Euvoplluhos
`Pnlanurnl
`European
`
`Patent Offlce 33'3'r='31"'"
`
`(11)
`
`EP1 716 216 B1
`
`(12)
`
`EUROPEAN PATENT SPECIFICATION
`
`(45) Date of publication and mention
`of the grant of the patent:
`18.11.2009 Bulletin 2009/47
`
`(21) Application number: 05744161.0
`
`(22) Date of filing: 29.04.2005
`
`(51) Int C|.:
`C09K 5/04(”“-””
`008d 9/14“'°"‘“”’
`
`c09K 3/30"”-0"
`
`(86) lntemational application number:
`PCT/US2005/014873
`
`(87) International publication number:
`WO 2005/105947 (10.11.2005 Gazette 2005/45)
`
`(54) COMPOSITIONS CONTAINING FLUORINE SUBSTITUTED OLEFINS
`
`ZUSAMMENSETZUNGEN MIT FLUORSUBSTITUIERTEN OLEFINEN
`
`COMPOSITIONS CONTENANT DES OLEFINES SUBSTITUEES PAR DU FLUOR
`
`(84) Designated Contracting States:
`AT BE BG CH CY CZ DE DK EE ES FI FR GR HU
`IE IS IT LI LT LU MC PL PT FIO SE SI SK TR
`
`0 THOMAS, Raymond, H.
`Pendleton, NY 14094 (US)
`
`(30) Priority: 29.04.2004 US 837525
`
`(43) Date of publication of application:
`02.11.2006 Bulletin 2006/44
`
`(60) Divisional application:
`09160311.8 I 2 085 422
`
`(73) Proprietor: Honeywell lntemational Inc.
`Morrlstown, NJ 07962-2245 (US)
`
`(72) Inventors:
`0 SINGH, Ftajlv, Ft.
`Getzville, NY 14068 (US)
`0 PHAM, Hang, T.
`Amherst, NY 14228 (US)
`0 WILSON, David, P.
`East Amherst. NY 14051 (US)
`
`(74) Representative: Clarke, Lionel Paul et al
`Gill Jennings & Every LLP
`Broadgate House
`7 Eldon Street
`
`London EC2M 7LH (GB)
`
`(56) References cited:
`EP-A- 0 398 147
`EP-A- 1 055 439
`
`EP-A- 0 974 571
`W0-A-03/064508
`
`W0-A-2004/037752 W0-A-20041037913
`GB-A- 950 876
`US-A- 3 723 318
`US-A- 3 884 828
`US-A- 5 714 083
`US-A- 6111 150
`US-A1- 2003127115
`US-B1- 6 258 292
`
`0 DATABASE WPI Section Ch, Week 199221
`Derwent Publications Ltd., London, GB; Class
`E16, AN 1992-172539 XP002343594 -8. JP 04
`110388 A (DAIKIN KOGYO KK) 10 April 1992
`(1992-04-10)
`
`EP1716216B1
`
`Note: Within nine months of the publication of the mention of the grant of the European patent in the European Patent
`Bulletin, any person may give notice to the European Patent Office of opposition to that patent, in accordance with the
`Implementing Regulations. Notice of opposition shall not be deemed to have been filed until the opposition fee has been
`paid. (Art. 99(1) European Patent Convention).
`
`1of10
`
`Arkema Exhibit 1026
`
`Printed by Jouve 75001 PAFIIS (FR)
`
`

`
`EP 1 716 216 B1
`
`
`
`
`
`
`
`Description
`
`FIELD OF THE INVENTION
`
`
`
`
`
`
`
`
`[0001] This invention relates to refrigerant compositions useful in automobile airconditioning systems.
`
`
`
`
`
`
`
`
`
`
`
`
`
`BACKGROUND OF THE INVENTION
`
`
`
`
`
`
`10
`
`
`
`
`20
`
`
`
`2b
`
`
`
`30
`
`
`
`
`
`40
`
`
`
`45
`
`
`
`
`
`55
`
`
`
`
`
`
`
`[0002]
`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 airconditioning, heat pump
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`and refrigeration applications. The vapor compression cycle is one ofthe most commonly used type methods to accom-
`plish 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 vaporto the liquid phase through heat removal at this relatively elevated
`pressure and temperature, and then reducing the pressure to start the cycle over again.
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`[0003] 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 highertemperature relative to the environment.
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`[0004] Certain fluorocarbons have been a preferred component in many heat exchange fluids, such as refrigerants,
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`for many years in many applications. For, example, fluoroalkanes, such as chlorofluoromethane and chlorofluoroethane
`derivatives, have gained widespread use as refrigerants in applications including air conditioning and heat pump appli-
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`cations owing to their unique combination of chemical and physical properties. Many ofthe refrigerants commonly utilized
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`in vapor compression systems are either single components fluids or azeotropic mixtures.
