WO2006094303A2 - Compositions comprising a fluoroolefin - Google Patents

Compositions comprising a fluoroolefin Download PDF

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Publication number
WO2006094303A2
WO2006094303A2 PCT/US2006/008164 US2006008164W WO2006094303A2 WO 2006094303 A2 WO2006094303 A2 WO 2006094303A2 US 2006008164 W US2006008164 W US 2006008164W WO 2006094303 A2 WO2006094303 A2 WO 2006094303A2
Authority
WO
WIPO (PCT)
Prior art keywords
weight percent
hfc
trans
weight
dimethylether
Prior art date
Application number
PCT/US2006/008164
Other languages
French (fr)
Other versions
WO2006094303A3 (en
Inventor
Barbara Haviland Minor
Velliyur Nott Mallikarjuna Rao
Donald Bernard Bivens
Deepak Perti
Original Assignee
E.I. Dupont De Nemours And Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=37233567&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2006094303(A2) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by E.I. Dupont De Nemours And Company filed Critical E.I. Dupont De Nemours And Company
Priority to EP14161825.6A priority Critical patent/EP2749623B2/en
Priority to EP19165699.0A priority patent/EP3524657B1/en
Priority to EP08014611.1A priority patent/EP1985680B2/en
Priority to PL17208709T priority patent/PL3330339T3/en
Priority to PL14161825.6T priority patent/PL2749623T5/en
Priority to EP18159202.3A priority patent/EP3348624B1/en
Priority to PL19165699T priority patent/PL3524657T3/en
Priority to PT182026542T priority patent/PT3461871T/en
Priority to EP20190991.8A priority patent/EP3786254A1/en
Priority to EP17179475.3A priority patent/EP3260516B1/en
Priority to PL18180357T priority patent/PL3406686T3/en
Priority to EP10010778.8A priority patent/EP2258791B1/en
Priority to EP17183434.4A priority patent/EP3263671B1/en
Priority to BR122017022773-4A priority patent/BR122017022773B1/en
Priority to EP22175443.5A priority patent/EP4074807A1/en
Priority to EP18202654.2A priority patent/EP3461871B1/en
Priority to EP18180357.8A priority patent/EP3406686B1/en
Priority to PL19171478.1T priority patent/PL3543310T5/en
Priority to EP17193353.4A priority patent/EP3299435B1/en
Priority to PL17203942.2T priority patent/PL3309233T5/en
Priority to PL18154365T priority patent/PL3351609T3/en
Priority to EP18154365.3A priority patent/EP3351609B1/en
Priority to PL18208197T priority patent/PL3470492T3/en
Priority to BR122017022767-0A priority patent/BR122017022767B1/en
Priority to EP18186309.3A priority patent/EP3428242A1/en
Priority to PL17188278T priority patent/PL3275965T3/en
Priority to EP17179466.2A priority patent/EP3255115B1/en
Priority to EP18164734.8A priority patent/EP3388495B1/en
Priority to CA2600319A priority patent/CA2600319C/en
Priority to EP18180358.6A priority patent/EP3406687A1/en
Priority to NO20231079A priority patent/NO20231079A1/en
Priority to EP18208197.6A priority patent/EP3470492B1/en
Priority to PL18169944.8T priority patent/PL3378919T5/en
Priority to EP06737345.6A priority patent/EP1853679B1/en
Priority to ES06737345.6T priority patent/ES2561114T3/en
Priority to BR122017022747-5A priority patent/BR122017022747B1/en
Priority to BRPI0607994-6A priority patent/BRPI0607994B1/en
Priority to KR1020077022509A priority patent/KR101368127B1/en
Priority to EP17198734.0A priority patent/EP3293242B1/en
Priority to EP17188278.0A priority patent/EP3275965B1/en
Priority to EP19171478.1A priority patent/EP3543310B2/en
Priority to MX2007010758A priority patent/MX2007010758A/en
Priority to JP2007558341A priority patent/JP5001181B2/en
Priority to PL17198734T priority patent/PL3293242T3/en
Priority to PL17179485.2T priority patent/PL3255116T5/en
Priority to BR122017022761-0A priority patent/BR122017022761B1/en
Priority to EP19177627.7A priority patent/EP3553119B1/en
Priority to PL06737345T priority patent/PL1853679T3/en
Priority to EP17179485.2A priority patent/EP3255116B2/en
Priority to MX2013003225A priority patent/MX361577B/en
Priority to EP17208709.0A priority patent/EP3330339B1/en
Priority to KR1020127030484A priority patent/KR101506777B1/en
Priority to EP18169944.8A priority patent/EP3378919B2/en
Priority to BR122017022758-0A priority patent/BR122017022758B1/en
Priority to PL17179475T priority patent/PL3260516T3/en
Priority to EP18182081.2A priority patent/EP3425017B1/en
Priority to PL17179466T priority patent/PL3255115T3/en
Priority to PL18159202T priority patent/PL3348624T3/en
Priority to EP17203942.2A priority patent/EP3309233B2/en
Priority to AU2006218376A priority patent/AU2006218376B2/en
Priority to PL17183434T priority patent/PL3263671T3/en
Priority to EP18180356.0A priority patent/EP3406685A1/en
Priority to PL18202654T priority patent/PL3461871T3/en
Publication of WO2006094303A2 publication Critical patent/WO2006094303A2/en
Publication of WO2006094303A3 publication Critical patent/WO2006094303A3/en
Priority to NO20074989A priority patent/NO347752B1/en

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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00Heat-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
    • C09K5/02Materials undergoing a change of physical state when used
    • C09K5/04Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
    • C09K5/041Materials 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
    • C09K5/044Materials 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
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/149Mixtures of blowing agents covered by more than one of the groups C08J9/141 - C08J9/143
    • AHUMAN NECESSITIES
    • A62LIFE-SAVING; FIRE-FIGHTING
    • A62DCHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D1/00Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
    • A62D1/0028Liquid extinguishing substances
    • A62D1/0057Polyhaloalkanes
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/143Halogen containing compounds
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K3/00Materials not provided for elsewhere
    • C09K3/30Materials not provided for elsewhere for aerosols
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00Heat-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
    • C09K5/02Materials undergoing a change of physical state when used
    • C09K5/04Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00Heat-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
    • C09K5/02Materials undergoing a change of physical state when used
    • C09K5/04Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
    • C09K5/041Materials 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
    • C09K5/044Materials 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
    • C09K5/045Materials 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
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M171/00Lubricating 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
    • C10M171/008Lubricant compositions compatible with refrigerants
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00Foams characterized by the expanding agent
    • C08J2203/12Organic compounds only containing carbon, hydrogen and oxygen atoms, e.g. ketone or alcohol
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00Foams characterized by the expanding agent
    • C08J2203/14Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00Foams characterized by the expanding agent
    • C08J2203/14Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • C08J2203/142Halogenated saturated hydrocarbons, e.g. H3C-CF3
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2207/00Foams characterised by their intended use
    • C08J2207/04Aerosol, e.g. polyurethane foam spray
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/10Components
    • C09K2205/106Carbon dioxide
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    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/10Components
    • C09K2205/11Ethers
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    • C09K2205/00Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/10Components
    • C09K2205/12Hydrocarbons
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    • C09K2205/00Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/10Components
    • C09K2205/12Hydrocarbons
    • C09K2205/122Halogenated hydrocarbons
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    • C09K2205/00Aspects relating to compounds used in compression type refrigeration systems
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    • C09K2205/12Hydrocarbons
    • C09K2205/126Unsaturated fluorinated hydrocarbons
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    • C09K2205/00Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/10Components
    • C09K2205/134Components containing sulfur
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/06Well-defined aromatic compounds
    • C10M2203/065Well-defined aromatic compounds used as base material
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/1006Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/0206Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers used as base material
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28Esters
    • C10M2207/283Esters of polyhydroxy compounds
    • C10M2207/2835Esters of polyhydroxy compounds used as base material
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/04Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol or ester thereof; bound to an aldehyde, ketonic, ether, ketal or acetal radical
    • C10M2209/043Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol or ester thereof; bound to an aldehyde, ketonic, ether, ketal or acetal radical used as base material
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/1033Polyethers, i.e. containing di- or higher polyoxyalkylene groups used as base material
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/09Characteristics associated with water
    • C10N2020/097Refrigerants
    • C10N2020/101Containing Hydrofluorocarbons
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/09Characteristics associated with water
    • C10N2020/097Refrigerants
    • C10N2020/103Containing Hydrocarbons
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25BREFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B2400/00General features or devices for refrigeration machines, plants or systems, combined heating and refrigeration systems or heat-pump systems, i.e. not limited to a particular subgroup of F25B
    • F25B2400/12Inflammable refrigerants
    • F25B2400/121Inflammable refrigerants using R1234

Definitions

  • the present invention relates to compositions for use in refrigeration, air-conditioning, and heat pump systems wherein the composition comprises a fluoroolefin and at least one other component.
  • the compositions of the present invention are useful in processes for producing cooling or heat, as heat transfer fluids, foam blowing agents, aerosol propellants, and fire suppression and fire extinguishing agents.
  • the object of the present invention is to provide novel refrigerant compositions and heat transfer fluid compositions that provide unique characteristics to meet the demands of low or zero ozone depletion potential and lower global warming potential as compared to current refrigerants.
  • the present invention relates to a composition
  • a composition comprising HFC-1225ye and at least one compound selected from the group consisting of:
  • the present invention further relates to a composition
  • a composition comprising HFC-1234ze and at least one compound selected from the group consisting of: HFC-1234yf, HFC-1234ye, HFC-1243zf, HFC-32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161 , HFC- 227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, n- butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethylether, CF 3 SCF 3 , CO 2 and CF 3 I.
  • the present invention further relates to a composition
  • a composition comprising HFC-1234yf and at least one compound selected from the group consisting of: HFC-1234ye, HFC-1243zf, HFC-32, HFC-125, HFC- 134, HFC-134a, HFC-143a, HFC-152a, HFC-161 , HFC-227ea, HFC- 236ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethylether, CF 3 SCF 3 , CO 2 and CF 3 I.
  • the present invention further relates to a composition
  • a composition comprising HFC-1234ye and at least one compound selected from the group consisting of: HFC-1243zf, HFC-32, HFC-125, HFC-134, HFC- 134a, HFC-143a, HFC-152a, HFC-161 , HFC-227ea, HFC-236ea, HFC- 236fa, HFC-245fa, HFC-365mfc, propane, n-butane, isobutane, 2- methylbutane, n-pentane, cyclopentane, dimethylether, CF 3 SCF 3 , CO 2 and CF 3 I.
  • the present invention further relates to a composition comprising HFC-1243zf and at least one compound selected from the group consisting of: HFC-32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161 , HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethylether, CF 3 SCF 3 , CO 2 and CF 3 I.
  • the present invention further relates to a composition comprising:
  • At least one lubricant selected from the group consisting of polyol esters, polyalkylene glycol, polyvinyl ethers, mineral oils, alkylbenzenes, synthetic paraffins, synthetic napthenes, and poly(alpha)olefins; and
  • composition selected from the group consisting of: about 1 weight percent to about 99 weight percent HFC-
  • the present invention further relates to a composition
  • a composition comprising: a) a refrigerant or heat transfer fluid composition selected from the group consisting of: about 1 weight percent to about 99 weight percent HFC-
  • Ri through Rs are independently selected from hydrogen, linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl radicals; and the molecular weight is from about 100 to about 300 atomic mass units; and x) esters represented by the general formula R 1 CO 2 R 2 , wherein R 1 and R 2 are independently selected from linear and cyclic, saturated and unsaturated, alkyl and aryl radicals; and wherein said esters have a molecular weight of from about 80 to about 550 atomic mass units.
  • the present invention further relates to a composition
  • a composition comprising: (a) at least one ultra-violet fluorescent dye selected from the group consisting of naphthalimides, perylenes, coumarins, anthracenes, phenanthracenes, xanthenes, thioxanthenes, naphthoxanthenes, fluoresceins, derivatives of said dye and combinations thereof; and
  • composition selected from the group consisting of: about 1 weight percent to about 99 weight percent HFC-
  • the present invention further relates to a method of solubilizing a refrigerant or heat transfer fluid composition in a refrigeration lubricant selected from the group consisting of mineral oils, alkylbenzenes, synthetic paraffins, synthetic napthenes, and poly(alpha)olefins, wherein said method comprises contacting said lubricant with said refrigerant or heat transfer fluid composition in the presence of an effective amount of a compatibilizer, wherein said refrigerant or heat transfer fluid comprises a composition selected from the group consisting of: about 1 weight percent to about 99 weight percent HFC- 1225ye and about 99 weight percent to about 1 weight percent HFC-152a; about 1 weight percent to about 99 weight percent HFC- 1225ye and about 99 weight percent to about 1 weight percent
  • HFC-1234yf about 1 weight percent to about 99 weight percent HFC- 1225ye and about 99 weight percent to about 1 weight percent trans-HFC-1234ze; about 1 weight percent to about 99 weight percent HFC-
  • HFC-227ea and about 1 weight percent to about 99 weight percent trans- HFC-1234ze and about 99 weight percent to about 1 weight percent CF 3 I; and wherein said compatibilizer is selected from the group consisting of: a) polyoxyalkylene glycol ethers represented by the formula R 1 [(OR 2 ) x OR 3 ] y , wherein: x is an integer from 1 to 3; y is an integer from 1 to 4; R 1 is selected from hydrogen and aliphatic hydrocarbon radicals having 1 to 6 carbon atoms and y bonding sites; R 2 is selected from aliphatic hydrocarbylene radicals having from 2 to 4 carbon atoms; R 3 is selected from hydrogen, and aliphatic and alicyclic hydrocarbon radicals having from 1 to 6 carbon atoms; at least one of R 1 and R 3 is selected from said hydrocarbon radicals; and wherein said polyoxyalkylene glycol ethers have a molecular weight of from about 100 to about 300 atomic mass units; b) amides
  • Ri through Rs are independently selected from hydrogen, linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl radicals; and the molecular weight is from about 100 to about 300 atomic mass units; and j) esters represented by the general formula R 1 CO 2 R 2 , wherein R 1 and R 2 are independently selected from linear and cyclic, saturated and unsaturated, alkyl and aryl radicals; and wherein said esters have a molecular weight of from about 80 to about 550 atomic mass units.
  • the present invention further relates to a method for replacing a high GWP refrigerant in a refrigeration, air-conditioning, or heat pump apparatus, wherein said high GWP refrigerant is selected from the group consisting of R134a, R22, R123, R11 , R245fa, R114, R236fa, R124, R12, R410A, R407C, R417A, R422A, R507A, R502, and R404A, said method comprising providing a composition selected from the group consisting of: about 1 weight percent to about 99 weight percent HFC- 1225ye and about 99 weight percent to about 1 weight percent HFC-152a; about 1 weight percent to about 99 weight percent HFC-
  • the present invention further relates to a method for early detection of a refrigerant leak in a refrigeration, air-conditioning or heat pump apparatus said method comprising using a non-azeotropic composition in said apparatus, and monitoring for a reduction in cooling performance.
  • the present invention relates to compositions comprising at least one fluoroolefin.
  • the compositions of the present invention further comprise at least one additional component that may be a second fluoroolefin, hydrofluorocarbon (HFC), hydrocarbon, dimethyl ether, bis(trifluoromethyl)sulfide, CF 3 I, or CO 2 .
  • HFC hydrofluorocarbon
  • the fluoroolefin compounds and other components of the present inventive compositions are listed in Table 1.
  • the fluoroolefin compounds used in the compositions of the present invention may exist as different configurational isomers or stereoisomers.
  • the present invention is intended to include all single configurational isomers, single stereoisomers or any combination or mixture thereof.
  • 1 ,3,3,3-tetra-fluoropropene (HFC-1234ze) is meant to represent the cis- isomer, trans-isomer, or any combination or mixture of both isomers in any ratio.
  • HFC-1225ye by which is represented the cis- isomer, trans-isomer, or any combination or mixture of both isomers in any ratio.
  • compositions of the present invention include the following: HFC-1225ye and at least one compound selected from the group consisting of HFC-1234ze, HFC-1234yf, HFC-1234ye, HFC-1243zf, HFC- 32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161 , HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethylether, CF 3 SCF 3 , CO 2 and CF 3 I;
  • HFC-1234yf and at least one compound selected from the group consisting of HFC-1234ye, HFC-1243zf, HFC-32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161 , HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, n-butane, isobutane, 2- methylbutane, n-pentane, cyclopentane, dimethylether, CF 3 SCF 3 , CO 2 and CF 3 I; and HFC-1243zf and at least one compound selected from the group consisting of HFC-1234ye, HFC-32, HFC-125, HFC-134, HFC-134a, HFC- 143a, HFC-152a, HFC-161 , HFC-227ea, HFC-236ea, HFC-236fa, HFC-
  • compositions of the present invention may be generally useful when the fluoroolefin is present at about 1 weight percent to about 99 weight percent, preferably about 20 weight percent to about 99 weight percent, more preferably about 40 weight percent to about 99 weight percent and still more preferably 50 weight percent to about 99 weight percent.
  • the present invention further provides compositions as listed in Table 2.
  • compositions of the present invention listed in Table 2 are generally expected to maintain the desired properties and functionality when the components are present in the concentrations as listed +/- 2 weight percent.
  • compositions containing CO 2 would be expected to maintain the desired properties and functionality when the CO2 was present at the listed concentration +/- 0.2 weight percent.
  • compositions of the present invention may be azeotropic or near-azeotropic compositions.
  • azeotropic composition is meant a constant-boiling mixture of two or more substances that behave as a single substance.
  • One way to characterize an azeotropic composition is that the vapor produced by partial evaporation or distillation of the liquid has the same composition as the liquid from which it is evaporated or distilled, i.e., the mixture distills/refluxes without compositional change.
  • Constant-boiling compositions are characterized as azeotropic because they exhibit either a maximum or minimum boiling point, as compared with that of the non-azeotropic mixture of the same compounds.
  • An azeotropic composition will not fractionate within a refrigeration or air conditioning system during operation, which may reduce efficiency of the system. Additionally, an azeotropic composition will not fractionate upon leakage from a refrigeration or air conditioning system. In the situation where one component of a mixture is flammable, fractionation during leakage could lead to a flammable composition either within the system or outside of the system.
  • a near-azeotropic composition (also commonly referred to as an "azeotrope-like composition”) is a substantially constant boiling liquid admixture of two or more substances that behaves essentially as a single substance.
  • a near-azeotropic composition One way to characterize a near-azeotropic composition is that the vapor produced by partial evaporation or distillation of the liquid has substantially the same composition as the liquid from which it was evaporated or distilled, that is, the admixture distills/refluxes without substantial composition change.
  • Another way to characterize a near- azeotropic composition is that the bubble point vapor pressure and the dew point vapor pressure of the composition at a particular temperature are substantially the same.
  • a composition is near-azeotropic if, after 50 weight percent of the composition is removed, such as by evaporation or boiling off, the difference in vapor pressure between the original composition and the composition remaining after 50 weight percent of the original composition has been removed is less than about 10 percent.
  • Azeotropic compositions of the present invention at a specified temperature are shown in Table 3.
  • ternary azeotropes composition have been found as listed in Table 4.
  • compositions of the present invention are non- azeotropic compositions. Those compositions of the present invention falling within the preferred ranges of Table 2, but outside of the near- azeotropic ranges of Table 5 and Table 6 may be considered to be non- azeotropic.
  • a non-azeotropic composition may have certain advantages over azetropic or near azeotropic mixtures.
  • a non-azeotropic composition is a mixture of two or more substances that behaves as a mixture rather than a single substance.
  • One way to characterize a non-azeotropic composition is that the vapor produced by partial evaporation or distillation of the liquid has a substantially different composition as the liquid from which it was evaporated or distilled, that is, the admixture distills/refluxes with substantial composition change.
  • Another way to characterize a non- azeotropic composition is that the bubble point vapor pressure and the dew point vapor pressure of the composition at a particular temperature are substantially different.
  • compositions of the present invention may be prepared by any convenient method to combine the desired amounts of the individual components. A preferred method is to weigh the desired component amounts and thereafter combine the components in an appropriate vessel. Agitation may be used, if desired.
  • An alternative means for making compositions of the present invention may be a method for making a refrigerant blend composition, wherein said refrigerant blend composition comprises a composition as disclosed herein, said method comprising (i) reclaiming a volume of one or more components of a refrigerant composition from at least one refrigerant container, (ii) removing impurities sufficiently to enable reuse of said one or more of the reclaimed components, (iii) and optionally, combining all or part of said reclaimed volume of components with at least one additional refrigerant composition or component.
  • a refrigerant container may be any container in which is stored a refrigerant blend composition that has been used in a refrigeration apparatus, air-conditioning apparatus or heat pump apparatus.
  • Said refrigerant container may be the refrigeration apparatus, air-conditioning apparatus or heat pump apparatus in which the refrigerant blend was used.
  • the refrigerant container may be a storage container for collecting reclaimed refrigerant blend components, including but not limited to pressurized gas cylinders.
  • Residual refrigerant means any amount of refrigerant blend or refrigerant blend component that may be moved out of the refrigerant container by any method known for transferring refrigerant blends or refrigerant blend components.
  • Impurities may be any component that is in the refrigerant blend or refrigerant blend component due to its use in a refrigeration apparatus, air- conditioning apparatus or heat pump apparatus.
  • Such impurities include but are not limited to refrigeration lubricants, being those described earlier herein, particulates including but not limited to metal, metal salt or elastomer particles, that may have come out of the refrigeration apparatus, air-conditioning apparatus or heat pump apparatus, and any other contaminants that may adversely effect the performance of the refrigerant blend composition.
  • Such impurities may be removed sufficiently to allow reuse of the refrigerant blend or refrigerant blend component without adversely effecting the performance or equipment within which the refrigerant blend or refrigerant blend component will be used.
  • compositions of the present invention have zero or low ozone depletion potential and low global warming potential (GWP). Additionally, the compositions of the present invention will have global warming potentials that are less than many hydrofluorocarbon refrigerants currently in use.
  • One aspect of the present invention is to provide, a refrigerant with a global warming potential of less than 1000, less than 500, less than 150, less than 100, or less than 50.
  • Another aspect of the present invention is to reduce the net GWP of refrigerant mixtures by adding fluoroolefins to said mixtures.
  • compositions of the present invention may be useful as low global warming potential (GWP) replacements for currently used refrigerants, including but not limited to R134a (or HFC-134a, 1 ,1 ,1 ,2- tetrafluoroethane), R22 (or HCFC-22, chlorodifluoromethane), R123 (or HFC-123, 2,2-dichloro-1 ,1 I 1-trifluoroethane), R11 (CFC-11 , fluorotrichloromethane), R12 (CFC-12, dichlorodifluoromethane), R245fa (or HFC-245fa, 1 ,1 ,1 ,3,3-pentafluoropropane), R114 (or CFC-114, 1 ,2- dichloro-1 ,1 ,2,2-tetrafluoroethane), R236fa (or HFC-236fa, 1 ,1 ,1 ,3,3,3- hexafluoropropan
  • compositions of the present invention may be useful as replacements for R12 (CFC-12, dichlorodifluoromethane) or R502 (ASHRAE designation for a blend of 51.2 weight percent CFC-115 (chloropentafluoroethane) and 48.8 weight percent HCFC-22).
  • compositions of the present invention may be useful as replacements for the above-mentioned refrigerants in original equipment. Additionally, the compositions of the present invention may be useful as replacements for the above mentioned refrigerants in equipment designed to use the above-mentioned refrigerants.
  • the compositions of the present invention may further comprise a lubricant.
  • Lubricants of the present invention comprise refrigeration lubricants, i.e. those lubricants suitable for use with refrigeration, air- conditioning, or heat pump apparatus.
  • these lubricants are those conventionally used in compression refrigeration apparatus utilizing chlorofluorocarbon refrigerants. Such lubricants and their properties are discussed in the 1990 ASHRAE Handbook, Refrigeration Systems and Applications, chapter 8, titled “Lubricants in Refrigeration Systems", pages 8.1 through 8.21.
  • Lubricants of the present invention may comprise those commonly known as "mineral oils” in the field of compression refrigeration lubrication. Mineral oils comprise paraffins (i.e. straight-chain and branched-carbon-chain, saturated hydrocarbons), naphthenes (i.e.
  • Lubricants of the present invention further comprise those commonly known as "synthetic oils" in the field of compression refrigeration lubrication. Synthetic oils comprise alkylaryls (i.e. linear and branched alkyl alkylbenzenes), synthetic paraffins and napthenes, and poly(alphaolefins).
  • Representative conventional lubricants of the present invention are the commercially available BVM 100 N (paraffinic mineral oil sold by BVA Oils), Suniso® 3GS and Suniso® 5GS (naphthenic mineral oil sold by Crompton Co.), Sontex® 372LT (naphthenic mineral oil sold by Pennzoil), Calumet® RO-30 (naphthenic mineral oil sold by Calumet Lubricants), Zerol® 75, Zerol® 150 and Zerol® 500 (linear alkylbenzenes sold by Scheve Chemicals) and HAB 22 (branched alkylbenzene sold by Nippon Oil).
  • BVM 100 N paraffinic mineral oil sold by BVA Oils
  • Suniso® 3GS and Suniso® 5GS naphthenic mineral oil sold by Crompton Co.
  • Sontex® 372LT naphthenic mineral oil sold by Pennzoil
  • Calumet® RO-30 naphthenic mineral oil sold by Calumet Lubricants
  • Lubricants of the present invention further comprise those that have been designed for use with hydrofluorocarbon refrigerants and are miscible with refrigerants of the present invention under compression refrigeration, air-conditioning, or heat pump apparatus' operating conditions. Such lubricants and their properties are discussed in
  • Synthetic Lubricants and High-Performance Fluids include, but are not limited to, polyol esters (POEs) such as Castrol® 100 (Castrol, United Kingdom), polyalkylene glycols (PAGs) such as RL-488A from Dow (Dow Chemical, Midland, Michigan), and polyvinyl ethers (PVEs). These lubricants are readily available from various commercial sources.
  • POEs polyol esters
  • PAGs polyalkylene glycols
  • PVEs polyvinyl ethers
  • Lubricants of the present invention are selected by considering a given compressor's requirements and the environment to which the lubricant will be exposed.
  • Lubricants of the present invention preferably have a kinematic viscosity of at least about 5 cs (centistokes) at 4O 0 C.
  • Commonly used refrigeration system additives may optionally be added, as desired, to compositions of the present invention in order to enhance lubricity and system stability. These additives are generally known within the field of refrigeration compressor lubrication, and include anti wear agents, extreme pressure lubricants, corrosion and oxidation inhibitors, metal surface deactivators, free radical scavengers, foaming and antifoam control agents, leak detectants and the like.
  • these additives are present only in small amounts relative to the overall lubricant composition. They are typically used at concentrations of from less than about 0.1 % to as much as about 3 % of each additive. These additives are selected on the basis of the individual system requirements. Some typical examples of such additives may include, but are not limited to, lubrication enhancing additives, such as alkyl or aryl esters of phosphoric acid and of thiophosphates. Additionally, the metal dialkyl dithiophosphates (e.g. zinc dialkyl dithiophosphate or ZDDP, Lubrizol 1375) and other members of this family of chemicals may be used in compositions of the present invention.
  • lubrication enhancing additives such as alkyl or aryl esters of phosphoric acid and of thiophosphates.
  • the metal dialkyl dithiophosphates e.g. zinc dialkyl dithiophosphate or ZDDP, Lubrizol 1375
  • other members of this family of chemicals may be used in
  • antiwear additives include natural product oils and assymetrical polyhydroxyl lubrication additives such as Synergol TMS (International Lubricants).
  • stabilizers such as anti oxidants, free radical scavengers, and water scavengers may be employed.
  • Compounds in this category can include, but are not limited to, butylated hydroxy toluene (BHT) and epoxides.
  • compositions of the present invention may further comprise about 0.01 weight percent to about 5 weight percent of an additive such as, for example, a stabilizer, free radical scavenger and/or antioxidant.
  • an additive such as, for example, a stabilizer, free radical scavenger and/or antioxidant.
  • additives include but are not limited to, nitromethane, hindered phenols, hydroxylamines, thiols, phosphites, or lactones. Single additives or combinations may be used.
  • compositions of the present invention may further comprise about 0.01 weight percent to about 5 weight percent of a water scavenger (drying compound).
  • a water scavenger drying compound
  • Such water scavengers may comprise ortho esters such as trimethyl-, triethyl-, or tripropylortho formate.
  • compositions of the present invention may further comprise a tracer selected from the group consisting of hydrofluorocarbons (HFCs), deuterated hydrocarbons, deuterated hydrofluorocarbons, perfluorocarbons, fluoroethers, brominated compounds, iodated compounds, alcohols, aldehydes, ketones, nitrous oxide (N 2 O) and combinations thereof.
  • HFCs hydrofluorocarbons
  • deuterated hydrocarbons deuterated hydrofluorocarbons
  • perfluorocarbons perfluorocarbons
  • fluoroethers brominated compounds
  • iodated compounds alcohols
  • aldehydes aldehydes
  • ketones nitrous oxide
  • N 2 O nitrous oxide
  • Single tracer compounds may be used in combination with a refrigeration/heating fluid in the compositions of the present invention or multiple tracer compounds may be combined in any proportion to serve as a tracer blend.
  • the tracer blend may contain multiple tracer compounds from the same class of compounds or multiple tracer compounds from different classes of compounds.
  • a tracer blend may contain 2 or more deuterated hydrofluorocarbons, or one deuterated hydrofluorocarbon in combination with one or more perfluorocarbons.
  • the tracer compound or tracer blend may be present in the compositions at a total concentration of about 50 parts per million by weight (ppm) to about 1000 ppm.
  • the tracer compound or tracer blend is present at a total concentration of about 50 ppm to about 500 ppm and most preferably, the tracer compound or tracer blend is present at a total concentration of about 100 ppm to about 300 ppm.
  • compositions of the present invention may further comprise a compatibilizer selected from the group consisting of polyoxyalkylene glycol ethers, amides, nitriles, ketones, chlorocarbons, esters, lactones, aryl ethers, fluoroethers and 1 ,1 ,1-trifluoroalkanes.
  • the compatibilizer is used to improve solubility of hydrofluorocarbon refrigerants in conventional refrigeration lubricants. Refrigeration lubricants are needed to lubricate the compressor of a refrigeration, air-conditioning or heat pump apparatus. The lubricant must move throughout the apparatus with the refrigerant in particular it must return from the non-compressor zones to the compressor to continue to function as lubricant and avoid compressor failure.
  • Hydrofluorocarbon refrigerants are generally not compatible with convention refrigeration lubricants such as mineral oils, alkylbenzenes, synthetic paraffins, synthetic napthenes and poly(alpha)olefins. Many replacement lubricants have been proposed, however, the polyalkylene glycols, polyol esters and polyvinyl ethers, suggested for use with hydrofluorocarbon refrigerants are expensive and absorb water readily. Water in a refrigeration, air-conditioning system or heat pump can lead to corrosion and the formation of particles that may plug the capillary tubes and other small orifices in the system, ultimately causing system failure. Additionally, in existing equipment, time-consuming and costly flushing procedures are required to change to a new lubricant. Therefore, it is desirable to continue to use the original lubricant if possible.
  • the compatibilizers of the present invention improve solubility of the hydrofluorocarbon refrigerants in conventional refrigeration lubricants and thus improve oil return to the compressor.
  • Polyoxyalkylene glycol ether compatibilizers of the present invention are represented by the formula R 1 [(OR 2 ) x OR 3 ] y , wherein: x is an integer from 1-3; y is an integer from 1-4; R 1 is selected from hydrogen and aliphatic hydrocarbon radicals having 1 to 6 carbon atoms and y bonding sites; R 2 is selected from aliphatic hydrocarbylene radicals having from 2 to 4 carbon atoms; R 3 is selected from hydrogen and aliphatic and alicyclic hydrocarbon radicals having from 1 to 6 carbon atoms; at least one of R 1 and R 3 is said hydrocarbon radical; and wherein said polyoxyalkylene glycol ethers have a molecular weight of from about 100 to about 300 atomic mass units.
  • bonding sites mean radical sites available to form covalent bonds with other radicals.
  • Hydrocarbylene radicals mean divalent hydrocarbon radicals.
  • preferred polyoxyalkylene glycol ether compatibilizers are represented by R 1 [(OR 2 ) x OR 3 ] y : x is preferably 1-2; y is preferably 1 ; R 1 and R 3 are preferably independently selected from hydrogen and aliphatic hydrocarbon radicals having 1 to 4 carbon atoms; R 2 is preferably selected from aliphatic hydrocarbylene radicals having from 2 or 3 carbon atoms, most preferably 3 carbon atoms; the polyoxyalkylene glycol ether molecular weight is preferably from about 100 to about 250 atomic mass units, most preferably from about 125 to about 250 atomic mass units.
  • the R 1 and R 3 hydrocarbon radicals having 1 to 6 carbon atoms may be linear, branched or cyclic.
  • Representative R 1 and R 3 hydrocarbon radicals include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, te/f-butyl, pentyl, isopentyl, neopentyl, ferf-pentyl, cyclopentyl, and cyclohexyl.
  • free hydroxyl radicals on the present polyoxyalkylene glycol ether compatibilizers may be incompatible with certain compression refrigeration apparatus materials of construction (e.g.
  • R 1 and R 3 are preferably aliphatic hydrocarbon radicals having 1 to 4 carbon atoms, most preferably 1 carbon atom.
  • the R 2 aliphatic hydrocarbylene radicals having from 2 to 4 carbon atoms form repeating oxyalkylene radicals - (OR 2 ) X - that include oxyethylene radicals, oxypropylene radicals, and oxybutylene radicals.
  • the oxyalkylene radical comprising R 2 in one polyoxyalkylene glycol ether compatibilizer molecule may be the same, or one molecule may contain different R 2 oxyalkylene groups.
  • the present polyoxyalkylene glycol ether compatibilizers preferably comprise at least one oxypropylene radical.
  • R 1 is an aliphatic or alicyclic hydrocarbon radical having 1 to 6 carbon atoms and y bonding sites
  • the radical may be linear, branched or cyclic.
  • Representative R 1 aliphatic hydrocarbon radicals having two bonding sites include, for example, an ethylene radical, a propylene radical, a butylene radical, a pentylene radical, a hexylene radical, a cyclopentylene radical and a cyclohexylene radical.
  • R 1 aliphatic hydrocarbon radicals having three or four bonding sites include residues derived from polyalcohols, such as trimethylolpropane, glycerin, pentaerythritol, 1 ,2,3-trihydroxycyclohexane and 1 ,3,5- trihydroxycyclohexane, by removing their hydroxyl radicals.
  • Representative polyoxyalkylene glycol ether compatibilizers include but are not limited to: CH 3 OCH 2 CH(CH 3 )O(H or CH 3 ) (propylene glycol methyl (or dimethyl) ether), CH 3 O[CH 2 CH(CH 3 )O] 2 (H or CH 3 ) (dipropylene glycol methyl (or dimethyl) ether), CH 3 O[CH 2 CH(CH 3 )O] 3 (H or CH 3 )
  • Amide compatibilizers of the present invention comprise those represented by the formulae R 1 C(O)NR 2 R 3 and cyclo-[R 4 C(O)N(R 5 )], wherein R 1 , R 2 , R 3 and R 5 are independently selected from aliphatic and alicyclic hydrocarbon radicals having from 1 to 12 carbon atoms; R 4 is selected from aliphatic hydrocarbylene radicals having from 3 to 12 carbon atoms; and wherein said amides have a molecular weight of from about 10O to about 300 atomic mass units. The molecular weight of said amides is preferably from about 160 to about 250 atomic mass units.
  • R 1 , R 2 , R 3 and R 5 may optionally include substituted hydrocarbon radicals, that is, radicals containing non-hydrocarbon substituents selected from halogens (e.g., fluorine, chlorine) and alkoxides (e.g. methoxy).
  • R 1 , R 2 , R 3 and R 5 may optionally include heteroatom-substituted hydrocarbon radicals, that is, radicals, which contain the atoms nitrogen (aza-), oxygen (oxa-) or sulfur (thia-) in a radical chain otherwise composed of carbon atoms.
  • amide compatibilizers consist of carbon, hydrogen, nitrogen and oxygen.
  • R 1 , R 2 , R 3 and R 5 aliphatic and alicyclic hydrocarbon radicals include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, fe/f-butyl, pentyl, isopentyl, neopentyl, terf-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and their configurational isomers.
  • a preferred embodiment of amide compatibilizers are those wherein R 4 in the aforementioned formula cyclo-[R 4 C(O)N(R 5 )-] may be represented by the hydrocarbylene radical (CR 6 R 7 ) n , in other words, the formula: cyclo-[(CR 6 R 7 ) n C(O)N(R 5 )-] wherein: the previously-stated values for molecular weight apply; n is an integer from 3 to 5; R 5 is a saturated hydrocarbon radical containing 1 to 12 carbon atoms; R 6 and R 7 are independently selected (for each n) by the rules previously offered defining R 1'3 .
  • R 6 and R 7 are preferably hydrogen, or contain a single saturated hydrocarbon radical among the n methylene units, and R 5 is a saturated hydrocarbon radical containing 3 to 12 carbon atoms.
  • R 5 is a saturated hydrocarbon radical containing 3 to 12 carbon atoms.
  • amide compatibilizers include but are not limited to: 1-octylpyrrolidin-2-one, 1-decylpyrrolidin-2-one, 1-octyl-5-methylpyrrolidin- 2-one, 1-butylcaprolactam, 1-cyclohexylpyrrolidin-2-one, 1 -butyl-5- methylpiperid-2-one, 1-pentyl-5-methylpiperid-2-one, 1-hexylcaprolactam, 1-hexyl-5-methylpyrrolidin-2-one, 5-methyl-1-pentylpiperid-2-one, 1 ,3- dimethylpiperid-2-one, 1-methylcaprolactam, 1-butyl-pyrrolidin-2-one, 1 ,5- dimethylpiperid-2-one, 1-decyl-5-methyIpyrrolidin-2-one, 1-dodecylpyrrolid- 2-one, N,N-dibutylformamide and N,N-diisopropylacet
  • Ketone compatibilizers of the present invention comprise ketones represented by the formula R 1 C(O)R 2 , wherein R 1 and R 2 are independently selected from aliphatic, alicyclic and aryl hydrocarbon radicals having from 1 to 12 carbon atoms, and wherein said ketones have a molecular weight of from about 70 to about 300 atomic mass units.
  • R 1 and R 2 in said ketones are preferably independently selected from aliphatic and alicyclic hydrocarbon radicals having 1 to 9 carbon atoms.
  • the molecular weight of said ketones is preferably from about 100 to 200 atomic mass units.
  • R 1 and R 2 may together form a hydrocarbylene radical connected and forming a five, six, or seven-membered ring cyclic ketone, for example, cyclopentanone, cyclohexanone, and cycloheptanone.
  • R 1 and R 2 may optionally include substituted hydrocarbon radicals, that is, radicals containing non-hydrocarbon substituents selected from halogens (e.g., fluorine, chlorine) and alkoxides (e.g. methoxy).
  • R 1 and R 2 may optionally include heteroatom-substituted hydrocarbon radicals, that is, radicals, which contain the atoms nitrogen (aza-), oxygen (keto-, oxa-) or sulfur (thia-) in a radical chain otherwise composed of carbon atoms.
  • heteroatom-substituted hydrocarbon radicals that is, radicals, which contain the atoms nitrogen (aza-), oxygen (keto-, oxa-) or sulfur (thia-) in a radical chain otherwise composed of carbon atoms.
  • no more than three non-hydrocarbon substituents and heteroatoms, and preferably no more than one, will be present for each 10 carbon atoms in R 1 and R 2 , and the presence of any such non- hydrocarbon substituents and heteroatoms must be considered in applying the aforementioned molecular weight limitations.
  • R 1 and R 2 aliphatic, alicyclic and aryl hydrocarbon radicals in the general formula R 1 C(O)R 2 include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, teff-butyl, pentyl, isopentyl, neopentyl, ferf-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and their configu rational isomers, as well as phenyl, benzyl, cumenyl, mesityl, tolyl, xylyl and phenethyl.
  • ketone compatibilizers include but are not limited to: 2-butanone, 2-pentanone, acetophenone, butyrophenone, hexanophenone, cyclohexanone, cycloheptanone, 2-heptanone, 3- heptanone, 5-methyl-2-hexanone, 2-octanone, 3-octanone, diisobutyl ketone, 4-ethylcyclohexanone, 2-nonanone, 5-nonanone, 2-decanone, 4- decanone, 2-decalone, 2-tridecanone, dihexyl ketone and dicyclohexyl ketone.
  • Nitrile compatibilizers of the present invention comprise nitriles represented by the formula R 1 CN, wherein R 1 is selected from aliphatic, alicyclic or aryl hydrocarbon radicals having from 5 to 12 carbon atoms, and wherein said nitriles have a molecular weight of from about 90 to about 200 atomic mass units.
  • R 1 in said nitrile compatibilizers is preferably selected from aliphatic and alicyclic hydrocarbon radicals having 8 to 10 carbon atoms.
  • the molecular weight of said nitrile compatibilizers is preferably from about 120 to about 140 atomic mass units.
  • R 1 may optionally include substituted hydrocarbon radicals, that is, radicals containing non-hydrocarbon substituents selected from halogens (e.g., fluorine, chlorine) and alkoxides (e.g. methoxy).
  • R 1 may optionally include heteroatom-substituted hydrocarbon radicals, that is, radicals, which contain the atoms nitrogen (aza-), oxygen (keto-, oxa-) or sulfur (thia-) in a radical chain otherwise composed of carbon atoms.
  • R 1 aliphatic, alicyclic and aryl hydrocarbon radicals in the general formula R 1 CN include pentyl, isopentyl, neopentyl, terf-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and their configurational isomers, as well as phenyl, benzyl, cumenyl, mesityl, tolyl, xylyl and phenethyl.
  • nitrile compatibilizers include but are not limited to: 1-cyanopentane, 2,2-dimethyl-4-cyanopentane, 1-cyanohexane, 1- cyanoheptane, 1-cyanooctane, 2-cyanooctane, 1-cyanononane, 1- cyanodecane, 2-cyanodecane, 1-cyanoundecane and 1-cyanododecane.
  • Chlorocarbon compatibilizers of the present invention comprise chlorocarbons represented by the formula RCI x , wherein; x is selected from the integers 1 or 2; R is selected from aliphatic and alicyclic hydrocarbon radicals having 1 to 12 carbon atoms; and wherein said chlorocarbons have a molecular weight of from about 100 to about 200 atomic mass units.
  • the molecular weight of said chiorocarbon compatibilizers is preferably from about 120 to 150 atomic mass units.
  • R aliphatic and alicyclic hydrocarbon radicals in the general formula RCI x include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, fe/f-butyl, pentyl, isopentyl, neopentyl, te/f-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and their configurational isomers.
  • chlorocarbon compatibilizers include but are not limited to: 3-(chloromethyl)pentane, 3-chloro-3-methylpentane, 1- chlorohexane, 1,6-dichlorohexane, 1-chloroheptane, 1-chlorooctane, 1- chlorononane, 1-chlorodecane, and 1 ,1 ,1-trichlorodecane.
  • Ester compatibilizers of the present invention comprise esters represented by the general formula R 1 CO 2 R 2 , wherein R 1 and R 2 are independently selected from linear and cyclic, saturated and unsaturated, alkyl and aryl radicals.
  • Preferred esters consist essentially of the elements C, H and O, have a molecular weight of from about 80 to about 550 atomic mass units.
  • esters include but are not limited to: (CH 3 )2CHCH2OOC(CH2)2-4OCOCH2CH(CH 3 )2 (diisobutyl dibasic ester), ethyl hexanoate, ethyl heptanoate, n-butyl propionate, n-propyl propionate, ethyl benzoate, di-n-propyl phthalate, benzoic acid ethoxyethyl ester, dipropyl carbonate, "Exxate 700" (a commercial C 7 alkyl acetate), "Exxate 800" (a commercial C 8 alkyl acetate), dibutyl phthalate, and tert-butyl acetate.
