(12)
`
`United States Patent
`
`Singh et al.
`
`(10) Patent No.:
`
`(45) Date of Patent:
`
`US 7,534,366 B2
`May 19, 2009
`
`US007534366B2
`
`(54)
`
`(75)
`
`(_'OMl’OSI'I‘IO.VS CONTAINING FLUORIN E
`SUBSTITUTED OLEFINS
`
`Inventors: Raj iv R. Singh. (jetzville. NY (US):
`Hang T. Pham. Amherst. NY (US);
`David P. Wilson. East Amherst. NY
`(US): Raymond H. Thomas. Pendleton.
`NY (US): Ian Shankland. Randolph. NJ
`(US)
`
`(73)
`
`Assigncc: Honeywell International Inc..
`Morristown. NJ (US)
`
`(*)
`
`Notice:
`
`Subject to any disclaimer. the term of this
`patent is extended or adjusted under 35
`U.S.(‘. 154(b) by 41 days.
`
`(21)
`
`Appl. No.: 10/694,273
`
`(22)
`
`Filed:
`
`Oct. 27, 2003
`
`(65)
`
`(60)
`
`(51)
`
`(52)
`
`(58)
`
`(56)
`
`Prior Publication Data
`
`US 2004/0119047 A1
`
`hm. 24. 2004
`
`Related U.S. Application Data
`
`Provisional application No. 60/421,263. filed on Oct.
`25. 2002. provisional application No. 60/421.435.
`filed on Oct. 25. 2002.
`
`Int. Cl.
`
`(2006.01)
`C09K 5/04
`U.S. Cl.
`........................... .. 252/681252/67: 252/69:
`252/71: 252/74
`Field oi'(Ilass1fication Search ................. .. 252/68.
`252/67. 69. 71. 74
`See application tile for complete search history.
`References Cited
`
`U.S. PATENT DOCUMENTS
`
`2.846.458 A
`2.834.748 A
`2.889.379 A
`2.917.480 A
`3.085.918 A
`3.723.318 A
`3.884.828 A
`4.465.786 A
`4.788.352 A
`4.798.818 A
`4.944.890 A
`4.945.119 A *
`
`51958 Haluska ................. .. 26054482
`1031958 Bailey et al.
`..
`........ .. 260542
`
`...... ..
`61959 Ruh et al.
`26056534
`................ .. 260542
`1231959 Bailey etal.
`4.1963 Sherlike1'et al.
`............ .. 134530
`31973 Butlcrct al.
`51975 Butleret al.
`81984 Zimmcr ct al. ............. . 5025169
`
`1151988 Smutny ......... ..
`.. 5705153
`.............. .. 5025228
`13198‘) Baizer et al.
`751990 Deebet al.
`7.'1990 Smits et al.
`
`............... .. 5215131
`
`5.250.208 A
`5.532.419 A
`5.578.137 A
`5.674.451 A
`5.679.875 A
`5.714.083 A
`6.041.621 A
`6.111.150 A
`6.258.292 B1
`6.274.779 B1
`6.300.378 B1 “
`6.327.866 Bl
`6.516.837 B2
`7.279.451 B2‘
`200350127115 Al
`
`5705167
`
`422.-‘34
`.
`.
`........... .. 5705156
`
`.\/ierchantetal.
`10.-1993
`71996 Van Der Puy etai.
`11.-1996 Sheaiyetal.
`10.1997 .\li1nitz et al.
`10.-1997 Aoyamaetal.
`21998 Turneret al.
`3.-2000 Os17ewskietai.
`82000 Sakyuetai.
`7.-2001 Turneretal.
`8.2001 .\/Ierkelet al.
`10.-2001 Tapscott
`................... .. 5145743
`12.2001 Novaketai.
`.............. .. 141.-‘67
`2.2003 Thomas etal.
`10.2007 Singh etal.
`............... .. 510.5412
`7.2003 Thomas etal.
`
`FOREIGN PATENT DOCUMENTS
`
`EP
`Iii’
`EP
`Iii’
`JP
`JP
`RU
`W0
`W0
`W(,)
`
`950 876
`0398147
`0974571
`1055439
`04110388
`2004110388
`2073058
`WO 03064508
`WO2004-037752
`WO2004-'037913
`
`“‘
`
`2: 1964
`11.-1990
`1: 2000
`11.-2000
`4.-1992
`4.-1992
`2: 1997
`8: 2003
`5.-2004
`5: 2004
`
`OTHER PUBLICATIONS
`
`Saunders and Frisch. “Polyurethanes Chemistry & Technology.” vol.
