WO2013138123A1 - Stabilized iodocarbon compositions - Google Patents

Stabilized iodocarbon compositions Download PDF

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Publication number
WO2013138123A1
WO2013138123A1 PCT/US2013/029256 US2013029256W WO2013138123A1 WO 2013138123 A1 WO2013138123 A1 WO 2013138123A1 US 2013029256 W US2013029256 W US 2013029256W WO 2013138123 A1 WO2013138123 A1 WO 2013138123A1
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WIPO (PCT)
Prior art keywords
present
composition
compositions
compounds
iodocarbon
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PCT/US2013/029256
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English (en)
French (fr)
Inventor
Rajiv Ratna Singh
Haridasan K. Nair
Raymond H. Thomas
Lawrence A. Ford
David P. Wilson
Original Assignee
Honeywell International Inc.
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 US13/419,071 external-priority patent/US9175201B2/en
Application filed by Honeywell International Inc. filed Critical Honeywell International Inc.
Priority to JP2015500461A priority Critical patent/JP6324368B2/ja
Priority to EP13760833.7A priority patent/EP2825610A4/en
Publication of WO2013138123A1 publication Critical patent/WO2013138123A1/en

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    • 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
    • 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
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/10—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic phosphorus-containing compound
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
    • C10M171/008—Lubricant compositions compatible with refrigerants
    • 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
    • C09K2205/12—Hydrocarbons
    • C09K2205/122—Halogenated hydrocarbons
    • 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
    • C09K2205/12—Hydrocarbons
    • C09K2205/126—Unsaturated fluorinated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/02—Well-defined aliphatic compounds
    • C10M2203/024—Well-defined aliphatic compounds unsaturated
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/021—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
    • C10M2207/042—Epoxides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
    • C10M2207/044—Cyclic ethers having four or more ring atoms, e.g. furans, dioxolanes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
    • C10M2207/046—Hydroxy ethers
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/1033—Polyethers, i.e. containing di- or higher polyoxyalkylene groups used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/049—Phosphite
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/09—Characteristics associated with water
    • C10N2020/097—Refrigerants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/09—Characteristics associated with water
    • C10N2020/097—Refrigerants
    • C10N2020/101—Containing Hydrofluorocarbons
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/08—Resistance to extreme temperature
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/66—Hydrolytic stability
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/30—Refrigerators lubricants or compressors lubricants

Definitions

  • Halogenated hydrocarbons have found widespread use in a variety of industrial applications, including as refrigerants, aerosol propellants, blowing agents, heat transfer media and gas dielectrics. Many of these applications have heretofore utilized compositions comprising major amounts of chlorofluorocarbons (“CFCs”) and hydrochlorofluorocarbons (“HCFCs”).
  • CFCs chlorofluorocarbons
  • HCFCs hydrochlorofluorocarbons
  • suspected environmental problems have become associated with the use of some of these halogenated hydrocarbons.
  • CFCs and HCFCs tend to exhibit relatively high global warming potentials. Accordingly, it has become desirable in many applications to use compositions which are otherwise acceptable for the intended use but which at the same time have lower global warming potentials than CFCs and other disfavored halogenated compounds.
  • compositions comprising iodinated compounds may be used advantageously to replace various chlorinated compounds, many of which have high global warming potentials, in refrigeration (and other) applications to reduce potential environmental damage caused thereby.
  • iodinated compounds such as
  • trifluoroiodomethane tend to be relatively unstable, and often significantly less stable than CFCs, HCFCs and hydrofluorocarbons (HFCs), especially under certain conventional refrigeration conditions.
  • compositions comprising iodinated compounds must be stabilized.
  • Applicants have recognized one possible way to produce suitable stable iodo-compositions is to use stabilizing compounds therein.
  • HFCs due to their exceptional stability, may or may not use stabilizers incorporated in their compositions as known in the art.
  • U.S. Patent No. 5,380,449 discloses compositions comprising dichlorotrifluoroethane and stabilizing amounts of at least one phenol and at least one aromatic or fluorinated alkyl epoxide.
  • iodo-compounds tend to be significantly less stable that CFCs and HCFCs, it cannot be predicted from teachings of stabilizers for CFCs and HCFCs (e.g.
  • compositions comprising iodo-compounds, such as trifluoroiodomethane, that are sufficiently stable for a variety of uses including as replacements for CFC, HCFC and HFC refrigerants.
  • Japanese Kokai 09-059612 (Application No. 07-220964) discloses refrigerant compositions comprising trifluoroiodomethane and one or more phenolic compounds. This patent document indicates that the phenolic compositions act to stabilize the trifluoroiodomethane against degradation.
  • compositions containing phenolic compounds as stabilizers for trifluoroiodomethane may enjoy a certain degree of success, in certain applications it may be desirable to not use phenolic compounds or to use such compounds in a lower concentration.
  • phenols are generally acidic due to the dissociability of the hydroxyl group and are relatively reactive. These characteristics may be undesirable in certain applications and/or in certain situations.
  • iodocarbon compounds such as trifluoroiodomethane (CF 3 I)
  • iodocarbon compounds such as trifluoroiodomethane (CF 3 I)
  • CF 3 I trifluoroiodomethane
  • iodocarbon compounds in general, and C1 - C5 iodocarbons, and even more preferably C1 - C2 iodocarbons, particularly (such as the preferred C1 iodocarbon trifluoroiodomethane) can be combined with one or more stabilizer compounds selected from a specific set of compounds to produce an exceptionally well stabilized iodocarbon-containing
  • composition preferably a trifluoroiodomethane-containing composition suitable for commercial, industrial or personal use, and particularly as heat transfer fluids for use in refrigeration systems, air conditioning systems (including automotive air conditioning systems) and the like.
  • present compositions preferably sufficiently stable for a variety of uses, but also, they tend to exhibit a unique combination of non- flammability and low combined ozone-depletion and global warming properties, making them particularly useful candidates as CFC, HCFC, and HFC refrigerant replacements.
  • iodocarbon refers to any compound containing at least one carbon-iodine bond, and is intended to cover iodofluorocarbons (compounds which have at least one carbon-iodine bond and at least one carbon-fluorine bond, but no other bonds except carbon-carbon bonds) and hydroiodofluorocarbons (compounds which have at least one carbon-iodine bond, at least one carbon-fluorine bond, at least on carbon-hydrogen bond, but no other bonds except carbon-carbon bonds).
  • compositions comprising at least one iodocarbon compound, preferably a
  • the composition may include any one or more of a class of stabilizers based on free-radical scavenging functionality, but in many preferred embodiments the stabilizer comprises, and preferably in at least major proportion, diene-based compound(s), certain phenol compounds, certain epoxides, certain phosphites, and certain phosphates.
  • the diene-based compounds are isoprene-based compound(s).
  • “diene-based compound” refers to both substituted and unsubstituted C3 - C5 compounds with two or more double bonds in the molecular structure and to compounds that can be formed by reaction(s) involving such C3 - C5 compounds, provided that at least one double-bonds is present in such reaction product compound.
  • the diene-based compound of the present invention comprises substituted and
  • isoprene-based compound refers to ispropene, compounds having an isoprene moiety, and to compounds capable of being formed by reaction(s) involving isoprene.
  • determined diene-based compounds include myrcene and farsenol, each of which has three carbon-carbon double bonds.
  • diene-based is not limited to compounds having only two double bonds, but includes compounds having fewer or more than two carbon - carbon double bonds. In the case of diene-based compounds which are formed by a combination of C3 - C5 dienes, the molecules which are combined can be the same or different.
  • iodocarbon compounds tend to be generally less stable than compounds, which have C-CI and C-F bonds in place of the C-l bond, and particularly when in the presence of lubricant compounds and even more particularly when in the presence of lubricant compounds under temperature conditions that are experienced by refrigerants in vapor compression cycle operation.
  • Applicants have thus recognized the desirability of providing compositions comprising iodocarbon compounds, such as trifluoroiodomethane, that are sufficiently stable for a variety of uses, including in heat transfer applications, including as refrigerants and even more preferably as replacements for CFC and HCFC refrigerants.
  • compositions provide the potential to reduce environmental damage that would be caused if CFC and HCFC-based compositions were used instead of the compositions of the present invention.
  • iodinated compounds generally tend to be relatively unstable, and often significantly less stable than CFCs and HCFCs under certain conditions of use, such as under conditions existing in conventional refrigeration systems.
  • the present inventors discovered that compounds comprising iodofluorocarbon produced the brown/black color of iodine, which is believed to have been formed from the degradation of the
  • iodocarbon compounds preferably C1 - C2 iodocarbons, more preferably C1 iodocarbons, and even more preferably trifluoroiodomethane
  • at least one stabilizing compound preferably a compound having free radical scavenging functionality, and even more preferably at least one compound selected from the group consisting of: (1 ) diene- based compounds, preferably diene-based compounds have at least two carbon-carbon double bonds and at least four carbon atoms; (2) epoxy compounds, including preferably epoxy compounds selected from substituted or unsubstituted compounds according to Formulas (E1 ) and (E2) below: where
  • R 1 is an aliphatic radical having at least 3 carbon atoms, preferably at least 4 carbon atoms, and more preferably in certain embodiments R 1 is an unsaturated aliphatic radical having from 4 to 6 carbon atoms, with R 1 being a 4 carbon unsaturated aliphatic radical in certain highly preferred embodiments;
  • R 2 is an alphiatic radical having 4 or 5 carbon atoms or a polycyclic aromatic radical, preferably a naphthyl radical, and combinations of these;
  • each R is independently a phenyl radical
  • mildly hindered phenol means a substituted phenol in which there are aliphatic substituents at the 2 and 6 positions on the phenol ring and wherein the total number of substituent carbon atoms at these positions is greater than four but less than eight. IN preferred embodiments, the total number of substituent carbon atoms at positions 2 and 6 is five or six, and even more preferably five.
  • unhindered phenol means a phenol in which there are a total of not greater than a total of two carbon atoms in the combination of any substituents present at either the 2 or 6 positions on the phenol ring.
  • the stabilizing compound used in accordance with the various aspects of the present invention comprises, and preferably comprises in major proportion, and more preferably in certain embodiments consists essentially of at least one compound selected from the group consisting of: (1 ) diene-based compounds, preferably diene-based compounds have at least two carbon- carbon double bonds and at least four carbon atoms; (2) epoxy
  • R 1 is an alphiatic radical having at least 3 carbon atoms, preferably at least 4 carbon atoms, and more preferably in certain embodiments R 1 is an unsaturated aliphatic radical having from 4 to 6 carbon atoms, with R 1 being a 4 carbon unsaturated aliphatic radical in certain highly preferred embodiments;
  • R 2 is an alphiatic radical having 4 or 5 carbon atoms or a polycyclic aromatic radical, preferably a naphthyl radical, and combinations of these;
  • each R is independently a phenyl radical
  • a carboxylate radical having at least 6 but less than 15 carbon atoms; and combinations of any two or more of these.