  • Lactone compatibilizers of the present invention comprise lactones represented by structures [A], [B] 1 and [C]:
  • lactones contain the functional group -CO 2 - in a ring of six (A), or preferably five atoms (B), wherein for structures [A] and [B], Ri through R 8 are independently selected from hydrogen or linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl radicals. Each Ri though Re may be connected forming a ring with another Ri through Rs.
  • the lactone may have an exocyclic alkylidene group as in structure [C], wherein Ri through RQ are independently selected from hydrogen or linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl radicals. Each Ri though R 6 may be connected forming a ring with another Ri through RQ.
  • the lactone compatibilizers have a molecular weight range of from about 80 to about 300 atomic mass units, preferred from about 80 to about 200 atomic mass units. Representative lactone compatibilizers include but are not limited to the compounds listed in Table 8.
  • Lactone compatibilizers generally have a kinematic viscosity of less than about 7 centistokes at 4O 0 C. For instance, gamma-undecalactone has kinematic viscosity of 5.4 centistokes and cis-(3-hexyl-5- methyl)dihydrofuran-2-one has viscosity of 4.5 centistokes both at 40°C. Lactone compatibilizers may be available commercially or prepared by methods as described in U. S. patent application 10/910,495 filed August 3, 2004, incorporated herein by reference.
  • Aryl ether compatibilizers of the present invention further comprise aryl ethers represented by the formula R 1 OR 2 , wherein: R 1 is selected from aryl hydrocarbon radicals having from 6 to 12 carbon atoms; R 2 is selected from aliphatic hydrocarbon radicals having from 1 to 4 carbon atoms; and wherein said aryl ethers have a molecular weight of from about 100 to about 150 atomic mass units.
  • R 1 aryl radicals in the general formula R 1 OR 2 include phenyl, biphenyl, cumenyl, mesityl, tolyl, xylyl, naphthyl and pyridyl.
  • R 2 aliphatic hydrocarbon radicals in the general formula R 1 OR 2 include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and te/f-butyl.
  • Representative aromatic ether compatibilizers include but are not limited to: methyl phenyl ether (anisole), 1 ,3-dimethyoxybenzene, ethyl phenyl ether and butyl phenyl ether.
  • Fluoroether compatibilizers of the present invention comprise those represented by the general formula R 1 OCF 2 CF 2 H, wherein R 1 is selected from aliphatic, alicyclic, and aromatic hydrocarbon radicals having from about 5 to about 15 carbon atoms, preferably primary, linear, saturated, alkyl radicals.
  • Representative fluoroether compatibilizers include but are not limited to: C 8 Hi 7 OCF 2 CF 2 H and C 6 H 13 OCF 2 CF 2 H. It should be noted that if the refrigerant is a fluoroether, then the compatibilizer may not be the same fluoroether.
  • Fluoroether compatibilizers may further comprise ethers derived from fluoroolefins and polyols.
  • Representative fluoroolefins are tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, and perfluoromethylvinyl ether.
  • the polyols may be linear or branched.
  • Linear polyols may be of the type HOCH 2 (CHOH) x (CRR')yCH 2 OH, wherein R and R' are hydrogen, or CH 3 , or C 2 H 5 and wherein x is an integer from 0-4, and y is an integer from 0-4.
  • Branched polyols may be of the type
  • Representative polyols are trimethylol propane, pentaerythritol, butanediol, and ethylene glycol.
  • 1 ,1 ,1-Trifluoroalkane compatibilizers of the present invention comprise 1 ,1,1 -trifluoroalkanes represented by the general formula CF 3 R 1 , wherein R 1 is selected from aliphatic and alicyclic hydrocarbon radicals having from about 5 to about 15 carbon atoms, preferably primary, linear, saturated, alkyl radicals.
  • Representative 1,1 ,1-trifluoroalkane compatibilizers include but are not limited to: 1 ,1 ,1-trifluorohexane and 1 ,1 ,1-trifluorododecane.
  • compositions of the present invention will typically contain from about 0.1 to about 40 weight percent, preferably from about 0.2 to about 20 weight percent, and most preferably from about 0.3 to about 10 weight percent compatibilizer in the compositions of the present invention.
  • the present invention further relates to a method of solubilizing a refrigerant or heat transfer fluid composition
  • a refrigeration lubricant selected from the group consisting of mineral oils, alkylbenzenes, synthetic paraffins, synthetic napthenes, and poly(alpha)olefins
  • said method comprises contacting said lubricant with said composition in the presence of an effective amount of a compatibilizer, wherein said compatibilizer is selected from the group consisting of polyoxyalkylene glycol ethers, amides, nitriles, ketones, chlorocarbons, esters, lactones, aryl ethers, fluoroethers and 1,1,1 -trifluoroalkanes.
  • the present invention further relates to a method for improving oil- return to the compressor in a compression refrigeration, air-conditioning or heat pump apparatus, said method comprising using a composition comprising compatibilizer in said apparatus.
  • compositions of the present invention may further comprise an ultra-violet (UV) dye and optionally a solubilizing agent.
  • UV dye is a useful component for detecting leaks of the composition by permitting one to observe the fluorescence of the dye in the composition at a leak point or in the vicinity of refrigeration, air-conditioning, or heat pump apparatus. One may observe the fluoroscence of the dye under an ultra-violet light. Solubilizing agents may be needed due to poor solubility of such UV dyes in some compositions.
  • ultra-violet dye is meant a UV fluorescent composition that absorbs light in the ultra-violet or “near” ultra-violet region of the electromagnetic spectrum.
  • the fluorescence produced by the UV fluorescent dye under illumination by a UV light that emits radiation with wavelength anywhere from 10 nanometer to 750 nanometer may be detected. Therefore, if a composition containing such a UV fluorescent dye is leaking from a given point in a refrigeration, air-conditioning, or heat pump apparatus, the fluorescence can be detected at the leak point.
  • UV fluorescent dyes include but are not limited to naphthalimides, perylenes, coumarins, anthracenes, phenanthracenes, xanthenes, thioxanthenes, naphthoxanthenes, fluoresceins, and derivatives or combinations thereof.
  • Solubilizing agents of the present invention comprise at least one compound selected from the group consisting of hydrocarbons, hydrocarbon ethers, polyoxyalkylene glycol ethers, amides, nitriles, ketones, chlorocarbons, esters, lactones, aryl ethers, fluoroethers and 1 ,1 ,1-trifluoroalkanes.
  • the polyoxyalkylene glycol ethers, amides, nitriles, ketones, chlorocarbons, esters, lactones, aryl ethers, fluoroethers and 1,1 ,1-trifluoroalkanes solubilizing agents have been defined previously herein as being compatibilizers for use with conventional refrigeration lubricants.
  • Hydrocarbon solubilizing agents of the present invention comprise hydrocarbons including straight chained, branched chain or cyclic alkanes or alkenes containing 5 or fewer carbon atoms and only hydrogen with no other functional groups.
  • Representative hydrocarbon solubilizing agents comprise propane, propylene, cyclopropane, n-butane, isobutane, 2- methylbutane and n-pentane. It should be noted that if the composition contains a hydrocarbon, then the solubilizing agent may not be the same hydrocarbon.
  • Hydrocarbon ether solubilizing agents of the present invention comprise ethers containing only carbon, hydrogen and oxygen, such as dimethyl ether (DME).
  • DME dimethyl ether
  • Solubilizing agents of the present invention may be present as a single compound, or may be present as a mixture of more than one solubilizing agent. Mixtures of solubilizing agents may contain two solubilizing agents from the same class of compounds, say two lactones, or two solubilizing agents from two different classes, such as a lactone and a polyoxyalkylene glycol ether.
  • compositions comprising refrigerant and UV fluorescent dye, or comprising heat transfer fluid and UV fluorescent dye, from about 0.001 weight percent to about 1.0 weight percent of the composition is UV dye, preferably from about 0.005 weight percent to about 0.5 weight percent, and most preferably from 0.01 weight percent to about 0.25 weight percent.
  • Solubilizing agents such as ketones may have an objectionable odor, which can be masked by addition of an odor masking agent or fragrance.
  • odor masking agents or fragrances may include Evergreen, Fresh Lemon, Cherry, Cinnamon, Peppermint, Floral or Orange Peel all commercially available, as well as d-limonene and pinene.
  • Such odor masking agents may be used at concentrations of from about 0.001% to as much as about 15% by weight based on the combined weight of odor masking agent and solubilizing agent.
  • the UV fluorescent dye could be dissolved in the refrigerant itself thereby not requiring any specialized method for introduction to the refrigeration, air conditioning apparatus, or heat pump.
  • the present invention relates to compositions including UV fluorescent dye, which may be introduced into the system as a solution in the refrigerant.
  • the inventive compositions will allow the storage and transport of dye- containing compositions even at low temperatures while maintaining the dye in solution.
  • compositions comprising refrigerant, UV fluorescent dye and solubilizing agent, or comprising heat transfer fluid and UV fluorescent dye and solubilizing agent, from about 1 to about 50 weight percent, preferably from about 2 to about 25 weight percent, and most preferably from about 5 to about 15 weight percent of the combined composition is solubilizing agent.
  • the UV fluorescent dye is present in a concentration from about 0.001 weight percent to about 1.0 weight percent, preferably from 0.005 weight percent to about 0.5 weight percent, and most preferably from 0.01 weight percent to about 0.25 weight percent.
  • the present invention further relates to a method of using the compositions further comprising ultraviolet fluorescent dye, and optionally, solubilizing agent, in refrigeration, air-conditioning, or heat pump apparatus.
  • the method comprises introducing the composition into the refrigeration, air-conditioning, or heat pump apparatus. This may be done by dissolving the UV fluorescent dye in the composition in the presence of a solubilizing agent and introducing the combination into the apparatus. Alternatively, this may be done by combining solubilizing agent and UV fluorescent dye and introducing said combination into refrigeration or air- conditioning apparatus containing refrigerant and/or heat transfer fluid. The resulting composition may be used in the refrigeration, air- conditioning, or heat pump apparatus.
  • the present invention further relates to a method of using the compositions comprising ultraviolet fluorescent dye to detect leaks.
  • the presence of the dye in the compositions allows for detection of leaking refrigerant in a refrigeration, air-conditioning, or heat pump apparatus.
  • Leak detection helps to address, resolve or prevent inefficient operation of the apparatus or system or equipment failure.
  • Leak detection also helps one contain chemicals used in the operation of the apparatus.
  • the method comprises providing the composition comprising refrigerant, ultra-violet fluorescent dye, as described herein, and optionally, a solubilizing agent as described herein, to refrigeration, air- conditioning, or heat pump apparatus and employing a suitable means for detecting the UV fluorescent dye-containing refrigerant.
  • suitable means for detecting the dye include, but are not limited to, ultra-violet lamps, often referred to as a "black light” or "blue light”. Such ultra-violet lamps are commercially available from numerous sources specifically designed for this purpose.
  • the present invention further relates to a method for replacing a high GWP refrigerant in a refrigeration, air-conditioning, or heat pump apparatus, wherein said high GWP refrigerant is selected from the group consisting of R134a, R22, R245fa, R114, R236fa, R124, R410A, R407C, R417A, R422A, R507A, and R404A, said method comprising providing a composition of the present invention to said refrigeration, air-conditioning, or heat pump apparatus that uses, used or is designed to use said high GWP refrigerant.
  • Vapor-compression refrigeration, air-conditioning, or heat pump systems include an evaporator, a compressor, a condenser, and an expansion device.
  • a vapor-compression cycle re-uses refrigerant in multiple steps producing a cooling effect in one step and a heating effect in a different step.
  • the cycle can be described simply as follows. Liquid refrigerant enters an evaporator through an expansion device, and the liquid refrigerant boils in the evaporator at a low temperature to form a gas and produce cooling. The low-pressure gas enters a compressor where the gas is compressed to raise its pressure and temperature.
  • mobile refrigeration apparatus or mobile air- conditioning apparatus refers to any refrigeration or air-conditioning apparatus incorporated into a transportation unit for the road, rail, sea or air.
  • apparatus which are meant to provide refrigeration or air- conditioning for a system independent of any moving carrier, known as "intermodal" systems, are included in the present invention.
  • Such intermodal systems include “containers” (combined sea/land transport) as well as “swap bodies” (combined road and rail transport).
  • the present invention is particularly useful for road transport refrigerating or air- conditioning apparatus, such as automobile air-conditioning apparatus or refrigerated road transport equipment.
  • the present invention further relates to a process for producing cooling comprising evaporating the compositions of the present invention in the vicinity of a body to be cooled, and thereafter condensing said compositions:
  • the present invention further relates to a process for producing heat comprising condensing the compositions of the present invention in the vicinity of a body to be heated, and thereafter evaporating said compositions.
  • the present invention further relates to a refrigeration, air- conditioning, or heat pump apparatus containing a composition of the present invention wherein said composition at least one fluoroolefin.
  • the present invention further relates to a mobile air-conditioning apparatus containing a composition of the present invention wherein said composition comprises at least one fluoroolefin.
  • the present invention further relates to a method for early detection of a refrigerant leak in a refrigeration, air-conditioning or heat pump apparatus said method comprising using a non-azeotropic composition in said apparatus, and monitoring for a reduction in cooling performance.
  • the non-azeotropic compositions will fractionate upon leakage from a refrigeration, air-conditioning or heat pump apparatus and the lower boiling (higher vapor pressure) component will leak out of the apparatus first. When this occurs, if the lower boiling component in that composition provides the majority of the refrigeration capacity, there will be a marked reduction in the capacity and thus performance of the apparatus.
  • the passengers in the automobile will detect a reduction in the cooling capability of the system. This reduction in cooling capability can be interpreted to mean that refrigerant is being leaked and that the system requires repair.
  • the present invention further relates to a method of using the compositions of the present invention as a heat transfer fluid composition, said process comprising transporting said composition from a heat source to a heat sink.
  • Heat transfer fluids are utilized to transfer, move or remove heat from one space, location, object or body to a different space, location, object or body by radiation, conduction, or convection.
  • a heat transfer fluid may function as a secondary coolant by providing means of transfer for cooling (or heating) from a remote refrigeration (or heating) system.
  • the heat transfer fluid may remain in a constant state throughout the transfer process (i.e., not evaporate or condense).
  • evaporative cooling processes may utilize heat transfer fluids as well.
  • a heat source may be defined as any space, location, object or body from which it is desirable to transfer, move or remove heat.
  • heat sources may be spaces (open or enclosed) requiring refrigeration or cooling, such as refrigerator or freezer cases in a supermarket, building spaces requiring air-conditioning, or the passenger compartment of an automobile requiring air-conditioning.
  • a heat sink may be defined as any space, location, object or body capable of absorbing heat.
  • a vapor compression refrigeration system is one example of such a heat sink.
  • the present invention relates to blowing agent compositions comprising the fluoroolefin-containing compositions as described herein for use in preparing foams.
  • the invention provides foamable compositions, and preferably polyurethane and polyisocyanate foam compositions, and method of preparing foams.
  • one or more of the present fluoroolefin- containing compositions are included as a blowing agent in foamable compositions, which composition preferably includes one or more additional components capable of reacting and foaming under the proper conditions to form a foam or cellular structure.
  • the present invention further relates to a method of forming a foam comprising: (a) adding to a foamable composition a fluoroolefin- containing composition of the present invention; and (b) reacting the foamable composition under conditions effective to form a foam.
  • Another embodiment of the present invention relates to the use of the fluoroolefin-containing compositions as described herein for use as propellants in sprayable compositions. Additionally, the present invention relates to a sprayable composition comprising the fluoroolefin-containing compositions as described herein.
  • the active ingredient to be sprayed together with inert ingredients, solvents and other materials may also be present in a sprayable composition.
  • the sprayable composition is an aerosol.
  • Suitable active materials to be sprayed include, without limitations, cosmetic materials, such as deodorants, perfumes, hair sprays, cleaners, and polishing agents as well as medicinal materials such as anti- asthma and anti-halitosis medications.
  • the present invention further relates to a process for producing aerosol products comprising the step of adding a fluoroolefin-containing composition as described herein to active ingredients in an aerosol container, wherein said composition functions as a propellant.
  • a further aspect provides methods of suppressing a flame, said methods comprising contacting a flame with a fluid comprising a fluoroolefin-containing composition of the present disclosure.
  • Any suitable methods for contacting the flame with the present composition may be used.
  • a fluoroolefin-containing composition of the present disclosure may be sprayed, poured, and the like onto the flame, or at least a portion of the flame may be immersed in the flame suppression 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 disclosure.
  • a further embodiment provides methods of extinguishing or suppressing a fire in a total-flood application comprising providing an agent comprising a fluoroolefin-containing composition of the present disclosure; disposing the agent in a pressurized discharge system; and discharging the agent into an area to extinguish or suppress fires in that area.
  • Another embodiment provides methods of inerting an area to prevent a fire or explosion comprising providing an agent comprising a fluoroolefin-containing composition of the present disclosure; disposing the agent in a pressurized discharge system; and discharging the agent into the area to prevent a fire or explosion from occurring.
  • a detector is usually used to detect an expanding fireball from an explosion, and the agent is discharged rapidly to suppress the explosion.
  • Explosion suppression is used primarily, but not solely, in defense applications.
  • a fluoroolefin-containing composition of the present disclosure is discharged into a space to prevent an explosion or a fire from being initiated.
  • a system similar or identical to that used for total-flood fire extinguishment or suppression is used.
  • the presence of a dangerous condition for example, dangerous concentrations of flammable or explosive gases
  • the fluoroolefin-containing composition of the present disclosure is then discharged to prevent the explosion or fire from occurring until the condition can be remedied.
  • the extinguishing method can be carried out by introducing the composition into an enclosed area surrounding a fire. Any of the known methods of introduction can be utilized provided that appropriate quantities of the composition are metered into the enclosed area at appropriate intervals.
  • a composition can be introduced by streaming, e.g., using conventional portable (or fixed) fire extinguishing equipment; by misting; or by flooding, e.g., by releasing (using appropriate piping, valves, and controls) the composition into an enclosed area surrounding a fire.
  • the composition can optionally be combined with an inert propellant, e.g., nitrogen, argon, decomposition products of glycidyl azide polymers or carbon dioxide, to increase the rate of discharge of the composition from the streaming or flooding equipment utilized.
  • the extinguishing process involves introducing a fluoroolefin-containing composition of the present disclosure to a fire or flame in an amount sufficient to extinguish the fire or flame.
  • a fluoroolefin-containing composition of the present disclosure to a fire or flame in an amount sufficient to extinguish the fire or flame.
  • the amount of flame suppressant needed to extinguish a particular fire will depend upon the nature and extent of the hazard.
  • cup burner test data is useful in determining the amount or concentration of flame suppressant required to extinguish a particular type and size of fire.
  • a vessel is charged with an initial composition at a temperature of either -25 °C or if specified, at 25 0 C, and the initial vapor pressure of the composition is measured.
  • the composition is allowed to leak from the vessel, while the temperature is held constant, until 50 weight percent of the initial composition is removed, at which time the vapor pressure of the composition remaining in the vessel is measured. Results are shown in Table 9.
  • HFC-32/HFC-125/HFC-1234yf (25 0 C) 40/50/10 240.6 1659 239.3 1650 0.5%
  • HFC-32/HFC-125/trans-HFC-1234ze (25 0 C) 30/40/30 221.5 1527 209.4 1444 5.5% 30/50/20 227.5 1569 220.2 1518 3.2%
  • compositions of the present invention would be azeotropic or near-azeotropic.
  • Refrigeration Performance Data Table 10 shows the performance of various refrigerant compositions of the present invention as compared to HFC-134a.
  • Evap Pres is evaporator pressure
  • Cond Pres is condenser pressure
  • Comp Disch T is compressor discharge temperature
  • COP energy efficiency
  • CAP capacity
  • compositions have even higher energy efficiency (COP) than HFC-134a while maintaining lower discharge pressures and temperatures. Capacity for the present compositions is also similar to R134a indicating these could be replacement refrigerants for R134a in refrigeration and air-conditioning, and in mobile air-conditioning applications in particular. Those compositions containing hydrocarbon may also improve oil solubility with conventional mineral oil and alkyl benzene lubricants.
  • Table 11 shows the performance of various refrigerant compositions of the present invention as compared to R404A and R422A.
  • Evap Pres is evaporator pressure
  • Cond Pres is condenser pressure
  • Comp Disch T is compressor discharge temperature
  • EER energy efficiency
  • CAP capacity
  • HFC-32/CF 3 I/HFC- 10/25/65 220 1542 107 1374 5.04
  • HFC-32/CF 3 I/HFC- 30/10/60 295 2020 123 1795 4.88
  • HFC-32/CF 3 I/HFC- 20/40/40 275 1861 121 1679 4.92
  • HFC-32/CF 3 I/HFC- 50/25/25 384 2468 145 2267 4.72

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Abstract

The present invention relates to compositions for use in refrigeration, air-conditioning, and heat pump systems wherein the composition comprises a fluoroolefin and at least one other component. The compositions of the present invention are useful in processes for producing cooling or heat, as heat transfer fluids, foam blowing agents, aerosol propellants, and fire suppression and fire extinguishing agents.

Description

TITLE OF INVENTION
COMPOSITIONS COMPRISING A FLUOROOLEFIN
CROSS REFERENCEfS) TO RELATED APPLICATION(S) This application claims the priority benefit of U.S. Provisional
Application 60/658,543, filed March 4, 2005, and U.S. Provisional Application 60/710,439, filed August 23, 2005, and U.S. Provisional Application 60/732,769, filed November 1 , 2005.
BACKGROUND OF THE INVENTION
1. Field of the Invention.
The present invention relates to compositions for use in refrigeration, air-conditioning, and heat pump systems wherein the composition comprises a fluoroolefin and at least one other component. The compositions of the present invention are useful in processes for producing cooling or heat, as heat transfer fluids, foam blowing agents, aerosol propellants, and fire suppression and fire extinguishing agents.
2. Description of Related Art.
The refrigeration industry has been working for the past few decades to find replacement refrigerants for the ozone depleting chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) being phased out as a result of the Montreal Protocol. The solution for most refrigerant producers has been the commercialization of hydrofluorocarbon (HFC) refrigerants. The new HFC refrigerants, HFC- 134a being the most widely used at this time, have zero ozone depletion potential and thus are not affected by the current regulatory phase out as a result of the Montreal Protocol.
Further environmental regulations may ultimately cause global phase out of certain HFC refrigerants. Currently, the automobile industry is facing regulations relating to global warming potential for refrigerants used in mobile air-conditioning. Therefore, there is a great current need to identify new refrigerants with reduced global warming potential for the mobile air-conditioning market. Should the regulations be more broadly applied in the future, an even greater need will be felt for refrigerants that can be used in all areas of the refrigeration and air-conditioning industry. Currently proposed replacement refrigerants for HFC-134a include HFC-152a, pure hydrocarbons such as butane or propane, or "natural" refrigerants such as CO2. Many of these suggested replacements are toxic, flammable, and/or have low energy efficiency. Therefore, new alternative refrigerants are being sought.
The object of the present invention is to provide novel refrigerant compositions and heat transfer fluid compositions that provide unique characteristics to meet the demands of low or zero ozone depletion potential and lower global warming potential as compared to current refrigerants.
BRIEF SUMMARY OF THE INVENTION
The present invention relates to a composition comprising HFC-1225ye and at least one compound selected from the group consisting of:
HFC-1234ze, HFC-1234yf, HFC-1234ye, HFC-1243zf, HFC-32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161 , HFC-227ea, HFC- 236ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethylether, CF3SCF31 CO2 and CF3I.
The present invention further relates to a composition comprising HFC-1234ze and at least one compound selected from the group consisting of: HFC-1234yf, HFC-1234ye, HFC-1243zf, HFC-32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161 , HFC- 227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, n- butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethylether, CF3SCF3, CO2 and CF3I.
The present invention further relates to a composition comprising HFC-1234yf and at least one compound selected from the group consisting of: HFC-1234ye, HFC-1243zf, HFC-32, HFC-125, HFC- 134, HFC-134a, HFC-143a, HFC-152a, HFC-161 , HFC-227ea, HFC- 236ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethylether, CF3SCF3, CO2 and CF3I. The present invention further relates to a composition comprising HFC-1234ye and at least one compound selected from the group consisting of: HFC-1243zf, HFC-32, HFC-125, HFC-134, HFC- 134a, HFC-143a, HFC-152a, HFC-161 , HFC-227ea, HFC-236ea, HFC- 236fa, HFC-245fa, HFC-365mfc, propane, n-butane, isobutane, 2- methylbutane, n-pentane, cyclopentane, dimethylether, CF3SCF3, CO2 and CF3I.
The present invention further relates to a composition comprising HFC-1243zf and at least one compound selected from the group consisting of: HFC-32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161 , HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethylether, CF3SCF3, CO2 and CF3I. The present invention further relates to a composition comprising:
(a) at least one lubricant selected from the group consisting of polyol esters, polyalkylene glycol, polyvinyl ethers, mineral oils, alkylbenzenes, synthetic paraffins, synthetic napthenes, and poly(alpha)olefins; and
(b) a composition selected from the group consisting of: about 1 weight percent to about 99 weight percent HFC-
1225ye and about 99 weight percent to about 1 weight percent HFC-152a; about 1 weight percent to about 99 weight percent HFC-
1225ye and about 99 weight percent to about 1 weight percent H FC-1234yf; about 1 weight percent to about 99 weight percent HFC-
1225ye and about 99 weight percent to about 1 weight percent trans-HFC-1234ze; about 1 weight percent to about 99 weight percent HFC- 1225ye and about 99 weight percent to about 1 weight percent HFC-1243zf; about 1 weight percent to about 99 weight percent trans- HFC-1234ze and about 99 weight percent to about 1 weight percent HFC-134a; about 1 weight percent to about 99 weight percent trans- HFC-1234ze and about 99 weight percent to about 1 weight percent HFC-152a; about 1 weight percent to about 99 weight percent trans- HFC-1234ze and about 99 weight percent to about 1 weight percent HFC-227ea; and about 1 weight percent to about 99 weight percent trans- HFC-1234ze and about 99 weight percent to about 1 weight percent CF3I.
The present invention further relates to a composition comprising: a) a refrigerant or heat transfer fluid composition selected from the group consisting of: about 1 weight percent to about 99 weight percent HFC-
1225ye and about 99 weight percent to about 1 weight percent HFC-152a; about 1 weight percent to about 99 weight percent HFC-
1225ye and about 99 weight percent to about 1 weight percent HFC-1234yf; about 1 weight percent to about 99 weight percent HFC- 1225ye and about 99 weight percent to about 1 weight percent trans-HFC-1234ze; about 1 weight percent to about 99 weight percent HFC- 1225ye and about 99 weight percent to about 1 weight percent HFC-1243zf; about 1 weight percent to about 99 weight percent trans- HFC-1234ze and about 99 weight percent to about 1 weight percent HFC-134a; about 1 weight percent to about 99 weight percent trans-
HFC-1234ze and about 99 weight percent to about 1 weight percent HFC-152a; about 1 weight percent to about 99 weight percent trans- HFC-1234ze and about 99 weight percent to about 1 weight percent HFC-227ea; and about 1 weight percent to about 99 weight percent trans- HFC-1234ze and about 99 weight percent to about 1 weight percent CF3I; and compatibilizer selected from the group consisting of: i) polyoxyalkylene glycol ethers represented by the formula R1[(OR2)xOR3]y, wherein: x is an integer from 1 to 3; y is an integer from 1 to 4; R1 is selected from hydrogen and aliphatic hydrocarbon radicals having 1 to 6 carbon atoms and y bonding sites; R2 is selected from aliphatic hydrocarbylene radicals having from 2 to 4 carbon atoms; R3 is selected from hydrogen, and aliphatic and alicyclic hydrocarbon radicals having from 1 to 6 carbon atoms; at least one of R1 and R3 is selected from said hydrocarbon radicals; and wherein said polyoxyalkylene glycol ethers have a molecular weight of from about 100 to about 300 atomic mass units; ii) amides represented by the formulae R1C(O)NR2R3 and cyclo-[R4CON(R5)-], wherein R1, R2, R3 and R5 are independently selected from aliphatic and alicyclic hydrocarbon radicals having from 1 to 12 carbon atoms, and at most one aromatic radical having from 6 to 12 carbon atoms; R4 is selected from aliphatic hydrocarbylene radicals having from 3 to 12 carbon atoms; and wherein said amides have a molecular weight of from about 100 to about 300 atomic mass units; iii) ketones represented by the formula R1C(O)R2, wherein R1 and R2 are independently selected from aliphatic, alicyclic and aryl hydrocarbon radicals having from 1 to 12 carbon atoms, and wherein said ketones have a molecular weight of from about 70 to about 300 atomic mass units; iv) nitriles represented by the formula R1CN, wherein R1 is selected from aliphatic, alicyclic or aryl hydrocarbon radicals having from 5 to 12 carbon atoms, and wherein said nitriles have a molecular weight of from about 90 to about 200 atomic mass units; v) chlorocarbons represented by the formula RCIx, wherein; x is 1 or 2; R is selected from aliphatic and alicyclic hydrocarbon radicals having from 1 to 12 carbon atoms; and wherein said chlorocarbons have a molecular weight of from about 100 to about 200 atomic mass units; vi) aryl ethers represented by the formula R1OR2, wherein: R1 is selected from aryl hydrocarbon radicals having from 6 to 12 carbon atoms; R2 is selected from aliphatic hydrocarbon radicals having from 1 to 4 carbon atoms; and wherein said aryl ethers have a molecular weight of from about 100 to about 150 atomic mass units; vii) 1 ,1 ,1-trifluoroalkanes represented by the formula CF3R1, wherein R1 is selected from aliphatic and alicyclic hydrocarbon radicals having from about 5 to about 15 carbon atoms; viii)fluoroethers represented by the formula R1OCFaCF2H, wherein R1 is selected from aliphatic, alicyclic, and aromatic hydrocarbon radicals having from about 5 to about 15 carbon atoms; or wherein said fluoroethers are derived from fluoroolefins and polyols, wherein said fluoroolefins are of the type CF2=CXY, wherein X is hydrogen, chlorine or fluorine, and Y is chlorine, fluorine, CF3 or ORf, wherein Rf is CF3, C2F5, or C3F7; and said polyols are linear or branched, wherein said linear polyols are of the type HOCH2(CHOH)X(CRR' )yCH2OH, wherein R and R' are hydrogen, CH3 or C2H5, x is an integer from 0-4, y is an integer from 0-3 and z is either zero or 1 , and said branched polyols are of the type C(OH)t(R)u(CH2OH)v[(CH2)mCH2OH]w, wherein R may be hydrogen, CH3 or C2H5, m is an integer from 0 to 3, t and u are 0 or 1 , v and w are integers from 0 to 4, and also wherein t + u + v + w = 4; and ix) lactones represented by structures [B]1 [C], and [D]:
Figure imgf000008_0001
[B] [C] [D]
wherein, Ri through Rs are independently selected from hydrogen, linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl radicals; and the molecular weight is from about 100 to about 300 atomic mass units; and x) esters represented by the general formula R1CO2R2, wherein R1 and R2 are independently selected from linear and cyclic, saturated and unsaturated, alkyl and aryl radicals; and wherein said esters have a molecular weight of from about 80 to about 550 atomic mass units.
The present invention further relates to a composition comprising: (a) at least one ultra-violet fluorescent dye selected from the group consisting of naphthalimides, perylenes, coumarins, anthracenes, phenanthracenes, xanthenes, thioxanthenes, naphthoxanthenes, fluoresceins, derivatives of said dye and combinations thereof; and
(b) a composition selected from the group consisting of: about 1 weight percent to about 99 weight percent HFC-
1225ye and about 99 weight percent to about 1 weight percent H FC-152a; about 1 weight percent to about 99 weight percent HFC-
1225ye and about 99 weight percent to about 1 weight percent HFC-1234yf; about 1 weight percent to about 99 weight percent HFC-
1225ye and about 99 weight percent to about 1 weight percent trans-HFC-1234ze; about 1 weight percent to about 99 weight percent HFC-
1225ye and about 99 weight percent to about 1 weight percent HFC-1243zf; about 1 weight percent to about 99 weight percent trans- HFC-1234ze and about 99 weight percent to about 1 weight percent HFC-134a; about 1 weight percent to about 99 weight percent trans- HFC-1234ze and about 99 weight percent to about 1 weight percent HFC-152a; about 1 weight percent to about 99 weight percent trans- HFC-1234ze and about 99 weight percent to about 1 weight percent HFC-227ea; and about 1 weight percent to about 99 weight percent trans-
HFC-1234ze and about 99 weight percent to about 1 weight percent CF3I.
The present invention further relates to a method of solubilizing a refrigerant or heat transfer fluid composition in a refrigeration lubricant selected from the group consisting of mineral oils, alkylbenzenes, synthetic paraffins, synthetic napthenes, and poly(alpha)olefins, wherein said method comprises contacting said lubricant with said refrigerant or heat transfer fluid composition in the presence of an effective amount of a compatibilizer, wherein said refrigerant or heat transfer fluid comprises a composition selected from the group consisting of: about 1 weight percent to about 99 weight percent HFC- 1225ye and about 99 weight percent to about 1 weight percent HFC-152a; about 1 weight percent to about 99 weight percent HFC- 1225ye and about 99 weight percent to about 1 weight percent
HFC-1234yf; about 1 weight percent to about 99 weight percent HFC- 1225ye and about 99 weight percent to about 1 weight percent trans-HFC-1234ze; about 1 weight percent to about 99 weight percent HFC-
1225ye and about 99 weight percent to about 1 weight percent HFC-1243zf; about 1 weight percent to about 99 weight percent trans- HFC-1234ze and about 99 weight percent to about 1 weight percent HFC-134a; about 1 weight percent to about 99 weight percent trans- HFC-1234ze and about 99 weight percent to about 1 weight percent HFC-152a; about 1 weight percent to about 99 weight percent trans- HFC-1234ze and about 99 weight percent to about 1 weight percent
HFC-227ea; and about 1 weight percent to about 99 weight percent trans- HFC-1234ze and about 99 weight percent to about 1 weight percent CF3I; and wherein said compatibilizer is selected from the group consisting of: a) polyoxyalkylene glycol ethers represented by the formula R1[(OR2)xOR3]y, wherein: x is an integer from 1 to 3; y is an integer from 1 to 4; R1 is selected from hydrogen and aliphatic hydrocarbon radicals having 1 to 6 carbon atoms and y bonding sites; R2 is selected from aliphatic hydrocarbylene radicals having from 2 to 4 carbon atoms; R3 is selected from hydrogen, and aliphatic and alicyclic hydrocarbon radicals having from 1 to 6 carbon atoms; at least one of R1 and R3 is selected from said hydrocarbon radicals; and wherein said polyoxyalkylene glycol ethers have a molecular weight of from about 100 to about 300 atomic mass units; b) amides represented by the formulae R1C(O)NR2R3 and cyclo- [R4CON(R5)-], wherein R1, R2, R3 and R5 are independently selected from aliphatic and alicyclic hydrocarbon radicals having from 1 to 12 carbon atoms, and at most one aromatic radical having from 6 to 12 carbon atoms; R4 is selected from aliphatic hydrocarbylene radicals having from 3 to 12 carbon atoms; and wherein said amides have a molecular weight of from about 100 to about 300 atomic mass units; c) ketones represented by the formula R1C(O)R2, wherein R1 and R2 are independently selected from aliphatic, alicyclic and aryl hydrocarbon radicals having from 1 to 12 carbon atoms, and wherein said ketones have a molecular weight of from about 70 to about 300 atomic mass units; d) nitriles represented by the formula R1CN, wherein R1 is selected from aliphatic, alicyclic or aryl hydrocarbon radicals having from 5 to 12 carbon atoms, and wherein said nitriles have a molecular weight of from about 90 to about 200 atomic mass units; e) chlorocarbons represented by the formula RCIx, wherein; x is 1 or 2; R is selected from aliphatic and alicyclic hydrocarbon radicals having from 1 to 12 carbon atoms; and wherein said chlorocarbons have a molecular weight of from about 100 to about 200 atomic mass units; f) aryl ethers represented by the formula R1OR2, wherein: R1 is selected from aryl hydrocarbon radicals having from 6 to 12 carbon atoms; R2 is selected from aliphatic hydrocarbon radicals having from 1 to 4 carbon atoms; and wherein said aryl ethers have a molecular weight of from about 100 to about 150 atomic mass units; g) 1 ,1 ,1 -trifluoroalkanes represented by the formula CF3R1 , wherein R1 is selected from aliphatic and alicyclic hydrocarbon radicals having from about 5 to about 15 carbon atoms; h) fluoroethers represented by the formula R1OCF2CF2H, wherein
R1 is selected from aliphatic and alicyclic hydrocarbon radicals having from about 5 to about 15 carbon atoms; or wherein said fluoroethers are derived from fluoro-olefins and polyols, wherein said fluoro-olefins are of the type CF2=CXY, wherein X is hydrogen, chlorine or fluorine, and Y is chlorine, fluorine, CF3 or ORf, wherein Rf is CF3, C2F5, or C3F7; and said polyols are of the type HOCH2CRR'(CH2)z(CHOH)xCH2(CH2OH)y, wherein R and R' are hydrogen, CH3 or C2H5, x is an integer from 0-4, y is an integer from 0-3 and z is either zero or 1 ; and i) lactones represented by structures [B], [C], and [D]:
Figure imgf000011_0001
[B] [C] [D] wherein, Ri through Rs are independently selected from hydrogen, linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl radicals; and the molecular weight is from about 100 to about 300 atomic mass units; and j) esters represented by the general formula R1CO2R2, wherein R1 and R2 are independently selected from linear and cyclic, saturated and unsaturated, alkyl and aryl radicals; and wherein said esters have a molecular weight of from about 80 to about 550 atomic mass units.
The present invention further relates to a method for replacing a high GWP refrigerant in a refrigeration, air-conditioning, or heat pump apparatus, wherein said high GWP refrigerant is selected from the group consisting of R134a, R22, R123, R11 , R245fa, R114, R236fa, R124, R12, R410A, R407C, R417A, R422A, R507A, R502, and R404A, said method comprising providing a composition selected from the group consisting of: about 1 weight percent to about 99 weight percent HFC- 1225ye and about 99 weight percent to about 1 weight percent HFC-152a; about 1 weight percent to about 99 weight percent HFC-
1225ye and about 99 weight percent to about 1 weight percent HFC-1234yf; about 1 weight percent to about 99 weight percent HFC- 1225ye and about 99 weight percent to about 1 weight percent trans-HFC-1234ze; about 1 weight percent to about 99 weight percent HFC- 1225ye and about 99 weight percent to about 1 weight percent HFC-1243zf; about 1 weight percent to about 99 weight percent trans- HFC-1234ze and about 99 weight percent to about 1 weight percent H FC-134a; about 1 weight percent to about 99 weight percent trans- HFC-1234ze and about 99 weight percent to about 1 weight percent HFC-152a; about 1 weight percent to about 99 weight percent trans- HFC-1234ze and about 99 weight percent to about 1 weight percent HFC-227ea; and about 1 weight percent to about 99 weight percent trans- HFC-1234ze and about 99 weight percent to about 1 weight percent CF3I; to said refrigeration, air-conditioning, or heat pump apparatus that uses, used or designed to use said high GWP refrigerant.
The present invention further relates to a method for early detection of a refrigerant leak in a refrigeration, air-conditioning or heat pump apparatus said method comprising using a non-azeotropic composition in said apparatus, and monitoring for a reduction in cooling performance.
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to compositions comprising at least one fluoroolefin. The compositions of the present invention further comprise at least one additional component that may be a second fluoroolefin, hydrofluorocarbon (HFC), hydrocarbon, dimethyl ether, bis(trifluoromethyl)sulfide, CF3I, or CO2. The fluoroolefin compounds and other components of the present inventive compositions are listed in Table 1.
TABLE 1
Figure imgf000013_0001
Figure imgf000014_0001
The individual components listed in Table 1 may be prepared by methods known in the art;
The fluoroolefin compounds used in the compositions of the present invention, HFC-1225ye, HFC-1234ze, and HFC-1234ye, may exist as different configurational isomers or stereoisomers. The present invention is intended to include all single configurational isomers, single stereoisomers or any combination or mixture thereof. For instance, 1 ,3,3,3-tetra-fluoropropene (HFC-1234ze) is meant to represent the cis- isomer, trans-isomer, or any combination or mixture of both isomers in any ratio. Another example is HFC-1225ye, by which is represented the cis- isomer, trans-isomer, or any combination or mixture of both isomers in any ratio.
The compositions of the present invention include the following: HFC-1225ye and at least one compound selected from the group consisting of HFC-1234ze, HFC-1234yf, HFC-1234ye, HFC-1243zf, HFC- 32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161 , HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethylether, CF3SCF3, CO2 and CF3I;
HFC-1234ze and at least one compound selected from the group consisting HFC-1225ye, HFC-1234yf, HFC-1234ye, HFC-1243zf, HFC-32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161 , HFC- 227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, n- butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethylether, CF3SCF3, CO2 and CF3I;
HFC-1234yf and at least one compound selected from the group consisting of HFC-1234ye, HFC-1243zf, HFC-32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161 , HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, n-butane, isobutane, 2- methylbutane, n-pentane, cyclopentane, dimethylether, CF3SCF3, CO2 and CF3I; and HFC-1243zf and at least one compound selected from the group consisting of HFC-1234ye, HFC-32, HFC-125, HFC-134, HFC-134a, HFC- 143a, HFC-152a, HFC-161 , HFC-227ea, HFC-236ea, HFC-236fa, HFC- 245fa, HFC-365mfc, propane, n-butane, isobutane, 2-methylbutane, n- pentane, cyclopentane, dimethylether, CF3SCF3, CO2 and CF3I; and HFC-1234ye and at least one compound selected from the group consisting of HFC-32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC- 152a, HFC-161 , HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC- 365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethylether, CF3SCF3, CO2 and CF3I. The compositions of the present invention may be generally useful when the fluoroolefin is present at about 1 weight percent to about 99 weight percent, preferably about 20 weight percent to about 99 weight percent, more preferably about 40 weight percent to about 99 weight percent and still more preferably 50 weight percent to about 99 weight percent.
The present invention further provides compositions as listed in Table 2.
TABLE 2
Figure imgf000015_0001
Figure imgf000016_0001
Figure imgf000017_0001
Figure imgf000018_0001
Figure imgf000019_0001
Figure imgf000020_0001
Figure imgf000021_0001
The most preferred compositions of the present invention listed in Table 2 are generally expected to maintain the desired properties and functionality when the components are present in the concentrations as listed +/- 2 weight percent. The compositions containing CO2 would be expected to maintain the desired properties and functionality when the CO2 was present at the listed concentration +/- 0.2 weight percent.
The compositions of the present invention may be azeotropic or near-azeotropic compositions. By azeotropic composition is meant a constant-boiling mixture of two or more substances that behave as a single substance. One way to characterize an azeotropic composition is that the vapor produced by partial evaporation or distillation of the liquid has the same composition as the liquid from which it is evaporated or distilled, i.e., the mixture distills/refluxes without compositional change. Constant-boiling compositions are characterized as azeotropic because they exhibit either a maximum or minimum boiling point, as compared with that of the non-azeotropic mixture of the same compounds. An azeotropic composition will not fractionate within a refrigeration or air conditioning system during operation, which may reduce efficiency of the system. Additionally, an azeotropic composition will not fractionate upon leakage from a refrigeration or air conditioning system. In the situation where one component of a mixture is flammable, fractionation during leakage could lead to a flammable composition either within the system or outside of the system.
A near-azeotropic composition (also commonly referred to as an "azeotrope-like composition") is a substantially constant boiling liquid admixture of two or more substances that behaves essentially as a single substance. One way to characterize a near-azeotropic composition is that the vapor produced by partial evaporation or distillation of the liquid has substantially the same composition as the liquid from which it was evaporated or distilled, that is, the admixture distills/refluxes without substantial composition change. Another way to characterize a near- azeotropic composition is that the bubble point vapor pressure and the dew point vapor pressure of the composition at a particular temperature are substantially the same. Herein, a composition is near-azeotropic if, after 50 weight percent of the composition is removed, such as by evaporation or boiling off, the difference in vapor pressure between the original composition and the composition remaining after 50 weight percent of the original composition has been removed is less than about 10 percent.
