WO2005094395A2 - Haloketone refrigerant compositions and uses thereof - Google Patents

Haloketone refrigerant compositions and uses thereof Download PDF

Info

Publication number
WO2005094395A2
WO2005094395A2 PCT/US2005/001511 US2005001511W WO2005094395A2 WO 2005094395 A2 WO2005094395 A2 WO 2005094395A2 US 2005001511 W US2005001511 W US 2005001511W WO 2005094395 A2 WO2005094395 A2 WO 2005094395A2
Authority
WO
WIPO (PCT)
Prior art keywords
cbrf
ocf
cbrfc
cbrfcf
cbr
Prior art date
Application number
PCT/US2005/001511
Other languages
French (fr)
Other versions
WO2005094395A3 (en
Inventor
Barbara Haviland Minor
Mario J. Nappa
Thomas J. Leck
Original Assignee
E.I. Dupont De Nemours And Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US11/014,006 external-priority patent/US7501074B2/en
Application filed by E.I. Dupont De Nemours And Company filed Critical E.I. Dupont De Nemours And Company
Priority to BRPI0508143-2A priority Critical patent/BRPI0508143A/en
Priority to AU2005227844A priority patent/AU2005227844A1/en
Priority to JP2007501773A priority patent/JP2007526384A/en
Priority to EP05722453A priority patent/EP1720953A2/en
Priority to RU2006134980/04A priority patent/RU2006134980A/en
Priority to CA002557874A priority patent/CA2557874A1/en
Publication of WO2005094395A2 publication Critical patent/WO2005094395A2/en
Publication of WO2005094395A3 publication Critical patent/WO2005094395A3/en
Priority to NO20064479A priority patent/NO20064479L/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
    • C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
    • C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
    • C09K5/045—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/10—Components
    • C09K2205/108—Aldehydes or ketones