  • compositions comprising, in addition to the iodocarbon, and preferably also the stabilizing agent, one or more other compounds, including especially HFCs, preferably C1 - C4 HFCs, and halogenated olefins, preferably C2 - C5 halogenated olefins.
  • compositions of the present invention are stable and suitable for use in many systems, apparatus and methods.
  • one aspect of the present invention provides systems, apparatus and methods that comprise the compositions of the present invention being included as a heating or cooling fluid (based on latent heat transfer and/or sensible heat transfer), such as in refrigeration applications, including particularly automotive air conditioning applications.
  • Other systems, apparatus and methods are also within the scope of the present invention, as explained more fully hereinafter.
  • the present invention provides methods, systems and apparatus for stabilizing a composition comprising at least one iodocarbon compound by use of a stabilizing agent which preferably , comprises one or more of the preferred stabilizing compounds mentioned herein, preferably in many preferred embodiments comprising a diene- based compound, in accordance with the present invention.
  • compositions comprise at least one iodocarbon, preferably a C1 iodofluorocarbon (such as trifluoroiodomethane (CF 3 I)), and preferably also at least one stabilizing agent, preferably one or more of the preferred stabilizing compounds mentioned herein, including diene- based compounds, preferably in an amount effective under conditions of use to stabilize the iodocarbon against degradation.
  • a C1 iodofluorocarbon such as trifluoroiodomethane (CF 3 I)
  • stabilizing agent preferably one or more of the preferred stabilizing compounds mentioned herein, including diene- based compounds, preferably in an amount effective under conditions of use to stabilize the iodocarbon against degradation.
  • compositions of the present invention comprise iodocarbon and at least one saturated HFC and/or at least one
  • haloalkene preferably one or more C1 - C4 HFCs and/or one or more , C2 - C5 haloalkenes.
  • the haloalkene preferably comprises C2 - C4 haloalkene, and even more preferably C2 - C4 haloalkene with at least two, and preferably at least three fluorine substituents.
  • HFO-1234yf 2,3,3,3- tetrafluoropropene
  • the composition comprises from about 5% to about 50% by weight of iodocarbon, more preferably from about 20% to about 40% by weight of iodocarbon, and even more preferably from about 25% to about 35% of iodocarbon, and from about 50% to about 95% by weight of HFCs, preferably C1 - C4 HFCs, and/or halogenated olefins, preferably C2 - C5 halogenated olefins, and even more preferably C2 - C4 haloalkene, more preferably from about 60% to about 80% by weight of HFCs, preferably C1 - C4 HFCs, and/or halogenated olefins, preferably C2 - C5
  • halogenated olefins and even more preferably C2 - C4 haloalkene, and even more preferably from about 65% to about 75% of HFCs, preferably C1 - C4 HFCs, and/or halogenated olefins, preferably C2 - C5
  • halogenated olefins and even more preferably haloalkene, based on the total weight of the iodocarbon and the haloalkene.
  • compositions of the present invention comprise iodocarbon and at least one C1 - C4 HFC, preferably C1 - C3 HFC, and even more preferably C1 - C2 HFC.
  • the composition comprises from about 50% to about 95% by weight of iodocarbon, more preferably form about 65% to about 85% of iodocarbon, and from about 5% to about 50% by weight of HFC, and even more preferably from about 15% to about 35% of HFC, based on the total weight of the iodocarbon and the HFC.
  • the present compositions have a Global Warming Potential (GWP) of not greater than about 1000, more preferably not greater than about 500, and even more preferably not greater than about 150, and in certain cases of not greater than about 100. In certain embodiments, the GWP of the present compositions is not greater than about 75.
  • GWP Global Warming Potential
  • compositions preferably also having an Ozone Depleting Potential (ODP) of not greater than about 0.05, more preferably not greater than about 0.02 and even more preferably about zero.
  • ODP Ozone Depleting Potential
  • “ODP” is as defined in "The Scientific Assessment of Ozone Depletion, 2002, A report of the World Meteorological Association's Global Ozone Research and Monitoring Project,” which is incorporated herein by reference.
  • the iodocarbon compound in accordance with the present invention may comprise one or more of a wide variety of such compounds.
  • the iodocarbon compound is a C1 - C6 iodocarbon, and even more preferably a C1 - C3 iodofluorocarbon.
  • the iodocarbon can be comprised of carbon, hydrogen, fluorine and iodine.
  • the iodocarbon comprises a C1 - C3 iodocarbon, more preferably a C1 iodocarbon, and even more preferably a C1 iodofluorocarbon.
  • the at least one iodocarbon compound comprises, and preferably comprises in major proportion on the basis of the total iodocarbon compounds, trifluoroiodomethane (CF 3 I).
  • the present compositions comprise at least one C1 compound containing only carbon-fluorine bonds and carbon-iodine bonds, with C1 compounds containing at least two carbon- fluorine bonds and at least one carbon-iodine bond being even more preferred.
  • Trifluoroiodomethane is readily available from a variety of commercial sources, including Matheson TriGas, Inc.
  • trifluoroiodomethane prepared via any of a variety of conventional methods may be used.
  • An example of one such conventional method of preparing trifluoroiodomethane is disclosed in JACS 72, 3806 (1950), "The Degradation of Silver Trifluoroacetate to Trifluoroiodomethane" by Albert L. Henne and William G. Finnegan, which is incorporated herein by reference.
  • the iodocarbon compounds may be present in the compositions in widely ranging amounts, depending on numerous factors, including for example the particular intended conditions of use of the compound.
  • iodocarbon compound(s) are present in the present composition in amounts, based on weight, of from about 5% to less than about 100%, more preferably from about 20% to less than about 100%.
  • the iodocarbon compound(s) are present in the present composition in amounts, based on weight, of from about 5% to about 35%, more preferably from about 45% to about 95%, and even more preferably from about 65% to about 95%.
  • the iodocarbon compound(s) are present in the present composition in amounts, based on weight, of from about 15% to about 50%, more preferably from about 20% to about 40%, and even more preferably from about 25% to about 35%.
  • the iodocarbon is present in an amount of from about 90% to about 99.999% by weight, more preferably from about 95 wt. % to about 99.99 wt. %, and even more preferably from about 96 wt. % to about 99.7 wt. %, based on the total weight of iodocarbon and stabilizing agent, preferably diene-based compounds in the composition.
  • the stabilizer compounds are present in the composition in amounts of from about 0.001 % to about 15 % by weight, more preferably from about 0.01 wt. % to about 10 wt. %, and even more preferably from about 0.3 wt. % to about 5 wt. %, and even more preferably from about 1 to about 2 wt.% based on the total weight of the composition, preferably composition that is comprised of the iodocarbon, and more preferably the refrigerant composition that is comprised of the iodocarbon.
  • the stabilizer compounds are present in the composition in amounts of from about 0.001 % to about 15 % by weight, more preferably from about 0.01 wt.
  • the stabilizer compound is present in amounts of from about 0.5 wt. % to about 2 wt. %, based on the total weight of composition, preferably the composition that is comprised of the iodocarbon.
  • any one or more of the available diene-based compounds are adaptable for use in accordance with the present invention and that those skilled in the art will be able, in view of the teachings contained herein, to select the number and type of such compound(s) appropriate for any particular application without undue experimentation.
  • the type and nature of the diene-based compound(s) to be used may depend, to at least some degree, upon the particular iodocarbon compound(s) being used in the composition, the expected conditions of use of the compositions, and related factors.
  • the amount of the diene-based stabilizer used in the compositions of the present invention can vary widely, depending upon factors such as the type of iodocarbon in the composition, the expected conditions of use of the composition, among other factors. In general, it is preferred to use diene-based stabilizer in an effective amount relative to the iodocarbon being used. As used herein, the term "effective amount" refers to an amount of diene-based
  • trifluoroiodomethane one of the important breakdown products is trifluoromethane, which is formed by the relevant iodocarbon compound, such as trifluoroiodomethane, results in a stabilized composition wherein the iodocarbon degrades more slowly and/or to lesser degree relative to the same composition, under the same, or similar, conditions, but in the absence of the diene-based compounds.
  • trifluoroiodomethane one of the important breakdown products is trifluoromethane, which is formed by the
  • An effective amount of stabilizer preferably will reduce the amount of decomposition of the iodocarbon such that the GWP of the refrigerant composition is below 1000, and even more preferably less than 150. Even without the consideration of GWP values, breakdown of a component of a refrigerant composition is undesirable.
  • the level of the breakdown product described above be less than 2.0 wt%, more preferably less than about 1 .0 wt. %, and even more preferably less than about 0.5 wt% of the total refrigerant composition.
  • the amount of the diene-based compound(s) is sufficient to result in a stabilized composition wherein at least one of the iodocarbon compound(s) therein degrades more slowly and/or to a lesser degree relative to the same composition but in the absence of the diene-base compound, when tested according to SAE J1662 (issued June 1993) and/or ASHRAE 97-1983R (issued 1997) standard tests.
  • iodocarbon is less than about 0.9 wt. %, and even more preferably less than about 0.7 wt% after the composition is maintained at about 300°F for about two weeks.
  • the diene-based compounds of the present invention may be cyclic or acyclic, with acyclic compounds being generally preferred in many embodiments.
  • the acyclic diene-based compounds for use in the present invention are preferably C5 - C30 diene-based compounds, more preferably C5 - C20 diene-based compounds and even more preferably C5 - C15 diene based compounds.
  • the compound may be aromatic or non-aromatic, with non-aromatic diene- based cyclic compounds being preferred in certain embodiments.
  • the diene-based compounds are selected from the group consisting of allyl ethers, propadiene, butadiene, isoprene-based compounds (including terpenes (such as myrcene, farnesene, and limonene),and terpene derivatives (such as farnesol, and geraniol)) and combinations of any two or more of these.
  • terpenes such as myrcene, farnesene, and limonene
  • terpene derivatives such as farnesol, and geraniol
  • each of the compounds identified in the immediately preceding list is intended to include both substituted and unsubstituted forms of the identified compounds.
  • the diene-based compounds comprise in major proportion, and even more preferably consist essentially of, propadiene.
  • the diene-based compounds comprise in major proportion, and even more preferably consist essentially of, terpenes, terpene derivatives or combinations of these.
  • terpene means a compound, which is comprised of at least ten carbon atoms and contains at least one, and preferably at least two isoprene moieties.
  • isoprene moiety refers to any portion of a molecule, which includes a radical, which can be formed from substituted or unsubstituted isoprene. In certain preferred embodiments, unsubstituted terpenes are preferred.
  • the terpene compound of the present invention comprises at least one head-to-tail condensation product of modified or unmodified isoprene molecules. It is contemplated that any one or more terpene compounds are adaptable for use in accordance with the present invention and that those skilled in the art will be able, in view of the teachings contained herein, to select the number and type of terpene compound(s) for any particular application without undue experimentation.
  • the preferred terpenes of the present invention are hydrocarbons having molecular formula (C5H 8 ) n in a cyclic or acyclic, saturated or unsaturated, substituted or unsubstituted structure, with n preferably being from 2 to about 6, and even more preferably 2 to 4.