`XVI. Part 1 and Pan 11 Technology. John Wiley and Sons. New York.
`.\1'Y(1962). pp. 193 to 201 and 219 to 223.
`Downing. Ralph C.. “1~'1uorca1'bon Refrigerants Handbook." Prentice
`Hall. Chapter 3 (1988). pp. 17 to 34.
`.\/1orrissey.CJ.: Nearly Azeotropic Mixtures to Replace Refrigerant
`12. In: National Aeronautics and Space Administration Contract No.
`NAS 7-918. Aug. 1992. NASA Tech Brief. vol. 16. No. 8. item #122.
`
`"‘ cited by examiner
`
`Primary E.\-aminer—Lorna M Douyon
`Assistant E.raminer—An1i11a Khan
`(74) Attorney, Agent. or Firm—Collecn D. Szuch
`
`(57)
`
`ABSTRACT
`
`The use ofpentailuoropropene (HFO-1225) and tetrafluoro-
`propene (HFO-1234) in refrigeration equipment is disclosed.
`These materials are generally useful as refrigerants for heat-
`ing and cooling. as blowing agents. as aerosol propellants. as
`solvent composition. and as fire extinguishing and suppress-
`ing agents.
`
`25 Claims. No Drawings
`
`Page 1 of 8
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`Arkema Exhibit 1023
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`Arkema Exhibit 1023
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`

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`US 7,534,366 B2
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`1
`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 priority
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`benefit of U.S. Provisional Application Nos. 60/421,263, and
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`60/421,435, each of which was filed on Oct. 25, 2002, and
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`each of which is incorporated herein by reference. The
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`present application is also related to and incorporates by
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`reference each of the following concurrently filed United
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`States Patent Applications: entitled “Fluorinated Alkene
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`Refrigerant Composition,” by Raymond Thomas and Rajiv
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`Singh, application Ser. No. 10/695,212, now abandoned in
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`favor of application Ser. No. 11/385,259, now pending, and
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`entitled “Process For Producing Fluoropropenes,” by Hsueh
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`Sung Tung et al, application Ser. No. 10/694,272, which
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`issued as U.S. Pat. No. 7,230,146.
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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
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`systems, and to methods and systems which utilize such
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`compositions. In preferred aspects, the present invention is
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`directed to refrigerant compositions which comprise at least
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`one 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 com-
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`pression cycle usually involves the phase change ofthe refrig-
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`erant from the liquid to the vapor phase through heat absorp-
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`tion at a relatively low pres sure and then from the vapor to the
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`liquid phase through heat removal at a relatively low pressure
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`and temperature, compressing the vapor to a relatively
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`elevated pressure, condensing the vapor to the liquid phase
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`through heat removal at this relatively elevated pressure and
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`temperature, and then reducing the pres sure to start the cycle
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`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 tempera-
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`ture, the primary purpose of a heat pump is to add heat at a
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`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, such
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`as chlorofluoromethane and chlorofluoroethane derivatives,
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`have gained widespread use as refrigerants in applications
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`including air conditioning and heat pump applications owing
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`to their unique combination of chemical and physical prop-
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`erties. Many of the refrigerants commonly utilized in vapor
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`compression systems are either single components fluids or
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`azeotropic mixtures.
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`Concern has increased in recent years about potential dam-
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`age to the earth’s atmosphere and climate, and certain chlo-
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`rine-based compounds have been identified as particularly
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`problematic in this regard. The use of chlorine-containing
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`compositions (such as chlorofluorocarbons (CFC’s), hydro-
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`chlorofluorocarbons (HCF’s) and the like) as refrigerants in
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`air-conditioning and refrigeration systems has become disfa-
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`vored because of the ozone-depleting properties associated
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`with many of such compounds. There has thus been an
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`increasing need for new fluorocarbon and hydrofluorocarbon
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`compounds and compositions that offer alternatives for
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`refrigeration and heat pump applications. For example, it has
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`become desirable to retrofit chlorine-containing refrigeration
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`systems by replacing chlorine-containing refrigerants with
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`non-chlorine-containing refrigerant compounds that will not
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`deplete the ozone layer, such as hydrofluorocarbons (HFC’ s).
