(12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT)
`
`(19) World Intellectual Property
`Organization
`International Bureau
`
`(43) lntemational Publication Date
`10 November 2005 (10.11.2005)
`
`(10) International Publication Number
`
`WO 2005/105947 A2
`
`(51) International Patent Classification7:
`3/30, C08] 9/14
`
`C09K 5/04,
`
`(21) International Application Number:
`PCT/US2005/014873
`
`(22) International Filing Date:
`
`29 April 2005 (29.04.2005)
`
`(25) Filing Language:
`
`(26) Publication Language:
`
`(30) Priority Data:
`10/837,525
`
`English
`
`English
`
`29 April 2004 (29.04.2004)
`
`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,
`NJ 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 14051 (US).
`THOIVIAS, Raymond, H. [US/US]; 5990 Hopi Court,
`Pendleton, NY 14094 (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, HR, HU, ID, IL, IN, IS, JP, KE,
`KG, KM, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MA,
`MD, MG, MK, MN, MW, MX, MZ, NA, NI, NO, NZ, OM,
`PG, PH, PL, PT, RO, RU, SC, SD, SE, SG, SK, SL, SM, SY,
`TJ, TM, TN, TR, TT, TZ, UA, UG, US, UZ, VC, VN, YU,
`ZA, ZM, ZW.
`
`(84) 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, 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).
`
`Declaration under Rule 4.17:
`
`of inventorship (Rule 4.17(iv))for US only
`
`Published:
`
`without international search report and to be republished
`upon receipt of that report
`
`(74) Agents: SZUCH, Colleen et al.; 101 Columbia Road, P.O.
`Box 2245, Morristown, NJ 07962-2245 (US).
`
`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: The use to e of tetrafluoropropenes, particularly (HFO—1234) in a vari-
`ety of applications, including refrigeration equipment, is 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.
`
`Arkema Exhibit 1029
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`N 4 1
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`In
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`aV
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`-1E
`In
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`aeN g
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`Arkema Exhibit 1029
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`COMPOSITIONS CONTAINING FLUORINE SUBSTITUTED OLEFINS
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`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
`
`multi—fluorinated 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 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
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`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 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
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`relatively insoluble andlor immiscible in the types of lubricants used
`
`traditionally with CFC’s and HFCs, including, for example, mineral oils,
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`alkylbenzenes or poly(alpha—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-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 HFCs, which might othen/vise 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.
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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 — 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 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, such compounds may have a boiling point, which is too
`
`high to make them useful as a refrigerant in certain applications.
`
`Bromofluoromethane and bromochlorofluoromethane derivatives,
`
`particularly bromotrifluoromethane (Halon 1301) and
`
`bromochlorodifluoromethane (Halon 1211) have gained widespread use
`
`as fire extinguishing agents in enclosed areas such as 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 humans at concentrations necessary to suppress or extinguish
`
`fire.
`
`Applicants have thus come to appreciate a need for compositions,
`
`and particularly heat transfer compositions, fire extinguishing/suppression
`
`compositions, blowing agents, solvent compositions, and compatabilizing
`
`agents, that are potentially useful in numerous applications, including
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`vapor compression heating and cooling 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 satisfied by compositions comprising one or more C3 or C4
`
`fluoroalkenes, preferably compounds having Formula I as follows:
`
`XCFZRB-z (I)
`
`where X is a C2 or a C3 unsaturated, substituted or unsubstituted, alkyl
`
`radical, each R is independently Cl, F, Br, lor H, and z is 1 to 3. Highly
`
`preferred among the compounds of Formula I are the cis- and trans-
`
`isomers of 1, 3, 3, 3-tetrafluoropropene (HFO~1234ze)
`
`The present invention provides also methods and systems which
`
`utilize the compositions of the present invention, including methods and
`
`systems for heat transfer, foam blowing, solvating, flavor and fragrance
`
`extraction and/or delivery, and aerosol generation.
`
`DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
`THE COMPOSITIONS
`
`The present invention is directed to compositions comprising at
`
`least one fluoroalkene containing from 3 to 4 carbon atoms, preferably
`
`three carbon atoms, and at least one carbon—carbon double bond. The
`
`fluoroalkene compounds of the present invention are sometimes referred
`
`to herein for the purpose of convenience as hydrof|uoro—olefins or “HFOs”
`
`if they contain at least one hydrogen. Although it is contemplated that the
`
`HFOs of the present invention may contain two carbon -~ carbon double
`
`bonds, such compounds 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
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`embodiments, the compositions include compounds of Formula II below:
`
`R\
`R/C
`
`T.,_
`i
`
`(ll)
`
`where each R is independently Cl, F, Br, I or H
`
`R’ is (CR2)nY,
`
`Y is CRF2
`
`and n is O or 1.
`
`In highly preferred embodiments, Y is CF3, n is O and at least one of the
`
`remaining Rs is F.