  • 6 are sometimes referred to herein as monoterpenes, while terpenes having the formula C15H24 (including substituted forms) are sometimes referred to herein as sesquiterpenes.
  • Terpenes according to the present invention having the formula C20H32 (including substituted forms) are sometimes referred to herein as diterpenes, while terpenes having the formula C3oH 24 (including substituted forms) are sometimes referred to as triterpenes, and so on.
  • Terpenes containing 30 or more carbons are usually formed by the fusion of two terpene precursors in a regular pattern.
  • the terpene compound(s) of present compositions comprise, preferably in major proportion, and even more preferably consist essentially of, one or more acyclic terpene compounds.
  • acyclic terpenes it is contemplated that such compounds may be within the class of compounds identified as head-to- tail linked isoprenoids or within the class of compounds that are not joined in that manner.
  • myrcene (2-methyl-6-methyleneocta-1 ,7-diene), allo-cimene, beta-ocimene.
  • the terpene compounds of the present invention may comprise cyclic terpene compounds.
  • cyclic terpenes mono-, bi-, tri-, or tetracyclic compounds having varying degrees of unsaturation are contemplated for use in accordance with the present invention.
  • the terpene compounds of the present composition comprise one or more sequiterpenes, preferably farnesol and/or farnesene.
  • farnesol is the compound 3,7,1 1 - trimethyl-2,6,10-dodecatrien-1 -ol, including any and all stereoisomers thereof.
  • Farnesol is a natural organic compound which is a sesquiterpene alcohol found as a colorless liquid and is insoluble in water, but miscible with oils. It has the chemical structure:
  • farnesene includes a-farnesene (i.e., 3,7, 1 1 - trimethyldocecadodeca-1 ,3,6,19-tetraene) and ⁇ -farnesene (i.e., 7,1 1 - dimethyl-3-methylene-1 ,6, 10-dodecatriene), including any and all stereoisomers thereof.
  • a-farnesene i.e., 3,7, 1 1 - trimethyldocecadodeca-1 ,3,6,19-tetraene
  • ⁇ -farnesene i.e., 7,1 1 - dimethyl-3-methylene-1 ,6, 10-dodecatriene
  • terpene derivatives in accordance with the present invention include oxygen-containing derivatives of terpenes such as alcohols, aldehydes or ketones containing hydroxyl groups or carbonyl groups, as well as hydrogenated derivates. Oxygen-containing derivatives of terpenes are sometimes referred to herein as terpenoids.
  • the diene-based compounds of the present invention comprise the terpenoid Carnosic acid.
  • Carnosic acid is a phenolic diterpene that corresponds to the empirical formula C2028O4. It occurs naturally in plants of the Libiatae family.
  • carnosic acid is a constituent of the species Salvia officinalis (sage) and Rosmarinus officinalis (rosemary) where it is mainly found in the leaves.
  • Carnosic acid is also found in thyme and marjoram (see Linde in Salvia officinalis [Helv. Chim Acta 47, 1234 (1962)] and Wenkert et al. in Rosmarinus officinalis [J. Org. Chem. 30, 2931 (1965)], and in various other species of sage, (see Salvia canariensis [Savona and Bruno, J. Nat. Prod.
  • the present compositions comprise a combination of at least one diene-based compound (such as isoprene, propadiene and myrcene) and one additional stabilizing compound chosen from epoxides, such as aromatic epoxides and fluorinated alkyl epoxides, hindered phenols such as DL- alpha -tocopherol and 2-tert-butyl-4,6-dimethylphenol, phosphites such as diphenyl phosphate (e.g., Doverphos 213) and triphenyl phosphite alone and in mixtures such as Doverphos 9EII, esters of phosphorous acid such as Doverphos 613 and mixtures of the above mentioned materials.
  • epoxides such as aromatic epoxides and fluorinated alkyl epoxides, hindered phenols such as DL- alpha -tocopherol and 2-tert-butyl-4,6-di
  • any suitable relative amount of the at least one diene-based compound and supplemental optional stabilizer compound(s) may be used.
  • the weight ratio of the diene-based compound(s) to other stabilizer compound(s) is in the range of from about 1 :99 to about 100:0.
  • the weight ratio of diene-based compound(s) to the optional stabilizers is from about 10:1 to about 1 :1 , more preferably from about 2: 1 to about 1 :1 , and even more preferably about 1 :1 . 2 - THE PHENOLS
  • phenol compounds are suitable for use as stabilizer in the present compositions. While applicants do not wish to be bound by or to any theory of operation, it is believed that the present phenols act as radical scavengers in the present compositions and thereby tend to increase the stability of such compositions.
  • phenol compound refers generally to any substituted or unsubstituted phenol.
  • Suitable phenol compounds include 4,4'-methylenebis(2,6-di-tert-butylphenol); 4,4'-bis(2,6-di-tert-butylphenol); 2,2- or 4,4-biphenyldiols including 4,4'-bis(2-methyl-6-tert-butylphenol); derivatives of 2,2- or 4,4-biphenyldiols; 2,2'-methylenebis(4-ethyl-6- tertbutylpheol); 2,2'-methylenebis(4-methyl-6-tert-butylphenol); 4,4,- butylidenebis(3-methyl-6-tert-butylphenol); 4,4,-isopropylidenebis(2,6-di- tert-butylphenol); 2,2'-methylenebis(4-methyl-6-nonylphenol); 2,2'- isobutylidenebis(4,6-dimethylphenol); 2,2'-methylenebis(4-methyl-6-
  • Suitable phenols include tocopherol, hydroquinone; t-butyl hydroquinone; and other derivatives of hydroquinone; and the like.
  • Certain preferred phenols include tocopherol, BHT, hydroquinone and the like.
  • Certain particularly preferred phenols include tocopherol and the like.
  • Most phenols are commercially available such as the Irganox compounds from Ciba. A single phenol compound and/or mixtures of two or more phenols may be used in the present compositions. 3 - THE EPOXIDES
  • epoxides are suitable for use in the compositions of the present invention.
  • aromatic epoxides and fluorinated alkyl epoxides are preferred additional stabilizers in certain embodiments. While applicants do not wish to be bound by or to any theory of operation, it is believed that the epoxides of the present invention act as acid scavengers in the CF 3 I compositions and thereby tend to increase the stability of such compositions.
  • suitable aromatic epoxides include those defined by the formula I below:
  • R is hydrogen, alkyl, fluoroalkyl, aryl, fluoroaryl, or
  • Ar is a substituted or unsubstituted phenylene or napthylene moiety.
  • Certain preferred aromatic epoxides of Formula I include:
  • butylphenylglycidyl ether pentylphenylglycidyl ether; hexylphenylglycidyl ether; heptylphenylglycidyl ether; octylphenylglycidyl ether;
  • nonylphenylglycidyl ether decylphenylglycidyl ether; glycidyl methyl phenyl ether; 1 ,4-diglycidyl phenyl diether and derivatives thereof; 1 ,4- diglycidyl naphthyl diether and derivatives thereof; and 2,2'[[[5- heptadecafluorooctyl]1 ,3phenylene]bis[[2,2,2trifluorome
  • aromatic epoxides include naphthyl glycidyl ether, 4-methoxyphenyl glycidyl ether, and derivatives of naphthyl glycidyl ether; and the like. Certain more preferred aromatic epoxides include butylphenyl glycidyl ether, and the like. A single aromatic epoxide and/or mixtures of two or more aromatic epoxides may be used in the present compositions. Any of a variety of alkyl and/or alkenyl epoxides is suitable for use in the present compositions. Examples of suitable alkyl and alkenyl epoxides include those of Formula II:
  • R a i k is a substituted or unsubstituted alkyl or alkenyl group having from about 1 to about 10 carbon atoms, more preferably from about 1 to about 6 carbon atoms.
  • Certain preferred alkyl epoxides of Formula II include n-butyl glycidyl ether, isobutyl glycidyl ether, hexanediol diglycidyl ether, and the like, as well as, fluorinated and perfluorinated alkyl epoxides. More preferred alkyl epoxides include hexanediol diglycidyl ether and 1 ,2-epoxyhexane.
  • Certain preferred alkenyl epoxides of Formula II include allyl glycidyl ether, fluorinated and perfluorinated alkenyl epoxides, and the like. More preferred alkenyl epoxides include allyl glycidyl ether and the like.
  • compositions may optionally incorporate other components depending upon the particular contemplated use and the specific iodocarbon and stabilization compounds being used.
  • compositions of the present invention may further comprise one or more components in addition to the iodocarbon and the stabilizing agent when present, depending upon the expected use of the composition.
  • the present compositions are generally adaptable for use in connection with the following applications, and various co-components may be associated with the compositions in connection with these and other applications: heat transfer (including refrigeration, chiller applications, closed Rankine cycle operations (CRC)); organic Rankine cycle operations (ORC); foam and/or foam forming operations (including as or part of a premix and/or blowing agent and/or foam (including thermosetting foams (such as polyurethane,
  • thermoplastic foams such as polystyrene and polyolefin
  • integral skin foams one or two component pressurized froth foam, and the like
  • solvent including solvent cleaning and extraction
  • aerosol oligomer and/or polymer production (such as monomer for polymerization reactions); propellants; fire extinguishing aids; surfactants; flushing applications; metered dose inhalers (MDI); lubricating agents; flame suppressants; therapeutic compositions;
  • pesticide compositions are pesticide compositions; herbicide compositions; solvent applications (including cleaning, extraction and deposition applications) and the like.
  • the present compositions have as a co-component one or more of the following components:
  • Hydrocarbons substituted and un-substituted, particularly C2-C6 hydrocarbons
  • Alcohols substituted and un-substituted, particularly C2-C6 alcohols
  • Ketones substituted and un-substituted, particularly C2-C5 ketones
  • Aldehydes substituted and un-substituted, particularly C2-C5 aldehydes
  • Ethers/Diethers substituted and un-substituted, particularly C2-C5 ethers
  • Fluoroethers substituted and un-substituted, particularly C2-C5 fluoroethers
  • Fluoroalkenes substituted and un-substituted, particularly C2-C6 fluoroalkenes
  • HFC particularly C2-C5 HFCs
  • HCC particularly C2-C5 HCCs
  • Haloalkenes including preferably fluoroalkenes (substituted and un- substituted, particularly C2-C6 fluoroalkenes);
  • HCIFO particularly C2-C5 HCIFOs
  • Carboxylic acid and derivatives thereof eg. carboxylic acid esters, such as methyl formate
  • HFO means compounds that consist of atoms of carbon, fluorine and hydrogen, and no other atoms, and in which there is at least one carbon-carbon double bond.
  • HCIFO means compounds that consist of atoms of carbon, chlorine, fluorine and hydrogen, and no other atoms, and in which there is at least one carbon-carbon double bond.
  • HBrFO means compounds that consist of atoms of carbon, bromine, fluorine and hydrogen, and no other atoms, and in which there is at least one carbon-carbon double bond.
