(12)
`
`United States Patent
`
`Singh et al.
`
`(10) Patent No.:
`(45) Date of Patent:
`
`US 7,279,451 B2
`*Oct. 9, 2007
`
`US007279451B2
`
`(54)
`
`(75)
`
`COMPOSITIONS CON'l'AI1\'ING FLUORINE
`SUBSTITUTED OLEFINS
`
`Inventors: Rajiv R. Singh. Getzville. NY (US):
`Hang T. Pllam. Amherst. NY (US); Ian
`Shankland. Randolph. NJ (US)
`
`(73)
`
`Assignec: Honeywell International Inc..
`Morristown. NJ (US)
`
`(*‘)
`
`Notice:
`
`Subject to any disclaimer. the tenn of this
`patent is extended or adjusted under 35
`U.S.C. l54(b) by 27 days.
`
`This patent is subject to a tenninal dis-
`claimcr.
`
`(21)
`
`Appl. N0.: 10/837,525
`
`(22)
`
`Filed:
`
`Apr. 29. 2004
`
`(65)
`
`(63)
`
`(60)
`
`(51)
`
`(52)
`
`(53)
`
`(56)
`
`Prior Publication Data
`
`US 2004/0256594 A]
`
`Dec. 23, 2004
`
`Related U.S. Application Data
`
`(‘ontinuation-in-part of application No. 10/694273.
`filed on Oct. 27. 2003. and a continuation-in-part of
`application No. 10/695212. filed on Oct. 27. 2003.
`now abandoned. and a continuation-in-part of appli-
`cation No. 10/694272. filed on Oct. 27. 2003. now
`Pat. No. 7.230.146.
`
`Provisional application No. 60/421.263. filed on Oct.
`25. 2002. provisional application No. 60/421435.
`filed on Oct. 25. 2002.
`
`Int. Cl.
`(2006.01)
`C09K 5/00
`U.S. Cl.
`.................... .. 510/412; 510/407: 510/408:
`510/410: 510/415
`Field of Classification Search .............. .. 510/407.
`510/408. 410, 411. 415. 412
`Sec application tile for complete search history.
`References Cited
`
`5616.275 A
`5.679.875 A
`5.714.083 A
`5.736.063 A
`5.744.052 A
`5.788.886 A
`6.041.621 A
`6.111.150 A "‘
`6.124.510 A
`6.258.292 B1
`6.274.779 Bl
`6.300.378 B1‘
`6.327.866 B1
`6.516.837 B2
`6.858.571 B2‘
`200310127115 A1
`200410127383 A1
`200410256594 A1
`200510054741 A1
`200510107246 A1
`
`5701167
`
`411997 (‘hisolm et al.
`1011997 Aoyamacta et al.
`2.11998 Turner etal.
`252167
`.
`411998 Richard et al.
`411998 Bivens ....................... . 252.‘67
`811998 Minor et ill.
`312000 (’)ls7ewski et al.
`812000 Sakyu et al.
`912000 Elsheikh et al.
`712001 Turner et al.
`812001 Merkel et al.
`1012001 Tapscott
`................... .. 5141743
`12.12001 Novak et al.
`2.12003 Thomas et al.
`2.12005 Pham et al.
`712003 Thomas et al.
`712004 Pham et al.
`12.12004 Singh ct a1
`312005 Zipfel et al.
`512005 Thomas ct al.
`
`
`
`141367
`5101408
`
`FOREIGN PATENT DOCUMFNTS
`
`EP
`EP
`EP
`EP
`EP
`GB
`JP
`W0
`W0
`W0
`WO
`W0
`WO
`
`0398147
`0644173 Al
`0974571
`105 5439
`1191080
`950876
`2004110388
`WO03"064508
`WO2004 "037752
`W02004037913
`WO2005"103187
`W02005"l03 188
`WO2005"105947
`
`1111990
`511993
`112000
`1112000
`712002
`211964
`411992
`812003
`512004
`512004
`1112005
`1112005
`1112005
`
`OTHER PUBLICATIONS
`
`U.S. Appl. No. 101694.272. filed Oct. 27. 2003. Process for Pro-
`ducing Fluoropropenes; Merkel et al.