`
`Applicants believe that, in general, the compounds of the above
`
`identified Formulas I and II are generally effective and exhibit utility in
`
`refrigerant compositions, blowing agent compositions, compatibilizers,
`
`aerosols, propellants, fragrances, flavor formulations, and solvent
`
`compositions of the present invention. However, applicants have
`
`surprisingly and unexpectedly found that 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 any and all compositions, which would othen/vise
`
`contain relatively toxic compounds 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, 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 effective
`
`and of beneficially low toxicity.
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`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
`
`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”
`
`therefore includes within its scope cisHFO—1234ze, transHFO—1234ze, and
`
`all combinations and mixtures of these.
`
`Although the propelties 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 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—tetraf|uoropropene 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=CHg by catalytic vapor phase fluorination of various saturated and
`
`unsaturated ha|ogen—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
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`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)g or Mg(OH)g_ 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 reference.
`
`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 negative affect on
`
`atmospheric chemistry, being negligible contributors to ozone depletion in
`
`comparison to some other halogenated species. The preferred
`
`compositions of the present invention thus have the advantage of not
`
`contributing substantially to ozone depletion. The preferred compositions
`
`also do not contribute substantially to global warming compared to many
`
`of the hydrofluoroalkanes presently in use.
`
`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.
`
`In certain embodiments, the GWP of the present
`
`compositions is not greater than about 100 and even more preferably not
`
`greater than about 75. As used herein, “GWP” is measured relative to that
`
`of carbon dioxide and over a 100—year time horizon, as defined in “The
`
`Scientific Assessment of Ozone Depletion, 2002, a report of the World
`
`Meteorological Association's Global Ozone Research and Monitoring
`
`Project,” which is incorporated herein by reference.
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`In certain preferred forms, the present compositions also preferably
`
`have an 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.
`
`The amount of the Formula I compounds, particularly HFO-1234,
`
`contained in the present compositions can vary widely, depending the
`
`particular application, and 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.
`
`ln
`
`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:
`
`Difluoromethane (HFC-32)
`
`Pentafluoroethane (HFC—125)
`
`1,1,2,2—tetrafluoroethane (HFC—134)
`
`1,1,1,2—Tetraf|uoroethane (HFC-134a)
`
`Difluoroethane (HFC—152a)
`
`1,1,1,2,3,3,3-Heptafluoropropane (HFC—227ea)
`
`1,1,1 ,3,3,3-hexafluoropropane (HFC-236fa)
`
`1,1,1,3,3—pentafluoropropane (HFC—245fa)
`
`1,1,1 ,3,3-pentafluorobutane (HFC—365mfc)
`
`water
`
`CO2
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`The relative amount of any of the above noted components, as well as any
`
`additional 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.
`
`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 cisstrans weight ratio of from about 1:99 to about
`
`10:99, more preferably from about 1:99 to about 5:95, and even more
`
`preferably from about 1:99 to about 3:97.
`
`The compositions of the present invention may include other
`
`components for the purpose of enhancing or providing certain functionality
`
`to the composition, or in some cases to reduce the cost of the
`
`composition. For example, refrigerant compositions according to 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
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`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 po|y(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
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`higher capacity, such embodiments of the present compositions provide a
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`potential advantage. Thus, It is preferred in certain embodiments to use
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`compositions of the present invention, particularly compositions
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`comprising a substantial proportion of, and in some embodiments
`
`consisting essentially of transHFO—1234ze, as a replacement for existing
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`refrigerants, such as HFC-134a.
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`In certain applications, the refrigerants of
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`the present invention potentially permit the beneficial use of larger
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`displacement compressors, thereby resulting in better energy efficiency
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`than other refrigerants, such as HFC-134a. Therefore the refrigerant
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`compositions of the present invention, particularly compositions
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`comprising transHFP-1234ze, provide the possibility of achieving a
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`competitive advantage on an energy basis for refrigerant replacement
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`applications.
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`It is contemplated that the compositions of the present, including
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`particularly those comprising HFO-1234ze, also have advantage (either in
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`original systems or when used as a replacement for refrigerants such as
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`R-12 and R-500), in chillers typically used in connection with commercial
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`air conditioning systems.
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`in certain of such embodiments it is preferred to
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`including in the present HFO-1234ze compositions from about 0.5 to about
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`5% of a flammability suppressant, such as CF3l.
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`The present methods, systems and compositions are thus
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`adaptable for use in connection with automotive air conditioning systems
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`and devices, commercial refrigeration systems and devices, chillers,
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`residential refrigerator and freezers, general air conditioning systems, heat
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`pumps, and the like.
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`BLOWING AGENTS, FOAMS AND FOAMABLE COMPOSITIONS
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`Blowing agents may also comprise or constitute one or more of the
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`present compositions. As mentioned above, the compositions of the
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`present invention may include the compounds of the present invention in
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`widely ranging amounts.