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`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 as
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`excellent heat transfer properties, chemical stability, low- or
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`no-toxicity, non-flammability and lubricant compatibility,
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`among others.
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`Applicants have come to appreciate that lubricant compat-
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`ibility is of particular importance in many of applications.
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`More particularly, it is highly desirably for refrigeration fluids
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`to be compatible with the lubricant utilized in the compressor
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`unit, used in mo st refrigeration systems. Unfortunately, many
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`non-chlorine-containing
`refrigeration
`including
`fluids,
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`HFC’s, are relatively insoluble and/or immiscible in the types
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`of lubricants used traditionally with CFC’s and HFC’s,
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`including, for example, mineral oils, alkylbenzenes or poly
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`(alpha-olefins). In order for a refrigeration fluid-lubricant
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`combination to work at a desirable level of efliciently within
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`a compression refrigeration, air-conditioning and/or heat
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`pump system, the lubricant should be sufliciently soluble in
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`the refrigeration liquid over a wide range of operating tem-
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`peratures. Such solubility lowers the viscosity ofthe lubricant
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`and allows it to flow more easily throughout the system. In the
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`absence of such solubility, lubricants tend to become lodged
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`in the coils of the evaporator of the refrigeration, air-condi-
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`tioning or heat pump system, as well as other parts of the
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`system, and thus reduce the system efliciency.
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`With regard to efficiency 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 engineer-
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`ing changes to conventional vapor compression technology
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`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 HFC’s which might otherwise be desirable for
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`used in refrigerant compositions are not nonflammable. For
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`example, the fluoroalkane difluoroethane (HFC-152a) and
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`the fluoroalkene 1,1,1-trifluorpropene (HFO-1243zf) are
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`each flammable and therefore not viable for use in many
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`applications.
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`Higher fluoroalkenes, that is fluorine-substituted alkenes
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`having at least five carbon atoms, have been suggested for use
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`as refrigerants. U.S. Pat. No. 4,788,352—Smutny is directed
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`to production of fluorinated C5 to C8 compounds having at
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`least some degree of unsaturation. The Smutny patent iden-
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`tifies such higher olefins as being known to have utility as
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`Page 2 of 8
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`US 7,534,366 B2
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`3
`refrigerants, pesticides, dielectric fluids, heat transfer fluids,
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`solvents, and intermediates in various chemical reactions.
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`(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 applications,
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`it is believed that such compounds may also have certain
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`disadvantages. For example, some of these compounds may
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`tend to attack substrates, particularly general-purpose plas-
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`tics such as acrylic resins and ABS resins. Furthermore, the
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`higher olefinic compounds described in Smutny may also be
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`undesirable in certain applications because of the potential
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`level of toxicity of such compounds which may arise as a
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`result of pesticide activity noted in Smutny. Also, such com-
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`pounds may have a boiling point which is too high to make
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`them useful as a refrigerant in certain applications.
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`Bromofluoromethane
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`bromochlorofluoromethane
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`(Halon
`derivatives, particularly bromotrifluoromethane
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`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 to
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`their high ozone depletion. Moreover, as halons are fre-
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`quently 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 com-
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`positions, and particularly heat transfer compositions, fire
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`extinguishing/suppression compositions, blowing agents,
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`solvent compositions, and compatabilizing agents, that are
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`potentially useful in numerous applications, including vapor
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`compression heating and cooling systems and methods, while
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`avoiding one or more of the disadvantages noted above.
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`SUMMARY
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`Applicants have found that the above-noted need, and other
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`needs, can be satisfied by compositions comprising one or
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`more C3 or C4 fluoroalkenes, preferably compounds having
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`Formula I as follows:
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`XCFZR3-
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`<1)
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`where X is a C2 or a C3 unsaturated, substituted or unsubsti-
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`tuted, alkyl radical, each R is independently Cl, F, Br, I or H,
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`and z is 1 to 3.
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`The present invention provides also methods and systems
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`which utilize the compositions of the present
`invention,
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`including methods and systems for heat transfer, foam blow-
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`ing, solvating, and aerosol generation.