Azeotropic compositions of the present invention at a specified temperature are shown in Table 3.
TABLE 3
Figure imgf000022_0001
Figure imgf000023_0001
Additionally, ternary azeotropes composition have been found as listed in Table 4.
TABLE 4
Figure imgf000023_0002
Figure imgf000024_0001
Figure imgf000025_0001
Figure imgf000026_0001
The near-azeotropic compositions of the present invention at a specified temperature are listed in Table 5.
TABLE 5
Figure imgf000026_0002
Figure imgf000027_0001
Figure imgf000028_0001
Ternary and higher order near-azeotrope compositions comprising fluoroolefin have also been identified as listed in Table 6.
TABLE 6
Figure imgf000028_0002
Figure imgf000029_0001
Figure imgf000030_0001
Figure imgf000031_0001
Certain of the compositions of the present invention are non- azeotropic compositions. Those compositions of the present invention falling within the preferred ranges of Table 2, but outside of the near- azeotropic ranges of Table 5 and Table 6 may be considered to be non- azeotropic.
A non-azeotropic composition may have certain advantages over azetropic or near azeotropic mixtures. A non-azeotropic composition is a mixture of two or more substances that behaves as a mixture rather than a single substance. One way to characterize a non-azeotropic composition is that the vapor produced by partial evaporation or distillation of the liquid has a substantially different composition as the liquid from which it was evaporated or distilled, that is, the admixture distills/refluxes with substantial composition change. Another way to characterize a non- azeotropic composition is that the bubble point vapor pressure and the dew point vapor pressure of the composition at a particular temperature are substantially different. Herein, a composition is non-azeotropic if, after 50 weight percent of the composition is removed, such as by evaporation or boiling off, the difference in vapor pressure between the original composition and the composition remaining after 50 weight percent of the original composition has been removed is greater than about 10 percent. The compositions of the present invention may be prepared by any convenient method to combine the desired amounts of the individual components. A preferred method is to weigh the desired component amounts and thereafter combine the components in an appropriate vessel. Agitation may be used, if desired.
An alternative means for making compositions of the present invention may be a method for making a refrigerant blend composition, wherein said refrigerant blend composition comprises a composition as disclosed herein, said method comprising (i) reclaiming a volume of one or more components of a refrigerant composition from at least one refrigerant container, (ii) removing impurities sufficiently to enable reuse of said one or more of the reclaimed components, (iii) and optionally, combining all or part of said reclaimed volume of components with at least one additional refrigerant composition or component.
A refrigerant container may be any container in which is stored a refrigerant blend composition that has been used in a refrigeration apparatus, air-conditioning apparatus or heat pump apparatus. Said refrigerant container may be the refrigeration apparatus, air-conditioning apparatus or heat pump apparatus in which the refrigerant blend was used. Additionally, the refrigerant container may be a storage container for collecting reclaimed refrigerant blend components, including but not limited to pressurized gas cylinders. Residual refrigerant means any amount of refrigerant blend or refrigerant blend component that may be moved out of the refrigerant container by any method known for transferring refrigerant blends or refrigerant blend components. Impurities may be any component that is in the refrigerant blend or refrigerant blend component due to its use in a refrigeration apparatus, air- conditioning apparatus or heat pump apparatus. Such impurities include but are not limited to refrigeration lubricants, being those described earlier herein, particulates including but not limited to metal, metal salt or elastomer particles, that may have come out of the refrigeration apparatus, air-conditioning apparatus or heat pump apparatus, and any other contaminants that may adversely effect the performance of the refrigerant blend composition.
Such impurities may be removed sufficiently to allow reuse of the refrigerant blend or refrigerant blend component without adversely effecting the performance or equipment within which the refrigerant blend or refrigerant blend component will be used.
It may be necessary to provide additional refrigerant blend or refrigerant blend component to the residual refrigerant blend or refrigerant blend component in order to produce a composition that meets the specifications required for a given product. For instance, if a refrigerant blend has 3 components in a particular weight percentage range, it may be necessary to add one or more of the components in a given amount in order to restore the composition to within the specification limits. Compositions of the present invention have zero or low ozone depletion potential and low global warming potential (GWP). Additionally, the compositions of the present invention will have global warming potentials that are less than many hydrofluorocarbon refrigerants currently in use. One aspect of the present invention is to provide, a refrigerant with a global warming potential of less than 1000, less than 500, less than 150, less than 100, or less than 50. Another aspect of the present invention is to reduce the net GWP of refrigerant mixtures by adding fluoroolefins to said mixtures.
The compositions of the present invention may be useful as low global warming potential (GWP) replacements for currently used refrigerants, including but not limited to R134a (or HFC-134a, 1 ,1 ,1 ,2- tetrafluoroethane), R22 (or HCFC-22, chlorodifluoromethane), R123 (or HFC-123, 2,2-dichloro-1 ,1 I1-trifluoroethane), R11 (CFC-11 , fluorotrichloromethane), R12 (CFC-12, dichlorodifluoromethane), R245fa (or HFC-245fa, 1 ,1 ,1 ,3,3-pentafluoropropane), R114 (or CFC-114, 1 ,2- dichloro-1 ,1 ,2,2-tetrafluoroethane), R236fa (or HFC-236fa, 1 ,1 ,1 ,3,3,3- hexafluoropropane), R124 (or HCFC-124, 2-chloro-1 , 1 ,1 ,2- tetrafluoroethane), R407C (ASHRAE designation for a blend of 52 weight percent R134a, 25 weight percent R125 (pentafluoroethane), and 23 weight percent R32 (difluoromethane), R410A (ASHRAE designation for a blend of 50 weight percent R125 and 50 weight percent R32), R417A, (ASHRAE designation for a blend of 46.6 weight percent R125, 50.0 weight percent R134a, and 3.4 weight percent n-butane), R422A (ASHRAE designation for a blend of 85.1 weight percent R125, 11.5 weight percent R134a, and 3.4 weight percent isobutane), R404A, (ASHRAE designation for a blend of 44 weight percent R125, 52 weight percent R143a (1 ,1 ,1-trifluoroethane), and 4.0 weight percent R134a) and R507A (ASHRAE designation for a blend of 50 weight percent R125 and 50 weight percent R143a). Additionally, the compositions of the present invention may be useful as replacements for R12 (CFC-12, dichlorodifluoromethane) or R502 (ASHRAE designation for a blend of 51.2 weight percent CFC-115 (chloropentafluoroethane) and 48.8 weight percent HCFC-22).
Often replacement refrigerants are most useful if capable of being used in the original refrigeration equipment designed for a different refrigerant. The compositions of the present invention may be useful as replacements for the above-mentioned refrigerants in original equipment. Additionally, the compositions of the present invention may be useful as replacements for the above mentioned refrigerants in equipment designed to use the above-mentioned refrigerants. The compositions of the present invention may further comprise a lubricant.
Lubricants of the present invention comprise refrigeration lubricants, i.e. those lubricants suitable for use with refrigeration, air- conditioning, or heat pump apparatus. Among these lubricants are those conventionally used in compression refrigeration apparatus utilizing chlorofluorocarbon refrigerants. Such lubricants and their properties are discussed in the 1990 ASHRAE Handbook, Refrigeration Systems and Applications, chapter 8, titled "Lubricants in Refrigeration Systems", pages 8.1 through 8.21. Lubricants of the present invention may comprise those commonly known as "mineral oils" in the field of compression refrigeration lubrication. Mineral oils comprise paraffins (i.e. straight-chain and branched-carbon-chain, saturated hydrocarbons), naphthenes (i.e. cyclic paraffins) and aromatics (i.e. unsaturated, cyclic hydrocarbons containing one or more rings characterized by alternating double bonds). Lubricants of the present invention further comprise those commonly known as "synthetic oils" in the field of compression refrigeration lubrication. Synthetic oils comprise alkylaryls (i.e. linear and branched alkyl alkylbenzenes), synthetic paraffins and napthenes, and poly(alphaolefins). Representative conventional lubricants of the present invention are the commercially available BVM 100 N (paraffinic mineral oil sold by BVA Oils), Suniso® 3GS and Suniso® 5GS (naphthenic mineral oil sold by Crompton Co.), Sontex® 372LT (naphthenic mineral oil sold by Pennzoil), Calumet® RO-30 (naphthenic mineral oil sold by Calumet Lubricants), Zerol® 75, Zerol® 150 and Zerol® 500 (linear alkylbenzenes sold by Shrieve Chemicals) and HAB 22 (branched alkylbenzene sold by Nippon Oil).
Lubricants of the present invention further comprise those that have been designed for use with hydrofluorocarbon refrigerants and are miscible with refrigerants of the present invention under compression refrigeration, air-conditioning, or heat pump apparatus' operating conditions. Such lubricants and their properties are discussed in
"Synthetic Lubricants and High-Performance Fluids", R. L. Shubkin, editor, Marcel Dekker, 1993. Such lubricants include, but are not limited to, polyol esters (POEs) such as Castrol® 100 (Castrol, United Kingdom), polyalkylene glycols (PAGs) such as RL-488A from Dow (Dow Chemical, Midland, Michigan), and polyvinyl ethers (PVEs). These lubricants are readily available from various commercial sources.
Lubricants of the present invention are selected by considering a given compressor's requirements and the environment to which the lubricant will be exposed. Lubricants of the present invention preferably have a kinematic viscosity of at least about 5 cs (centistokes) at 4O0C. Commonly used refrigeration system additives may optionally be added, as desired, to compositions of the present invention in order to enhance lubricity and system stability. These additives are generally known within the field of refrigeration compressor lubrication, and include anti wear agents, extreme pressure lubricants, corrosion and oxidation inhibitors, metal surface deactivators, free radical scavengers, foaming and antifoam control agents, leak detectants and the like. In general, these additives are present only in small amounts relative to the overall lubricant composition. They are typically used at concentrations of from less than about 0.1 % to as much as about 3 % of each additive. These additives are selected on the basis of the individual system requirements. Some typical examples of such additives may include, but are not limited to, lubrication enhancing additives, such as alkyl or aryl esters of phosphoric acid and of thiophosphates. Additionally, the metal dialkyl dithiophosphates (e.g. zinc dialkyl dithiophosphate or ZDDP, Lubrizol 1375) and other members of this family of chemicals may be used in compositions of the present invention. Other antiwear additives include natural product oils and assymetrical polyhydroxyl lubrication additives such as Synergol TMS (International Lubricants). Similarly, stabilizers such as anti oxidants, free radical scavengers, and water scavengers may be employed. Compounds in this category can include, but are not limited to, butylated hydroxy toluene (BHT) and epoxides.
The compositions of the present invention may further comprise about 0.01 weight percent to about 5 weight percent of an additive such as, for example, a stabilizer, free radical scavenger and/or antioxidant. Such additives include but are not limited to, nitromethane, hindered phenols, hydroxylamines, thiols, phosphites, or lactones. Single additives or combinations may be used.
The compositions of the present invention may further comprise about 0.01 weight percent to about 5 weight percent of a water scavenger (drying compound). Such water scavengers may comprise ortho esters such as trimethyl-, triethyl-, or tripropylortho formate.
The compositions of the present invention may further comprise a tracer selected from the group consisting of hydrofluorocarbons (HFCs), deuterated hydrocarbons, deuterated hydrofluorocarbons, perfluorocarbons, fluoroethers, brominated compounds, iodated compounds, alcohols, aldehydes, ketones, nitrous oxide (N2O) and combinations thereof. The tracer compounds are added to the compositions in previously determined quantities to allow detection of any dilution, contamination or other alteration of the composition, as described in U. S. Patent application serial no. 11/062044, filed February 18, 2005. Typical tracer compounds for use in the present compositions are listed in Table 7.
TABLE 7
Figure imgf000037_0001
Figure imgf000038_0001
Figure imgf000039_0002
Figure imgf000039_0003
Figure imgf000039_0001
Perfluoromethyldecalin (cis or trans C11F20 (see structure below) and all additional possible isomers)
Figure imgf000040_0001
The compounds listed in Table 7 are available commercially (from chemical supply houses) or may be prepared by processes known in the art.
Single tracer compounds may be used in combination with a refrigeration/heating fluid in the compositions of the present invention or multiple tracer compounds may be combined in any proportion to serve as a tracer blend. The tracer blend may contain multiple tracer compounds from the same class of compounds or multiple tracer compounds from different classes of compounds. For example, a tracer blend may contain 2 or more deuterated hydrofluorocarbons, or one deuterated hydrofluorocarbon in combination with one or more perfluorocarbons.
Additionally, some of the compounds in Table 7 exist as multiple isomers, structural or optical. Single isomers or multiple isomers of the same compound may be used in any proportion to prepare the tracer compound. Further, single or multiple isomers of a given compound may be combined in any proportion with any number of other compounds to serve as a tracer blend.
The tracer compound or tracer blend may be present in the compositions at a total concentration of about 50 parts per million by weight (ppm) to about 1000 ppm. Preferably, the tracer compound or tracer blend is present at a total concentration of about 50 ppm to about 500 ppm and most preferably, the tracer compound or tracer blend is present at a total concentration of about 100 ppm to about 300 ppm.
The compositions of the present invention may further comprise a compatibilizer selected from the group consisting of polyoxyalkylene glycol ethers, amides, nitriles, ketones, chlorocarbons, esters, lactones, aryl ethers, fluoroethers and 1 ,1 ,1-trifluoroalkanes. The compatibilizer is used to improve solubility of hydrofluorocarbon refrigerants in conventional refrigeration lubricants. Refrigeration lubricants are needed to lubricate the compressor of a refrigeration, air-conditioning or heat pump apparatus. The lubricant must move throughout the apparatus with the refrigerant in particular it must return from the non-compressor zones to the compressor to continue to function as lubricant and avoid compressor failure.
Hydrofluorocarbon refrigerants are generally not compatible with convention refrigeration lubricants such as mineral oils, alkylbenzenes, synthetic paraffins, synthetic napthenes and poly(alpha)olefins. Many replacement lubricants have been proposed, however, the polyalkylene glycols, polyol esters and polyvinyl ethers, suggested for use with hydrofluorocarbon refrigerants are expensive and absorb water readily. Water in a refrigeration, air-conditioning system or heat pump can lead to corrosion and the formation of particles that may plug the capillary tubes and other small orifices in the system, ultimately causing system failure. Additionally, in existing equipment, time-consuming and costly flushing procedures are required to change to a new lubricant. Therefore, it is desirable to continue to use the original lubricant if possible. The compatibilizers of the present invention improve solubility of the hydrofluorocarbon refrigerants in conventional refrigeration lubricants and thus improve oil return to the compressor.
Polyoxyalkylene glycol ether compatibilizers of the present invention are represented by the formula R1[(OR2)xOR3]y, wherein: x is an integer from 1-3; y is an integer from 1-4; R1 is selected from hydrogen and aliphatic hydrocarbon radicals having 1 to 6 carbon atoms and y bonding sites; R2 is selected from aliphatic hydrocarbylene radicals having from 2 to 4 carbon atoms; R3 is selected from hydrogen and aliphatic and alicyclic hydrocarbon radicals having from 1 to 6 carbon atoms; at least one of R1 and R3 is said hydrocarbon radical; and wherein said polyoxyalkylene glycol ethers have a molecular weight of from about 100 to about 300 atomic mass units. As used herein, bonding sites mean radical sites available to form covalent bonds with other radicals. Hydrocarbylene radicals mean divalent hydrocarbon radicals. In the present invention, preferred polyoxyalkylene glycol ether compatibilizers are represented by R1[(OR2)xOR3]y: x is preferably 1-2; y is preferably 1 ; R1 and R3 are preferably independently selected from hydrogen and aliphatic hydrocarbon radicals having 1 to 4 carbon atoms; R2 is preferably selected from aliphatic hydrocarbylene radicals having from 2 or 3 carbon atoms, most preferably 3 carbon atoms; the polyoxyalkylene glycol ether molecular weight is preferably from about 100 to about 250 atomic mass units, most preferably from about 125 to about 250 atomic mass units. The R1 and R3 hydrocarbon radicals having 1 to 6 carbon atoms may be linear, branched or cyclic. Representative R1 and R3 hydrocarbon radicals include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, te/f-butyl, pentyl, isopentyl, neopentyl, ferf-pentyl, cyclopentyl, and cyclohexyl. Where free hydroxyl radicals on the present polyoxyalkylene glycol ether compatibilizers may be incompatible with certain compression refrigeration apparatus materials of construction (e.g. Mylar®), R1 and R3 are preferably aliphatic hydrocarbon radicals having 1 to 4 carbon atoms, most preferably 1 carbon atom. The R2 aliphatic hydrocarbylene radicals having from 2 to 4 carbon atoms form repeating oxyalkylene radicals - (OR2)X - that include oxyethylene radicals, oxypropylene radicals, and oxybutylene radicals. The oxyalkylene radical comprising R2 in one polyoxyalkylene glycol ether compatibilizer molecule may be the same, or one molecule may contain different R2 oxyalkylene groups. The present polyoxyalkylene glycol ether compatibilizers preferably comprise at least one oxypropylene radical. Where R1 is an aliphatic or alicyclic hydrocarbon radical having 1 to 6 carbon atoms and y bonding sites, the radical may be linear, branched or cyclic. Representative R1 aliphatic hydrocarbon radicals having two bonding sites include, for example, an ethylene radical, a propylene radical, a butylene radical, a pentylene radical, a hexylene radical, a cyclopentylene radical and a cyclohexylene radical. Representative R1 aliphatic hydrocarbon radicals having three or four bonding sites include residues derived from polyalcohols, such as trimethylolpropane, glycerin, pentaerythritol, 1 ,2,3-trihydroxycyclohexane and 1 ,3,5- trihydroxycyclohexane, by removing their hydroxyl radicals.
Representative polyoxyalkylene glycol ether compatibilizers include but are not limited to: CH3OCH2CH(CH3)O(H or CH3) (propylene glycol methyl (or dimethyl) ether), CH3O[CH2CH(CH3)O]2(H or CH3) (dipropylene glycol methyl (or dimethyl) ether), CH3O[CH2CH(CH3)O]3(H or CH3)
(tripropylene glycol methyl (or dimethyl) ether), C2H5OCH2CH(CH3)O(H or C2H5) (propylene glycol ethyl (or diethyl) ether), C2H5O[CH2CH(CH3)O]2(H or C2H5) (dipropylene glycol ethyl (or diethyl) ether), C2H5O[CH2CH(CH3)O]3(H or C2H5) (tripropylene glycol ethyl (or diethyl) ether), C3H7OCH2CH(CH3)O(H or C3H7) (propylene glycol n-propyl (or di- n-propyl) ether), C3H7O[CH2CH(CH3)O]2(H or C3H7) (dipropylene glycol n- propyl (or di-n-propyl) ether) , C3H7O[CH2CH(CH3)O]3(H or C3H7) (tripropylene glycol n-propyl (or di-n-propyl) ether), C4HgOCH2CH(CH3)OH (propylene glycol n-butyl ether), C4H9O[CH2CH(CH3)O]2(H or C4H9) (dipropylene glycol n-butyl (or di-n-butyl) ether), C4H9O[CH2CH(CH3)O]3(H or C4H9) (tripropylene glycol n-butyl (or di-n-butyl) ether), (CHS)3COCH2CH(CH3)OH (propylene glycol t-butyl ether), (CH3)3CO[CH2CH(CH3)O]2(H or (CH3)3) (dipropylene glycol t-butyl (or di-t- butyl) ether), (CHa)3CO[CH2CH(CH3)O]3(H or (CH3J3) (tripropylene glycol t- butyl (or di-t-butyl) ether), C5Hi1OCH2CH(CH3)OH (propylene glycol n- pentyl ether), C4H9OCH2CH(C2H5)OH (butylene glycol n-butyl ether), C4H9O[CH2CH(C2H5)O]2H (dibutylene glycol n-butyl ether), trimethylolpropane tri-n-butyl ether (C2H5C(CH2O(CH2)3CH3)3) and trimethylolpropane di-n-butyl ether (C2H5C(CH2OC(CH2)3CH3)2CH2OH). Amide compatibilizers of the present invention comprise those represented by the formulae R1C(O)NR2R3 and cyclo-[R4C(O)N(R5)], wherein R1, R2, R3 and R5 are independently selected from aliphatic and alicyclic hydrocarbon radicals having from 1 to 12 carbon atoms; R4 is selected from aliphatic hydrocarbylene radicals having from 3 to 12 carbon atoms; and wherein said amides have a molecular weight of from about 10O to about 300 atomic mass units. The molecular weight of said amides is preferably from about 160 to about 250 atomic mass units. R1, R2, R3 and R5 may optionally include substituted hydrocarbon radicals, that is, radicals containing non-hydrocarbon substituents selected from halogens (e.g., fluorine, chlorine) and alkoxides (e.g. methoxy). R1, R2, R3 and R5 may optionally include heteroatom-substituted hydrocarbon radicals, that is, radicals, which contain the atoms nitrogen (aza-), oxygen (oxa-) or sulfur (thia-) in a radical chain otherwise composed of carbon atoms. In general, no more than three non-hydrocarbon substituents and heteroatoms, and preferably no more than one, will be present for each 10 carbon atoms in R1"3, and the presence of any such non-hydrocarbon substituents and heteroatoms must be considered in applying the aforementioned molecular weight limitations. Preferred amide compatibilizers consist of carbon, hydrogen, nitrogen and oxygen. Representative R1, R2, R3 and R5 aliphatic and alicyclic hydrocarbon radicals include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, fe/f-butyl, pentyl, isopentyl, neopentyl, terf-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and their configurational isomers. A preferred embodiment of amide compatibilizers are those wherein R4 in the aforementioned formula cyclo-[R4C(O)N(R5)-] may be represented by the hydrocarbylene radical (CR6R7)n, in other words, the formula: cyclo-[(CR6R7)nC(O)N(R5)-] wherein: the previously-stated values for molecular weight apply; n is an integer from 3 to 5; R5 is a saturated hydrocarbon radical containing 1 to 12 carbon atoms; R6 and R7 are independently selected (for each n) by the rules previously offered defining R1'3. In the lactams represented by the formula: cyclo- [(CR6R7)nC(O)N(R5)-], all R6 and R7 are preferably hydrogen, or contain a single saturated hydrocarbon radical among the n methylene units, and R5 is a saturated hydrocarbon radical containing 3 to 12 carbon atoms. For example, 1 -(saturated hydrocarbon radical)-5-methylpyrrolidin-2-ones.
Representative amide compatibilizers include but are not limited to: 1-octylpyrrolidin-2-one, 1-decylpyrrolidin-2-one, 1-octyl-5-methylpyrrolidin- 2-one, 1-butylcaprolactam, 1-cyclohexylpyrrolidin-2-one, 1 -butyl-5- methylpiperid-2-one, 1-pentyl-5-methylpiperid-2-one, 1-hexylcaprolactam, 1-hexyl-5-methylpyrrolidin-2-one, 5-methyl-1-pentylpiperid-2-one, 1 ,3- dimethylpiperid-2-one, 1-methylcaprolactam, 1-butyl-pyrrolidin-2-one, 1 ,5- dimethylpiperid-2-one, 1-decyl-5-methyIpyrrolidin-2-one, 1-dodecylpyrrolid- 2-one, N,N-dibutylformamide and N,N-diisopropylacetamide.
Ketone compatibilizers of the present invention comprise ketones represented by the formula R1C(O)R2, wherein R1 and R2 are independently selected from aliphatic, alicyclic and aryl hydrocarbon radicals having from 1 to 12 carbon atoms, and wherein said ketones have a molecular weight of from about 70 to about 300 atomic mass units. R1 and R2 in said ketones are preferably independently selected from aliphatic and alicyclic hydrocarbon radicals having 1 to 9 carbon atoms. The molecular weight of said ketones is preferably from about 100 to 200 atomic mass units. R1 and R2 may together form a hydrocarbylene radical connected and forming a five, six, or seven-membered ring cyclic ketone, for example, cyclopentanone, cyclohexanone, and cycloheptanone. R1 and R2 may optionally include substituted hydrocarbon radicals, that is, radicals containing non-hydrocarbon substituents selected from halogens (e.g., fluorine, chlorine) and alkoxides (e.g. methoxy). R1 and R2 may optionally include heteroatom-substituted hydrocarbon radicals, that is, radicals, which contain the atoms nitrogen (aza-), oxygen (keto-, oxa-) or sulfur (thia-) in a radical chain otherwise composed of carbon atoms. In general, no more than three non-hydrocarbon substituents and heteroatoms, and preferably no more than one, will be present for each 10 carbon atoms in R1 and R2, and the presence of any such non- hydrocarbon substituents and heteroatoms must be considered in applying the aforementioned molecular weight limitations. Representative R1 and R2 aliphatic, alicyclic and aryl hydrocarbon radicals in the general formula R1C(O)R2 include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, teff-butyl, pentyl, isopentyl, neopentyl, ferf-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and their configu rational isomers, as well as phenyl, benzyl, cumenyl, mesityl, tolyl, xylyl and phenethyl.
Representative ketone compatibilizers include but are not limited to: 2-butanone, 2-pentanone, acetophenone, butyrophenone, hexanophenone, cyclohexanone, cycloheptanone, 2-heptanone, 3- heptanone, 5-methyl-2-hexanone, 2-octanone, 3-octanone, diisobutyl ketone, 4-ethylcyclohexanone, 2-nonanone, 5-nonanone, 2-decanone, 4- decanone, 2-decalone, 2-tridecanone, dihexyl ketone and dicyclohexyl ketone.
Nitrile compatibilizers of the present invention comprise nitriles represented by the formula R1CN, wherein R1 is selected from aliphatic, alicyclic or aryl hydrocarbon radicals having from 5 to 12 carbon atoms, and wherein said nitriles have a molecular weight of from about 90 to about 200 atomic mass units. R1 in said nitrile compatibilizers is preferably selected from aliphatic and alicyclic hydrocarbon radicals having 8 to 10 carbon atoms. The molecular weight of said nitrile compatibilizers is preferably from about 120 to about 140 atomic mass units. R1 may optionally include substituted hydrocarbon radicals, that is, radicals containing non-hydrocarbon substituents selected from halogens (e.g., fluorine, chlorine) and alkoxides (e.g. methoxy). R1 may optionally include heteroatom-substituted hydrocarbon radicals, that is, radicals, which contain the atoms nitrogen (aza-), oxygen (keto-, oxa-) or sulfur (thia-) in a radical chain otherwise composed of carbon atoms. In general, no more than three non-hydrocarbon substituents and heteroatoms, and preferably no more than one, will be present for each 10 carbon atoms in R1, and the presence of any such non-hydrocarbon substituents and heteroatoms must be considered in applying the aforementioned molecular weight limitations. Representative R1 aliphatic, alicyclic and aryl hydrocarbon radicals in the general formula R1CN include pentyl, isopentyl, neopentyl, terf-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and their configurational isomers, as well as phenyl, benzyl, cumenyl, mesityl, tolyl, xylyl and phenethyl.
Representative nitrile compatibilizers include but are not limited to: 1-cyanopentane, 2,2-dimethyl-4-cyanopentane, 1-cyanohexane, 1- cyanoheptane, 1-cyanooctane, 2-cyanooctane, 1-cyanononane, 1- cyanodecane, 2-cyanodecane, 1-cyanoundecane and 1-cyanododecane.
Chlorocarbon compatibilizers of the present invention comprise chlorocarbons represented by the formula RCIx, wherein; x is selected from the integers 1 or 2; R is selected from aliphatic and alicyclic hydrocarbon radicals having 1 to 12 carbon atoms; and wherein said chlorocarbons have a molecular weight of from about 100 to about 200 atomic mass units. The molecular weight of said chiorocarbon compatibilizers is preferably from about 120 to 150 atomic mass units. Representative R aliphatic and alicyclic hydrocarbon radicals in the general formula RCIx include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, fe/f-butyl, pentyl, isopentyl, neopentyl, te/f-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and their configurational isomers.
Representative chlorocarbon compatibilizers include but are not limited to: 3-(chloromethyl)pentane, 3-chloro-3-methylpentane, 1- chlorohexane, 1,6-dichlorohexane, 1-chloroheptane, 1-chlorooctane, 1- chlorononane, 1-chlorodecane, and 1 ,1 ,1-trichlorodecane.
Ester compatibilizers of the present invention comprise esters represented by the general formula R1CO2R2, wherein R1 and R2 are independently selected from linear and cyclic, saturated and unsaturated, alkyl and aryl radicals. Preferred esters consist essentially of the elements C, H and O, have a molecular weight of from about 80 to about 550 atomic mass units.
Representative esters include but are not limited to: (CH3)2CHCH2OOC(CH2)2-4OCOCH2CH(CH3)2 (diisobutyl dibasic ester), ethyl hexanoate, ethyl heptanoate, n-butyl propionate, n-propyl propionate, ethyl benzoate, di-n-propyl phthalate, benzoic acid ethoxyethyl ester, dipropyl carbonate, "Exxate 700" (a commercial C7 alkyl acetate), "Exxate 800" (a commercial C8 alkyl acetate), dibutyl phthalate, and tert-butyl acetate. Lactone compatibilizers of the present invention comprise lactones represented by structures [A], [B]1 and [C]:
Figure imgf000048_0001
[A] [B] [C]
These lactones contain the functional group -CO2- in a ring of six (A), or preferably five atoms (B), wherein for structures [A] and [B], Ri through R8 are independently selected from hydrogen or linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl radicals. Each Ri though Re may be connected forming a ring with another Ri through Rs. The lactone may have an exocyclic alkylidene group as in structure [C], wherein Ri through RQ are independently selected from hydrogen or linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl radicals. Each Ri though R6 may be connected forming a ring with another Ri through RQ. The lactone compatibilizers have a molecular weight range of from about 80 to about 300 atomic mass units, preferred from about 80 to about 200 atomic mass units. Representative lactone compatibilizers include but are not limited to the compounds listed in Table 8.
TABLE 8
Figure imgf000048_0002
Figure imgf000049_0001
Figure imgf000050_0001
Lactone compatibilizers generally have a kinematic viscosity of less than about 7 centistokes at 4O0C. For instance, gamma-undecalactone has kinematic viscosity of 5.4 centistokes and cis-(3-hexyl-5- methyl)dihydrofuran-2-one has viscosity of 4.5 centistokes both at 40°C. Lactone compatibilizers may be available commercially or prepared by methods as described in U. S. patent application 10/910,495 filed August 3, 2004, incorporated herein by reference.
Aryl ether compatibilizers of the present invention further comprise aryl ethers represented by the formula R1OR2, wherein: R1 is selected from aryl hydrocarbon radicals having from 6 to 12 carbon atoms; R2 is selected from aliphatic hydrocarbon radicals having from 1 to 4 carbon atoms; and wherein said aryl ethers have a molecular weight of from about 100 to about 150 atomic mass units. Representative R1 aryl radicals in the general formula R1OR2 include phenyl, biphenyl, cumenyl, mesityl, tolyl, xylyl, naphthyl and pyridyl. Representative R2 aliphatic hydrocarbon radicals in the general formula R1OR2 include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and te/f-butyl. Representative aromatic ether compatibilizers include but are not limited to: methyl phenyl ether (anisole), 1 ,3-dimethyoxybenzene, ethyl phenyl ether and butyl phenyl ether.
Fluoroether compatibilizers of the present invention comprise those represented by the general formula R1OCF2CF2H, wherein R1 is selected from aliphatic, alicyclic, and aromatic hydrocarbon radicals having from about 5 to about 15 carbon atoms, preferably primary, linear, saturated, alkyl radicals. Representative fluoroether compatibilizers include but are not limited to: C8Hi7OCF2CF2H and C6H13OCF2CF2H. It should be noted that if the refrigerant is a fluoroether, then the compatibilizer may not be the same fluoroether. Fluoroether compatibilizers may further comprise ethers derived from fluoroolefins and polyols. The fluoroolefins may be of the type CF2=CXY, wherein X is hydrogen, chlorine or fluorine, and Y is chlorine, fluorine, CF3 or ORf, wherein Rf is CF3, C2F5, or C3F7. Representative fluoroolefins are tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, and perfluoromethylvinyl ether. The polyols may be linear or branched. Linear polyols may be of the type HOCH2(CHOH)x(CRR')yCH2OH, wherein R and R' are hydrogen, or CH3, or C2H5 and wherein x is an integer from 0-4, and y is an integer from 0-4. Branched polyols may be of the type
C(OH)t(R)u(CH2OH)v[(CH2)mCH2OH]w, wherein R may be hydrogen, CH3 or C2Hs, m may be an integer from 0 to 3, t and u may be 0 or 1 , v and w are integers from 0 to 4, and also wherein t + u + v + w = 4. Representative polyols are trimethylol propane, pentaerythritol, butanediol, and ethylene glycol.
1 ,1 ,1-Trifluoroalkane compatibilizers of the present invention comprise 1 ,1,1 -trifluoroalkanes represented by the general formula CF3R1 , wherein R1 is selected from aliphatic and alicyclic hydrocarbon radicals having from about 5 to about 15 carbon atoms, preferably primary, linear, saturated, alkyl radicals. Representative 1,1 ,1-trifluoroalkane compatibilizers include but are not limited to: 1 ,1 ,1-trifluorohexane and 1 ,1 ,1-trifluorododecane.
By effective amount of compatibilizer is meant that amount of compatibilizer that leads to efficient solubilizing of the lubricant in the composition and thus provides adequate oil return to optimize operation of the refrigeration, air-conditioning or heat pump apparatus. The compositions of the present invention will typically contain from about 0.1 to about 40 weight percent, preferably from about 0.2 to about 20 weight percent, and most preferably from about 0.3 to about 10 weight percent compatibilizer in the compositions of the present invention. The present invention further relates to a method of solubilizing a refrigerant or heat transfer fluid composition comprising the compositions of the present invention in a refrigeration lubricant selected from the group consisting of mineral oils, alkylbenzenes, synthetic paraffins, synthetic napthenes, and poly(alpha)olefins, wherein said method comprises contacting said lubricant with said composition in the presence of an effective amount of a compatibilizer, wherein said compatibilizer is selected from the group consisting of polyoxyalkylene glycol ethers, amides, nitriles, ketones, chlorocarbons, esters, lactones, aryl ethers, fluoroethers and 1,1,1 -trifluoroalkanes.
The present invention further relates to a method for improving oil- return to the compressor in a compression refrigeration, air-conditioning or heat pump apparatus, said method comprising using a composition comprising compatibilizer in said apparatus.
The compositions of the present invention may further comprise an ultra-violet (UV) dye and optionally a solubilizing agent. The UV dye is a useful component for detecting leaks of the composition by permitting one to observe the fluorescence of the dye in the composition at a leak point or in the vicinity of refrigeration, air-conditioning, or heat pump apparatus. One may observe the fluoroscence of the dye under an ultra-violet light. Solubilizing agents may be needed due to poor solubility of such UV dyes in some compositions.
By "ultra-violet" dye is meant a UV fluorescent composition that absorbs light in the ultra-violet or "near" ultra-violet region of the electromagnetic spectrum. The fluorescence produced by the UV fluorescent dye under illumination by a UV light that emits radiation with wavelength anywhere from 10 nanometer to 750 nanometer may be detected. Therefore, if a composition containing such a UV fluorescent dye is leaking from a given point in a refrigeration, air-conditioning, or heat pump apparatus, the fluorescence can be detected at the leak point. Such UV fluorescent dyes include but are not limited to naphthalimides, perylenes, coumarins, anthracenes, phenanthracenes, xanthenes, thioxanthenes, naphthoxanthenes, fluoresceins, and derivatives or combinations thereof.
Solubilizing agents of the present invention comprise at least one compound selected from the group consisting of hydrocarbons, hydrocarbon ethers, polyoxyalkylene glycol ethers, amides, nitriles, ketones, chlorocarbons, esters, lactones, aryl ethers, fluoroethers and 1 ,1 ,1-trifluoroalkanes. The polyoxyalkylene glycol ethers, amides, nitriles, ketones, chlorocarbons, esters, lactones, aryl ethers, fluoroethers and 1,1 ,1-trifluoroalkanes solubilizing agents have been defined previously herein as being compatibilizers for use with conventional refrigeration lubricants.
Hydrocarbon solubilizing agents of the present invention comprise hydrocarbons including straight chained, branched chain or cyclic alkanes or alkenes containing 5 or fewer carbon atoms and only hydrogen with no other functional groups. Representative hydrocarbon solubilizing agents comprise propane, propylene, cyclopropane, n-butane, isobutane, 2- methylbutane and n-pentane. It should be noted that if the composition contains a hydrocarbon, then the solubilizing agent may not be the same hydrocarbon.
Hydrocarbon ether solubilizing agents of the present invention comprise ethers containing only carbon, hydrogen and oxygen, such as dimethyl ether (DME).
Solubilizing agents of the present invention may be present as a single compound, or may be present as a mixture of more than one solubilizing agent. Mixtures of solubilizing agents may contain two solubilizing agents from the same class of compounds, say two lactones, or two solubilizing agents from two different classes, such as a lactone and a polyoxyalkylene glycol ether.
In the present compositions comprising refrigerant and UV fluorescent dye, or comprising heat transfer fluid and UV fluorescent dye, from about 0.001 weight percent to about 1.0 weight percent of the composition is UV dye, preferably from about 0.005 weight percent to about 0.5 weight percent, and most preferably from 0.01 weight percent to about 0.25 weight percent.
Solubilizing agents such as ketones may have an objectionable odor, which can be masked by addition of an odor masking agent or fragrance. Typical examples of odor masking agents or fragrances may include Evergreen, Fresh Lemon, Cherry, Cinnamon, Peppermint, Floral or Orange Peel all commercially available, as well as d-limonene and pinene. Such odor masking agents may be used at concentrations of from about 0.001% to as much as about 15% by weight based on the combined weight of odor masking agent and solubilizing agent.
Solubility of these UV fluorescent dyes in the compositions of the present invention may be poor. Therefore, methods for introducing these dyes into the refrigeration, air-conditioning, or heat pump apparatus have been awkward, costly and time consuming. US patent no. RE 36,951 describes a method, which utilizes a dye powder, solid pellet or slurry of dye that may be inserted into a component of the refrigeration, air- conditioning, or heat pump apparatus. As refrigerant and lubricant are circulated through the apparatus, the dye is dissolved or dispersed and carried throughout the apparatus. Numerous other methods for introducing dye into a refrigeration or air conditioning apparatus are described in the literature.
Ideally, the UV fluorescent dye could be dissolved in the refrigerant itself thereby not requiring any specialized method for introduction to the refrigeration, air conditioning apparatus, or heat pump. The present invention relates to compositions including UV fluorescent dye, which may be introduced into the system as a solution in the refrigerant. The inventive compositions will allow the storage and transport of dye- containing compositions even at low temperatures while maintaining the dye in solution.
In the present compositions comprising refrigerant, UV fluorescent dye and solubilizing agent, or comprising heat transfer fluid and UV fluorescent dye and solubilizing agent, from about 1 to about 50 weight percent, preferably from about 2 to about 25 weight percent, and most preferably from about 5 to about 15 weight percent of the combined composition is solubilizing agent. In the compositions of the present invention the UV fluorescent dye is present in a concentration from about 0.001 weight percent to about 1.0 weight percent, preferably from 0.005 weight percent to about 0.5 weight percent, and most preferably from 0.01 weight percent to about 0.25 weight percent.
The present invention further relates to a method of using the compositions further comprising ultraviolet fluorescent dye, and optionally, solubilizing agent, in refrigeration, air-conditioning, or heat pump apparatus. The method comprises introducing the composition into the refrigeration, air-conditioning, or heat pump apparatus. This may be done by dissolving the UV fluorescent dye in the composition in the presence of a solubilizing agent and introducing the combination into the apparatus. Alternatively, this may be done by combining solubilizing agent and UV fluorescent dye and introducing said combination into refrigeration or air- conditioning apparatus containing refrigerant and/or heat transfer fluid. The resulting composition may be used in the refrigeration, air- conditioning, or heat pump apparatus.
The present invention further relates to a method of using the compositions comprising ultraviolet fluorescent dye to detect leaks. The presence of the dye in the compositions allows for detection of leaking refrigerant in a refrigeration, air-conditioning, or heat pump apparatus. Leak detection helps to address, resolve or prevent inefficient operation of the apparatus or system or equipment failure. Leak detection also helps one contain chemicals used in the operation of the apparatus.
The method comprises providing the composition comprising refrigerant, ultra-violet fluorescent dye, as described herein, and optionally, a solubilizing agent as described herein, to refrigeration, air- conditioning, or heat pump apparatus and employing a suitable means for detecting the UV fluorescent dye-containing refrigerant. Suitable means for detecting the dye include, but are not limited to, ultra-violet lamps, often referred to as a "black light" or "blue light". Such ultra-violet lamps are commercially available from numerous sources specifically designed for this purpose. Once the ultra-violet fluorescent dye containing composition has been introduced to the refrigeration, air-conditioning, or heat pump apparatus and has been allowed to circulate throughout the system, a leak can be found by shining said ultra-violet lamp on the apparatus and observing the fluorescence of the dye in the vicinity of any leak point.
The present invention further relates to a method for replacing a high GWP refrigerant in a refrigeration, air-conditioning, or heat pump apparatus, wherein said high GWP refrigerant is selected from the group consisting of R134a, R22, R245fa, R114, R236fa, R124, R410A, R407C, R417A, R422A, R507A, and R404A,, said method comprising providing a composition of the present invention to said refrigeration, air-conditioning, or heat pump apparatus that uses, used or is designed to use said high GWP refrigerant. Vapor-compression refrigeration, air-conditioning, or heat pump systems include an evaporator, a compressor, a condenser, and an expansion device. A vapor-compression cycle re-uses refrigerant in multiple steps producing a cooling effect in one step and a heating effect in a different step. The cycle can be described simply as follows. Liquid refrigerant enters an evaporator through an expansion device, and the liquid refrigerant boils in the evaporator at a low temperature to form a gas and produce cooling. The low-pressure gas enters a compressor where the gas is compressed to raise its pressure and temperature. The higher- pressure (compressed) gaseous refrigerant then enters the condenser in which the refrigerant condenses and discharges its heat to the environment. The refrigerant returns to the expansion device through which the liquid expands from the higher-pressure level in the condenser to the low-pressure level in the evaporator, thus repeating the cycle. As used herein, mobile refrigeration apparatus or mobile air- conditioning apparatus refers to any refrigeration or air-conditioning apparatus incorporated into a transportation unit for the road, rail, sea or air. In addition, apparatus, which are meant to provide refrigeration or air- conditioning for a system independent of any moving carrier, known as "intermodal" systems, are included in the present invention. Such intermodal systems include "containers" (combined sea/land transport) as well as "swap bodies" (combined road and rail transport). The present invention is particularly useful for road transport refrigerating or air- conditioning apparatus, such as automobile air-conditioning apparatus or refrigerated road transport equipment.
The present invention further relates to a process for producing cooling comprising evaporating the compositions of the present invention in the vicinity of a body to be cooled, and thereafter condensing said compositions:
The present invention further relates to a process for producing heat comprising condensing the compositions of the present invention in the vicinity of a body to be heated, and thereafter evaporating said compositions.
The present invention further relates to a refrigeration, air- conditioning, or heat pump apparatus containing a composition of the present invention wherein said composition at least one fluoroolefin. The present invention further relates to a mobile air-conditioning apparatus containing a composition of the present invention wherein said composition comprises at least one fluoroolefin.
The present invention further relates to a method for early detection of a refrigerant leak in a refrigeration, air-conditioning or heat pump apparatus said method comprising using a non-azeotropic composition in said apparatus, and monitoring for a reduction in cooling performance. The non-azeotropic compositions will fractionate upon leakage from a refrigeration, air-conditioning or heat pump apparatus and the lower boiling (higher vapor pressure) component will leak out of the apparatus first. When this occurs, if the lower boiling component in that composition provides the majority of the refrigeration capacity, there will be a marked reduction in the capacity and thus performance of the apparatus. In an automobile air-conditioning system, as an example, the passengers in the automobile will detect a reduction in the cooling capability of the system. This reduction in cooling capability can be interpreted to mean that refrigerant is being leaked and that the system requires repair.