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`It is generally preferred, however, that for
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`preferred compositions for use as blowing agents in accordance with the
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`present invention, compound(s) in accordance with Formula I, and even
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`more preferably Formula ll, are present in an amount that is at least about
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`5 ‘/0 by weight, and even more preferably at least about 15 % by weight, of
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`the composition.
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`in certain preferred embodiments, the blowing agent
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`compositions of the present invention and include, in addition to HFO-
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`1234 (preferably HFO~1234ze) one or more of the following components
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`as a co—blowing agent, filler, vapor pressure modifier, or for any other
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`purpose:
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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 (HFC-152a)
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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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`CO2
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`it is contemplated that the blowing agent compositions of the present
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`invention may comprise cisHFO-1234ze, transHFO1234ze or
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`combinations thereof.
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`In certain preferred embodiments, the blowing
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`agent composition of the present invention comprise his a combination of
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`cisHFO-1234ze and transHFO1234ze in a cisztrans weight ratio of from
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`about 1 :99 to about 10:99, and even more preferably from about 1:99 to
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`about 5:95.
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`In other embodiments, the invention provides foamabie
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`compositions, and preferably polyurethane, polyisocyanurate and extruded
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`thermoplastic foam compositions, prepared using the compositions of the
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`present invention.
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`In such foam embodiments, one or more of the
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`present compositions are included as or part of a blowing agent in a
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`foamabie composition, which composition preferably includes one or more
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`additional components capable of reacting and/or foaming under the
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`proper conditions to form a foam or cellular structure, as is well known in
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`the art. The invention also relates to foam, and preferably closed cell
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`foam, prepared from a polymer foam formulation containing a blowing
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`agent comprising the compositions of the invention.
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`In yet other
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`embodiments, the invention provides foamabie compositions comprising
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`thermoplastic or polyolefin foams, such as polystyrene (PS), polyethylene
`
`(PE), polypropylene (PP) and polyethyleneterpthalate (PET) foams,
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`preferably low-density foams.
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`In certain preferred embodiments, dispersing agents, cell
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`stabilizers, surfactants and other additives may also be incorporated into
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`the blowing agent compositions of the present invention. Surfactants are
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`optionally but preferably added to serve as cell stabilizers. Some
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`representative materials are sold under the names of DC-193, B—8404,
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`and L-5340 which are, generally, polysiloxane polyoxyalkylene block co-
`
`polymers such as those disclosed in U.S. Patent Nos. 2,834,748,
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`2,917,480, and 2,846,458, each of which is incorporated herein by
`
`reference. Other optional additives for the blowing agent mixture may
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`include flame retardants such as tri(2-chloroethy|)phosphate, tri(2-
`
`chloropropyl)phosphate, tri(2,3—dibromopropyl)-phosphate, tri(1,3-
`
`dichloropropyl) phosphate, diammonium phosphate, various halogenated
`
`aromatic compounds, antimony oxide, aluminum trihydrate, polyvinyl
`
`chloride, and the like.
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`PROPELLANT AND AEROSOL COMPOSITIONS
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`in another aspect, the present invention provides propellant
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`compositions comprising or consisting essentially of a composition of the
`
`present invention, such propellant composition preferably being a
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`sprayable composition. The propellant compositions of the present
`
`invention preferably comprise a material to be sprayed and a propellant
`
`comprising, consisting essentially of, or consisting of a composition in
`
`accordance with the present invention.
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`lnert ingredients, solvents, and
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`other materials may also be present in the sprayable mixture. Preferably,
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`the sprayable composition is an aerosol. Suitable materials to be sprayed
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`include, without limitation, cosmetic materials such as deodorants,
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`perfumes, hair sprays, cleansers, and polishing agents as well as
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`medicinal materials such as anti—asthma components, anti—halitosis
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`components and any other medication or the like, including preferably any
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`other medicament or agent intended to be inhaled. The medicament or
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`other therapeutic agent is preferably present in the composition in a
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`therapeutic amount, with a substantial portion of the balance of the
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`composition comprising a compound of Formula I of the present invention,
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`preferably HFO-1234, and even more preferably HFO—1234ze.
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`Aerosol products for industrial, consumer or medical use typically
`
`contain one or more propellants along with one or more active ingredients,
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`inert ingredients or solvents. The propellant provides the force that expels
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`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. Dlmethyl 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
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`aerosol formulations will often result in flammable aerosol products.
`
`Applicants have come to appreciate the continuing need for
`
`nonflammable, 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 delivery of
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`medicaments to accessible mucous membranes or intranasally. The
`
`present invention thus includes methods for treating ailments, diseases
`
`and similar health related problems of an organism (such as a human or
`
`animal) comprising applying a composition of the present invention
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`con