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`DETAILED DESCRIPTION OF PREFERRED
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`EMBODIMENTS
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`The Compositions
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`The present invention is directed to compositions compris-
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`ing at least one fluoroalkene containing from 3 to 4 carbon
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`atoms and at least one carbon-carbon double bond. The fluo-
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`roalkene compounds of the present invention are sometimes
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`referred to herein for the purpose of convenience as hydrof-
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`luoro-olefins or “HFOs” if they contain at least one hydrogen
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`Although it is contemplated that the HFOs of the president
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`mentioned may contain two carbon—carbon double bonds,
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`such compounds at the present time are not considered to be
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`preferred.
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`As mentioned above, the present compositions comprise
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`one or compounds in accordance with Formula I. In preferred
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`embodiments, the compositions include compounds of For-
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`mula II below:
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`Page 3 of 8
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`60
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`65
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`(H)
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`where each R is independently Cl, F, Br, I or H
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`R‘ is (CR2)nY,
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`Y is CRF2
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`and n is 0 or 1.
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`In highly preferred embodiments, Y is CF3, n is 0 and at least
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`one of the remaining Rs is F.
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`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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`exhibit utility in refrigerant compositions, blowing agent
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`compositions, compatibilzers, and solvent compositions of
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`the present invention. However, applicants have surprisingly
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`and unexpectedly found that certain ofthe compounds having
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`a structure in accordance with the formulas described above
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`exhibit a highly desirable low level of toxicity compared to
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`other of such compounds. As can be readily appreciated, this
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`discovery is of potentially enormous advantage and benefit
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`for the formulation of not only refrigerant compositions, but
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`also any and all compositions which would otherwise contain
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`relatively toxic compounds satisfying the formulas described
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`above. More particularly, applicants believe that a relatively
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`low toxicity level is associated with compounds of Formula
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`II, preferably whereinY is CF3, wherein at least one R on the
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`unsaturated terminal carbon is H, and at least one of the
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`remaining Rs is F. Applicants believe also that all structural,
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`geometric and stereoisomers of such compounds are effective
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`and of beneficially low toxicity.
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`In highly preferred embodiments, especially embodiments
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`which comprise the low toxicity compounds described above,
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`n is zero. Thus, in certain preferred embodiments the compo-
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`sitions of the present invention comprise one or more com-
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`pounds selected from the group consisting of tetrafluoropro-
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`penes (HFO-1234), pentafluoropropenes (HFO-1225) and
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`combinations of these.
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`It is even more preferred that the compounds ofthe present
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`invention are the tetrafluoroprpoene and pentafluoropropene
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`compounds in which the unsaturated terminal carbon has not
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`more than one F substituent, specifically: 1,3,3,3-tetrafluoro-
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`propene (HFO-1234ze); 2,3,3,3-tetrafluoropropene (HFO-
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`1234yf); and 1,2,3,3,3-pentafluoropropene (HFO-1225ye),
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`and any and all stereoisomers of each of these. Applicant has
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`discovered that such compounds have a very low acute tox-
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`icity level, as measured by inhalation exposure to mice and
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`rats. On the other hand, applicants have found that a relatively
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`high degree of toxicity may be associated with certain com-
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`pounds adaptable for use with the present compositions,
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`namely, those compounds which have more than one F on the
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`terminal unsaturated carbon, or which do not have at least one
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`H on the terminal unsaturated carbon. For example, appli-
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`cants have discovered that 1,1,3,3,3-pentafluoropropene
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`(HFO-1225zc) exhibits an unacceptably high degree of tox-
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`icity, as measured by inhalation exposure to mice and rats.
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`The preferred compounds ofthe present invention, namely,
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`HFO-1225 and HFO-1234 are known materials and are listed
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`in Chemical Abstracts databases. HFO-1225 is commercially
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`available, from example from Syntex Chemical Co. Further-
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`more, methods are described generally in the patent literature
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`for producing fluoroalkenes. For example, the production of
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`fluoropropenes such as CF3CH:CH2 by catalytic vapor
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`Page 3 of 8
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`

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`US 7,534,366 B2
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`5
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`phase fluorination of various saturated and unsaturated halo-
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`gen-containing C3 compounds is described in U.S. Pat. Nos.