  • C1 - C5 and like usages refer to compounds having at least one carbon atom and up to about five carbon atoms, etc.
  • HFC-32 Difluoromethane
  • HFC-134a 1 ,1 ,1 ,2-Tetrafluoroethane
  • HFC-236fa 1 ,1 ,1 ,3,3,3-hexafluoropropane
  • dichlorotrifluoroethanes such as 2,2-dichloro-1 ,1 ,1 trifluoroethane (HCFC- 123)); and chlorotetrafluoroethane (HCFC-124), including any and all isomers of each.
  • HCCs While it is contemplated that a wide variety of HCCs may be used in the present compositions and methods, in certain preferred embodiments it is preferred to use separately or in any combination: dichloroethenes (such as 1 ,2-dichloroethane, including trans- 1 ,2-dichloroethyene);
  • CFCs such as 1 ,1 ,2- trichlorotrifluoroethane (CFC-1 13)
  • trichlorotrifluoroethanes such as 1 ,1 ,2- trichlorotrifluoroethane (CFC-1 13)
  • CFC-1 13 trichlorotrifluoroethane
  • compositions comprise one or more C3 or C4 fluoroalkenes, preferably compounds having Formula I as follows: XCF z R 3 -z (I)
  • fluroethenes preferred for use in certain embodiments of the present invention are: C2H3F (monofluoroethylene or Vinyl Fluoride or VF); C2H2F2 (such as 1 ,1 -Difluoroethylene (Vinylidene Fluoride or VDF); C2HF3 (trifluoroethylene or THFE); and C ⁇ F 4 (tetrafluoroethylene or TFE).
  • C2H3F monofluoroethylene or Vinyl Fluoride or VF
  • C2H2F2 such as 1 ,1 -Difluoroethylene (Vinylidene Fluoride or VDF)
  • C2HF3 trifluoroethylene or THFE
  • C ⁇ F 4 tetrafluoroethylene or TFE
  • embodiments of the present invention are: C3H3F3 (including all isomers, such as 3,3,3-trifluoropropene (HFO-1243zf); C 3 H 2 F 4 (such as cis- and trans- isomers of 1 ,3,3,3-etrafluoropro3pene (HFO-1234ze), and 2,3,3,3- tetrafluoropropene (HFO-1234yf)); and C 3 HF 5 (such as isomers of HFO- 1225).
  • C3H3F3 including all isomers, such as 3,3,3-trifluoropropene (HFO-1243zf)
  • C 3 H 2 F 4 such as cis- and trans- isomers of 1 ,3,3,3-etrafluoropro3pene (HFO-1234ze), and 2,3,3,3- tetrafluoropropene (HFO-1234yf)
  • C 3 HF 5 such as isomers of HFO- 1225.
  • HFO-1234 is used herein to refer to all
  • HFO- 1234yf tetrafluoropropenes.
  • HFO-1234yf and HFO-1234ze are used herein generically to refer to 1 , 1 , 1 , 2-tetrafluoropropene and 1 , 1 , 1 , 3-tetrafluoropropene, respectively, independent of its stero isometry.
  • HFO-1234 compounds are known materials and are listed in Chemical Abstracts databases.
  • EP 974,571 discloses the preparation of 1 ,1 ,1 ,3-tetrafluoropropene by contacting 1 ,1 ,1 ,3,3-pentafluoropropane (HFC-245fa) in the vapor phase with a chromium-based catalyst at elevated temperature, or in the liquid phase with an alcoholic solution of KOH, NaOH, Ca(OH) 2 or Mg(OH) 2 .
  • fluorobutenes preferred for use in certain embodiments of the present invention are: C 4 H 4 F 4 (including all isomers thereof);
  • chlorofluroethenes preferred for use in certain embodiments of the present invention are: C 2 F 3 CI (CTFE).
  • chlorofluoropropenes preferred for use in certain embodiments of the present invention are mono- or di-chlorinated compounds, including for example: C 3 H 2 F 4 CI (such as 2-chloro-3,3,3- trifluoro-1 -propene (including HCFO-1233xf) and 1 -chloro-3,3,3-trifluoro-1 - propene (including all isomers of HCFO-1233zd).
  • C 3 H 2 F 4 CI such as 2-chloro-3,3,3- trifluoro-1 -propene (including HCFO-1233xf) and 1 -chloro-3,3,3-trifluoro-1 - propene (including all isomers of HCFO-1233zd).
  • compositions include at least one fluoroalkenes of Formula II below:
  • each R is independently CI, F, Br, I or H
  • R' is (CR 2 ) n Y
  • n 0 or 1 .
  • Y is CF 3
  • n is 0
  • at least one of the remaining Rs is F.
  • compositions, compatibilizers, aerosols, propellants, fragrances, flavor formulations, and solvent compositions of the present invention exhibit a highly desirable low level of toxicity compared to other of such compounds.
  • this discovery is of potentially enormous advantage and benefit for the formulation of not only refrigerant compositions, but also any and all compositions, which would otherwise contain relatively toxic compounds satisfying the formulas described above.
  • a relatively low toxicity level is associated with compounds of Formula II, preferably wherein Y is CF 3 , wherein at least one R on the unsaturated terminal carbon is H, and at least one of the remaining Rs is F.
  • Applicants believe also that all structural, geometric and stereoisomers of such compounds are effective and of beneficially low toxicity.
  • compositions of the present invention comprise one or more tetrafluoropropenes.
  • the term "HFO- 1234" is used herein to refer to all tetrafluoropropenes.
  • HFO-1234yf is highly preferred for use in connection with heat transfer compositions, methods and systems.
  • HFO-1234ze cis- and trans-1 , 3, 3, 3-tetrafluoropropene
  • HFO- 1234ze is used herein generically to refer to 1 , 3, 3, 3-tetrafluoropropene, independent of whether it is the cis- or trans- form.
  • cisHFO- 1234ze and “transHFO-1234ze” are used herein to describe the cis- and trans- forms of 1 , 3, 3, 3-tetrafluoropropene respectively.
  • HFO- 1234ze therefore includes within its scope cisHFO-1234ze, transHFO- 1234ze, and all combinations and mixtures of these.
  • transHFO-1234ze may be preferred for use in certain refrigeration systems because of its relatively low boiling point (-19° C)
  • cisHFO- 1234ze with a boiling point of +9° C, also has utility in certain refrigeration systems of the present invention.
  • HFO-1234ze and 1 , 3, 3, 3-tetrafluoropropene refer to both stereo isomers, and the use of this term is intended to indicate that each of the cis-and trans- forms applies and/or is useful for the stated purpose unless otherwise indicated.
  • HFO-1234 compounds are known materials and are listed in Chemical Abstracts databases.
  • EP 974,571 discloses the preparation of 1 ,1 ,1 , 3-tetrafluoropropene by contacting 1 ,1 ,1 ,3,3-pentafluoropropane (HFC-245fa) in the vapor phase with a chromium-based catalyst at elevated temperature, or in the liquid phase with an alcoholic solution of KOH, NaOH, Ca(OH)2 or Mg(OH)2.
  • compositions particularly those comprising HFO-1234, and HFO-1234yf, are believed to possess properties that are
  • the fluoroolefins of the present invention will not have a substantial negative affect on atmospheric chemistry, being negligible contributors to ozone depletion in comparison to some other halogenated species.
  • the preferred compositions of the present invention thus have the advantage of not contributing substantially to ozone depletion.
  • the preferred compositions also do not contribute substantially to global warming compared to many of the hydrofluoroalkanes presently in use.
  • compositions can vary widely, depending the particular application, and compositions containing more than about 1 % by weight and less than 100% of the compound are within broad the scope of the present invention. In preferred embodiments, the present
  • compositions comprise HFO-1234, preferably HFO-1234yf, in amounts from about 5% by weight to about 99% by weight, and even more preferably from about 5% to about 95%.
  • compositions may comprise, in addition to the iodocarbon compounds of the present invention (and in addition to the stabilizer compound when present), fluoroalkene
  • compositions may comprise, in addition to the stabilizer which is preferably present and any oil or lubricant that is also preferably present in the heat transfer fluids in accordance with the present invention, CF 3 I and one or more fluoroalkene compounds.
  • fluoroalkene consists essentially of tetrafluoropropene, more preferably HFO-1234yf.
  • intermediate and more specific composition ranges are indicated in the table below, with the percentages being based on the total of the components is indicated in the Table 2 below.
  • Certain highly preferred embodiments of the present invention comprise heat transfer fluids, particularly for use in automotive air conditioning systems, comprising from about 65 to about 75 wt% of HFO- 1234yf and from about 25 to about 35 wt% CF3I, and even more preferably about 70 wt% of HFO-1234yf and about 30 wt% CF 3 I, said percentages being based on the total combined weight of HFO and CF 3 I.
  • compositions may comprise, in addition to any stabilizer that is present in accordance with the present invention, CF 3 I, certain fluoroalkene compounds (preferably HFO-1234ze) of the present invention, and/or certain HFCs (preferably HFC-152a) in accordance with broad, intermediate and more specific composition ranges (all amounts understood to be preceded by "about”) as indicated in the table below, with the percentages being based on the total of the three components indicated in the Table 3.
  • compositions may comprise, in addition to the stabilizer of the present invention, CF 3 I, certain fluoroalkene compounds of the present invention, and/or certain HFCs (preferably HFC-32) in accordance with broad, intermediate and more specific composition ranges (all amounts understood to be preceded by "about”) as indicated in the table below, with the percentages being based on the total of the three components indicated in the Table 4.
  • the composition comprises, in addition to the iodocarbon compound(s), a lubricant or oil.
  • a lubricant or oil Any of a variety of conventional lubricants may be used in the compositions of the present invention. Such compositions are especially well adapted for use as refrigerants in heating or cooling cycle equipment, as explained more fully hereinafter.
  • the composition then contains a at least one lubricant having hydrogen atoms and carbon atoms, wherein no more than 17% of the total number of hydrogen atoms which are attached to a carbon atom are tertiary hydrogen atoms.
  • the lubricant has less than 1 % of the total number of hydrogen atoms which are attached to a carbon atom are tertiary hydrogen atoms, and more preferably has no tertiary hydrogen atoms, that is wherein about 0 % of the total number of hydrogen atoms which are attached to a carbon atom are tertiary hydrogen atoms.
  • It preferably also has a relatively low percentage of oxygen, and preferably no oxygen in the molecule. It is also generally preferred to use a lubricant or oil having little inherent concentration of polar solvent, particularly water. An important requirement for the lubricant is that there must be enough lubricant returning to the compressor of the system such that the compressor is lubricated. Thus suitability of the lubricant is determined partly by the refrigerant/lubricant characteristics and partly by the system characteristics.
  • suitable lubricants include mineral oil, alkyl benzenes, including a synthetic lubricant, specifically polyalkyleneglycol (PAG) lubricant, and preferably a PAG consisting essentially of 2 or more oxypropylene groups and having a viscosity of from about 10 to about 200 centistokes at about 37. degree. C. (sold under the trade designation ND-8 by Idemitsu Kosan), and PAG sold under the trade designation RL-897 by DOW, polyvinyl ethers (PVEs), and the like.