Definitions

  • the present invention relates to compositions for use in refrigeration and air conditioning systems comprising at least one haloketone or combinations thereof. Further, the present invention relates to compositions for use in refrigeration and air-conditioning systems employing a centrifugal compressor comprising at least one haloketone or combinations thereof.
  • the compositions of the present invention are useful in processes for producing refrigeration or heat or as heat transfer fluids.
  • the object of the present invention is to provide novel refrigerant compositions and heat transfer fluids that provide unique characteristics to meet the demands of low or zero ozone depletion potential and lower global warming potential as compared to current refrigerants.
  • the present invention relates to a haloketone refrigerant or heat transfer fluid selected from the group consisting of: 1 ,1 ,1 ,2,2,4,5, 5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone; 1 ,1 ,1 ,2,4,5,5,5-octafluoro-2,4-bis(trifluoromethyl)-3 pentanone; 1 ,1 ,1 ,2,4 .
  • Disclosed herein also are the above listed compounds for use in refrigeration or air conditioning systems employing a centrifugal compressor, refrigeration or air conditioning systems employing a multi- ⁇ stage centrifugal compressor, and/or employing a single slab/single pass heat exchanger, or refrigeration or air conditioning systems employing a 2-stage centrifugal compressor. Also disclosed herein are processes for producing refrigeration, heat, and transfer of heat from a heat source to a heat sink using the0 present inventive compositions.
  • the haloketone refrigerant compositions of the present invention comprise a single compound or a combination comprising more ⁇ than one haloketone compound.
  • Compositions of the present invention have no ozone depletion potential and low global warming potential .
  • haloketones, alone or in mixtures will have global warming potentials lower than many HFC refrigerants currently in use.
  • the haloketones of the present invention are compounds containing fluorine, carbon, at least one ketone group oxygen, and ⁇ optionally hydrogen, chlorine or bromine.
  • Haloketones may be represented by the formula R 3 COR 4 , wherein R 3 and R 4 are independently selected from straight or branched chain, saturated or unsaturated, aliphatic or alicyclic fluorinated carbon radicals that may optionally contain hydrogen, chlorine, or bromine. R 3 and R 4 may be joined to form a cyclic0 haloketone ring.
  • the haloketones may contain from about 2 to 10 carbon atoms. Preferred haloketones contain 4 to 8 carbon atoms.
  • the haloketones of the present invention may further contain heteroatoms, such as oxygen thus forming additional ketone groups, ether groups, aldehyde groups, or ester groups. Representative haloketones are listed ⁇ in Table 1.
  • the bromofiuoroketones of the present invention comprise at least one selected from the group consisting of: monobromoperfluoroketones, monohydromonobromoperfluoroketones, (perfluoroalkoxy)monobromoperfluoroketones,0 (fluoroalkoxy)monobromoperfluoroketones, and monochloromonobromoperfluoroketones.
  • the following compounds are representative of the monobromoperfluoroketones, monohydromonobromoperfluoroketones, (perfluoroalkoxy)monobromoperfluoroketones, ⁇ (fluoroalkoxy)monobromoperfluoroketones, and monochloromonobromoperfluoroketones of the present invention: CF 3 C(0)CBrFCF 2 CF3, CF 3 C(0)CF 2 CF2CBrF2. CBrF 2 C(0)CF(CF 3 ) 2 . CF 3 C(0)CBr(CF 3 )2.
  • PEIK 1 ,1 ,1 ,2,2,4, ⁇ , ⁇ , ⁇ -nonafluoro-4-(trifluoromethyl)-3-pentanone
  • PIK is commercially available from 3MTM (St. Paul, Minnesota).
  • bromofluoroketones of the present invention described previously including monobromoperfluoroketones, monohydromonobromoperfluoroketones, (perfluoroalkoxy)monobromoperfluoroketones,0 (fluoroalkoxy)monobromoperfluoroketones, and monochloromonobromoperfluoroketones can be prepared as described in the following.
  • Monobromoperfluoroketones CF 3 C(0)CF 2 CF 2 CBrF 2 , CF 3 CF2C(0)CF2CF 2 CBrF2 and CF 3 C(0)CF2CF2CF2CF 2 CBrF2 of the ⁇ present invention may be prepared by bromination of the corresponding monohydroperfluoroketones by the technique of Kolenko and Plashkin in Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, pages 1648 to 1650 (1977), and by Zapevalov, et al. in Zhumal Organicheskoi Khimii, Vol. 26, pages 265 to 272 (1990).
  • CF 3 C(0)CF 2 CF 2 CBrF2 may be0 prepared by bromination of monohydroperfluoroketone CF 3 C(0)CF2CF2CHF2, which may be prepared by isomerization of an epoxide as described by Zapelov et al. in Zhumal Vsesoyuznogo Khimicheskogo Obshchestva im. D. I. Mendeleeva, Vol. 18, pages ⁇ 91 to 693 (1973).
  • CF 3 CF 2 C(0)CF 2 CF 2 CBrF 2 and CF 3 C(0)CF 2 CF 2 CF 2 CBrF 2 may be prepared by bromination of monohydroperfluoroketones CF 3 CF 2 C(0)CF 2 CF 2 CHF 2 and CF 3 C(0)CF 2 CF 2 CF 2 CHF2, respectively, by the technique of Saloutina, et al. in Zhumal Organicheskoi Khimii, Vol. 29, pages 132 ⁇ to 1336 (1993).
  • Preparation of monobromoperfluoroketones CF 3 C(0)CF 2 CF 2 CBrF 2 , CF 3 CF 2 C(0)CF 2 CF 2 CBrF2 and CF 3 C(0)CF2CF2CF 2 CF 2 CBrF 2 of the present invention by conversion of the monohydroperfluoroketone terminal C-H bond to a terminal C-Br may be carried out using brominating agents such as elemental bromine, 0 phosphorous pentabromide, or a mixture of bromine and phosphorous tribromide.
  • the preferred brominating agent is a mixture of bromine and phosphorous tribromide.
  • Reaction of a monohydroperfluoroketone and a brominating agent may be carried out under substantially anhydrous conditions in the ⁇ vapor phase or liquid phase in a container fabricated from materials of construction suitable for contact with bromine and hydrogen bromide at temperatures of about 300°C to 600°C.
  • materials of construction include metallic alloys containing a nickel such as, for example, HastelloyTM C and HastelloyTM B.
  • the reaction takes place0 under the autogenous pressures of the reactants at the reaction temperature.
  • the ratio of the brominating agent to the monohydroperfluoroketones is at least about 1 mole of brominating agent per mole of monohydroperfluoroketone and preferably about 1.3 moles of ⁇ brominating agent per mole of monohydroperfluoroketone. More than 1.7 moles of brominating agent per mole of monohydroperfluoroketone provides little benefit.
  • Brominating the monohydroperfluoroketone may be conducted at temperatures of from about 300°C to about 600°C. Using the preferred0 brominating agent, the temperature is preferably conducted from about 300°C to 3 ⁇ O°C. Contact times between the brominating agent and the monohydroperfluoroketone may be from about one hour to about twenty hours.
  • reaction mixture is cooled ⁇ and then treated with a reagent to decompose the brominating agent such as sodium sulfite.
  • a reagent such as sodium sulfite.
  • the monobromoperfluoroketone may be isolated by collecting the organic phase followed by distillation.
  • the perfluoroolefin epoxides may be prepared by contacting perfluoroolefin with an alkali metal hypohalite as described by Kolenko, et al. in Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, pages 2609-2612 (1979).
  • the contact of perfluoroolefin epoxides with alkali metal bromides may be carried out in a polar non-protic solvent such as glycol ethers such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether, N,N-dimethyl formamide, N,N-dimethyl acetamide, dimethyl0 sulfolane, dimethylsulfoxide, N-methylpyrrolidinone, and alkane nitriles such as acetonitrile, propionitrile, and butyronitrile.
  • glycol ethers such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether, N,N-dimethyl formamide, N,N-dimethyl acetamide, dimethyl0 sulfolane, dimethylsulfoxide,
  • Preferred solvents for contacting perfluoroolefin epoxides with alkali metal bromides are glycol ethers such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ⁇ ether, and alkane nitriles such as acetonitrile, propionitrile, and butyronitrile.
  • Alkali metal bromides suitable for opening the perfluoroolefin epoxide ring and formation of a C-Br bond include lithium bromide, sodium bromide, potassium bromide, and cesium bromide; sodium and lithium0 bromide are preferred.
  • the mole ratio of the alkali metal bromide to the perfluoroolefin epoxide is at least about 2:1 , preferably about 10:1.
  • Reaction of alkali metal bromides and perfluoolefin epoxide may be conducted in the liquid phase under substantially anhydrous ⁇ conditions at temperatures of from about 10°C to about 1 ⁇ 0°C, with contact times of from about O. ⁇ hour to about thirty-six hours. Specific pressure conditions are not critical.
  • the reaction mixture may be distilled to isolate the monobromoperfluoroketone.
  • Monobromoperfluoroketones of the present invention CBrF 2 C(0)CF(CF 3 ) .
  • ⁇ CF 3 CF 2 C(0)CF 2 CF2CF 2 CBrF2, CBrF 2 CF 2 CF 2 C(0)CF(CF 3 ) 2) and CBrF2CF 2 C(0)CF(CF 3 )CF 2 CF3 may be prepared by reacting a monobromoperfluoroacyl fluoride with a perfluoroolefin.
  • Monobromoperfluoroketones of the present invention CF 3 C(0)CBr(CF 3 ) 2 , CF 3 CBrFC(0)CF 2 CF 2 CF 3 , CF 3 C(0)CBr(CF 3 )CF 2 CF 3 , CF 3 C(0)CF(CF 3 )CBrFCF 3 , CF 3 CF 2 CF 2 C(0)CBr(CF 3 ) 2 , may be prepared0 by reacting a perfluoroacyl fluoride with a monobromoperfluoroolefin.
  • Representative (perfluoroalkoxy)monobromoperfluoroketones of the present invention include CBrF 2 C(0)CF(CF 3 )OCF 3 , CBrF 2 CF 2 C(0)CF(CF 3 )OCF 3l ⁇ CBrF 2 CF 2 CF 2 C(0)CF(CF 3 )OCF3, CBrF 2 C(0)CF(CF 3 )OC 2 F 5 , CBrF 2 CF 2 C(0)CF(CF 3 )OC 2 F 5 , CBrF 2 C(0)CF(CF 3 )OCF 2 C 2 F 5> CBrF 2 CF2C(0)CF(CF3)OCF 2 C2F5, CBrF 2 C(0)CF(CF3)OCF(CF 3 )2, CBrF 2 CF 2 C(0)CF(CF 3 )OCF(CF3)2, CF 3 CBrFC(0)CF(CF 3 )OCF(CF 3 ) 2 , CF 3 CBrFC(0)CF(CF 3 )OCF(
  • (Perfluoroalkoxy)monobromoperfluoroketones of the formula R 1 C(0)CF(CF 3 )OR F may also be obtained by reacting perfluoroalkoxyperfluoroacyl fluorides of the formula R F OCF(CF 3 )C(0)F with a monobromoperfluoroolefin.
  • Representative ⁇ (perfluoroalkoxy)monobromoperfluoroketones of the present invention include CF 3 CBrFC(0)CF(CF 3 )OCF 3 .
  • ⁇ CF 3 CBrFC(0)CF(CF 3 )OCF 2 C 2 F 5 may be prepared by reacting C 2 F 5 CF 2 OC(CF 3 )FC(0)F with CF 2
  • Representative (fluoroalkoxy)monobromoperfluoroketones include0 CBrF 2 C(0)CF(OCF 2 CHF2)CF3, CBrF 2 C(0)CH(OCF2CHF 2 )CF 3 , CBrF 2 C(0)CF(OCH 3 )CF 3 , and CBrF 2 C(0)CF(CF 2 OCH 3 )CF3.
  • the reaction of fluoroacyl fluorides with fluoroolefins is described by Fawcett, et al. in U. S. Patent No. 3,186,734 and Journal of the American Chemical Society, Vol. 84, pages 428 ⁇ to 4288 (1962).
  • references may also be applied to the preparation of (perfluoroalkoxy)monobromoperfluoroketones by the reaction of0 monobromoperfluoroacyl fluorides with perfluorovinyl ethers, or by the reaction of perfluoroalkoxyperfluoroacyl fluorides with monobromoperfluoroolefins.
  • Preferred solvents for reacting fluoroacyl fluorides with fluoroolefin are glycol ethers.
  • the reaction may be run under substantially anhydrous conditions. 0
  • the mole ratio of the fluoroolefin to fluoroacyl fluoride during the reaction may be at least about 1:1 to about 2:1, and preferably is about 1.1.
  • the reaction of fluoroacyl fluoride with fluoroolefin is preferably conducted in the presence of a fluoride ion source such as an alkali metal ⁇ fluoride, alkali metal hydrogen difluoride (i.e., a bifluoride), alkali-earth metal fluoride, tetraalkylammonium fluoride, tetraaikylammonium hydrogen fluoride, trialkylammonium fluoride, or non-oxidizing transition metal fluorides.
  • a fluoride ion source such as an alkali metal ⁇ fluoride, alkali metal hydrogen difluoride (i.e., a bifluoride), alkali-earth metal fluoride, tetraalkylammonium fluoride, tetraaikylammonium hydrogen fluoride, trialkylammonium fluoride, or non-oxidizing transition metal fluorides.
  • a fluoride ion source such as an al
  • the fluoride ion source may be present0 at a level of ⁇ mole percent to 20 mole percent, preferably about 10 mole percent, based on the quantity of fluoroolefin present. Temperatures of from about ⁇ 0°C to about 2 ⁇ O°C, preferably from about 100°C to about 1 ⁇ 0°C are effective to produce any of the fluorinated ketones of the present invention by reaction of a fluoroacyl ⁇ fluoride with a fluoroolefin.
  • the reaction of fluoroacyl fluoride with fluoroolefin may take place in batch mode or in semi-batch mode with the fluoroacyl fluoride added gradually to the mixture of the fluoroolefin, solvent, and fluoride ion source. Contact times suitable for the reaction may be from about O. ⁇ 0 hour to about 24 hours.
  • the reaction typically takes place under autogenous pressure provided by the reactants at the reaction temperature.
  • hydrogen fluoride may be present in small amounts during the reactions of fluoroacyl ⁇ fluorides due to the presence of traces of water.
  • Reaction of fluoroacyl fluorides with fluoroolefins may be conducted in a vessel formed of materials compatible with hydrogen fluoride at elevated temperatures and pressures.
  • haloketone products may be isolated from the reaction mixture as a lower liquid layer or by distillation. After removing traces of fluoride salts by washing with water, such products may be purified by distillation.
  • the present invention further includes 0 monohydromonobromoperfluoroketones in which one of the C-F bonds in a perfluoroketone has been replaced by a C-Br bond, and in addition, another of the C-F bonds in said perfluoroketone has been replaced by a C-H bond.
  • Monohydromonobromoperfluoroketones of the present invention comprise CHF2CF 2 C(0)CBrFCF 3 , (CF 3 )2CHC(0)CBrFCF 3 ,5 CHF 2 CF 2 C(0)CBr(CF 3 ) 2 .
  • CBrF 2 CF 2 C(0)CH(CF 3 ) 2 may be prepared by reacting CBrF 2 CF
  • the production of monohydromonobromoperfluoroketones by the reaction of monohydroperfluoroacyl fluorides with monobromoperfluoroolefins, as well as by the reaction of0 monobromoperfluoroacyl fluorides with monohydroperfluoroolefins, may use reaction conditions and procedure similar to those discussed hereinabove for the reaction of a fluoroacyl fluoride with a fluoroolefin.
  • the present invention further comprises monochloromonobromoperfluoroketones in which one of the C-F bonds in ⁇ a perfluoroketone has been replaced by a C-Br bond, and in addition, another one of the C-F bonds in said perfluoroketone has been replaced by a C-CI bond.
  • Monochloromonobromoperfluoroketones of the present invention comprise compounds of the formula CXF 2 CFYC(0)CFRCF 3 , wherein X is CI and Y is Br, or wherein X is Br and Y is CI, and wherein R is F, a CF3 radical, or a C2F5 radical.
  • Monochloromonobromoperfluoroketones of the present invention further comprise CCIF 2 C(0)CBr(CF 3 ) 2 , CCIF 2 CF 2 C(0)CBr(CF 3 ) 2 .5 CF 3 CCIFC(0)CBr(CF 3 ) 2) CCIF 2 C(0)CBrFCF 3 .
  • CCIF2CF 2 C(0)CBrFCF 3l and CF 3 CCIFC(0)CBrFCF 3 which may be prepared by reacting a monochloroperfluoroacyl fluoride with a monobromoperfluoroolefin.
  • Monochloromonobromoperfluoroketones of the present invention further include CBrF 2 C(0)CCI(CF 3 ) 2 .
  • CBrF 2 CF 2 C(0)CCI(CF3)2, CBrF 2 C(0)CCIFCF 3 , and CBrF 2 CF 2 C(0)CCIFCF 3 which may be prepared by reacting a monobromoperfluoroacyl fluoride with a0 monochloroperfluoroolefin.
  • the formation of monohydromonobromoperfluoroketones by the reaction of fluoroacyl fluorides of the formula CXF 2 CFYC(0)F with
  • compositions may be prepared by any convenient method to combine the desired amounts of the individual components. A preferred method is to weigh the desired component amounts and thereafter combine the components in an appropriate vessel. Agitation may be0 used, if desired.
  • the refrigerant or heat transfer compositions of the present invention include: 1 ,1 ,1 ,2,2,4, ⁇ , ⁇ , ⁇ -nonafluoro-4-(trifluoromethyl)-3-pentanone; 1 ,1 ,1 ,3,4,4,4-heptafluoro-3-(trifluoromethyl)-2-butanone; ⁇ 1 ,1 ,1 ,2,4, ⁇ , ⁇ , ⁇ -octafluoro-2,4-bis(trifluoromethyl)-3 pentanone; 1 ,1 ,1 ,2,4,4, ⁇ , ⁇ -octafluoro-2-(trifluoromethyl)-3-pentanone; 1 ,1 ,1 ,2,4,4, ⁇ , ⁇ ,6,6,6-undecafluoro-2-(trifluoromethyl)-3-hexanone; 1 ,1 , 2,2,4, ⁇ , ⁇ , ⁇ -octafluoro-1-(trifluoromethoxy)-4-(tri
  • compositions of the present invention may further comprise about 0.01 weight percent to about 5 weight percent of a thermal0 stabilizer such as nitromethane.
  • the compositions of the present invention may further comprise an ultra-violet (UV) dye and optionally a solubilizing agent.
  • UV dye is a useful component for detecting leaks of the refrigerant composition by permitting one to observe the fluorescence of the dye ⁇ under an ultra-violet light at the point of a leak within a refrigeration or air- conditioning system. Solubilizing agents may be needed due to poor solubility of such UV dyes in some refrigerants.
  • ultra-violet dye is meant a UV fluorescent composition that absorbs light in the ultra-violet or “near" ultra-violet region of the0 electromagnetic spectrum.
  • the fluorescence produced by the UV fluorescent dye under illumination by a UV light that emits radiation with wavelength anywhere from 10 nanometer to 760 nanometer may be detected. Therefore, if refrigerant containing such a UV fluorescent dye is leaking from a given point in a refrigeration or air conditioning apparatus, ⁇ the fluorescence can be detected at the leak point.
  • UV fluorescent dyes include but are not limited to naphthalimides, perylenes, coumarins, anthracenes, phenanthracenes, xanthenes, thioxanthenes, naphthoxanthenes, fluoresceins, and derivatives or mixtures thereof.
  • Solubilizing agents of the present invention comprise at least one compound selected from the group consisting of hydrocarbons, hydrocarbon ethers, polyoxyalkylene glycol ethers, amides, nitriles, ⁇ ketones, chlorocarbons, esters, lactones, aryl ethers, fluoroethers and 1 ,1 ,1-trifluoroalkanes.
  • Hydrocarbon solubilizing agents of the present invention comprise hydrocarbons including straight chained, branched chain or cyclic alkanes or alkenes containing ⁇ or fewer carbon atoms and only0 hydrogen with no other functional groups.
  • Representative hydrocarbon solubilizing agents comprise propane, propylene, cyclopropane, n-butane, isobutane, and n-pentane. It should be noted that if the refrigerant is a hydrocarbon, then the solubilizing agent may not be the same hydrocarbon.
  • Hydrocarbon ether solubilizing agents of the present invention comprise ethers containing only carbon, hydrogen and oxygen, such as dimethyl ether (DME).
  • Polyoxyalkylene glycol ether solubilizing agents of the present invention are represented by the formula R 1 [(OR 2 ) x OR 3 ] y , wherein: x is an0 integer from 1-3; y is an integer from 1-4; R 1 is selected from hydrogen and aliphatic hydrocarbon radicals having 1 to 6 carbon atoms and y bonding sites; R 2 is selected from aliphatic hydrocarbylene radicals having from 2 to 4 carbon atoms; R 3 is selected from hydrogen and aliphatic and alicyclic hydrocarbon radicals having from 1 to 6 carbon atoms; at least ⁇ one of R 1 and R 3 is said hydrocarbon radical; and wherein said polyoxyalkylene glycol ethers have a molecular weight of from about 100 to about 300 atomic mass units.
  • polyoxyalkylene glycol ether solubilizing agents represented by R 1 [(OR 2 ) x OR 3 j y : x is preferably 1- 2; y is preferably 1 ; R 1 and R 3 are preferably independently selected from0 hydrogen and aliphatic hydrocarbon radicals having 1 to 4 carbon atoms; R 2 is preferably selected from aliphatic hydrocarbylene radicals having from 2 or 3 carbon atoms, most preferably 3 carbon atoms; the polyoxyalkylene glycol ether molecular weight is preferably from about 100 to about 2 ⁇ 0 atomic mass units, most preferably from about 12 ⁇ to about ⁇ 2 ⁇ 0 atomic mass units.
  • the R 1 and R 3 hydrocarbon radicals having 1 to 6 carbon atoms may be linear, branched or cyclic.
  • Representative R 1 and R 3 hydrocarbon radicals include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, terf-butyl, pentyl, isopentyl, neopentyl, tetf-pentyl, cyclopentyl, and cyclohexyl.
  • free hydroxyl radicals on the present polyoxyalkylene glycol ether solubilizing agents may be incompatible with certain compression refrigeration apparatus materials of construction (e.g.
  • R 1 and R 3 are preferably aliphatic hydrocarbon radicals having 1 to 4 carbon atoms, most preferably 1 carbon atom.
  • the R 2 aliphatic hydrocarbylene radicals having from 2 to 4 carbon atoms form repeating oxyalkylene radicals - (OR 2 ) x - that include oxyethylene radicals, oxypropylene radicals, and oxybutylene radicals.
  • the oxyalkylene radical0 comprising R 2 in one polyoxyalkylene glycol ether solubilizing agent molecule may be the same, or one molecule may contain different R 2 oxyalkylene groups.
  • the present polyoxyalkylene glycol ether solubilizing agents preferably comprise at least one oxypropylene radical.
  • R 1 is an aliphatic or alicyclic hydrocarbon radical having 1 to 6 carbon atoms ⁇ and y bonding sites
  • the radical may be linear, branched or cyclic.
  • Representative R 1 aliphatic hydrocarbon radicals having two bonding sites include, for example, an ethylene radical, a propylene radical, a butylene radical, a pentylene radical, a hexylene radical, a cyclopentylene radical and a cyclohexylene radical.
  • R 1 aliphatic hydrocarbon0 radicals having three or four bonding sites include residues derived from polyalcohols, such as trimethylolpropane, glycerin, pentaerythritol, 1 ,2,3- trihydroxycyclohexane and 1 ,3, ⁇ -trihydroxycyclohexane, by removing their hydroxyl radicals.
  • Representative polyoxyalkylene glycol ether solubilizing agents ⁇ include but are not limited to: CH 3 OCH 2 CH(CH 3 )0(H or CH 3 ) (propylene glycol methyl (or dimethyl) ether), CH 3 0[CH 2 CH(CH 3 )0] 2 (H or CH 3 ) (dipropylene glycol methyl (or dimethyl) ether), CH 3 0[CH 2 CH(CH 3 )0] 3 (H or CH 3 ) (tripropylene glycol methyl (or dimethyl) ether), C 2 H 5 OCH 2 CH(CH 3 )0(H or C 2 H 5 ) (propylene glycol ethyl (or diethyl) ether),0 C 2 H 5 0[CH 2 CH(CH 3 )0] 2 (H or C 2 H 5 ) (dipropylene glycol ethyl (or diethyl) ether), C 2 H 5 0[CH 2 CH(CH 3 )0] 3 (H
  • R 1 , R 2 , R 3 and R 5 may optionally include substituted hydrocarbon radicals, that is, radicals containing non-hydrocarbon substituents selected from halogens0 (e.g., fluorine, chlorine) and alkoxides (e.g. methoxy).
  • R 1 , R 2 , R 3 and R 5 may optionally include heteroatom-substituted hydrocarbon radicals, that is, radicals, which contain the atoms nitrogen (aza-), oxygen (oxa-) or sulfur (thia-) in a radical chain otherwise composed of carbon atoms.
  • amide solubilizing agents consist of carbon, hydrogen, nitrogen and oxygen.
  • R 1 , R 2 , R 3 and R 5 aliphatic and alicyclic hydrocarbon radicals include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tetf-butyl, pentyl, isopentyl, neopentyl, terf-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and their configu rational isomers.
  • a preferred embodiment of amide solubilizing agents are those wherein R 4 ⁇ in the aforementioned formula cyclo-[R 4 CON(R 5 )-] may be represented by the hydrocarbylene radical (CR 6 R 7 ) n , in other words, the formula: cyclo- [(CR 6 R 7 ) n CON(R 5 )-] wherein: the previously-stated values for molecular weight apply; n is an integer from 3 to ⁇ ; R 5 is a saturated hydrocarbon radical containing 1 to 12 carbon atoms; R 6 and R 7 are independently selected (for each n) by the rules previously offered defining R 1"3 .
  • R 6 and ⁇ R 7 are preferably hydrogen, or contain a single saturated hydrocarbon radical among the n methylene units, and R 5 is a saturated hydrocarbon radical containing 3 to 12 carbon atoms.
  • R 5 is a saturated hydrocarbon radical containing 3 to 12 carbon atoms.
  • 1 -(saturated hydrocarbon radical)- ⁇ -methylpyrrolidin-2-ones 1 -(saturated hydrocarbon radical)- ⁇ -methylpyrrolidin-2-ones.
  • amide solubilizing agents include but are not0 limited to: 1-octylpyrrolidin-2-one, 1-decylpyrrolidin-2-one, 1-octyl- ⁇ - methylpyrrolidin-2-one, 1 -butylcaprolactam, 1 -cyclohexylpyrrolidin-2-one, 1 -butyl- ⁇ -methylpiperid-2-one, 1 -pentyl-5-methylpiperid-2-one, 1 - hexylcaprolactam, 1-hexyl-5-methylpyrrolidin-2-one, ⁇ -methyl-1- pentylpiperid-2-one, 1 ,3-dimethylpiperid-2-one, 1-methylcaprolactam, 1-5 butyl-pyrrolidin-2-one, 1 ,5-dimethylpiperid-2-one, 1-decyl- ⁇ - methylpyrrolidin-2-one, 1-dodecylpyrrolid-2-one, N,N-di
  • Ketone solubilizing agents of the present invention comprise ketones represented by the formula R 1 COR 2 , wherein R 1 and R 2 are0 independently selected from aliphatic, alicyclic and aryl hydrocarbon radicals having from 1 to 12 carbon atoms, and wherein said ketones have a molecular weight of from about 70 to about 300 atomic mass units.
  • R 1 and R 2 in said ketones are preferably independently selected from aliphatic and alicyclic hydrocarbon radicals having 1 to 9 carbon atoms. ⁇
  • the molecular weight of said ketones is preferably from about 100 to 200 atomic mass units.
  • R and R 2 may together form a hydrocarbylene radical connected and forming a five, six, or seven-membered ring cyclic ketone, for example, cyclopentanone, cyclohexanone, and cycloheptanone.
  • R 1 and R 2 may optionally include substituted hydrocarbon radicals, that is,0 radicals containing non-hydrocarbon substituents selected from halogens (e.g., fluorine, chlorine) and alkoxides (e.g. methoxy).
  • R 1 and R 2 may optionally include heteroatom-substituted hydrocarbon radicals, that is, radicals, which contain the atoms nitrogen (aza-), oxygen (keto-, oxa-) or sulfur (thia-) in a radical chain otherwise composed of carbon atoms.