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`2,889,379; 4,798,818 and 4,465,786, each ofwhich is incor-
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`porated herein by reference. U.S. Pat. No. 5,532,419, whichis
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`also incorporated herein by reference, discloses a vapor phase
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`catalytic process for the preparation of fluoroalkene using a
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`chloro- or bromo-halofluorocarbon and HF. EP 974,571, also
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`incorporated herein by reference, discloses the preparation of
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`1,1,1,3-tetrafluoropropene by contacting
`1,1,1,3,3-pen-
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`tafluoropropane (HFC-245fa) in the vapor phase with a chro-
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`mium-based catalyst at elevated temperature, or in the liquid
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`phase with an alcoholic solution of KOH, NaOH, Ca(OH)2 or
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`Mg(OH)2. In addition, methods for producing compounds in
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`accordance with the present invention are described generally
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`in connection with concurrently filed U.S. patent application
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`Ser. No. 10/694,272 entitled “Process for Producing Fluor-
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`propenes” which is also incorporated herein by reference.
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`The present compositions are believed to possess proper-
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`ties that are advantageous for a number of important reasons.
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`For example, applicants believe, based at least in part on
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`mathematical modeling, that the fluoroolefins of the present
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`invention will not have a substantial negative affect on atmo-
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`spheric chemistry, being negligible contributors to ozone
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`depletion in comparison to some other halogenated species.
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`The preferred compositions ofthe present invention thus have
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`the advantage of not contributing substantially to ozone
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`depletion. The preferred compositions also do not contribute
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`substantially to global warming compared to many of the
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`hydrofluoroalkanes presently in use.
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`Preferably, the compositions of the present invention have
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`a Global Warming Potential (GWP) of not greater than 150,
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`more preferably not greater than 100 and even more prefer-
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`ably not greater than 75. As used herein, “GWP” is measured
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`relative to that of carbon dioxide and over a 100 year time
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`horizon, as defined in “The Scientific Assessment of Ozone
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`Depletion, 2002, a report of the World Meteorological Asso-
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`ciation’s Global Ozone Research and Monitoring Project,”
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`which is incorporated herein by reference.
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`The present compositions also preferably have an Ozone
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`Depletion Potential (ODP) of not greater than 0.05, more
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`preferably not greater than 0.02 and even more preferably
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`about zero. As used herein, “ODP” is as defined in “The
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`Scientific Assessment of Ozone Depletion, 2002, A report of
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`the World Meteorological Association’s Global Ozone
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`Research and Monitoring Project,” which is incorporated
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`herein by reference.
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`Heat Transfer Compositions
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`Although it is contemplated that the compositions of the
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`present invention may include the compounds of the present
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`invention in widely ranging amounts, it is generally preferred
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`that refrigerant compositions of the present invention com-
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`prise compound(s) in accordance with Formula I, and even
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`more preferably Formula II, in an amount that is at least about
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`50% by weight, and even more preferably at least about 70%
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`by weight, of the composition.
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`The compositions of the present invention may include
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`other components for the purpose of enhancing or providing
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`certain functionality to the composition, or in some cases to
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`reduce the cost of the composition. For example, refrigerant
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`compositions according to the present invention, especially
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`those used in vapor compression systems, include a lubricant,
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`generally in amounts of from about 30 to about 50 percent by
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`weight of the composition. Furthermore, the present compo-
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`sitions may also include a compatibilzer, such as propane, for
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`the purpose of aiding compatibility and/or solubility of the
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`lubricant. Such compatibilizers, including propane, butanes
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`and pentanes, are preferably present in amounts of from about
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`Page 4 of 8
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`6
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`0.5 to about 5 percent by weight of the composition. Combi-
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`nations of surfactants and solubilizing agents may also be
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`added to the present compositions to aid oil solubility, as
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`disclosed by U.S. Pat. No. 6,516,837, the disclosure ofwhich
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`is incorporated by reference. Commonly used refrigeration
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`lubricants such as Polyol Esters (POEs) and Poly Alkylene
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`Glycols (PAGs) that are used in refrigeration machinery with
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`hydrofluorocarbon (HFC) refrigerants may be used with the
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`refrigerant compositions of the present invention.