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`[0005] 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 re-
`frigerants in air-conditioning and refrigeration systems has become disfavored because ofthe ozone—depleting properties
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`associated with many of such compounds. There has thus been an increasing need for newfluorocarbon and hydrofluor-
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`ocarbon 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
`[0006]
`
`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.
`
`
`
`
`
`
`
`
`[0007] Applicants have come to appreciate that lubricant compatibility is of particular importance in many of applica-
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`tions. More particularly,
`it is highly desirably for refrigeration fluids to be compatible with the lubricant utilized in the
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`compressor unit, used in most refrigeration systems. Unfortunately, many non-chlorine-containing refrigeration fluids,
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`including HFCs, are relatively insoluble and/or immiscible in the types of lubricants used traditionally with CFC’s and
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`HFCs, including, for example, mineral oils, alkylbenzenes orpo|y(alpha~olefins). In orderfor 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 easilythroughout 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.
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`[0008] 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 in-
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`creased demand for electrical energy.
`Furthermore, it is generally considered desirably for CFC refrigerant substitutes to be effective without major
`[0009]
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`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
`[0010]
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`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. Unfortu
`nately, 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 (HFO-1243zf) are
`each flammable and therefore not viable for use in many applications.
`
`
`
`
`
`
`
`
`
`
`
`
`20f10
`
`
`
`2 of 10
`
`

`
`EP1716 216 B1
`
`
`
`
`
`
`[0011] Higherfluoroalkenes, thatisfluorinesubstituted alkenes having at leastfive carbon atoms, have been suggested
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`for use as refrigerants. US. Patent No. 4, 788,352 - Smutny is directed to production offluorinated C5 to C8 compounds
`
`
`having at least some degree of unsaturation. The Smutny patent identifies such higher olelins 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).
`[0012] While the fluorinated olefins described in Smutny may have some level of effectiveness in heat transfer appli-
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`cations, it is believedthat such compounds may also have certain disadvantages. For example, some ofthese 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.
`[0013] Bromofluoromethane and bromochlorofluoromethane derivatives, particularly bromotrifluoromethane (Halon
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`1301) and bromochlorodifluoromethane (Halon 1211) have gained widespread use as fire extinguishing agents in en-
`closed areas such as airplane oabins 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.
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`JP 04 110 388 A is directed to obtaining novel fluids for heat transfer purposes which are suitable for heat
`[0014]
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`pumps and heat engines. The disclosed invention is a heat transfer medium comprising an organic compound which
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`can be represented by the molecular formula C3HmFn (where m is from 1 to 5, n is from 1 to 5, and m + n = 6) and which
`has one double bond in the molecular structure.
`
`
`
`
`
`
`
`
`[0015] US 6,111,150 discloses a method for producing a fluorinated alkane, namely, 1,1,1,3,3—pentafluoropropane,
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`which is said to be useful as a foaming agent, a refrigerant and the like. The method includes a step of adding hydrogen
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`fluoride to 1,1,1,3,3-pentafluoropropene in a liquid phase in the presence of a hydrohalogenation catalyst. A method is
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`also disclosed for forming 1,3,3,S~tetraf|uoropropene, which is said to be useful as an intermediate of medicines, of
`agricultural chemicals, and as functional materials, and as a refrigerant and the like.
`
`
`
`
`
`
`
`
`
`
`
`
`
`[0016] US 6,089,032 discloses a kit and method for retro-fitting an R—12 air conditioner into an R134A air conditioner.
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`SUMMARY
`
`
`
`[0017] Applicants have found that compositions comprising atetrafluoropropene (HFO—1234) are useful in automobile
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`airconditioning systems.
`
`DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS THE COMPOSITIONS
`
`
`
`
`
`
`
`
`
`[0018] The present invention is directed to the use of compositions comprising at least one tetrafluoropropene in
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`automobile airconditioning systems.
`
`
`
`[0019] Applicants have surprisingly and unexpectedly found that certain of the compounds useful in the invention
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`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 otherwise contain relativelytoxic compounds satisfying theformulas described
`above.
`
`
`
`
`
`[0020] The compositions of the present invention comprise one or more tetrafluoropropenes. The term "HFO-1234"
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`is used herein to referto all tetrafluoropropenes. Among the tetrafluoropropenes, both cis- and trans-1 , 3, 3, 3—tetrafluor—
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`opropene (HFO-1234ze) are particularly preferred. The term HFO—1284ze is used herein generically to referto 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
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`"H FO-1 234ze" therefore includes within its scope cisHFO—1234ze, transHFO—1234ze, and all combinations and mixtures
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`of these.