  • heteroatom-substituted hydrocarbon radicals that is, radicals, which contain the atoms nitrogen (aza-), oxygen (keto-, oxa-) or sulfur (thia-) in a radical chain otherwise composed of carbon atoms.
  • no more than three non-hydrocarbon substituents and heteroatoms, and preferably no more than one, will be present for each 10 carbon atoms in R 1 and R 2 , and the presence of any such non- hydrocarbon substituents and heteroatoms must be considered in applying the aforementioned molecular weight limitations.
  • R and R 2 aliphatic, alicyclic and aryl hydrocarbon radicals in the general formula R 1 COR 2 include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, ⁇ te/f-butyl, pentyl, isopentyl, neopentyl, terf-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and their configu rational isomers, as well as phenyl, benzyl, cumenyl, mesityl, tolyl, xylyl and phenethyl.
  • ketone solubilizing agents include but are not0 limited to: 2-butanone, 2-pentanone, acetophenone, butyrophenone, hexanophenone, cyclohexanone, cycloheptanone, 2-heptanone, 3- heptanone, ⁇ -methyl-2-hexanone, 2-octanone, 3-octanone, diisobutyl ketone, 4-ethylcyclohexanone, 2-nonanone, ⁇ -nonanone, 2-decanone, 4- decanone, 2-decalone, 2-tridecanone, dihexyl ketone and dicyclohexyl ⁇ ketone.
  • Nitrile solubilizing agents of the present invention comprise nitriles represented by the formula R 1 CN, wherein R 1 is selected from aliphatic, alicyclic or aryl hydrocarbon radicals having from 5 to 12 carbon atoms, and wherein said nitriles have a molecular weight of from about 900 to about 200 atomic mass units.
  • R in said nitrile solubilizing agents is preferably selected from aliphatic and alicyclic hydrocarbon radicals having 8 to 10 carbon atoms.
  • the molecular weight of said nitrile solubilizing agents is preferably from about 120 to about 140 atomic mass units.
  • R 1 may optionally include substituted hydrocarbon radicals, that is,5 radicals containing non-hydrocarbon substituents selected from halogens (e.g., fluorine, chlorine) and alkoxides (e.g. methoxy).
  • R 1 may optionally include heteroatom-substituted hydrocarbon radicals, that is, radicals, which contain the atoms nitrogen (aza-), oxygen (keto-, oxa-) or sulfur (thia-) in a radical chain otherwise composed of carbon atoms.
  • R 1 aliphatic, alicyclic and aryl ⁇ hydrocarbon radicals in the general formula R 1 CN include pentyl, isopentyl, neopentyl, tetf-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and their configu rational isomers, as well as phenyl, benzyl, cumenyl, mesityl, tolyl, xylyl and phenethyl.
  • nitrile solubilizing agents include but are not limited to: 1- cyanopentane, 2,2-dimethyl-4-cyanopentane, 1-cyanohexane, 1- cyanoheptane, 1 -cyanooctane, 2-cyanooctane, 1-cyanononane, 1- cyanodecane, 2-cyanodecane, 1-cyanoundecane and 1-cyanododecane.
  • Chlorocarbon solubilizing agents of the present invention comprise chlorocarbons represented by the formula RCI X , wherein; x is selected from the integers 1 or 2; R is selected from aliphatic and alicyclic hydrocarbon radicals having 1 to 12 carbon atoms; and wherein said chlorocarbons have a molecular weight of from about 100 to about 200 atomic mass units.
  • the molecular weight of said chlorocarbon solubilizing agents is preferably from about 120 to 150 atomic mass units.
  • R aliphatic and alicyclic hydrocarbon radicals in the general formula RCI X include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, terf-butyl, pentyl, isopentyl, neopentyl, ferf-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and their configurational isomers.
  • chlorocarbon solubilizing agents include but are not limited to: 3-(chloromethyl)pentane, 3-chloro-3-methylpentane, 1- chlorohexane, 1 ,6-dichlorohexane, 1-chloroheptane, 1-chlorooctane, 1- chlorononane, 1-chlorodecane, and 1 ,1 ,1-trichlorodecane.
  • Ester solubilizing agents of the present invention comprise esters represented by the general formula R 1 C ⁇ 2 R 2 , wherein R 1 and R 2 are independently selected from linear and cyclic, saturated and unsaturated, alkyl and aryl radicals.
  • esters consist essentially of the elements C, H and O, have a molecular weight of from about 80 to about 560 atomic mass units.
  • Representative esters include but are not limited to: (CH 3 )2CHCH2 ⁇ OC(CH2)2-4 ⁇ COCH 2 CH(CH3)2 (diisobutyl dibasic ester), ethyl hexanoate, ethyl heptanoate, n-butyl propionate, n-propyl propionate, ethyl benzoate, di-n-propyl phthalate, benzoic acid ethoxyethyl ester, dipropyl carbonate, "Exxate 700" (a commercial C alkyl acetate), "Exxate 800" (a commercial C 3 alkyl acetate), dibutyl phthalate, and tert-butyl acetate.
  • Lactone solubilizing agents of the present invention comprise lactones represented by structures [A], [B], and [C
  • lactones contain the functional group -CO 2 - in a ring of six (A), or preferably five atoms (B), wherein for structures [A] and [B], Ri through R 8 are independently selected from hydrogen or linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl radicals. Each Ri though R 8 may be connected forming a ring with another Ri through Rs.
  • the lactone may have an exocyclic alkylidene group as in structure [C], wherein Ri through R 6 are independently selected from hydrogen or linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl radicals. Each R-i though Re may be connected forming a ring with another Ri through R ⁇ .
  • the lactone solubilizing agents have a molecular weight range of from about 80 to about 300 atomic mass units, preferred from about 80 to about 200 atomic mass units.
  • lactone solubilizing agents include but are not limited to the compounds listed in Table 2. TABLE 2
  • Lactone solubilizing agents generally have a kinematic viscosity of less than about 7 centistokes at 40°C.
  • gamma- undecalactone has kinematic viscosity of ⁇ .4 centistokes and cis-(3-hexyl- ⁇ -methyl)dihydrofuran-2-one has viscosity of 4.6 centistokes both at 40°C.
  • Lactone solubilizing agents may be available commercially or prepared by methods as described in U. S. patent application 10/910,496 (inventors being P. J. Fagan and C. J. Brandenburg), filed August 3, 2004, incorporated herein by reference.
  • Aryl ether solubilizing agents of the present invention further comprise aryl ethers represented by the formula R 1 OR 2 , wherein: R 1 is selected from aryl hydrocarbon radicals having from 6 to 12 carbon atoms; R 2 is selected from aliphatic hydrocarbon radicals having from 1 to 4 carbon atoms; and wherein said aryl ethers have a molecular weight of from about 100 to about 150 atomic mass units.
  • R 1 aryl radicals in the general formula R 1 OR 2 include phenyl, biphenyl, cumenyl, mesityl, tolyl, xylyl, naphthyl and pyridyl.
  • R 2 aliphatic hydrocarbon radicals in the general formula R 1 OR 2 include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and terf-butyl.
  • Representative aromatic ether solubilizing agents include but are not limited to: methyl phenyl ether (anisole), 1 ,3-dimethyoxybenzene, ethyl phenyl ether and butyl phenyl ether.
  • Fluoroether solubilizing agents of the present invention comprise those represented by the general formula R 1 OCF 2 CF 2 H, wherein R 1 is selected from aliphatic and alicyclic hydrocarbon radicals having from about ⁇ to about 1 ⁇ carbon atoms, preferably primary, linear, saturated, alkyl radicals.
  • Representative fluoroether solubilizing agents include but are not limited to: C 8 H ⁇ 7 OCF 2 CF 2 H and C 6 H 13 OCF 2 CF 2 H. It should be noted that if the refrigerant is a fluoroether, then the solubilizing agent may not be the same fluoroether.
  • 1 ,1 ,1-Trifluoroalkane solubilizing agents of the present invention comprise 1 ,1 ,1-trifluoroalkanes represented by the general formula CF 3 R 1 , wherein R 1 is selected from aliphatic and alicyclic hydrocarbon radicals having from about 5 to about 1 ⁇ carbon atoms, preferably primary, linear, saturated, alkyl radicals.
  • Representative 1 ,1 ,1- trifluoroalkane solubilizing agents include but are not limited to: 1 ,1 ,1- trifluorohexane and 1 ,1 ,1-trifluorododecane.
  • Solubilizing agents of the present invention may be present as a single compound, or may be present as a mixture of more than one solubilizing agent. Mixtures of solubilizing agents may contain two solubilizing agents from the same class of compounds, say two lactones, or two solubilizing agents from two different classes, such as a lactone and a polyoxyalkylene glycol ether.
  • the present compositions comprising refrigerant and UV fluorescent dye, from about 0.001 weight percent to about 1.0 weight percent of the composition is UV dye, preferably from about 0.005 weight percent to about 0.5 weight percent, and most preferably from 0.01 weight percent to about 0.25 weight percent. Solubility of these UV fluorescent dyes in refrigerants may be poor,.
  • US patent no. RE 36,951 describes a method, which utilizes a dye powder, solid pellet or slurry of dye that may be inserted into a component of the refrigeration or air conditioning apparatus. As refrigerant and lubricant are circulated through the apparatus, the dye is dissolved or dispersed and carried throughout the apparatus. Numerous other methods for introducing dye into a refrigeration or air conditioning apparatus are described in the literature. Ideally, the UV fluorescent dye could be dissolved in the refrigerant itself thereby not requiring any specialized method for introduction to the refrigeration or air conditioning apparatus.
  • the present invention relates to compositions including UV fluorescent dye, which may be introduced into the system dissolved in the refrigerant.
  • inventive compositions will allow the storage and transport of dye-containing refrigerant even at low temperatures while maintaining the dye in solution.
  • present compositions comprising refrigerant, UV fluorescent dye and solubilizing agent, from about 1 to about 50 weight percent, preferably from about 2 to about 25 weight percent, and most preferably from about 5 to about 1 ⁇ weight percent of the combined composition is solubilizing agent in the refrigerant.
  • the UV fluorescent dye is present in a concentration from about 0.001 weight percent to about 1.0 weight percent in the refrigerant, preferably from 0.006 weight percent to about O. ⁇ weight percent, and most preferably from 0.01 weight percent to about 0.2 ⁇ weight percent.
  • commonly used refrigeration system additives may optionally be added, as desired, to compositions of the present invention in order to enhance performance and system stability. These additives are known within the field of refrigeration, and include, but are not limited to, anti wear agents, extreme pressure lubricants, corrosion and oxidation inhibitors, metal surface deactivators, free radical scavengers, and foam control agents,. In general, these additives are present in the inventive compositions in small amounts relative to the overall composition.
  • concentrations of from less than about 0.1 weight percent to as much as about 3 weight percent of each additive are used.
  • additives are selected on the basis of the individual system requirements.
  • These additives include members of the triaryl phosphate family of EP ⁇ (extreme pressure) lubricity additives, such as butylated triphenyl phosphates (BTPP), or other alkylated triaryl phosphate esters, e.g. Syn- 0-Ad 8478 from Akzo Chemicals, tricrecyl phosphates and related compounds.
  • BTPP butylated triphenyl phosphates
  • alkylated triaryl phosphate esters e.g. Syn- 0-Ad 8478 from Akzo Chemicals, tricrecyl phosphates and related compounds.
  • the metal dialkyl dithiophosphates e.g.
  • ZDDP zinc dialkyl dithiophosphate
  • Lubrizol 1376 other members of0 this family of chemicals
  • Other antiwear additives include natural product oils and asymmetrical polyhydroxyl lubrication additives, such as Synergol TMS (International Lubricants).
  • stabilizers such as anti oxidants, free radical scavengers, and water scavengers may be employed. ⁇
  • Compounds in this category can include, but are not limited to, butylated hydroxy toluene (BHT) and epoxides. Solubilizing agents such as ketones may have an objectionable odor, which can be masked by addition of an odor masking agent or fragrance.
  • odor masking agents or fragrances may0 include Evergreen, Fresh Lemon, Cherry, Cinnamon, Peppermint, Floral or Orange Peel or sold by Intercontinental Fragrance, as well as d- limonene and pinene.
  • Such odor masking agents may be used at concentrations of from about 0.001% to as much as about 1 ⁇ % by weight based on the combined weight of odor masking agent and solubilizing ⁇ agent.
  • the present invention further relates to a method of using the refrigerant or heat transfer fluid compositions further comprising ultraviolet fluorescent dye, and optionally, solubilizing agent, in refrigeration or air conditioning apparatus. The method comprises introducing the refrigerant0 or heat transfer fluid composition into the refrigeration or air conditioning apparatus.
  • the present invention further relates to a method of using the refrigerant or heat transfer fluid compositions comprising ultraviolet ⁇ fluorescent dye to detect leaks.
  • the presence of the dye in the compostions allows for detection of leaking refrigerant in the refrigeration or air conditioning apparatus. Leak detection helps to address, resolve or prevent inefficient operation of the apparatus or system or equipment failure.
  • Leak detection also helps one contain chemicals used in the 0 operation of the apparatus.
  • the method comprises providing the composition comprising refrigerant, ultra-violet fluorescent dye as described herein, and optionally, a solubilizing agent as described herein, to refrigeration and air conditioning apparatus and employing a sutiable means for detecting the ⁇ UV fluorescent dye-containing refrigerant.
  • Suitable means for detecting the dye include, but are not limited to, ultra-violet lamp, often referred to as a "black light” or "blue light”. Such ultra-violet lamps are commercially available from numerous sources specifically designed for this purpose.
  • the present invention further relates to a method of using the ⁇ compositions of the present invention for producing refrigeration or heat, wherein the method comprises producing refrigeration by evaporating said composition in the vicinity of a body to be cooled and thereafter condensing said composition; or producing heat by condensing the said composition in the vicinity of the body to be heated and thereafter0 evaporating said composition.
  • Vapor-compression refrigeration systems include an evaporator, a compressor, a condenser, and an expansion device.
  • a vapor-compression cycle re-uses refrigerant in multiple steps producing a cooling effect in one step and a heating effect in a different step. The cycle can be described simply as follows.
  • Liquid refrigerant enters an evaporator through an expansion device, and the liquid refrigerant boils in ⁇ the evaporator at a low temperature to form a gas and produce cooling.
  • the low-pressure gas enters a compressor where the gas is compressed to raise its pressure and temperature.
  • the higher-pressure (compressed) gaseous refrigerant then enters the condenser in which the refrigerant condenses and discharges its heat to the environment.
  • the refrigerant0 returns to the expansion device through which the liquid expands from the higher-pressure level in the condenser to the low-pressure level in the evaporator, thus repeating the cycle.
  • compressors There are various types of compressors that may be used in refrigeration applications.
  • Compressors can be generally classified as ⁇ reciprocating, rotary, jet, centrifugal, scroll, screw or axial-flow, depending on the mechanical means to compress the fluid, or as positive- displacement (e.g., reciprocating, scroll or screw) or dynamic (e.g., centrifugal or jet), depending on how the mechanical elements act on the fluid to be compressed.0 Either positive displacement or dynamic compressors may be used in the present inventive process.
  • a centrifugal type compressor is the preferred equipment for the present refrigerant compositions.
  • a centrifugal compressor uses rotating elements to accelerate the refrigerant radially, and typically includes an impeller and diffuser ⁇ housed in a casing.
  • Centrifugal compressors usually take fluid in at an impeller eye, or central inlet of a circulating impeller, and accelerate it radially outward. Some static pressure rise occurs in the impeller, but most of the pressure rise occurs in the diffuser section of the casing, where velocity is converted to static pressure.
  • Each impeller-diffuser set is0 a stage of the compressor.
  • Centrifugal compressors are built with from 1 to 12 or more stages, depending on the final pressure desired and the volume of refrigerant to be handled.
  • the pressure ratio, or compression ratio, of a compressor is the ratio of absolute discharge pressure to the absolute inlet pressure.6 Pressure delivered by a centrifugal compressor is practically constant over a relatively wide range of capacities.
  • Positive displacement compressors draw vapor into a chamber, and the chamber decreases in volume to compress the vapor. After being compressed, the vapor is forced from the chamber by further decreasing the volume of the chamber to zero or nearly zero.
  • a positive displacement compressor can build up a pressure, which is limited only by the volumetric efficiency and the strength of the parts to withstand the pressure.
  • a centrifugal compressor depends entirely on the centrifugal force of the high-speed impeller to compress the vapor passing through the impeller. There is no positive displacement, but rather what is called dynamic-compression. The pressure a centrifugal compressor can develop depends on the tip speed of the impeller.
  • Tip speed is the speed of the impeller measured at its tip and is related to the diameter of the impeller and its revolutions per minute.
  • the capacity of the centrifugal compressor is determined by the size of the passages through the impeller. This makes the size of the compressor more dependent on the pressure required than the capacity. Because of its high-speed operation, a centrifugal compressor is fundamentally a high volume, low-pressure machine.
  • a centrifugal compressor works best with a low-pressure refrigerant, such as trichlorofluoromethane (CFC-11) or 1 ,2,2-trichlorotrifluoroethane (CFC- 113). Large centrifugal compressors typically operate at 3000 to 7000 revolutions per minute (rpm).
  • Small turbine centrifugal compressors are designed for high speeds, from about 40,000 to about 70,000 (rpm), and have small impeller sizes, typically less than 0.15 meters.
  • a multi-stage impeller may be used in a centrifugal compressor to improve compressor efficiency thus requiring less power in use.
  • the discharge of the first stage impeller goes to the suction intake of a second impeller.
  • Both impellers may operate by use of a single shaft (or axle).
  • Each stage can build up a compression ratio of about 4 to 1 ; that is, the absolute discharge pressure can be four times the absolute suction pressure.
  • An example of a two- stage centrifugal compressor system, in this case for automotive applications, is described in US 5,065,990, incorporated herein by reference.
  • compositions of the present invention suitable for use in a refrigeration or air conditioning systems employing a centrifugal compressor comprise at least one of: 1 ,1 ,1 ,2,2,4, ⁇ , ⁇ , ⁇ -nonafluoro-4-(trifluoromethyl)-3-pentanone; ⁇ 1 ,1 ,1 ,3,4,4,4-heptafluoro-3-(trifluoromethyl)-2-butanone; 1 ,1 ,1 ,2,4, ⁇ , ⁇ , ⁇ -octafluoro-2,4-bis(trifluoromethyl)-3 pentanone; 1 ,1 ,1 ,2,4,4, ⁇ , ⁇ -octafluoro-2-(trifluoromethyl)-3-pentanone; 1 ,1 ,1 ,2,4,4, ⁇ , ⁇ ,6,6,6-undecafluoro-2-(trifluoromethyl)-3-hexanone; 1 ,1 ,2,2,4, ⁇ , ⁇ , ⁇ -octaflu
  • compositions of the present invention are also suitable for use in two- stage centrifugal compressor systems.
  • the compositions of the present invention may be used in stationary air-conditioning, heat pumps or mobile air-conditioning and refrigeration systems.
  • Stationary air conditioning and heat pump6 applications include window, ductless, ducted, packaged terminal, chillers and commercial, including packaged rooftop.
  • Refrigeration applications include domestic or home refrigerators and freezers, ice machines, self- contained coolers and freezers, walk-in coolers and freezers and transport refrigeration systems.0
  • the compositions of the present invention may additionally be used in air-conditioning, heating and refrigeration systems that employ fin and tube heat exchangers, microchannel heat exchangers and vertical or horizontal single pass tube or plate type heat exchangers.
  • Conventional microchannel heat exchangers may not be ideal6 for the low pressure refrigerant compositions of the present invention.
  • the low operating pressure and density result in high flow velocities and high frictional losses in all components. In these cases, the evaporator design may be modified.
  • a single slab/single pass heat0 exchanger arrangement may be used. Therefore, a preferred heat exchanger for the low pressure refrigerants of the present invention is a single slab/single pass heat exchanger.
  • compositions of the present invention are suitable for use in refrigeration or air conditioning systems employing a single ⁇ slab/single pass heat exchanger: 1 ,1,1 ,2,2,4, ⁇ , ⁇ , ⁇ -nonafluoro-4-(trifluoromethyl)-3-pentanone; 1 ,1 ,1 ,3,4,4,4-heptafluoro-3-(trifluoromethyl)-2-butanone 1 ,1 ,1 ,2,4,5,5,5-octafluoro-2,4-bis(trifluoromethyl)-3 pentanone; 1 ,1 ,1 ,2,4,4,5, ⁇ -octafluoro-2-(trifluoromethyl)-3-pentanone; 1 ,1 ,1 ,2,4 ,4,5,6,6,6, 6-undecafIuoro-2-(trifluoromethyl)-3-hexanone; 1 ,1 ,2,2,4,5,5,5-octafluoro-1-(trifluorome
  • compositions of the present invention are particularly useful in small turbine centrifugal compressors, which can be used in auto and window air conditioning or heat pumps as well as other applications. These high efficiency miniature centrifugal compressors may be driven by an electric motor and can therefore be operated independently of the0 engine speed.
  • a constant compressor speed allows the system to provide a relatively constant cooling capacity at all engine speeds. This provides an opportunity for efficiency improvements especially at higher engine speeds as compared to a conventional R-134a automobile air-conditioning system. When the cycling operation of conventional systems at high ⁇ driving speeds is taken into account, the advantage of these low pressure systems becomes even greater.
  • the present invention relates to a process for producing refrigeration comprising evaporating the compositions of the present invention in the vicinity of a body to be cooled, and thereafter condensing said compositions.
  • the present invention further relates to a process for producing6 heat comprising condensing the compositions of the present invention in the vicinity of a body to be heated, and thereafter evaporating said compositions.
  • the present invention further relates to a process for transfer of heat from a heat source to a heat sink via a heat transfer fluid, wherein the0 compositions of the present invention serve as heat transfer fluids.
  • Said process for heat transfer comprises transferring the compositions of the present invention from a heat source to a heat sink.
  • Heat transfer fluids are utilized to transfer, move or remove heat from one space, location, object or body to a different space, location, ⁇ object or body by radiation, conduction, or convection.
  • a heat transfer fluid may function as a secondary coolant by providing means of transfer for cooling (or heating) from a remote refrigeration (or heating) system.
  • the heat transfer fluid may remain in a constant state throughout the transfer process (i.e., not evaporate or condense).
  • evaporative cooling processes may utilize heat transfer fluids as well, ⁇
  • a heat source may be defined as any space, location, object or body from which it is desirable to transfer, move or remove heat.
  • heat sources may be spaces (open or enclosed) requiring refrigeration or cooling, such as refrigerator or freezer cases in a supermarket, building spaces requiring air conditioning, or the passenger0 compartment of an automobile requiring air conditioning.
  • a heat sink may be defined as any space, location, object or body capable of absorbing heat.
  • a vapor compression refrigeration system is one example of such a heat sink. 5 EXAMPLES
  • Tip Speed to Develop Pressure can be estimated by making some fundamental0 relationships for refrigeration equipment that use centrifugal compressors.
  • the torque an impeller ideally imparts to a gas is defined as
  • T m*(v2*r2-v ⁇ *p
  • Equation 8 is based on some fundamental assumptions, it provides a good estimate of the tip speed of the impeller and provides an important way to compare tip speeds of refrigerants.
  • Table 3 shows theoretical tip speeds that are calculated for 1 ,2,2-trichlorotrifluoroethane (CFC-113) and compositions of the present invention. The conditions assumed for this comparison are:
  • Table 4 shows the performance of various refrigerants compared to CFC-113. The data are based on the following conditions. Evaporator temperature 40.0°F (4.4°C) Condenser temperature 110.0°F (43.3°C) Subcool temperature 10.0°F (5.5°C) Return gas temperature 7 ⁇ .0°F (23.8°C) Compressor efficiency is 70%
  • compositions of the present invention have evaporator and condenser pressures similar to CFC-113. Some compositions also have higher capacity or energy efficiency (COP) than CFC-113.
  • COP energy efficiency