The present invention further relates to a method of using the compositions of the present invention as a heat transfer fluid composition, said process comprising transporting said composition from a heat source to a heat sink.
Heat transfer fluids are utilized to transfer, move or remove heat from one space, location, object or body to a different space, location, object or body by radiation, conduction, or convection. A heat transfer fluid may function as a secondary coolant by providing means of transfer for cooling (or heating) from a remote refrigeration (or heating) system. In some systems, the heat transfer fluid may remain in a constant state throughout the transfer process (i.e., not evaporate or condense). Alternatively, evaporative cooling processes may utilize heat transfer fluids as well. A heat source may be defined as any space, location, object or body from which it is desirable to transfer, move or remove heat. Examples of heat sources may be spaces (open or enclosed) requiring refrigeration or cooling, such as refrigerator or freezer cases in a supermarket, building spaces requiring air-conditioning, or the passenger compartment of an automobile requiring air-conditioning. A heat sink may be defined as any space, location, object or body capable of absorbing heat. A vapor compression refrigeration system is one example of such a heat sink.
In another embodiment, the present invention relates to blowing agent compositions comprising the fluoroolefin-containing compositions as described herein for use in preparing foams. In other embodiments the invention provides foamable compositions, and preferably polyurethane and polyisocyanate foam compositions, and method of preparing foams. In such foam embodiments, one or more of the present fluoroolefin- containing compositions are included as a blowing agent in foamable compositions, which composition preferably includes one or more additional components capable of reacting and foaming under the proper conditions to form a foam or cellular structure. 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, N.Y., which is incorporated herein by reference, may be used or adapted for use in accordance with the foam embodiments of the present invention.
The present invention further relates to a method of forming a foam comprising: (a) adding to a foamable composition a fluoroolefin- containing composition of the present invention; and (b) reacting the foamable composition under conditions effective to form a foam.
Another embodiment of the present invention relates to the use of the fluoroolefin-containing compositions as described herein for use as propellants in sprayable compositions. Additionally, the present invention relates to a sprayable composition comprising the fluoroolefin-containing compositions as described herein. The active ingredient to be sprayed together with inert ingredients, solvents and other materials may also be present in a sprayable composition. Preferably, the sprayable composition is an aerosol. Suitable active materials to be sprayed include, without limitations, cosmetic materials, such as deodorants, perfumes, hair sprays, cleaners, and polishing agents as well as medicinal materials such as anti- asthma and anti-halitosis medications.
The present invention further relates to a process for producing aerosol products comprising the step of adding a fluoroolefin-containing composition as described herein to active ingredients in an aerosol container, wherein said composition functions as a propellant.
A further aspect provides methods of suppressing a flame, said methods comprising contacting a flame with a fluid comprising a fluoroolefin-containing composition of the present disclosure. Any suitable methods for contacting the flame with the present composition may be used. For example, a fluoroolefin-containing composition of the present disclosure may be sprayed, poured, and the like onto the flame, or at least a portion of the flame may be immersed in the flame suppression composition. In light of the teachings herein, 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 disclosure. A further embodiment provides methods of extinguishing or suppressing a fire in a total-flood application comprising providing an agent comprising a fluoroolefin-containing composition of the present disclosure; disposing the agent in a pressurized discharge system; and discharging the agent into an area to extinguish or suppress fires in that area. Another embodiment provides methods of inerting an area to prevent a fire or explosion comprising providing an agent comprising a fluoroolefin-containing composition of the present disclosure; disposing the agent in a pressurized discharge system; and discharging the agent into the area to prevent a fire or explosion from occurring.
The term "extinguishment" is usually used to denote complete elimination of a fire; whereas, "suppression" is often used to denote reduction, but not necessarily total elimination, of a fire or explosion. As used herein, terms "extinguishment" and "suppression" will be used interchangeably. There are four general types of halocarbon fire and explosion protection applications. (1) In total-flood fire extinguishment and/or suppression applications, the agent is discharged into a space to achieve a concentration sufficient to extinguish or suppress an existing fire. Total flooding use includes protection of enclosed, potentially occupied spaces such, as computer rooms as well as specialized, often unoccupied spaces such as aircraft engine nacelles and engine compartments in vehicles. (2) In streaming applications, the agent is applied directly onto a fire or into the region of a fire. This is usually accomplished using manually operated wheeled or portable units. A second method, included as a streaming application, uses a "localized" system, which discharges agent toward a fire from one or more fixed nozzles. Localized systems may be activated either manually or automatically. (3) In explosion suppression, a fluoroolefin-containing composition of the present disclosure is discharged to suppress an explosion that has already been initiated. The term "suppression" is normally used in this application because the explosion is usually self- limiting. However, the use of this term does not necessarily imply that the explosion is not extinguished by the agent. In this application, a detector is usually used to detect an expanding fireball from an explosion, and the agent is discharged rapidly to suppress the explosion. Explosion suppression is used primarily, but not solely, in defense applications. (4) In inertion, a fluoroolefin-containing composition of the present disclosure is discharged into a space to prevent an explosion or a fire from being initiated. Often, a system similar or identical to that used for total-flood fire extinguishment or suppression is used. Usually, the presence of a dangerous condition (for example, dangerous concentrations of flammable or explosive gases) is detected, and the fluoroolefin-containing composition of the present disclosure is then discharged to prevent the explosion or fire from occurring until the condition can be remedied.
The extinguishing method can be carried out by introducing the composition into an enclosed area surrounding a fire. Any of the known methods of introduction can be utilized provided that appropriate quantities of the composition are metered into the enclosed area at appropriate intervals. For example, a composition can be introduced by streaming, e.g., using conventional portable (or fixed) fire extinguishing equipment; by misting; or by flooding, e.g., by releasing (using appropriate piping, valves, and controls) the composition into an enclosed area surrounding a fire. The composition can optionally be combined with an inert propellant, e.g., nitrogen, argon, decomposition products of glycidyl azide polymers or carbon dioxide, to increase the rate of discharge of the composition from the streaming or flooding equipment utilized.
Preferably, the extinguishing process involves introducing a fluoroolefin-containing composition of the present disclosure to a fire or flame in an amount sufficient to extinguish the fire or flame. One skilled in this field will recognize that the amount of flame suppressant needed to extinguish a particular fire will depend upon the nature and extent of the hazard. When the flame suppressant is to be introduced by flooding, cup burner test data is useful in determining the amount or concentration of flame suppressant required to extinguish a particular type and size of fire. Laboratory tests useful for determining effective concentration ranges of fluoroolefin-containing compositions when used in conjunction with extinguishing or suppressing a fire in a total-flood application or fire inertion are described, for example, in U.S. Patent No. 5,759,430, which is hereby incorporated by reference.
EXAMPLES
EXAMPLE 1 Impact of vapor leakage
A vessel is charged with an initial composition at a temperature of either -25 °C or if specified, at 25 0C, and the initial vapor pressure of the composition is measured. The composition is allowed to leak from the vessel, while the temperature is held constant, until 50 weight percent of the initial composition is removed, at which time the vapor pressure of the composition remaining in the vessel is measured. Results are shown in Table 9.
TABLE 9
Composition Initial Initial After After Delta P wt% P P 50% 50% (%)
(Psia) (kPa) Leak Leak
(Psia) (kPa)
HFC-1234yf/HFC-32
7.4/92.6 49.2 339 49.2 339 0.0%
1/99 49.2 339 49.2 339 0.0%
20/80 49.0 338 48.8 337 0.3%
40/60 47.5 327 47.0 324 1.0%
57/43 44.9 309 40.5 280 9.6%
58/42 44.6 308 40.1 276 10.2%
HFC-1234yf/HFC-125
10.9/89.1 40.8 281 40.8 281 0.0%
1/99 40.3 278 40.2 277 0.0%
20/80 40.5 279 40.3 278 0.4%
40/60 38.7 267 37.0 255 4.4%
50/50 37.4 258 34.0 235 9.0%
51/49 37.3 257 33.7 232 9.6%
52/48 37.1 256 33.3 229 10.3%
HFC-1234yf/HFC-134
1/99 11.7 81 11.6 80 0.7%
10/90 12.8 88 12.2 84 4.5%
20/80 13.7 95 13.0 89 5.6%
40/60 15.2 105 14.6 101 4.1%
60/40 16.3 113 16.0 110 2.0%
80/20 17.2 119 17.1 118 0.6%
90/10 17.6 121 17.5 121 0.2%
99/1 17.8 123 17.8 123 0.0%
HFC-1234yf/HFC-134a
70.4/29.6 18.4 127 18.4 127 0.0%
80/20 18.3 126 18.3 126 0.1%
90/10 18.2 125 18.1 125 0.1%
99/1 17.9 123 17.9 123 0.1% 40/60 17.9 123 17.8 123 0.7%
20/80 17.0 117 16.7 115 1.7%
10/90 16.4 113 16.1 111 1.5%
1/99 15.6 107 15.6 107 0.3%
HFC-1234yf/HFC-152a
91.0/9.0 17.9 123 17.9 123 0.0%
99/1 17.9 123 17.8 123 0.1 %
60/40 17.4 120 17.2 119 0.7%
40/60 16.6 115 16.4 113 1.6%
20/80 15.7 108 15.4 106 2.0%
10/90 15.1 104 14.9 103 1.5%
1/99 14.6 100 14.5 100 0.2%
HFC-1234yf/HFC-161
1/99 25.3 174 25.3 174 0.0%
10/90 25.2 174 25.2 174 0.1 %
20/80 24.9 172 24.8 171 0.8%
40/60 23.8 164 23.2 160 2.6%
60/40 22.0 152 21.3 147 3.2%
80/20 19.8 137 19.5 134 1.9%
90/10 18.8 129 18.6 128 0.9%
99/1 17.9 123 17.9 123 0.1%
HFC-1234yf/FC-143a
17.3/82.7 39.5 272 39.5 272 0.0%
10/90 39.3 271 39.3 271 0.1 %
1/99 38.7 267 38.6 266 0.1 %
40/60 38.5 266 37.8 260 1.9%
60/40 36.3 250 32.8 226 9.5%
61/39 36.1 249 32.4 223 10.2%
HFC-1234yf/HFC-227ea
84.6/15.4 18.0 124 18.0 124 0.0%
90/10 18.0 124 18.0 124 0.0%
99/1 17.9 123 17.9 123 0.0%
60/40 17.6 121 17.4 120 1.2%
40/60 16.7 115 15.8 109 5.4%
29/71 15.8 109 14.2 98 9.7%
28/72 15.7 108 14.1 97 10.2%
HFC-1234yf/HFC-236fa
99/1 17.8 122 17.7 122 0.2%
90/10 17.0 117 16.6 115 2.4%
80/20 16.2 112 15.4 106 5.1 %
70/30 15.3 106 14.0 97 8.5%
66/34 15.0 103 13.5 93 10.0% HFC-1234yf/HFC-1225ye
1/99 11.6 80 11.5 79 0.5%
10/90 12.6 87 12.2 84 3.2%
20/80 13.5 93 12.9 89 4.3%
40/60 15.0 103 14.4 99 3.7%
60/40 16.2 111 15.8 109 2.2%
80/20 17.1 118 16.9 117 0.9%
90/10 17.5 120 17.4 120 0.3%
99/1 17.8 123 17.8 123 0.0%
HFC-1234yf/trans-HFC-1234ze
1/99 11.3 78 11.3 78 0.4%
10/90 12.2 84 11.8 81 3.3%
20/80 13.1 90 12.5 86 4.6%
40/60 14.6 101 14.0 96 4.3%
60/40 15.8 109 15.4 106 2.7%
80/20 16.9 117 16.7 115 1.1 %
90/10 17.4 120 17.3 119 0.5%
99/1 17.8 123 17.8 123 0.1%
HFC-1234yf/HFC-1243zf
1/99 13.1 90 13.0 90 0.2%
10/90 13.7 94 13.5 93 1.6%
20/80 14.3 99 14.0 97 2.4%
40/60 15.5 107 15.1 104 2.2%
60/40 16.4 113 16.2 112 1.4%
80/20 17.2 119 17.1 118 0.5%
90/10 17.5 121 17.5 121 0.2%
99/1 17.8 123 17.8 123 0.0%
HFC-1234yf/propane
51.5/48.5 33.5 231 33.5 231 0.0%
60/40 33.4 230 33.3 229 0.4%
80/20 31.8 220 29.0 200 8.9%
81/19 31.7 218 28.5 196 10.0%
40/60 33.3 230 33.1 228 0.6%
20/80 32.1 221 31.2 215 2.9%
10/90 31.0 214 30.2 208 2.6%
1/99 29.6 204 29.5 203 0.4%
HFC-1234yf/n-butane
98.1/1.9 17.9 123 17.9 123 0.0%
99/1 17.9 123 17.9 123 0.0%
100/0 17.8 123 17.8 123 0.0%
80/20 16.9 116 16.1 111 4.4%
70/30 16.2 112 14.4 99 10.8%
71/29 16.3 112 14.6 101 9.9% HFC-1234yf/isobutane
88.1/11.9 19.0 131 19.0 131 0.0%
95/5 18.7 129 18.6 128 0.7%
99/1 18.1 125 18.0 124 0.6%
60/40 17.9 123 16.0 110 10.3%
61/39 17.9 123 16.2 112 9.4%
HFC-1234yf/DME
53.5/46.5 13.1 90 13.1 90 0.0%
40/60 13.3 92 13.2 91 0.7%
20/80 14.1 97 13.9 96 1.3%
10/90 14.3 99 14.3 98 0.5%
1/99 14.5 100 14.5 100 0.0%
80/20 14.5 100 14.0 96 3.3%
90/10 15.8 109 15.3 105 3.5%
99/1 17.6 121 17.5 121 0.6%
HFC-1234yf/CF3SCF3
1/99 12.1 83 12.0 83 0.2%
10/90 12.9 89 12.7 87 2.0%
20/80 13.8 95 13.4 92 2.8%
40/60 15.1 104 14.7 101 2.7%
60/40 16.2 112 15.9 110 1.9%
80/20 17.1 118 16.9 117 0.9%
90/10 17.5 120 17.4 120 0.5%
99/1 17.8 123 17.8 123 0.0%
HFC-1234yf/CF3l
1/99 12.0 83 12.0 83 0.2%
10/90 12.9 89 12.7 87 1.7%
20/80 13.7 94 13.3 92 2.6%
40/60 15.1 104 14.7 101 2.7%
60/40 16.2 111 15.8 109 2.0%
80/20 17.1 118 16.9 116 1.1%
90/10 17.5 120 17.4 120 0.5%
99/1 17.8 123 17.8 123 0.1 %
HFC-125/HFC-1234yf/isobutane (25 °C)
85.1/11.5/3.4 201.3 1388 201.3 1388 0.0%
HFC-125/HFC-1234yf/n-butane (25 0C)
67/32/1 194.4 1340 190.2 1311 2.2%
HFC-32/HFC-125/HFC-1234yf (25 0C) 40/50/10 240.6 1659 239.3 1650 0.5%
23/25/52 212.6 1466 192.9 1330 9.3%
15/45/40 213.2 1470 201.3 1388 5.6%
10/60/30 213.0 1469 206.0 1420 3.3% HFC-1225ye/trans-HFC-1234ze
63.0/37.0 11.7 81 11.7 81 0.0%
80/20 11.6 80 11.6 80 0.0%
90/10 11.6 80 11.6 80 0.1%
99/1 11.5 79 11.5 79 0.0%
60/40 11.7 81 11.7 81 0.0%
40/60 11.6 80 11.6 80 0.1%
20/80 11.5 79 11.4 79 0.2%
10/90 11.3 78 11.3 78 0.1%
1/99 11.2 77 11.2 77 0.1%
HFC-1225ya mFC-1243zf
40.0/60.0 13.6 94 13.6 94 0.0%
20/80 13.4 93 13.4 92 0.1%
10/90 13.2 91 13.2 91 0.2%
1/99 13.0 90 13.0 90 0.0%
60/40 13.4 92 13.4 92 0.4%
80/20 12.8 88 12.6 87 1.4%
90/10 12.3 85 12.1 83 1.5%
99/1 11.6 80 11.5 79 0.3%
HFC-1225ye/HFC-134
52.2/47.8 12.8 88 12.8 88 0.0%
80/20 12.4 85 12.3 85 0.6%
90/10 12.0 83 11.9 82 0.8%
99/1 11.5 79 11.5 79 0.2%
40/60 12.7 88 12.7 87 0.2%
20/80 12.3 85 12.2 84 0.8%
10/90 12.0 83 11.9 82 0.9%
1/99 11.6 80 11.6 80 0.2%
HFC-1225ye/HFC-134a
1/99 15.5 107 15.5 107 0.0%
10/90 15.2 105 15.2 105 0.3%
20/80 15.0 103 14.9 103 0.5%
40/60 14.4 99 14.2 98 1.0%
60/40 13.6 94 13.4 93 1.4%
80/20 12.7 88 12.5 86 1.6%
90/10 12.2 84 12.0 83 1.3%
99/1 11.5 80 11.5 79 0.2%
HFC-1225ye/HFC-152a
7.3/92.7 14.5 100 14.5 100 0.0%
1/99 14.5 100 14.5 100 0.0%
40/60 14.2 98 14.2 98 0.4%
60/40 13.7 95 13.6 93 1.1%
80/20 12.9 89 12.7 87 1.5% 90/10 12.2 84 12.1 83 1.1%
99/1 11.5 80 11.5 79 0.1%
HFC-1225ye/HFC-161
1/99 25.2 174 25.2 174 0.0%
10/90 24.9 172 24.8 171 0.6%
20/80 24.5 169 24.0 165 2.0%
40/60 22.9 158 21.4 148 6.5%
56/44 20.9 144 18.8 130 10.0%
99/1 11.7 81 11.6 80 1.0%
90/10 14.1 97 13.0 90 7.5%
84/16 15.5 107 14.0 96 9.9%
83/17 15.8 109 14.2 98 10.2%
HFC-1225ye/HFC-227ea
1/99 10.0 69 10.0 69 0.0%
10/90 10.1 70 10.1 70 0.2%
20/80 10.3 71 10.3 71 0.2%
40/60 10.6 73 10.6 73 0.4%
60/40 10.9 75 10.9 75 0.4%
80/20 11.2 77 11.2 77 0.3%
90/10 11.3 78 11.3 78 0.1 %
99/1 11.5 79 11.5 79 0.0%
HFC-1225ye/HFC-236ea
99/1 11.4 79 11.4 79 0.0%
90/10 11.3 78 11.2 77 0.5%
80/20 11.0 75 10.7 74 2.0%
60/40 10.2 70 9.4 65 8.3%
57/43 10.1 69 9.1 63 9.9%
56/44 10.0 69 9.0 62 10.6%
HFC-1225ye/HFC-236fa
99/1 11.4 79 11.4 79 0.1 %
90/10 11.1 77 11.0 76 1.1 %
80/20 10.7 74 10.4 72 2.4%
60/40 9.8 68 9.2 63 6.6%
48/52 9.2 63 8.2 57 10.0%
HFC-1225ye/HFC-245fa
99/1 11.4 79 11.4 78 0.3%
90/10 10.9 75 10.6 73 2.5%
80/20 10.4 72 9.8 68 5.7%
70/30 9.9 68 8.9 61 9.9%
69/21 9.8 68 8.8 60 10.5%
HFC-1225ye/propane
29.7/70.3 30.4 209 30.4 209 0.0% 20/80 30.3 209 30.2 208 0.2%
10/90 30.0 207 29.9 206 0.4%
1/99 29.5 203 29.5 203 0.1%
60/40 29.5 203 28.5 197 3.3%
72/28 28.4 195 25.6 176 9.8%
73/27 28.2 195 25.2 174 10.8%
HFC-1225ye/n-butane 89.5/10.5 12.3 85 12.3 85 0.0%
99/1 11.7 81 11.6 80 0.9%
80/20 12.2 84 12.0 83 1.5%
65/35 11.7 80 10.5 72 9.9%
64/36 11.6 80 10.4 71 10.9%
HFC-1225ye/isobutane 79.3/20.7 13.9 96 13.9 96 0.0%
90/10 13.6 94 13.3 92 2.4%
99/1 11.9 82 11.6 80 2.8%
60/40 13.5 93 13.0 89 4.1%
50/50 13.1 91 11.9 82 9.6%
49/51 13.1 90 11.8 81 10.2%
HFC-1225ye/DME 82.1/17.9 10.8 74 10.8 74 0.0%
90/10 10.9 75 10.9 75 0.3%
99/1 11.4 78 11.4 78 0.2%
60/40 11.5 79 11.2 77 2.4%
40/60 12.8 88 12.1 84 4.8%
20/80 13.9 96 13.5 93 3.0%
10/90 14.3 98 14.1 97 1.1 %
1/99 14.5 100 14.4 100 0.1%
HFC-1225ye/CF3l 1/99 11.9 82 11.9 82 0.0%
10/90 11.9 82 11.8 82 0.1 %
20/80 11.8 81 11.8 81 0.0%
40/60 11.7 80 11.7 80 0.0%
60/40 11.6 80 11.6 80 0.0%
80/20 11.5 79 11.5 79 0.0%
90/10 11.5 79 11.5 79 0.0%
99/1 11.5 79 11.5 79 0.0%
HFC-1225ye/CF3SCF3 37.0/63.0 12.4 86 12.4 86 0.0%
20/80 12.3 85 12.3 85 0.1 %
10/90 12.2 84 12.2 84 0.1%
1/99 12.0 83 12.0 83 0.1 %
60/40 12.3 85 12.3 85 0.2% 80/20 12.0 83 11.9 82 0.4%
90/10 11.7 81 11.7 81 0.3% 99/1 11.5 79 11.5 79 0.1%
HFC-1225ye/HFC-134a/HFC-152a (25 0C)
76/9/15 81.3 561 80.5 555 1.0%
HFC-1225ye/HFC-134a/HFC-161 (25 0C)
86/10/4 82.1 566 80.2 553 2.3%
HFC-1225ye/HFC-134a/isobutane (25 °C)
87/10/3 83.4 575 80.3 554 3.7%
HFC-1225ye/HFC-134a/DME (25 0C)
87/10/3 77.2 532 76.0 524 1.6%
HFC-1225ye/HFC-152a/isobutane (25°C)
85/13/2 81.2 560 79.3 547 2.3%
HFC-1225ye/HFC-152a/DME (25 °C)
85/13/2 76.6 528 76.0 524 0.8%
HFC-1225ye/HFC-1234yf/HFC-134a (25 °C)
70/20/10 86.0 593 84.0 579 2.3%
20/70/10 98.2 677 97.5 672 .0.7%
HFC-1225ye/HFC-1234yf/HFC-152a (25 0C)
70/25/5 85.1 587 83.4 575 2.0%
25/70/5 95.4 658 94.9 654 0.5%
HFC-1225ye/HFC-1234yf/HFC-125 (25 °C)
25/71/4 105.8 729 96.3 664 9.0%
75/21/4 89.5 617 83.0 572 7.3%
75/24/1 85.3 588 82.3 567 3.5%
25/74/1 98.0 676 95.1 656 3.0%
HFC-1225ye/HFC-1234yf/CF3l (25 0C)
40/40/20 87.5 603 86.0 593 1.7%
45/45/10 89.1 614 87.7 605 1.6%
HFC-1225ye/HFC-134a/HFC-152a/HFC-32 (25 °C) 74/8/17/1 86.1 594 81.5 562 5.3%
HFC-125/HFC-1225ye/isobutane (25 °C)
85.1/11.5/3.4 186.2 1284 179.2 1236 3.8%
HFC-32/HFC-125/HFC-1225ye (25 0C) 30/40/30 212.7 1467 194.6 1342 8.5% trans-HFC-1234ze/cis-HFC-1234ze
99/1 11.1 77 11.1 76 0.4%
90/10 10.5 72 10.1 70 3.4%
80/20 9.8 68 9.1 63 7.1 %
73/27 9.3 64 8.4 58 9.9%
72/28 9.3 64 8.3 57 10.3% trans-HFC-1234ze/HFC-1243zf
17.0/83.0 13.0 90 13.0 90 0.0%
10/90 13.0 90 13.0 90 0.0%
1/99 13.0 90 13.0 90 0.0%
40/60 12.9 89 12.9 89 0.1%
60/40 12.6 87 12.5 86 0.6%
80/20 12.1 83 12.0 82 0.8%
90/10 11.7 80 11.6 80 0.7%
99/1 11.2 77 11.2 77 0.1 % trans-HFC-1234ze/HFC-134
45.7/54.3 12.5 86 12.5 86 0.0%
60/40 12.4 85 12.4 85 0.2%
80/20 12.0 83 11.9 82 0.7%
90/10 11.7 80 11.6 80 0.7%
99/1 11.2 77 11.2 77 0.1%
20/80 12.2 84 12.2 84 0.4%
10/90 11.9 82 11.9 82 0.6%
1/99 11.6 80 11.6 80 0.1 % trans-HFC-1234ze/HFC-134a
9.5/90.5 15.5 107 15.5 107 0.0%
1/99 15.5 107 15.5 107 0.0%
40/60 15.1 104 15.0 103 0.9%
60/40 14.3 99 14.0 96 2.5%
80/20 13.1 90 12.6 87 4.0%
90/10 12.3 85 11.9 82 3.3%
99/1 11.3 78 11.3 78 0.5% trans-HFC-1234ze/HFC-152a
21.6/78.4 14.6 101 14.6 101 0.0%
10/90 14.6 101 14.6 101 0.0%
1/99 14.5 100 14.5 100 0.0%
40/60 14.5 100 14.5 100 0.1%
60/40 14.1 97 13.9 96 1.1 %
80/20 13.2 91 12.8 88 2.5%
90/10 12.4 85 12.0 83 2.6%
99/1 11.3 78 11.3 78 0.4% trans-HFC-1234ze/HFC-161
1/99 25.2 174 25.2 174 0.0%
10/90 25.0 172 24.8 171 0.6%
20/80 24.5 169 24.0 165 2.1%
40/60 22.8 157 21.2 146 7.0%
52/48 21.3 147 19.2 132 9.9%
53/47 21.2 146 19.0 131 10.2%
99/1 11.5 79 11.3 78 1.2%
90/10 13.8 95 12.6 87 8.6%
88/12 14.3 99 12.9 89 9.5%
87/13 14.5 100 13.1 90 10.0% trans-H FC-1234ze/H FC-227eε I
59.2/40.8 11.7 81 11.7 81 0.0%
40/60 11.6 80 11.5 79 0.3%
20/80 11.1 76 10.9 75 1.3%
10/90 10.6 73 10.5 72 1.3%
1/99 10.0 69 10.0 69 0.2%
80/20 11.6 80 11.5 80 0.2%
90/10 11.4 79 11.4 78 0.3%
99/1 11.2 77 11.2 77 0.0% trans-HFC-1234ze/HFC-236es I
99/1 11.2 77 11.2 77 0.0%
90/10 11.0 76 11.0 76 0.4%
80/20 10.8 75 10.6 73 1.6%
60/40 10.2 70 9.5 66 6.6%
54/46 9.9 69 9.0 62 9.5%
53/47 9.9 68 8.9 61 10.1% trans-HFC-1234ze/HFC-236fa
99/1 11.2 77 11.2 77 0.1 %
90/10 10.9 75 10.8 75 0.8%
80/20 10.6 73 10.4 71 2.0%
60/40 9.8 67 9.3 64 5.4%
44/56 9.0 62 8.1 56 9.7%
43/57 8.9 62 8.0 55 10.1% trans-HFC-1234ze/HFC~245fa
99/1 11.2 77 11.1 77 0.2%
90/10 10.7 74 10.5 73 2.0%
80/20 10.3 71 9.8 68 4.7%
70/30 9.8 68 9.0 62 8.2%
67/33 9.7 67 8.7 60 9.7%
66/34 9.6 66 8.7 60 10.2% trans-H FC-1234ze/propane
28.5/71.5 30.3 209 30.3 209 0.0% 10/90 30.0 206 29.9 206 0.3%
1/99 29.5 203 29.5 203 0.1%
40/60 30.2 208 30.1 207 0.4%
60/40 29.3 202 28.3 195 3.4%
71/29 28.4 196 25.7 177 9.3%
72/28 28.3 195 25.4 175 10.2% trans-HFC-1234ze/n-butane
88.6/11.4 11.9 82 11.9 82 0.0%
95/5 11.7 81 11.7 80 0.7%
99/1 11.4 78 11.3 78 0.6%
70/30 11.5 79 11.0 76 4.2%
62/38 11.2 77 10.2 70 9.3%
61/39 11.2 77 10.0 69 10.1% trans-HFC-1234ze/isobutane
77.9/22.1 12.9 89 12.9 89 0.0%
90/10 12.6 87 12.4 85 1.6%
99/1 11.4 79 11.3 78 1.1 %
60/40 12.6 87 12.3 85 2.4%
39/61 11.7 81 10.6 73 9.8%
38/62 11.7 81 10.5 72 10.1%
trans-HFC-1234ze/DME
84.1/15.9 10.8 74 10.8 74 0.0%
90/10 10.8 75 10.8 75 0.0%
99/1 11.1 77 11.1 77 0.0%
60/40 11.5 79 11.3 78 2.2%
40/60 12.7 88 12.2 84 4.4%
20/80 13.9 96 13.5 93 2.9%
10/90 14.3 98 14.1 97 1.0%
1/99 14.5 100 14.5 100 0.0%
trans-HFC-1234ze/CF3SCF3
34.3/65.7 12.7 87 12.7 87 0.0%
20/80 12.6 87 12.6 87 0.2%
10/90 12.4 85 12.3 85 0.3%
1/99 12.0 83 12.0 83 0.1%
60/40 12.4 86 12.4 85 0.5%
80/20 12.0 82 11.8 81 1.1%
90/10 11.6 80 11.5 79 0.9%
99/1 11.2 77 11.2 77 0.2%
trans-HFC-1234ze/CF3l
1/99 11.9 82 11.9 82 0.0%
10/90 11.9 82 11.9 82 0.0%
20/80 11.8 81 11.8 81 . 0.0%
40/60 11.6 80 11.6 80 0.1% 60/40 11.4 79 11.4 79 0.1%
80/20 11.3 78 11.3 78 0.1 % 90/10 11.3 78 11.2 77 0.1% 99/1 11.2 77 11.2 77 0.0%
HFC-32/HFC-125/trans-HFC-1234ze (25 0C) 30/40/30 221.5 1527 209.4 1444 5.5% 30/50/20 227.5 1569 220.2 1518 3.2%
HFC-125/trans-HFC-1234ze/n-butane (25°C)
66/32/2 180.4 1244 170.3 1174 5.6%
HFC-1243zf/HFC-134
63.0/37.0 13.5 93 13.5 93 0.0%
80/20 13.4 93 13.4 92 0.1%
90/10 13.2 91 13.2 91 0.2%
99/1 13.0 90 13.0 90 0.0%
40/60 13.3 92 13.3 91 0.5%
20/80 12.7 88 12.6 87 1.3%
10/90 12.3 84 12.1 83 1.5%
1/99 11.6 80 11.6 80 0.3%
HFC-1243zf/HFC-134a
25.1/74.9 15.9 110 15.9 110 0.0%
10/90 15.8 109 15.8 109 0.1 %
1/99 15.5 107 15.5 107 0.1 %
40/60 15.8 109 15.8 109 0.2%
60/40 15.3 106 15.1 104 1.2%
80/20 14.4 99 14.1 97 2.1 %
90/10 13.8 95 13.5 93 1.7%
99/1 13.1 90 13.0 90 0.2%
HFC-1243zf/HFC-152a
40.7/59.3 15.2 104 15.2 104 0.0%
20/80 15.0 103 15.0 103 0.2%
10/90 14.8 102 14.7 102 0.3%
1/99 14.5 100 14.5 100 0.1 %
60/40 15.0 103 14.9 103 0.3%
80/20 14.4 99 14.2 98 1.1 %
90/10 13.8 95 13.6 94 1.2%
99/1 13.1 90 13.1 90 0.2%
HFC-1243zf/HFC-161
1/99 25.2 174 25.2 174 0.0%
10/90 24.9 172 24.8 171 0.3%
20/80 24.5 169 24.2 167 0.9%
40/60 23.3 160 22.6 156 2.9%
60/40 21.5 148 20.1 139 6.3% 78/22 18.8 130 16.9 117 10.0%
90/10 16.2 111 14.6 101 9.5%
99/1 13.4 92 13.1 90 1.7%
HFC-1243zf/HFC-227ea
78.5/21.5 13.1 90 13.1 90 0.0%
90/10 13.1 90 13.1 90 0.0%
99/1 13.0 90 13.0 90 0.0%
60/40 13.0 90 13.0 89 0.2%
40/60 12.6 87 12.5 86 1.1%
20/80 11.8 81 11.5 79 2.7%
10/90 11.1 76 10.7 74 2.8%
1/99 10.1 69 10.0 69 0.6%
HFC-1243zf/HFC-236ea
99/1 13.0 89 13.0 89 0.0%
90/10 12.8 88 12.7 87 0.5%
80/20 12.5 86 12.3 84 1.8%
60/40 11.7 81 11.0 76 6.6%
53/47 11.4 79 10.3 71 9.9%
52/48 11.4 78 10.2 70 10.5%
HFC-1243zf/HFC-236fa
99/1 13.0 89 12.9 89 0.1%
90/10 12.6 87 12.5 86 1.0%
80/20 12.2 84 11.9 82 2.5%
60/40 11.3 78 10.5 73 6.6%
49/51 10.6 73 9.6 66 9.9%
48/52 10.6 73 9.5 65 10.2%
HFC-1243zf/HFC-245fa
99/1 12.9 89 12.9 89 0.2%
90/10 12.5 86 12.2 84 2.1%
80/20 12.0 83 11.4 79 4.6%
70/30 11.5 79 10.6 73 7.9%
66/34 11.3 78 10.2 70 9.6%
65/35 11.2 77 10.1 69 10.2%
HFC-1243zf/propane
32.8/67.2 31.0 213 31.0 213 0.0%
10/90 30.3 209 30.1 207 0.7%
1/99 29.5 204 29.5 203 0.1%
60/40 30.1 208 29.2 201 3.2%
72/28 29.0 200 26.1 180 10.2%
71/29 29.2 201 26.5 182 9.3%
HFC-1243zf/n-butane
90.3/9.7 13.5 93 13.5 93 0.0% 99/1 13.1 90 13.1 90 0.2%
62/38 12.6 87 11.4 79 9.4%
61/39 12.6 87 11.3 78 10.3%
HFC-1243zf/isobutane
80.7/19.3 14.3 98 14.3 98 0.0%
90/10 14.1 97 14.0 96 0.9%
99/1 13.2 91 13.1 90 0.7%
60/40 13.8 95 13.4 92 3.2%
45/55 13.1 91 11.9 82 9.5%
44/56 13.1 90 11.8 81 10.1%
HFC-1243zf/DME
72.7/27.3 12.0 83 12.0 83 0.0%
90/10 12.4 85 12.3 85 0.5%
99/1 12.9 89 12.9 89 0.1 %
60/40 12.2 84 12.1 84 0.5%
40/60 13.0 90 12.7 88 2.2%
20/80 14.0 96 13.7 95 2.0%
10/90 14.3 99 14.2 98 0.6%
1/99 14.5 100 14.5 100 0.0% cis-HFC-1234ze/HFC-236ea (25 °C)
20.9/79.1 30.3 209 30.3 209 0.0%
10/90 30.2 208 30.2 208 0.0%
1/99 29.9 206 29.9 206 0.0%
40/60 30.0 207 30.0 207 0.2%
60/40 29.2 201 28.9 199 0.9%
80/20 27.8 191 27.4 189 1.4%
90/10 26.8 185 26.5 183 1.1%
99/1 25.9 178 25.8 178 0.2% cis-H FC-1234ze/HFC-236fa (25 0C)
1/99 39.3 271 39.3 271 0.0%
10/90 38.6 266 38.4 265 0.3%
20/80 37.6 259 37.3 257 0.9%
40/60 35.4 244 34.5 238 2.5%
60/40 32.8 226 31.4 216 4.3%
78/22 29.6 204 28.2 195 4.8%
90/10 27.8 192 26.9 185 3.4%
99/1 26.0 179 25.8 178 0.5%
cis-HFC-1234ze/HFC-245fa (25 0C)
76.2/23.7 26.2 180 26.2 180 0.0%
90/10 26.0 179 26.0 179 0.0%
99/1 25.8 178 25.8 178 0.0%
60/40 26.0 179 25.9 179 0.2%
40/60 25.3 174 25.0 173 0.9% 20/80 23.9 164 23.5 162 1.7%
10/90 22.8 157 22.5 155 1.5%
1/99 21.6 149 21.5 149 0.2% cis-HFC-1234ze/n-butane
51.4/48.6 6.1 42 6.1 42 0.0%
80/20 5.8 40 5.2 36 9.3%
81/19 5.8 40 5.2 36 10.4%
40/60 6.1 42 6.0 41 0.7%
20/80 5.8 40 5.6 39 3.3%
10/90 5.6 38 5.4 37 3.1 %
1/99 5.3 36 5.2 36 0.6% cis-HFC-1234ze/isobutane
26.2/73.8 8.7 60 . 8.7 60 0.0%
10/90 8.7 60 8.6 59 0.3%
1/99 8.5 59 8.5 59 0.0%
40/60 8.7 60 8.6 60 0.5%
60/40 8.4 58 8.0 55 4.3%
70/30 8.1 56 7.3 50 10.3%
69/31 8.2 56 7.4 51 9.4% cis-HFC-1234ze/2-methylbutane (25 °C)
86.6/13.4 27.3 188 27.3 188 0.0%
90/10 27.2 187 27.2 187 0.1 %
99/1 26.0 180 25.9 179 0.5%
60/40 25.8 178 24.0 166 6.9%
55/45 25.3 174 22.8 157 10.0% cis-HFC-1234ze/n-pentane (25 0C)
92.9/9.1 26.2 181 26.2 181 0.0%
99/1 25.9 178 25.9 178 0.1 %
80/20 25.6 177 25.2 174 1.8%
70/30 24.8 171 23.5 162 5.6%
64/36 24.3 167 22.0 152 9.2%
63/37 24.2 167 21.8 150 9.9%
HFC-1234ye/HFC-134 (25 0C)
1/99 75.9 523 75.8 523 0.1 %
10/90 73.8 509 73.0 503 1.1 %
20/80 71.3 491 69.0 476 3.1 %
38/62 66.0 455 59.6 411 9.7%
39/61 65.7 453 58.9 406 10.2%
HFC-1234ye/HFC-236ea (-25 ° C)
24.0/76.0 3.4 23 3.4 23 0.0%
10/90 3.3 23 3.3 23 0.3% 1/99 3.3 23 3.3 23 0.0%
40/60 3.3 23 3.3 23 0.0%
60/40 3.2 22 3.2 22 0.9%
80/20 3.1 21 3.0 21 1.6%
90/10 2.9 20 2.9 20 1.4%
99/1 2.8 19 2.8 19 0.0%
HFC-1234ye/HFC-236fa (25 0C)
1/99 39.2 270 39.2 270 0.1 %
10/90 37.7 260 37.3 257 1.1 %
20/80 36.1 249 35.2 243 2.5%
40/60 32.8 226 31.0 213 5.7%
60/40 29.3 202 26.7 184 8.8%
78/22 25.4 175 23.1 159 9.1 %
90/10 23.2 160 21.7 150 6.3%
99/1 21.0 145 20.8 144 0.8%
HFC-1234ye/HFC-245fa (25 0C)
42.5/57.5 22.8 157 22.8 157 0.0%
20/80 22.5 155 22.4 155 0.3%
10/90 22.1 152 22.0 152 0.3%
1/99 21.5 148 21.5 148 0.0%
60/40 22.6 156 22.6 156 0.2%
80/20 22.0 152 21.9 151 0.6%
90/10 21.5 148 21.3 147 0.6%
99/1 20.8 144 20.8 143 0.1 %
HFC-1234ye/cis-HFC-1234ze (25 0C)
1/99 25.7 177 25.7 177 0.0%
10/90 25.6 176 25.6 176 0.0%
20/80 25.3 175 25.3 174 0.1 %
40/60 24.7 170 24.5 169 0.5%
60/40 23.7 163 23.5 162 1.0%
78/22 22.4 155 22.2 153 1.2%
90/10 21.7 149 21.5 148 0.9%
99/1 20.9 144 20.8 144 0.1 %
HFC~1234ye/n-butane (25 °C)
41.2/58.8 38.0 262 38.0 262 0.0%
20/80 37.3 257 37.0 255 0.8%
10/90 36.4 251 36.1 249 0.9%
1/99 35.4 244 35.3 243 0.2%
60/40 37.4 258 36.9 254 1.4%
70/30 36.5 252 34.9 241 4.4%
78/22 35.3 243 31.8 219 9.9%
79/21 35.1 242 31.3 216 10.9% HFC-1234ye/cyclopentane (25 c 'C) 99/1 20.7 143 20.7 143 0.0%
90/10 20.3 140 20.0 138 1.0%
80/20 19.5 134 18.7 129 4.1 %
70/30 18.6 128 16.9 116 9.5%
69/31 18.5 128 16.6 115 10.3%
HFC-1234ye/isobutane (25 0C) 16.4/83.6 50.9 351 50.9 351 0.0%
10/90 50.9 351 50.9 351 0.0%
1/99 50.5 348 50.5 348 0.0%
40/60 50.1 345 49.6 342 1.0%
60/40 47.8 330 45.4 313 5.2%
68/32 46.4 320 42.0 289 9.5%
69/31 46.2 318 41.4 286 10.3%
HFC-1234ye/2-methylbutane (25 0C) 80.3/19.7 23.1 159 23.1 159 0.0%
90/10 22.8 157 22.6 156 1.1%
99/1 21.2 146 20.9 144 1.0%
60/40 22.5 155 21.7 149 3.6%
47/53 21.5 148 19.4 134 9.6%
46/54 21.4 148 19.2 133 10.1 %
HFC-1234ye/n-pentane (25 °C) 87.7/12.3 21.8 150 21.8 150 0.0%
95/5 21.5 149 21.4 148 0.5%
99/1 21.0 145 20.9 144 0.4%
60/40 20.5 141 18.9 131 7.7%
57/43 20.3 140 18.3 126 9.7%
56/44 20.2 139 18.1 125 10.4%
The difference in vapor pressure between the original composition and the composition remaining after 50 weight percent is removed is less then about 10 percent for compositions of the present invention. This indicates that the compositions of the present invention would be azeotropic or near-azeotropic.
EXAMPLE 2
Refrigeration Performance Data Table 10 shows the performance of various refrigerant compositions of the present invention as compared to HFC-134a. In Table 10, Evap Pres is evaporator pressure, Cond Pres is condenser pressure, Comp Disch T is compressor discharge temperature, COP is energy efficiency, and CAP is capacity. The data are based on the following conditions.
Evaporator temperature 40.00F (4.40C)
Condenser temperature 130.00F (54.40C)
Subcool temperature 10.0°F (5.5°C)
Return gas temperature 60.00F (15.6°C)
Compressor efficiency is 100%
Note that the superheat is included in cooling capacity calculations.
TABLE 10
Figure imgf000079_0001
Figure imgf000080_0001
Several compositions have even higher energy efficiency (COP) than HFC-134a while maintaining lower discharge pressures and temperatures. Capacity for the present compositions is also similar to R134a indicating these could be replacement refrigerants for R134a in refrigeration and air-conditioning, and in mobile air-conditioning applications in particular. Those compositions containing hydrocarbon may also improve oil solubility with conventional mineral oil and alkyl benzene lubricants.
EXAMPLE 3
Refrigeration Performance Data
Table 11 shows the performance of various refrigerant compositions of the present invention as compared to R404A and R422A. In Table 11 , Evap Pres is evaporator pressure, Cond Pres is condenser pressure, Comp Disch T is compressor discharge temperature, EER is energy efficiency, and CAP is capacity. The data are based on the following conditions.