`US. Appl. No. 101694.273. filed Oct. 27. 2003. Compositions
`Containing Fluorine Substituted Olefins; Singh et al.
`US. Appl. No. 101695.212. filed Oct. 27. 2003. Fluorinated Alkene
`Refrigerant Compositions; Thomas et al.
`
`* cited by examiner
`
`Primary Examiner—Irina S Zcmcl
`(74) .4ttorne_v. Agent, or Firm—Co1leen D Szuch
`
`U.S. PA'1'1:'N'1' DOCUM1iN'l'S
`
`(57)
`
`ABSTRACT
`
`2.931.840 A "
`2.996.555 A “
`3.723.318 A
`3.884.828 A
`4.788.352 A
`4.798.818 A
`4.944.890 A
`5.250.208 A
`5.578.137 A
`
`41960 Marquis ................... .. 570.-‘159
`81961 Rausch ..................... .. 570.1156
`31973 Butler et al.
`5“i975 Butler et al.
`1111988 Smutny .................... .. 570.-“I53
`1“i989 Baizer et al.
`711990 Deeb et al.
`10“i993 Merchant et al.
`1111996 Shealy
`
`The use to c of tctrafluoropropcncs. particularly (1 1170- 1 234)
`in a variety of applications. including refrigeration equip-
`ment. 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.
`
`50 Claims, 1 Drawing Sheet
`
`Page 1 of 12
`
`Arkema Exhibit 1021
`
`Arkema Exhibit 1021
`
`

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`U.S. Patent
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`
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`Oct. 9, 2007
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`US 7,279,451 B2
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`Figure 1
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`Page 2 of 12
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`Page 2 of 12
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`

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`US 7,279,451 B2
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`1
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`COMPOSITIONS CONTAINING FLUORINE
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`SUBSTITUTED OLEFINS
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`RELATED APPLICATIONS
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`The present application is related to and claims the
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`priority benefit of U.S. Provisional Application Nos. 60/421,
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`263, and 60/421,435, each of which was filed on Oct. 25,
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`2002, and each of which is incorporated herein by reference.
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`The present application is also related to and incorporates by
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`reference each of the following pending U.S. patent appli-
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`cations Ser. No. 10/694,273, filed Oct. 27, 2003; Ser. No.
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`10/695,212, filed Oct. 27, 2003; and Ser. No. 10/694,272
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`filed Oct. 27, 2003.
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`The present application is related to each of the following
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`U.S. Provisional Applications, each of which is filed con-
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`currently herewith and incorporated herein by reference:
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`60/567,426 and 60/567,427, each entitled “Processes for
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`Synthesis of 1,3,3,3-tetrafluoropropene.”
`The present application is related to the following regular
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`U.S. Applications, each of which is filed concurrently here-
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`with and incorporated herein by reference: Ser. No. 10/837,
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`521 entitled “Heat Transfer Fluid Comprising Trans-1,3,3,
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`3-tetrafluoropropene,” and Ser. No. 10/837,526, entitled
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`“Azeotrope-like Compositions Of Tetrafluoropropene and
`Carbon Dioxide.”
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`FIELD OF THE INVENTION
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`This invention relates to compositions having utility in
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`numerous applications, including particularly refrigeration
`systems, and to methods and systems utilizing such com-
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`positions.
`In preferred aspects,
`the present
`invention is
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`directed to refrigerant compositions comprising at least one
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`multi-fluorinated olefin of the present invention.
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`BACKGROUND OF THE INVENTION
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`Fluorocarbon based fluids have found widespread use in
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`many commercial and industrial applications. For example,
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`fluorocarbon based fluids are frequently used as a working
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`fluid in systems such as air conditioning, heat pump and
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`refrigeration applications. The vapor compression cycle is
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`one of the most commonly used type methods to accomplish
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`cooling or heating in a refrigeration system. The vapor
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`compression cycle usually involves the phase change of the
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`refrigerant from the liquid to the vapor phase through heat
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`absorption at a relatively low pressure and then from the
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`vapor to the liquid phase through heat removal at a relatively
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`low pressure and temperature, compressing the vapor to a
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`relatively elevated pressure, condensing the vapor to the
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`liquid phase through heat removal at this relatively elevated
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`pressure and temperature, and then reducing the pressure to
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`start the cycle over again.