`
`
`[0021] Although the properties of cisHFO—1234ze and transHFO-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. Accordingly, it is to be understood that the terms "HFO—1234ze" and 1, 8, 8, 3—tetrafluoropropene referto
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`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.
`
`
`
`
`
`
`
`
`
`[0022] HFO-1234 compounds are known materials and are listed in Chemical Abstracts databases. The production
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`of fluoropropenes such as CF3CH:CH2 by catalytic vapor phase fluorination of various saturated and unsaturated
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`halogen-containing C3 compounds is described in U.S. Patent Nos. 2,889,379; 4,798,818 and 4,465,786, each of which
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`is incorporated herein by reference. EP 974,571, also incorporated herein by reference, discloses the preparation of
`1,1,1,3—tetrafluoropropene by contacting 1 ,1 ,1 ,3,8—pentafluoropropane (H FC—245fa) in the vapor phase with a chromium-
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`10
`
`
`
`
`20
`
`
`
`2b
`
`
`
`30
`
`
`
`
`
`40
`
`
`
`45
`
`
`
`
`
`55
`
`
`
`30f10
`
`
`
`3 of 10
`
`

`
`
`
`10
`
`
`
`
`20
`
`
`
`2b
`
`
`
`30
`
`
`
`
`
`40
`
`
`
`45
`
`
`
`
`
`55
`
`
`
`EP1716 216 B1
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`based catalyst at elevated temperature, or in the liquid phase with an alcoholic solution of KOH, NaOH, Ca(OH)2 or Mg
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`(OH)2. In addition, methods for producing compounds in accordance with the present invention are described generally
`
`in connection with pending United States Patent Application entitled "Process for Producing Fluoropropenes" bearing
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`attorney docket number (H0003789 (26267)), which is also incorporated herein by reference.
`[0023] The compositions for use in the present invention, 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, the compositions for use in the present invention have a Global Warming Potential
`[0024]
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`(GWP) of not greaterthan about 1000, more preferably not greaterthan 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—yeartime 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.
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`In certain preferred forms, the compositions for use in the present invention also preferably have an Ozone
`[0025]
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`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.
`
`
`[0026] The amount of 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 for use in the present invention can be azeotropic,
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`azeotrope-like or non-azeotropic. In preferred embodiments, the 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 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—184)
`
`
`
`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—hexaf|uoropropane (H FC—236fa)
`
`
`
`
`
`
`
`
`1,1,1,8,3-pentafluoropropane (HFC-245fa)
`
`
`
`
`1,1,1,3,3—pentafluorobutane (H FC-365mfc)
`water
`
`
`C02
`
`
`
`[0027] The relative amount of any of the above noted components, as well as any additional components which may
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`be included in the compositions for use in the present invention, can vary widely within the general broad scope of the
`present invention accordingto the particular application forthe composition, and all such relative amounts are considered
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`to be within the scope hereof.
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`[0028] Although it is contemplated that the compositions for use in the present invention may include a HFO—1234 in
`
`widely ranging amounts, it is generally preferred that the compositions comprise a HFO—1234, and 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 compositions for use in the present invention comprise
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`transHFO-1234ze.
`In certain preferred embodiments, the compositions for use in the present invention comprise a
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`combination of cisHFO—1234ze and transHFO1234ze in a cisztrans 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.
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`[0029] The compositions for use in the present invention may include other components forthe purpose of enhancing
`or providing certain functionality to the composition, or in some cases to reduce the cost ofthe composition. For example,
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`the compositions may include a lubricant, generally in amounts of from about 30 to about 50 percent by weight of the
`composition. Furthermore, the compositions may also include a compatibilizer, such as propane, for the purpose of
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`40f10
`
`
`
`4 of 10
`
`

`
`
`
`10
`
`
`
`
`20
`
`
`
`2b
`
`
`
`30
`
`
`
`
`
`40
`
`
`
`45
`
`
`
`
`
`55
`
`
`
`EP1716 216 B1
`
`
`
`
`
`
`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
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`US. 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
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`(a|pha—olefin) (PAO) that are used in refrigeration machinery with hydrofluorocarbon (HFC) refrigerants may be used
`with the compositions for use in the present invention.
`
`
`
`
`
`
`
`
`
`[0030] 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
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`withoutsystem modification. The compositions useful in 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 lowercapacity refrigerantcomposition, for reasons of cost forexample, to replace a refrigerant
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`of higher capacity, embodiments ofthe compositions useful in the present invention provide a potential advantage. Thus,
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`it is preferred in certain embodiments to use compositions, 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. Thereforethe compositions useful in the present invention, particularly compositions comprising transH FO—1234ze,
`
`
`
`
`
`
`
`
`
`
`
`
`
`provide the possibility of achieving a competitive advantage on an energy basis for refrigerant replacement applications.