  • PAG polyalkyleneglycol
  • PAG polyalkyleneglycol
  • mineral oils include Witco LP 250 (registered trademark) from Witco, Zerol 300 (registered trademark) from Shrieve Chemical, Sunisco 3GS from Witco, and Calumet R015 from Calumet.
  • Commercially available alkyl benzene lubricants include Zerol 150
  • esters include neopentyl glycol dipelargonate, which is available as Emery 2917 (registered trademark) and Hatcol 2370 (registered trademark).
  • Other useful esters include phosphate esters, dibasic acid esters, and fluoroesters.
  • hydrocarbon based oils are have sufficient solubility with the refrigerant that is comprised of an iodocarbon, the combination of the iodocarbon and the hydrocarbon oil might more stable than other types of lubricant. Such combination may therefore be advantageous.
  • Preferred lubricants include polyalkylene glycols and esters. Polyalkylene glycols are highly preferred in certain embodiments because they are currently in use in particular applications such as mobile air-conditioning. Mixtures of different lubricants may be used.
  • a lubricant comprising in major proportion by weight, and even more preferably at least about 75% by weight of alkyl benzene-based compounds, mineral oil compounds, and combinations of these.
  • alkyl benzene applicants have found that such compounds are preferred from among the numerous other lubricant compounds which have heretofore been available due to the relatively high level of miscibility in the preferred refrigerant compositions and the relatively high level of stability that such molecules exhibit in the heat transfer compositions and the heat transfer systems of the present invention.
  • Another preferred molecule for use in connection with the present invention is referred to herein, by way of convenience but not by way of limitation, as ethylene oxide/propylene oxide (EO/PO) molecules.
  • EO/PO ethylene oxide/propylene oxide
  • EO/PO molecules which are also referred to herein as "dual capped EO/PO molecules" due to the presence of the methyl radical on each end of the molecule, or alternatively other relatively low chain length alkyl group" can provide the ability to adjust, to suit each particular application, the n and the m values.
  • a lubricant molecule can be selected to achieve a highly advantageous combination of miscibility and stability.
  • An advantage that dual capped molecules perform substantially better in many respects and similar molecules which are only capped at one end as illustrated in the examples below.
  • United States Patent 4,975,212 which is incorporated herein by reference, discloses techniques for capping molecules of this type. Although it is not generally preferred, is also possible to combine the preferred lubricants of the present invention with one or more conventional lubricants.
  • Suitable polyol ester lubricants suitable for air conditioning or refrigeration use are typically prepared by the condensation of a poly alcohol or polyol compound such as pentaerythritol, dipentaerythritol, neopentyl glycol or trimethylpropanol with either pure or mixed, linear or branched aliphatic carboxylic acids such as a linear or branched monocarboxylic acid having from about 4 to about 10 carbon atoms.
  • a poly alcohol or polyol compound such as pentaerythritol, dipentaerythritol, neopentyl glycol or trimethylpropanol
  • linear or branched aliphatic carboxylic acids such as a linear or branched monocarboxylic acid having from about 4 to about 10 carbon atoms.
  • Polyol ester base stocks polyols are available from Hatco Corporation.
  • Hatcol 3307 is a pure polyol ester basestock based on neopentyl glycol.
  • Hatcol 3329 and Hatcol 3504 are a pure polyol ester refrigeration base stocks based on pentaerythritol mixed fatty acids esters.
  • Hatcol 3316 is a polyol ester of dipentaerythritol and short chain fatty acids.
  • compositions according to the invention include a lubricant in amounts of from about 20 wt. % to about 50 wt. %, preferably from about 20 wt. %to about 30 wt. % by weight of the composition.
  • any of a variety of other additives may be used in the compositions of the present invention.
  • suitable additives include metal passivators such as nitromethane, extreme pressure (EP) additives that improve the lubricity and load bearing characteristics of the lubricant.
  • EP additives are described in US Patent Serial No. 4,755,316 (Table D) and incorporated here.
  • EP additives are organophosphates including Lubrizol ® 8478 manufactured by the Lubrizol Corporation. Corrosion inhibitors are also useful and disclosed in
  • compositions of the present invention may include each of the compounds mentioned herein in widely ranging amounts, it is generally preferred that heat transfer compositions, and particularly refrigerant compositions of the present invention comprise iodocarbon compound(s), and even more preferably C1 - C3 iodofluorocarbon compounds, in an amount that is at least about 25 % by weight of the composition.
  • the composition comprises HFC and particularly HFC-152a
  • the compositions comprise at least about 40 % by weight, and even more preferably at least about 50% by weight of HFC-152a.
  • Preferred refrigerant or heat transfer compositions according to the present invention include a lubricant, generally in amounts of from about 30 to about 50 % by weight of the composition.
  • a lubricant generally in amounts of from about 30 to about 50 % by weight of the composition.
  • An important requirement for the lubricant is that there must be enough lubricant returning to the compressor of the system such that the compressor is lubricated.
  • suitability of the lubricant is determined partly by the refrigerant/lubricant characteristics and partly by the system characteristics.
  • suitable lubricants include mineral oil, alkyl benzenes, polyol esters, including polyalkylene glycols, polyvinyl ethers (PVEs), and the like.
  • Mineral oil which comprises paraffin oil or naphthenic oil, is commercially available.
  • mineral oils include Witco LP 250 (registered trademark) from Witco, Zerol 300 (registered trademark) from Shrieve Chemical, Sunisco 3GS from Witco, and Calumet R015 from Calumet.
  • Commercially available alkyl benzene lubricants include Zerol 150 (registered
  • esters include neopentyl glycol dipelargonate, which is available as Emery 2917 (registered trademark) and Hatcol 2370 (registered trademark).
  • Other useful esters include phosphate esters, dibasic acid esters, and fluoroesters.
  • hydrocarbon based oils are have sufficient solubility with the refrigerant that is comprised of an iodocarbon, the combination of the iodocarbon and the hydrocarbon oil might more stable than other types of lubricant. Such combination may therefore be advantageous.
  • Preferred lubricants include polyalkylene glycols and esters. Polyalkylene glycols are highly preferred in certain embodiments because they are currently in use in particular applications such as mobile air-conditioning. Of course, different mixtures of different types of lubricants may be used.
  • Preferred forms of the present compositions may also include a compatibilizer, such as propane, for the purpose of aiding compatibility and/or solubility of the lubricant.
  • a compatibilizer such as propane
  • Such compatibilizers including propane, butanes and pentanes, are preferably present in amounts of from about 0.5 to about 5 percent by weight of the composition.
  • Combinations of surfactants and solubilizing agents may also be added to the present compositions to aid oil solubility, as disclosed by U.S. Patent Serial No. 6,516,837, the disclosure of which is incorporated by reference.
  • compositions of the present invention are believed to be adaptable for use in many of such systems, either with or without system modification.
  • the compositions of the present invention may provide an advantage as a replacement in systems, which are currently based on refrigerants having a relatively high capacity.
  • embodiments where it is desired to use a lower capacity refrigerant composition of the present invention for reasons of cost for example, to replace a refrigerant of higher capacity, such embodiments of the present compositions provide a potential advantage.
  • compositions of the present invention particularly compositions comprising a substantial proportion of, and in some embodiments comprising a major proportion of transHFO-1234yf, as a replacement for existing refrigerants, such as HFC-134a.
  • the refrigerants of the present invention potentially permit the beneficial use of larger displacement compressors, thereby resulting in better energy efficiency than other refrigerants, such as HFC-134a. Therefore the refrigerant compositions of the present invention, particularly compositions comprising transHFP-1234ze, provide the possibility of achieving a competitive advantage on an energy basis for refrigerant replacement applications.
  • compositions of the present including particularly those comprising HFO-1234 (and particularly HFO-1234yf), also have advantage (either in original systems or when used as a replacement for refrigerants such as R-12 and R-500), in chillers typically used in connection with commercial air conditioning systems.
  • the present methods, systems and compositions are thus adaptable for use in connection with automotive air conditioning systems and devices, commercial refrigeration systems and devices, chillers, residential refrigerator and freezers, general air conditioning systems, heat pumps, ORCs, CRCs and the like.
  • Blowing agents may also comprise or constitute one or more of the present compositions.
  • the compositions of the present invention may include the iodocarbon compound(s) and the diene- based compound(s) of the present invention in widely ranging amounts. It is generally preferred, however, that for preferred compositions for use as blowing agents in accordance with the present invention the iodocarbon compound(s) are present in an amount that is at least about 1 % by weight, and even more preferably at least about 50% by weight, of the
  • blowing agent compositions of the present invention include, in addition to HFO-1234 (preferably HFO-1234ze) one or more of the following components as a co-blowing agent, filler, vapor pressure modifier, or for any other purpose:
  • HFC-134a 1 ,1 ,1 ,2-Tetrafluoroethane
  • HFC-236fa 1 ,1 ,1 ,3,3,3-hexafluoropropane
  • blowing agent compositions of the present invention may comprise cisHFO-1234ze, transHF01234ze or combinations thereof.
  • the blowing agent composition of the present invention comprise a combination of cisHFO-1234ze and transHF01234ze in a cis:trans weight ratio of from about 1 :99 to about 30:70, and even more preferably from about 1 :99 to about 5:95.
  • the invention provides foamable
  • compositions and preferably polyurethane, polyisocyanurate, phenolic foams, extruded thermoplastic foam compositions, integral skin foams and one or two component pressurized froth foams prepared using the compositions of the present invention.
  • one or more of the present compositions are included as or part of a blowing agent in a foamable composition, which composition preferably includes one or more additional components capable of reacting and/or foaming under the proper conditions to form a foam or cellular structure, as is well known in the art.
  • the invention also relates to foam, and preferably closed cell foam, prepared from a polymer foam formulation containing a blowing agent comprising the compositions of the invention.
  • the invention provides foamable compositions comprising thermoplastic foams, such as such as polystyrene (PS), polyethylene (PE), polypropylene (PP) and polyethyleneterpthalate (PET) foams, preferably low-density foams.
  • thermoplastic foams such as polystyrene (PS), polyethylene (PE), polypropylene (PP) and polyethyleneterpthalate (PET) foams, preferably low-density foams.
  • dispersing agents may also be incorporated into the blowing agent compositions of the present invention.
  • Surfactants are optionally but preferably added to serve as cell stabilizers.
  • Some representative materials are sold under the names of DC-193, B-8404, and L-5340 which are, generally, polysiloxane polyoxyalkylene block copolymers such as those disclosed in U.S. Patent Serial Nos. 2,834,748; 2,917,480; and 2,846,458, each of which is incorporated herein by reference.
  • blowing agent mixture may include flame retardants such as tri(2-chloroethyl)phosphate, tri(2- chloropropyl)phosphate, tri(2,3-dibromopropyl)-phosphate, tri(1 ,3- dichloropropyl) phosphate, diammonium phosphate, various halogenated aromatic compounds, antimony oxide, aluminum trihydrate, polyvinyl chloride, and the like.