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`While the primary purpose of refrigeration is to remove
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`heat from an object or other fluid at a relatively low
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`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
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`many heat exchange fluids, such as refrigerants, for many
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`years in many applications. For, example, fluoroalkanes,
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`such as chlorofluoromethane and chlorofluoroethane deriva-
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`tives, have gained widespread use as refrigerants in appli-
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`cations including air conditioning and heat pump applica-
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`tions owing to their unique combination of chemical and
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`physical properties. Many of the refrigerants commonly
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`2
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`utilized in vapor compression systems are either single
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`components fluids or azeotropic mixtures.
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`Concern has increased in recent years about potential
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`damage to the earth’s atmosphere and climate, and certain
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`chlorine-based compounds have been identified as particu-
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`larly problematic in this regard. The use of chlorine-con-
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`taining compositions (such as chlorofluorocarbons (CFCs),
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`hydrochlorofluorocarbons (HCFCs) and the like) as refrig-
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`erants in air-conditioning and refrigeration systems has
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`become disfavored because of the ozone-depleting proper-
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`ties associated with many of such compounds. There has
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`thus been an increasing need for new fluorocarbon and
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`hydrofluorocarbon compounds and compositions that ofler
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`alternatives for refrigeration and heat pump applications.
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`For example,
`it has become desirable to retrofit chlorine-
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`containing refrigeration systems by replacing chlorine-con-
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`taining refrigerants with non-chlorine-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
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`potential substitute refrigerant must also possess those prop-
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`erties present in many of the most widely used fluids, such
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`as excellent heat transfer properties, chemical stability, low-
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`or no-toxicity, non-flamrnability and lubricant compatibility,
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`among others.
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`Applicants have come to appreciate that lubricant com-
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`patibility is of particular importance in many of applications.
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`More particularly,
`it is highly desirably for refrigeration
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`fluids to be compatible with the lubricant utilized in the
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`compressor unit, used in most refrigeration systems. Unfor-
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`tunately, many non-chlorine-containing refrigeration fluids,
`including HFCs, are relatively insoluble and/or immiscible
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`in the types of lubricants used traditionally with CFC’s and
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`HFCs, including, for example, mineral oils, alkylbenzenes
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`or poly(alpha-olefins). In order for a refrigeration fluid-
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`lubricant combination to work at a desirable level of efli-
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`ciently within a compression refrigeration, air-conditioning
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`and/or heat pump system, the lubricant should be sufliciently
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`soluble in the refrigeration liquid over a wide range of
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`operating temperatures. Such solubility lowers the viscosity
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`of the lubricant and allows it to flow more easily throughout
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`the system. In the absence of such solubility, lubricants tend
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`to become lodged in the coils of the evaporator of the
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`refrigeration, air-conditioning or heat pump system, as well
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`as other parts of the system, and thus reduce the system
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`efliciency.
`With regard to efliciency in use, it is important to note that
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`a loss in refrigerant thermodynamic performance or energy
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`efliciency may have secondary environmental
`impacts
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`through increased fossil fuel usage arising from an increased
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`demand for electrical energy.
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`Furthermore, it is generally considered desirably for CFC
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`refrigerant substitutes to be effective without major engi-
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`neering changes to conventional vapor compression tech-
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`nology currently used with CFC refrigerants.
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`Flammability is another important property for many
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`applications. That is, it is considered either important or
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`essential in many applications, including particularly in heat
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`transfer applications, to use compositions, which are non-
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`flammable. Thus, it is frequently beneficial to use in such
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`compositions compounds, which are nonflammable. As used
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`herein, the term “nonflammable” refers to compounds or
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`compositions, which are determined to be nonflammable as
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`determined in accordance with ASTM standard E-681, dated
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`2002, which is incorporated herein by reference. Unfortu-
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`nately, many HFCs, which might otherwise be desirable for
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`used in refrigerant compositions are not nonflammable. For
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`Page 3 of 12
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`US 7,279,451 B2
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`3
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`example, the fluoroalkane difluoroethane (HFC-152a) and
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`the fluoroalkene 1,1,1-trifluoropropene (HFO-1243zf) are
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`each flammable and therefore not viable for use in many
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`applications.