Evaporator temperature -17.8°C
Condenser temperature 46.1 °C
Subcool temperature 5.5°C
Return gas temperature 15.60C
Compressor efficiency is 70% Note that the superheat is included in cooling capacity calculations. TABLE 11
Evap Cond P Compr
Press Press Disch T CAP
Existing Refrigerant (kPa» (kPa) (C) (kJ/m3) EER
Product
R22 267 1774 144 1697 4.99 R404A 330 2103 101.1 1769 4.64 R507A 342 2151 100.3 1801 4.61 R422A 324 2124 95.0 1699 4.54
Candidate wt%
Replacement
HFC-125/HFC- 85.1/11.5/3.4 330 2137 93.3 1699 4.50
1225ye/isobutane
HFC-125/trans-HFC- 86.1/11.5/2.4 319 2096 94.4 1669 4.52
1234ze/isobutane
HFC-125/HFC- 87.1/11.5/1.4 343 2186 93.3 1758 4.52
1234yf/isobutane HFC-125/HFC- 85.1/11.5/3.4 322 2106 93.5 1674 4.52
1225ye/n-butane
HFC-125/trans-HFC- 86.1/11.5/2.4 314 2083 94.8 1653 4.53
1234ze/n-butane
HFC-125/HFC- 87.1/11.5/1.4 340 2173 93.4 1748 4.53
1234yf/n-butane
HFC-32/HFC- 10/10/'80 173 1435 107 1159 4.97
125/HFC-1225ye
HFC-32/HFC- 25/25/50 276 2041 120 1689 4.73
125/HFC-1225ye
HFC-32/HFC- 25/40/35 314 2217 119 1840 4.66
125/HFC-1225ye
HFC-32/HFC- 30/10/60 265 1990 125 1664 4.78
125/HFC-1225ye
HFC-32/HFC- 30/15/55 276 2046 125 1710 4.76
125/HFC-1225ye
HFC-32/HFC- 30/20/50 287 2102 124 1757 4.73
125/HFC-1225ye
HFC-32/HFC- 30/30/40 311 2218 124 1855 4.68
125/HFC-1225ye
HFC-32/HFC- 30/35/35 324 2271 123 1906 4.66
125/HFC-1225ye
HFC-32/HFC- 35/15/50 296 2157 129 1820 4.72
125/HFC-1225ye
HFC-32/HFC- 35/20/45 308 2212 129 1868 4.70
125/HFC-1225ye
HFC-32/HFC- 35/30/35 332 2321 127 1968 4.66
125/HFC-1225ye
HFC-32/HFC- 35/40/25 357 2424 126 2068 4.64
125/HFC-1225ye
HFC-32/HFC- 50/30/20 390 2584 138 2277 4.54
125/HFC-1225ye
HFC-32/HFC- 40/30/30 353 2418 131 2077 4.66
125/HFC-1225ye
HFC-32/HFC- 40/35/25 364 2465 131 2124 4.64
125/HFC-1225ye
HFC-32/HFC- 45/30/25 372 2505 135 2180 4.66
125/HFC-1225ye
HFC-32/HFC- 10/20/10/60 190 1517 110 1255 4.97
125/HFC-152a/HFC-
1225ye
HFC-32/HFC- 15/25/10/50 221 1709 115 1422 4.90
125/HFC-152a/HFC-
1225ye
HFC-32/HFC- 20/20/15/45 229 1755 121 1485 4.90
125/HFC-152a/HFC-
1225ye
HFC-32/HFC- 30/20/50 272 1984 130 1706 4.80
125/HFC-152a/HFC-
1225ye
HFC-32/HFC- 40/10/50 299 2159 137 1860 1.00
125/HFC-152a/HFC-
1225ye
HFC-32/HFC- 30/30/40 286 2030 133 1774 4.80
125/HFC-152a/HFC-
1225ye
HFC-32/HFC- 30/60/10 314 2120 144 1911 4.75 125/HFC-152a/HFC-
1225ye
HFC-32/HFC- 40/20/40 315 2214 139 1936 4.73
125/HFC-152a/HFC-
1225ye
HFC-32/HFC- 30/50/20 309 2101 139 1885 4.78
125/HFC-152a/HFC-
1225ye
HFC-32/HFC- 40/40/20 346 2309 145 2079 4.71
125/HFC-152a/HFC-
1225ye
HFC-32/HFC- 45/45/10 373 2432 152 2217 4.67
125/HFC-152a/HFC-
1225ye
HFC-32/HFC- 45/10/45 319 2260 141 1964 4.71
125/HFC-152a/HFC-
1225ye
HFC-32/HFC- 50/10/40 338 2353 145 2065 4.68
125/HFC-152a/HFC-
1225ye
HFC-32/HFC- 50/20/30 356 2410 147 2150 4.68
125/HFC-152a/HFC-
1225ye
HFC-32/HFC- 25/5/70 230 1781 122 1495 4.90
125/HFC-152a/HFC-
1225ye
HFC-32/HFC- 60/30/10 409 2626 158 2434 4.66
125/HFC-152a/HFC-
1225ye
HFC-32/HFC- 50/25/25 364 2437 149 2192 4.68
125/HFC-152a/HFC-
1225ye
HFC-32/HFC- 50/20/30 356 2410 147 2156 4.68
125/HFC-152a/HFC-
1225ye
HFC-32/HFC- 25/50/25 284 1964 134 1754 4.85
125/HFC-152a/HFC-
1225ye
HFC-32/HFC- 45/30/25 353 2368 146 2124 4.71
125/HFC-152a/HFC-
1225ye
HFC-32/CF3I/HFC- 5/50/45 199 1377 107 1254 5.11
1234yf
HFC-32/CF3l/HFC- 5/30/65 197 1382 103 1241 5.11
1234yf
HFC-32/CF3I/HFC- 10/25/65 220 1542 107 1374 5.04
1234yf
HFC-32/CF3l/HFC- 20/10/70 255 1786 114 1577 4.95
1234yf
HFC-32/CF3I/HFC- 30/10/60 295 2020 123 1795 4.88
1234yf
HFC-32/CF3I/HFC- 30/20/50 305 2057 125 1843 4.85
1234yf
HFC-32/CF3I/HFC- 30/30/40 314 2091 128 1887 4.85
1234yf
HFC-32/CF3I/HFC- 20/40/40 275 1861 121 1679 4.92
1234yf HFC-32/CF3l/HFC- 10/40/50 225 1558 111 1404 5.04
1234yf
HFC-32/CF3I/HFC- 50/20/30 378 2447 143 2238 4.73
1234yf
HFC-32/CF3I/HFC- 40/30/30 354 2305 137 2099 4.76
1234yf
HFC-32/CF3I/HFC- 40/40/20 360 2336 142 2136 4.74
1234yf
HFC-32/CF3I/HFC- 35/35/30 338 2217 135 2015 4.78
1234yf
HFC-32/CF3I/HFC- 35/30/35 334 2202 133 1996 4.80
1234yf
HFC-32/CF3I/HFC- 50/25/25 384 2468 145 2267 4.72
1234yf
HFC-32/CF3l/HFC- 40/20/20/20 331 2246 136 1999 4.76
1225ye/HFC-1234yf
HFC-32/CF3l/HFC- 30/20/25/25 290 2029 127 1782 4.83
1225ye/HFC-1234yf
HFC-32/CF3l/HFC- 30/10/30/30 279 1987 125 1728 4.83
1225ye/HFC-1234yf
HFC-32/HFC- 25/25/25/25 297 2089 118 1772 4.76
125/HFC-
1234yf/HFC-1225ye
HFC-32/HFC- 20/30/25/25 286 2025 113 1702 4.64
125/HFC-
1234yf/HFC-1225ye
HFC-32/HFC- 20/30/30/20 290 2033 113 1717 4.76
125/HFC-
1234yf/HFC-1225ye
HFC-32/HFC- 20/30/40/10 297 2048 112 1746 4.78
125/HFC-
1234yf/HFC-1225ye
HFC-32/HFC- 30/30/20/20 328 2251 122 1925 4.71
125/HFC-
1234yf/HFC-1225ye
HFC-32/HFC- 30/30/1/39 312 2217 123 1858 4.68
125/HFC-
1234yf/HFC-1225ye
HFC-32/HFC- 30/30/39/1 342 2275 120 1979 4.73
125/HFC-
1234yf/HFC-1225ye
HFC-32/HFC- 30/30/10/30 320 2235 123 1891 4.68
125/HFC-
1234yf/HFC-1225ye
HFC-32/HFC- 35/30/5/30 337 2330 127 1986 4.66
125/HFC-
1234yf/HFC-1225ye
HFC-32/HFC- 20/15/10/55 240 1818 115 1513 4.85
125/HFC-
1234yf/HFC-1225ye
HFC-32/HFC- 30/15/10/45 284 2066 124 1743 4.76
125/HFC-
1234yf/HFC-1225ye
HFC-32/HFC- 40/30/15/15 341 2364 132 2022 4.66
125/HFC-
1234yf/HFC-1225ye
HFC-32/HFC- 30/25/5/35/5 335 2240 121 1954 4.76 125/CF3I/HFC-
1234yf/HFC-1225ye
HFC-32/HFC- 30/25/5/40 338 2245 121 1966 4.76
125/CF3l/HFC-1234yf
HFC-32/HFC- 25/35/35/5 323 2195 115 1837 4.64
125/HFC-
1225ye/isobutane
HFC-32/HFC- 25/38/35/2 318 2214 117 1837 4.64
125/HFC-
1225ye/isobutane
HFC-32/HFC- 25/38/35/2 330 2297 118 1892 4.59
125/HFC-
1225ye/propane
HFC-32/CF3l/HFC- 50/20/25/5 321 2252 150 2010 4.76
1225ye/DME
HFC-32/HFC- 35/30/30/5 293 2135 131 1823 4.76
125/HFC-
1225ye/DME
HFC-32/HFC- 35/33/30/2 320 2268 129 1925 4.68
125/HFC-
1225ye/DME
HFC-32/HFC- 35/35/28/2 324 2288 129 1943 4.68
125/HFC-
1225ye/DME
HFC-32/HFC- 25/50/25 365 2376 115 2040 4.66
125/HFC-1234yf
HFC-32/HFC- 30/30/40 343 2276 120 1982 4.73
125/HFC-1234yf
HFC-32/HFC- 20/30/50 303 2059 112 1770 4.78
125/HFC-1234yf
HFC-32/HFC- 25/25/10/40 323 2154 118 1884 4.78
125/CF3l/HFC-1234yf
HFC-32/HFC- 25/25/10/40 291 2088 121 1757 4.73
I25/CF3I/HFC-
1225ye
HFC-32/HFC- 20/30/10/40 279 2017 117 1680 4.73
125/CF3I/HFC-
1225ye
HFC-32/HFC- 20/35/5/40 285 2056 116 1699 4.71
125/CF3I/HFC-
1225ye
Several compositions have energy efficiency (COP) comparable top R404A and R422A. Discharge temperatures are also lower than R404A and R507A. Capacity for the present compositions is also similar to R404A, R507A, and R422A indicating these could be replacement refrigerants for in refrigeration and air-conditioning. Those compositions containing hydrocarbon may also improve oil solubility with conventional mineral oil and alkyl benzene lubricants.
EXAMPLE 4 Refrigeration Performance Data
Table 12 shows the performance of various refrigerant compositions of the present invention as compared to HCFC-22, R410A, R407C, and R417A. In Table 12, Evap Pres is evaporator pressure, Cond Pres is condenser pressure, Comp Disch T is compressor discharge temperature, EER is energy efficiency, and CAP is capacity. The data are based on the following conditions.
Evaporator temperature 4.4°C
Condenser temperature 54.40C 0 Subcool temperature 5.5°C
Return gas temperature 15.6°C
Compressor efficiency is 100% Note that the superheat is included in cooling capacity calculations.
TABLE 12
Evap Cond Compr
Press Press Disch T CAP
Existing Refrigerant (kPa)) (kPa) (C) (kJ/m3) EER
Product
R22 573 2149 88.6 3494 14.73
R410A 911 3343 89.1 4787 13.07
R407C 567 2309 80.0 3397 14.06
R417A 494 1979 67.8 2768 13.78
Candidate Replacement wt%
HFC-32/HFC-125/HFC- 30/40/30 732 2823 81.1 3937 13.20
1225ye
HFC-32/HFC-125/HFC- 23/25/52 598 2429 78.0 3409 13.54
1225ye
HFC-32/HFC-125/trans- 30/50/20 749 2865 81.7 3975 13.10
HFC-1234ze
HFC-32/HFC-125/trans- 23/25/52 546 2252 78.9 3222 13.80
HFC-1234ze
HFC-32/HFC-125/HFC- 40/50/10 868 3185 84.4 4496 13.06
1234yf
HFC-32/HFC-125/HFC- 23/25/52 656 2517 76.7 3587 13.62
1234yf
HFC-32/HFC-125/HFC- 15/45/40 669 2537 73.3 3494 13.28
1234yf
HFC-32/HFC-125/HFC- 10/60/30 689 2586 71.3 3447 12.96
1234yf
HFC-125/HFC-1225ye/n- 65/32/3 563 2213 66.1 2701 12.87 butane 6 008164
HFC-125/trans-HFC- 66/32/2 532 2130 67.2 2794 13.08
1234ze/n-butane
HFC-125/HFC-1234yf/n- 67/32/1 623 2344 66.1 3043 12.85 butane
HFC-125/HFC- 65/32/3 574 2244 66.2 2874 12.79
1225ye/isobutane
HFC-125/trans-HFC- 66/32/2 538 2146 67.4 2808 13.04
1234ze/isobutane
HFC-125/HFC- 67/32/1 626 2352 66.3 3051 12.83
1234yf/isobutane
Compositions have energy efficiency (EER) comparable to R22, R407C, R417A, and R41 OA while maintaining low discharge temperatures. Capacity for the present compositions is also similar to 5 R22, R407C and R417A indicating these could be replacement refrigerants for in refrigeration and air-conditioning. Those compositions containing hydrocarbon may also improve oil solubility with conventional mineral oil and alkyl benzene lubricant.
0 EXAMPLE 5
Refrigeration Performance Data Table 12 shows the performance of various refrigerant compositions of the present invention as compared to HCFC-22 and R410A. In Table 12, Evap Pres is evaporator pressure, Cond Pres is 5 condenser pressure, Comp Disch T is compressor discharge temperature, EER is energy efficiency, and CAP is capacity. The data are based on the following conditions.
Evaporator temperature 4°C Condenser temperature 430C 0 Subcool temperature 60C
Return gas temperature 180C Compressor efficiency is 70% Note that the superheat is included in cooling capacity calculations.
5 TABLE 13
Composition (wt%) Evap Cond Compr CAP EER
Press Press Disch (kJ/m3) (kPa) (kPa) Temp (C)
Figure imgf000088_0001
Compositions have energy efficiency (EER) comparable to R22 and R410A while maintaining reasonable discharge temperatures. Capacity for the present compositions is also similar to R22 indicating these could be replacement refrigerants for in refrigeration and air-conditioning.
EXAMPLE 6
Flammability
Flammable compounds may be identified by testing under ASTM (American Society of Testing and Materials) E681-01 , with an electronic ignition source. Such tests of flammability were conducted on HFC- 1234yf, HFC-1225ye and a mixture of the present disclosure at 101 kPa (14.7 psia), 100 0C (212 0F), and 50 percent relative humidity, at various concentrations in air in order to determine the lower flammability limit (LFL) and upper flammability limit (UFL). The results are given in Table 13.
TABLE 14
Figure imgf000089_0001
The results indicate that while HFC-1234yf is flammable, addition of HFC-1225ye reduces the flammability. Therefore, compositions comprising about 1 weight percent to about 49 weight percent HFC-1234yf and about 99 weight percent to about 51 weight percent HFC-1225ye are preferred.

Claims

What is claimed is:
1. A composition comprising HFC-1225ye and at least one compound selected from the group consisting of:
HFC-1234ze, HFC-1234yf, HFC-1234ye, HFC-1243zf, HFC- 32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, n-butane, isobutane, 2-methyibutane, n-pentane, cyclopentane, dimethylether, CF3SCF3i CO2 and CF3I.
2. A composition comprising HFC-1234ze and at least one compound selected from the group consisting of:
HFC-1234yf, HFC-1234ye, HFC-1243zf, HFC-32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161 , HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC- 365mfc, propane, n-butane, isobutane, 2-methylbutane, n- pentane, cyclopentane, dimethylether, CF3SCF3, CO2 and CF3I.
3. A composition comprising HFC-1234yf and at least one compound selected from the group consisting of:
HFC-1234ye, HFC-1243zf, HFC-32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161 , HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethylether, CF3SCF31 CO2 and CF3I.
4. A composition comprising HFC-1234ye and at least one compound selected from the group consisting of:
HFC-1243zf, HFC-32, HFC-125, HFC-134, HFC-134a, HFC- 143a, HFC-152a, HFC-161 , HFC-227ea, HFC-236ea, HFC- 236fa, HFC-245fa, HFC-365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethylether, CF3SCF3, CO2 and CF3I. 5. A composition comprising HFC-1243zf and at least one compound selected from the group consisting of:
HFC-32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC- 152a, HFC-161, HFC-227ea, HFC-236ea, HFC-236fa, HFC- 245fa, HFC-365mfc, propane, n-butane, isobutane, 2- methylbutane, n-pentane, cyclopentane, dimethylether, CF3SCF3, CO2 and CF3I.
6. A composition of claim 1 selected from the group consisting of:
HFC-1225ye and HFC-32; HFC-1225ye and HFC-134a; HFC-1225ye and HFC-134; HFC-1225ye and CO2; HFC-1225ye, HFC-152a, and HFC-32; HFC-1225ye, HFC-152a, and CO2; HFC-1225ye, HFC-152a, and propane; HFC-1225ye, HFC-152a, and isobutane; HFC-1225ye, HFC-152a, and dimethylether; HFC-1225ye, HFC-134a, and HFC-152a; HFC-1225ye, HFC-134a, HFC-152a and HFC-32; HFC-1225ye, HFC-134a, and HFC-32; HFC-1225ye, HFC-134a, and HFC-161; HFC-1225ye, HFC-134a, and CO2; HFC-1225ye, HFC-134a, and propane; HFC-1225ye, HFC-134a, and isobutane; HFC-1225ye, HFC-134a, and dimethylether; HFC-1225ye, HFC-134, and HFC-32; HFC-1225ye, HFC-1234yf and HFC-134a; HFC-1225ye, HFC-1234yf and HFC-32; HFC-1225ye, HFC-1234yf and HFC-152a; HFC-1225ye, HFC-1234yf and HFC-125; HFC-1225ye, HFC-1234yf and CF3I; HFC-1225ye, HFC-32 and HFC-125; HFC-1225ye, HFC-125 and n-butane; HFC-1225ye, HFC-125 and isobutane; HFC-1225ye, trans-HFC-1234ze and HFC-134; HFC-1225ye, trans-HFC-1234ze and HFC-227ea; HFC-1225ye, trans-HFC-1234ze and propane; HFC-1225ye, trans-HFC-1234ze and n-butane; HFC-1225ye, trans-HFC-1234ze and dimethylether; HFC-1225ye, trans-HFC-1234ze and CF3SCF3; HFC-1225ye, HFC-1243zf and HFC-134; HFC-1225ye, HFC-1243zf and n-butane; HFC-1225ye, HFC-1243zf and isobutane; HFC-1225ye, HFC-1243zf and dimethylether; HFC-1225ye, HFC-1243zf and CF3I; HFC-1225ye, HFC-134 and HFC-152a; HFC-1225ye, HFC-134 and HFC-227ea; HFC-1225ye, HFC-134 and n-butane; HFC-1225ye, HFC-134 and isobutane; HFC-1225ye, HFC-134 and dimethylether; HFC-1225ye, HFC-227ea and dimethylether; HFC-1225ye, n-butane and dimethylether; HFC-1225ye, n-butane and CF3SCF3; HFC-1225ye, isobutane and dimethylether; HFC-1225ye, isobutane and CF3I; HFC-1225ye, HFC-32 and CF3I; HFC-1225ye, HFC-1234yf, HFC-32 and HFC-125; HFC-1225ye, HFC-1234yf, HFC-32, HFC-125 and CF3I; HFC-1225ye, HFC-32, HFC-125 and HFC-152a; HFC-1225ye, HFC-32, HFC-125 and isobutane; HFC-1225ye, HFC-32, HFC-125 and propane; HFC-1225ye, HFC-32, HFC-125 and dimethylether; HFC-1225ye, HFC-32, CF3I and dimethylether; HFC-1225ye, HFC-32, HFC-125 and CF3I; and HFC-1225ye, HFC-1234yf, HFC-32 and HFC-134a.
7. A composition of claim 1 selected from the group consisting of: about 1 weight percent to about 99 weight percent HFC-1225ye and about 99 weight percent to about 1 weight percent HFC-32; about 1 weight percent to about 99 weight percent HFC-1225ye and about 99 weight percent to about 1 weight percent HFC- 134a; about 0.1 weight percent to about 99.9 weight percent HFC-1225ye and about 99.9 weight percent to about 0.1 weight percent CO2; about 1 weight percent to about 98 weight percent HFC-1225ye, about 1 weight percent to about 98 weight percent HFC-152a, and about 1 to about 98 weight percent HFC-32; about 1 weight percent to about 98 weight percent HFC-1225ye, about 1 weight percent to about 98 weight percent HFC-152a, and about 0.1 to about 98 weight percent CO2; about 1 weight percent to about 98 weight percent HFC-1225ye, about 1 weight percent to about 98 weight percent HFC-152a, and about 1 to about 98 weight percent propane; about 1 weight percent to about 98 weight percent HFC-1225ye, about 1 weight percent to about 98 weight percent HFC-152a, and about 1 to about 98 weight percent isobutane; about 1 weight percent to about 98 weight percent HFC-1225ye, about 1 weight percent to about 98 weight percent HFC-152a, and about 1 to about 98 weight percent dimethylether; about 1 weight percent to about 98 weight percent HFC-1225ye, about 1 weight percent to about 98 weight percent HFC-134a, and about 1 to about 98 weight percent HFC-152a; about 1 weight percent to about 97 weight percent HFC-1225ye, about 1 weight percent to about 97 weight percent HFC-134a, about 1 weight percent to about 97 weight percent HFC-152a, and about 0.1 weight percent to about 97 weight percent HFC- 32; about 1 weight percent to about 98 weight percent HFC-1225ye, about 1 weight percent to about 98 weight percent HFC-134a, and about 1 weight percent to about 98 weight percent HFC-32; about 1 weight percent to about 98 weight percent HFC-1225ye, about 1 weight percent to about 98 weight percent HFC-134a, and about 1 weight percent to about 98 weight percent HFC- 161; about 1 weight percent to about 98 weight percent HFC-1225ye, about 1 weight percent to about 98 weight percent HFC-134a, and about 0.1 weight percent to about 98 weight percent CO2; about 1 weight percent to about 98 weight percent HFC-1225ye, about 1 weight percent to about 98 weight percent HFC-134a, and about 1 weight percent to about 98 weight percent propane; about 1 weight percent to about 98 weight percent HFC-1225ye, about 1 weight percent to about 98 weight percent HFC-134a, and about 1 weight percent to about 98 weight percent isobutane; about 1 weight percent to about 98 weight percent HFC-1225ye, about 1 weight percent to about 98 weight percent HFC-134a, and about 1 weight percent to about 98 weight percent dimethylether; and about 1 weight percent to about 98 weight percent HFC-1225ye, about 1 weight percent to about 98 weight percent HFC-134, and about 1 weight percent to about 98 weight percent HFC-32; about 1 weight percent to about 98 weight percent HFC-1225ye, about 1 weight percent to about 98 weight percent HFC-1234yf, and about 0.1 weight percent to about 98 weight percent HFC- 134a; about 1 weight percent to about 98 weight percent HFC-1225ye, about 1 weight percent to about 98 weight percent HFC-1234yf, and about 0.1 weight percent to about 98 weight percent HFC- 32; about 1 weight percent to about 98 weight percent HFC-1225ye, about 1 weight percent to about 98 weight percent HFC-1234yf, and about 0.1 weight percent to about 98 weight percent HFC- 152a; about 1 weight percent to about 98 weight percent HFC-1225ye, about 1 weight percent to about 98 weight percent HFC-1234yf, and about 0.1 weight percent to about 98 weight percent HFC- 125; about 1 weight percent to about 98 weight percent HFC-1225ye, about 1 weight percent to about 98 weight percent HFC-1234yf, and about 0.1 weight percent to about 98 weight percent CF3I; about 0.1 weight percent to about 98 weight percent HFC-32, about 0.1 weight percent to about 98 weight percent HFC-125, and about 0.1 weight percent to about 98 weight percent HFC- 1225ye; about 0.1 weight percent to about 98 weight percent HFC-125, about 0.1 weight percent to about 98 weight percent HFC- 1225ye, and about 0.1 weight percent to about 98 weight percent n-butane; and about 0.1 weight percent to about 98 weight percent HFC-125, about 0.1 weight percent to about 98 weight percent HFC- 1225ye, and about 0.1 weight percent to about 98 weight percent isobutane; about 1 weight percent to about 98 weight percent HFC-1225ye, about 1 weight percent to about 98 weight percent trans-HFC- 1234ze and about 1 weight percent to about 98 weight percent HFC-134; about 1 weight percent to about 98 weight percent HFC-1225ye, about 1 weight percent to about 98 weight percent trans-HFC- 1234ze and about 1 weight percent to about 98 weight percent HFC-227ea; about 1 weight percent to about 60 weight percent HFC-1225ye, about 1 weight percent to about 60 weight percent trans-HFC- 1234ze and about 39 weight percent to about 98 weight percent propane; about 1 weight percent to about 98 weight percent HFC-1225ye, about 1 weight percent to about 98 weight percent trans-HFC- 1234ze and about 1 weight percent to about 30 weight percent n-butane; about 1 weight percent to about 98 weight percent HFC-1225ye, about 1 weight percent to about 98 weight percent trans-HFC- 1234ze and about 1 weight percent to about 98 weight percent dimethylether; about 1 weight percent to about 98 weight percent HFC-1225ye, about 1 weight percent to about 98 weight percent trans-HFC- 1234ze and about 1 weight percent to about 98 weight percent CF3SCF3; about 1 weight percent to about 98 weight percent HFC-1225ye, about 1 weight percent to about 98 weight percent HFC-1243zf and about 1 weight percent to about 98 weight percent HFC- 134; about 1 weight percent to about 98 weight percent HFC-1225ye, about 1 weight percent to about 98 weight percent HFC~1243zf and about 1 weight percent to about 30 weight percent n- butane; about 1 weight percent to about 98 weight percent HFC-1225ye, about 1 weight percent to about 98 weight percent HFC-1243zf and about 1 weight percent to about 40 weight percent isobutane; about 1 weight percent to about 98 weight percent HFC-1225ye, about 1 weight percent to about 98 weight percent HFC-1243zf and about 1 weight percent to about 98 weight percent dimethylether; about 1 weight percent to about 98 weight percent HFC-1225ye, about 1 weight percent to about 98 weight percent HFC-1243zf and about 1 weight percent to about 98 weight percent CF3I; about 1 weight percent to about 98 weight percent HFC-1225ye, about 1 weight percent to about 98 weight percent HFC-134 and about 1 weight percent to about 98 weight percent HFC-152a; about 1 weight percent to about 98 weight percent HFC-1225ye, about 1 weight percent to about 98 weight percent HFC-134 and about 1 weight percent to about 98 weight percent HFC-227ea; about 1 weight percent to about 98 weight percent HFC-1225ye, about 1 weight percent to about 98 weight percent HFC-134 and about 1 weight percent to about 40 weight percent n-butane; about 1 weight percent to about 98 weight percent HFC-1225ye, about 1 weight percent to about 98 weight percent HFC-134 and about 1 weight percent to about 40 weight percent isobutane; about 1 weight percent to about 98 weight percent HFC-1225ye, about 1 weight percent to about 98 weight percent HFC-134 and about 1 weight percent to about 40 weight percent dimethylether; about 40 weight percent to about 98 weight percent HFC-1225ye, about 1 weight percent to about 59 weight percent HFC-227ea and about 1 weight percent to about 30 weight percent dimethylether; about 1 weight percent to about 98 weight percent HFC-1225ye, about 1 weight percent to about 30 weight percent n-butane and about 1 weight percent to about 98 weight percent dimethylether; about 1 weight percent to about 98 weight percent HFC-1225ye, about 1 weight percent to about 20 weight percent n-butane and about 1 weight percent to about 98 weight percent CF3SCF3; about 1 weight percent to about 98 weight percent HFC-1225ye, about 1 weight percent to about 60 weight percent isobutane and about 1 weight percent to about 98 weight percent dimethylether; about 1 weight percent to about 98 weight percent HFC-1225ye, about 1 weight percent to about 40 weight percent isobutane and about 1 weight percent to about 98 weight percent CF3I; about 1 weight percent to about 98 weight percent HFC-1225ye, about 1 weight percent to about 98 weight percent HFC-32 and about 1 weight percent to about 98 weight percent CF3I; about 1 weight percent to about 97 weight percent HFC-1225ye, about 1 weight percent to about 97 weight percent HFC-1234yf and about 1 weight percent to about 97 weight percent HFC-32 and about 1 weight percent to about 97 weight percent HFC- 125; about 1 weight percent to about 97 weight percent HFC-1225ye, about 1 weight percent to about 97 weight percent HFC-1234yf and about 1 weight percent to about 97 weight percent HFC-32 and about 1 weight percent to about 97 weight percent HFC- 134a; about 1 weight percent to about 96 weight percent HFC-1225ye, about 1 weight percent to about 96 weight percent HFC-1234yf and about 1 weight percent to about 96 weight percent HFC-32 and about 1 weight percent to about 96 weight percent HFC-125 and about 1 weight percent to about 97 weight percent CF3I; about 1 weight percent to about 97 weight percent HFC-1225ye, about 1 weight percent to about 97 weight percent HFC-32 and about 1 weight percent to about 97 weight percent HFC-125 and about 1 weight percent to about 97 weight percent HFC-152a; about 1 weight percent to about 97 weight percent HFC-1225ye, about 1 weight percent to about 97 weight percent HFC-32 and about 1 weight percent to about 97 weight percent HFC-125 and about 1 weight percent to about 50 weight percent isobutane; about 1 weight percent to about 97 weight percent HFC-1225ye, about 1 weight percent to about 97 weight percent HFC-32 and about 1 weight percent to about 97 weight percent HFC-125 and about 1 weight percent to about 50 weight percent propane; about 1 weight percent to about 97 weight percent HFC-1225ye, about 1 weight percent to about 97 weight percent HFC-32 and about 1 weight percent to about 97 weight percent HFC-125 and about 1 weight percent to about 50 weight percent DME; about 1 weight percent to about 97 weight percent HFC-1225ye, about 1 weight percent to about 97 weight percent HFC-32 and about 1 weight percent to about 97 weight percent HFC-125 and about 1 weight percent to about 97 weight percent CF3I; and about 1 weight percent to about 97 weight percent HFC-1225ye, about 1 weight percent to about 97 weight percent HFC-32 and about 1 weight percent to about 97 weight percent CF3I and about 1 weight percent to about 50 weight percent DME.
8. A composition of claim 1 selected from the group consisting of: about 50 weight percent to about 99 weight percent HFC-1225ye and about 50 weight percent to about 1 weight percent HFC-32; about 40 weight percent to about 99 weight percent HFC-1225ye and about 60 weight percent to about 1 weight percent HFC-
134a; about 70 weight percent to about 99.7 weight percent HFC-1225ye and about 30 weight percent to about 0.3 weight percent CO2; about 51 weight percent to about 99 weight percent HFC-1225ye and about 49 weight percent to about 1 weight percent HFC-
1234yf; about 50 weight percent to about 98 weight percent HFC-1225ye, about 1 weight percent to about 40 weight percent HFC-152a, and about 1 to about 40 weight percent HFC-32; about 50 weight percent to about 98 weight percent HFC-1225ye, about 1 weight percent to about 40 weight percent HFC-152a, and about 0.3 to about 30 weight percent HFC-CO2; about 50 weight percent to about 98 weight percent HFC-1225ye, about 1 weight percent to about 40 weight percent HFC-152a, and about 1 to about 20 weight percent propane; about 50 weight percent to about 98 weight percent HFC-1225ye, about 1 weight percent to about 40 weight percent HFC-152a, and about 1 weight percent to about 20 weight percent isobutane; about 50 weight percent to about 98 weight percent HFC-1225ye, about 1 weight percent to about 40 weight percent HFC-152a, and about 1 weight percent to about 20 weight percent dimethylether; about 40 weight percent to about 98 weight percent HFC-1225ye, about 1 weight percent to about 50 weight percent HFC-134a, and about 1 weight percent to about 40 weight percent HFC- 152a; about 20 weight percent to about 97 weight percent HFC-1225ye, about 1 weight percent to about 80 weight percent HFC-134a, about 1 weight percent to about 50 weight percent HFC-152a, and about 0.1 weight percent to about 50 weight percent HFC- 32; about 20 weight percent to about 98 weight percent HFC-1225ye, about 1 weight percent to about 50 weight percent HFC-134a, and about 1 weight percent to about 40 weight percent HFC-32; about 40 weight percent to about 98 weight percent HFC-1225ye, about 1 weight percent to about 50 weight percent HFC-134a, and about 1 weight percent to about 20 weight percent HFC- 161; about 40 weight percent to about 98 weight percent HFC-1225ye, about 1 weight percent to about 50 weight percent HFC-134a, and about 0.3 weight percent to about 30 weight percent CO2; 64
about 40 weight percent to about 98 weight percent HFC-1225ye, about 1 weight percent to about 50 weight percent HFC-134a, and about 1 weight percent to about 20 weight percent propane; about 40 weight percent to about 98 weight percent HFC-1225ye, about 1 weight percent to about 50 weight percent HFC-134a, and about 1 weight percent to about 20 weight percent isobutane; about 40 weight percent to about 98 weight percent HFC-1225ye, about 1 weight percent to about 50 weight percent HFC-134a, and about 1 weight percent to about 20 weight percent dimethylether; about 40 weight percent to about 98 weight percent HFC-1225ye, about 1 weight percent to about 50 weight percent HFC-134, and about 1 weight percent to about 40 weight percent HFC-32; about 10 weight percent to about 90 weight percent HFC-1225ye, about 10 weight percent to about 90 weight percent HFC- 1234yf, and about 0.1 weight percent to about 50 weight percent H FC- 134a; about 10 weight percent to about 90 weight percent HFC-1225ye, about 11 weight percent to about 90 weight percent HFC- 1234yf, and about 0.1 weight percent to about 50 weight percent HFC-32; about 10 weight percent to about 90 weight percent HFC-1225ye, about 10 weight percent to about 90 weight percent HFC- 1234yf, and about 0.1 weight percent to about 50 weight percent HFC-152a; about 10 weight percent to about 90 weight percent HFC-1225ye, about 10 weight percent to about 90 weight percent HFC- 1234yf, and about 0.1 weight percent to about 50 weight percent HFC-125; about 9 weight percent to about 90 weight percent HFC-1225ye, about 9 weight percent to about 90 weight percent HFC-1234yf, and about 1 weight percent to about 60 weight percent CF3I; about 5 weight percent to about 70 weight percent HFC-32, about 5 weight percent to about 70 weight percent HFC-125, and about 5 weight percent to about 70 weight percent HFC-1225ye; about 5 weight percent to about 70 weight percent HFC-125, about 5 weight percent to about 70 weight percent HFC-1225ye, and about 1 weight percent to about 20 weight percent n-butane; about 5 weight percent to about 70 weight percent HFC-125, about 5 weight percent to about 70 weight percent HFC-1225ye, and about 1 weight percent to about 20 weight percent isobutane; about 10 weight percent to about 80 weight percent HFC-1225ye, about 10 weight percent to about 80 weight percent trans-HFC- 1234ze and about 10 weight percent to about 80 weight percent HFC-134; about 10 weight percent to about 80 weight percent HFC-1225ye, about 10 weight percent to about 80 weight percent trans-HFC- 1234ze and about 10 weight percent to about 80 weight percent HFC-227ea; about 10 weight percent to about 60 weight percent HFC-1225ye, about 10 weight percent to about 60 weight percent trans-HFC- 1234ze and about 39 weight percent to about 80 weight percent propane; about 10 weight percent to about 80 weight percent HFC-1225ye, about 10 weight percent to about 80 weight percent trans-HFC- 1234ze and about 1 weight percent to about 20 weight percent n-butane; about 10 weight percent to about 80 weight percent HFC-1225ye, about 10 weight percent to about 80 weight percent trans-HFC- 1234ze and about 1 weight percent to about 30 weight percent dimethylether; about 10 weight percent to about 80 weight percent HFC-1225ye, about 10 weight percent to about 80 weight percent trans-HFC- 1234ze and about 10 weight percent to about 80 weight percent CF3SCF3; about 10 weight percent to about 80 weight percent HFC-1225ye, about 10 weight percent to about 80 weight percent HFC-1243zf and about 10 weight percent to about 80 weight percent HFC- 134; about 10 weight percent to about 80 weight percent HFC-1225ye, about 10 weight percent to about 80 weight percent HFC-1243zf and about 1 weight percent to about 20 weight percent n- butane; about 10 weight percent to about 80 weight percent HFC-1225ye, about 10 weight percent to about 80 weight percent HFC-1243zf and about 1 weight percent to about 30 weight percent isobutane; about 10 weight percent to about 80 weight percent HFC-1225ye, about 10 weight percent to about 80 weight percent HFC-1243zf and about 1 weight percent to about 30 weight percent dimethylether; about 10 weight percent to about 80 weight percent HFC-1225ye, about 10 weight percent to about 80 weight percent HFC-1243zf and about 10 weight percent to about 80 weight percent CF3I; about 10 weight percent to about 80 weight percent HFC-1225ye about 10 weight percent to about 80 weight percent, HFC-134 and about 1 weight percent to about 50 weight percent HFC-
152a; about 10 weight percent to about 80 weight percent HFC-1225ye, about 10 weight percent to about 80 weight percent HFC-134 and about 10 weight percent to about 80 weight percent HFC-
227ea; about 10 weight percent to about 80 weight percent HFC-1225ye, about 10 weight percent to about 80 weight percent HFC-134 and about 1 weight percent to about 30 weight percent n- butane; about 10 weight percent to about 80 weight percent HFC-1225ye, about 10 weight percent to about 80 weight percent HFC-134 and about 1 weight percent to about 30 weight percent isobutane; about 10 weight percent to about 80 weight percent HFC-1225ye, about 10 weight percent to about 80 weight percent HFC-134 and about 1 weight percent to about 30 weight percent dimethylether; about 50 weight percent to about 80 weight percent HFC-1225ye, about 1 weight percent to about 49 weight percent HFC-227ea and about 1 weight percent to about 20 weight percent dimethylether; about 60 weight percent to about 98 weight percent HFC-1225ye, about 1 weight percent to about 20 weight percent n-butane and about 1 weight percent to about 20 weight percent dimethylether; about 10 weight percent to about 80 weight percent HFC-1225ye, about 1 weight percent to about 10 weight percent n-butane and about 10 weight percent to about 80 weight percent CF3SCF3; about 40 weight percent to about 90 weight percent HFC-1225ye, about 1 weight percent to about 30 weight percent isobutane and about 1 weight percent to about 30 weight percent dimethylether; and about 10 weight percent to about 80 weight percent HFC-1225ye, about 1 weight percent to about 30 weight percent isobutane and about 10 weight percent to about 80 weight percent CF3I; about 5 weight percent to about 80 weight percent HFC-1225ye, about 1 weight percent to about 70 weight percent HFC-32 and about 1 weight percent to about 80 weight percent CF3I; about 1 weight percent to about 80 weight percent HFC-1225ye, about 1 weight percent to about 70 weight percent HFC-1234yf and about 5 weight percent to about 70 weight percent HFC-32 and about 5 weight percent to about 70 weight percent HFC- 125; about 5 weight percent to about 80 weight percent HFC-1225ye, about 5 weight percent to about 70 weight percent HFC-1234yf and about 5 weight percent to about 70 weight percent HFC-32 and about 5 weight percent to about 70 weight percent HFC- 134a; about 1 weight percent to about 70 weight percent HFC-1225ye, about 1 weight percent to about 60 weight percent HFC-1234yf and about 1 weight percent to about 70 weight percent HFC-32 and about 1 weight percent to about 60 weight percent HFC-125 and about 1 weight percent to about 60 weight percent CF3I; about 10 weight percent to about 80 weight percent HFC-1225ye, about 5 weight percent to about 70 weight percent HFC-32 and about 5 weight percent to about 70 weight percent HFC-125 and about 5 weight percent to about 70 weight percent HFC-152a; about 5 weight percent to about 70 weight percent HFC-1225ye, about 5 weight percent to about 70 weight percent HFC-32 and about 5 weight percent to about 70 weight percent HFC-125 and about 1 weight percent to about 30 weight percent isobutane; about 5 weight percent to about 70 weight percent HFC-1225ye, about 5 weight percent to about 70 weight percent HFC-32 and about 5 weight percent to about 70 weight percent HFC-125 and about 1 weight percent to about 30 weight percent propane; about 5 weight percent to about 70 weight percent HFC-1225ye, about 5 weight percent to about 70 weight percent HFC-32 and about 5 weight percent to about 70 weight percent HFC-125 and about 1 weight percent to about 30 weight percent DME; about 10 weight percent to about 80 weight percent HFC-1225ye, about 5 weight percent to about 70 weight percent HFC-32 and about 5 weight percent to about 70 weight percent HFC-125 and about 1 weight percent to about 80 weight percent CF3I; and about 5 weight percent to about 70 weight percent HFC-1225ye, about 5 weight percent to about 70 weight percent HFC-32 and about 5 weight percent to about 70 weight percent CF3I and about 1 weight percent to about 30 weight percent DME.