  • flame retardants such as tri(2-chloroethyl)phosphate, tri(2- chloropropyl)phosphate, tri(2,3-dibromopropyl)-phosphate, tri(1 ,3- dichloropropyl) phosphate, diammonium phosphate, various halogenated aromatic compounds, antimony oxide, aluminum trihydrate, polyvinyl chloride, and the like.
  • the present invention provides propellant compositions comprising or consisting essentially of a composition of the present invention, such propellant compositions preferably being sprayable compositions.
  • the propellant compositions of the present invention preferably comprise a material to be sprayed and a propellant comprising, consisting essentially of, or consisting of a composition in accordance with the present invention. Inert ingredients, solvents, and other materials may also be present in the sprayable mixture.
  • the sprayable composition is an aerosol.
  • Suitable materials to be sprayed include, without limitation, cosmetic materials such as deodorants, perfumes, hair sprays, cleansers, and polishing agents as well as medicinal materials such as anti-asthma and anti-halitosis medications, and any other medication or the like, including preferably any other medicament or agent intended to be inhaled.
  • the medicament or other therapeutic agent is preferably present in the composition in a therapeutic amount, with a substantial portion of the balance of the composition comprising a compound of Formula I of the present invention, preferably HFO-1234, and even more preferably HFO-1234ze.
  • Aerosol products for industrial, consumer or medical use typically contain one or more propellants along with one or more active ingredients, inert ingredients or solvents.
  • the propellant provides the force that expels the product in aerosolized form. While some aerosol products are propelled with compressed gases like carbon dioxide, nitrogen, nitrous oxide and even air, most commercial aerosols use liquefied gas propellants.
  • the most commonly used liquefied gas propellants are hydrocarbons such as butane, isobutane, and propane. Dimethyl ether and HFC-152a (1 , 1 -difluoroethane) are also used, either alone or in blends with the hydrocarbon propellants. Unfortunately, all of these liquefied gas propellants are highly flammable and their incorporation into aerosol formulations will often result in flammable aerosol products.
  • compositions of the present invention particularly and preferably compositions comprising HFO-1234, and even more preferably HFO-1234ze and/or HFO-1234yf, for use in certain industrial aerosol products, including for example spray cleaners, lubricants, and the like, and in medicinal aerosols, including for example to deliver medications to the lungs or mucosal membranes.
  • HFO-1234 preferably compositions comprising HFO-1234, and even more preferably HFO-1234ze and/or HFO-1234yf
  • HFO-1234 preferably compositions comprising HFO-1234, and even more preferably HFO-1234ze and/or HFO-1234yf
  • HFO-1234 preferably compositions comprising HFO-1234, and even more preferably HFO-1234ze and/or HFO-1234yf
  • HFO-1234 preferably compositions comprising HFO-1234, and even more preferably HFO-1234ze and/or HFO-1234yf
  • MMIs metered dose inhalers
  • the present invention thus includes methods for treating ailments, diseases and similar health related problems of an organism (such as a human or animal) comprising applying a composition of the present invention containing a medicament or other therapeutic component to the organism in need of treatment.
  • the step of applying the present composition comprises providing a MDI containing the composition of the present invention (for example, introducing the composition into the MDI) and then discharging the present composition from the MDI.
  • compositions of the present invention are capable of providing nonflammable, liquefied gas propellant and aerosols that do not contribute substantially to global warming.
  • HFO-1234 preferably HFO- 1234ze and/or HFO-1234yf
  • the present compositions can be used to formulate a variety of industrial aerosols or other sprayable compositions such as contact cleaners, dusters, lubricant sprays, and the like, and consumer aerosols such as personal care products, household products and automotive products.
  • HFO-1234ze is particularly preferred for use as an important component of propellant compositions for in medicinal aerosols such as metered dose inhalers.
  • the medicinal aerosol and/or propellant and/or sprayable compositions of the present invention in many applications include, in addition to compound of formula (I) or (II)
  • compositions of the present invention unlike many compositions previously used in these applications, have good
  • compositions therefore provide in certain preferred embodiments substantially nonflammable, liquefied gas propellants having very low Global Warming potentials.
  • compositions of the present invention also provide advantage when used as part of, and in particular as a carrier for, flavor formulations and fragrance formulations.
  • the suitability of the present compositions for this purpose is demonstrated by a test procedure in which 0.39 grams of Jasmone were put into a heavy walled glass tube. 1 .73 grams of R- 1234ze were added to the glass tube. The tube was then frozen and sealed. Upon thawing the tube, it was found that the mixture had one liquid phase. The solution contained 20 wt. % Jasome and 80 wt. % R- 1234ze, thus establishing its favorable use as a carrier or part of delivery system for flavor formulations, in aerosol and other formulations.
  • the present composition in extraction applications with the present fluid in its supercritical state. This and other applications of involving use of the present compositions in the supercritical or near supercritical state are described hereinafter.
  • the present invention provides in one aspect a stabilizer composition for use as an additive in any one of the above-noted compositions, or more generally as an additive for any composition, which contains or will be exposed to iodocarbon compound(s).
  • iodocarbon compound(s) iodocarbon compound(s)
  • the stabilizer composition of the present invention comprises a combination of diene- based compound(s) and at least one additional stabilizer selected from the group of additional stabilizers described above, preferably selected from the group consisting of phenol compound(s), epoxy compound(s), phosphites, phosphates and combinations of these.
  • compositions of the present invention are useful in connection with numerous methods and systems, including as heat transfer fluids in methods and systems for transferring heat, such as refrigerants used in refrigeration, air conditioning and heat pump systems.
  • the present compositions are also advantageous for use in systems and methods of generating aerosols, preferably comprising or consisting of the aerosol propellant in such systems and methods.
  • Methods of forming foams and methods of extinguishing and suppressing fire are also included in certain aspects of the present invention.
  • the present invention also provides in certain aspects methods of removing residue from articles in which the present compositions are used as solvent compositions in such methods and systems.
  • the preferred heat transfer methods generally comprise providing a composition of the present invention and causing heat to be transferred to or from the composition, preferably by changing the phase of the composition and/or by sensible heat transfer.
  • the present methods provide cooling by absorbing heat from a fluid or article, preferably by evaporating the present refrigerant composition in the vicinity of the body or fluid to be cooled to produce vapor comprising the present composition.
  • the methods include the further step of compressing the refrigerant vapor, usually with a compressor or similar equipment to produce vapor of the present composition at a relatively elevated pressure.
  • the step of compressing the vapor results in the addition of heat to the vapor, thus causing an increase in the temperature of the relatively high pressure vapor.
  • the present methods include removing from this relatively high temperature, high pressure vapor at least a portion of the heat added by the evaporation and compression steps.
  • the heat removal step preferably includes
  • This relatively high pressure liquid preferably then undergoes a nominally isoenthalpic reduction in pressure to produce a relatively low temperature, low pressure liquid. In such embodiments, it is this reduced temperature refrigerant liquid which is then vaporized by heat transferred from the body or fluid to be cooled.
  • compositions of the invention may be used in a method for producing heating which comprises condensing a refrigerant comprising the compositions in the vicinity of a liquid or body to be heated.
  • a method for producing heating which comprises condensing a refrigerant comprising the compositions in the vicinity of a liquid or body to be heated.
  • One embodiment of the present invention relates to methods of forming foams, and preferably polyurethane and polyisocyanurate foams.
  • the methods generally comprise providing a blowing agent composition of the present invention, adding (directly or indirectly) the blowing agent composition to a foamable composition, and reacting the foamable composition under conditions effective to form a foam or cellular structure, as is well known in the art. Any of the methods well known in the art, such as those described in "Polyurethanes Chemistry and Technology," Volumes I and II, Saunders and Frisch, 1962, John Wiley and Sons, New York, NY, which is incorporated herein by reference, may be used or adapted for use in accordance with the foam embodiments of the present invention.
  • such preferred methods comprise preparing polyurethane or polyisocyanurate foams by combining an isocyanate, a polyol or mixture of polyols, a blowing agent or mixture of blowing agents comprising one or more of the present compositions, and other materials such as catalysts, surfactants, and optionally, flame retardants, colorants, or other additives.
  • the foam formulation is pre-blended into two components.
  • the isocyanate and optionally certain surfactants and blowing agents comprise the first component, commonly referred to as the "A" component.
  • the polyol or polyol mixture, surfactant, catalysts, blowing agents, flame retardant, and other isocyanate reactive components comprise the second component, commonly referred to as the "B" component.
  • polyurethane or polyisocyanurate foams are readily prepared by bringing together the A and B side components either by hand mix for small preparations and, preferably, machine mix techniques to form blocks, slabs, laminates, pour-in-place panels and other items, spray applied foams, froths, and the like.
  • ingredients such as fire retardants, colorants, blowing agents, and even other polyols can be added as a third stream to the mix head or reaction site.
  • each of these components can be added partially to the B-component and partially as a third stream to the mix head or reaction site. Most preferably, however, they are all incorporated into one B-component as described above.
  • thermoplastic foams using the compositions of the invention.
  • conventional polystyrene and polyethylene formulations may be combined with the compositions in a conventional manner to produce rigid foams.
  • the present invention also provides methods of removing containments from a product, part, component, substrate, or any other article or portion thereof by applying to the article a composition of the present invention.
  • article is used herein to refer to all such products, parts, components, substrates, and the like and is further intended to refer to any surface or portion thereof.
  • contaminant is intended to refer to any unwanted material or substance present on the article, even if such substance is placed on the article intentionally.
  • contaminant as used herein is intended to cover and encompass such a photo resist material.
  • Preferred methods of the present invention comprise applying the present composition to the article. Although it is contemplated that numerous and varied cleaning techniques can employ the compositions of the present invention to good advantage, it is considered to be particularly advantageous to use the present compositions in connection with supercritical cleaning techniques.
  • Supercritical cleaning is disclosed in US Patent No. 6,589,355, which is assigned to the assignee of the present invention and incorporated herein by reference.
  • HFO-1234 preferably HFO- 1234ze
  • additional components such as C0 2 and other additional components known for use in connection with supercritical cleaning applications.
  • vapor degreasing and solvent cleaning methods consist of exposing an article, preferably at room temperature, to the vapors of a boiling solvent. Vapors condensing on the object have the advantage of providing a relatively clean, distilled solvent to wash away grease or other contamination. Such processes thus have an additional advantage in that final evaporation of the present solvent composition from the object leaves behind relatively little residue as compared to the case where the object is simply washed in liquid solvent.
  • the present methods involve raising the temperature of the solvent composition of the present invention above ambient or to any other temperature that is effective in such application to substantially improve the cleaning action of the solvent.
  • Such processes are also generally preferred for large volume assembly line operations where the cleaning of the article, particularly metal parts and assemblies, must be done efficiently and quickly.