`Higher fluoroalkenes, that is fluorine-substituted alkenes
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`having at least five carbon atoms, have been suggested for
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`use as refrigerants. U.S. Pat. No. 4,788,352—Smutny is
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`directed to production of fluorinated C5 to C8 compounds
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`having at least some degree of unsaturation. The Smutny
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`patent identifies such higher olefins as being known to have
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`utility as refrigerants, pesticides, dielectric fluids, heat trans-
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`fer fluids, solvents, and intermediates in various chemical
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`reactions. (See colunm 1, lines 11-22).
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`While the fluorinated olefins described in Smutny may
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`have some level of effectiveness in heat transfer applica-
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`tions,
`it is believed that such compounds may also have
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`certain disadvantages. For example, some of these com-
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`pounds may tend to attack substrates, particularly general-
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`purpose plastics such as acrylic resins and ABS resins.
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`Furthermore, the higher olefinic compounds described in
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`Smutny may also be undesirable in certain applications
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`because of the potential level of toxicity of such compounds
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`which may arise as a result of pesticide activity noted in
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`Smutny. Also, such compounds may have a boiling point,
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`which is too high to make them useful as a refrigerant in
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`certain applications.
`bromochlorofluoromethane
`Bromofluoromethane
`and
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`(Halon
`derivatives, particularly bromotrifluoromethane
`1301) and bromochlorodifluoromethane (Halon 1211) have
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`gained widespread use as fire extinguishing agents in
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`enclosed areas such as airplane cabins and computer rooms.
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`However, the use of various halons is being phased out due
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`to their high ozone depletion. Moreover, as halons are
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`frequently used in areas where humans are present, suitable
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`replacements must also be safe to humans at concentrations
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`necessary to suppress or extinguish fire.
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`Applicants have thus come to appreciate a need for
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`compositions, and particularly heat transfer compositions,
`
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`
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`extinguishing/suppression
`compositions,
`blowing
`fire
`agents, solvent compositions, and compatabilizing agents,
`
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`
`that are potentially useful in numerous applications, includ-
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`
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`
`
`ing vapor compression heating and cooling systems and
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`
`
`methods, while avoiding one or more of the disadvantages
`
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`
`
`noted above.
`
`
`
`SUMMARY
`
`
`4
`
`DETAILED DESCRIPTION OF PREFERRED
`
`
`EMBODIMENTS
`
`
`
`
`The Compositions
`
`
`The present invention is directed to compositions com-
`
`
`
`
`
`
`prising at least one fluoroalkene containing from 3 to 4
`
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`
`
`carbon atoms, preferably three carbon atoms, and at least
`
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`
`
`one carbon-carbon double bond. The fluoroalkene com-
`
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`
`
`
`
`pounds of the present invention are sometimes referred to
`
`
`
`
`
`
`
`herein for the purpose of convenience as hydrofluoro-olefins
`
`
`
`
`
`
`or “HFOs” if they contain at least one hydrogen. Although
`
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`
`
`it is contemplated that the HFOs of the present invention
`
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`
`
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`
`
`may contain two carbon-carbon double bonds, such com-
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`
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`pounds at the present time are not considered to be preferred.
`
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`
`
`As mentioned above, the present compositions comprise
`
`
`
`
`
`
`
`one or more compounds in accordance with Formula I. In
`
`
`
`
`
`
`
`preferred embodiments,
`the compositions include com-
`
`
`
`
`
`
`pounds of Formula II below:
`
`
`
`
`(11)
`
`
`
`where each R is independently Cl, F, Br, I or H
`
`
`
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`
`
`R‘ is (CR2)nY,
`
`
`Y is CRF2
`
`
`and n is 0 or 1.
`
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`
`
`In highly preferred embodiments, Y is CF3, n is 0 and at least
`
`
`
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`
`
`one of the remaining Rs is F.