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`The polyalkylene glycol lubricants suitable foruse with the
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`present invention typically containing from about 5 to 50
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`oxyakylene repeating units that contain from 1 to 5 carbon
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`atoms. The polyalkylene glycol can be straight chain or
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`branched and can be a homopolymer or co-polymer of 2, 3 or
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`more oxyethylene, oxypropylene, oxybutylene or oxypenty-
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`lene groups or combinations thereof in any proportions. Pre-
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`ferred polyalkylene glycols contain at least 50% oxypropy-
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`lene groups. Compositions according to the present invention
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`may contain one or more polyalkylene glycols as the lubri-
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`cant, one or more polyalkylene glycol esters as the lubricant,
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`or a mixture of one of more polyalkylene glycols and one or
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`more polyalkylene glycol esters. Vinyl ethers are also useful
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`in this invention. While suitable polyalkylene glycols include
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`glycols terminating at each end with a hydroxyl group, other
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`suitable HFO lubricants include polyalkylene glycols in
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`which either or both terminal hydroxyl group is capped. The
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`hydroxyl group may be capped with alkyl groups containing
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`from 1 to 10 carbon atoms, 1 to 10 carbon atom alkyl groups
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`containing heteroatoms
`such as nitrogen.
`In preferred
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`embodiments, the lubricants ofthis invention have viscosities
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`of from about 1 to 1000 centistokes at about 37° C., more
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`preferably in the range of from about 10 to about 200 centis-
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`tokes at about 37° C. and even more preferably of from about
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`30 to about 150 centistokes.
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`Blowing Agents, Foams and Foamable Compositions
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`Blowing agents may also comprise or constitute one or
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`more of the present compositions. As mentioned above, the
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`compositions of the present invention may include the com-
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`pounds ofthe present invention in widely ranging amounts,. It
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`is generally preferred, however, that for preferred composi-
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`tions for use as blowing agents in accordance with the present
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`invention, compound(s) in accordance with Formula I, and
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`even more preferably Formula II, are present in an amount
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`that is at least about 5% by weight, and even more preferably
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`at least about 15% by weight, of the composition.
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`In other embodiments, the invention provides foamable
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`compositions, and preferably polyurethane, polyisocyanu-
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`rate and extruded thermoplastic foam compositions, prepared
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`using the compositions ofthe present invention. In such foam
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`embodiments, one or more of the present compositions are
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`included as or part of a blowing agent in a foamable compo-
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`sition, which composition preferably includes one or more
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`additional components capable of reacting and/or foaming
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`under the proper conditions to form a foam or cellular struc-
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`ture, as is well known in the art. The invention also relates to
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`foam, and preferably closed cell foam, prepared from a poly-
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`mer foam formulation containing a blowing agent comprising
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`the compositions of the invention. In yet another embodi-
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`ments, the invention provides a foamable composition com-
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`prising thermoplastic foams, such as polystyrene and poly-
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`ethylene (PE), preferably low density PE.
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`In certain preferred embodiments, dispersing agents, cell
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`stabilizers, surfactants and other additives may also be incor-
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`porated into the blowing agent compositions of the present
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`invention. Surfactants are optionally but preferably added to
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`serve as cell stabilizers. Some representative materials are
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`sold under the names ofDC-193, B-8404, and L-5340 which
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`Page 4 of 8
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`US 7,534,366 B2
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`7
`are, generally, polysiloxane polyoxyalkylene block co-poly-
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`mers such as those disclosed in U.S. Pat. Nos. 2,834,748,
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`2,917,480, and 2,846,458, each of which is incorporated
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`herein by reference. Other optional additives for the blowing
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`agent mixture may include flame retardants such as tri(2-
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`chloroethyl)phosphate,
`tri(2-chloropropyl)phosphate,
`tri(2,
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`3-dibromopropyl)-phosphate, tri(l,3-dichloropropyl) phos-
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`various
`diammonium phosphate,
`halogenated
`phate,
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`aromatic compounds, antimony oxide, aluminum trihydrate,
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`polyvinyl chloride, and the like.
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`Propellant Compositions
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`In another aspect, the present invention provided propel-
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`lant compositions comprising or consisting essentially of a
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`composition of the present invention, such propellant com-
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`position preferably being a sprayable composition. The pro-
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`pellant compositions ofthe present invention preferably com-
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`prise a material to be sprayed and a propellant comprising,
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`consisting essentially of, or consisting of a co