 3, 3-tetrafluoropropene refer to both stereo isomers, and the
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`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.
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`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
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`compounds is described in U.S. Patent Nos. 2,889,379; 4,798,818 and 4,465,786, each
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`of which is incorporated herein by reference. EP 974,571, also incorporated herein by
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`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
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`catalyst at elevated temperature, or in the liquid phase with an alcoholic solution of
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`KOH, NaOH, Ca(OH)2 or Mg(OH)2_ In addition, methods for producing compounds in
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`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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`Fluoropropenes” bearing attorney docket number (HOOO3789 (26267)), which is also
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`incorporated herein by reference.
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`The present compositions, particularly those comprising HFO-1234ze, are
`
`believed to possess properties that are advantageous for a number of important
`
`reasons. For example, applicants believe, based at least in part on mathematical
`
`modeling, that the fluoroolefins of the present invention will not have a substantial
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`negative affect on atmospheric chemistry, being negligible contributors to ozone
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`depletion in comparison to some other halogenated species. The preferred
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`compositions of the present invention thus have the advantage of not contributing
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`Attorney Docket No. H0003965DlV1 A
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`substantially to ozone depletion. The preferred compositions also do not contribute
`
`substantially to global warming compared to many of the hydrofluoroalkanes presently
`
`in use.
`
`In certain preferred forms, compositions of the present invention have a Global
`
`Warming Potential (GWP) of not greater than about 1000, more preferably not greater
`
`than about 500, and even more preferably not greater than about 150.
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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
`
`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
`
`Association's Global Ozone Research and Monitoring Project,” which is incorporated
`
`herein by reference.
`
`In certain preferred forms, the present compositions also preferably have an
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`Ozone Depletion Potential (ODP) of not greater than 0.05, more preferably 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 World
`
`Meteorological Association's Global Ozone Research and Monitoring Project,” which is
`
`incorporated herein by reference.
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`The amount of the Formula I compounds, particularly HFO-1234, contained in
`
`the present compositions can vary widely, depending the particular application, and
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`compositions containing more than trace amounts and less than 100% of the compound
`
`are within broad the scope of the present invention. Moreover, the compositions of the
`
`present invention can be azeotropic, azeotrope-like or non—azeotropic.
`
`In preferred
`
`embodiments, the present compositions comprise HFO-1234, preferably HFO-1234ze,
`
`in amounts from about 5% by weight to about 99% by weight, and even more preferably
`
`from about 5% to about 95%. Many additional compounds may be included in the
`
`present compositions, and the presence of all such compounds is within the broad
`
`scope of the invention.
`
`In certain preferred embodiments, the present compositions
`
`include, in addition to HFO-1234ze, one or more of the following:
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`Difluoromethane (HFC-32)
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`Pentafluoroethane (HFC-125)
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`Attorney Docket No. HOOO3965DlV1 A
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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 (H FC—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 components, as well as any additional
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`components which may be included in present compositions, can vary widely within the
`
`general broad scope of the present invention according to the particular application for
`
`the composition, and all such relative amounts are considered to be within the scope
`
`hereof.
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`HEAT TRANSFER COMPOSITIONS
`
`Although 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, more preferably in accordance with Formula
`
`II, and even more preferably HFO-1234ze, in an amount that is at least about 50% by
`
`weight, and even more preferably at least about 70 % by weight, of the composition.
`
`In
`
`many embodiments, it is preferred that the heat transfer compositions of the present
`
`invention comprise transHFO-1234ze.
`
`In certain preferred embodiments, the heat
`
`transfer compositions of the present invention comprise a combination of cisHFO-
`
`1234ze and transHFO1234ze in a cis:trans weight ratio of from about 1 :99 to about
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`10:99, more preferably from about 1 :99 to about 5:95, and even more preferably from
`
`about 1:99 to about 3:97.
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`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
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`Attorney Docket No. HOOO3965DlV1 A
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`according to the present invention, especially those used in vapor compression
`
`systems, include a lubricant, generally in amounts of from about 30 to about 50 percent
`
`by weight of the composition. Furthermore, the present compositions may also include
`
`a compatibilizer, 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 solubilizing 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 (POEs) and Poly Alkylene Glycols
`
`(PAGs), silicone oil, mineral oil, alkyl benzenes (ABs) and poly(alpha—olefin) (PAO) that
`
`are used in refrigeration machinery with hydrofluorocarbon (HFC) refrigerants may be
`
`used with the refrigerant compositions of the present invention.