`
`
`
`
`Applicants believe that, in general, the compounds of the
`
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`
`
`above identified Formulas I and II are generally effective and
`
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`
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`
`
`
`exhibit utility in refrigerant compositions, blowing agent
`
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`
`
`compositions, compatibilizers, aerosols, propellants,
`fra-
`grances, flavor formulations, and solvent compositions of
`
`
`
`
`
`
`
`the present invention. However, applicants have surprisingly
`
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`
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`
`
`and unexpectedly found that certain of the compounds
`
`
`
`
`
`
`
`
`having a structure in accordance with the formulas described
`
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`
`
`
`above exhibit a highly desirable low level of toxicity com-
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`
`
`
`pared to other of such compounds. As can be readily
`
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`
`
`appreciated,
`this discovery is of potentially enormous
`
`
`
`
`
`
`
`advantage and benefit for the formulation of not only
`
`
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`
`
`
`
`
`refrigerant compositions, but also any and all compositions,
`
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`
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`
`
`
`which would otherwise 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
`
`
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`
`
`
`terminal carbon is H, and at least one of the remaining Rs is
`
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`
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`F. Applicants believe also that all structural, geometric and
`
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`
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`stereoisomers of such compounds are effective and of ben-
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`
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`eficially low toxicity.
`In highly preferred embodiments, especially embodi-
`
`
`
`
`
`
`ments comprising the low toxicity compounds described
`
`
`
`
`
`
`
`above, n is zero. In certain highly preferred embodiments the
`
`
`
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`
`
`
`compositions of the present invention comprise one or more
`
`
`
`
`
`
`
`tetrafluoropropenes. The term “HFO-1234” is used herein to
`
`
`
`
`
`
`refer to all tetrafluoropropenes. Among the tetrafluoropro-
`
`
`
`
`
`penes, 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-tetrafluoropro-
`
`
`
`
`
`
`
`pene, independent of whether it is the cis- or trans-forrn. The
`
`
`
`
`
`
`
`terms “cisHFO-1234ze” and “transHFO-1234ze” are used
`
`
`
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`
`
`herein to describe the cis- and trans-forrns of 1,3,3,3-
`
`
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`
`
`5
`
`
`
`10
`
`15
`
`20
`
`
`25
`
`
`30
`
`
`35
`
`
`40
`
`
`45
`
`
`50
`
`
`55
`
`
`60
`
`
`65
`
`
`Applicants have found that the above-noted need, and
`
`
`
`
`
`
`
`
`other needs, can be satisfied by compositions comprising
`
`
`
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`
`
`
`one or more C3 or C4 fluoroalkenes, preferably compounds
`
`
`
`
`
`having Formula I as follows:
`
`
`
`
`XCFzR3—z
`
`(1)
`
`
`
`
`
`where X is a C2 or a C3 unsaturated, substituted or unsub-
`
`
`
`
`stituted, alkyl radical, each R is independently Cl, F, Br, I or
`
`
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`
`
`
`
`
`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-
`
`
`
`
`
`
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`
`
`
`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
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`delivery, and aerosol generation.
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`Page 4 of 12
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`Page 4 of 12
`
`

`
`
`
`US 7,279,451 B2
`
`
`
`6
`
`as defined in “The Scientific Assessment of Ozone Deple-
`
`
`
`
`
`
`
`tion, 2002, A report of the World Meteorological Associa-
`
`
`
`
`
`
`
`
`tion’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 composi-
`tions 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-azeotro-
`
`
`
`
`
`pic. 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
`
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`
`
`
`
`more preferably from about 5% to about 95%. Many addi-
`
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`
`
`tional compounds may be included in the present composi-
`
`
`
`
`
`
`
`tions, and the presence of all such compounds is within the
`
`
`
`
`
`
`
`
`broad scope of the invention. In certain preferred embodi-
`
`
`
`
`
`
`
`
`ments,
`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-Tetrafluoroethane (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-3 65mfc)
`water
`
`
`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 pre-
`
`
`
`
`
`
`
`ferred 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 10:99, more preferably from about 1:99 to
`
`
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`
`
`
`
`
`
`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 lubri-
`
`
`
`
`
`
`
`cant, 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
`
`
`
`
`
`
`
`
`
`
`
`
`
`co,
`
`10
`
`15
`
`20
`
`
`
`25
`
`
`30
`
`
`
`35
`
`
`40
`
`
`
`45
`
`50
`
`
`
`55
`
`
`60
`
`65
`
`
`5
`
`tetrafluoropropene respectively. The term “HFO-1234ze”
`
`
`
`
`
`therefore includes within its scope cisHFO-1234ze, trans
`
`
`
`
`
`
`
`HFO-1234ze, and all combinations and mixtures of these.