Abstract

Disclosed herein are haloketone refrigerant or heat transfer fluid compositions that are useful in refrigeration or air conditioning apparatus or as heat transfer fluids. The compositions of the present invention are also useful in centrifugal compressor systems that employ two-stage compressors or single slab/single pass heat exchangers.

Description

TITLE OF INVENTION
HALOKETONE REFRIGERANT COMPOSITIONS AND USES THEREOF
CROSS REFERENCE(S) TO RELATED APPLICATION(S) This application claims the priority benefit of U.S. Provisional
Application 60/549,978, filed March 4, 2004, and U.S. Provisional Application 60/575,037, filed May 26, 2004, and U.S. Provisional Application 60/584,785, filed June 29, 2004. BACKGROUND OF THE INVENTION
1. Field of the Invention. The present invention relates to compositions for use in refrigeration and air conditioning systems comprising at least one haloketone or combinations thereof. Further, the present invention relates to compositions for use in refrigeration and air-conditioning systems employing a centrifugal compressor comprising at least one haloketone or combinations thereof. The compositions of the present invention are useful in processes for producing refrigeration or heat or as heat transfer fluids.
2. Description of Related Art. The refrigeration industry has been working for the past few decades to find replacement refrigerants for the ozone depleting chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) being phased out as a result of the Montreal Protocol. The solution for most refrigerant producers has been the commercialization of hydrofluorocarbon (HFC) refrigerants. The new HFC refrigerants, HFC- 134a being the most widely used at this time, have zero ozone depletion potential and thus are not affected by the current regulatory phase out as a result of the Montreal Protocol. Further environmental regulations may ultimately cause global phase out of certain HFC refrigerants. Currently, the automobile industry is facing regulations relating to global warming potential for refrigerants used in mobile air-conditioning. Therefore, there is a great current need to identify new refrigerants with reduced global warming potential for the automobile air-conditioning market. Should the regulations be more broadly applied in the future, an even greater need will be felt for refrigerants that can be used in all areas of the refrigeration and air- conditioning industry. Currently proposed replacement refrigerants for HFC-134a include HFC-152a, pure hydrocarbons such as butane or propane, or "natural" refrigerants such as C02 or ammonia. Many of these suggested replacements are toxic, flammable, and/or have low energy efficiency. Therefore, new alternatives are constantly being sought. The object of the present invention is to provide novel refrigerant compositions and heat transfer fluids that provide unique characteristics to meet the demands of low or zero ozone depletion potential and lower global warming potential as compared to current refrigerants.
BRIEF SUMMARY OF THE INVENTION The present invention relates to a haloketone refrigerant or heat transfer fluid selected from the group consisting of: 1 ,1 ,1 ,2,2,4,5, 5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone; 1 ,1 ,1 ,2,4,5,5,5-octafluoro-2,4-bis(trifluoromethyl)-3 pentanone; 1 ,1 ,1 ,2,4.4,5,5-octafluoro-2-(trifluoromethyl)-3-pentanone; 1 ,1 ,1 ^Aδ.δ.δ.e.θ-undecafluoro^-ttrifluoromethyiy-S-hexanone; 1 ,1 ,2,2,4,5,5,5-octafluoro-1-(trifluoromethoxy)-4-(trifluoromethyl)-3- pentanone; 1 ,1 ,1 ,3,4,4,4-heptafluoro-3-(trifluoromethyl)-2-butanone; 1 ,1 ,1 ,2,2,5,5,5-octafluoro-4-(trifluoromethyl)-3-pentanone; 2-chloro-1 ,1 ,1 ,4,4,5,5,5-octafluoro-2-(trif luoromethyl)-3-pentanone; CF3C(0)CBrFCF2CF3;
Figure imgf000003_0001
CBrF2CF2C(0)CF2CF3; CF3CBrFC(0)CF2CF3; CF3CBrFC(0)CF2CF2CF3; CF3CF2C(0)CBrFCF2CF3; CF3CF2C(0)CF2CF2CBrF2; CF3C(0)CBr(CF3)CF2CF3; CF3C(0)CF(CF3)CBrFCF3; CF3C(0)CBrFCF2CF2CF2CF3; CF3C(0)CF2CF2CF2CF2CBrF2; CF3CBrFC(0)CF2CF2CF2CF3; CF3CF2C(0)CBrFCF2CF2CF3; CF3CF2C(0)CF2CF2CF2CBrF2; δ CF3CF2CBrFC(0)CF2CF2CF3; CBrF2CF2C(0)CF(CF3)CF2CF3; CF3CBrFC(0)CF(CF3)CF2CF3; CF3CF2C(0)CBr(CF3)CF2CF3; CF3CF2C(0)CF(CBrF2)CF2CF3;0 CBrF2CF2CF2C(0)CF(CF3)2; CF3CF2CBrFC(0)CF(CF3)2; CF3CF2CF2C(0)CBr(CF3)2; (CF3)2CBrC(0)CF(CF3)2; CF3CBrFCF2C(0)CF(CF3)2;5 CHF2CF2C(0)CBr(CF3)2; (CF3)2CHC(0)CBr(CF3)2; CHF2CF2C(0)CBrFCF3; (CF3)2CHC(0)CBrFCF3; (CF3)2CHC(0)CBrF2;0 CBrF2CF2C(0)CH(CF3)2. CBrF2C(0)CF(CF3)OCF3; CBrF2CF2C(0)CF(CF3)OCF3; CBrF2CF2CF2C(0)CF(CF3)OCF3; CBrF2C(0)CF(CF3)OC2F5.5 CBrF2CF2C(0)CF(CF3)OC2F5; CBrF2C(0)CF(CF3)OCF2C2F5; CBrF2CF2C(0)CF(CF3)OCF2C2F5; CBrF2C(0)CF(CF3)OCF(CF3)2; CBrF2CF2C(0)CF(CF3)OCF(CF3)2;0 CF3CBrFC(0)CF(CF3)OCF(CF3)2; CF3CBrFC(0)CF(CF3)OCF3; CF3CBrFC(0)CF(CF3)OC2F5; CF3CBrFC(0)CF(CF3)OCF3; (CF3)2CBrC(0)CF(CF3)OCF3;δ CF3CBrFC(0)CF(CF3)OC2F5; (CF3)2CBrC(0)CF(CF3)OC2F5; CF3CBrFC(0)CF(CF3)OCF2C2F5; CF3CBrFC(0)CF(CF3)OCF(CF3)2. CBrF2C(0)CF(OCF2CHF2)CF3; CBrF2C(0)CH(OCF2CHF2)CF3; CBrF2C(0)CF(OCH3)CF3; δ CBrF2C(0)CF(CF2OCH3)CF3; CCIF2CFBrC(0)CF2CF3; CBrF2CFCIC(0)CF2CF3; CClF2CFBrC(0)CF(CF3)2; CBrF2CFCIC(0)CF(CF3)2;0 CCIF2CFBrC(0)CF(CF3)(C2F5); CBrF2CFClC(0)CF(CF3)(C2F5); CCIF2C(0)CBr(CF3)2; CCIF2CF2C(0)CBr(CF3)2; CF3CCIFC(0)CBr(CF3)2;5 CCIF2C(0)CBrFCF3; CCIF2CF2(0)CCBrFCF3; CF3CCIFC(0)CBrFCF3; CBrF2C(0)CCI(CF3)2; CBrF2CF2C(0)CCI(CF3)2;0 CBrF2C(0)CCIFCF3; CBrF2CF2C(0)CCIFCF3; and combinations thereof. Disclosed herein also are the above listed compounds for use in refrigeration or air conditioning systems employing a centrifugal compressor, refrigeration or air conditioning systems employing a multi-δ stage centrifugal compressor, and/or employing a single slab/single pass heat exchanger, or refrigeration or air conditioning systems employing a 2-stage centrifugal compressor. Also disclosed herein are processes for producing refrigeration, heat, and transfer of heat from a heat source to a heat sink using the0 present inventive compositions.
DETAILED DESCRIPTION OF THE INVENTION The haloketone refrigerant compositions of the present invention comprise a single compound or a combination comprising moreδ than one haloketone compound. Compositions of the present invention have no ozone depletion potential and low global warming potential . For example, haloketones, alone or in mixtures will have global warming potentials lower than many HFC refrigerants currently in use. The haloketones of the present invention are compounds containing fluorine, carbon, at least one ketone group oxygen, and δ optionally hydrogen, chlorine or bromine. Haloketones may be represented by the formula R3COR4, wherein R3 and R4 are independently selected from straight or branched chain, saturated or unsaturated, aliphatic or alicyclic fluorinated carbon radicals that may optionally contain hydrogen, chlorine, or bromine. R3 and R4 may be joined to form a cyclic0 haloketone ring. The haloketones may contain from about 2 to 10 carbon atoms. Preferred haloketones contain 4 to 8 carbon atoms. The haloketones of the present invention may further contain heteroatoms, such as oxygen thus forming additional ketone groups, ether groups, aldehyde groups, or ester groups. Representative haloketones are listedδ in Table 1. The bromofiuoroketones of the present invention comprise at least one selected from the group consisting of: monobromoperfluoroketones, monohydromonobromoperfluoroketones, (perfluoroalkoxy)monobromoperfluoroketones,0 (fluoroalkoxy)monobromoperfluoroketones, and monochloromonobromoperfluoroketones. The following compounds are representative of the monobromoperfluoroketones, monohydromonobromoperfluoroketones, (perfluoroalkoxy)monobromoperfluoroketones,δ (fluoroalkoxy)monobromoperfluoroketones, and monochloromonobromoperfluoroketones of the present invention: CF3C(0)CBrFCF2CF3, CF3C(0)CF2CF2CBrF2. CBrF2C(0)CF(CF3)2. CF3C(0)CBr(CF3)2. CBrF2CF2C(0)CF2CF3, CF3CBrFC(0)CF2CF3, CF3CBrFC(0)CF2CF2CF3, CF3CF2C(0)CBrFCF2CF3,0 CF3CF2C(0)CF2CF2CBrF2, CF3C(0)CBr(CF3)CF2CF3, CF3C(0)CF(CF3)CBrFCF3. CF3C(0)CBrFCF2CF2CF2CF3, CF3C(0)CF2CF2CF2CF2CBrF2, CF3CBrFC(0)CF2CF2CF2CF3, CF3CF2C(0)CBrFCF2CF2CF3, CF3CF2C(0)CF2CF2CF2CBrF2, CF3CF2CBrFC(0)CF2CF2CF3, CBrF2CF2C(0)CF(CF3)CF2CF3,δ CF3CBrFC(0)CF(CF3)CF2CF3, CF3CF2C(0)CBr(CF3)CF2CF3, CF3CF2C(0)CF(CBrF2)CF2CF3. CBrF2CF2CF2C(0)CF(CF3)2. CF3CF2CBrFC(0)CF(CF3)2, CF3CF2CF2C(0)CBr(CF3)2, (CF3)2CBrC(0)CF(CF3)2. CF3CBrFCF2C(0)CF(CF3)2, CHF2CF2C(0)CBr(CF3)2, (CF3)2CHC(0)CBr(CF3)2, CHF2CF2C(0)CBrFCF3. (CF3)2CHC(0)CBrFCF3, (CF3)2CHC(0)CBrF2, CBrF2CF2C(0)CH(CF3)2, CBrF2C(0)CF(CF3)OCF3, CBrF2CF2C(0)CF(CF3)OCF3, CBrF2CF2CF2C(0)CF(CF3)OCF3l CBrF2C(0)CF(CF3)OC2F5, CBrF2CF2C(0)CF(CF3)OC2F5, CBrF2C(0)CF(CF3)OCF2C2F5, CBrF2CF2C(0)CF(CF3)OCF2C2F5, CBrF2C(0)CF(CF3)OCF(CF3)2, CBrF2CF2C(0)CF(CF3)OCF(CF3)2, CF3CBrFC(0)CF(CF3)OCF(CF3)2, CF3CBrFC(0)CF(CF3)OCF3, CF3CBrFC(0)CF(CF3)OC2F5, CF3CBrFC(0)CF(CF3)OCF3, (CF3)2CBrC(0)CF(CF3)OCF3, CF3CBrFC(0)CF(CF3)OC2F5) (CF3)2CBrC(0)CF(CF3)OC2F5, CF3CBrFC(0)CF(CF3)OCF2C2F5, CF3CBrFC(0)CF(CF3)OCF(CF3)2, CBrF2C(0)CF(OCF2CHF2)CF3, CBrF2C(0)CH(OCF2CHF2)CF3, CBrF2C(0)CF(OCH3)CF3, CBrF2C(0)CF(CF2OCH3)CF3, CCIF2CFBrC(0)CF2CF3. CBrF2CFCIC(0)CF2CF3, CCIF2CFBrC(0)CF(CF3)2, CBrF2CFCIC(0)CF(CF3)2, CCIF2CFBrC(0)CF(CF3)(C2F5) , CBrF2CFCIC(0)CF(CF3)(C2F5) , CCIF2C(0)CBr(CF3)2, CCIF2CF2C(0)CBr(CF3)2, CF3CCIFC(0)CBr(CF3)2) CCIF2C(0)CBrFCF3, CCIF2CF2(0)CCBrFCF3, CF3CCIFC(0)CBrFCF3, CBrF2C(0)CCI(CF3)2, CBrF2CF2C(0)CCI(CF3)2, CBrF2C(0)CCIFCF3 and CBrF2CF2C(0)CCIFCF3.
TABLE 1
Figure imgf000007_0001
Figure imgf000008_0001
1 ,1 ,1 ,2,2,4,δ,δ,δ-nonafluoro-4-(trifluoromethyl)-3-pentanone (PEIK) is commercially available from 3M™ (St. Paul, Minnesota). 1 ,1 ,1 ,3,4,4,4-heptafluoro-3-(trifluoromethyl)-2-butanone (PMIK); 1 ,1 ,1 ,2,4,δ,δ,δ-octafluoro-2,4-bis(trifluoromethyl)-3 pentanone; δ 1 ,1 ,1 ,2,4,4,δ,δ-octafluoro-2-(trifluoromethyl)-3-pentanone; 1 ,1 ,1 ,2,4,4,δ,δ,6,6,6-undecafluoro-2-(trifluoromethyl)-3-hexanone; 1 ,1 ,2,2,4,δ,δ,δ-octafluoro-1-(trifluoromethoxy)-4-(trifluoromethyl)-3- pentanone; and 1 ,1 ,1 ,3,4,4,4-heptafluoro-3-(trifluoromethyI)-2-butanone may be prepared as described in US 6,478,979 incorporated herein by 0 reference. 1 ,1 ,1 ,2,2,δ,δ,δ-octafluoro-4-(trifluoromethyl)-3-pentanone may be prepared from "HFP dimer" as described by England in Journal of Organic Chemistry, volume 49(no. 21), pages 4007 to 4008 (1984). 2- chloro-1 ,1 ,1 ,4,4,δ,δ,δ-octafluoro-2-(trifluoromethyl)-3-pentanone may be prepared as described by Saloutina, et al. in Izvestiya Adademii Nauk δ SSSR, Seriya Khimicheskaya, pages 1893 to 1896 (1982). The bromofluoroketones of the present invention described previously including monobromoperfluoroketones, monohydromonobromoperfluoroketones, (perfluoroalkoxy)monobromoperfluoroketones,0 (fluoroalkoxy)monobromoperfluoroketones, and monochloromonobromoperfluoroketones can be prepared as described in the following. Monobromoperfluoroketones CF3C(0)CF2CF2CBrF2, CF3CF2C(0)CF2CF2CBrF2 and CF3C(0)CF2CF2CF2CF2CBrF2 of theδ present invention may be prepared by bromination of the corresponding monohydroperfluoroketones by the technique of Kolenko and Plashkin in Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, pages 1648 to 1650 (1977), and by Zapevalov, et al. in Zhumal Organicheskoi Khimii, Vol. 26, pages 265 to 272 (1990). CF3C(0)CF2CF2CBrF2 may be0 prepared by bromination of monohydroperfluoroketone CF3C(0)CF2CF2CHF2, which may be prepared by isomerization of an epoxide as described by Zapelov et al. in Zhumal Vsesoyuznogo Khimicheskogo Obshchestva im. D. I. Mendeleeva, Vol. 18, pages δ91 to 693 (1973). CF3CF2C(0)CF2CF2CBrF2 and CF3C(0)CF2CF2CF2CF2CBrF2 may be prepared by bromination of monohydroperfluoroketones CF3CF2C(0)CF2CF2CHF2 and CF3C(0)CF2CF2CF2CF2CHF2, respectively, by the technique of Saloutina, et al. in Zhumal Organicheskoi Khimii, Vol. 29, pages 132δ to 1336 (1993). δ Preparation of monobromoperfluoroketones CF3C(0)CF2CF2CBrF2, CF3CF2C(0)CF2CF2CBrF2 and CF3C(0)CF2CF2CF2CF2CBrF2 of the present invention by conversion of the monohydroperfluoroketone terminal C-H bond to a terminal C-Br may be carried out using brominating agents such as elemental bromine, 0 phosphorous pentabromide, or a mixture of bromine and phosphorous tribromide. The preferred brominating agent is a mixture of bromine and phosphorous tribromide. Reaction of a monohydroperfluoroketone and a brominating agent may be carried out under substantially anhydrous conditions in the δ vapor phase or liquid phase in a container fabricated from materials of construction suitable for contact with bromine and hydrogen bromide at temperatures of about 300°C to 600°C. Examples of such materials of construction include metallic alloys containing a nickel such as, for example, Hastelloy™ C and Hastelloy™ B. The reaction takes place0 under the autogenous pressures of the reactants at the reaction temperature. The ratio of the brominating agent to the monohydroperfluoroketones is at least about 1 mole of brominating agent per mole of monohydroperfluoroketone and preferably about 1.3 moles ofδ brominating agent per mole of monohydroperfluoroketone. More than 1.7 moles of brominating agent per mole of monohydroperfluoroketone provides little benefit. Brominating the monohydroperfluoroketone may be conducted at temperatures of from about 300°C to about 600°C. Using the preferred0 brominating agent, the temperature is preferably conducted from about 300°C to 3δO°C. Contact times between the brominating agent and the monohydroperfluoroketone may be from about one hour to about twenty hours. At the end of the contact period the reaction mixture is cooledδ and then treated with a reagent to decompose the brominating agent such as sodium sulfite. The monobromoperfluoroketone may be isolated by collecting the organic phase followed by distillation. Monobromoperfluoroketones CF3CF2C(0)CBrFCF2CF3, CF3CF2CBrFC(0)CF(CF3)2) (CF3)2CBrC(0)CF(CF3)2, CF3CF2C(0)CBr(CF3)CF2CF3 and CF3CBrFC(0)CF(CF3)CF2CF3) as well as mixtures of monobromoperfluoroketones of the present invention δ CF3C(0)CBrFCF2CF3 and CF3CBrFC(0)CF2CF3, or CF3C(0)CBrFCF2CF2CF2CF3 and CF3CBrFC(0)CF2CF2CF2CF3, or CF3CF2C(0)CBrFCF2CF2CF3 and CF3CF2CBrFC(0)CF2CF2CF3, may be prepared by contacting perfluoroolefin epoxides, such as the epoxide of perfluoro-2-pentene, perfluoro-2-heptene, or perfluoro-3-heptene, with an0 alkali metal bromide as described by Saloutina et al. in Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, pages 1893 to 1896 (1982). The perfluoroolefin epoxides may be prepared by contacting perfluoroolefin with an alkali metal hypohalite as described by Kolenko, et al. in Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, pages 2609-2612 (1979). δ The contact of perfluoroolefin epoxides with alkali metal bromides may be carried out in a polar non-protic solvent such as glycol ethers such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether, N,N-dimethyl formamide, N,N-dimethyl acetamide, dimethyl0 sulfolane, dimethylsulfoxide, N-methylpyrrolidinone, and alkane nitriles such as acetonitrile, propionitrile, and butyronitrile. Preferred solvents for contacting perfluoroolefin epoxides with alkali metal bromides are glycol ethers such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and tetraethylene glycol dimethylδ ether, and alkane nitriles such as acetonitrile, propionitrile, and butyronitrile. Alkali metal bromides suitable for opening the perfluoroolefin epoxide ring and formation of a C-Br bond include lithium bromide, sodium bromide, potassium bromide, and cesium bromide; sodium and lithium0 bromide are preferred. The mole ratio of the alkali metal bromide to the perfluoroolefin epoxide is at least about 2:1 , preferably about 10:1. Reaction of alkali metal bromides and perfluoolefin epoxide may be conducted in the liquid phase under substantially anhydrousδ conditions at temperatures of from about 10°C to about 1 δ0°C, with contact times of from about O.δ hour to about thirty-six hours. Specific pressure conditions are not critical. At the end of the contact period the reaction mixture may be distilled to isolate the monobromoperfluoroketone. Monobromoperfluoroketones of the present invention CBrF2C(0)CF(CF3) . CBrF2CF2C(0)CF2CF3, CF3CBrFCF2C(0)CF(CF3)2. δ CF3CF2C(0)CF2CF2CF2CBrF2, CBrF2CF2CF2C(0)CF(CF3)2) and CBrF2CF2C(0)CF(CF3)CF2CF3 may be prepared by reacting a monobromoperfluoroacyl fluoride with a perfluoroolefin. CBrF2C(0)CF(CF3)2 may be prepared by reacting CBrF2C(0)F with CF3CF=CF2; CBrF2CF2C(0)CF2CF3 may be prepared by reacting 0 CBrF2CF2C(0)F with CF2=CF2; CF3CF2C(0)CF2CF2CF2CBrF2 may be prepared by reacting CBrF2CF2CF2CF2C(0)F with CF2=CF2; CBrF2CF2CF2C(0)CF(CF3)2 may be prepared by reacting CBrF2CF2CF2C(0)F with CF3CF=CF2; CBrF2CF2C(0)CF(CF3)CF2CF3 may be prepared by reacting CBrF2CF2C(0)F with CF3CF=CFCF3; and δ CF3CBrFCF2C(0)CF(CF3)2 may be prepared by reacting CF3CBrFCF2C(0)F with CF3CF=CF2. Monobromoperfluoroketones of the present invention CF3C(0)CBr(CF3)2, CF3CBrFC(0)CF2CF2CF3, CF3C(0)CBr(CF3)CF2CF3, CF3C(0)CF(CF3)CBrFCF3, CF3CF2CF2C(0)CBr(CF3)2, may be prepared0 by reacting a perfluoroacyl fluoride with a monobromoperfluoroolefin. CF3C(0)CBr(CF3)2 may be prepared by reacting CF3C(0)F with CF3CBr=CF2; CF3CBrFC(0)CF2CF2CF3 may be prepared by reacting CBrF=CF2 with CF3CF2CF2C(0)F; a mixture of CF3C(0)CBr(CF3)CF2CF3 and CF3C(0)CF(CF3)CBrFCF3 may be prepared by reactingδ CF3CBr=CFCF3 with CF3C(0)F; and CF3CF2CF2C(0)CBr(CF3)2 may be prepared by reacting CF3CF2CF2C(0)F with CF3CBr=CF2. (Perfluoroalkoxy)monobromoperfluoroketones of the present invention are of the formula R1C(0)CF(CF3)ORF, wherein R1 is a Ci to C3 monobromoperfluoroalkyl radical, and RF is a Ci to C3 perfluoroalkyl0 radical, may be obtained by reacting monobromoperfluoroacyl fluorides of the formula R1C(0)F with perfluorovinyl ethers of the formula CF2=CFORF. Representative (perfluoroalkoxy)monobromoperfluoroketones of the present invention include CBrF2C(0)CF(CF3)OCF3, CBrF2CF2C(0)CF(CF3)OCF3lδ CBrF2CF2CF2C(0)CF(CF3)OCF3, CBrF2C(0)CF(CF3)OC2F5, CBrF2CF2C(0)CF(CF3)OC2F5, CBrF2C(0)CF(CF3)OCF2C2F5> CBrF2CF2C(0)CF(CF3)OCF2C2F5, CBrF2C(0)CF(CF3)OCF(CF3)2, CBrF2CF2C(0)CF(CF3)OCF(CF3)2, CF3CBrFC(0)CF(CF3)OCF(CF3)2, CF3CBrFC(0)CF(CF3)OCF3, and CF3CBrFC(0)CF(CF3)OC2F5. CBrF2C(0)CF(CF3)OCF3 may be prepared by reacting δ CBrF2C(0)F with CF2=CFOCF3; CBrF2CF2C(0)CF(CF3)OCF3 may be prepared by reacting CBrF2CF2C(0)F with CF2=CFOCF3; CBrF2CF2CF2C(0)CF(CF3)OCF3 may be prepared by reacting CBrF2CF2CF2C(0)F with CF2=CFOCF3; CBrF2C(0)CF(CF3)OC2F5 may be prepared by reacting CBrF2C(0)F with CF2=CFOC2F5; 0 CBrF2CF2C(0)CF(CF3)OC2F5 may be prepared by reacting CBrF2CF2C(0)F with CF2=CFOC2F5; CBrF2C(0)CF(CF3)OCF2C2F5 may be prepared by reacting CBrF2C(0)F with
Figure imgf000012_0001
CBrF2CF2C(0)CF(CF3)OCF2C2F5 may be prepared by reacting CBrF2CF2C(0)F with CF2=CFOCF2C2F5; CBrF2C(0)CF(CF3)OCF(CF3)2 δ may be prepared by reacting CBrF2C(0)F with CF2=CFOCF(CF3)2; CBrF2CF2C(0)CF(CF3)OCF(CF3)2 may be prepared by reacting CBrF2CF2C(0)F with CF2=CFOCF(CF3)2; CF3CBrFC(0)CF(CF3)OCF3 may be prepared by reacting CF3CBrFC(0)F with CF2=CFOCF3; and CF3CBrFC(0)CF(CF3)OC2F5 may be prepared by reacting CF3CBrFC(0)F0 with CF2=CFOC2F5. (Perfluoroalkoxy)monobromoperfluoroketones of the formula R1C(0)CF(CF3)ORF may also be obtained by reacting perfluoroalkoxyperfluoroacyl fluorides of the formula RFOCF(CF3)C(0)F with a monobromoperfluoroolefin. Representativeδ (perfluoroalkoxy)monobromoperfluoroketones of the present invention include CF3CBrFC(0)CF(CF3)OCF3. (CF3)2CBrC(0)CF(CF3)OCF3, CF3CBrFC(0)CF(CF3)OC2F5, (CF3)2CBrC(0)CF(CF3)OC2F5, CF3CBrFC(0)CF(CF3)OCF2C2F5, and CF3CBrFC(0)CF(CF3)OCF(CF3)2. CF3CBrFC(0)CF(CF3)OCF3 may be prepared by reacting0 CF3OC(CF3)FC(0)F with CF2=CBrF; (CF3)2CBrC(0)CF(CF3)OCF3 may be prepared by reacting CF3OC(CF3)FC(0)F with CF3CBr=CF2; CF3CBrFC(0)CF(CF3)OC2F5 may be prepared by reacting C2F5OC(CF3)FC(0)F with CF2=CBrF; (CF3)2CBrC(0)CF(CF3)OC2F5 may be prepared by reacting C2F5OC(CF3)FC(0)F with CF3CBr=CF2;δ CF3CBrFC(0)CF(CF3)OCF2C2F5 may be prepared by reacting C2F5CF2OC(CF3)FC(0)F with CF2=CBrF; and CF3CBrFC(0)CF(CF3)OCF(CF3)2 may be prepared by reacting (CF3)2CFOC(CF3)FC(0)F with CF2=CBrF. (Fluoroalkoxy)monobromoperfluoroketones of the present invention are of the formula R1C(0)CX(CF3)0R2, wherein X is H or F, R1 is δ a Ci, C2, or C3 bromoperfluoroalkyl radical, and R2 is a Ci to C3 alkyl or fluoroalkyl radical, may be prepared by reacting monobromoperfluoroacyl fluorides of the formula R1C(0)F with hydrofluorovinyl ethers of the formula CF2=CXOR2. Representative (fluoroalkoxy)monobromoperfluoroketones include0 CBrF2C(0)CF(OCF2CHF2)CF3, CBrF2C(0)CH(OCF2CHF2)CF3, CBrF2C(0)CF(OCH3)CF3, and CBrF2C(0)CF(CF2OCH3)CF3. CBrF2C(0)CF(OCF2CHF2)CF3 may be prepared by reacting CBrF2C(0)F with CF2=CFOCF2CHF2; CBrF2C(0)CH(OCF2CHF2)CF3 may be prepared by reacting CBrF2C(0)F with CF2=CHOCF2CHF2; and δ CBrF2C(0)CF(OCH3)CF3 may be prepared by reacting CBrF2C(0)F with CF2=CFOCH3. Another (fluoroalkoxy)monobromoperfluoroketone of the present invention includes CBrF2C(0)CF(CF2θCH3)CF3, prepared by reacting CBrF2C(0)F with CF3CF=CFOCH3.0 The reaction of fluoroacyl fluorides with fluoroolefins is described by Fawcett, et al. in U. S. Patent No. 3,186,734 and Journal of the American Chemical Society, Vol. 84, pages 428δ to 4288 (1962). The teachings of these references may be applied to the aforementioned preparation of monobromoperfluoroketones by the reaction ofδ monobromoperfluoroacyl fluorides with perfluoroolefins as well as the aforementioned preparation of monobromoperfluoroketones by the reaction of perfluoroacyl fluorides with monobromoperfluoroolefins. These references may also be applied to the preparation of (perfluoroalkoxy)monobromoperfluoroketones by the reaction of0 monobromoperfluoroacyl fluorides with perfluorovinyl ethers, or by the reaction of perfluoroalkoxyperfluoroacyl fluorides with monobromoperfluoroolefins. These references may also be applied to the preparation of (fluoroalkoxy)monobromoperfluoroketones by the reaction of monobromoperfluoroacyl fluorides with hydrofluorovinyl ethers.δ Though not essential for preparing the ketones of the present invention, reaction of a fluoroacyl fluoride (such as a perfluoroacyl fluoride or monobromoperfluoroacyl fluoride) with a fluoroolefin (such as a perfluoroolefin, monobromoperfluoroolefin, perfluorovinyl ether or hydrofluorovinyl ether) may be performed in a polar non-protic solvent such as N.N-dimethyl formamide, N,N-dimethyl acetamide, dimethyl sulfolane, dimethylsulfoxide, N-methylpyrrolidinone, and glycol ethers such δ as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether. Preferred solvents for reacting fluoroacyl fluorides with fluoroolefin are glycol ethers. The reaction may be run under substantially anhydrous conditions. 0 The mole ratio of the fluoroolefin to fluoroacyl fluoride during the reaction may be at least about 1:1 to about 2:1, and preferably is about 1.1. The reaction of fluoroacyl fluoride with fluoroolefin is preferably conducted in the presence of a fluoride ion source such as an alkali metalδ fluoride, alkali metal hydrogen difluoride (i.e., a bifluoride), alkali-earth metal fluoride, tetraalkylammonium fluoride, tetraaikylammonium hydrogen fluoride, trialkylammonium fluoride, or non-oxidizing transition metal fluorides. Preferred fluoride ion sources are potassium fluoride, cesium fluoride, and potassium bifluoride. The fluoride ion source may be present0 at a level of δ mole percent to 20 mole percent, preferably about 10 mole percent, based on the quantity of fluoroolefin present. Temperatures of from about δ0°C to about 2δO°C, preferably from about 100°C to about 1δ0°C are effective to produce any of the fluorinated ketones of the present invention by reaction of a fluoroacylδ fluoride with a fluoroolefin. The reaction of fluoroacyl fluoride with fluoroolefin may take place in batch mode or in semi-batch mode with the fluoroacyl fluoride added gradually to the mixture of the fluoroolefin, solvent, and fluoride ion source. Contact times suitable for the reaction may be from about O.δ0 hour to about 24 hours. The reaction typically takes place under autogenous pressure provided by the reactants at the reaction temperature. Though not added intentionally to the reactions, hydrogen fluoride may be present in small amounts during the reactions of fluoroacylδ fluorides due to the presence of traces of water. Reaction of fluoroacyl fluorides with fluoroolefins may be conducted in a vessel formed of materials compatible with hydrogen fluoride at elevated temperatures and pressures. Examples of such materials include stainless steels, in particular of the austenitic type, the well-known high nickel alloys, such as TM TM Monel nickel-copper alloys, Hastelloy nickel-based alloys and, TM Inconel nickel-chromium alloys, and copper-clad steel, δ The haloketone products may be isolated from the reaction mixture as a lower liquid layer or by distillation. After removing traces of fluoride salts by washing with water, such products may be purified by distillation. The present invention further includes 0 monohydromonobromoperfluoroketones in which one of the C-F bonds in a perfluoroketone has been replaced by a C-Br bond, and in addition, another of the C-F bonds in said perfluoroketone has been replaced by a C-H bond. Monohydromonobromoperfluoroketones of the present invention comprise CHF2CF2C(0)CBrFCF3, (CF3)2CHC(0)CBrFCF3,5 CHF2CF2C(0)CBr(CF3)2. (CF3)2CHC(0)CBr(CF3)2, (CF3)2CHC(0)CBrF2 and CBrF2CF2C(0)CH(CF3)2. CHF2CF2C(0)CBrFCF3 may be prepared by reacting CHF2CF2C(0)F with CBrF=CF2; (CF3)2CHC(0)CBrFCF3 may be prepared by reacting (CF3)2CHC(0)F with CBrF=CF2; CHF2CF2C(0)CBr(CF3)2 may0 be prepared by reacting CHF2CF C(0)F with CF3CBr=CF2; (CF3)2CHC(0)CBr(CF3)2 may be prepared by reacting (CF3)2CHC(0)F with CF3CBr=CF2; and CBrF2CF2C(0)CH(CF3)2 may be prepared by reacting CBrF2CF2C(0)F with CF3CH=CF2. The monohydromonobromoperfluoroketone (CF3)2CHC(0)CBrF2 may be5 prepared by the reaction of the bromofluoroacyl fluoride CBrF2C(0)F with the monohydroperfluoroolefin CF3CH=CF2. The production of monohydromonobromoperfluoroketones by the reaction of monohydroperfluoroacyl fluorides with monobromoperfluoroolefins, as well as by the reaction of0 monobromoperfluoroacyl fluorides with monohydroperfluoroolefins, may use reaction conditions and procedure similar to those discussed hereinabove for the reaction of a fluoroacyl fluoride with a fluoroolefin. The present invention further comprises monochloromonobromoperfluoroketones in which one of the C-F bonds inδ a perfluoroketone has been replaced by a C-Br bond, and in addition, another one of the C-F bonds in said perfluoroketone has been replaced by a C-CI bond. Monochloromonobromoperfluoroketones of the present invention comprise compounds of the formula CXF2CFYC(0)CFRCF3, wherein X is CI and Y is Br, or wherein X is Br and Y is CI, and wherein R is F, a CF3 radical, or a C2F5 radical. These compounds may be prepared by contacting an acid fluoride of the formula CXF CFYC(0)F, prepared as δ disclosed by Darst, et al. in U. S. Patent No. δ,δ57,010, with a perfluoroolefin of the formula CFR=CFR. Representative monochloromonobromoperfluoroketones include CCIF2CFBrC(0)CF2CF3, prepared by reacting CCIF2CFBrC(0)F with CF2=CF2; CBrF2CCIFC(0)CF2CF3, prepared by reacting CBrF2CCIFC(0)F with0 CF2=CF2; CCIF2CFBrC(0)CF(CF3)2. prepared by reacting CCIF2CFBrC(0)F with CF2=CFCF3; and CBrF2CCIFC(0)CF(CF3)2, prepared by reacting CBrF2CCIFC(0)F with CF2=CFCF3. Monochloromonobromoperfluoroketones of the present invention further comprise CCIF2C(0)CBr(CF3)2, CCIF2CF2C(0)CBr(CF3)2.5 CF3CCIFC(0)CBr(CF3)2) CCIF2C(0)CBrFCF3. CCIF2CF2C(0)CBrFCF3l and CF3CCIFC(0)CBrFCF3 which may be prepared by reacting a monochloroperfluoroacyl fluoride with a monobromoperfluoroolefin. CCIF2C(0)CBr(CF3)2 may be prepared by reacting CCIF2C(0)F with CF3CBr=CF2; CCIF2CF2C(0)CBr(CF3)2 may be prepared by reacting0 CCIF2CF2C(0)F with CF3CBr=CF2; CF3CCIFC(0)CBr(CF3)2 may be prepared by reacting CF3CCIFC(0)F with CF3CBr=CF2; CCIF2C(0)CBrFCF3 may be prepared by reacting CCIF2C(0)F with CF2=CBrF; CCIF2CF2C(0)CBrFCF3 may be prepared by reacting CCIF2CF2(0)F with CF2=CBrF; CF3CCIFC(0)CBrFCF3 may be preparedδ by reacting CF3CCIFC(0)F with CF2=CBrF. Monochloromonobromoperfluoroketones of the present invention further include CBrF2C(0)CCI(CF3)2. CBrF2CF2C(0)CCI(CF3)2, CBrF2C(0)CCIFCF3, and CBrF2CF2C(0)CCIFCF3 which may be prepared by reacting a monobromoperfluoroacyl fluoride with a0 monochloroperfluoroolefin. CBrF2C(0)CCI(CF3)2 may be prepared by reacting CBrF2C(0)F with CF3CCI=CF2; CBrF2CF2C(0)CCI(CF3)2 may be prepared by reacting CBrF2CF2C(0)F with CF3CCI=CF2; CBrF2C(0)CCIFCF3 may be prepared by reacting CBrF2C(0)F with CF2=CCIF; and CBrF2CF2C(0)CCIFCF3 mayδ be prepared by reacting CBrF2CF2C(0)F with CF2=CCIF. The formation of monohydromonobromoperfluoroketones by the reaction of fluoroacyl fluorides of the formula CXF2CFYC(0)F with