9. A composition of claim 1 selected from the group consisting of: about 95 weight percent HFC-1225ye and about 5 weight percent HFC-32; about 97 weight percent HFC-1225ye and about 3 weight percent HFC-32; about 90 weight percent HFC-1225ye and about 10 weight percent HFC-134a; about 99 weight percent HFC-1225ye and about 1 weight percent CO2; about 75 weight percent HFC-1225ye and about 25 weight percent HFC-1234yf; about 60 weight percent HFC-1225ye and about 40 weight percent HFC-1234yf; about 85 weight percent HFC-1225ye, about 10 weight percent
HFC-152a, and about 5 weight percent HFC-32; about 81 weight percent HFC-1225ye, about 15 weight percent
HFC-152a, and about 4 weight percent HFC-32; about 82 weight percent HFC-1225ye, about 15 weight percent
HFC-152a, and about 3 weight percent HFC-32; about 84 weight percent HFC-1225ye, about 15 weight percent
HFC-152a, and about 1 weight percent CO2; about 84 weight percent HFC-1225ye, about 15.5 weight percent HFC-152a, and about 0.5 weight percent CO2; about 85 weight percent HFC-1225ye, about 13 weight percent
HFC-152a, and about 2 weight percent propane; about 85 weight percent HFC-1225ye, about 13 weight percent
HFC-152a, and about 2 weight percent isobutane; about 85 weight percent HFC-1225ye, about 13 weight percent
HFC-152a, and about 2 weight percent dimethylether; about 76 weight percent HFC-1225ye, about 9 weight percent
HFC-134a, and about 15 weight percent HFC-152a; about 74 weight percent HFC-1225ye, about 8 weight percent
HFC-134a, 17 weight percent HFC-152a, and about 1 weight percent HFC-32; about 88 weight percent HFC-1225ye, about 9 weight percent
HFC-134a, and about 3 weight percent HFC-32; about 86 weight percent HFC-1225ye, about 10 weight percent
HFC-134a, and about 4 weight percent HFC-161 ; about 88.5 weight percent HFC-1225ye, about 11 weight percent HFC-134a, and about 0.5 weight percent CO2; about 87 weight percent HFC-1225ye, about 10 weight percent
HFC-134a, and about 3 weight percent propane; about 87 weight percent HFC-1225ye, about 10 weight percent
HFC-134a, and about 3 weight percent isobutane; about 87 weight percent HFC-1225ye, about 10 weight percent
HFC-134a, and about 3 weight percent dimethylether; about 88 weight percent HFC-1225ye, about 9 weight percent
HFC-134, and about 3 weight percent HFC-32; about 70 weight percent HFC-1225ye, about 20 weight percent
HFC-1234yf, and about 10 weight percent HFC-134a; about 20 weight percent HFC-1225ye, about 70 weight percent
HFC-1234yf, and about 10 weight percent HFC-134a; about 25 weight percent HFC-1225ye, about 73 weight percent
HFC-1234yf, and about 2 weight percent HFC-32; about 75 weight percent HFC-1225ye, about 23 weight percent
HFC-1234yf, and about 2 weight percent HFC-32; about 70 weight percent HFC-1225ye, about 25 weight percent
HFC-1234yf, and about 5 weight percent HFC-152a; about 25 weight percent HFC-1225ye, about 70 weight percent
HFC-1234yf, and about 5 weight percent HFC-152a; about 25 weight percent HFC-1225ye, about 71 weight percent
HFC-1234yf, and about 4 weight percent HFC-125; about 75 weight percent HFC-1225ye, about 21 weight percent
HFC-1234yf, and about 4 weight percent HFC-125; about 75 weight percent HFC-1225ye, about 24 weight percent
HFC-1234yf, and about 1 weight percent HFC-125; about 40 weight percent HFC-1225ye, about 40 weight percent
HFC-1234yf, and about 20 weight percent CF3I; about 45 weight percent HFC-1225ye, about 45 weight percent
HFC-1234yf, and about 10 weight percent CF3I; about 25 weight percent HFC-1225ye, about 74 weight percent
HFC-1234yf, and about 1 weight percent HFC-125; about 30 weight percent HFC-32, about 40 weight percent
HFC-125, and about 30 weight percent HFC-1225ye; about 23 weight percent HFC-32, about 25 weight percent
HFC-125, and about 52 weight percent HFC-1225ye; about 65 weight percent HFC-125, about 32 weight percent
HFC-1225ye, and about 3 weight percent n-butane; and about 85.1 weight percent HFC-125, about 11.5 weight percent
HFC-1225ye, and about 3.4 weight percent isobutane.
10. A composition of claim 2 selected from the group consisting of: cis-HFC-1234ze and HFC-1234ye; cis-HFC-1234ze and HFC-236ea; cis-HFC-1234ze and HFC-236fa; cis-HFC-1234ze and HFC-245fa; cis-HFC-1234ze and n-butane; cis-HFC-1234ze and isobutane; cis-HFC-1234ze and 2-methylbutane; cis-HFC-1234ze and n-pentane; trans-HFC~1234ze and HFC-134a; trans-HFC-1234ze and HFC-152a; trans-HFC-1234ze and HFC-32; trans-HFC~1234ze, HFC-125 and n-butane; trans-HFC-1234ze, HFC-32 and HFC-125; trans-HFC-1234ze, HFC-125 and isobutane; trans-HFC-1234ze, HFC-1243zf and HFC-227ea; trans-HFC-1234ze, HFC-1243zf and n-butane; trans-HFC-1234ze, HFC-1243zf and isobutane; trans-HFC-1234ze, HFC-1243zf and dimethylether; trans-HFC-1234ze, HFC-134 and HFC-152a; trans-HFC-1234ze, HFC-134 and HFC-227ea; trans-HFC-1234ze, HFC-134 and diemthylether; trans-HFC-1234ze, HFC-134a and HFC-152a; trans-HFC-1234ze, HFC-152a and n-butane; trans-HFC-1234ze, HFC-152a and dimethylether; trans-HFC-1234ze, HFC-227ea and n-butane; trans-HFC-1234ze, n-butane and dimethylether; trans-HFC-1234ze, n-butane and CF3I; trans-HFC-1234ze, isobutane and dimethylether; trans-HFC-1234ze, isobutane and CF3I; and trans-HFC-1234ze, isobutane and CF3SCF3.
11. A composition of claim 2 selected from the group consisting of: about 1 weight percent to about 99 weight percent cis-HFC-
1234ze and about 99 weight percent to about 1 weight percent HFC-1234ye; about 1 weight percent to about 99 weight percent cis-HFC-
1234ze and about 99 weight percent to about 1 weight percent HFC-236ea; about 1 weight percent to about 99 weight percent cis-HFC-
1234ze and about 99 weight percent to about 1 weight percent HFC-236fa; about 1 weight percent to about 99 weight percent cis-HFC-
1234ze and about 99 weight percent to about 1 weight percent HFC-245fa; about 1 weight percent to about 80 weight percent cis-HFC-
1234ze and about 99 weight percent to about 20 weight percent n-butane; about 1 weight percent to about 69 weight percent cis-HFC-
1234ze and about 99 weight percent to about 31 weight percent isobutane; about 60 weight percent to about 99 weight percent cis-HFC-
1234ze and about 40 weight percent to about 1 weight percent 2-methylbutane; about 63 weight percent to about 99 weight percent cis-HFC-
1234ze and about 37 weight percent to about 1 weight percent n-pentane; about 1 weight percent to about 99 weight percent trans-HFC-
1234ze and about 99 weight percent to about 1 weight percent HFC-134a; about 1 weight percent to about 99 weight percent trans-HFC-
1234ze and about 99 weight percent to about 1 weight percent HFC-32; about 1 weight percent to about 99 weight percent trans-HFC-
1234ze and about 99 weight percent to about 1 weight percent H FC- 152a; about 0.1 weight percent to about 98 weight percent HFC-32, about 0.1 weight percent to about 98 weight percent HFC-
125, and about 0.1 weight percent to about 98 weight percent trans-HFC-1234ze; about 0.1 weight percent to about 98 weight percent HFC-125, about 0.1 weight percent to about 98 weight percent trans-
HFC-1234ze, and about 0.1 weight percent to about 98 weight percent n-butane; about 0.1 weight percent to about 98 weight percent HFC-125, about 0.1 weight percent to about 98 weight percent trans- HFC-1234ze, and about 0.1 weight percent to about 98 weight percent isobutane; about 1 weight percent to about 98 weight percent trans-HFC- 1234ze, about 1 weight percent to about 98 weight percent HFC-1243zf and about 1 weight percent to about 98 weight percent HFC-227ea; about 1 weight percent to about 98 weight percent trans-HFC- 1234ze, about 1 weight percent to about 98 weight percent HFC-1243zf and about 1 weight percent to about 30 weight percent n-butane; about 1 weight percent to about 98 weight percent trans-H FC- 1234ze, about 1 weight percent to about 98 weight percent HFC-1243zf and about 1 weight percent to about 40 weight percent isobutane; about 1 weight percent to about 98 weight percent trans-HFC- 1234ze, about 1 weight percent to about 98 weight percent HFC-1243zf and about 1 weight percent to about 98 weight percent dimethylether; about 1 weight percent to about 98 weight percent trans-HFC- 1234ze, about 1 weight percent to about 98 weight percent HFC-134 and about 1 weight percent to about 98 weight percent HFC-152a; about 1 weight percent to about 98 weight percent trans-HFC- 1234ze, about 1 weight percent to about 98 weight percent HFC-134 and about 1 weight percent to about 98 weight percent HFC-227ea; about 1 weight percent to about 98 weight percent trans-HFC- 1234ze, about 1 weight percent to about 98 weight percent HFC-134 and about 1 weight percent to about 40 weight percent dimethylether; about 1 weight percent to about 98 weight percent trans-HFC- 1234ze, about 1 weight percent to about 98 weight percent HFC-134a and about 1 weight percent to about 98 weight percent HFC-152a; about 1 weight percent to about 98 weight percent trans-HFC- 1234ze, about 1 weight percent to about 98 weight percent HFC-152a and about 1 weight percent to about 50 weight percent n-butane; about 1 weight percent to about 98 weight percent trans-HFC- 1234ze, about 1 weight percent to about 98 weight percent HFC-152a and about 1 weight percent to about 98 weight percent dimethylether; about 1 weight percent to about 98 weight percent trans-HFC- 1234ze, about 1 weight percent to about 98 weight percent HFC-227ea and about 1 weight percent to about 40 weight percent n-butane; about 1 weight percent to about 98 weight percent trans-HFC- 1234ze, about 1 weight percent to about 40 weight percent n-butane and about 1 weight percent to about 98 weight percent dimethylether; about 1 weight percent to about 98 weight percent trans-HFC- 1234ze, about 1 weight percent to about 30 weight percent n-butane and about 1 weight percent to about 98 weight percent CF3I; about 1 weight percent to about 98 weight percent trans-HFC- 1234ze, about 1 weight percent to about 60 weight percent isobutane and about 1 weight percent to about 98 weight percent dimethylether; about 1 weight percent to about 98 weight percent trans-HFC- 1234ze, about 1 weight percent to about 40 weight percent isobutane and about 1 weight percent to about 98 weight percent CF3I; and about 1 weight percent to about 98 weight percent trans-HFC- 1234ze, about 1 weight percent to about 40 weight percent isobutane and about 1 weight percent to about 98 weight percent CF3SCF3.
12. A composition of claim 2 selected from the group consisting of: about 30 weight percent to about 99 weight percent trans-HFC-
1234ze and about 70 weight percent to about 1 weight percent HFC-134a; about 40 weight percent to about 99 weight percent trans-HFC-
1234ze and about 60 weight percent to about 1 weight percent HFC-32; about 40 weight percent to about 99 weight percent trans-HFC- 1234ze and about 60 weight percent to about 1 weight percent HFC-152a; about 5 weight percent to about 70 weight percent HFC-32, about 5 weight percent to about 70 weight percent HFC- 125, and about 5 weight percent to about 70 weight percent trans-HFC-1234ze; about 5 weight percent to about 70 weight percent HFC-125, about 5 weight percent to about 70 weight percent trans- HFC-1234ze, and about 1 weight percent to about 20 weight percent n-butane; and about 5 weight percent to about 70 weight percent HFC-125, about 5 weight percent to about 70weight percent trans- HFC-1234ze, and about 1 weight percent to about 20 weight percent isobutane; about 10 weight percent to about 80 weight percent trans-HFC- 1234ze, about 10 weight percent to about 80 weight percent HFC-1243zf and about 10 weight percent to about 80 weight percent HFC-227ea; about 10 weight percent to about 80 weight percent trans-HFC- 1234ze, about 10 weight percent to about 80 weight percent HFC-1243zf and about 1 weight percent to about 20 weight percent n-butane; about 10 weight percent to about 80 weight percent trans-HFC- 1234ze, about 10 weight percent to about 80 weight percent HFC-1243zf and about 1 weight percent to about 30 weight percent isobutane; about 10 weight percent to about 80 weight percent trans-HFC- 1234ze, about 10 weight percent to about 80 weight percent HFC-1243zf and about 1 weight percent to about 40 weight percent dimethylether; about 10 weight percent to about 80 weight percent trans-HFC- 1234ze, about 10 weight percent to about 80 weight percent HFC-134 and about 1 weight percent to about 50 weight percent HFC-152a; about 10 weight percent to about 80 weight percent trans-HFC- 1234ze, about 10 weight percent to about 80 weight percent HFC-134 and about 10 weight percent to about 80 weight percent HFC~227ea; about 10 weight percent to about 80 weight percent trans-HFC-
1234ze, about 10 weight percent to about 80 weight percent
HFC-134 and about 1 weight percent to about 30 weight percent diemthylether; about 10 weight percent to about 80 weight percent trans-HFC-
1234ze, about 10 weight percent to about 80 weight percent
HFC-134a and about 1 weight percent to about 50 weight percent H FC-152a; about 10 weight percent to about 80 weight percent trans-HFC-
1234ze, about 10 weight percent to about 80 weight percent
HFC-152a and about 1 weight percent to about 30 weight percent n-butane; about 20 weight percent to about 90 weight percent trans-HFC-
1234ze, about 1 weight percent to about 50 weight percent
HFC-152a and about 1 weight percent to about 30 weight percent dimethyiether; about 10 weight percent to about 80 weight percent trans-HFC-
1234ze, about 10 weight percent to about 80 weight percent
HFC-227ea and about 1 weight percent to about 30 weight percent n-butane; about 10 weight percent to about 90 weight percent trans-HFC-
1234ze, about 1 weight percent to about 30 weight percent n-butane and about 1 weight percent to about 30 weight percent dimethyiether; about 10 weight percent to about 80 weight percent trans-HFC-
1234ze, about 1 weight percent to about 20 weight percent n-butane and about 10 weight percent to about 80 weight percent CF3I; about 10 weight percent to about 90 weight percent trans-HFC-
1234ze, about 1 weight percent to about 30 weight percent isobutane and about 1 weight percent to about 30 weight percent dimethyiether; about 10 weight percent to about 80 weight percent trans-HFC-
1234ze, about 1 weight percent to about 20 weight percent isobutane and about 10 weight percent to about 80 weight percent CF3I; and about 10 weight percent to about 80 weight percent trans-HFC- 1234ze, about 1 weight percent to about 20 weight percent isobutane and about 10 weight percent to about 80 weight percent CF3SCF3..
13. A composition of claim 2 selected from the group consisting of: about 90 weight percent trans-HFC-1234ze and about 10 weight percent HFC-134a; about 95 weight percent trans-HFC-1234ze and about 5 weight percent HFC-32; about 80 weight percent trans-HFC-1234ze and about 20 weight percent HFC-152a; about 30 weight percent HFC-32, about 50 weight percent HFC-
125, and about 20 weight percent trans-HFC-1234ze; about 23 weight percent HFC-32, about 25 weight percent HFC-
125, and about 52 weight percent trans-HFC-1234ze; about 66 weight percent HFC-125, about 32 weight percent trans-HFC-1234ze, and about 2 weight percent n-butane; and about 86.1 weight percent HFC-125, about 11.5 weight percent trans-HFC-1234ze, and about 2.4 weight percent isobutane.
14. A composition of claim 3 selected from the group consisting of:
HFC-1234yf and HFC-134a; HFC-1234yf and HFC-152a; HFC-1234yf and HFC-32; HFC-1234yf, HFC-125 and n-butane; HFC-1234yf, HFC-32 and HFC-125; HFC-1234yf, HFC-125 and isobutane; HFC-1234yf, HFC-32 and HFC-143a; HFC-1234yf, HFC-32 and isobutane; HFC-1234yf, HFC-125 and HFC-143a; HFC-1234yf, HFC-125 and isobutane; HFC-1234yf, HFC-134 and propane; HFC-1234yf, HFC-134 and dimethylether; HFC-1234yf, HFC-134a and propane; HFC-1234yf, HFC-134a and n-butane; HFC-1234yf, HFC-134a and isobutane; HFC-1234yf, HFC-134a and dimethylether; HFC-1234yf, HFC-143a and propane; HFC-1234yf, HFC-143a and dimethylether; HFC-1234yf, HFC-152a and n-butane; HFC-1234yf, HFC-152a and isobutane; HFC-1234yf, HFC-152a and dimethylether; HFC-1234yf, HFC-227ea and propane; HFC-1234yf, HFC-227ea and n-butane; HFC-1234yf, HFC-227ea and isobutane; HFC-1234yf, HFC-227ea and dimethylether; HFC-1234yf, n-butane and dimethylether; HFC-1234yf, isobutane and dimethylether; HFC-1234yf, dimethylether and CF3I; HFC-1234yf, dimethylether and CF3SCF3; HFC-1234yf, HFC-32 and CF3I; HFC-1234yf, HFC-32 and HFC-125; . HFC-1234yf, HFC-32, HFC-125 and CF3I; and HFC-1234yf, HFC-32, HFC-134a and CF3I.
15. A composition of claim 3 selected from the group consisting of: about 1 weight percent to about 99 weight percent HFC-1234yf and about 99 weight percent to about 1 weight percent HFC-134a; about 1 weight percent to about 99 weight percent HFC-1234yf and about 99 weight percent to about 1 weight percent HFC-32; about 1 weight percent to about 99 weight percent HFC-1234yf and about 99 weight percent to about 1 weight percent HFC-152a; about 0.1 weight percent to about 98 weight percent HFC-32, about 0.1 weight percent to about 98 weight percent HFC- 125, and about 0.1 weight percent to about 98 weight percent H FC-1234yf; about 0.1 weight percent to about 98 weight percent HFC-125, about 0.1 weight percent to about 98 weight percent HFC- 1234yf, and about 0.1 weight percent to about 98 weight percent n-butane; and about 0.1 weight percent to about 98 weight percent HFC-125, about 0.1 weight percent to about 98 weight percent HFC- 1234yf, and about 0.1 weight percent to about 98 weight percent isobutane; about 1 weight percent to about 50 weight percent HFC-1234yf, about 1 weight percent to about 98 weight percent HFC-32 and about 1 weight percent to about 98 weight percent HFC- 143a; about 1 weight percent to about 40 weight percent HFC-1234yf, about 59 weight percent to about 98 weight percent HFC-32 and about 1 weight percent to about 30 weight percent isobutane; about 1 weight percent to about 60 weight percent HFC-1234yf, about 1 weight percent to about 98 weight percent HFC-125 and about 1 weight percent to about 98 weight percent HFC- 143a; about 1 weight percent to about 40 weight percent HFC-1234yf, about 59 weight percent to about 98 weight percent HFC- 125 and about 1 weight percent to about 20 weight percent isobutane; about 1 weight percent to about 80 weight percent HFC-1234yf, about 1 weight percent to about 70 weight percent HFC-134 and about 19 weight percent to about 90 weight percent propane; about 1 weight percent to about 70 weight percent HFC-1234yf, about 1 weight percent to about 98 weight percent HFC-134 and about 29 weight percent to about 98 weight percent dimethylether; about 1 weight percent to about 80 weight percent HFC-1234yf, about 1 weight percent to about 80 weight percent HFC- 134a and about 19 weight percent to about 98 weight percent propane; about 1 weight percent to about 98 weight percent HFC-1234yf, about 1 weight percent to about 98 weight percent HFC- 134a and about 1 weight percent to about 30 weight percent n-butane; about 1 weight percent to about 98 weight percent HFC-1234yf, about 1 weight percent to about 98 weight percent HFC- 134a and about 1 weight percent to about 30 weight percent isobutane; about 1 weight percent to about 98 weight percent HFC-1234yf, about 1 weight percent to about 98 weight percent HFC- 134a and about 1 weight percent to about 40 weight percent dimethylether; about 1 weight percent to about 80 weight percent HFC-1234yf, about 1 weight percent to about 98 weight percent HFC- 143a and about 1 weight percent to about 98 weight percent propane; about 1 weight percent to about 40 weight percent HFC-1234yf, about 59 weight percent to about 98 weight percent HFC- 143a and about 1 weight percent to about 20 weight percent dimethylether; about 1 weight percent to about 98 weight percent HFC-1234yf, about 1 weight percent to about 98 weight percent HFC- 152a and about 1 weight percent to about 30 weight percent n-butane; about 1 weight percent to about 98 weight percent HFC-1234yf, about 1 weight percent to about 90 weight percent HFC- 152a and about 1 weight percent to about 40 weight percent isobutane; about 1 weight percent to about 70 weight percent HFC-1234yf, about 1 weight percent to about 98 weight percent HFC- 152a and about 1 weight percent to about 98 weight percent dimethylether; about 1 weight percent to about 80 weight percent HFC-1234yf, about 1 weight percent to about 70 weight percent HFC- 227ea and about 29 weight percent to about 98 weight percent propane; about 40 weight percent to about 98 weight percent HFC- 1234yf, about 1 weight percent to about 59 weight percent HFC-227ea and about 1 weight percent to about 20 weight percent n-butane; about 30 weight percent to about 98 weight percent HFC- 1234yf, about 1 weight percent to about 69 weight percent HFC-227ea and about 1 weight percent to about 30 weight percent isobutane; about 1 weight percent to about 98 weight percent HFC-1234yf, about 1 weight percent to about 80 weight percent HFC- 227ea and about 1 weight percent to about 98 weight percent dimethylether; about 1 weight percent to about 98 weight percent HFC-1234yf, about 1 weight percent to about 40 weight percent n-butane and about 1 weight percent to about 98 weight percent dimethylether; about 1 weight percent to about 98 weight percent HFC-1234yf, about 1 weight percent to about 50 weight percent isobutane and about 1 weight percent to about 98 weight percent dimethylether; about 1 weight percent to about 98 weight percent HFC-1234yf, about 1 weight percent to about 98 weight percent dimethylether and about 1 weight percent to about 98 weight percent CF3I; about 1 weight percent to about 98 weight percent HFC-1234yf, about 1 weight percent to about 40 weight percent dimethylether and about 1 weight percent to about 98 weight percent CF3SCF3; about 1 weight percent to about 98 weight percent HFC-1234yf, about 1 weight percent to about 98 weight percent HFC-32 and about 1 weight percent to about 98 weight percent HFC- 125; about 1 weight percent to about 97 weight percent HFC-1234yf, about 1 weight percent to about 97 weight percent HFC-32 and about 1 weight percent to about 97 weight percent HFC- 125 and about 1 weight percent to about 97 weight percent CF3I; about 1 weight percent to about 97 weight percent HFC-1234yf, about 1 weight percent to about 97 weight percent HFC-32 and about 1 weight percent to about 97 weight percent HFC- 134a and about 1 weight percent to about 97 weight percent CF3I; and about 1 weight percent to about 98 weight percent HFC-1234yf, about 1 weight percent to about 98 weight percent HFC-32 and about 1 weight percent to about 98 weight percent CF3I.
16. A composition of claim 3 selected from the group consisting of: about 30 weight percent to about 99 weight percent HFC-1234yf and about 70 weight percent to about 1 weight percent
HFC-134a; about 40 weight percent to about 99 weight percent HFC~1234yf and about 60 weight percent to about 1 weight percent
HFC-32; about 40 weight percent to about 99 weight percent HFC-1234yf and about 60 weight percent to about 1 weight percent
HFC-152a about 5 weight percent to about 70 weight percent HFC-32, about 5 weight percent to about 70 weight percent HFC-
125, and about 5 weight percent to about 70 weight percent
HFC-1234yf; about 5 weight percent to about 70 weight percent HFC-125, about 5 weight percent to 70 weight percent HFC-1234yf, and about 1 weight percent to about 20 weight percent n- butane; about 5 weight percent to about 70 weight percent HFC-125, about 5 weight percent to about 70 weight percent HFC-
1234yf, and about 1 weight percentjo about 20 weight percent isobutane; about 15 weight percent to about 50 weight percent HFC- 1234yf, about 20 weight percent to about 80 weight percent HFC-32 and about 5 weight percent to about 60 weight percent HFC-143a; about 10 weight percent to about 40 weight percent HFC- 1234yf, about 59 weight percent to about 90 weight percent HFC-32 and about 1 weight percent to about 10 weight percent isobutane; about 10 weight percent to about 60 weight percent HFC-
1234yf, about 20 weight percent to about 70 weight percent
HFC-125 and about 20 weight percent to about 70 weight percent HFC-143a; about 10 weight percent to about 40 weight percent HFC-
1234yf, about 59 weight percent to about 90 weight percent
HFC-125 and about 1 weight percent to about 10 weight percent isobutane; about 20 weight percent to about 80 weight percent HFC-
1234yf, about 10 weight percent to about 70 weight percent
HFC-134 and about 19 weight percent to about 50 weight percent propane; about 20 weight percent to about 70 weight percent HFC-
1234yf, about 10 weight percent to about 70 weight percent
HFC-134 and about 29 weight percent to about 50 weight percent dimethylether; about 10 weight percent to about 80 weight percent HFC-
1234yf, about 10 weight percent to about 80 weight percent
HFC-134a and about 19 weight percent to about 50 weight percent propane; about 10 weight percent to about 80 weight percent HFC-
1234yf, about 10 weight percent to about 80 weight percent
HFC-134a and about 1 weight percent to about 20 weight percent n-butane; about 10 weight percent to about 80 weight percent HFC-
1234yf, about 10 weight percent to about 80 weight percent
HFC-134a and about 1 weight percent to about 20 weight percent isobutane; about 10 weight percent to about 80 weight percent HFC-
1234yf, about 10 weight percent to about 80 weight percent
HFC-134a and about 1 weight percent to about 20 weight percent dimethylether; about 10 weight percent to about 80 weight percent HFC-
1234yf, about 10 weight percent to about 80 weight percent HFC-143a and about 1 weight percent to about 50 weight percent propane; about 5 weight percent to about 40 weight percent HFC~1234yf, about 59 weight percent to about 90 weight percent HFC-
143a and about 1 weight percent to about 10 weight percent dimethylether; about 10 weight percent to about 80 weight percent HFC-
1234yf, about 10 weight percent to about 80 weight percent
HFC-152a and about 1 weight percent to about 20 weight percent n-butane; about 10 weight percent to about 80 weight percent HFC-
1234yf, about 10 weight percent to about 80 weight percent
HFC-152a and about 1 weight percent to about 20 weight percent isobutane; about 10 weight percent to about 70 weight percent HFC-
1234yf, about 10 weight percent to about 80 weight percent
HFC-152a and about 1 weight percent to about 20 weight percent dimethylether; about 10 weight percent to about 60 weight percent HFC-
1234yf, about 10 weight percent to about 60 weight percent
HFC-227ea and about 29 weight percent to about 50 weight percent propane; about 50 weight percent to about 98 weight percent HFC-
1234yf, about 10 weight percent to about 49 weight percent
HFC-227ea and about 1 weight percent to about 10 weight percent n-butane; about 50 weight percent to about 98 weight percent HFC-
1234yf, about 10 weight percent to about 49 weight percent
HFC-227ea and about 1 weight percent to about 10 weight percent isobutane; about 10 weight percent to about 80 weight percent HFC-
1234yf, about 10 weight percent to about 80 weight percent
HFC-227ea and about 1 weight percent to about 20 weight percent dimethylether; about 10 weight percent to about 80 weight percent HFC-
1234yf, about 10 weight percent to about 40 weight percent n-butane and about 1 weight percent to about 20 weight percent dimethylether; about 10 weight percent to about 90 weight percent HFC- 1234yf, about 1 weight percent to about 40 weight percent isobutane and about 1 weight percent to about 20 weight percent dimethylether; about 10 weight percent to about 80 weight percent HFC- 1234yf, about 1 weight percent to about 20 weight percent dimethylether and about 10 weight percent to about 80 weight percent CF3I; about 10 weight percent to about 80 weight percent HFC- 1234yf, about 1 weight percent to about 20 weight percent dimethylether and about 10 weight percent to about 70 weight percent CF3SCF3; about 10 weight percent to about 80 weight percent HFC- 1234yf, about 10 weight percent to about 80 weight percent HFC-32 and about 10 weight percent to about 80 weight percent HFC-125; about 10 weight percent to about 80 weight percent HFC- 1234yf, about 5 weight percent to about 70 weight percent HFC-32 and about 10 weight percent to about 80 weight percent HFC-125 and about 5 weight percent to about 80 weight percent CF3I; about 1 weight percent to about 70 weight percent HFC-1234yf, about 5 weight percent to about 70 weight percent HFC-32 and about 5 weight percent to about 80 weight percent HFC- 134a and about 5 weight percent to about 70 weight percent CF3I; and about 10 weight percent to about 80 weight percent HFC- 1234yf, about 1 weight percent to about 70 weight percent HFC-32 and about 1 weight percent to about 80 weight percent CF3I.
17. A composition of claim 3 selected from the group consisting of: about 90 weight percent HFC-1234yf and about 10 weight percent HFC-134a; about 95 weight percent HFC-1234yf and about 5 weight percent HFC-32; about 80 weight percent HFC-1234yf and about 20 weight percent HFC-152a about 40 weight percent HFC-32, about 50 weight percent HFC-
125, and about 10 weight percent HFC-1234yf; about 23 weight percent HFC-32, about 25 weight percent HFC-
125, and about 52 weight percent HFC-1234yf; about 15 weight percent HFC-32, about 45 weight percent HFC-
125, and about 40 weight percent HFC-1234yf; about 10 weight percent HFC-32, about 60 weight percent HFC-
125, and about 30 weight percent HFC-1234yf; about 67 weight percent HFC-125, about 32 weight percent
HFC-1234yf, and about 1 weight percent n-butane; and about 87.1 weight percent HFC-125, about 11.5 weight percent
HFC-1234yf, and about 1.4 weight percent isobutane.
18. A composition of claim 5 selected from the group consisting of: HFC-1243zf, HFC-134 and HFC-227ea;
HFC-1243zf, HFC-134 and n-butane; HFC-1243zf, HFC-134 and dimethylether; HFC-1243zf, HFC-134 and CF3I; HFC-1243zf, HFC-134a and HFC-152a; HFC-1243zf, HFC-134a and n-butane; HFC-1243zf, HFC-152a and propane; HFC-1243zf, HFC-152a and n-butane; HFC-1243zf, HFC-152a and isobutane; HFC-1243zf, HFC-152a and dimethylether; HFC-1243zf, HFC-227ea and n-butane; HFC-1243zf, HFC-227ea and isobutane; HFC-1243zf, HFC-227ea and dimethylether; HFC-1243zf, n-butane and dimethylether; HFC-1243zf, isobutane and dimethylether; HFC-1243zf, isobutane and CF3I; and HFC-1243zf, dimethylether and CF3SCF3.
19. A composition of claim 5 selected from the group consisting of: about 1 weight percent to about 98 weight percent HFC-1243zf, about 1 weight percent to about 98 weight percent HFC-134 and about 1 weight percent to about 98 weight percent HFC-227ea; about 1 weight percent to about 98 weight percent HFC-1243zf, about 1 weight percent to about 98 weight percent HFC-134 and about 1 weight percent to about 40 weight percent n- butane; about 1 weight percent to about 98 weight percent HFC-1243zf, about 1 weight percent to about 98 weight percent HFC-134 and about 1 weight percent to about 98 weight percent dimethylether; about 1 weight percent to about 98 weight percent HFC-1243zf, about 1 weight percent to about 98 weight percent HFC-134 and about 1 weight percent to about 98 weight percent CF3I; about 1 weight percent to about 98 weight percent HFC-1243zf, about 1 weight percent to about 98 weight percent HFC- 134a and about 1 weight percent to about 98 weight percent HFC-152a; about 1 weight percent to about 98 weight percent HFC-1243zf, about 1 weight percent to about 98 weight percent HFC- 134a and about 1 weight percent to about 40 weight percent n-butane; about 1 weight percent to about 70 weight percent HFC-1243zf, about 1 weight percent to about 70 weight percent HFC- 152a and about 29 weight percent to about 98 weight percent propane; about 1 weight percent to about 98 weight percent HFC-1243zf, about 1 weight percent to about 98 weight percent HFC- 152a and about 1 weight percent to about 30 weight percent n-butane; about 1 weight percent to about 98 weight percent HFC-1243zf, about 1 weight percent to about 98 weight percent HFC- 152a and about 1 weight percent to about 40 weight percent isobutane; about 1 weight percent to about 98 weight percent HFC-1243zf, about 1 weight percent to about 98 weight percent HFC- 152a and about 1 weight percent to about 98 weight percent dimethylether; about 1 weight percent to about 98 weight percent HFC-1243zf, about 1 weight percent to about 98 weight percent HFC-
227ea and about 1 weight percent to about 40 weight percent n-butane; about 1 weight percent to about 98 weight percent HFC-1243zf, about 1 weight percent to about 90 weight percent HFC-
227ea and about 1 weight percent to about 50 weight percent isobutane; about 1 weight percent to about 98 weight percent HFC-1243zf, about 1 weight percent to about 80 weight percent HFC-
227ea and about 1 weight percent to about 90 weight percent dimethyiether; about 1 weight percent to about 98 weight percent HFC-1243zf, about 1 weight percent to about 40 weight percent n-butane and about 1 weight percent to about 98 weight percent dimethylether; about 1 weight percent to about 98 weight percent HFC-1243zf, about 1 weight percent to about 60 weight percent isobutane and about 1 weight percent to about 98 weight percent dimethylether; about 1 weight percent to about 98 weight percent HFC-1243zf, about 1 weight percent to about 40 weight percent isobutane and about 1 weight percent to about 98 weight percent CF3I; and about 1 weight percent to about 98 weight percent HFC-1243zf, about 1 weight percent to about 40 weight percent dimethylether and about 1 weight percent to about 90 weight percent CF3SCF3.
20. A composition of claim 5 selected from the group consisting of: about 10 weight percent to about 80 weight percent HFC- 1243zf, about 10 weight percent to about 80 weight percent HFC-134 and about 10 weight percent to about 80 weight percent HFC-227ea; about 10 weight percent to about 80 weight percent HFC- 1243zf, about 10 weight percent to about 80 weight percent HFC-134 and about 1 weight percent to about 30 weight percent n-butane; about 10 weight percent to about 80 weight percent HFC- 1243zf, about 10 weight percent to about 80 weight percent HFC-134 and about 1 weight percent to about 30 weight percent dimethylether; about 10 weight percent to about 80 weight percent HFC- 1243zf, about 10 weight percent to about 80 weight percent HFC-134 and about 10 weight percent to about 80 weight percent CF3I; about 10 weight percent to about 80 weight percent HFC- 1243zf, about 10 weight percent to about 80 weight percent HFC-134a and about 1 weight percent to about 50 weight percent HFC-152a; about 10 weight percent to about 80 weight percent HFC- 1243zf, about 10 weight percent to about 80 weight percent HFC-134a and about 1 weight percent to about 30 weight percent n-butane; about 10 weight percent to about 70 weight percent HFC- 1243zf, about 1 weight percent to about 50 weight percent HFC-152a and about 29 weight percent to about 40 weight percent propane; about 10 weight percent to about 80 weight percent HFC- 1243zf, about 1 weight percent to about 80 weight percent HFC-152a and about 1 weight percent to about 20 weight percent n-butane; about 10 weight percent to about 80 weight percent HFC- 1243zf, about 1 weight percent to about 80 weight percent HFC-152a and about 1 weight percent to about 30 weight percent isobutane; about 10 weight percent to about 80 weight percent HFC- 1243zf, about 1 weight percent to about 80 weight percent HFC-152a and about 1 weight percent to about 30 weight percent dimethylether; about 10 weight percent to about 80 weight percent HFC- 1243zf, about 1 weight percent to about 80 weight percent HFC-227ea and about 1 weight percent to about 30 weight percent n-butane; about 10 weight percent to about 80 weight percent HFC- 1243zf, about 1 weight percent to about 80 weight percent HFC-227ea and about 1 weight percent to about 30 weight percent isobutane; about 10 weight percent to about 80 weight percent HFC- 1243zf, about 1 weight percent to about 80 weight percent HFC-227ea and about 1 weight percent to about 30 weight percent dimethylether; about 10 weight percent to about 90 weight percent HFC- 1243zf, about 109 weight percent to about 30 weight percent n-butane and about 1 weight percent to about 30 weight percent dimethylether; about 10 weight percent to about 90 weight percent HFC- 1243zf, about 1 weight percent to about 30 weight percent isobutane and about 1 weight percent to about 30 weight percent dimethylether; about 10 weight percent to about 80 weight percent HFC- 1243zf, about 1 weight percent to about 30 weight percent isobutane and about 10 weight percent to about 80 weight percent CF3I; and about 10 weight percent to about 80 weight percent HFC- 1243zf, about 1 weight percent to about 30 weight percent dimethylether and about 10 weight percent to about 80 weight percent CF3SCF3.
21. A composition of claim 1 comprising an azeotropic or near-azeotropic composition selected from the group consisting of: about 1 to about 34 weight percent HFC-1225ye and about 99 to about 66 weight percent HFC-1234yf; about 1 weight percent to about 99 weight percent HFC- 1225ye and about 99 weight percent to about 1 weight percent trans-HFC-1234ze; about 1 weight percent to about 99 weight percent HFC- 1225ye and about 99 weight percent to about 1 weight percent HFC-1243zf; about 1 weight percent to about 99 weight percent HFC- 1225ye and about 99 weight percent to about 1 weight percent HFC-134; about 1 weight percent to about 99 weight percent HFC- 1225ye and about 99 weight percent to about 1 weight percent HFC-134a; about 1 weight percent to about 84 weight percent HFC- 1225ye and about 99 weight percent to about 16 weight percent HFC-161 and about 90 weight percent to about 99 weight percent HFC-1225ye and about 10 weight percent to about 1 weight percent HFC-161 ; about 1 weight percent to about 99 weight percent HFC- 1225ye and about 99 weight percent to about 1 weight percent HFC-227ea; about 57 weight percent to about 99 weight percent HFC- 1225ye and about 43 weight percent to about 1 weight percent HFC-236ea; about 48 weight percent to about 99 weight percent HFC- 1225ye and about 52 weight percent to about 1 weight percent HFC-236fa; about 70 weight percent to about 99 weight percent HFC- 1225ye and about 30 weight percent to about 1 weight percent HFC-245fa; about 1 weight percent to about 72 weight percent HFC- 1225ye and about 99 weight percent to about 28 weight percent propane; about 65 weight percent to about 99 weight percent HFC- 1225ye and about 35 weight percent to about 1 weight percent n- butane; about 50 weight percent to about 99 weight percent HFC- 1225ye and about 50 weight percent to about 1 weight percent isobutane; about 1 weight percent to about 99 weight percent HFC- 1225ye and about 99 weight percent to about 1 weight percent dimethylether; about 1 weight percent to about 99 weight percent HFC- 1225ye and about 99 weight percent to about 1 weight percent bis(trifluoromethyl) sulfide; about 1 weight percent to about 99 weight percent HFC- 1225ye and about 99 weight percent to about 1 weight percent CF3I; about 1 weight percent to about 98 weight percent HFC- 1225ye, about 1 weight percent to about 98 weight percent HFC- 134a, and about 1 weight percent to about 98 weight percent HFC- 152a; about 1 weight percent to about 98 weight percent HFC- 1225ye, about 1 weight percent to about 98 weight percent HFC- 134a, and about 1 weight percent to about 98 weight percent HFC- 161 ; about 1 weight percent to about 98 weight percent HFC- 1225ye, about 1 weight percent to about 98 weight percent HFC- 134a, and about 1 weight percent to about 40 weight percent isobutane; about 1 weight percent to about 98 weight percent HFC- 1225ye, about 1 weight percent to about 98 weight percent HFC- 134a, and about 1 weight percent to about 20 weight percent dimethylether; about 1 weight percent to about 98 weight percent HFC- 1225ye, about 1 weight percent to about 98 weight percent HFC- 152a, and about 1 weight percent to about 50 weight percent isobutane; about 1 weight percent to about 98 weight percent HFC- 1225ye, about 1 weight percent to about 98 weight percent HFC- 152a, and about 1 weight percent to about 98 weight percent dimethylether; about 1 weight percent to about 98 weight percent HFC- 1225ye, about 1 weight percent to about 98 weight percent HFC- 1234yf, and about 1 weight percent to about 98 weight percent HFC-134a; about 1 weight percent to about 98 weight percent HFC- 1225ye, about 1 weight percent to about 98 weight percent HFC- 1234yf, and about 1 weight percent to about 98 weight percent HFC-152a; about 1 weight percent to about 98 weight percent HFC- 1225ye, about 1 weight percent to about 98 weight percent HFC- 1234yf, and about 1 weight percent to about 20 weight percent HFC-125; about 1 weight percent to about 98 weight percent HFC- 1225ye, about 1 weight percent to about 98 weight percent HFC- 1234yf, and about 1 weight percent to about 98 weight percent CF3I; about 1 weight percent to about 97 weight percent HFC- 1225ye, about 1 weight percent to about 97 weight percent HFC- 134a, about 1 weight percent to about 97 weight percent HFC- 152a, and about 1 weight percent to about 10 weight percent HFC- 32; about 80 weight percent to about 98 weight percent HFC- 125, about 1 weight percent to about 19 weight percent HFC- 1225ye, and about 1 weight percent to about 10 weight percent isobutane; about 1 weight percent to about 98 weight percent HFC-32, about 1 weight percent to about 98 weight percent HFC-125, and about 1 weight percent to about 4 weight percent HFC-1225ye; about 1 weight percent to about 98 weight percent HFC- 1225ye, about 1 weight percent to about 98 weight percent trans- HFC-1234ze and about 1 weight percent to about 98 weight percent HFC-134; about 1 weight percent to about 98 weight percent HFC- 1225ye, about 1 weight percent to about 98 weight percent trans- HFC-1234ze and about 1 weight percent to about 98 weight percent HFC-227ea; about 1 weight percent to about 60 weight percent HFC- 1225ye, about 1 weight percent to about 60 weight percent trans- HFC-1234ze and about 3 weight percent to about 98 weight percent propane; about 1 weight percent to about 98 weight percent HFC- 1225ye, about 1 weight percent to about 98 weight percent trans- HFC-1234ze and about 1 weight percent to about 30 weight percent n-butane; about 1 weight percent to about 98 weight percent HFC- 1225ye, about 1 weight percent to about 98 weight percent trans- HFC-1234ze and about 1 weight percent to about 98 weight percent dimethylether; about 1 weight percent to about 98 weight percent HFC- 1225ye, about 1 weight percent to about 98 weight percent trans- HFC-1234ze and about 1 weight percent to about 98 weight percent CF3SCF3; about 1 weight percent to about 98 weight percent HFC- 1225ye, about 1 weight percent to about 98 weight percent HFC- 1243zf and about 1 weight percent to about 98 weight percent HFC-134; about 1 weight percent to about 98 weight percent HFC- 1225ye, about 1 weight percent to about 98 weight percent HFC- 1243zf and about 1 weight percent to about 30 weight percent n- butane; about 1 weight percent to about 98 weight percent HFC- 1225ye, about 1 weight percent to about 98 weight percent HFC- 1243zf and about 1 weight percent to about 40 weight percent isobutane; about 1 weight percent to about 98 weight percent HFC- 1225ye, about 1 weight percent to about 98 weight percent HFC- 1243zf and about 1 weight percent to about 98 weight percent dimethylether; about 1 weight percent to about 98 weight percent HFC- 1225ye, about 1 weight percent to about 98 weight percent HFC- 1243zf and about 1 weight percent to about 98 weight percent CF3I; about 1 weight percent to about 98 weight percent HFC- 1225ye, about 1 weight percent to about 98 weight percent HFC- 134 and about 1 weight percent to about 98 weight percent HFC- 152a; about 1 weight percent to about 98 weight percent HFC- 1225ye, about 1 weight percent to about 98 weight percent HFC- 134 and about 1 weight percent to about 98 weight percent HFC- 227ea; about 1 weight percent to about 98 weight percent HFC- 1225ye, about 1 weight percent to about 98 weight percent HFC- 134 and about 1 weight percent to about 40 weight percent n- butane; about 1 weight percent to about 98 weight percent HFC- 1225ye, about 1 weight percent to about 98 weight percent HFC- 134 and about 1 weight percent to about 40 weight percent isobutane; about 1 weight percent to about 98 weight percent HFC- 1225ye, about 1 weight percent to about 98 weight percent HFC- 134 and about 1 weight percent to about 40 weight percent dimethylether; about 40 weight percent to about 98 weight percent HFC- 1225ye, about 1 weight percent to about 59 weight percent HFC- 227ea and about 1 weight percent to about 30 weight percent dimethylether; about 1 weight percent to about 98 weight percent HFC- 1225ye, about 1 weight percent to about 30 weight percent n- butane and about 1 weight percent to about 98 weight percent dimethylether; about 1 weight percent to about 98 weight percent HFC- 1225ye, about 1 weight percent to about 20 weight percent n- butane and about 1 weight percent to about 98 weight percent CF3SCF3; about 1 weight percent to about 98 weight percent HFC- 1225ye, about 1 weight percent to about 60 weight percent isobutane and about 1 weight percent to about 98 weight percent dimethylether; and about 1 weight percent to about 98 weight percent HFC- 1225ye, about 1 weight percent to about 40 weight percent isobutane and about 1 weight percent to about 98 weight percent CF3I. 22. A composition of claim 2 comprising an azeotropic or near- azeotropic composition selected from the group consisting of: about 1 weight percent to about 99 weight percent trans- HFC-1234ze and about 99 weight percent to about 1 weight percent HFC-1234yf; about 1 weight percent to about 99 weight percent trans- HFC-1234ze and about 99 weight percent to about 1 weight percent HFC-1243zf; about 1 weight percent to about 99 weight percent trans- HFC-1234ze and about 99 weight percent to about 1 weight percent HFC-134; about 1 weight percent to about 99 weight percent trans- HFC-1234ze and about 99 weight percent to about 1 weight percent HFC-134a; about 1 weight percent to about 99 weight percent trans- HFC-1234ze and about 99 weight percent to about 1 weight percent HFC-152a; about 1 weight percent to about 52 weight percent trans- HFC-1234ze and about 99 weight percent to about 48 weight percent HFC-161 and about 87 weight percent to about 99 weight percent trans-HFC-1234ze and about 13 weight percent to about 1 weight percent HFC-161 ; about 1 weight percent to about 99 weight percent trans- HFC-1234ze and about 99 weight percent to about 1 weight percent HFC-227ea; about 54 weight percent to about 99 weight percent trans- HFC-1234ze and about 46 weight percent to about 1 weight percent HFC-236ea; about 44 weight percent to about 99 weight percent trans- HFC-1234ze and about 56 weight percent to about 1 weight percent HFC-236fa; about 67 weight percent to about 99 weight percent trans- HFC-1234ze and about 33 weight percent to about 1 weight percent HFC-245fa; about 1 weight percent to about 71 weight percent trans- HFC-1234ze and about 99 weight percent to about 29 weight percent propane; about 62 weight percent to about 99 weight percent trans- HFC-1234ze and about 38 weight percent to about 1 weight percent n-butane; about 39 weight percent to about 99 weight percent trans- HFC-1234ze and about 61 weight percent to about 1 weight percent isobutane; about 1 weight percent to about 99 weight percent trans- HFC-1234ze and about 99 weight percent to about 1 weight percent dimethylether; about 1 weight percent to about 99 weight percent trans- HFC-1234ze and about 99 weight percent to about 1 weight percent bis(trifluoromethy)sulfide; about 1 weight percent to about 99 weight percent trans- HFC-1234ze and about 99 weight percent to about 1 weight percent CF3I; about 80 weight percent to about 98 weight percent HFC- 125, about 1 weight percent to about 19 weight percent trans-HFC- 1234ze and about 1 weight percent to about 10 weight percent isobutane; about 1 weight percent to about 98 weight percent HFC-32, about 1 weight percent to about 98 weight percent HFC-125, and about 1 weight percent to about 5 weight percent trans-HFC- 1234ze; about 80 weight percent to about 98 weight percent HFC- 125, about 1 weight percent to about 19 weight percent trans-HFC- 1234ze and about 1 weight percent to about 10 weight percent n- butane; about 1 weight percent to about 99 weight percent cis-HFC- 1234ze and about 99 weight percent to about 1 weight percent HFC-1234ye; about 1 weight percent to about 99 weight percent cis-HFC- 1234ze and about 99 weight percent to about 1 weight percent HFC-236ea; about 1 weight percent to about 99 weight percent cis-HFC- 1234ze and about 99 weight percent to about 1 weight percent HFC-236fa; about 1 weight percent to about 99 weight percent cis-HFC- 1234ze and about 99 weight percent to about 1 weight percent HFC-245fa; about 1 weight percent to about 80 weight percent cis-HFC- 1234ze and about 99 weight percent to about 20 weight percent n- butane; about 1 weight percent to about 69 weight percent cis-HFC- 1234ze and about 99 weight percent to about 31 weight percent isobutane; about 60 weight percent to about 99 weight percent cis-HFC- 1234ze and about 40 weight percent to about 1 weight percent 2- methylbutane;
. about 63 weight percent to about 99 weight percent cis-HFC- 1234ze and about 37 weight percent to about 1 weight percent n- pentane; about 1 weight percent to about 98 weight percent trans- HFC-1234ze, about 1 weight percent to about 98 weight percent HFC-1243zf and about 1 weight percent to about 98 weight percent HFC-227ea; about 1 weight percent to about 98 weight percent trans- HFC-1234ze, about 1 weight percent to about 98 weight percent HFC-1243zf and about 1 weight percent to about 30 weight percent n-butane; about 1 weight percent to about 98 weight percent trans- HFC-1234ze, about 1 weight percent to about 98 weight percent HFC-1243zf and about 1 weight percent to about 40 weight percent isobutane; about 1 weight percent to about 98 weight percent trans- HFC-1234ze, about 1 weight percent to about 98 weight percent HFC-1243zf and about 1 weight percent to about 98 weight percent dimethylether; about 1 weight percent to about 98 weight percent trans- HFC-1234ze, about 1 weight percent to about 98 weight percent HFC-134 and about 1 weight percent to about 98 weight percent HFC-152a; about 1 weight percent to about 98 weight percent trans- HFC-1234ze, about 1 weight percent to about 98 weight percent HFC-134 and about 1 weight percent to about 98 weight percent HFC-227ea; about 1 weight percent to about 98 weight percent trans- HFC-1234ze, about 1 weight percent to about 98 weight percent HFC-134 and about 1 weight percent to about 40 weight percent dimethylether; about 1 weight percent to about 98 weight percent trans- HFC-1234ze, about 1 weight percent to about 98 weight percent HFC-134a and about 1 weight percent to about 98 weight percent HFC-152a; about 1 weight percent to about 98 weight percent trans- HFC-1234ze, about 1 weight percent to about 98 weight percent HFC-152a and about 1 weight percent to about 50 weight percent n-butane; about 1 weight percent to about 98 weight percent trans- HFC-1234ze, about 1 weight percent to about 98 weight percent HFC-152a and about 1 weight percent to about 98 weight percent dimethylether; about 1 weight percent to about 98 weight percent trans- HFC-1234ze, about 1 weight percent to about 98 weight percent HFC-227ea and about 1 weight percent to about 40 weight percent n-butane; about 1 weight percent to about 98 weight percent trans- HFC-1234ze, about 1 weight percent to about 40 weight percent n- butane and about 1 weight percent to about 98 weight percent dimethylether; about 1 weight percent to about 98 weight percent trans- HFC-1234ze, about 1 weight percent to about 30 weight percent n- butane and about 1 weight percent to about 98 weight percent CF3I; about 1 weight percent to about 98 weight percent trans- HFC-1234ze, about 1 weight percent to about 60 weight percent isobutane and about 1 weight percent to about 98 weight percent dimethylether; about 1 weight percent to about 98 weight percent trans- HFC-1234ze, about 1 weight percent to about 40 weight percent isobutane and about 1 weight percent to about 98 weight percent CF3I; and about 1 weight percent to about 98 weight percent trans- HFC-1234ze, about 1 weight percent to about 40 weight percent isobutane and about 1 weight percent to about 98 weight percent CF3SCF3.