`
`Many existing refrigeration systems are currently adapted for use in connection
`
`with existing refrigerants, and the compositions of the present invention are believed to
`
`be adaptable for use in many of such systems, either with or without system
`
`modification.
`
`in many applications the compositions of the present invention may
`
`provide an advantage as a replacement in systems, which are currently based on
`
`refrigerants having a relatively high capacity. Furthermore, in embodiments where it is
`
`desired to use a lower capacity refrigerant composition of the present invention, for
`
`reasons of cost for example, to replace a refrigerant of higher capacity, such
`
`embodiments of the present compositions provide a potential advantage. Thus, it is
`
`preferred in certain embodiments to use compositions of the present invention,
`
`particularly compositions comprising a substantial proportion of, and in some
`
`embodiments consisting essentially of transHFO-1234ze, as a replacement for existing
`
`refrigerants, such as HFC-134a.
`
`In certain applications, the refrigerants of the present
`
`invention potentially permit the beneficial use of larger displacement compressors,
`
`thereby resulting in better energy efficiency than other refrigerants, such as HFC-134a.
`
`Therefore the refrigerant compositions of the present invention, particularly
`
`compositions comprising transHFP-1234ze, provide the possibility of achieving a
`
`competitive advantage on an energy basis for refrigerant replacement applications.
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`PATENT
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`Attorney Docket No. HOOO3965DlV1 A
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`It is contemplated that the compositions of the present, including particularly
`
`those comprising HFO-1234ze, also have advantage (either in original systems or when
`
`used as a replacement for refrigerants such as R-12 and R-500), in chillers typically
`
`used in connection with commercial air conditioning systems.
`
`In certain of such
`
`embodiments it is preferred to including in the present HFO-1234ze compositions from
`
`about 0.5 to about 5% of a flammability suppressant, such as CF31.
`
`The present methods, systems and compositions are thus adaptable for use in
`
`connection with automotive air conditioning systems and devices, commercial
`
`refrigeration systems and devices, chillers, residential refrigerator and freezers, general
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`air conditioning systems, heat pumps, and the like.
`
`BLOWING AGENTS, FOAMS AND FOAMABLE COMPOSITIONS
`
`Blowing agents may also comprise or constitute one or more of the present
`
`compositions. As mentioned above, the compositions of the present invention may
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`
`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 Formula II, are present in an amount that is at least about 5
`
`% by weight, and even more preferably at least about 15 % by weight, of the
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`composition.
`
`In certain preferred embodiments, the blowing agent compositions of the
`
`present invention and include, in addition to HFO-1234 (preferably HFO-1234ze) one or
`
`more of the following components as a co-blowing agent, filler, vapor pressure modifier,
`
`or for any other purpose:
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`Difluoromethane (HFC-32)
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`25
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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 (H FC—227ea)
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`30
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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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`

`
`PATENT
`
`Attorney Docket No. HOOO3965DlV1 A
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`1,1,1,3,3-pentafluorobutane (HFC-365mfc)
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`water
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`CO2
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`it is contemplated that the blowing agent compositions of the present invention may
`
`comprise cisHFO—1234ze, transHFO1234ze or combinations thereof.
`
`In certain
`
`preferred embodiments, the blowing agent composition of the present invention
`
`comprise his a combination of cisHFO-1234ze and transHFO1234ze in a cis:trans
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`weight ratio of from about 1 :99 to about 10:99, and even more preferably from about
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`1:99 to about 5:95.
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`In other embodiments, the invention provides foamable compositions, and
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`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
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`blowing agent in a foamable composition, which composition preferably includes one or
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`more additional components capable of reacting and/or foaming under the proper
`
`conditions to form a foam or cellular structure, as is well known in the art. The invention
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`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 other embodiments, the invention provides foamable compositions comprising
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`thermoplastic or polyolefin foams, such as polystyrene (PS), polyethylene (PE),
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`polypropylene (PP) and polyethyleneterpthalate (PET) foams, preferably low-density
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`foams.
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`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,
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`B—8404, and L-5340 which are, generally, polysiloxane polyoxyalkylene block co-
`
`polymers such as those disclosed in U.S. Patent Nos. 2,834,748, 2,917,480, and
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`15
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`20
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`25
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`2,846,458, each of which is incorporated herein by reference. Other optional additives
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`30
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`for the blowing agent mixture may include flame retardants such as tri(2-
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`chloroethyl)phosphate, tri(2—chloropropyl)phosphate, tri(2,3-dibromopropyl)-phosphate,
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`

`
`PATENT
`
`Attorney Docket No. HOOO3965DlV1 A
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`tri(1,3-dichloropropyl) phosphate, diammonium phosphate, various halogenated
`
`aromatic compounds, antimony oxide, aluminum trihydrate, polyvinyl chloride, and the
`
`like.