1 δ perfluoroolefins, or by the reaction of monochloroperfluoroacyl fluorides with monobromoperfluoroolefins, or by the reaction of monobromoperfluoroacyl fluorides with monochloroperfluoroolefins, may use reaction conditions and procedure similar to those discussed δ hereinabove for the reaction of a fluoroacyl fluoride with a fluoroolefin. The compositions may be prepared by any convenient method to combine the desired amounts of the individual components. A preferred method is to weigh the desired component amounts and thereafter combine the components in an appropriate vessel. Agitation may be0 used, if desired. The refrigerant or heat transfer compositions of the present invention include: 1 ,1 ,1 ,2,2,4,δ,δ,δ-nonafluoro-4-(trifluoromethyl)-3-pentanone; 1 ,1 ,1 ,3,4,4,4-heptafluoro-3-(trifluoromethyl)-2-butanone; δ 1 ,1 ,1 ,2,4,δ,δ,δ-octafluoro-2,4-bis(trifluoromethyl)-3 pentanone; 1 ,1 ,1 ,2,4,4,δ,δ-octafluoro-2-(trifluoromethyl)-3-pentanone; 1 ,1 ,1 ,2,4,4, δ,δ,6,6,6-undecafluoro-2-(trifluoromethyl)-3-hexanone; 1 ,1 , 2,2,4, δ,δ,δ-octafluoro-1-(trifluoromethoxy)-4-(trifluoromethyl)-3- pentanone;0 1 ,1 ,1 ,2,2,δ,δ,δ-octafluoro-4-(trifluoromethyl)-3-pentanone; 2-chloro-1 ,1 ,1 ,4,4,δ,δ,δ-octafluoro-2-(trifluoromethyl)-3-pentanone; CF3C(0)CBrFCF2CF3;
Figure imgf000017_0001
δ CF3C(0)CBr(CF3)2;
Figure imgf000017_0002
CF3CBrFC(0)CF2CF3; CF3CBrFC(0)CF2CF2CF3; CF3CF2C(0)CBrFCF2CF3;0 CF3CF2C(0)CF2CF2CBrF2; CF3C(0)CBr(CF3)CF2CF3; CF3C(0)CF(CF3)CBrFCF3; CF3C(0)CBrFCF2CF2CF2CF3; CF3C(0)CF2CF2CF2CF2CBrF2;δ CF3CBrFC(0)CF2CF2CF2CF3; CF3CF2C(0)CBrFCF2CF2CF3; CF3CF2C(0)CF2CF2CF2CBrF2; CF3CF2CBrFC(0)CF2CF2CF3;
CBrF2CF2C(0)CF(CF3)CF2CF3;
CF3CBrFC(0)CF(CF3)CF2CF3;
CF3CF2C(0)CBr(CF3)CF2CF3; CF3CF2C(0)CF(CBrF2)CF2CF3;
CBrF2CF2CF2C(0)CF(CF3)2;
CF3CF2CBrFC(0)CF(CF3)2;
CF3CF2CF2C(0)CBr(CF3)2;
(CF3)2CBrC(0)CF(CF3)2; CF3CBrFCF2C(0)CF(CF3)2;
CHF2CF2C(0)CBr(CF3)2;
(CF3)2CHC(0)CBr(CF3)2;
CHF2CF2C(0)CBrFCF3;
(CF3)2CHC(0)CBrFCF3; (CF3)2CHC(0)CBrF2;
CBrF2CF2C(0)CH(CF3)2;
CBrF2C(0)CF(CF3)OCF3;
CBrF2CF2C(0)CF(CF3)OCF3;
CBrF2CF2CF2C(0)CF(CF3)OCF3; CBrF2C(0)CF(CF3)OC2F5;
CBrF2CF2C(0)CF(CF3)OC2F5;
CBrF2C(0)CF(CF3)OCF2C2F5;
CBrF2CF2C(0)CF(CF3)OCF2C2F5;
CBrF2C(0)CF(CF3)OCF(CF3)2; CBrF2CF2C(0)CF(CF3)OCF(CF3)2;
CF3CBrFC(0)CF(CF3)OCF(CF3)2;
CF3CBrFC(0)CF(CF3)OCF3;
CF3CBrFC(0)CF(CF3)OC2F5;
CF3CBrFC(0)CF(CF3)OCF3; (CF3)2CBrC(0)CF(CF3)OCF3;
CF3CBrFC(0)CF(CF3)OC2F5;
(CF3)2CBrC(0)CF(CF3)OC2F5;
CF3CBrFC(0)CF(CF3)OCF2C2F5;
CF3CBrFC(0)CF(CF3)OCF(CF3)2; CBrF2C(0)CF(OCF2CHF2)CF3;
CBrF2C(0)CH(OCF2CHF2)CF3;
CBrF2C(0)CF(OCH3)CF3; CBrF2C(0)CF(CF2θCH3)CF3; CCIF2CFBrC(0)CF2CF3; CBrF2CFCIC(0)CF2CF3; CCIF2CFBrC(0)CF(CF3)2; δ CBrF2CFCIC(0)CF(CF3)2; CCIF2CFBrC(0)CF(CF3)(C2F5); CBrF2CFCIC(0)CF(CF3)(C2F5); CCIF2C(0)CBr(CF3)2; CCIF2CF2C(0)CBr(CF3)2;0 CF3CCIFC(0)CBr(CF3)2; CCIF2C(0)CBrFCF3; CCIF2CF2(0)CCBrFCF3; CF3CCIFC(0)CBrFCF3;
Figure imgf000019_0001
5 CBrF2CF2C(0)CCI(CF3)2; CBrF2C(0)CCIFCF3; CBrF2CF2C(0)CCIFCF3; and combinations thereof. The compositions of the present invention may further comprise about 0.01 weight percent to about 5 weight percent of a thermal0 stabilizer such as nitromethane. The compositions of the present invention may further comprise an ultra-violet (UV) dye and optionally a solubilizing agent. The UV dye is a useful component for detecting leaks of the refrigerant composition by permitting one to observe the fluorescence of the dyeδ under an ultra-violet light at the point of a leak within a refrigeration or air- conditioning system. Solubilizing agents may be needed due to poor solubility of such UV dyes in some refrigerants. By "ultra-violet" dye is meant a UV fluorescent composition that absorbs light in the ultra-violet or "near" ultra-violet region of the0 electromagnetic spectrum. The fluorescence produced by the UV fluorescent dye under illumination by a UV light that emits radiation with wavelength anywhere from 10 nanometer to 760 nanometer may be detected. Therefore, if refrigerant containing such a UV fluorescent dye is leaking from a given point in a refrigeration or air conditioning apparatus,δ the fluorescence can be detected at the leak point. Such UV fluorescent dyes include but are not limited to naphthalimides, perylenes, coumarins, anthracenes, phenanthracenes, xanthenes, thioxanthenes, naphthoxanthenes, fluoresceins, and derivatives or mixtures thereof. Solubilizing agents of the present invention comprise at least one compound selected from the group consisting of hydrocarbons, hydrocarbon ethers, polyoxyalkylene glycol ethers, amides, nitriles, δ ketones, chlorocarbons, esters, lactones, aryl ethers, fluoroethers and 1 ,1 ,1-trifluoroalkanes. Hydrocarbon solubilizing agents of the present invention comprise hydrocarbons including straight chained, branched chain or cyclic alkanes or alkenes containing δ or fewer carbon atoms and only0 hydrogen with no other functional groups. Representative hydrocarbon solubilizing agents comprise propane, propylene, cyclopropane, n-butane, isobutane, and n-pentane. It should be noted that if the refrigerant is a hydrocarbon, then the solubilizing agent may not be the same hydrocarbon. δ Hydrocarbon ether solubilizing agents of the present invention comprise ethers containing only carbon, hydrogen and oxygen, such as dimethyl ether (DME). Polyoxyalkylene glycol ether solubilizing agents of the present invention are represented by the formula R1[(OR2)xOR3]y, wherein: x is an0 integer from 1-3; y is an integer from 1-4; R1 is selected from hydrogen and aliphatic hydrocarbon radicals having 1 to 6 carbon atoms and y bonding sites; R2 is selected from aliphatic hydrocarbylene radicals having from 2 to 4 carbon atoms; R3 is selected from hydrogen and aliphatic and alicyclic hydrocarbon radicals having from 1 to 6 carbon atoms; at leastδ one of R1 and R3 is said hydrocarbon radical; and wherein said polyoxyalkylene glycol ethers have a molecular weight of from about 100 to about 300 atomic mass units. In the present polyoxyalkylene glycol ether solubilizing agents represented by R1[(OR2)xOR3jy: x is preferably 1- 2; y is preferably 1 ; R1 and R3 are preferably independently selected from0 hydrogen and aliphatic hydrocarbon radicals having 1 to 4 carbon atoms; R2 is preferably selected from aliphatic hydrocarbylene radicals having from 2 or 3 carbon atoms, most preferably 3 carbon atoms; the polyoxyalkylene glycol ether molecular weight is preferably from about 100 to about 2δ0 atomic mass units, most preferably from about 12δ to aboutδ 2δ0 atomic mass units. The R1 and R3 hydrocarbon radicals having 1 to 6 carbon atoms may be linear, branched or cyclic. Representative R1 and R3 hydrocarbon radicals include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, terf-butyl, pentyl, isopentyl, neopentyl, tetf-pentyl, cyclopentyl, and cyclohexyl. Where free hydroxyl radicals on the present polyoxyalkylene glycol ether solubilizing agents may be incompatible with certain compression refrigeration apparatus materials of construction (e.g. δ Mylar®), R1 and R3 are preferably aliphatic hydrocarbon radicals having 1 to 4 carbon atoms, most preferably 1 carbon atom. The R2 aliphatic hydrocarbylene radicals having from 2 to 4 carbon atoms form repeating oxyalkylene radicals - (OR2)x - that include oxyethylene radicals, oxypropylene radicals, and oxybutylene radicals. The oxyalkylene radical0 comprising R2 in one polyoxyalkylene glycol ether solubilizing agent molecule may be the same, or one molecule may contain different R2 oxyalkylene groups. The present polyoxyalkylene glycol ether solubilizing agents preferably comprise at least one oxypropylene radical. Where R1 is an aliphatic or alicyclic hydrocarbon radical having 1 to 6 carbon atomsδ and y bonding sites, the radical may be linear, branched or cyclic. Representative R1 aliphatic hydrocarbon radicals having two bonding sites include, for example, an ethylene radical, a propylene radical, a butylene radical, a pentylene radical, a hexylene radical, a cyclopentylene radical and a cyclohexylene radical. Representative R1 aliphatic hydrocarbon0 radicals having three or four bonding sites include residues derived from polyalcohols, such as trimethylolpropane, glycerin, pentaerythritol, 1 ,2,3- trihydroxycyclohexane and 1 ,3,δ-trihydroxycyclohexane, by removing their hydroxyl radicals. Representative polyoxyalkylene glycol ether solubilizing agentsδ include but are not limited to: CH3OCH2CH(CH3)0(H or CH3) (propylene glycol methyl (or dimethyl) ether), CH30[CH2CH(CH3)0]2(H or CH3) (dipropylene glycol methyl (or dimethyl) ether), CH30[CH2CH(CH3)0]3(H or CH3) (tripropylene glycol methyl (or dimethyl) ether), C2H5OCH2CH(CH3)0(H or C2H5) (propylene glycol ethyl (or diethyl) ether),0 C2H50[CH2CH(CH3)0]2(H or C2H5) (dipropylene glycol ethyl (or diethyl) ether), C2H50[CH2CH(CH3)0]3(H or C2H5) (tripropylene glycol ethyl (or diethyl) ether), C3H7OCH2CH(CH3)0(H or C3H7) (propylene glycol n-propyl (or di-n-propyl) ether), C3H70[CH2CH(CH3)0]2(H or C3H7) (dipropylene glycol n-propyl (or di-n-propyl) ether) , C3H70[CH2CH(CH3)0]3(H or C3H7)δ (tripropylene glycol n-propyl (or di-n-propyl) ether), C-4HgOCH2CH(CH3)OH (propylene glycol n-butyl ether), C4H90[CH2CH(CH3)0]2(H or C4H9) (dipropylene glycol n-butyl (or di-n-butyl) ether), C4H90[CH2CH(CH3)0]3(H or C4H9) (tripropylene glycol n-butyl (or di-n-butyl) ether), (CH3)3COCH2CH(CH3)OH (propylene glycol t-butyl ether), (CH3)3CO[CH2CH(CH3)0]2(H or (CH3)3) (dipropylene glycol t-butyl (or di-t- butyl) ether), (CH3)3CO[CH2CH(CH3)0]3(H or (CH3)3) (tripropylene glycol t- δ butyl (or di-t-butyl) ether), C5HnOCH2CH(CH3)OH (propylene glycol n- pentyl ether), C4H9OCH2CH(C2H5)OH (butylene glycol n-butyl ether), C4H90[CH2CH(C2H5)0]2H (dibutylene glycol n-butyl ether), trimethylolpropane tri-n-butyl ether (C2H5C(CH20(CH2)3CH3)3) and trimethylolpropane di-n-butyl ether (C2H5C(CH2OC(CH2)3CH3)2CH2θH).0 Amide solubilizing agents of the present invention comprise those represented by the formulae R1CONR2R3 and cyclo-[R4CON(R5)-], wherein R1, R2, R3 and R5 are independently selected from aliphatic and alicyclic hydrocarbon radicals having from 1 to 12 carbon atoms; R4 is selected from aliphatic hydrocarbylene radicals having from 3 to 12 carbon δ atoms; and wherein said amides have a molecular weight of from about 100 to about 300 atomic mass units. The molecular weight of said amides is preferably from about 160 to about 2δ0 atomic mass units. R1, R2, R3 and R5 may optionally include substituted hydrocarbon radicals, that is, radicals containing non-hydrocarbon substituents selected from halogens0 (e.g., fluorine, chlorine) and alkoxides (e.g. methoxy). R1, R2, R3 and R5 may optionally include heteroatom-substituted hydrocarbon radicals, that is, radicals, which contain the atoms nitrogen (aza-), oxygen (oxa-) or sulfur (thia-) in a radical chain otherwise composed of carbon atoms. In general, no more than three non-hydrocarbon substituents andδ heteroatoms, and preferably no more than one, will be present for each 10 carbon atoms in R1"3, and the presence of any such non-hydrocarbon substituents and heteroatoms must be considered in applying the aforementioned molecular weight limitations. Preferred amide solubilizing agents consist of carbon, hydrogen, nitrogen and oxygen. Representative0 R1, R2, R3 and R5 aliphatic and alicyclic hydrocarbon radicals include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tetf-butyl, pentyl, isopentyl, neopentyl, terf-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and their configu rational isomers. A preferred embodiment of amide solubilizing agents are those wherein R4δ in the aforementioned formula cyclo-[R4CON(R5)-] may be represented by the hydrocarbylene radical (CR6R7)n, in other words, the formula: cyclo- [(CR6R7)nCON(R5)-] wherein: the previously-stated values for molecular weight apply; n is an integer from 3 to δ; R5 is a saturated hydrocarbon radical containing 1 to 12 carbon atoms; R6 and R7 are independently selected (for each n) by the rules previously offered defining R1"3. In the lactams represented by the formula: cyclo-[(CR6R7)nCON(R5)-], all R6 and δ R7 are preferably hydrogen, or contain a single saturated hydrocarbon radical among the n methylene units, and R5 is a saturated hydrocarbon radical containing 3 to 12 carbon atoms. For example, 1 -(saturated hydrocarbon radical)-δ-methylpyrrolidin-2-ones. Representative amide solubilizing agents include but are not0 limited to: 1-octylpyrrolidin-2-one, 1-decylpyrrolidin-2-one, 1-octyl-δ- methylpyrrolidin-2-one, 1 -butylcaprolactam, 1 -cyclohexylpyrrolidin-2-one, 1 -butyl-δ-methylpiperid-2-one, 1 -pentyl-5-methylpiperid-2-one, 1 - hexylcaprolactam, 1-hexyl-5-methylpyrrolidin-2-one, δ-methyl-1- pentylpiperid-2-one, 1 ,3-dimethylpiperid-2-one, 1-methylcaprolactam, 1-5 butyl-pyrrolidin-2-one, 1 ,5-dimethylpiperid-2-one, 1-decyl-δ- methylpyrrolidin-2-one, 1-dodecylpyrrolid-2-one, N,N-dibutylformamide and N,N-diisopropylacetamide. Ketone solubilizing agents of the present invention comprise ketones represented by the formula R1COR2, wherein R1 and R2 are0 independently selected from aliphatic, alicyclic and aryl hydrocarbon radicals having from 1 to 12 carbon atoms, and wherein said ketones have a molecular weight of from about 70 to about 300 atomic mass units. R1 and R2 in said ketones are preferably independently selected from aliphatic and alicyclic hydrocarbon radicals having 1 to 9 carbon atoms.δ The molecular weight of said ketones is preferably from about 100 to 200 atomic mass units. R and R2 may together form a hydrocarbylene radical connected and forming a five, six, or seven-membered ring cyclic ketone, for example, cyclopentanone, cyclohexanone, and cycloheptanone. R1 and R2 may optionally include substituted hydrocarbon radicals, that is,0 radicals containing non-hydrocarbon substituents selected from halogens (e.g., fluorine, chlorine) and alkoxides (e.g. methoxy). R1 and R2 may optionally include heteroatom-substituted hydrocarbon radicals, that is, radicals, which contain the atoms nitrogen (aza-), oxygen (keto-, oxa-) or sulfur (thia-) in a radical chain otherwise composed of carbon atoms. Inδ general, no more than three non-hydrocarbon substituents and heteroatoms, and preferably no more than one, will be present for each 10 carbon atoms in R1 and R2, and the presence of any such non- hydrocarbon substituents and heteroatoms must be considered in applying the aforementioned molecular weight limitations. Representative R and R2 aliphatic, alicyclic and aryl hydrocarbon radicals in the general formula R1COR2 include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, δ te/f-butyl, pentyl, isopentyl, neopentyl, terf-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and their configu rational isomers, as well as phenyl, benzyl, cumenyl, mesityl, tolyl, xylyl and phenethyl. Representative ketone solubilizing agents include but are not0 limited to: 2-butanone, 2-pentanone, acetophenone, butyrophenone, hexanophenone, cyclohexanone, cycloheptanone, 2-heptanone, 3- heptanone, δ-methyl-2-hexanone, 2-octanone, 3-octanone, diisobutyl ketone, 4-ethylcyclohexanone, 2-nonanone, δ-nonanone, 2-decanone, 4- decanone, 2-decalone, 2-tridecanone, dihexyl ketone and dicyclohexylδ ketone. Nitrile solubilizing agents of the present invention comprise nitriles represented by the formula R1CN, wherein R1 is selected from aliphatic, alicyclic or aryl hydrocarbon radicals having from 5 to 12 carbon atoms, and wherein said nitriles have a molecular weight of from about 900 to about 200 atomic mass units. R in said nitrile solubilizing agents is preferably selected from aliphatic and alicyclic hydrocarbon radicals having 8 to 10 carbon atoms. The molecular weight of said nitrile solubilizing agents is preferably from about 120 to about 140 atomic mass units. R1 may optionally include substituted hydrocarbon radicals, that is,5 radicals containing non-hydrocarbon substituents selected from halogens (e.g., fluorine, chlorine) and alkoxides (e.g. methoxy). R1 may optionally include heteroatom-substituted hydrocarbon radicals, that is, radicals, which contain the atoms nitrogen (aza-), oxygen (keto-, oxa-) or sulfur (thia-) in a radical chain otherwise composed of carbon atoms. In general,0 no more than three non-hydrocarbon substituents and heteroatoms, and preferably no more than one, will be present for each 10 carbon atoms in R1, and the presence of any such non-hydrocarbon substituents and heteroatoms must be considered in applying the aforementioned molecular weight limitations. Representative R1 aliphatic, alicyclic and arylδ hydrocarbon radicals in the general formula R1CN include pentyl, isopentyl, neopentyl, tetf-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and their configu rational isomers, as well as phenyl, benzyl, cumenyl, mesityl, tolyl, xylyl and phenethyl. Representative nitrile solubilizing agents include but are not limited to: 1- cyanopentane, 2,2-dimethyl-4-cyanopentane, 1-cyanohexane, 1- cyanoheptane, 1 -cyanooctane, 2-cyanooctane, 1-cyanononane, 1- cyanodecane, 2-cyanodecane, 1-cyanoundecane and 1-cyanododecane. Chlorocarbon solubilizing agents of the present invention comprise chlorocarbons represented by the formula RCIX, wherein; x is selected from the integers 1 or 2; R is selected from aliphatic and alicyclic hydrocarbon radicals having 1 to 12 carbon atoms; and wherein said chlorocarbons have a molecular weight of from about 100 to about 200 atomic mass units. The molecular weight of said chlorocarbon solubilizing agents is preferably from about 120 to 150 atomic mass units. Representative R aliphatic and alicyclic hydrocarbon radicals in the general formula RCIX include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, terf-butyl, pentyl, isopentyl, neopentyl, ferf-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and their configurational isomers. Representative chlorocarbon solubilizing agents include but are not limited to: 3-(chloromethyl)pentane, 3-chloro-3-methylpentane, 1- chlorohexane, 1 ,6-dichlorohexane, 1-chloroheptane, 1-chlorooctane, 1- chlorononane, 1-chlorodecane, and 1 ,1 ,1-trichlorodecane. Ester solubilizing agents of the present invention comprise esters represented by the general formula R1Cθ2R2, wherein R1 and R2 are independently selected from linear and cyclic, saturated and unsaturated, alkyl and aryl radicals. Preferred esters consist essentially of the elements C, H and O, have a molecular weight of from about 80 to about 560 atomic mass units. Representative esters include but are not limited to: (CH3)2CHCH2θOC(CH2)2-4θCOCH2CH(CH3)2 (diisobutyl dibasic ester), ethyl hexanoate, ethyl heptanoate, n-butyl propionate, n-propyl propionate, ethyl benzoate, di-n-propyl phthalate, benzoic acid ethoxyethyl ester, dipropyl carbonate, "Exxate 700" (a commercial C alkyl acetate), "Exxate 800" (a commercial C3 alkyl acetate), dibutyl phthalate, and tert-butyl acetate. Lactone solubilizing agents of the present invention comprise lactones represented by structures [A], [B], and [C]:
Figure imgf000026_0001
[A] [B] [C]
These lactones contain the functional group -CO2- in a ring of six (A), or preferably five atoms (B), wherein for structures [A] and [B], Ri through R8 are independently selected from hydrogen or linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl radicals. Each Ri though R8 may be connected forming a ring with another Ri through Rs. The lactone may have an exocyclic alkylidene group as in structure [C], wherein Ri through R6 are independently selected from hydrogen or linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl radicals. Each R-i though Re may be connected forming a ring with another Ri through Rδ. The lactone solubilizing agents have a molecular weight range of from about 80 to about 300 atomic mass units, preferred from about 80 to about 200 atomic mass units.
Representative lactone solubilizing agents include but are not limited to the compounds listed in Table 2. TABLE 2
Figure imgf000026_0002
Figure imgf000027_0001
Figure imgf000028_0001