`
`
`
`
`
`
`Although the properties of cisHFO-1234ze and trans
`
`
`
`
`
`
`
`HFO-1234ze differ in at least some respects, it is contem-
`
`
`
`
`
`
`
`
`plated 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 refrig-
`
`
`
`
`
`
`
`eration systems because of its relatively low boiling point
`
`
`
`
`
`
`
`(—19° C.),
`is nevertheless contemplated that cisHFO-
`it
`
`
`
`
`
`
`
`
`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 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 fluoro-
`
`
`
`
`
`
`
`propenes such as CF3CH=CH2 by catalytic vapor phase
`
`
`
`
`
`
`fluorination of various saturated and unsaturated halogen-
`
`
`
`
`
`
`
`containing C3 compounds is described in U.S. Pat. Nos.
`
`
`
`
`
`
`
`2,889,379; 4,798,818 and 4,465,786, each ofwhich is incor-
`
`
`
`
`
`
`
`porated 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-pentafluoropro-
`pane (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 gener-
`
`
`
`
`
`
`
`
`ally in connection with pending U.S. 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 math-
`
`
`
`
`
`
`
`ematical modeling,
`the fluoroolefins of the present
`that
`
`
`
`
`
`
`
`
`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
`
`
`
`
`
`
`
`
`
`
`In certain embodiments,
`the GWP of the present
`150.
`
`
`
`
`
`
`
`
`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 Assess-
`
`
`
`
`
`
`
`ment of Ozone Depletion, 2002, a report of the World
`
`
`
`
`
`
`
`
`Meteorological Association’s Global Ozone Research and
`
`
`
`
`
`
`Monitoring Project,” which is incorporated herein by refer-
`
`
`
`
`
`
`ence.
`
`
`
`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
`
`
`
`
`
`
`
`
`
`Page 5 of 12
`
`Page 5 of 12
`
`

`
`
`
`US 7,279,451 B2
`
`
`
`co,
`
`7
`
`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 com-
`
`
`
`
`
`
`
`
`
`positions to aid oil solubility, as disclosed by U.S. Pat. No.
`
`
`
`
`
`
`
`
`
`6,516,837, the disclosure of which is incorporated by ref-
`
`
`
`
`
`
`
`erence. Commonly used refrigeration lubricants such as
`
`
`
`
`
`
`
`
`
`
`
`
`
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`Polyol Esters (POEs) and Poly Alkylene Glycols (PAGs),
`silicone oil, mineral oil, alkyl benzenes (ABs) and poly
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`(alpha-olefin) (PAO) that are used in refrigeration machinery
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`with hydrofluorocarbon (HFC) refrigerants may be used
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`with the refrigerant compositions of the present invention.
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`Many existing refrigeration systems are currently adapted
`for use in connection with existing refrigerants, and the
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`compositions of the present invention are believed to be
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`adaptable for use in many of such systems, either with or
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`without system modification. In many applications the com-
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`positions of the present invention may provide an advantage
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`as a replacement in systems, which are currently based on
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`refrigerants having a relatively high capacity. Furthermore,
`in embodiments where it is desired to use a lower capacity
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`refrigerant composition of the present invention, for reasons
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`of cost for example,
`to replace a refrigerant of higher
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`capacity, such embodiments of the present compositions
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`provide a potential advantage. Thus, It is preferred in certain
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`embodiments to use compositions of the present invention,
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`particularly compositions comprising a substantial propor-
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`tion of, and in some embodiments consisting essentially of
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`transHFO-1234ze, as a replacement for existing refrigerants,
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`such as HFC-134a. In certain applications, the refrigerants
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`of the present invention potentially permit the beneficial use
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`of larger displacement compressors,
`thereby resulting in
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`better energy efficiency than other refrigerants, such as
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`HFC-134a. Therefore the refrigerant compositions of the
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`invention, particularly compositions comprising
`present
`transHFP-1234ze, provide the possibility of achieving a
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`competitive advantage on an energy basis for refrigerant
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`replacement applications.
`It is contemplated that the compositions of the present,
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