23. A composition of claim 3 comprising an azeotropic or near- azeotropic composition selected from the group consisting of : about 1 weight percent to about 57 weight percent HFC- 1234yf and about 99 weight percent to about 43 weight percent HFC-32; about 1 weight percent to about 51 weight percent HFC- 1234yf and about 99 weight percent to about 49 weight percent HFC-125; about 1 weight percent to about 99 weight percent HFC- 1234yf and about 99 weight percent to about 1 weight percent HFC-134; about 1 weight percent to about 99 weight percent HFC- 1234yf and about 99 weight percent to about 1 weight percent HFC-134a; about 1 weight percent to about 99 weight percent HFC- 1234yf and about 99 weight percent to about 1 weight percent HFC-152a; about 1 weight percent to about 99 weight percent HFC- 1234yf and about 99 weight percent to about 1 weight percent HFC-161 ; about 1 weight percent to about 60 weight percent HFC- 1234yf and about 40 weight percent to about 1 weight percent HFC-143a; about 29 weight percent to about 99 weight percent HFC- 1234yf and about 71 weight percent to about 1 weight percent HFC-227ea; about 66 weight percent to about 99 weight percent HFC- 1234yf and about 34 weight percent to about 1 weight percent HFC-236fa; about 1 weight percent to about 99 weight percent HFC- 1234yf and about 99 weight percent to about 1 weight percent HFC-1243zf; about 1 weight percent to about 80 weight percent HFC- 1234yf and about 99 weight percent to about 20 weight percent propane; about 71 weight percent to about 99 weight percent HFC- 1234yf and about 29 weight percent to about 1 weight percent n- butane; about 60 weight percent to about 99 weight percent HFC- 1234yf and about 40 weight percent to about 1 weight percent isobutane; about 1 weight percent to about 99 weight percent HFC- 1234yf and about 99 weight percent to about 1 weight percent dimethylether; about 80 weight percent to about 98 weight percent HFC- 125, about 1 weight percent to about 19 weight percent HFC- 1234yf, and about 1 weight percent to about 10 weight percent isobutane; about 80 weight percent to about 98 weight percent HFC- 125, about 1 weight percent to about 19 weight percent HFC- 1234yf, and about 1 weight percent to about 10 weight percent n- butane; about 1 weight percent to about 98 weight percent HFC-32, about 1 weight percent to about 98 weight percent HFC-125, and about 1 weight percent to about 55 weight percent HFC-1234yf; about 1 weight percent to about 50 weight percent HFC- 1234yf, about 1 weight percent to about 98 weight percent HFC-32 and about 1 weight percent to about 98 weight percent HFC-143a; about 1 weight percent to about 40 weight percent HFC- 1234yf, about 59 weight percent to about 98 weight percent HFC- 32 and about 1 weight percent to about 30 weight percent isobutane; about 1 weight percent to about 60 weight percent HFC- 1234yf, about 1 weight percent to about 98 weight percent HFC- 125 and about 1 weight percent to about 98 weight percent HFC- 143a; about 1 weight percent to about 40 weight percent HFC- 1234yf, about 59 weight percent to about 98 weight percent HFC- 125 and about 1 weight percent to about 20 weight percent isobutane; about 1 weight percent to about 80 weight percent HFC- 1234yf, about 1 weight percent to about 70 weight percent HFC- 134 and about 19 weight percent to about 90 weight percent propane; about 1 weight percent to about 70 weight percent HFC- 1234yf, about 1 weight percent to about 98 weight percent HFC- 134 and about 29 weight percent to about 98 weight percent dimethyiether; about 1 weight percent to about 80 weight percent HFC- 1234yf, about 1 weight percent to about 80 weight percent HFC- 134a and about 19 weight percent to about 98 weight percent propane; about 1 weight percent to about 98 weight percent HFC- 1234yf, about 1 weight percent to about 98 weight percent HFC- 134a and about 1 weight percent to about 30 weight percent n- butane; about 1 weight percent to about 98 weight percent HFC- 1234yf, about 1 weight percent to about 98 weight percent HFC- 134a and about 1 weight percent to about 30 weight percent isobutane; about 1 weight percent to about 98 weight percent HFC- 1234yf, about 1 weight percent to about 98 weight percent HFC- 134a and about 1 weight percent to about 40 weight percent dimethyiether; about 1 weight percent to about 80 weight percent HFC- 1234yf, about 1 weight percent to about 98 weight percent HFC- 143a and about 1 weight percent to about 98 weight percent propane; about 1 weight percent to about 40 weight percent HFC- 1234yf, about 59 weight percent to about 98 weight percent HFC- 143a and about 1 weight percent to about 20 weight percent dimethyiether; about 1 weight percent to about 98 weight percent HFC- 1234yf, about 1 weight percent to about 98 weight percent HFC- 152a and about 1 weight percent to about 30 weight percent n- butane; about 1 weight percent to about 98 weight percent HFC- 1234yf, about 1 weight percent to about 90 weight percent HFC- 152a and about 1 weight percent to about 40 weight percent isobutane; about 1 weight percent to about 70 weight percent HFC- 1234yf, about 1 weight percent to about 98 weight percent HFC- 152a and about 1 weight percent to about 98 weight percent dimethylether; about 1 weight percent to about 80 weight percent HFC- 1234yf, about 1 weight percent to about 70 weight percent HFC- 227ea and about 29 weight percent to about 98 weight percent propane; about 40 weight percent to about 98 weight percent HFC- 1234yf, about 1 weight percent to about 59 weight percent HFC- 227ea and about 1 weight percent to about 20 weight percent n- butane; about 30 weight percent to about 98 weight percent HFC- 1234yf, about 1 weight percent to about 69 weight percent HFC- 227ea and about 1 weight percent to about 30 weight percent isobutane; about 1 weight percent to about 98 weight percent HFC- 1234yf, about 1 weight percent to about 80 weight percent HFC- 227ea and about 1 weight percent to about 98 weight percent dimethylether; about 1 weight percent to about 98 weight percent HFC- 1234yf, about 1 weight percent to about 40 weight percent n- butane and about 1 weight percent to about 98 weight percent dimethylether; about 1 weight percent to about 98 weight percent HFC- 1234yf, about 1 weight percent to about 50 weight percent isobutane and about 1 weight percent to about 98 weight percent dimethylether; about 1 weight percent to about 98 weight percent HFC- 1234yf, about 1 weight percent to about 98 weight percent dimethylether and about 1 weight percent to about 98 weight percent CF3I; and about 1 weight percent to about 98 weight percent HFC- 1234yf, about 1 weight percent to about 40 weight percent dimethylether and about 1 weight percent to about 98 weight percent CF3SCF3.
24. A composition of claim 4 comprising an azeotropic or near- azeotropic composition selected from the group consisting of: about 38 weight percent to about 99 weight percent HFC- 1234ye and about 62 weight percent to about 1 weight percent HFC-134; about 1 weight percent to about 99 weight percent HFC- 1234ye and about 99 weight percent to about 1 weight percent HFC-236ea; about 1 weight percent to about 99 weight percent HFC- 1234ye and about 99 weight percent to about 1 weight percent HFC-236fa; about 1 weight percent to about 99 weight percent HFC- 1234ye and about 99 weight percent to about 1 weight percent HFC-245fa; about 1 weight percent to about 78 weight percent HFC- 1234ye and about 99 weight percent to about 22 weight percent n- butane; about 70 weight percent to about 99 weight percent HFC- 1234ye and about 30 weight percent to about 1 weight percent cyclopentane; about 1 weight percent to about 68 weight percent HFC- 1234ye and about 99 weight percent to about 32 weight percent isobutane; about 47 weight percent to about 99 weight percent HFC- 1234ye and about 53 weight percent to about 1 weight percent 2- methylbutane; and about 57 weight percent to about 99 weight percent HFC- 1234ye and about 43 weight percent to about 1 weight percent n- pentane. 25. A composition of claim 5 comprising an azeotropic or near- azeotropic composition selected from the group consisting of: about 1 weight percent to about 99 weight percent HFC- 1243zf and about weight percent 99 to about 1 weight percent HFC-134; about 1 weight percent to about 99 weight percent HFC- 1243zf and about 99 weight percent to about 1 weight percent HFC-134a; about 1 weight percent to about 99 weight percent HFC- 1243zf and about 99 weight percent to about 1 weight percent HFC-152a; about 1 weight percent to about 99 weight percent HFC- 1243zf and about 99 weight percent to about 1 weight percent HFC-161; about 1 weight percent to about 99 weight percent HFC- 1243zf and about 99 weight percent to about 1 weight percent HFC-227ea; about 53 weight percent to about 99 weight percent HFC- 1243zf and about 47 to about 1 weight percent HFC-236ea; about 49 weight percent to about 99 weight percent HFC- 1243zf and about 51 weight percent to about 1 weight percent HFC-236fa; about 66 weight percent to about 99 weight percent HFC- 1243zf and about 34 weight percent to about 1 weight percent HFC-245fa; about 1 weight percent to about 71 weight percent HFC- 1243zf and about 99 weight percent to about 29 weight percent propane; about 62 weight percent to about 99 weight percent HFC- 1243zf and about 38 weight percent to about 1 weight percent n- butane; about 45 weight percent to about 99 weight percent HFC- 1243zf and about 55 weight percent to about 1 weight percent isobutane; about 1 weight percent to about 99 weight percent HFC- 1243zf and about 99 weight percent to about 1 weight percent dimethylether; about 1 weight percent to about 98 weight percent HFC- 1243zf, about 1 weight percent to about 98 weight percent HFC- 134 and about 1 weight percent to about 98 weight percent HFC- 227ea; about 1 weight percent to about 98 weight percent HFC- 1243zf, about 1 weight percent to about 98 weight percent HFC- 134 and about 1 weight percent to about 40 weight percent n- butane; about 1 weight percent to about 98 weight percent HFC- 1243zf, about 1 weight percent to about 98 weight percent HFC- 134 and about 1 weight percent to about 98 weight percent dimethylether; about 1 weight percent to about 98 weight percent HFC- 1243zf, about 1 weight percent to about 98 weight percent HFC- 134 and about 1 weight percent to about 98 weight percent CF3I; about 1 weight percent to about 98 weight percent HFC- 1243zf, about 1 weight percent to about 98 weight percent HFC- 134a and about 1 weight percent to about 98 weight percent HFC- 152a; about 1 weight percent to about 98 weight percent HFC- 1243zf, about 1 weight percent to about 98 weight percent HFC- 134a and about 1 weight percent to about 40 weight percent n- butane; about 1 weight percent to about 70 weight percent HFC- 1243zf, about 1 weight percent to about 70 weight percent HFC- 152a and about 29 weight percent to about 98 weight percent propane; about 1 weight percent to about 98 weight percent HFC- 1243zf, about 1 weight percent to about 98 weight percent HFC- 152a and about 1 weight percent to about 30 weight percent n- butane; about 1 weight percent to about 98 weight percent HFC- 1243zf, about 1 weight percent to about 98 weight percent HFC- 152a and about 1 weight percent to about 40 weight percent isobutane; about 1 weight percent to about 98 weight percent HFC- 1243zf, about 1 weight percent to about 98 weight percent HFC- 152a and about 1 weight percent to about 98 weight percent dimethylether; about 1 weight percent to about 98 weight percent HFC- 1243zf, about 1 weight percent to about 98 weight percent HFC- 227ea and about 1 weight percent to about 40 weight percent n- butane; about 1 weight percent to about 98 weight percent HFC- 1243zf, about 1 weight percent to about 90 weight percent HFC- 227ea and about 1 weight percent to about 50 weight percent isobutane; about 1 weight percent to about 98 weight percent HFC- 1243zf, about 1 weight percent to about 80 weight percent HFC- 227ea and about 1 weight percent to about 90 weight percent dimethylether; about 1 weight percent to about 98 weight percent HFC- 1243zf, about 1 weight percent to about 40 weight percent n-butane and about 1 weight percent to about 98 weight percent dimethylether; about 1 weight percent to about 98 weight percent HFC- 1243zf, about 1 weight percent to about 60 weight percent isobutane and about 1 weight percent to about 98 weight percent dimethylether; about 1 weight percent to about 98 weight percent HFC- 1243zf, about 1 weight percent to about 40 weight percent isobutane and about 1 weight percent to about 98 weight percent CF3I; and about 1 weight percent to about 98 weight percent HFC- 1243zf, about 1 weight percent to about 40 weight percent dimethylether and about 1 weight percent to about 90 weight percent CF3SCF3.
26. A composition of claim 1 comprising an azeotropic composition selected from the group consisting of:
63.0 weight percent HFC-1225ye and 37.0 weight percent trans-HFC-1234ze having a vapor pressure of about 11.7 psia (81 kPa) at a temperature of about -25 °C; 40.0 weight percent HFC-1225ye and 60.0 weight percent HFC-1243zf having a vapor pressure of about 13.6 psia (94 kPa) at a temperature of about -25 °C;
52.2 weight percent HFC-1225ye and 47.8 weight percent HFC-134 having a vapor pressure of about 12.8 psia (88 kPa) at a temperature of about -25 °C;
7.3 weight percent HFC-1225ye and 92.7 weight percent HFC-152a having a vapor pressure of about 14.5 psia (100 kPa) at a temperature of about -25 °C;
29.7 weight percent HFC-1225ye and 70.3 weight percent propane having a vapor pressure of about 30.3 psia (209 kPa) at a temperature of about -25 0C;
89.5 weight percent HFC-1225ye and 10.5 weight percent n- butane having a vapor pressure of about 12.3 psia (85 kPa) at a temperature of about -25 0C;
79.3 weight percent HFC-1225ye and 20.7 weight percent isobutane having a vapor pressure of about 13.9 psia (96 kPa) at a temperature of about -25 °C;
82.1 weight percent HFC-1225ye and 17.9 weight percent dimethylether having a vapor pressure of about 10.8 psia (74 kPa) at a temperature of about -25 0C; and
37.0 weight percent HFC-1225ye and 63.0 weight percent CF3SCF3 having a vapor pressure of about 12.4 psia (85 kPa) at a temperature of about -25 0C;
47.4 weight percent HFC-1225ye, 5.6 weight percent trans HFC-1234ze, and 47.0 weight percent HFC-134 having a vapor pressure of about 12.8 psia (88 kPa) at a temperature of about -25 0C;
28.4 weight percent HFC-1225ye, 52.6 weight percent trans HFC-1234ze, and 19.0 weight percent HFC-227ea having a vapor pressure of about 11.6 psia (80.2 kPa) at a temperature of about -25 0C;
20.9 weight percent HFC-1225ye, 9.1 weight percent trans HFC-1234ze, and 70.0 weight percent propane having a vapor pressure of about 30.4 psia (209 kPa) at a temperature of about -25 °C; 65.8 weight percent HFC-1225ye, 24.1 weight percent trans HFC-1234ze, and 10.1 weight percent HFC-134 having a vapor pressure of about 12.4 psia (85.4 kPa) at a temperature of about - 25 0C;
41.0 weight percent HFC-1225ye, 40.1 weight percent trans HFC-1234ze, and 18.9 weight percent dimethylether having a vapor pressure of about 11.0 psia (75.7 kPa) at a temperature of about - 25 0C;
1.0 weight percent HFC-1225ye, 33.7 weight percent trans HFC-1234ze, and 65.2 weight percent CF3SCF3 having a vapor pressure of about 12.7 psia (87.3 kPa) at a temperature of about - 25 0C;
28.7 weight percent HFC-1225ye, 47.3 weight percent HFC- 1243zf, and 24.1 weight percent HFC-134 having a vapor pressure of about 13.8 psia (95.1 kPa) at a temperature of about -25 0C;
37.5 weight percent HFC-1225ye, 55.0 weight percent HFC- 1243zf, and 7.5 weight percent n-butane having a vapor pressure of about 14.0 psia (96.2 kPa) at a temperature of about -25 0C;
40.5 weight percent HFC-1225ye, 43.2 weight percent HFC- 1243zf, and 16.3 weight percent isobutane having a vapor pressure of about 14.8 psia (102 kPa) at a temperature of about -25 0C;
19.1 weight percent HFC-1225ye, 51.0 weight percent HFC- 1243zf, and 29.9 weight percent dimethylether having a vapor pressure of about 12.2 psia (83.8 kPa) at a temperature of about - 25 0C;
10.3 weight percent HFC-1225ye, 27.3 weight percent HFC- 1243zf, and 62.3 weight percent CF3I having a vapor pressure of about 14.1 psia (96.9 kPa) at a temperature of about -25 0C;
63.6 weight percent HFC-1225ye, 26.8 weight percent HFC- 134, and 9.6 weight percent HFC-152a having a vapor pressure of about 12.4 psia (85.4 kPa) at a temperature of about -25 0C;
1.3 weight percent HFC-1225ye, 52.3 weight percent HFC- 134, and 46.4 weight percent HFC-227ea having a vapor pressure of about 12.3 psia (84.9 kPa) at a temperature of about -25 0C;
18.1 weight percent HFC-1225ye, 67.1 weight percent HFC- 134, and 14.9 weight percent n-butane having a vapor pressure of about 14.5 psia (100 kPa) at a temperature of about -25 0C; 0.7 weight percent HFC-1225ye, 74.0 weight percent HFC- 134, and 25.3 weight percent isobutane having a vapor pressure of about 16.7 psia (115 kPa) at a temperature of about -25 °C;
29.8 weight percent HFC-1225ye, 52.5 weight percent HFC- 134, and 17.8 weight percent dimethylether having a vapor pressure of about 9.8 psia (67.4 kPa) at a temperature of about -25 oC;
63.1 weight percent HFC-1225ye, 31.0 weight percent HFC- 227ea, and 5.8 weight percent dimethylether having a vapor pressure of about 10.9 psia (75.4 kPa) at a temperature of about - 25 °C;
66.0 weight percent HFC-1225ye, 13.0 weight percent n- butane, and 21.1 weight percent dimethylether having a vapor pressure of about 11.3 psia (78.2 kPa) at a temperature of about - 25 °C;
71.3 weight percent HFC-1225ye, 5.6 weight percent n- butane, and 23.0 weight percent CF3SCF3 having a vapor pressure of about 12.3 psia (84.5 kPa) at a temperature of about -25 °C;
49.9 weight percent HFC-1225ye, 29.7 weight percent isobutane, and 20.4 weight percent dimethylether having a vapor pressure of about 12.8 psia (88.5 kPa) at a temperature of about - 25 0C; and
27.7 weight percent HFC-1225ye, 2.2 weight percent isobutane, and 70.1 weight percent CF3I having a vapor pressure of about 13.2 psia (90.9 kPa) at a temperature of about -25 °C.
27. A composition of claim 2 comprising an azeotropic composition selected from the group consisting of:
17.0 weight percent trans-HFC-1234ze and 83.0 weight percent HFC-1243zf having a vapor pressure of about 13.0 psia (90 kPa) at a temperature of about -25 0C;
45.7 weight percent trans-HFC-1234ze and 54.3 weight percent HFC-134 having a vapor pressure of about 12.5 psia (86 kPa) at a temperature of about -25 0C; 9.5 weight percent trans-HFC-1234ze and 90.5 weight percent HFC-134a having a vapor pressure of about 15.5 psia (107 kPa) at a temperature of about -25 0C;
21.6 weight percent trans-HFC-1234ze and 78.4 weight percent HFC-152a having a vapor pressure of about 14.6 psia (101 kPa) at a temperature of about -25 °C;
59.2 weight percent trans-HFC-1234ze and 40.8 weight percent HFC-227ea having a vapor pressure of about 11.7 psia (81 kPa) at a temperature of about -25 0C;
28.5 weight percent trans-H FC- 1234ze and 71.5 weight percent propane having a vapor pressure of about 30.3 psia (209 kPa) at a temperature of about -25 0C;
88.6 weight percent trans-H FC-1234ze and 11.4 weight percent n-butane having a vapor pressure of about 11.9 psia (82 kPa) at a temperature of about -25 0C;
77.9 weight percent trans-HFC-1234ze and 22.1 weight percent isobutane having a vapor pressure of about 12.9 psia (89 kPa) at a temperature of about -25 0C;
84.1 weight percent trans-H FC- 1234ze and 15.9 weight percent dimethylether having a vapor pressure of about 10.8 psia (74 kPa) at a temperature of about -25 0C;
34.3 weight percent trans-HFC-1234ze and 65.7 weight percent CF3SCF3 having a vapor pressure of about 12.7 psia (88 kPa) at a temperature of about -25 °C;
7.1 weight percent trans-H FC- 1234ze, 73.7 weight percent HFC-1243zf, and 19.2 weight percent HFC-227ea having a vapor pressure of about 13.1 psia (90.4 kPa) at a temperature of about - 25 0C;
9.5 weight percent trans-HFC-1234ze, 81.2 weight percent HFC-1243zf, and 9.3 weight percent n-butane having a vapor pressure of about 13.5 psia (92.9 kPa) at a temperature of about - 25 °C;
3.3 weight percent trans-H FC-1234ze, 77.6 weight percent HFC-1243zf, and 19.1 weight percent isobutane having a vapor pressure of about 14.3 psia (98.3 kPa) at a temperature of about - 25 °C; 2.6 weight percent trans-HFC-1234ze, 70.0 weight percent HFC-1243zf, and 27.4 weight percent dimethylether having a vapor pressure of about 12.0 psia (82.9 kPa) at a temperature of about - 25 0C;
52.0 weight percent trans-HFC-1234ze, 42.9 weight percent HFC-134, and 5.1 weight percent HFC-152a having a vapor pressure of about 12.4 psia (85.3 kPa) at a temperature of about - 25 0C;
30.0 weight percent trans-HFC-1234ze, 43.2 weight percent HFC-134, and 26.8 weight percent HFC-227ea having a vapor pressure of about 12.6 psia (86.9 kPa) at a temperature of about - 25 0C;
27.7 weight percent trans-HFC-1234ze, 54.7 weight percent HFC-134, and 17.7 weight percent dimethylether having a vapor pressure of about 9.8 psia (67.3 kPa) at a temperature of about -25 °C;
14.4 weight percent trans-HFC-1234ze, 34.7 weight percent HFC-134a, and 51.0 weight percent HFC-152a having a vapor pressure of about 14.4 psia (99.4 kPa) at a temperature of about - 25 °C;
5.4 weight percent trans-HFC-1234ze, 80.5 weight percent HFC-152a, and 14.1 weight percent n-butane having a vapor pressure of about 15.4 psia (106 kPa) at a temperature of about -25 °C;
59.1 weight percent trans-HFC-1234ze, 16.4 weight percent HFC-152a, and 24.5 weight percent dimethylether having a vapor pressure of about 10.8 psia (74.5 kPa) at a temperature of about - 25 0C;
40.1 weight percent trans-HFC-1234ze, 48.5 weight percent HFC-227ea, and 11.3 weight percent n-butane having a vapor pressure of about 12.6 psia (86.9 kPa) at a temperature of about - 25 0C;
68.1 weight percent trans-HFC-1234ze, 13.0 weight percent n-butane, and 18.9 weight percent dimethylether having a vapor pressure of about 11.3 psia (77.8 kPa) at a temperature of about - 25 0C; 81.2 weight percent trans-HFC-1234ze, 9.7 weight percent n-butane, and 9.1 weight percent CF3I having a vapor pressure of about 11.9 psia (81.8 kPa) at a temperature of about -25 °C;
55.5 weight percent trans-HFC-1234ze, 28.7 weight percent isobutane, and 15.8 weight percent dimethylether having a vapor pressure of about 12.4 psia (85.4 kPa) at a temperature of about - 25 °C;
34.9 weight percent trans-HFC-1234ze, 6.1 weight percent isobutane, and 59.0 weight percent CF3I having a vapor pressure of about 12.6 psia (86.7 kPa) at a temperature of about -25 0C;
37.7 weight percent trans-HFC-1234ze, 1.1 weight percent isobutane, and 61.7 weight percent CF3SCF3 having a vapor pressure of about 12.7 psia (87.3 kPa) at a temperature of about - 25 0C;
20.9 weight percent cis-HFC-1234ze and 79.1 weight percent HFC-236ea having a vapor pressure of about 30.3 psia (209 kPa) at a temperature of about 25 °C;
76.2 weight percent cis-HFC-1234ze and 23.8 weight percent HFC-245fa having a vapor pressure of about 26.1 psia (180 kPa) at a temperature of about 25 0C;
51.4 weight percent cis-HFC-1234ze and 48.6 weight percent n-butane having a vapor pressure of about 6.1 psia (41.9 kPa) at a temperature of about -25 °C;
26.2 weight percent cis-HFC-1234ze and 73.8 weight percent isobutane having a vapor pressure of about 8.7 psia (60.3 kPa) at a temperature of about -25 0C;
86.6 weight percent cis-HFC-1234ze and 13.4 weight percent 2-methylbutane having a vapor pressure of about 27.2 psia (188 kPa) at a temperature of about 25 0C; and
92.9 weight percent cis-HFC-1234ze and 7.1 weight percent n-pentane having a vapor pressure of about 26.2 psia (181 kPa) at a temperature of about 25 0C;
28. The composition of claim 3 comprising an azeotropic composition selected from the group consisting of: 7.4 weight percent HFC-1234yf and 92.6 weight percent HFC-32 having a vapor pressure of about 49.2 psia (339 kPa) at a temperature of about -25 °C;
10.9 weight percent HFC-1234yf and 89.1 weight percent HFC-125 having a vapor pressure of about 40.7 psia (281 kPa) at a temperature of about -25 0C;
70.4 weight percent HFC-1234yf and 29.6 weight percent HFC-134a having a vapor pressure of about 18.4 psia (127 kPa) at a temperature of about -25 0C;
91.0 weight percent HFC-1234yf and 9.0 weight percent HFC-152a having a vapor pressure of about 17.9 psia (123 kPa) at a temperature of about -25 °C;
17.3 weight percent HFC-1234yf and 82.7 weight percent HFC-143a having a vapor pressure of about 29.5 psia (272 kPa) at a temperature of about -25 °C;
84.6 weight percent HFC-1234yf and 15.4 weight percent HFC-227ea having a vapor pressure of about 18.0 psia (124 kPa) at a temperature of about -25 °C;
51.5 weight percent HFC-1234yf and 48.5 weight percent propane having a vapor pressure of about 33.5 psia (231 kPa) at a temperature of about -25 0C;
98.1 weight percent HFC-1234yf and 1.9 weight percent n- butane having a vapor pressure of about 17.9 psia (123 kPa) at a temperature of about -25 0C;
88.1 weight percent HFC-1234yf and 11.9 weight percent isobutane having a vapor pressure of about 19.0 psia (131 kPa) at a temperature of about -25 0C;
53.5 weight percent HFC-1234yf and 46.5 weight percent dimethylether having a vapor pressure of about 13.1 psia (90 kPa) at a temperature of about -25 °C;
89.1 weight percent HFC-125, 9.7 weight percent HFC- 1234yf and 1.2 weight percent isobutane having a vapor pressure of about 40.8 psia (281 kPa) at a temperature of about -25 °C;
3.9 weight percent HFC-1234yf, 74.3 weight percent HFC- 32, and 21.8 weight percent HFC-143a having a vapor pressure of about 50.0 psia (345 kPa) at a temperature of about -25 °C; 1.1 weight percent HFC-1234yf, 92.1 weight percent HFC-32 and 6.8 weight percent isobutane having a vapor pressure of about 50.0 psia (345 kPa) at a temperature of about -25 0C;
14.4 weight percent HFC-1234yf, 43.5 weight percent HFC- 125 and 42.1 weight percent HFC-143a having a vapor pressure of about 38.6 psia (266 kPa) at a temperature of about -25 0C;
4.3 weight percent HFC-1234yf, 39.1 weight percent HFC- 134 and 56.7 weight percent propane having a vapor pressure of about 34.3 psia (236 kPa) at a temperature of about -25 0C;
15.2 weight percent HFC-1234yf, 67.0 weight percent HFC- 134 and 17.8 weight percent dimethylether having a vapor pressure of about 10.4 psia (71.6 kPa) at a temperature of about -25 0C;
24.5 weight percent HFC-1234yf, 31.1 weight percent HFC- 134a and 44.5 weight percent propane having a vapor pressure of about 34.0 psia (234 kPa) at a temperature of about -25 0C;
60.3 weight percent HFC-1234yf, 35.2 weight percent HFC- 134a and 4.5 weight percent n-butane having a vapor pressure of about 18.6 psia (128 kPa) at a temperature of about -25 °C;
48.6 weight percent HFC-1234yf, 37.2 weight percent HFC- 134a and 14.3 weight percent isobutane having a vapor pressure of about 19.9 psia (137 kPa) at a temperature of about -25 0C;
24.0 weight percent HFC-1234yf, 67.9 weight percent HFC- 134a and 8.1 weight percent dimethylether having a vapor pressure of about 17.2 psia (119 kPa) at a temperature of about -25 0C;
17.7 weight percent HFC-1234yf, 71.0 weight percent HFC- 143a and 11.3 weight percent propane having a vapor pressure of about 40.4 psia (279 kPa) at a temperature of about -25 °C;
5.7 weight percent HFC-1234yf, 93.0 weight percent HFC- 143a and 1.3 weight percent dimethylether having a vapor pressure of about 39.1 psia (269 kPa) at a temperature of about -25 0C;
86.6 weight percent HFC-1234yf, 10.8 weight percent HFC- 152a and 2.7 weight percent n-butane having a vapor pressure of about 18.0 psia (124 kPa) at a temperature of about -25 0C;
75.3 weight percent HFC-1234yf, 11.8 weight percent HFC- 152a and 12.9 weight percent isobutane having a vapor pressure of about 19.1 psia (132 kPa) at a temperature of about -25 0C; 24.6 weight percent HFC-1234yf, 43.3 weight percent HFC- 152a and 32.1 weight percent dimethylether having a vapor pressure of about 11.8 psia (81.2 kPa) at a temperature of about - 25 0C;
35.6 weight percent HFC-1234yf, 17.8 weight percent HFC- 227ea and 46.7 weight percent propane having a vapor pressure of about 33.8 psia (233 kPa) at a temperature of about -25 °C;
81.9 weight percent HFC-1234yf, 16.0 weight percent HFC- 227ea and 2.1 weight percent n-butane having a vapor pressure of about 18.1 psia (125 kPa) at a temperature of about -25 °C;
86.6 weight percent HFC-1234yf, 10.8 weight percent HFC- 152a and 2.7 weight percent n-butane having a vapor pressure of about 18.0 psia (124 kPa) at a temperature of about -25 °C;
70.2 weight percent HFC-1234yf, 18.2 weight percent HFC- 227ea and 11.6 weight percent isobutane having a vapor pressure of about 19.3 psia (133 kPa) at a temperature of about -25 °C;
28.3 weight percent HFC-1234yf, 55.6 weight percent HFC- 227ea and 16.1 weight percent dimethylether having a vapor pressure of about 15.0 psia (104 kPa) at a temperature of about -25 0C;
48.9 weight percent HFC-1234yf, 4.6 weight percent n- butane and 46.4 weight percent dimethylether having a vapor pressure of about 13.2 psia (90.7 kPa) at a temperature of about - 25 °C;
31.2 weight percent HFC-1234yf, 26.2 weight percent isobutane and 42.6 weight percent dimethylether having a vapor pressure of about 14.2 psia (97.8 kPa) at a temperature of about - 25 0C;
16.3 weight percent HFC-1234yf, 10.0 weight percent dimethylether and 73.7 weight percent CF3I having a vapor pressure of about 15.7 psia (108 kPa) at a temperature of about -25 °C; and
34.3 weight percent HFC-1234yf, 10.5 weight percent dimethylether and 55.2 weight percent CF3SCF3 having a vapor pressure of about 14.6 psia (100 kPa) at a temperature of about -25 0C. 29. The composition of claim 4 comprising an azeotropic composition selected from the group consisting of:
24.0 weight percent HFC-1234ye and 76.0 weight percent HFC-236ea having a vapor pressure of about 3.35 psia (23.1 kPa) at a temperature of about -25 0C;
42.5 weight percent HFC-1234ye and 57.5 weight percent HFC-245fa having a vapor pressure of about 22.8 psia (157 kPa) at a temperature of about 25 0C;
41.2 weight percent HFC-1234ye and 58.8 weight percent n- butane having a vapor pressure of about 38.0 psia (262 kPa) at a temperature of about 25 0C;
16.4 weight percent HFC-1234ye and 83.6 weight percent isobutane having a vapor pressure of about 50.9 psia (351 kPa) at a temperature of about 25 0C;
80.3 weight percent HFC-1234ye and 19.7 weight percent 2- methylbutane having a vapor pressure of about 23.1 psia (159 kPa) at a temperature of about 25 0C; and
87.7 weight percent HFC-1234ye and 12.3 weight percent n- pentane having a vapor pressure of about 21.8 psia (150 kPa) at a temperature of about 25 0C.
30. The composition of claim 5 comprising an azeotropic composition selected from the group consisting of:
63.0 weight percent HFC-1243zf and 37.0 weight percent HFC-134 having a vapor pressure of about 13.5 psia (93 kPa) at a temperature of about -25 0C;
25.1 weight percent HFC-1243zf and 74.9 weight percent HFC-134a having a vapor pressure of about 15.9 psia (110 kPa) at a temperature of about -25 0C;
40.7 weight percent HFC-1243zf and 59.3 weight percent HFC-152a having a vapor pressure of about 15.2 psia (104 kPa) at a temperature of about -25 °C;
78.5 weight percent HFC-1243zf and 21.5 weight percent HFC-227ea having a vapor pressure of about 13.1 psia (90 kPa) at a temperature of about -25 0C; 32.8 weight percent HFC-1243zf and 67.2 weight percent propane having a vapor pressure of about 31.0 psia (213 kPa) at a temperature of about -25 0C;
90.3 weight percent HFC-1243zf and 9.7 weight percent n- butane having a vapor pressure of about 13.5 psia (93 kPa) at a temperature of about -25 0C;
80.7 weight percent HFC-1243zf and 19.3 weight percent isobutane having a vapor pressure of about 14.3 psia (98 kPa) at a temperature of about -25 0C; and
72.7 weight percent HFC-1243zf and 27.3 weight percent dimethylether having a vapor pressure of about 12.0 psia (83 kPa) at a temperature of about -25 0C;
58.6 weight percent HFC-1243zf, 34.1 weight percent HFC- 134, and 7.3 weight percent HFC-227ea having a vapor pressure of about 13.5 psia (93.4 kPa) at a temperature of about -25 0C;
27.5 weight percent HFC-1243zf, 58.7 weight percent HFC- 134, and 13.9 weight percent n-butane having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about -25 0C;
18.7 weight percent HFC-1243zf, 63.5 weight percent HFC- 134, and 17.8 weight percent dimethylether having a vapor pressure of about 10.1 psia (69.7 kPa) at a temperature of about - 25 0C;
11.4 weight percent HFC-1243zf, 23.9 weight percent HFC- 134, and 64.7 weight percent CF3I having a vapor pressure of about 14.5 psia (99.6 kPa) at a temperature of about -25 0C;
41.5 weight percent HFC-1243zf, 21.5 weight percent HFC- 134a, and 37.1 weight percent HFC-152a having a vapor pressure of about 15.0 psia (103 kPa) at a temperature of about -25 0C;
7.0 weight percent HFC-1243zf, 81.4 weight percent HFC- 134a, and 11.6 weight percent n-butane having a vapor pressure of about 17.0 psia (117 kPa) at a temperature of about -25 0C;
2.9 weight percent HFC-1243zf, 34.0 weight percent HFC- 152a, and 63.0 weight percent propane having a vapor pressure of about 31.7 psia (219 kPa) at a temperature of about -25 0C;
28.8 weight percent HFC-1243zf, 60.3 weight percent HFC- 152a, and 11.0 weight percent n-butane having a vapor pressure of about 15.7 psia (108 kPa) at a temperature of about -25 °C; 6.2 weight percent HFC-1243zf, 68.5 weight percent HFC- 152a, and 25.3 weight percent isobutane having a vapor pressure of about 17.1 psia (118 kPa) at a temperature of about -25 0C;
33.1 weight percent HFC-1243zf, 36.8 weight percent HFC- 152a, and 30.1 weight percent dimethylether having a vapor pressure of about 11.4 psia (78.7 kPa) at a temperature of about - 25 °C;
62.0 weight percent HFC-1243zf, 28.4 weight percent HFC- 227ea, and 9.6 weight percent n-butane having a vapor pressure of about 13.7 psia (94.3 kPa) at a temperature of about -25 °C;
27.9 weight percent HFC-1243zf, 51.0 weight percent HFC- 227ea, and 21.1 weight percent isobutane having a vapor pressure of about 15.0 psia (103 kPa) at a temperature of about -25 0C;
48.1 weight percent HFC-1243zf, 44.8 weight percent HFC- 227ea, and 7.2 weight percent dimethylether having a vapor pressure of about 12.8 psia (88.1 kPa) at a temperature of about - 25 0C;
60.3 weight percent HFC-1243zf, 10.1 weight percent n- butane, and 29.6 weight percent dimethylether having a vapor pressure of about 12.3 psia (84.7 kPa) at a temperature of about - 25 0C;
47.1 weight percent HFC-1243zf, 26.9 weight percent isobutane, and 25.9 weight percent dimethylether having a vapor pressure of about 13.2 psia (90.7 kPa) at a temperature of about - 25 0C;
32.8 weight percent HFC-1243zf, 1.1 weight percent isobutane, and 66.1 weight percent CF3I having a vapor pressure of about 14.0 psia (96.3 kPa) at a temperature of about -25 0C; and
41.1 weight percent HFC-1243zf, 2.3 weight percent dimethylether, and 56.6 weight percent CF3SCF3 having a vapor pressure of about 13.6 psia (93.8 kPa) at a temperature of about - 25 0C.