`
`PROPELLANT AND AEROSOL COMPOSITIONS
`
`In another aspect, the present invention provides propellant compositions
`
`comprising or consisting essentially of a composition of the present invention, such
`
`propellant composition preferably being a sprayable composition. The propellant
`
`compositions of the present invention preferably comprise a material to be sprayed and
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`a propellant comprising, consisting essentially of, or consisting of a composition in
`
`accordance with the present invention.
`
`lnert ingredients, solvents, and other materials
`
`may also be present in the sprayable mixture. Preferably, the sprayable composition is
`
`an aerosol. Suitable materials to be sprayed include, without limitation, cosmetic
`
`materials such as deodorants, perfumes, hair sprays, cleansers, and polishing agents
`
`as well as medicinal materials such as anti-asthma components, anti-halitosis
`
`components and any other medication or the like, including preferably any other
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`medicament or agent intended to be inhaled. The medicament or other therapeutic
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`agent is preferably present in the composition in a therapeutic amount, with a
`
`substantial portion of the balance of the composition comprising a compound of
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`Formula I of the present invention, preferably HFO—1234, and even more preferably
`
`HFO-1234ze.
`
`Aerosol products for industrial, consumer or medical use typically contain one or
`
`more propellants along with one or more active ingredients, inert ingredients or
`
`solvents. The propellant provides the force that expels the product in aerosolized form.
`
`While some aerosol products are propelled with compressed gases like carbon dioxide,
`
`nitrogen, nitrous oxide and even air, most commercial aerosols use liquefied gas
`
`propellants. The most commonly used liquefied gas propellants are hydrocarbons such
`
`as butane, isobutane, and propane. Dimethyl ether and HFC-152a (1, 1-difluoroethane)
`
`are also used, either alone or in blends with the hydrocarbon propellants. Unfortunately,
`
`all of these liquefied gas propellants are highly flammable and their incorporation into
`
`aerosol formulations will often result in flammable aerosol products.
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`15
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`

`
`PATENT
`
`Attorney Docket No. HOOO3965DlV1 A
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`Applicants have come to appreciate the continuing need for nonflammable,
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`liquefied gas propellants with which to formulate aerosol products. The present
`
`invention provides compositions of the present invention, particularly and preferably
`
`compositions comprising HFO-1234, and even more preferably HFO-1234ze, for use in
`
`certain industrial aerosol products, including for example spray cleaners, lubricants, and
`
`the like, and in medicinal aerosols, including for example to deliver medications to the
`
`lungs or mucosal membranes. Examples of this includes metered dose inhalers (MDls)
`
`for the treatment of asthma and other chronic obstructive pulmonary diseases and for
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`delivery of medicaments to accessible mucous membranes or intranasally. The
`
`present invention thus includes methods for treating ailments, diseases and similar
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`health related problems of an organism (such as a human or animal) comprising
`
`applying a composition of the present invention containing a medicament or other
`
`therapeutic component to the organism in need of treatment.
`
`In certain preferred
`
`embodiments, the step of applying the present composition comprises providing a MDI
`
`containing the composition of the present invention (for example, introducing the
`
`composition into the MDI) and then discharging the present composition from the MDI.
`
`The compositions of the present invention, particularly compositions comprising
`
`or consisting essentially of HFO-1234ze, are capable of providing nonflammable,
`
`liquefied gas propellant and aerosols that do not contribute substantially to global
`
`warming. The present compositions can be used to formulate a variety of industrial
`
`aerosols or other sprayable compositions such as contact cleaners, dusters, lubricant
`
`sprays, and the like, and consumer aerosols such as personal care products, household
`
`products and automotive products. HFO-1234ze is particularly preferred for use as an
`
`important component of propellant compositions for in medicinal aerosols such as
`
`metered dose inhalers. The medicinal aerosol and/or propellant and/or sprayable
`
`compositions of the present invention in many applications include, in addition to
`
`compound of formula (I) or (II) (preferably HFO-1234ze), a medicament such as a beta-
`
`agonist, a corticosteroid or other medicament, and, o