Lactone solubilizing agents generally have a kinematic viscosity of less than about 7 centistokes at 40°C. For instance, gamma- undecalactone has kinematic viscosity of δ.4 centistokes and cis-(3-hexyl- δ-methyl)dihydrofuran-2-one has viscosity of 4.6 centistokes both at 40°C. Lactone solubilizing agents may be available commercially or prepared by methods as described in U. S. patent application 10/910,496 (inventors being P. J. Fagan and C. J. Brandenburg), filed August 3, 2004, incorporated herein by reference. Aryl ether solubilizing agents of the present invention further comprise aryl ethers represented by the formula R1OR2, wherein: R1 is selected from aryl hydrocarbon radicals having from 6 to 12 carbon atoms; R2 is selected from aliphatic hydrocarbon radicals having from 1 to 4 carbon atoms; and wherein said aryl ethers have a molecular weight of from about 100 to about 150 atomic mass units. Representative R1 aryl radicals in the general formula R1OR2 include phenyl, biphenyl, cumenyl, mesityl, tolyl, xylyl, naphthyl and pyridyl. Representative R2 aliphatic hydrocarbon radicals in the general formula R1OR2 include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and terf-butyl. Representative aromatic ether solubilizing agents include but are not limited to: methyl phenyl ether (anisole), 1 ,3-dimethyoxybenzene, ethyl phenyl ether and butyl phenyl ether. Fluoroether solubilizing agents of the present invention comprise those represented by the general formula R1OCF2CF2H, wherein R1 is selected from aliphatic and alicyclic hydrocarbon radicals having from about δ to about 1δ carbon atoms, preferably primary, linear, saturated, alkyl radicals. Representative fluoroether solubilizing agents include but are not limited to: C8Hι7OCF2CF2H and C6H13OCF2CF2H. It should be noted that if the refrigerant is a fluoroether, then the solubilizing agent may not be the same fluoroether. 1 ,1 ,1-Trifluoroalkane solubilizing agents of the present invention comprise 1 ,1 ,1-trifluoroalkanes represented by the general formula CF3R1, wherein R1 is selected from aliphatic and alicyclic hydrocarbon radicals having from about 5 to about 1δ carbon atoms, preferably primary, linear, saturated, alkyl radicals. Representative 1 ,1 ,1- trifluoroalkane solubilizing agents include but are not limited to: 1 ,1 ,1- trifluorohexane and 1 ,1 ,1-trifluorododecane. Solubilizing agents of the present invention may be present as a single compound, or may be present as a mixture of more than one solubilizing agent. Mixtures of solubilizing agents may contain two solubilizing agents from the same class of compounds, say two lactones, or two solubilizing agents from two different classes, such as a lactone and a polyoxyalkylene glycol ether. In the present compositions comprising refrigerant and UV fluorescent dye, from about 0.001 weight percent to about 1.0 weight percent of the composition is UV dye, preferably from about 0.005 weight percent to about 0.5 weight percent, and most preferably from 0.01 weight percent to about 0.25 weight percent. Solubility of these UV fluorescent dyes in refrigerants may be poor,. Therefore, methods for introducing these dyes into the refrigeration or air conditioning apparatus have been awkward, costly and time consuming. US patent no. RE 36,951 describes a method, which utilizes a dye powder, solid pellet or slurry of dye that may be inserted into a component of the refrigeration or air conditioning apparatus. As refrigerant and lubricant are circulated through the apparatus, the dye is dissolved or dispersed and carried throughout the apparatus. Numerous other methods for introducing dye into a refrigeration or air conditioning apparatus are described in the literature. Ideally, the UV fluorescent dye could be dissolved in the refrigerant itself thereby not requiring any specialized method for introduction to the refrigeration or air conditioning apparatus. The present invention relates to compositions including UV fluorescent dye, which may be introduced into the system dissolved in the refrigerant. The inventive compositions will allow the storage and transport of dye-containing refrigerant even at low temperatures while maintaining the dye in solution. In the present compositions comprising refrigerant, UV fluorescent dye and solubilizing agent, from about 1 to about 50 weight percent, preferably from about 2 to about 25 weight percent, and most preferably from about 5 to about 1 δ weight percent of the combined composition is solubilizing agent in the refrigerant. In the compositions of the present invention the UV fluorescent dye is present in a concentration from about 0.001 weight percent to about 1.0 weight percent in the refrigerant, preferably from 0.006 weight percent to about O.δ weight percent, and most preferably from 0.01 weight percent to about 0.2δ weight percent. Optionally, commonly used refrigeration system additives may optionally be added, as desired, to compositions of the present invention in order to enhance performance and system stability. These additives are known within the field of refrigeration, and include, but are not limited to, anti wear agents, extreme pressure lubricants, corrosion and oxidation inhibitors, metal surface deactivators, free radical scavengers, and foam control agents,. In general, these additives are present in the inventive compositions in small amounts relative to the overall composition. Typically concentrations of from less than about 0.1 weight percent to as much as about 3 weight percent of each additive are used. These additives are selected on the basis of the individual system requirements. These additives include members of the triaryl phosphate family of EP δ (extreme pressure) lubricity additives, such as butylated triphenyl phosphates (BTPP), or other alkylated triaryl phosphate esters, e.g. Syn- 0-Ad 8478 from Akzo Chemicals, tricrecyl phosphates and related compounds. Additionally, the metal dialkyl dithiophosphates (e.g. zinc dialkyl dithiophosphate (or ZDDP), Lubrizol 1376 and other members of0 this family of chemicals may be used in compositions of the present invention. Other antiwear additives include natural product oils and asymmetrical polyhydroxyl lubrication additives, such as Synergol TMS (International Lubricants). Similarly, stabilizers such as anti oxidants, free radical scavengers, and water scavengers may be employed.δ Compounds in this category can include, but are not limited to, butylated hydroxy toluene (BHT) and epoxides. Solubilizing agents such as ketones may have an objectionable odor, which can be masked by addition of an odor masking agent or fragrance. Typical examples of odor masking agents or fragrances may0 include Evergreen, Fresh Lemon, Cherry, Cinnamon, Peppermint, Floral or Orange Peel or sold by Intercontinental Fragrance, as well as d- limonene and pinene. Such odor masking agents may be used at concentrations of from about 0.001% to as much as about 1δ% by weight based on the combined weight of odor masking agent and solubilizingδ agent. The present invention further relates to a method of using the refrigerant or heat transfer fluid compositions further comprising ultraviolet fluorescent dye, and optionally, solubilizing agent, in refrigeration or air conditioning apparatus. The method comprises introducing the refrigerant0 or heat transfer fluid composition into the refrigeration or air conditioning apparatus. This may be done by dissolving the UV fluorescent dye in the refrigerant or heat transfer fluid composition in the presence of a solubilizing agent and introducing the combination into the apparatus. Alternatively, this may be done by combining solubilizing agent and andδ UV fluorescent dye and introducing said combination into refrigeration or air conditioning apparatus containing refrigerant and/or heat transfer fluid. The resulting composition is may be used in the refrigeration or air conditioning apparatus. The present invention further relates to a method of using the refrigerant or heat transfer fluid compositions comprising ultraviolet δ fluorescent dye to detect leaks. The presence of the dye in the compostions allows for detection of leaking refrigerant in the refrigeration or air conditioning apparatus. Leak detection helps to address, resolve or prevent inefficient operation of the apparatus or system or equipment failure. Leak detection also helps one contain chemicals used in the 0 operation of the apparatus. The method comprises providing the composition comprising refrigerant, ultra-violet fluorescent dye as described herein, and optionally, a solubilizing agent as described herein, to refrigeration and air conditioning apparatus and employing a sutiable means for detecting the δ UV fluorescent dye-containing refrigerant. Suitable means for detecting the dye include, but are not limited to, ultra-violet lamp, often referred to as a "black light" or "blue light". Such ultra-violet lamps are commercially available from numerous sources specifically designed for this purpose. Once the ultra-violet fluorescent dye containing composition has been0 introduced to the refrigeration or air conditioning apparatus and has been allowed to circulate throughout the system, a leak can be found by shining said ultra-violet lamp on the apparatus and observing the fluorescence of the dye in the vicinity of any leak point. The present invention further relates to a method of using theδ compositions of the present invention for producing refrigeration or heat, wherein the method comprises producing refrigeration by evaporating said composition in the vicinity of a body to be cooled and thereafter condensing said composition; or producing heat by condensing the said composition in the vicinity of the body to be heated and thereafter0 evaporating said composition. Mechanical refrigeration is primarily an application of thermodynamics wherein a cooling medium, such as a refrigerant, goes through a cycle so that it can be recovered for reuse. Commonly used cycles include vapor-compression, absorption, steam-jet or steam-ejector,5 and air. Vapor-compression refrigeration systems include an evaporator, a compressor, a condenser, and an expansion device. A vapor-compression cycle re-uses refrigerant in multiple steps producing a cooling effect in one step and a heating effect in a different step. The cycle can be described simply as follows. Liquid refrigerant enters an evaporator through an expansion device, and the liquid refrigerant boils in δ the evaporator at a low temperature to form a gas and produce cooling. The low-pressure gas enters a compressor where the gas is compressed to raise its pressure and temperature. The higher-pressure (compressed) gaseous refrigerant then enters the condenser in which the refrigerant condenses and discharges its heat to the environment. The refrigerant0 returns to the expansion device through which the liquid expands from the higher-pressure level in the condenser to the low-pressure level in the evaporator, thus repeating the cycle. There are various types of compressors that may be used in refrigeration applications. Compressors can be generally classified asδ reciprocating, rotary, jet, centrifugal, scroll, screw or axial-flow, depending on the mechanical means to compress the fluid, or as positive- displacement (e.g., reciprocating, scroll or screw) or dynamic (e.g., centrifugal or jet), depending on how the mechanical elements act on the fluid to be compressed.0 Either positive displacement or dynamic compressors may be used in the present inventive process. A centrifugal type compressor is the preferred equipment for the present refrigerant compositions. A centrifugal compressor uses rotating elements to accelerate the refrigerant radially, and typically includes an impeller and diffuserδ housed in a casing. Centrifugal compressors usually take fluid in at an impeller eye, or central inlet of a circulating impeller, and accelerate it radially outward. Some static pressure rise occurs in the impeller, but most of the pressure rise occurs in the diffuser section of the casing, where velocity is converted to static pressure. Each impeller-diffuser set is0 a stage of the compressor. Centrifugal compressors are built with from 1 to 12 or more stages, depending on the final pressure desired and the volume of refrigerant to be handled. The pressure ratio, or compression ratio, of a compressor is the ratio of absolute discharge pressure to the absolute inlet pressure.6 Pressure delivered by a centrifugal compressor is practically constant over a relatively wide range of capacities. Positive displacement compressors draw vapor into a chamber, and the chamber decreases in volume to compress the vapor. After being compressed, the vapor is forced from the chamber by further decreasing the volume of the chamber to zero or nearly zero. A positive displacement compressor can build up a pressure, which is limited only by the volumetric efficiency and the strength of the parts to withstand the pressure. Unlike a positive displacement compressor, a centrifugal compressor depends entirely on the centrifugal force of the high-speed impeller to compress the vapor passing through the impeller. There is no positive displacement, but rather what is called dynamic-compression. The pressure a centrifugal compressor can develop depends on the tip speed of the impeller. Tip speed is the speed of the impeller measured at its tip and is related to the diameter of the impeller and its revolutions per minute. The capacity of the centrifugal compressor is determined by the size of the passages through the impeller. This makes the size of the compressor more dependent on the pressure required than the capacity. Because of its high-speed operation, a centrifugal compressor is fundamentally a high volume, low-pressure machine. A centrifugal compressor works best with a low-pressure refrigerant, such as trichlorofluoromethane (CFC-11) or 1 ,2,2-trichlorotrifluoroethane (CFC- 113). Large centrifugal compressors typically operate at 3000 to 7000 revolutions per minute (rpm). Small turbine centrifugal compressors are designed for high speeds, from about 40,000 to about 70,000 (rpm), and have small impeller sizes, typically less than 0.15 meters. A multi-stage impeller may be used in a centrifugal compressor to improve compressor efficiency thus requiring less power in use. For a two-stage system, in operation, the discharge of the first stage impeller goes to the suction intake of a second impeller. Both impellers may operate by use of a single shaft (or axle). Each stage can build up a compression ratio of about 4 to 1 ; that is, the absolute discharge pressure can be four times the absolute suction pressure. An example of a two- stage centrifugal compressor system, in this case for automotive applications, is described in US 5,065,990, incorporated herein by reference. The compositions of the present invention suitable for use in a refrigeration or air conditioning systems employing a centrifugal compressor comprise at least one of: 1 ,1 ,1 ,2,2,4, δ,δ,δ-nonafluoro-4-(trifluoromethyl)-3-pentanone; δ 1 ,1 ,1 ,3,4,4,4-heptafluoro-3-(trifluoromethyl)-2-butanone; 1 ,1 ,1 ,2,4,δ,δ,δ-octafluoro-2,4-bis(trifluoromethyl)-3 pentanone; 1 ,1 ,1 ,2,4,4,δ,δ-octafluoro-2-(trifluoromethyl)-3-pentanone; 1 ,1 ,1 ,2,4,4, δ,δ,6,6,6-undecafluoro-2-(trifluoromethyl)-3-hexanone; 1 ,1 ,2,2,4,δ,δ,δ-octafluoro-1-(trifluoromethoxy)-4-(trifluoromethyl)-3-0 pentanone; 1 ,1 ,1 ,2,2,δ,δ,δ-octafluoro-4-(trifluoromethyl)-3-pentanone; 2-chloro-1 ,1 ,1 ,4,4,δ,5,5-octafluoro-2-(trifluoromethyl)-3-pentanone; CF3C(0)CBrFCF2CF3; CF3C(0)CF2CF2CBrF2;δ CBrF2C(0)CF(CF3)2; CF3C(0)CBr(CF3)2; CBrF2CF2C(0)CF2CF3; CF3CBrFC(0)CF2CF3; CF3CBrFC(0)CF2CF2CF3;0 CF3CF2C(0)CBrFCF2CF3; CF3CF2C(0)CF2CF2CBrF2; CF3C(0)CBr(CF3)CF2CF3; CF3C(0)CF(CF3)CBrFCF3; CF3C(0)CBrFCF2CF2CF2CF3;δ CF3C(0)CF2CF2CF2CF2CBrF2; CF3CBrFC(0)CF2CF2CF2CF3; CF3CF2C(0)CBrFCF2CF2CF3; CF3CF2C(0)CF2CF2CF2CBrF2; CF3CF2CBrFC(0)CF2CF2CF3;0 CBrF2CF2C(0)CF(CF3)CF2CF3; CF3CBrFC(0)CF(CF3)CF2CF3; CF3CF2C(0)CBr(CF3)CF2CF3; CF3CF2C(0)CF(CBrF2)CF2CF3; CBrF2CF2CF2C(0)CF(CF3)2;δ CF3CF2CBrFC(0)CF(CF3)2; CF3CF2CF2C(0)CBr(CF3)2; (CF3)2CBrC(0)CF(CF3)2; CF3CBrFCF2C(0)CF(CF3)2;
CHF2CF2C(0)CBr(CF3)2;
(CF3)2CHC(0)CBr(CF3)2;
CHF2CF2C(0)CBrFCF3; (CF3)2CHC(0)CBrFCF3;
(CF3)2CHC(0)CBrF2;
CBrF2CF2C(0)CH(CF3)2;
CBrF2C(0)CF(CF3)OCF3;
CBrF2CF2C(0)CF(CF3)OCF3; CBrF2CF2CF2C(0)CF(CF3)OCF3;
CBrF2C(0)CF(CF3)OC2F5;
CBrF2CF2C(0)CF(CF3)OC2F5;
CBrF2C(0)CF(CF3)OCF2C2F5;
CBrF2CF2C(0)CF(CF3)OCF2C2F5; CBrF2C(0)CF(CF3)OCF(CF3)2;
CBrF2CF2C(0)CF(CF3)OCF(CF3)2;
CF3CBrFC(0)CF(CF3)OCF(CF3)2;
CF3CBrFC(0)CF(CF3)OCF3;
CF3CBrFC(0)CF(CF3)OC2F5; CF3CBrFC(0)CF(CF3)OCF3;
(CF3)2CBrC(0)CF(CF3)OCF3;
CF3CBrFC(0)CF(CF3)OC2F5;
(CF3)2CBrC(0)CF(CF3)OC2F5;
CF3CBrFC(0)CF(CF3)OCF2C2F5; CF3CBrFC(0)CF(CF3)OCF(CF3)2;
CBrF2C(0)CF(OCF2CHF2)CF3;
CBrF2C(0)CH(OCF2CHF2)CF3;
CBrF2C(0)CF(OCH3)CF3;
CBrF2C(0)CF(CF2OCH3)CF3; CCIF2CFBrC(0)CF2CF3;
CBrF2CFCIC(0)CF2CF3;
CCIF2CFBrC(0)CF(CF3)2;
CBrF2CFCIC(0)CF(CF3)2;
CCIF2CFBrC(0)CF(CF3)(C2F5); CBrF2CFCIC(0)CF(CF3)(C2F5);
CCIF2C(0)CBr(CF3)2;
CCIF2CF2C(0)CBr(CF3)2;
3δ CF3CCIFC(0)CBr(CF3)2; CCIF2C(0)CBrFCF3; CCIF2CF2(0)CCBrFCF3; CF3CCIFC(0)CBrFCF3; δ CBrF2C(0)CCI(CF3)2; CBrF2CF2C(0)CCI(CF3)2; CBrF2C(0)CCIFCF3; CBrF2CF2C(0)CCIFCF3; or combinations thereof. 0 These above-listed compositions are also suitable for use in two- stage centrifugal compressor systems. The compositions of the present invention may be used in stationary air-conditioning, heat pumps or mobile air-conditioning and refrigeration systems. Stationary air conditioning and heat pump6 applications include window, ductless, ducted, packaged terminal, chillers and commercial, including packaged rooftop. Refrigeration applications include domestic or home refrigerators and freezers, ice machines, self- contained coolers and freezers, walk-in coolers and freezers and transport refrigeration systems.0 The compositions of the present invention may additionally be used in air-conditioning, heating and refrigeration systems that employ fin and tube heat exchangers, microchannel heat exchangers and vertical or horizontal single pass tube or plate type heat exchangers. Conventional microchannel heat exchangers may not be ideal6 for the low pressure refrigerant compositions of the present invention. The low operating pressure and density result in high flow velocities and high frictional losses in all components. In these cases, the evaporator design may be modified. Rather than several microchannel slabs connected in series (with respect to the refrigerant path) a single slab/single pass heat0 exchanger arrangement may be used. Therefore, a preferred heat exchanger for the low pressure refrigerants of the present invention is a single slab/single pass heat exchanger. The following compositions of the present invention are suitable for use in refrigeration or air conditioning systems employing a singleδ slab/single pass heat exchanger: 1 ,1,1 ,2,2,4,δ,δ,δ-nonafluoro-4-(trifluoromethyl)-3-pentanone; 1 ,1 ,1 ,3,4,4,4-heptafluoro-3-(trifluoromethyl)-2-butanone 1 ,1 ,1 ,2,4,5,5,5-octafluoro-2,4-bis(trifluoromethyl)-3 pentanone; 1 ,1 ,1 ,2,4,4,5, δ-octafluoro-2-(trifluoromethyl)-3-pentanone; 1 ,1 ,1 ,2,4 ,4,5,6,6,6, 6-undecafIuoro-2-(trifluoromethyl)-3-hexanone; 1 ,1 ,2,2,4,5,5,5-octafluoro-1-(trifluoromethoxy)-4-(trifluoromethyl)-3- δ pentanone; 1 ,1 ,1 ,2,2,δ,δ,δ-octafluoro-4-(trifluoromethyl)-3-pentanone; 2-chloro-1 ,1 ,1 ,4,4,5,δ,δ-octafluoro-2-(trifluoromethyl)-3-pentanone; CF3C(0)CBrFCF2CF3; CF3C(0)CF2CF2CBrF2;0 CBrF2C(0)CF(CF3)2; CF3C(0)CBr(CF3)2; CBrF2CF2C(0)CF2CF3; CF3CBrFC(0)CF2CF3; CF3CBrFC(0)CF2CF2CF3;δ CF3CF2C(0)CBrFCF2CF3; CF3CF2C(0)CF2CF2CBrF2; CF3C(0)CBr(CF3)CF2CF3; CF3C(0)CF(CF3)CBrFCF3; CF3C(0)CBrFCF2CF2CF2CF3;0 CF3C(0)CF2CF2CF2CF2CBrF2; CF3CBrFC(0)CF2CF2CF2CF3; CF3CF2C(0)CBrFCF2CF2CF3; CF3CF2C(0)CF2CF2CF2CBrF2; CF3CF2CBrFC(0)CF2CF2CF3;δ CBrF2CF2C(0)CF(CF3)CF2CF3; CF3CBrFC(0)CF(CF3)CF2CF3; CF3CF2C(0)CBr(CF3)CF2CF3; CF3CF2C(0)CF(CBrF2)CF2CF3; CBrF2CF2CF2C(0)CF(CF3)2;0 CF3CF2CBrFC(0)CF(CF3)2; CF3CF2CF2C(0)CBr(CF3)2; (CF3)2CBrC(0)CF(CF3)2; CF3CBrFCF2C(0)CF(CF3)2; CHF2CF2C(0)CBr(CF3)2;δ (CF3)2CHC(0)CBr(CF3)2; CHF2CF2C(0)CBrFCF3; (CF3)2CHC(0)CBrFCF3; (CF3)2CHC(0)CBrF2; CBrF2CF2C(0)CH(CF3)2; CBrF2C(0)CF(CF3)OCF3; CBrF2CF2C(0)CF(CF3)OCF3; δ CBrF2CF2CF2C(0)CF(CF3)OCF3; CBrF2C(0)CF(CF3)OC2F5; CBrF2CF2C(0)CF(CF3)OC2F5; CBrF2C(0)CF(CF3)OCF2C2F5; CBrF2CF2C(0)CF(CF3)OCF2C2F5;0 CBrF2C(0)CF(CF3)OCF(CF3)2; CBrF2CF2C(0)CF(CF3)OCF(CF3)2; CF3CBrFC(0)CF(CF3)OCF(CF3)2; CF3CBrFC(0)CF(CF3)OCF3; CF3CBrFC(0)CF(CF3)OC2F5;6 CF3CBrFC(0)CF(CF3)OCF3; (CF3)2CBrC(0)CF(CF3)OCF3; CF3CBrFC(0)CF(CF3)OC2F5; (CF3)2CBrC(0)CF(CF3)OC2F5; CF3CBrFC(0)CF(CF3)OCF2C2F5;0 CF3CBrFC(0)CF(CF3)OCF(CF3)2; CBrF2C(0)CF(OCF2CHF2)CF3; CBrF2C(0)CH(OCF2CHF2)CF3; CBrF2C(0)CF(OCH3)CF3; CBrF2C(0)CF(CF2OCH3)CF3;6 CCIF2CFBrC(0)CF2CF3; CBrF2CFCIC(0)CF2CF3; CCIF2CFBrC(0)CF(CF3)2; CBrF2CFCIC(0)CF(CF3)2; CCIF2CFBrC(0)CF(CF3)(C2F5);0 CBrF2CFCIC(0)CF(CF3)(C2F5); CCIF2C(0)CBr(CF3)2; CClF2CF2C(0)CBr(CF3)2; CF3CCIFC(0)CBr(CF3)2; CCIF2C(0)CBrFCF3;δ CCIF2CF2(0)CCBrFCF3; CF3CCIFC(0)CBrFCF3; CBrF2C(0)CCI(CF3)2; CBrF2CF2C(0)CCI(CF3)2; CBrF2C(0)CCIFCF3; CBrF2CF2C(0)CClFCF3; or combinations thereof.
δ The compositions of the present invention are particularly useful in small turbine centrifugal compressors, which can be used in auto and window air conditioning or heat pumps as well as other applications. These high efficiency miniature centrifugal compressors may be driven by an electric motor and can therefore be operated independently of the0 engine speed. A constant compressor speed allows the system to provide a relatively constant cooling capacity at all engine speeds. This provides an opportunity for efficiency improvements especially at higher engine speeds as compared to a conventional R-134a automobile air-conditioning system. When the cycling operation of conventional systems at high δ driving speeds is taken into account, the advantage of these low pressure systems becomes even greater. Some of the low pressure refrigerant fluids of the present invention may be suitable as drop-in replacements for CFC-113 in existing centrifugal equipment.0 The present invention relates to a process for producing refrigeration comprising evaporating the compositions of the present invention in the vicinity of a body to be cooled, and thereafter condensing said compositions. The present invention further relates to a process for producing6 heat comprising condensing the compositions of the present invention in the vicinity of a body to be heated, and thereafter evaporating said compositions. The present invention further relates to a process for transfer of heat from a heat source to a heat sink via a heat transfer fluid, wherein the0 compositions of the present invention serve as heat transfer fluids. Said process for heat transfer comprises transferring the compositions of the present invention from a heat source to a heat sink. Heat transfer fluids are utilized to transfer, move or remove heat from one space, location, object or body to a different space, location,δ object or body by radiation, conduction, or convection. A heat transfer fluid may function as a secondary coolant by providing means of transfer for cooling (or heating) from a remote refrigeration (or heating) system. In some systems, the heat transfer fluid may remain in a constant state throughout the transfer process (i.e., not evaporate or condense). Alternatively, evaporative cooling processes may utilize heat transfer fluids as well, δ A heat source may be defined as any space, location, object or body from which it is desirable to transfer, move or remove heat. Examples of heat sources may be spaces (open or enclosed) requiring refrigeration or cooling, such as refrigerator or freezer cases in a supermarket, building spaces requiring air conditioning, or the passenger0 compartment of an automobile requiring air conditioning. A heat sink may be defined as any space, location, object or body capable of absorbing heat. A vapor compression refrigeration system is one example of such a heat sink. 5 EXAMPLES
EXAMPLE 1 Tip Speed to Develop Pressure Tip speed can be estimated by making some fundamental0 relationships for refrigeration equipment that use centrifugal compressors. The torque an impeller ideally imparts to a gas is defined as
T = m*(v2*r2-vι *p| ) Equation 1 where5 T = torque, N*m m = mass rate of flow, kg/s V2 = tangential velocity of refrigerant leaving impeller (tip speed), m/s r2 = radius of exit impeller, m0 v-j = tangential velocity of refrigerant entering impeller, m/s r<ι = radius of inlet of impeller, m
Assuming the refrigerant enters the impeller in an essentially radial direction, the tangential component of the velocity v1 = 0, thereforeδ T = m*V2*r2 Equation 2 The power required at the shaft is the product of the torque and the rotative speed P = T*w Equation 3 where P = power, W w = rotative speed, rez/s therefore, P = T*w = m*V2*r2*w Equation 4 At low refrigerant flow rates, the tip speed of the impeller and the tangential velocity of the refrigerant are nearly identical; therefore r2*w = V2 Equation 5 and P = m*V2*V2 Equation 6
Another expression for ideal power is the product of the mass rate of flow and the isentropic work of compression, P = m*Hj*(1000J/kJ) Equation 7 where Hj = Difference in enthalpy of the refrigerant from a saturated vapor at the evaporating conditions to saturated condensing conditions, kJ/kg. Combining the two expressions Equation 6 and 7 produces, V2*V2 = 1000*Hj Equation 8
Although Equation 8 is based on some fundamental assumptions, it provides a good estimate of the tip speed of the impeller and provides an important way to compare tip speeds of refrigerants. Table 3 below shows theoretical tip speeds that are calculated for 1 ,2,2-trichlorotrifluoroethane (CFC-113) and compositions of the present invention. The conditions assumed for this comparison are:
Evaporator temperature 40.0°F (4.4°C) Condenser temperature 110.0°F (43.3°C) Liquid subcool temperature 10.0°F (δ.δ°C) Return gas temperature 7δ.0°F (23.8°C) Compressor efficiency is 70%
These are typical conditions under which small turbine centrifugal compressors perform. TABLE 3
Figure imgf000043_0001
The data shows that compounds of the present invention have tip speeds within about +/- 5 percent of CFC-113 and would be effective replacements for CFC-113 with minimal compressor design changes.
EXAMPLE 2 Performance Data
Table 4 shows the performance of various refrigerants compared to CFC-113. The data are based on the following conditions. Evaporator temperature 40.0°F (4.4°C) Condenser temperature 110.0°F (43.3°C) Subcool temperature 10.0°F (5.5°C) Return gas temperature 7δ.0°F (23.8°C) Compressor efficiency is 70%
TABLE 4
Figure imgf000043_0002
Figure imgf000044_0001
Data show the compositions of the present invention have evaporator and condenser pressures similar to CFC-113. Some compositions also have higher capacity or energy efficiency (COP) than CFC-113.