  • the cleaning methods of the present invention comprise immersing the article to be cleaned in liquid solvent at an elevated temperature, and even more preferably at about the boiling point of the solvent. In such operations, this step preferably removes a substantial amount, and even more preferably a major portion, of the target contaminant from the article. This step is then preferably followed by immersing the article in solvent, preferably freshly distilled solvent, which is at a temperature below the temperature of the liquid solvent in the preceding immersion step, preferably at about ambient or room
  • the preferred methods also include the step of then contacting the article with relatively hot vapor of the present solvent composition, preferably by exposing the article to solvent vapors rising from the hot/boiling solvent associated with the first mentioned immersion step. This preferably results in condensation of the solvent vapor on the article.
  • the article may be sprayed with distilled solvent before final rinsing.
  • Sherliker et al. includes a boiling sump for containing a solvent composition, a clean sump for containing distilled solvent, a water separator, and other ancillary equipment.
  • the present cleaning methods may also comprise cold cleaning in which the contaminated article is either immersed in the fluid composition of the present invention under ambient or room temperature conditions or wiped under such conditions with rags or similar objects soaked in solvents.
  • Certain preferred cleaning methods comprise flushing the substrate with a composition in accordance with the present invention.
  • the present invention provides methods for reducing the flammability of fluids, said methods comprising adding a compound or composition of the present invention to said fluid.
  • the flammability associated with any of a wide range of otherwise flammable fluids may be reduced according to the present invention.
  • the flammability associated with fluids such as ethylene oxide, flammable hydrofluorocarbons and hydrocarbons, including: HFC-152a, 1 ,1 ,1 -trifluoroethane (HFC-143a), difluoromethane (HFC-32), propane, hexane, octane, and the like can be reduced according to the present invention.
  • compositions according to the present invention may include CF 3 I and HFC-152a in amounts, based on the total weight of these two components, of from greater than 0 to about 38.5% of CF 3 I, more preferably from greater than 0 to about 35% of CF 3 I, and from about 61 .5 to less than 100, and even more preferably from about 65 to less than about 100 of HFC-152a.
  • a flammable fluid may be any fluid exhibiting flammability ranges in air as measured via any standard conventional test method, such as ASTM E-681 , and the like.
  • any suitable amounts of the present compounds or compositions may be added to reduce flammability of a fluid according to the present invention.
  • the amount added will depend, at least in part, on the degree to which the subject fluid is flammable and the degree to which it is desired to reduce the flammability thereof.
  • the amount of compound or composition added to the flammable fluid is effective to render the resulting fluid substantially non-flammable.
  • the present invention further provides methods of suppressing a flame, said methods comprising contacting a flame with a fluid comprising a compound or composition of the present invention.
  • Any suitable methods for contacting the flame with the present composition may be used.
  • a composition of the present invention may be sprayed, poured, and the like onto the flame, or at least a portion of the flame may be immersed in the composition.
  • those of skill in the art will be readily able to adapt a variety of conventional apparatus and methods of flame suppression for use in the present invention.
  • the present invention provides methods of sterilizing comprising contacting the articles, devices or material to be sterilized with a compound or composition of the present invention. Such methods may be either high or low-temperature sterilization methods.
  • high- temperature sterilization comprises exposing the articles, device or material to be sterilized to a hot fluid comprising a compound or composition of the present invention at a temperature of from about 250°F to about 270°F, preferably in a substantially sealed chamber. The process can be completed usually in less than about 2 hours.
  • some articles, such as plastic articles and electrical components cannot withstand such high temperatures and require low-temperature
  • Low-temperature sterilization of the present invention involves the use of a compound or composition of the present invention at a
  • the compounds of the present invention may be combined with other common chemical sterilants, including, for example, ethylene oxide (EO), formaldehyde, hydrogen peroxide, chlorine dioxide, and ozone to form a sterilant composition of the present invention.
  • EO ethylene oxide
  • formaldehyde formaldehyde
  • hydrogen peroxide chlorine dioxide
  • ozone ozone
  • the low-temperature sterilization of the present invention is preferably at least a two-step process performed in a substantially sealed, preferably air tight, chamber.
  • the first step the sterilization step
  • the articles having been cleaned and wrapped in gas permeable bags are placed in the chamber.
  • Air is then evacuated from the chamber by pulling a vacuum and perhaps by displacing the air with steam.
  • Such humidities may maximize the sterilizing effectiveness of the sterilant, which is introduced into the chamber after the desired relative humidity is achieved.
  • the sterilant and steam are evacuated from the chamber.
  • the articles are aerated to remove sterilant residues. Removing such residues is particularly important in the case of toxic sterilants, although it is optional in those cases in which the substantially non-toxic compounds of the present invention are used.
  • Typical aeration processes include air washes, continuous aeration, and a combination of the two.
  • An air wash is a batch process and usually comprises evacuating the chamber for a relatively short period, for example, 12 minutes, and then introducing air at atmospheric pressure or higher into the chamber. This cycle is repeated any number of times until the desired removal of sterilant is achieved.
  • Continuous aeration typically involves introducing air through an inlet at one side of the chamber and then drawing it out through an outlet on the other side of the chamber by applying a slight vacuum to the outlet.
  • a common approach involves performing air washes and then an aeration cycle.
  • the present invention further provides methods for stabilizing a composition comprising iodocarbons, such as trifluoroiodomethane.
  • the preferred method steps comprise providing at least one iodocarbon compound and stabilizing said at least one iodocarbon compound by exposing the compound to a diene-based compound(s) of the present invention.
  • the iodocarbon providing step comprises providing a composition, including the specific types of compositions described above, and adding to such composition and a diene-based compound of the present invention, preferably by mixing an effective amount of a stabilizer composition of the present invention with said iodocarbon composition.
  • the present compositions may be utilized in solvent and solvent extraction applications mentioned herein, particularly for use in connection with materials such as alkaloids (which are commonly derived from plant sources), for example caffeine, codeine and papaverine, for organometallic materials such as metallocenes, which are generally useful as catalysts, and for fragrances and flavors such as Jasmone.
  • alkaloids which are commonly derived from plant sources
  • codeine and papaverine for example caffeine, codeine and papaverine
  • organometallic materials such as metallocenes, which are generally useful as catalysts
  • fragrances and flavors such as Jasmone.
  • the present compositions can be used in connection with methods involving the deposit of catalysts, particularly organometallic catalysts, on solid supports.
  • these methods include the step of generating finely divided catalyst particles, preferably by precipitating such catalyst particles from the present compositions in the supercritical or near supercritical state. It is expected that in certain preferred embodiment
  • catalysts prepared in accordance with the present methods will exhibit excellent activity.
  • certain of the MDI methods and devices described herein may utilize medicaments in finely divided form, and in such situations it is contemplated that the present invention provides methods which include the step of incorporating such finely divided medicament particles, such as albuterol, into the present fluids, preferably by dissolving such particles, in the present composition, preferably in the supercritical or near supercritical state.
  • entrainers such as alcohols.
  • compositions in the supercritical or near supercritical state may be used to clean circuit boards and other electronic materials and articles.
  • Certain materials may have very limited solubility in the present compositions, particularly when in the supercritical or near supercritical state.
  • the present compositions may be used as anti- solvents for the precipitation of such low solubility solutes from solution in another supercritical or near supercritical solvent, such as carbon dioxide.
  • supercritical carbon dioxide is utilized frequently used in the extrusion process of thermoplastic foams, and the present compositions may be used to precipitation certain materials contained therein.
  • This example illustrates a stabilized composition of the present invention comprising CF 3 I, PAG oil, and isoprene.
  • a mixture (1 .6 grams) of trifluoroiodomethane (25 wt. %) and HFO- 1234yf (75 wt. %) is added to 3 grams of a composition containing 99% by weight of PAG oil and 1 % by weight of isoprene.
  • the resulting mixture is placed into a glass tube with metal coupons of aluminum, steel, and copper, and the tube is then sealed.
  • the sealed glass tube is put into an oven at 300°F for two weeks. After such time the tube is removed and observed.
  • the mixture is one phase, indicating that the refrigerant has during the period remained miscible and soluble in the PAG oil.
  • the liquid in the tube is clear with a light yellow color. The steel coupon appears unchanged.
  • HFC-23 trifluoromethane
  • This example illustrates a stabilized composition of the present invention comprising CF 3 I, PAG oil, and myrcene.
  • a mixture (1 .6 grams) of trifluoroiodomethane (25 wt. %) and HFO- 1234yf (75 wt. %) is added to 3 grams of a composition containing 99% by weight of PAG oil and 1 % by weight of myrcene.
  • the resulting mixture is placed into a glass tube with metal coupons of aluminum, steel, and copper, and the tube is then sealed.
  • the sealed glass tube is put into an oven at 300°F for two weeks. After such time the tube is removed and observed.
  • the mixture is one phase, indicating that the refrigerant has during the period remained miscible and soluble in the PAG oil.
  • the liquid in the tube is clear with a light yellow color. The steel coupon appears unchanged.
  • HFC-23 trifluoromethane
  • This example illustrates a stabilized composition of the present invention comprising CF 3 I, PAG oil, and farnesol.
  • a mixture (1 .6 grams) of trifluoroiodomethane (25 wt. %) and HFO- 1234yf (75 wt. %) is added to 3 grams of a composition containing 99% by weight of PAG oil and 1 % by weight of farnesol.
  • the resulting mixture is placed into a glass tube with metal coupons of aluminum, steel, and copper, and the tube is then sealed.
  • the sealed glass tube is put into an oven at 300°F for two weeks. After such time the tube is removed and observed.
  • the mixture is one phase, indicating that the refrigerant has during the period remained miscible and soluble in the PAG oil.
  • the liquid in the tube is clear with a light yellow color. The steel coupon appears unchanged.
  • HFC-23 trifluoromethane
  • This example illustrates a stabilized composition of the present invention comprising CF 3 I, PAG oil, and geraniol.
  • a mixture (1 .6 grams) of trifluoroiodomethane (25 wt. %) and HFO- 1234yf (75 wt. %) is added to 3 grams of a composition containing 99% by weight of PAG oil and 1 % by weight of geraniol.
  • the resulting mixture is placed into a glass tube with metal coupons of aluminum, steel, and copper, and the tube is then sealed.
  • the sealed glass tube is put into an oven at 300°F for two weeks. After such time the tube is removed and observed.
  • the mixture is one phase, indicating that the refrigerant has during the period remained miscible and soluble in the PAG oil.
  • the liquid in the tube is clear with a light yellow color. The steel coupon appears unchanged.
  • HFC-23 trifluoromethane
  • This example illustrates a stabilized composition of the present invention comprising CF 3 I, polyalkylene glycol lubricant, and myrcene with a triphenylphosphite (DP213-available from Dover Chemical) as additives in the oil.
  • DP213-available from Dover Chemical triphenylphosphite
  • the resulting mixture is placed into a glass tube with metal coupons of aluminum, steel, and copper, and the tube is then sealed. The sealed glass tube is put into an oven at 300°F for two weeks. After such time the tube is removed and observed.