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`EXAMPLES
`
`
`
`[0031] The following examples are provided forthe purpose of illustrating the present invention but without limiting
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`the scope thereof.
`
`
`
`EXAMPLE 1
`
`
`
`
`[0032] The coeffoient of performance (GOP) is a universally accepted measure of refrigerant performance, especially
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`useful in representing the relative thermodynamic efficiency of a refrigerant In a specific heating or cooling cycle involving
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`evaporation or condensation of the refrigerant. In refrigeration engineering, this term expresses the ratio of useful re-
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`frigeration to the energy applied by the compressor In compressing the vapor. The capacity of a refrigerant represents
`the amount of cooling or heating it provides and provides some measure of the capability of a compressor to pump
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`quantities of heat for a given volumetric flow rate of refrigerant. In otherwords, given a specific compressor, a refrigerant
`with a higher capacity will deliver more cooling or heating power. One means for estimating COP of a refrigerant at
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`specific operating conditions is from the thermodynamic properties of the refrigerant using standard refrigeration cycle
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`analysis techniques (see for example, R.C. Downing, FLUOROCARBON REFRIGERANTS HANDBOOK, Chapter 3,
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`Prentice—Hall, 1988).
`[0033] A refrigeration /air conditioning cycle system is provided where the condenser temperature is about 150°F and
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`the evaporator temperature is about -35°F under nominally isentropic compression with a compressor inlet temperature
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`of about 50°F. COP is determined for several compositions of the present invention over a range of condenser and
`evaporator temperatures and reported in Table I below, based upon HFC-134a having a COP value of 1.00, a capacity
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`value of 1.00 and a discharge temperature of 175 “F.
`
`
`
`
`
`
`
`
`
`
`
`TABLE I
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`*Not covered by the present invention.
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`[0034] This example shows that certain of the preferred compositions for use in the present invention each have a
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`better energy efficiency than HFC-134a (1.02, 1.04 and 1.13 compared to 1.00) and the compressor using the present
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`refrigerant compositions will produce discharge temperatures (158, 165 and 155 compared to 175), which is advanta-
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`50f10
`
`
`
`5 of 10
`
`

`
`EP 1 716 216 B1
`
`
`
`
`
`
`geous since such result will likely leading to reduced maintenance problems.
`
`
`
`
`
`
`
`
`
`
`
`
`EXAMPLE 2
`
`
`
`
`
`
`10
`
`
`
`
`20
`
`
`
`2b
`
`
`
`30
`
`
`
`
`
`40
`
`
`
`45
`
`
`
`
`
`[0035] The miscibility of HFO-1 225ye (not covered bythe present invention) and H F0-1234ze with various refrigeration
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`lubricants is tested. The lubricants tested are mineral oil (C3), alkyl benzene (Zerol 150), ester oil (Mobil EAL 22 cc and
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`Solest 120), polyalkylene glycol (PAG) oil (Goodwrench Refrigeration Oil for 134a systems), and a poly(alpha—o|efin) oil
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`(CP-6005-100). For each refrigerant/oil combination, three compositions are tested, namely 5, 20 and 50 weight percent
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`of lubricant, with the balance of each being the compound of the present invention being tested
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`[0036] The lubricant compositions are placed in heavy-walled glass tubes. The tubes are evacuated, the refrigerant
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`compound in accordance with the present invention is added, and the tubes are then sealed. The tubes are then put
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`into an air batch environmental chamber, the temperature of which is varied from about -50°C to 70°C. At roughly 10°C
`intervals, visual observations of the lube contents are made for the existence of one or more liquid phases. In a case
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`where more than one liquid phase is observed, the mixture is reported to be immiscible. In a case where there is only
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`one liquid phase observed, the mixture is reported to be miscible. In those cases where two liquid phases were observed,
`but with one of the liquid phases occupying only a very small volume, the mixture is reported to be partially miscible.
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`[0037] The polyalkylene glycol and ester oil lubricants were judged to be miscible in all tested proportions over the
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`entire temperature range, except that for the HFO-1225ye mixtures with polyalkylene glycol, the refrigerant mixture was
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`found to be immiscible over the temperature range of -50°C to —30°C and to be partially miscible over from -20 to 50°C.
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`At 50 weight percent concentration of the PAG in refrigerant and at 60°, the refrigerant/PAG mixture was miscible. At
`70°C, it was miscible from 5 weight percent lubricant in refrigerant to 50 weight percent lubricant in refrigerant.
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`EXAMPLE 3
`
`
`
`
`[0038] The compatibility of the refrigerant compositions useful in the present invention with PAG lubricating oils while
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`in Contact with metals used in refrigeration and air conditioning systems is tested at