Claims

CLAIM(S) What is claimed is : 1. A haloketone refrigerant or heat transfer fluid composition said composition selected from the group consisting of: δ 1 ,1 ,1 ,2,2,4,δ,δ,δ-nonafluoro-4-(trifluoromethyl)-3-pentanone; 1 ,1 ,1 ,2,4,5,δ,δ-octafluoro-2,4-bis(trifluoromethyl)-3 pentanone; 1 ,1 ,1 ,2,4,4,δ,5-octafluoro-2-(trifluoromethyl)-3-pentanone; 1 ,1 ,1 ,2,4,4, δ,5,6,6,6-undecafluoro-2-(trifluoromethyl)-3-hexanone; 1 ,1 ,2,2,4,5,δ,5-octafluoro-1 -(trifluoromethoxy)-4-(trifluoromethyl)-3-0 pentanone; 1 ,1 ,1 ,3,4,4,4-heptafluoro-3-(trifluoromethyl)-2-butanone; 1 ,1 ,1 ,2,2,δ,5,δ-octafluoro-4-(trifluoromethyl)-3-pentanone; 2-chloro-1 ,1 ,1 ,4,4,5,5,5-octafluoro-2-(trifluoromethyl)-3-pentanone; CF3C(0)CBrFCF2CF3;
Figure imgf000045_0001
CBrF2C(0)CF(CF3)2; CF3C(0)CBr(CF3)2; CBrF2CF2C(0)CF2CF3; CF3CBrFC(0)CF2CF3;0 CF3CBrFC(0)CF2CF2CF3; CF3CF2C(0)CBrFCF2CF3; CF3CF2C(0)CF2CF2CBrF2; CF3C(0)CBr(CF3)CF2CF3; CF3C(0)CF(CF3)CBrFCF3;6 CF3C(0)CBrFCF2CF2CF2CF3; CF3C(0)CF2CF2CF2CF2CBrF2; CF3CBrFC(0)CF2CF2CF2CF3; CF3CF2C(0)CBrFCF2CF2CF3; CF3CF2C(0)CF2CF2CF2CBrF2;0 CF3CF2CBrFC(0)CF2CF2CF3; CBrF2CF2C(0)CF(CF3)CF2CF3; CF3CBrFC(0)CF(CF3)CF2CF3; CF3CF2C(0)CBr(CF3)CF2CF3; CF3CF2C(0)CF(CBrF2)CF2CF3;5 CBrF2CF2CF2C(0)CF(CF3)2; CF3CF2CBrFC(0)CF(CF3)2; CF3CF2CF2C(0)CBr(CF3)2; (CF3)2CBrC(0)CF(CF3)2;
CF3CBrFCF2C(0)CF(CF3)2;
CHF2CF2C(0)CBr(CF3)2;
(CF3)2CHC(0)CBr(CF3)2; CHF2CF2C(0)CBrFCF3;
(CF3)2CHC(0)CBrFCF3;
(CF3)2CHC(0)CBrF2;
CBrF2CF2C(0)CH(CF3)2;
CBrF2C(0)CF(CF3)OCF3; CBrF2CF2C(0)CF(CF3)OCF3;
CBrF2CF2CF2C(0)CF(CF3)OCF3;
CBrF2C(0)CF(CF3)OC2F5;
CBrF2CF2C(0)CF(CF3)OC2F5;
CBrF2C(0)CF(CF3)OCF2C2F5; CBrF2CF2C(0)CF(CF3)OCF2C2F5;
CBrF2C(0)CF(CF3)OCF(CF3)2;
CBrF2CF2C(0)CF(CF3)OCF(CF3)2;
CF3CBrFC(0)CF(CF3)OCF(CF3)2;
CF3CBrFC(0)CF(CF3)OCF3; CF3CBrFC(0)CF(CF3)OC2F5;
CF3CBrFC(0)CF(CF3)OCF3;
(CF3)2CBrC(0)CF(CF3)OCF3;
CF3CBrFC(0)CF(CF3)OC2F5;
(CF3)2CBrC(0)CF(CF3)OC2F5; CF3CBrFC(0)CF(CF3)OCF2C2F5;
CF3CBrFC(0)CF(CF3)OCF(CF3)2;
CBrF2C(0)CF(OCF2CHF2)CF3;
CBrF2C(0)CH(OCF2CHF2)CF3;
CBrF2C(0)CF(OCH3)CF3; CBrF2C(0)CF(CF2OCH3)CF3;
CCIF2CFBrC(0)CF2CF3;
CBrF2CFCIC(0)CF2CF3;
CCIF2CFBrC(0)CF(CF3)2;
CBrF2CFCIC(0)CF(CF3)2; CCIF2CFBrC(0)CF(CF3)(C2F5);
CBrF2CFCIC(0)CF(CF3)(C2F5);
CCIF2C(0)CBr(CF3)2; CCIF2CF2C(0)CBr(CF3)2; CF3CCIFC(0)CBr(CF3)2; CCIF2C(0)CBrFCF3; CCIF2CF2(0)CCBrFCF3; δ CF3CCIFC(0)CBrFCF3; CBrF2C(0)CCI(CF3)2; CBrF2CF2C(0)CCI(CF3)2; CBrF2C(0)CCIFCF3; CBrF2CF2C(0)CClFCF3; and combinations thereof.0 2. A refrigerant or heat transfer fluid composition suitable for use in refrigeration or air conditioning apparatus employing a centrifugal compressor, said composition selected from the group consisting of:6 1 ,1 ,1 ,2,2,4,5,6, δ-nonafluoro-4-(trifluoromethyl)-3-pentanone; 1 ,1 ,1 ,2,4,5,δ,5-octafluoro-2,4-bis(trifluoromethyl)-3 pentanone; 1 ,1 ,1 ,2,4,4,δ,5-octafluoro-2-(trifluoromethyl)-3-pentanone; 1 ,1 ,1 ,2,4,4, δ,δ, 6,6, 6-undecafluoro-2-(trifluoromethyl)-3-hexanone; 1 ,1 ,2,2,4,5,δ,δ-octafluoro-1 -(trifluoromethoxy)-4-(trifluoromethyl)-3-0 pentanone; 1 ,1 ,1 ,3,4,4,4-heptafluoro-3-(trifluoromethyl)-2-butanone; 1 ,1 ,1 ,2,
2,6,5, δ-octafluoro-4-(trifluoromethyl)-3-pentanone; 2-chloro-1 ,1 ,1 ,4,4,5,δ,δ-octafluoro-2-(trifluoromethyl)-3-pentanone; CF3C(0)CBrFCF2CF3;
Figure imgf000047_0001
CBrF2C(0)CF(CF3)2; CF3C(0)CBr(CF3)2;
Figure imgf000047_0002
CF3CBrFC(0)CF2CF3;0 CF3CBrFC(0)CF2CF2CF3; CF3CF2C(0)CBrFCF2CF3; CF3CF2C(0)CF2CF2CBrF2; CF3C(0)CBr(CF3)CF2CF3; CF3C(0)CF(CF3)CBrFCF3;6 CF3C(0)CBrFCF2CF2CF2CF3; CF3C(0)CF2CF2CF2CF2CBrF2; CF3CBrFC(0)CF2CF2CF2CF3; CF3CF2C(0)CBrFCF2CF2CF3; CF3CF2C(0)CF2CF2CF2CBrF2; CF3CF2CBrFC(0)CF2CF2CF3; CBrF2CF2C(0)CF(CF3)CF2CF3; δ CF3CBrFC(0)CF(CF3)CF2CF3; CF3CF2C(0)CBr(CF3)CF2CF3; CF3CF2C(0)CF(CBrF2)CF2CF3; CBrF2CF2CF2C(0)CF(CF3)2; CF3CF2CBrFC(0)CF(CF3)2;0 CF3CF2CF2C(0)CBr(CF3)2; (CF3)2CBrC(0)CF(CF3)2; CF3CBrFCF2C(0)CF(CF3)2; CHF2CF2C(0)CBr(CF3)2; (CF3)2CHC(0)CBr(CF3)2;5 CHF2CF2C(0)CBrFCF3; (CF3)2CHC(0)CBrFCF3; (CF3)2CHC(0)CBrF2; CBrF2CF2C(0)CH(CF3)2; CBrF2C(0)CF(CF3)OCF3;0 CBrF2CF2C(0)CF(CF3)OCF3; CBrF2CF2CF2C(0)CF(CF3)OCF3; CBrF2C(0)CF(CF3)OC2F5; CBrF2CF2C(0)CF(CF3)OC2F5; CBrF2C(0)CF(CF3)OCF2C2F5;5 CBrF2CF2C(0)CF(CF3)OCF2C2F5; CBrF2C(0)CF(CF3)OCF(CF3)2; CBrF2CF2C(0)CF(CF3)OCF(CF3)2; CF3CBrFC(0)CF(CF3)OCF(CF3)2; CF3CBrFC(0)CF(CF3)OCF3;0 CF3CBrFC(0)CF(CF3)OC2F5; CF3CBrFC(0)CF(CF3)OCF3; (CF3)2CBrC(0)CF(CF3)OCF3; CF3CBrFC(0)CF(CF3)OC2F5; (CF3)2CBrC(0)CF(CF3)OC2F5;δ CF3CBrFC(0)CF(CF3)OCF2C2F5; CF3CBrFC(0)CF(CF3)OCF(CF3)2; CBrF2C(0)CF(OCF2CHF2)CF3; CBrF2C(0)CH(OCF2CHF2)CF3; CBrF2C(0)CF(OCH3)CF3; CBrF2C(0)CF(CF2OCH3)CF3; CCIF2CFBrC(0)CF2CF3; CBrF2CFCIC(0)CF2CF3; CCIF2CFBrC(0)CF(CF3)2; CBrF2CFClC(0)CF(CF3)2; CCIF2CFBrC(0)CF(CF3)(C2F5); CBrF2CFClC(0)CF(CF3)(C2F5); CCIF2C(0)CBr(CF3)2; CCIF2CF2C(0)CBr(CF3)2; CF3CCIFC(0)CBr(CF3)2; CCIF2C(0)CBrFCF3; CCIF2CF2(0)CCBrFCF3; CF3CCIFC(0)CBrFCF3; CBrF2C(0)CCI(CF3)2; CBrF2CF2C(0)CCI(CF3)2; CBrF2C(0)CCIFCF3; CBrF2CF2C(0)CCIFCF3; and combinations thereof.
3. A refrigerant or heat transfer fluid composition suitable for use in refrigeration or air conditioning apparatus employing a multistage or centrifugal compressor or a single slab/single pass heat exchanger, said composition selected from the group consisting of: 1 ,1 ,1 ,2,2,4, 5,5, 5-nonafluoro-4-(trifluoromethyl)-3-pentanone; 1 ,1 ,1 ,2,4,5,5,δ-octafluoro-2,4-bis(trifluoromethyl)-3 pentanone; 1 ,1 ,1 ,2,4,4,δ,5-octafluoro-2-(trifluoromethyl)-3-pentanone; 1 ,1 ,1 ,2,4,4,5,6,6,6, 6-undecafluoro-2-(trifluoromethyl)-3-hexanone; 1 ,1 , 2,2,4, δ.δ.δ-octafluoro-l-^rifluoromethoxyH-^rifluoromethy -S- pentanone; 1 ,1 ,1 ,3,4,4,4-heptafluoro-3-(trifluoromethyl)-2-butanone; 1 ,1 ,1 ,2,2,δ,5,δ-octafluoro-4-(trifluoromethyl)-3-pentanone; 2-chloro-1 ,1 ,1 ,4,4,δ,5,δ-octafluoro-2-(trifluoromethyl)-3-pentanone; CF3C(0)CBrFCF2CF3; CF3C(0)CF2CF2CBrF2; CBrF2C(0)CF(CF3)2; CF3C(0)CBr(CF3)2;
Figure imgf000050_0001
CF3CBrFC(0)CF2CF3;
CF3CBrFC(0)CF2CF2CF3;
CF3CF2C(0)CBrFCF2CF3; CF3CF2C(0)CF2CF2CBrF2;
CF3C(0)CBr(CF3)CF2CF3;
CF3C(0)CF(CF3)CBrFCF3;
CF3C(0)CBrFCF2CF2CF2CF3;
CF3C(0)CF2CF2CF2CF2CBrF2; CF3CBrFC(0)CF2CF2CF2CF3;
CF3CF2C(0)CBrFCF2CF2CF3;
CF3CF2C(0)CF2CF2CF2CBrF2;
CF3CF2CBrFC(0)CF2CF2CF3;
CBrF2CF2C(0)CF(CF3)CF2CF3; CF3CBrFC(0)CF(CF3)CF2CF3;
CF3CF2C(0)CBr(CF3)CF2CF3;
CF3CF2C(0)CF(CBrF2)CF2CF3;
CBrF2CF2CF2C(0)CF(CF3)2;
CF3CF2CBrFC(0)CF(CF3)2; CF3CF2CF2C(0)CBr(CF3)2;
(CF3)2CBrC(0)CF(CF3)2;
CF3CBrFCF2C(0)CF(CF3)2;
CHF2CF2C(0)CBr(CF3)2;
(CF3)2CHC(0)CBr(CF3)2; CHF2CF2C(0)CBrFCF3;
(CF3)2CHC(0)CBrFCF3;
(CF3)2CHC(0)CBrF2;
CBrF2CF2C(0)CH(CF3)2;
CBrF2C(0)CF(CF3)OCF3; CBrF2CF2C(0)CF(CF3)OCF3;
CBrF2CF2CF2C(0)CF(CF3)OCF3;
CBrF2C(0)CF(CF3)OC2F5;
CBrF2CF2C(0)CF(CF3)OC2F5;
CBrF2C(0)CF(CF3)OCF2C2F5; CBrF2CF2C(0)CF(CF3)OCF2C2F5;
CBrF2C(0)CF(CF3)OCF(CF3)2;
CBrF2CF2C(0)CF(CF3)OCF(CF3)2; CF3CBrFC(0)CF(CF3)OCF(CF3)2; CF3CBrFC(0)CF(CF3)OCF3; CF3CBrFC(0)CF(CF3)OC2F5; CF3CBrFC(0)CF(CF3)OCF3; 5 (CF3)2CBrC(0)CF(CF3)OCF3; CF3CBrFC(0)CF(CF3)OC2F5; (CF3)2CBrC(0)CF(CF3)0C2F5; CF3CBrFC(0)CF(CF3)0CF2C2F5; CF3CBrFC(0)CF(CF3)0CF(CF3)2;0 CBrF2C(0)CF(OCF2CHF2)CF3; CBrF2C(0)CH(OCF2CHF2)CF3; CBrF2C(0)CF(OCH3)CF3; CBrF2C(0)CF(CF2OCH3)CF3; CCIF2CFBrC(0)C'F2CF3;6 CBrF2CFCIC(0)CF2CF3; CCIF2CFBrC(0)CF(CF3)2; CBrF2CFCIC(0)CF(CF3)2; CCIF2CFBrC(0)CF(CF3)(C2F5); CBrF2CFCIC(0)CF(CF3)(C2F5);0 CCIF2C(0)CBr(CF3)2; CCIF2CF2C(0)CBr(CF3)2; CF3CCIFC(0)CBr(CF3)2; CCIF2C(0)CBrFCF3; CCIF2CF2(0)CCBrFCF3;δ CF3CCIFC(0)CBrFCF3; CBrF2C(0)CCI(CF3)2; CBrF2CF2C(0)CCI(CF3)2; CBrF2C(0)CCIFCF3; CBrF2CF2C(0)CCIFCF3; and combinations thereof.0 4. The composition of claim 3, wherein said composition is suitable for use in refrigeration or air conditioning apparatus employing a two-stage centrifugal compressor. 5 5. A haloketone refrigerant or heat transfer fluid composition represented by the formula R3COR4, wherein R3 and R4are independently selected from straight or branched chain, saturated or unsaturated,
60 aliphatic or alicyclic fluorinated carbon radicals that may optionally contain hydrogen, chlorine, or bromine, and wherein R3 and R4 may optionally be joined to form a cyclic haloketone ring, and combinations of said haloketones represented by said formula, δ 6. A composition according to claim 5, said composition selected from the group consisting of 1 ,1 ,1 ,2,2,4,δ,5,δ-nonafluoro-4-(trifluoromethyl)-3-pentanone; 1 ,1 ,1 ,2,4,5,δ,5-octafluoro-2,4-bis(trifluoromethyl)-3 pentanone;0 1 ,1 ,1 ,2,4,4, δ,5-octafluoro-2-(trifluoromethyl)-3-pentanone; 1 ,1 ,1 ,2,4 ,
4,6,
5,6,6,
6-undecafluoro-2-(trifluoromethyl)-3-hexanone; I ^^^.δ.δ.δ-octafluoro-l-^rifluoromethoxyH-^rifluoromethy -S- pentanone; 1,1 ,1 ,3,4,4,4-heptafluoro-3-(trifluoromethyl)-2-butanone;6 1 ,1 ,1 ,2,2,5,δ,δ-octafluoro-4-(trifluoromethyl)-3-pentanone; and 2-chloro-1 ,1 ,1 ,4,4,5,5, 5-octafluoro-2-(trifluoromethyl)-3-pentanone.
7. The composition of claim 5, said composition comprising at least one brominated haloketone selected from the group consisting of0 monobromoperfluoroketones, monohydromonobromoperfluoroketones, perfluoroalkoxy)monobromoperfluoroketones, fluoroalkoxy)monobromoperfluoroketones, and monochloromonobromoperfluoroketones. 6
8. The composition of claim 7, said composition comprising at least one selected from the group consisting of: CF3C(0)CBrFCF2CF3; CF3C(0)CF2CF2CBrF2; CBrF2C(0)CF(CF3)2;0 CF3C(0)CBr(CF3)2; CBrF2CF2C(0)CF2CF3; CF3CBrFC(0)CF2CF3; CF3CBrFC(0)CF2CF2CF3; CF3CF2C(0)CBrFCF2CF3;5 CF3CF2C(0)CF2CF2CBrF2; CF3C(0)CBr(CF3)CF2CF3; CF3C(0)CF(CF3)CBrFCF3; CF3C(0)CBrFCF2CF2CF2CF3;
CF3C(0)CF2CF2CF2CF2CBrF2;
CF3CBrFC(0)CF2CF2CF2CF3;
CF3CF2C(0)CBrFCF2CF2CF3; CF3CF2C(0)CF2CF2CF2CBrF2;
CF3CF2CBrFC(0)CF2CF2CF3;
CBrF2CF2C(0)CF(CF3)CF2CF3;
CF3CBrFC(0)CF(CF3)CF2CF3;
CF3CF2C(0)CBr(CF3)CF2CF3; CF3CF2C(0)CF(CBrF2)CF2CF3;
CBrF2CF2CF2C(0)CF(CF3)2;
CF3CF2CBrFC(0)CF(CF3)2;
CF3CF2CF2C(0)CBr(CF3)2;
(CF3)2CBrC(0)CF(CF3)2; CF3CBrFCF2C(0)CF(CF3)2;
CHF2CF2C(0)CBr(CF3)2;
(CF3)2CHC(0)CBr(CF3)2;
CHF2CF2C(0)CBrFCF3;
(CF3)2CHC(0)CBrFCF3; (CF3)2CHC(0)CBrF2;
CBrF2CF2C(0)CH(CF3)2;
CBrF2C(0)CF(CF3)OCF3;
CBrF2CF2C(0)CF(CF3)OCF3;
CBrF2CF2CF2C(0)CF(CF3)OCF3; CBrF2C(0)CF(CF3)OC2F5;
CBrF2CF2C(0)CF(CF3)OC2F5;
CBrF2C(0)CF(CF3)OCF2C2F5;
CBrF2CF2C(0)CF(CF3)OCF2C2F5;
CBrF2C(0)CF(CF3)OCF(CF3)2; CBrF2CF2C(0)CF(CF3)OCF(CF3)2;
CF3CBrFC(0)CF(CF3)OCF(CF3)2;
CF3CBrFC(0)CF(CF3)OCF3;
CF3CBrFC(0)CF(CF3)OC2F5;
CF3CBrFC(0)CF(CF3)OCF3; (CF3)2CBrC(0)CF(CF3)OCF3;
CF3CBrFC(0)CF(CF3)OC2F5;
(CF3)2CBrC(0)CF(CF3)OC2F5; CF3CBrFC(0)CF(CF3)OCF2C2F5; CF3CBrFC(0)CF(CF3)OCF(CF3)2; CBrF2C(0)CF(OCF2CHF2)CF3; CBrF2C(0)CH(OCF2CHF2)CF3; δ CBrF2C(0)CF(OCH3)CF3; CBrF2C(0)CF(CF2OCH3)CF3; CCIF2CFBrC(0)CF2CF3; CBrF2CFClC(0)CF2CF3; CCIF2CFBrC(0)CF(CF3)2;0 CBrF2CFCIC(0)CF(CF3)2; CCIF2CFBrC(0)CF(CF3)(C2F5); CBrF2CFCIC(0)CF(CF3)(C2F5); CCIF2C(0)CBr(CF3)2; CCIF2CF2C(0)CBr(CF3)2;5 CF3CCIFC(0)CBr(CF3)2; CCIF2C(0)CBrFCF3; CCIF2CF2(0)CCBrFCF3; CF3CCIFC(0)CBrFCF3; CBrF2C(0)CCI(CF3)2;0 CBrF2CF2C(0)CCI(CF3)2; CBrF2C(0)CCIFCF3; and CBrF2CF2C(0)CCIFCF3.
9. A process for producing refrigeration, said process5 comprising evaporating the composition of claim 1 , 2, 3, 4, or 5 in the vicinity of a body to be cooled, and thereafter condensing said composition.
10. A process for producing heat, said process comprising0 condensing the composition of claim 1 , 2, 3, 4, or δ in the vicinity of a body to be heated, and thereafter evaporating said composition.
11. A method of using the compositions of claim 1 , 2, 3, 4, or δ for heat transfer, said method comprising transferring said composition6 from a heat source to a heat sink.
63
12. The composition of claim 1 , further comprising ultra-violet fluorescent dye selected from the group consisting of naphthalimides, perylenes, coumarins, anthracenes, phenanthracenes, xanthenes, thioxanthenes, naphthoxanthenes, fluoresceins, derivatives of said dye δ and combinations thereof.
13. The composition of claim 2, 3, 4, or δ, further comprising at least one ultra-violet fluorescent dye selected from the group consisting of naphthalimides, perylenes, coumarins, anthracenes, phenanthracenes,0 xanthenes, thioxanthenes, naphthoxanthenes, fluoresceins, derivatives of said dye and combinations thereof.
14. The composition of claim 12, further comprising at least one solubilizing agent selected from the group consisting of hydrocarbons,δ dimethylether, polyoxyalkylene glycol ethers, amides, ketones, nitriles, chlorocarbons, esters, lactones, aryl ethers, fluoroethers, and 1 ,1 ,1- trifluoroalkanes.
15. The composition of claim 14, wherein said solubilizing agent is0 selected from the group consisting of: a) polyoxyalkylene glycol ethers represented by the formula R1[(OR2)xOR3]y, wherein: x is an integer from 1 to 3; y is an integer from 1 to 4; R1 is selected from hydrogen and aliphatic hydrocarbon radicals having 1 to 6 carbon atoms and y5 bonding sites; R2 is selected from aliphatic hydrocarbylene radicals having from 2 to 4 carbon atoms; R3 is selected from hydrogen, and aliphatic and alicyclic hydrocarbon radicals having from 1 to 6 carbon atoms; at least one of R1 and R3 is selected from said hydrocarbon radicals; and wherein said0 polyoxyalkylene glycol ethers have a molecular weight of from about 100 to about 300 atomic mass units; b) amides represented by the formulae R1CONR2R3 and cyclo- [R4CON(R5)-], wherein R1, R2, R3 and R5are independently selected from aliphatic and alicyclic hydrocarbon radicals5 having from 1 to 12 carbon atoms, and at most one aromatic radical having from 6 to 12 carbon atoms; R4 is selected from aliphatic hydrocarbylene radicals having from 3 to 12 carbon atoms; and wherein said amides have a molecular weight of from about 100 to about 300 atomic mass units; c) ketones represented by the formula R1COR2, wherein R1 and R2 are independently selected from aliphatic, alicyclic and aryl hydrocarbon radicals having from 1 to 12 carbon atoms, and wherein said ketones have a molecular weight of from about 70 to about 300 atomic mass units; d) nitriles represented by the formula R1CN, wherein R1 is selected from aliphatic, alicyclic or aryl hydrocarbon radicals having from 5 to 12 carbon atoms, and wherein said nitriles have a molecular weight of from about 90 to about 200 atomic mass units; e) chlorocarbons represented by the formula RCIx, wherein; x is selected from the integers 1 or 2; R is selected from aliphatic and alicyclic hydrocarbon radicals having from 1 to 12 carbon atoms; and wherein said chlorocarbons have a molecular weight of from about 100 to about 200 atomic mass units; f) aryl ethers represented by the formula R1OR2, wherein: R1 is selected from aryl hydrocarbon radicals having from 6 to 12 carbon atoms; R2 is selected from aliphatic hydrocarbon radicals having from 1 to 4 carbon atoms; and wherein said aryl ethers have a molecular weight of from about 100 to about 150 atomic mass units; g) 1 ,1 ,1-trifluoroalkanes represented by the formula CF3R1, wherein R1 is selected from aliphatic and alicyclic hydrocarbon radicals having from about 5 to about 1δ carbon atoms; i) fluoroethers represented by the formula R1OCF CF2H, wherein R1 is selected from aliphatic and alicyclic hydrocarbon radicals having from about 6 to about 15 carbon atoms; and j) lactones represented by structures [Bj, [C], and [Dj:
Figure imgf000056_0001
[B] [C] [D] wherein, Ri through R3 are independently selected from hydrogen, linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl radicals; and the molecular weight is from about 100 to about 300 atomic mass units; and k) esters represented by the general formula R1Cθ2R2, wherein R1 and R2are independently selected from linear and cyclic, saturated and unsaturated, alkyl and aryl radicals; and wherein said esters have a molecular weight of from about 80 to about 560 atomic mass units.
16. A method for using the composition of claim 12 or 14, said method comprising, (a) introducing the composition into a compression refrigeration or air conditioning apparatus by (i) dissolving the ultraviolet fluorescent dye in the refrigerant composition of heat transfer fluid in the presence of the solubilizing agent, and introducing the combination into said compression refrigeration or air conditioning apparatus or (ii), combining solubilizing agent and and UV flurorescent dye and introducing said combination into refrigeration or air conditioning apparatus containing refrigerant and/or heat transfer fluid.
17. A method for using the composition of claim 12 or 14 in compression refrigeration ot air conditioning apparatus, said method comprising providing said composition to said apparatus, and providing a suitable means for detecting saif composition in the vicinity of said apparatus.
18. A method of using the composition of claim 12 or 14, said method comprising: (i) producing refrigeration by evaporating said composition in the vicinity of a body to be cooled and thereafter condensing said composition; or (ii) producing heat by condensing said composition in the vicinity of the body to be heated and thereafter evaporation said composition.
19. The composition of claim 11 , further comprising an odor- masking agent, fragrance, or thermal stabilizer.
20. The composition of claim 18, wherein the thermal stabilizer is nitromethane.
67
PCT/US2005/001511 2004-03-04 2005-01-12 Haloketone refrigerant compositions and uses thereof WO2005094395A2 (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
BRPI0508143-2A BRPI0508143A (en) 2004-03-04 2005-01-12 heat transfer or refrigerant fluid compositions, refrigeration and heat production processes and methods of using the compositions
AU2005227844A AU2005227844A1 (en) 2004-03-04 2005-01-12 Haloketone refrigerant compositions and uses thereof
JP2007501773A JP2007526384A (en) 2004-03-04 2005-01-12 Haloketone refrigerant composition and use thereof
EP05722453A EP1720953A2 (en) 2004-03-04 2005-01-12 Haloketone refrigerant compositions and uses thereof
RU2006134980/04A RU2006134980A (en) 2004-03-04 2005-01-12 COMPOSITIONS OF HALOGENKETONE REFRIGERANTS AND THEIR APPLICATION
CA002557874A CA2557874A1 (en) 2004-03-04 2005-01-12 Haloketone refrigerant compositions and uses thereof
NO20064479A NO20064479L (en) 2004-03-04 2006-10-03 Haloketone refrigerant compositions and their use