  • the mixture is one phase, indicating that the iodocarbon compound during this period remains miscible and soluble in the PAG oil.
  • the liquid in the tube is clear with a light yellow color. The steel coupon appears unchanged.
  • the glass tube is opened and the gas is extracted.
  • the gas is examined by gas chromatography for the presence of HFC-23, which is a decomposition product of the oil reacting with the trifluoroiodide.
  • the level of HFC-23 found is about 0.2 wt. %.
  • This example illustrates a stabilized composition of the present invention comprising CF 3 I and polyalkylene glycol lubricant, and a stabilizer consisting of myrcene.
  • Trifluoroiodomethane (1 .6 grams) is added to 3 grams of the polyalkylene glycol lubricant containing myrcene, with the myrcene being present on the basis of 1 wt.% based on the total weight of the lubricant.
  • the resulting mixture is placed into a glass tube with metal coupons of aluminum, steel, and copper and the tube is sealed.
  • the sealed glass tube is put into an oven at 300°F for two weeks. After such time the tube is removed and observed.
  • the mixture is one phase, indicating that the refrigerant is miscible and soluble in the PAG oil.
  • the liquid in the tube is clear with a light yellow color. The steel coupon appears unchanged.
  • HFC-23 trifluoromethane
  • a mixture (1 .6 grams) of trifluoroiodomethane (25 wt. %) and HFO- 1234yf (75 wt. %) is added to 3 grams of mineral oil.
  • the mineral oil contained 0.5 wt. % of myrcene and 0.5 wt. % Doverphos DP-213.
  • the resulting mixture is placed into a glass tube with metal coupons of aluminum, steel, and copper, and the tube is then sealed. The sealed glass tube is put into an oven at 300°F for two weeks. After such time the tube is removed.
  • the glass tube was opened and the gas was extracted.
  • the gas was examined by gas chromatography for the presence of
  • HFC-23 trifluoromethane
  • the level of HFC-23 found is 0.08 wt. %.
  • the experiment is repeated and the result is 0.08 wt% of HFC-23.
  • the resulting mixture is placed into a glass tube with metal coupons of aluminum, steel, and copper, and the tube is then sealed. The sealed glass tube is put into an oven at 300°F for two weeks. After such time the tube is removed and observed.
  • the mixture is one phase, indicating that the refrigerant composition during this period remains miscible and soluble in the mineral oil.
  • the metal coupons are discolored and the color of the lubricant is dark brown.
  • the glass tube is opened and the gas is extracted.
  • the gas is examined by gas chromatography for the presence of HFC-23 that is decomposition product of the oil reacting with the trifluoroiodide. The level of HFC-23 found is about 1 .0 wt. %.
  • a mixture (1 .6 grams) of trifluoroiodomethane (25 wt. %) and HFO- 1234yf (75 wt. %) is added to 3 grams of mineral oil.
  • the resulting mixture is placed into a glass tube with metal coupons of aluminum, steel, and copper, and the tube is then sealed. The sealed glass tube is put into an oven at 300°F for two weeks.
  • HFC-23 trifluoromethane
  • compositions of the present invention comprising a 30/70 blend of CF 3 l/HFO-1234yf, PAG oil (RL-897), and a stabilization compound.
  • RL-897 a 30/70 blend of CF 3 l/HFO-1234yf
  • PAG oil RL-897
  • a stabilization compound a 30/70 blend of CF 3 l/HFO-1234yf, PAG oil (RL-897), and a stabilization compound.
  • results for the stabilizers phosphate, 2,4-dimethyl-6-tert- butylphenol, allyl glycidyl ether, tocopherol, and hexane glycidyl ether indicate that breakdown of CF 3 I to R23 is reduced in the 30/70 blend of CF 3 l/HFO-1234yf.
  • compositions of the present invention comprising a 30/70 blend of CF 3 l/HFC-32, PAG oil (ND-8), and a stabilization compound.
  • ND-8 PAG oil
  • stabilization compound Two grams of ND-8 and two grams of CF 3 I/HFC- 32 blend were put into a sealed glass tube along with a metal assembly made of aluminum, steel and copper. The sealed tube was put into an oven at 300°C for 1 week. The tubes were removed from the oven, cooled, opened, and the gas is extracted.
  • the breakdown products of CF 3 I will be R- 23 in the gas phase and iodide ions in the oil.
  • the oil was therefore analyzed for the amount of iodide in it.
  • the gas was analyzed for the amount of R23 in it.
  • the baseline for 30/70 blend produces 0.73% R23 and an iodide concentration of 195 ppm.
  • the amount of R23 produced is greater, indicating that certain additives may be harmful.
  • the corresponding iodide concentrations are either greater or not much reduced.
  • Results for farnesol as used in the 10/90 CF 3 l/HFC-32 blend demonstrates a reduction in both the R23 and iodide concentrations.

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PCT/US2013/029256 2012-03-13 2013-03-06 Stabilized iodocarbon compositions WO2013138123A1 (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9410105B2 (en) 2012-11-16 2016-08-09 Basf Se Lubricant compositions comprising epoxide compounds
US10301236B2 (en) 2015-05-21 2019-05-28 The Chemours Company Fc, Llc Hydrofluorination of a halogenated olefin with SbF5 in the liquid phase
WO2020002789A1 (fr) 2018-06-25 2020-01-02 Arkema France Stabilisation du trifluoroiodomethane
EP3666861A4 (en) * 2017-08-08 2021-04-07 Idemitsu Kosan Co., Ltd. REFRIGERATOR OIL COMPOSITION
WO2022164670A1 (en) * 2021-01-31 2022-08-04 Milliken & Company Stabilized lubricant compositions and heat transfer compositions containing the same
US11993742B2 (en) 2019-07-05 2024-05-28 Eneos Corporation Working fluid composition for refrigerator, and refrigerator oil
US12091606B2 (en) 2019-07-05 2024-09-17 Eneos Corporation Working fluid composition for refrigerator, refrigerator oil and refrigerator

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4342698A3 (en) * 2018-10-04 2024-06-12 The Chemours Company FC, LLC Azeotropic compositions of hfo-1234yf and hydrocarbons
JPWO2021015128A1 (enrdf_load_stackoverflow) * 2019-07-25 2021-01-28
US20220364007A1 (en) * 2019-09-27 2022-11-17 Idemitsu Kosan Co.,Ltd. Lubricating oil composition for refrigerators
US12221591B2 (en) * 2020-07-21 2025-02-11 Mitsubishi Electric Corporation Refrigeration cycle apparatus
JP7731862B2 (ja) * 2021-11-26 2025-09-01 ダイキン工業株式会社 組成物

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040256594A1 (en) * 2002-10-25 2004-12-23 Honeywell International, Inc. Compositions containing fluorine substituted olefins
US20090283712A1 (en) * 2008-05-15 2009-11-19 Honeywell International Inc. Sesquiterpene stabilized compositions
US20100282999A1 (en) * 2007-10-29 2010-11-11 Nippon Oil Corporation Refrigerator oil and working fluid composition for refrigerating machine
EP2292715A1 (en) * 2004-04-16 2011-03-09 Honeywell International Inc. Azeotrope-like compositions of tetrafluoropropene and trifluoroiodomethane

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11228946A (ja) * 1998-02-13 1999-08-24 Matsushita Electric Ind Co Ltd 混合作動流体およびそれを用いた冷凍サイクル装置
JP2000309789A (ja) * 1999-04-26 2000-11-07 Sanyo Electric Co Ltd 着火爆発性のない混合作動流体およびそれを用いた冷凍装置
US7341984B2 (en) * 2004-04-16 2008-03-11 Honeywell International Inc. Azeotrope-like compositions of tetrafluoropropene and trifluoroiodomethane
US7622435B2 (en) * 2004-04-16 2009-11-24 Honeywell International Inc. Methods of replacing refrigerant
MXPA06011978A (es) * 2004-04-16 2007-01-25 Honeywell Int Inc Composiciones estabilizadas de trifluoroyodometano.
MY155312A (en) * 2004-12-21 2015-09-30 Honeywell Int Inc Stabilized iodocarbon compositions
US8535556B2 (en) * 2006-03-30 2013-09-17 E I Du Pont De Nemours And Company Compositions comprising iodotrifluoromethane and stabilizers
US20100025619A1 (en) * 2006-07-12 2010-02-04 Solvay Fluor Gmbh Method for heating and cooling using fluoroether compounds, compositions suitable therefore and their use
US20100200799A1 (en) * 2007-09-28 2010-08-12 E.I. Du Pont De Nemours And Company Ionic liquid stabilizer compositions

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040256594A1 (en) * 2002-10-25 2004-12-23 Honeywell International, Inc. Compositions containing fluorine substituted olefins
EP2292715A1 (en) * 2004-04-16 2011-03-09 Honeywell International Inc. Azeotrope-like compositions of tetrafluoropropene and trifluoroiodomethane
US20100282999A1 (en) * 2007-10-29 2010-11-11 Nippon Oil Corporation Refrigerator oil and working fluid composition for refrigerating machine
US20090283712A1 (en) * 2008-05-15 2009-11-19 Honeywell International Inc. Sesquiterpene stabilized compositions

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP2825610A4 *

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9410105B2 (en) 2012-11-16 2016-08-09 Basf Se Lubricant compositions comprising epoxide compounds
US10301236B2 (en) 2015-05-21 2019-05-28 The Chemours Company Fc, Llc Hydrofluorination of a halogenated olefin with SbF5 in the liquid phase
US10988422B2 (en) 2015-05-21 2021-04-27 The Chemours Company Fc, Llc Hydrofluoroalkane composition
US11008267B2 (en) 2015-05-21 2021-05-18 The Chemours Company Fc, Llc Hydrofluoroalkane composition
US11572326B2 (en) 2015-05-21 2023-02-07 The Chemours Company Fc, Llc Method for preparing 1,1,1,2,2-pentafluoropropane
US12006274B2 (en) 2015-05-21 2024-06-11 The Chemours Company Fc, Llc Compositions including olefin and hydrofluoroalkane
EP3666861A4 (en) * 2017-08-08 2021-04-07 Idemitsu Kosan Co., Ltd. REFRIGERATOR OIL COMPOSITION
WO2020002789A1 (fr) 2018-06-25 2020-01-02 Arkema France Stabilisation du trifluoroiodomethane
US11993742B2 (en) 2019-07-05 2024-05-28 Eneos Corporation Working fluid composition for refrigerator, and refrigerator oil
US12091606B2 (en) 2019-07-05 2024-09-17 Eneos Corporation Working fluid composition for refrigerator, refrigerator oil and refrigerator
WO2022164670A1 (en) * 2021-01-31 2022-08-04 Milliken & Company Stabilized lubricant compositions and heat transfer compositions containing the same
US11725159B2 (en) 2021-01-31 2023-08-15 Milliken & Company Stabilized lubricant compositions and heat transfer compositions containing the same

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EP2825610A1 (en) 2015-01-21

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