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US54997804P 2004-03-04 2004-03-04
US60/549,978 2004-03-04
US11/014,006 2004-12-16
US11/014,006 US7501074B2 (en) 2004-03-04 2004-12-16 Haloketone refrigerant compositions and uses thereof

Publications (2)

Publication Number Publication Date
WO2005094395A2 true WO2005094395A2 (en) 2005-10-13
WO2005094395A3 WO2005094395A3 (en) 2006-05-04

Family

ID=35064349

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2005/001511 WO2005094395A2 (en) 2004-03-04 2005-01-12 Haloketone refrigerant compositions and uses thereof

Country Status (11)

Country Link
EP (1) EP1720953A2 (en)
JP (1) JP2007526384A (en)
KR (1) KR20060128041A (en)
AR (1) AR048079A1 (en)
AU (1) AU2005227844A1 (en)
BR (1) BRPI0508143A (en)
CA (1) CA2557874A1 (en)
NO (1) NO20064479L (en)
RU (1) RU2006134980A (en)
SG (1) SG135205A1 (en)
WO (1) WO2005094395A2 (en)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008027518A3 (en) * 2006-09-01 2008-07-24 Du Pont Ascorbic acid, terephthalate, or nitromethane stabilizers for fluoroolefins
FR2930019A1 (en) * 2008-04-09 2009-10-16 Airbus France Sas Process for cooling an element such as an electric component confined in a fluid coolant circulating in a heat exchanger, where the element is useful in fuselage or cockpit of an aircraft
US8075796B2 (en) 2006-09-01 2011-12-13 E. I. Du Pont De Nemours And Company Phenol stabilizers for fluoroolefins
US8101094B2 (en) 2006-09-01 2012-01-24 E. I. Du Pont De Nemours And Company Terpene, terpenoid, and fullerene stabilizers for fluoroolefins
US8383004B2 (en) 2006-09-01 2013-02-26 E I Du Pont De Nemours And Company Amine stabilizers for fluoroolefins
US8394286B2 (en) 2006-09-01 2013-03-12 E I Du Pont De Nemours And Company Thiol and thioether stabilizers for fluoroolefins
US8529786B2 (en) 2006-09-01 2013-09-10 E I Du Pont De Nemours And Company Phosphorus-containing stabilizers for fluoroolefins
US8535555B2 (en) 2006-09-01 2013-09-17 E I Du Pont De Nemours And Company Epoxide and fluorinated epoxide stabilizers for fluoroolefins
US9254468B2 (en) 2008-03-07 2016-02-09 Arkema Inc. Stable formulated systems with chloro-3,3,3-trifluoropropene

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PL2247562T3 (en) * 2008-03-07 2018-03-30 Arkema, Inc. Use of r-1233 in liquid chillers
DE102017203043A1 (en) * 2017-02-24 2018-08-30 Siemens Aktiengesellschaft Heat pump assembly and method of operating a heat pump assembly

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000024814A1 (en) * 1998-10-26 2000-05-04 3M Innovative Properties Company Process for preparation of polymeric foam using fluorinated ketones as blowing agents
US6423673B1 (en) * 2001-09-07 2002-07-23 3M Innovation Properties Company Azeotrope-like compositions and their use
US6478979B1 (en) * 1999-07-20 2002-11-12 3M Innovative Properties Company Use of fluorinated ketones in fire extinguishing compositions

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000024814A1 (en) * 1998-10-26 2000-05-04 3M Innovative Properties Company Process for preparation of polymeric foam using fluorinated ketones as blowing agents
US6478979B1 (en) * 1999-07-20 2002-11-12 3M Innovative Properties Company Use of fluorinated ketones in fire extinguishing compositions
US6423673B1 (en) * 2001-09-07 2002-07-23 3M Innovation Properties Company Azeotrope-like compositions and their use

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8663494B2 (en) 2006-09-01 2014-03-04 E I Du Pont De Nemours And Company Terpene, terpenoid, and fullerene stabilizers for fluoroolefins
US10550302B2 (en) 2006-09-01 2020-02-04 The Chemours Company Fc, Llc Epoxide and fluorinated epoxide stabilizers for fluoroolefins
US8075796B2 (en) 2006-09-01 2011-12-13 E. I. Du Pont De Nemours And Company Phenol stabilizers for fluoroolefins
US8097181B2 (en) 2006-09-01 2012-01-17 E.I. Du Pont De Nemours And Company Ascorbic acid, terephthalate and nitromethane stabilizers for fluoroolefins
US8101094B2 (en) 2006-09-01 2012-01-24 E. I. Du Pont De Nemours And Company Terpene, terpenoid, and fullerene stabilizers for fluoroolefins
US8383004B2 (en) 2006-09-01 2013-02-26 E I Du Pont De Nemours And Company Amine stabilizers for fluoroolefins
US8394286B2 (en) 2006-09-01 2013-03-12 E I Du Pont De Nemours And Company Thiol and thioether stabilizers for fluoroolefins
WO2008027518A3 (en) * 2006-09-01 2008-07-24 Du Pont Ascorbic acid, terephthalate, or nitromethane stabilizers for fluoroolefins
US11851602B2 (en) 2006-09-01 2023-12-26 The Chemours Company Fc, Llc Epoxide and fluorinated epoxide stabilizers for fluoroolefins
US8529786B2 (en) 2006-09-01 2013-09-10 E I Du Pont De Nemours And Company Phosphorus-containing stabilizers for fluoroolefins
US8496846B2 (en) 2006-09-01 2013-07-30 E I Du Pont De Nemours And Company Phenol stabilizers for fluoroolefins
US8668791B2 (en) 2006-09-01 2014-03-11 E I Du Pont De Nemours And Company Ascorbic acid, terephthalate and nitromethane stabilizers for fluoroolefins
US8815114B2 (en) 2006-09-01 2014-08-26 E I Du Pont De Nemours And Company Phenol stabilizers for fluoroolefins
US9133381B2 (en) 2006-09-01 2015-09-15 The Chemours Company Fc, Llc Epoxide and fluorinated epoxide stabilizers for fluoroolefins
US11130894B2 (en) 2006-09-01 2021-09-28 The Chemours Company Fc, Llc Epoxide and fluorinated epoxide stabilizers for fluoroolefins
US9777204B2 (en) 2006-09-01 2017-10-03 The Chemours Company Fc, Llc Epoxide and fluorinated epoxide stabilizers for fluoroolefins
US8535555B2 (en) 2006-09-01 2013-09-17 E I Du Pont De Nemours And Company Epoxide and fluorinated epoxide stabilizers for fluoroolefins
US10072192B2 (en) 2008-03-07 2018-09-11 Arkema Inc. Stable formulated systems with chloro-3,3,3-trifluoropropene
US9254468B2 (en) 2008-03-07 2016-02-09 Arkema Inc. Stable formulated systems with chloro-3,3,3-trifluoropropene
FR2930019A1 (en) * 2008-04-09 2009-10-16 Airbus France Sas Process for cooling an element such as an electric component confined in a fluid coolant circulating in a heat exchanger, where the element is useful in fuselage or cockpit of an aircraft

Also Published As

Publication number Publication date
SG135205A1 (en) 2007-09-28
NO20064479L (en) 2006-12-01
WO2005094395A3 (en) 2006-05-04
KR20060128041A (en) 2006-12-13
EP1720953A2 (en) 2006-11-15
AU2005227844A1 (en) 2005-10-13
CA2557874A1 (en) 2005-10-13
RU2006134980A (en) 2008-04-10
BRPI0508143A (en) 2007-07-24
JP2007526384A (en) 2007-09-13
AR048079A1 (en) 2006-03-29

Similar Documents

Publication Publication Date Title
US7276177B2 (en) Hydrofluorocarbon refrigerant compositions and uses thereof
WO2005094395A2 (en) Haloketone refrigerant compositions and uses thereof
US7416679B2 (en) 1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone refrigerant and heat transfer compositions comprising a fluoroether
WO2006012097A1 (en) Refrigerant compositions comprising functionalized organic compounds and uses thereof
US7338616B2 (en) 1,1,1,2,2,4,5,5,5-Nonafluoro-4-(trifluoromethyl)-3-pentanone refrigerant compositions comprising a hydrocarbon and uses thereof
US20050151110A1 (en) Fluoroether refrigerant compositions and uses thereof
US20050285076A1 (en) 1,1,1,2,2,3,3,4,4-Nonafluoro-4-methoxybutane refrigerant compositions comprising functionalized organic compounds and uses thereof
US7413675B2 (en) Hydrocarbon refrigerant compositions and uses thereof
US7351352B2 (en) 1,1,1,2,2,3,3,4,4-Nonafluoro-4-methoxybutane refrigerant compositions comprising a fluoroether and uses thereof
JP2008505215A (en) 1-ethoxy-1,1,2,2,3,3,4,4,4-nonafluorobutane refrigerant composition containing hydrocarbon and use thereof
AU2005205600A1 (en) 1,1,1,2,2,3,3,4,4-nonafluoro-4-methoxybutane refrigerant compositions comprising a fluoroether and uses thereof
US7501074B2 (en) Haloketone refrigerant compositions and uses thereof
EP1706468A2 (en) 1,1,1,3,3-pentafluorobutane refrigerant or heat transfer fluid compositions comprising hydrofluorocarbon and uses thereof
US7208100B2 (en) 1-ethoxy-1,1,2,2,3,3,4,4,4-nonafluorobutane refrigerant compositions comprising a fluoroether and uses thereof
AU2005250878A1 (en) 1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone refrigerant and heat transfer compositions comprising a fluoroether
WO2005067559A2 (en) Fluoroether refrigerant compositions and uses thereof
WO2005067556A2 (en) 1,1,1,3,3,-pentafluoroybutane refrigerant compositions comprising fluoroether and uses thereof
JP2008505214A (en) 1,1,1,2,2,3,3,4,4-nonafluoro-4-methoxybutane refrigerant composition containing hydrocarbon and use thereof
EP1751246A2 (en) 1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone refrigerant compositions comprising a hydrocarbon and uses thereof

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A2

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SM SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A2

Designated state(s): BW GH GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

DPEN Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed from 20040101)
WWE Wipo information: entry into national phase

Ref document number: 2005227844

Country of ref document: AU

WWE Wipo information: entry into national phase

Ref document number: 2557874

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: 2005722453

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2007501773

Country of ref document: JP

Ref document number: 5095/DELNP/2006

Country of ref document: IN

NENP Non-entry into the national phase

Ref country code: DE

WWW Wipo information: withdrawn in national office

Ref document number: DE

ENP Entry into the national phase

Ref document number: 2005227844

Country of ref document: AU

Date of ref document: 20050112

Kind code of ref document: A

WWP Wipo information: published in national office

Ref document number: 2005227844

Country of ref document: AU

WWE Wipo information: entry into national phase

Ref document number: 1020067020556

Country of ref document: KR

WWE Wipo information: entry into national phase

Ref document number: 2006134980

Country of ref document: RU

121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 200580014260.3

Country of ref document: CN

WWP Wipo information: published in national office

Ref document number: 2005722453

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1020067020556

Country of ref document: KR

ENP Entry into the national phase

Ref document number: PI0508143

Country of ref document: BR