31. The composition as in any of claims 1-30, further comprising a lubricant selected from the group consisting of polyol esters, polyalkylene glycols, polyvinyl ethers, mineral oil, alkylbenzenes, synthetic paraffins, synthetic napthenes, and poly(alpha)olefins. 32. The composition as in any of claims 1-30, further comprising a tracer selected from the group consisting of hydrofluorocarbons, deuterated hydrocarbons, deuterated hydrofluorocarbons, perfluorocarbons, fluoroethers, brominated compounds, iodated compounds, alcohols, aldehydes, ketones, nitrous oxide (N2O) and combinations thereof.
33. The composition of claim 32, further comprising a tracer selected from the group consisting of CD3CD3, CD3CD2CD3, CD2F2, CF3CD2CF3, CD2FCF3, CD3CF3, CDF2CF3, CF3CDFCF3, CF3CF2CDF2, CDF2CDF2, CF3CF2CD3, CF3CD2CH3, CF2CH2CD3, CF3CF3, cyclo-CF2CF2CF2-, CF3CF2CF3, CyCIo-CF2CF2CF2CF2-, CF3CF2CF2CF3, CF3CF(CF3)2, cyclo- CF(CF3)CF2CF(CF3)CF2-, trans-cyclo-CF2CF(CF3)CF(CF3)CF2-, cis-cyclo- CF2CF(CF3)CF(CF3)CF2-, CF3OCHF2, CF3OCH2F, CF3OCH3, CF3OCHFCF3, CF3OCH2CF3, CF3OCH2CHF2, CF3CH2OCHF2 CH3OCF2CF3, CH3CF2OCF3 CF3CF2CF2OCHFCF3, CF3CF2CF2OCF(CF3)CF2OCHFCF3, CHF3, CH2FCH3, CHF2CH3, CHF2CHF2, CF3CHFCF3, CF3CF2CHF2, CF3CF2CH2F, CHF2CHFCF3, CF3CH2CF3, CF3CF2CH3, CF3CH2CHF2, CHF2CF2CH3, CF3CHFCH3, CF3CH2CH3, CH3CF2CH3, CH3CHFCH3, CH2FCH2CH3, CHF2CF2CF2CF3, (CF3)2CHCF3, CF3CH2CF2CF3, CHF2CF2CF2CHF2, CH3CF2CF2CF3, CF3CHFCHFCF2CF3, perfluoromethylcyclopentane, perfluoromethylcyclohexane, perfluorodimethylcyclohexane (ortho, meta, or para), perfluoroethylcyclohexane, perfluoroindan, perfluorotrimethylcyclohexane and isomers thereof, perfluoroisopropylcyclohexane, cis-perfluorodecalin, trans- perfluorodecalin, cis- or trans-perfluoromethyldecalin and isomers thereof, CH3Br, CH2FBr, CHF2Br, CHFBr2, CHBr3, CH2BrCH3, CHBr=CH2, CH2BrCH2Br, CFBr=CHF, CF3I, CHF2I, CH2FI, CF2ICH2F, CF2ICHF2, CF2ICF2I, C6F5I1 ethanol, n-propanol, isopropanol, acetone, n-propanal, n- butanal, methyl ethyl ketone, nitrous oxide, and combinations thereof.
34. The composition as in any of claims 1-30, further comprising a compatibilizer selected from the group consisting of: a) polyoxyalkylene glycol ethers represented by the formula R1[(OR2)xOR3]y, wherein: x is an integer from 1 to 3; y is an integer from 1 to 4; R1 is selected from hydrogen and aliphatic hydrocarbon radicals having 1 to 6 carbon atoms and y bonding sites; R2 is selected from aliphatic hydrocarbylene radicals having from 2 to 4 carbon atoms; R3 is selected from hydrogen, and aliphatic and alicyclic hydrocarbon radicals having from 1 to 6 carbon atoms; at least one of R1 and R3 is selected from said hydrocarbon radicals; and wherein said polyoxyalkylene glycol ethers have a molecular weight of from about 100 to about 300 atomic mass units; b) amides represented by the formulae R1C(O)NR2R3 and cyclo- [R4CON(R5)-], wherein R1, R2, R3 and R5 are independently selected from aliphatic and alicyclic hydrocarbon radicals having from 1 to 12 carbon atoms, and at most one aromatic radical having from 6 to 12 carbon atoms; R4 is selected from aliphatic hydrocarbylene radicals having from 3 to 12 carbon atoms; and wherein said amides have a molecular weight of from about 100 to about 300 atomic mass units; c) ketones represented by the formula R1C(O)R2, wherein R1 and R2 are independently selected from aliphatic, alicyclic and aryl hydrocarbon radicals having from 1 to 12 carbon atoms, and wherein said ketones have a molecular weight of from about 70 to about 300 atomic mass units; d) nitriles represented by the formula R1CN, wherein R1 is selected from aliphatic, alicyclic or aryl hydrocarbon radicals having from 5 to 12 carbon atoms, and wherein said nitriles have a molecular weight of from about 90 to about 200 atomic mass units; e) chlorocarbons represented by the formula RCIx, wherein; x is 1 or 2; R is selected from aliphatic and alicyclic hydrocarbon radicals having from 1 to 12 carbon atoms; and wherein said chlorocarbons have a molecular weight of from about 100 to about 200 atomic mass units; f) aryl ethers represented by the formula R1OR2, wherein: R1 is selected from aryl hydrocarbon radicals having from 6 to 12 carbon atoms; R2 is selected from aliphatic hydrocarbon radicals having from 1 to 4 carbon atoms; and wherein said aryl ethers have a molecular weight of from about 100 to about 150 atomic mass units; g) 1 ,1 ,1-trifluoroalkanes represented by the formula CF3R1, wherein R1 is selected from aliphatic and alicyclic hydrocarbon radicals having from about 5 to about 15 carbon atoms; h) fluoroethers represented by the formula R1OCF2CF2H, wherein R1 is selected from aliphatic, alicyclic, and aromatic hydrocarbon radicals having from about 5 to about 15 carbon atoms; or wherein said fluoroethers are derived from fluoroolefins and polyols, wherein said fluoroolefins are of the type CF2=CXY, wherein X is hydrogen, chlorine or fluorine, and Y is chlorine, fluorine, CF3 or ORf, wherein Rf is CF3, C2F5, or C3F7; and said polyols are linear or branched, wherein said linear polyols are of the type HOCH2(CHOH)X(CRR' )yCH2OH, wherein R and R' are hydrogen, CH3 or C2H5, x is an integer from 0-4, y is an integer from 0-3 and z is either zero or 1 , and said branched polyols are of the type C(OH)t(R)u(CH2OH)v[(CH2)mCH2OH]w, wherein R may be hydrogen, CH3 or C2Hs, m is an integer from 0 to 3, t and u are 0 or 1 , v and w are integers from 0 to 4, and also wherein t + u + v + w = 4; and i) lactones represented by structures [B], [C], and [D]:
Figure imgf000158_0001
[B] [C] [D]
wherein, Ri through Re are independently selected from hydrogen, linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl radicals; and the molecular weight is from about 100 to about 300 atomic mass units; and j) esters represented by the general formula R1CO2R2, wherein R1 and R2 are independently selected from linear and cyclic, saturated and unsaturated, alkyl and aryl radicals; and wherein said esters have a molecular weight of from about 80 to about 550 atomic mass units. 35.The composition any of claims 1-30, further comprising at least one ultra-violet fluorescent dye selected from the group consisting of naphthalimides, perylenes, coumarins, anthracenes, phenanthracenes, xanthenes, thioxanthenes, naphthoxanthenes, fluoresceins, derivatives of said dye and combinations thereof.
36. The composition of claim 35, further comprising at least one solubilizing agent selected from the group consisting of hydrocarbons, dimethylether, polyoxyalkylene glycol ethers, amides, ketones, nitriles, chlorocarbons, esters, lactones, aryl ethers, hydrofluoroethers, and 1,1 ,1-trifluoroalkanes.
37. The composition of claim 36, wherein said solubilizing agent is selected from the group consisting of: a) polyoxyalkylene glycol ethers represented by the formula R1[(OR2)xOR3]y, wherein: x is an integer from 1 to 3; y is an integer from 1 to 4; R1 is selected from hydrogen and aliphatic hydrocarbon radicals having 1 to 6 carbon atoms and y bonding sites; R2 is selected from aliphatic hydrocarbylene radicals having from 2 to 4 carbon atoms; R3 is selected from hydrogen, and aliphatic and alicyclic hydrocarbon radicals having from 1 to 6 carbon atoms; at least one of R1 and R3 is selected from said hydrocarbon radicals; and wherein said polyoxyalkylene glycol ethers have a molecular weight of from about 100 to about 300 atomic mass units; b) amides represented by the formulae R1C(O)NR2R3 and cyclo- [R4CON(R5)-], wherein R1, R2, R3 and R5 are independently selected from aliphatic and alicyclic hydrocarbon radicals having from 1 to 12 carbon atoms, and at most one aromatic radical having from 6 to 12 carbon atoms; R4 is selected from aliphatic hydrocarbylene radicals having from 3 to 12 carbon atoms; and wherein said amides have a molecular weight of from about 100 to about 300 atomic mass units; c) ketones represented by the formula R1C(O)R2, wherein R1 and R2 are independently selected from aliphatic, alicyclic and aryl hydrocarbon radicals having from 1 to 12 carbon atoms, and wherein said ketones have a molecular weight of from about 70 to about 300 atomic mass units; d) nitriles represented by the formula R1CN, wherein R1 is selected from aliphatic, alicyclic or aryl hydrocarbon radicals having from 5 to 12 carbon atoms, and wherein said nitriles have a molecular weight of from about 90 to about 200 atomic mass units; e) chlorocarbons represented by the formula RCIx, wherein; x is 1 or 2; R is selected from aliphatic and alicyclic hydrocarbon radicals having from 1 to 12 carbon atoms; and wherein said chlorocarbons have a molecular weight of from about 100 to about 200 atomic mass units; f) aryl ethers represented by the formula R1OR2, wherein: R1 is selected from aryl hydrocarbon radicals having from 6 to 12 carbon atoms; R2 is selected from aliphatic hydrocarbon radicals having from 1 to 4 carbon atoms; and wherein said aryl ethers have a molecular weight of from about 100 to about 150 atomic mass units; g) 1 ,1 ,1-trifluoroalkanes represented by the formula CF3R1, wherein R1 is selected from aliphatic and alicyclic hydrocarbon radicals having from about 5 to about 15 carbon atoms; h) fluoroethers represented by the formula R1OCFaCF2H, wherein R1 is selected from aliphatic, alicyclic, and aromatic hydrocarbon radicals having from about 5 to about 15 carbon atoms; or wherein said fluoroethers are derived from fluoroolefins and polyols, wherein said fluoroolefins are of the type CF2=CXY1 wherein X is hydrogen, chlorine or fluorine, and Y is chlorine, fluorine, CF3 or ORf, wherein Rf is CF3, C2Fs, or C3F7; and said polyols are linear or branched, wherein said linear polyols are of the type HOCH2(CHOH)X(CRR' )yCH2OH, wherein R and R' are hydrogen, CH3 or C2Hs, x is an integer from 0-4, y is an integer from 0-3 and z is either zero or 1 , and said branched polyols are of the type C(OH)t(R)u(CH2OH)v[(CH2)mCH2OH]w, wherein R may be hydrogen, CH3 or C2Hs, m is an integer from 0 to 3, t and u are 0 or 1 , v and w are integers from 0 to 4, and also wherein t + u + v + w = 4; and i) lactones represented by structures [B], [C], and [D]:
Figure imgf000161_0001
[B] [C] [D]
wherein, Ri through R8 are independently selected from hydrogen, linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl radicals; and the molecular weight is from about 100 to about 300 atomic mass units; and j) esters represented by the general formula R1CO2R2, wherein R1 and R2 are independently selected from linear and cyclic, saturated and unsaturated, alkyl and aryl radicals; and wherein said esters have a molecular weight of from about 80 to about 550 atomic mass units.
38.The composition of any of claims 1-30, further comprising a stabilizer, water scavenger, or odor masking agent.
39.The composition of claim 38, wherein said stabilizer is selected from the group consisting of nitromethane, hindered phenols, hydroxylamines, thiols, phosphites and lactones.
40. A composition comprising:
(a) at least one lubricant selected from the group consisting of polyol esters, polyalkylene glycol, polyvinyl ethers, mineral oils, alkylbenzenes, synthetic paraffins, synthetic napthenes, and poly(alpha)olefins; and
(b) a composition selected from the group consisting of: about 1 weight percent to about 99 weight percent HFC- 1225ye and about 99 weight percent to about 1 weight percent HFC-152a; about 1 weight percent to about 99 weight percent HFC- 1225ye and about 99 weight percent to about 1 weight percent HFC-1234yf; about 1 weight percent to about 99 weight percent HFC- 1225ye and about 99 weight percent to about 1 weight percent trans-HFC-1234ze; about 1 weight percent to about 99 weight percent HFC- 1225ye and about 99 weight percent to about 1 weight percent HFC-1243zf; about 1 weight percent to about 99 weight percent trans- HFC-1234ze and about 99 weight percent to about 1 weight percent HFC-134a; about 1 weight percent to about 99 weight percent trans- HFC-1234ze and about 99 weight percent to about 1 weight percent HFC-152a; about 1 weight percent to about 99 weight percent trans- HFC-1234ze and about 99 weight percent to about 1 weight percent HFC-227ea; and about 1 weight percent to about 99 weight percent trans- HFC-1234ze and about 99 weight percent to about 1 weight percent CF3I.
41.
A composition comprising: b) a refrigerant or heat transfer fluid composition selected from the group consisting of: about 1 weight percent to about 99 weight percent HFC- 1225ye and about 99 weight percent to about 1 weight percent HFC-152a; about 1 weight percent to about 99 weight percent HFC- 1225ye and about 99 weight percent to about 1 weight percent HFC-1234yf; about 1 weight percent to about 99 weight percent HFC- 1225ye and about 99 weight percent to about 1 weight percent trans-HFC-1234ze; about 1 weight percent to about 99 weight percent HFC- 1225ye and about 99 weight percent to about 1 weight percent HFC-1243zf; about 1 weight percent to about 99 weight percent trans- HFC-1234ze and about 99 weight percent to about 1 weight percent HFC-134a; about 1 weight percent to about 99 weight percent trans- HFC-1234ze and about 99 weight percent to about 1 weight percent HFC-152a; about 1 weight percent to about 99 weight percent trans- HFC-1234ze and about 99 weight percent to about 1 weight percent HFC-227ea; and about 1 weight percent to about 99 weight percent trans- HFC-1234ze and about 99 weight percent to about 1 weight percent CF3I; and compatibilizer selected from the group consisting of: i) polyoxyalkylene glycol ethers represented by the formula R1[(OR2)xOR3]y, wherein: x is an integer from 1 to 3; y is an integer from 1 to 4; R1 is selected from hydrogen and aliphatic hydrocarbon radicals having 1 to 6 carbon atoms and y bonding sites; R2 is selected from aliphatic hydrocarbylene radicals having from 2 to 4 carbon atoms; R3 is selected from hydrogen, and aliphatic and alicyclic hydrocarbon radicals having from 1 to 6 carbon atoms; at least one of R1 and R3 is selected from said hydrocarbon radicals; and wherein said polyoxyalkylene glycol ethers have a molecular weight of from about 100 to about 300 atomic mass units; ii) amides represented by the formulae R1C(O)NR2R3 and cyclo-[R4CON(R5)-], wherein R1, R2, R3 and R5 are independently selected from aliphatic and alicyclic hydrocarbon radicals having from 1 to 12 carbon atoms, and at most one aromatic radical having from 6 to 12 carbon atoms; R4 is selected from aliphatic hydrocarbylene radicals having from 3 to 12 carbon atoms; and wherein said amides have a molecular weight of from about 100 to about 300 atomic mass units; iii) ketones represented by the formula R1C(O)R2, wherein R1 and R2 are independently selected from aliphatic, alicyclic and aryl hydrocarbon radicals having from 1 to 12 carbon atoms, and wherein said ketones have a molecular weight of from about 70 to about 300 atomic mass units; iv) nitriles represented by the formula R1CN, wherein R1 is selected from aliphatic, alicyclic or aryl hydrocarbon radicals having from 5 to 12 carbon atoms, and wherein said nitriles have a molecular weight of from about 90 to about 200 atomic mass units; v) chlorocarbons represented by the formula RCIx, wherein; x is 1 or 2; R is selected from aliphatic and alicyclic hydrocarbon radicals having from 1 to 12 carbon atoms; and wherein said chlorocarbons have a molecular weight of from about 100 to about 200 atomic mass units; vi) aryl ethers represented by the formula R1OR2, wherein: R1 is selected from aryl hydrocarbon radicals having from 6 to 12 carbon atoms; R2 is selected from aliphatic hydrocarbon radicals having from 1 to 4 carbon atoms; and wherein said aryl ethers have a molecular weight of from about 100 to about 150 atomic mass units; vii) 1,1,1 -trif luoroalkanes represented by the formula CF3R1 , wherein R1 is selected from aliphatic and alicyclic hydrocarbon radicals having from about 5 to about 15 carbon atoms; viii)fluoroethers represented by the formula R1OCF2CF2H, wherein R1 is selected from aliphatic, alicyclic, and aromatic hydrocarbon radicals having from about 5 to about 15 carbon atoms; or wherein said fluoroethers are derived from fluoroolefins and polyols, wherein said fluoroolefins are of the type CF2=CXY, wherein X is hydrogen, chlorine or fluorine, and Y is chlorine, fluorine, CF3 or ORf, wherein Rf is CF3, C2F5, or C3F7; and said polyols are linear or branched, wherein said linear polyols are of the type HOCH2(CHOH)X(CRR1 )yCH2OH, wherein R and R' are hydrogen, CH3 or C2H5, x is an integer from 0-4, y is an integer from 0-3 and z is either zero or 1, and said branched polyols are of the type C(OH)t(R)u(CH2OH)v[(CH2)mCH2OH]w, wherein R may be hydrogen, CH3 or C2H5, m is an integer from 0 to 3, t and u are 0 or 1 , v and w are integers from 0 to 4, and also wherein t + u + v + w = 4; and ix) lactones represented by structures [B]1 [C]1 and [D]:
Figure imgf000165_0001
[B] [C] [D]
wherein, Ri through Re are independently selected from hydrogen, linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl radicals; and the molecular weight is from about 100 to about 300 atomic mass units; and x) esters represented by the general formula R1COaR2, wherein R1 and R2 are independently selected from linear and cyclic, saturated and unsaturated, alkyl and aryl radicals; and wherein said esters have a molecular weight of from about 80 to about 550 atomic mass units.
42. A composition comprising:
(a) at least one ultra-violet fluorescent dye selected from the group consisting of naphthalimides, perylenes, coumarins, anthracenes, phenanthracenes, xanthenes, thioxanthenes, naphthoxanthenes, fluoresceins, derivatives of said dye and combinations thereof; and
(b) a composition selected from the group consisting of: about 1 weight percent to about 99 weight percent HFC-
1225ye and about 99 weight percent to about 1 weight percent H FC-152a; about 1 weight percent to about 99 weight percent HFC- 1225ye and about 99 weight percent to about 1 weight percent HFC-1234yf; about 1 weight percent to about 99 weight percent HFC- 1225ye and about 99 weight percent to about 1 weight percent trans-HFC-1234ze; about 1 weight percent to about 99 weight percent HFC- 1225ye and about 99 weight percent to about 1 weight percent HFC-1243zf; about 1 weight percent to about 99 weight percent trans- HFC-1234ze and about 99 weight percent to about 1 weight percent HFC-134a; about 1 weight percent to about 99 weight percent trans- HFC-1234ze and about 99 weight percent to about 1 weight percent HFC-152a; about 1 weight percent to about 99 weight percent trans- HFC-1234ze and about 99 weight percent to about 1 weight percent HFC-227ea; and about 1 weight percent to about 99 weight percent trans- HFC-1234ze and about 99 weight percent to about 1 weight percent CF3I.
43. The composition of claim 42, further comprising at least one solubilizing agent selected from the group consisting of hydrocarbons, dimethylether, polyoxyalkylene glycol ethers, amides, ketones, nitriles, chlorocarbons, esters, lactones, aryl ethers, hydrofluoroethers, and 1,1,1- trifluoroalkanes.
44. The composition of claim 43, wherein said solubilizing agent is selected from the group consisting of: a) polyoxyalkylene glycol ethers represented by the formula R1[(OR2)xOR3]y, wherein: x is an integer from 1 to 3; y is an integer from 1 to 4; R1 is selected from hydrogen and aliphatic hydrocarbon radicals having 1 to 6 carbon atoms and y bonding sites; R2 is selected from aliphatic hydrocarbylene radicals having from 2 to 4 carbon atoms; R3 is selected from hydrogen, and aliphatic and alicyclic hydrocarbon radicals having from 1 to 6 carbon atoms; at least one of R1 and R3 is selected from said hydrocarbon radicals; and wherein said polyoxyalkylene glycol ethers have a molecular weight of from about 100 to about 300 atomic mass units; b) amides represented by the formulae R1C(O)NR2R3 and cyclo- [R4CON(R5)-], wherein R1, R2, R3 and R5 are independently selected from aliphatic and alicyclic hydrocarbon. radicals having from 1 to 12 carbon atoms, and at most one aromatic radical having from 6 to 12 carbon atoms; R4 is selected from aliphatic hydrocarbylene radicals having from 3 to 12 carbon
, atoms; and wherein said amides have a molecular weight of from about 100 to about 300 atomic mass units; c) ketones represented by the formula R1C(O)R2, wherein R1 and R2 are independently selected from aliphatic, alicyclic and aryl hydrocarbon radicals having from 1 to 12 carbon atoms, and wherein said ketones have a molecular weight of from about 70 to about 300 atomic mass units; d) nitriles represented by the formula R1CN, wherein R1 is selected from aliphatic, alicyclic or aryl hydrocarbon radicals having from 5 to 12 carbon atoms, and wherein said nitriles have a molecular weight of from about 90 to about 200 atomic mass units; e) chlorocarbons represented by the formula RCIx, wherein; x is 1 or 2; R is selected from aliphatic and alicyclic hydrocarbon radicals having from 1 to 12 carbon atoms; and wherein said chlorocarbons have a molecular weight of from about 100 to about 200 atomic mass units; f) aryl ethers represented by the formula R1OR2, wherein: R1 is selected from aryl hydrocarbon radicals having from 6 to 12 carbon atoms; R2 is selected from aliphatic hydrocarbon radicals having from 1 to 4 carbon atoms; and wherein said aryl ethers have a molecular weight of from about 100 to about 150 atomic mass units; g) 1 ,1 ,1-trifluoroalkanes represented by the formula CF3R1, wherein R1 is selected from aliphatic and alicyclic hydrocarbon radicals having from about 5 to about 15 carbon atoms; h) fluoroethers represented by the formula R1OCF2CFaH, wherein R1 is selected from aliphatic and alicyclic hydrocarbon radicals having from about 5 to about 15 carbon atoms; or wherein said T/US2006/008164
fluoroethers are derived from fluoro-olefins and polyols, wherein said fluoro-olefins are of the type CF2=CXY, wherein X is hydrogen, chlorine or fluorine, and Y is chlorine, fluorine, CF3 or ORf, wherein Rf is CF3, C2F5, or C3F7; and said polyols are of the type HOCH2CRR'(CH2)z(CHOH)xCH2(CH2OH)y, wherein R and R1 are hydrogen, CH3 or C2H5, x is an integer from 0-4, y is an integer from 0-3 and z is either zero or 1 ; and i) lactones represented by structures [B], [C], and [D]:
Figure imgf000168_0001
[B] [C] [D]
wherein, Ri through R8 are independently selected from hydrogen, linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl radicals; and the molecular weight is from about 100 to about 300 atomic mass units; and j) esters represented by the general formula R1CO2R2, wherein R1 and R2 are independently selected from linear and cyclic, saturated and unsaturated, alkyl and aryl radicals; and wherein said esters have a molecular weight of from about 80 to about 550 atomic mass units.
45. A method of producing cooling, said method comprising: evaporating said composition of any of claims 1-30 in the vicinity of a body to be cooled and thereafter condensing said composition.
46. A method of producing heat, said method comprising: condensing said composition of any of claims 1 -30 in the vicinity of a body to be heated and thereafter evaporating said composition.
47. A method of producing cooling, said method comprising: evaporating the composition of claim 41 , 42, or 43 in the vicinity of a body to be cooled and thereafter condensing said composition. 48. A method of producing heat, said method comprising: condensing said composition of claim 41 , 42, or 43 in the vicinity of a body to be heated and thereafter evaporating said composition.
49. A method for detecting the composition of claim 35 in a compression refrigeration, air conditioning, or heat pump apparatus, said method comprising providing said composition to said apparatus, and providing a suitable means for detecting said composition at a leak point or in the vicinity of said apparatus.
50. A method for detecting the composition of claim 42 or 43 in a compression refrigeration, air conditioning, or heat pump apparatus, said method comprising providing said composition to said apparatus, and providing a suitable means for detecting said composition at a leak point or in the vicinity of said apparatus.
51. A method of solubilizing a refrigerant or heat transfer fluid composition comprising the composition of any of claims 1-30 in a refrigeration lubricant selected from the group consisting of mineral oils, alkylbenzenes, synthetic paraffins, synthetic napthenes, and poly(alpha)olefins, wherein said method comprises contacting said lubricant with said composition in the presence of an effective amount of a compatibilizer, wherein said compatibilizer is selected from the group consisting of: a) polyoxyalkylene glycol ethers represented by the formula R1[(OR2)xOR3]y, wherein: x is an integer from 1 to 3; y is an integer from 1 to 4; R1 is selected from hydrogen and aliphatic hydrocarbon radicals having 1 to 6 carbon atoms and y bonding sites; R2 is selected from aliphatic hydrocarbylene radicals having from 2 to 4 carbon atoms; R3 is selected from hydrogen, and aliphatic and alicyclic hydrocarbon radicals having from 1 to 6 carbon atoms; at least one of R1 and R3 is selected from said hydrocarbon radicals; and wherein said polyoxyalkylene glycol ethers have a molecular weight of from about 100 to about 300 atomic mass units; 64
b) amides represented by the formulae R1C(O)NR2R3 and cyclo- [R4CON(R5)-], wherein R1, R2, R3 and R5 are independently selected from aliphatic and alicyclic hydrocarbon radicals having from 1 to 12 carbon atoms, and at most one aromatic radical having from 6 to 12 carbon atoms; R4 is selected from aliphatic hydrocarbylene radicals having from 3 to 12 carbon atoms; and wherein said amides have a molecular weight of from about 100 to about 300 atomic mass units; c) ketones represented by the formula R1C(O)R2, wherein R1 and R2 are independently selected from aliphatic, alicyclic and aryl hydrocarbon radicals having from 1 to 12 carbon atoms, and wherein said ketones have a molecular weight of from about 70 to about 300 atomic mass units; d) nitriles represented by the formula R1CN, wherein R1 is selected from aliphatic, alicyclic or aryl hydrocarbon radicals having from 5 to 12 carbon atoms, and wherein said nitriles have a molecular weight of from about 90 to about 200 atomic mass units; e) chlorocarbons represented by the formula RCIx, wherein; x is 1 or 2; R is selected from aliphatic and alicyclic hydrocarbon radicals having from 1 to 12 carbon atoms; and wherein said chlorocarbons have a molecular weight of from about 100 to about 200 atomic mass units; f) aryl ethers represented by the formula R1OR2, wherein: R1 is selected from aryl hydrocarbon radicals having from 6 to 12 carbon atoms; R2 is selected from aliphatic hydrocarbon radicals having from 1 to 4 carbon atoms; and wherein said aryl ethers have a molecular weight of from about 100 to about 150 atomic mass units; g) 1 ,1 ,1-trifluoroalkanes represented by the formula CF3R1, wherein R1 is selected from aliphatic and alicyclic hydrocarbon radicals having from about 5 to about 15 carbon atoms; h) fluoroethers represented by the formula R1OCF2CF2H1 wherein R1 is selected from aliphatic and alicyclic hydrocarbon radicals having from about 5 to about 15 carbon atoms; or wherein said fluoroethers are derived from fluoro-olefins and polyols, wherein said fluoro-olefins are of the type CF2=CXY, wherein X is hydrogen, chlorine or fluorine, and Y is chlorine, fluorine, CF3 or ORf, wherein Rf is CF3, C2F5, or C3F7; and said polyols are of the type HOCH2CRR'(CH2)z(CHOH)χCH2(CH2θH)y, wherein R and R' are hydrogen, CH3 or C2Hs, x is an integer from 0-4, y is an integer from 0-3 and z is either zero or 1 ; and i) lactones represented by structures [B], [C], and [D]:
Figure imgf000171_0001
[B] [C] [D]
wherein, Ri through R8 are independently selected from hydrogen, linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl radicals; and the molecular weight is from about 100 to about 300 atomic mass units; and j) esters represented by the general formula R1CO2R2, wherein R1 and R2 are independently selected from linear and cyclic, saturated and unsaturated, alkyl and aryl radicals; and wherein said esters have a molecular weight of from about 80 to about 550 atomic mass units.
52. A method for improving oil-return to the compressor in a compression refrigeration, air-conditioning or heat pump apparatus, said method comprising using the composition of claim 31 in said apparatus.
53. A method of solubilizing a refrigerant or heat transfer fluid composition in a refrigeration lubricant selected from the group consisting of mineral oils, alkylbenzenes, synthetic paraffins, synthetic napthenes, and poly(alpha)olefιns, wherein said method comprises contacting said lubricant with said refrigerant or heat transfer fluid composition in the presence of an effective amount of a compatibilizer, wherein said refrigerant or heat transfer fluid comprises a composition selected from the group consisting of: about 1 weight percent to about 99 weight percent HFC- 1225ye and about 99 weight percent to about 1 weight percent HFC-152a; about 1 weight percent to about 99 weight percent HFC- 1225ye and about 99 weight percent to about 1 weight percent trans-HFC-1234ze; about 1 weight percent to about 99 weight percent HFC- 1225ye and about 99 weight percent to about 1 weight percent HFC-1243zf; about 1 weight percent to about 99 weight percent trans- HFC-1234ze and about 99 weight percent to about 1 weight percent HFC-134a; about 1 weight percent to about 99 weight percent trans- HFC-1234ze and about 99 weight percent to about 1 weight percent HFC-152a; about 1 weight percent to about 99 weight percent trans- HFC- 1234ze and about 99 weight percent to about 1 weight percent HFC-227ea; and about 1 weight percent to about 99 weight percent trans- HFC-1234ze and about 99 weight percent to about 1 weight percent CF3I; and wherein said compatibilizer is selected from the group consisting of: a) polyoxyalkylene glycol ethers represented by the formula R1[(OR2)xOR3]y, wherein: x is an integer from 1 to 3; y is an integer from 1 to 4; R1 is selected from hydrogen and aliphatic hydrocarbon radicals having 1 to 6 carbon atoms and y bonding sites; R2 is selected from aliphatic hydrocarbylene radicals having from 2 to 4 carbon atoms; R3 is selected from hydrogen, and aliphatic and alicyclic hydrocarbon radicals having from 1 to 6 carbon atoms; at least one of R1 and R3 is selected from said hydrocarbon radicals; and wherein said polyoxyalkylene glycol ethers have a molecular weight of from about 100 to about 300 atomic mass units; b) amides represented by the formulae R1C(O)NR2R3 and cyclo- [R4CON(R5)-], wherein R1, R2, R3 and R5 are independently selected from aliphatic and alicyclic hydrocarbon radicals having from 1 to 12 carbon atoms, and at most one aromatic radical having from 6 to 12 carbon atoms; R4 is selected from aliphatic hydrocarbylene radicals having from 3 to 12 carbon atoms; and wherein said amides have a molecular weight of from about 100 to about 300 atomic mass units; c) ketones represented by the formula R1C(O)R2, wherein R1 and R2 are independently selected from aliphatic, alicyclic and aryl hydrocarbon radicals having from 1 to 12 carbon atoms, and wherein said ketones have a molecular weight of from about 70 to about 300 atomic mass units; d) nitriles represented by the formula R1CN, wherein R1 is selected from aliphatic, alicyclic or aryl hydrocarbon radicals having from 5 to 12 carbon atoms, and wherein said nitriles have a molecular weight of from about 90 to about 200 atomic mass units; e) chlorocarbons represented by the formula RCIx, wherein; x is 1 or 2; R is selected from aliphatic and alicyclic hydrocarbon radicals having from 1 to 12 carbon atoms; and wherein said chlorocarbons have a molecular weight of from about 100 to about 200 atomic mass units; f) aryl ethers represented by the formula R1OR2, wherein: R1 is selected from aryl hydrocarbon radicals having from 6 to 12 carbon atoms; R2 is selected from aliphatic hydrocarbon radicals having from 1 to 4 carbon atoms; and wherein said aryl ethers have a molecular weight of from about 100 to about 150 atomic mass units; g) 1 ,1 ,1-trifluoroalkanes represented by the formula CF3R1, wherein R1 is selected from aliphatic and alicyclic hydrocarbon radicals having from about 5 to about 15 carbon atoms; h) fluoroethers represented by the formula R1OCF2CF2H, wherein R1 is selected from aliphatic and alicyclic hydrocarbon radicals having from about 5 to about 15 carbon atoms; or wherein said fluoroethers are derived from fluoro-olefins and polyols, wherein said fluoro-olefins are of the type CF2=CXY, wherein X is hydrogen, chlorine or fluorine, and Y is chlorine, fluorine, CF3 or ORf, wherein Rf is CF3, C2F5, or C3F7; and said polyols are of the type HOCH2CRR'(CH2)z(CHOH)xCH2(CH2θH)y, wherein R and R' are hydrogen, CH3 or C2H5, x is an integer from 0-4, y is an integer from 0-3 and z is either zero or 1 ; and i) lactones represented by structures [B], [C], and [D]:
Figure imgf000174_0001
[B] [C] [D]
wherein, Ri through Rs are independently selected from hydrogen, linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl radicals; and the molecular weight is from about 100 to about 300 atomic mass units; and
]) esters represented by the general formula R1C^R2, wherein R1 and R2 are independently selected from linear and cyclic, saturated and unsaturated, alkyl and aryl radicals; and wherein said esters have a molecular weight of from about 80 to about 550 atomic mass units.
54. A method for improving oil-return to the compressor in a compression refrigeration, air-conditioning or heat pump apparatus, said method comprising using the composition of claim 41 in said apparatus.
55. A method for replacing a high GWP refrigerant in a refrigeration, air-conditioning, or heat pump apparatus, wherein said high GWP refrigerant is selected from the group consisting of R134a, R22, R123, R11, R245fa, R114, R236fa, R124, R12, R410A, R407C, R417A, R422A, R507A, R502, and R404A, said method comprising providing the composition of any of claims 1-30 to said refrigeration, air-conditioning, or heat pump apparatus that uses, used or is designed to use said high GWP refrigerant.
56. A method for replacing a high GWP refrigerant in a refrigeration, air-conditioning, or heat pump apparatus, wherein said high GWP refrigerant is selected from the group consisting of R134a, R22, R123, R11, R245fa, R114, R236fa, R124, R12, R410A, R407C, R417A, R422A, R507A, R502, and R404A, said method comprising providing a composition selected from the group consisting of: about 1 weight percent to about 99 weight percent HFC- 1225ye and about 99 weight percent to about 1 weight percent HFC-152a; about 1 weight percent to about 99 weight percent HFC- 1225ye and about 99 weight percent to about 1 weight percent HFC-1234yf; about 1. weight percent to about 99 weight percent HFC- 1225ye and about 99 weight percent to about 1 weight percent trans-HFC-1234ze; about 1 weight percent to about 99 weight percent HFC- 1225ye and about 99 weight percent to about 1 weight percent HFC-1243zf; about 1 weight percent to about 99 weight percent trans- HFC-1234ze and about 99 weight percent to about I weight percent HFC-134a; about 1 weight percent to about 99 weight percent trans- HFC-1234ze and about 99 weight percent to about 1 weight percent HFC-152a; about 1 weight percent to about 99 weight percent trans- HFC-1234ze and about 99 weight percent to about 1 weight percent HFC-227ea; and about 1 weight percent to about 99 weight percent trans- HFC-1234ze and about 99 weight percent to about 1 weight percent CF3I; to said refrigeration, air-conditioning, or heat pump apparatus that uses, used or is designed to use said high GWP refrigerant.
57. A method of using the composition of any of claims 1-30 as a heat transfer fluid composition, said process comprising comprises transporting said composition from a heat source to a heat sink.
58. A method for making the composition of any of claims 1-30, said method comprising: (i) reclaiming a volume of one or more components of a refrigerant composition from at least one refrigerant container, (ii) removing impurities sufficiently to enable reuse of said one or more of the reclaimed components, (iii) and optionally, combining all or part of said reclaimed volume of components with at least one additional refrigerant composition or component.
59. A refrigeration, air-conditioning, or heat pump apparatus containing a composition as claimed in any one of claims 1-30, 40, 41 , or 42.
60. The refrigeration, air-conditioning, or heat pump apparatus of claim comprising a mobile air-conditioning apparatus.
61. A method for early detection of a refrigerant leak in a refrigeration, air-conditioning or heat pump apparatus said method comprising using a non-azeotropic composition in said apparatus, and monitoring for a reduction in cooling performance.
62. A foam blowing agent comprising the composition of any of claims 1-30.
63. A method of forming a foam comprising:
(a) adding to a foamable composition the composition of any of claims 1-30; and
(b) reacting the foamable composition under conditions effective to form a foam.
64. A sprayable composition comprising the composition of any of claims 1-30.
65. A process for producing aerosol products comprising the step of adding a composition of any of claims 1-30 to active ingredients in an aerosol container, wherein said composition functions as a propellant.
66. A method of suppressing a flame comprising contacting the flame with a fluid comprising the composition of any of claims 1-30. 67. A method of extinguishing or suppressing a fire in a total-flood application comprising:
(a) providing an agent comprising the composition of any of claims 1-30;
(b) disposing the agent in a pressurized discharge system; and
(c) discharging the agent into an area to extinguish or suppress fires in that area.
68. A method of inerting an area to prevent a fire or explosion comprising:
(a) providing an agent comprising the composition of any of claims 1-30;
(b) disposing the agent in a pressurized discharge system; and
(c) discharging the agent into the area to prevent a fire or explosion from occurring.
PCT/US2006/008164 2005-03-04 2006-03-03 Compositions comprising a fluoroolefin WO2006094303A2 (en)

Priority Applications (64)

Application Number Priority Date Filing Date Title
EP14161825.6A EP2749623B2 (en) 2005-03-04 2006-03-03 Method for replacing a high GWP refrigerant in a refrigeration, air-conditioning, or heat pump apparatus
EP19165699.0A EP3524657B1 (en) 2005-03-04 2006-03-03 Compositions comprising hfc-1234yf and hfc-32
EP08014611.1A EP1985680B2 (en) 2005-03-04 2006-03-03 Composition comprising a HFC-1234ze isomer
PL17208709T PL3330339T3 (en) 2005-03-04 2006-03-03 Compositions comprising hfc-1234ze
PL14161825.6T PL2749623T5 (en) 2005-03-04 2006-03-03 Compositions comprising a fluoroolefin
EP18159202.3A EP3348624B1 (en) 2005-03-04 2006-03-03 Compositions comprising hfc-1234yf
PL19165699T PL3524657T3 (en) 2005-03-04 2006-03-03 Compositions comprising hfc-1234yf and hfc-32
PT182026542T PT3461871T (en) 2005-03-04 2006-03-03 Compositions comprising a fluoroolefin
EP20190991.8A EP3786254A1 (en) 2005-03-04 2006-03-03 Compositions comprising hfc-1234yf and hfc-161
EP17179475.3A EP3260516B1 (en) 2005-03-04 2006-03-03 Compositions comprising a fluoroolefin
PL18180357T PL3406686T3 (en) 2005-03-04 2006-03-03 Compositions comprising a fluoroolefin
EP10010778.8A EP2258791B1 (en) 2005-03-04 2006-03-03 Compositions comprising a fluoroolefin
EP17183434.4A EP3263671B1 (en) 2005-03-04 2006-03-03 Compositions comprising carbon dioxide and a fluoroolefin
BR122017022773-4A BR122017022773B1 (en) 2005-03-04 2006-03-03 COMPOSITION, COOLING PRODUCTION METHOD, HEAT PRODUCTION METHOD AND METHOD OF USING THE COMPOSITION
EP22175443.5A EP4074807A1 (en) 2005-03-04 2006-03-03 Compositions comprising a fluoroolefin
EP18202654.2A EP3461871B1 (en) 2005-03-04 2006-03-03 Compositions comprising trans hfc-1234ze and hfc-1234yf
EP18180357.8A EP3406686B1 (en) 2005-03-04 2006-03-03 Compositions comprising a fluoroolefin
PL19171478.1T PL3543310T5 (en) 2005-03-04 2006-03-03 Compositions comprising hfc-1234yf and hfc-32
EP17193353.4A EP3299435B1 (en) 2005-03-04 2006-03-03 Method of preparing a composition comprising hfc-1234yf
PL17203942.2T PL3309233T5 (en) 2005-03-04 2006-03-03 Compositions comprising hfc-1234yf and hfc-152a
PL18154365T PL3351609T3 (en) 2005-03-04 2006-03-03 Method for replacing a high gwp refrigerant by compositions comprising hfc-1234yf
EP18154365.3A EP3351609B1 (en) 2005-03-04 2006-03-03 Method for replacing a high gwp refrigerant by compositions comprising hfc-1234yf
PL18208197T PL3470492T3 (en) 2005-03-04 2006-03-03 Compositions comprising hfc-1234ze and hfc-227ea
BR122017022767-0A BR122017022767B1 (en) 2005-03-04 2006-03-03 COMPOSITION, COOLING PRODUCTION METHOD, HEAT PRODUCTION METHOD AND COMPOSITION USE METHOD
EP18186309.3A EP3428242A1 (en) 2005-03-04 2006-03-03 Compositions comprising hfc-1225ye and co2
PL17188278T PL3275965T3 (en) 2005-03-04 2006-03-03 Compositions comprising a fluoroolefin
EP17179466.2A EP3255115B1 (en) 2005-03-04 2006-03-03 Compositions consisting of hfc-1234yf and hfc-134a
EP18164734.8A EP3388495B1 (en) 2005-03-04 2006-03-03 Compositions comprising a fluoroolefin
CA2600319A CA2600319C (en) 2005-03-04 2006-03-03 Compositions comprising a fluoroolefin
EP18180358.6A EP3406687A1 (en) 2005-03-04 2006-03-03 Compositions comprising a fluoroolefin
NO20231079A NO20231079A1 (en) 2005-03-04 2006-03-03 COMPOSITIONS CONTAINING A FLUOROOLEFIN
EP18208197.6A EP3470492B1 (en) 2005-03-04 2006-03-03 Compositions comprising hfc-1234ze and hfc-227ea
PL18169944.8T PL3378919T5 (en) 2005-03-04 2006-03-03 Compositions comprising hfc-1234yf and hfc-32
EP06737345.6A EP1853679B1 (en) 2005-03-04 2006-03-03 Compositions comprising a fluoroolefin
ES06737345.6T ES2561114T3 (en) 2005-03-04 2006-03-03 Compositions comprising a fluoroolefin
BR122017022747-5A BR122017022747B1 (en) 2005-03-04 2006-03-03 COMPOSITION, COOLING PRODUCTION METHOD, HEAT PRODUCTION METHOD AND COMPOSITION USE METHOD
BRPI0607994-6A BRPI0607994B1 (en) 2005-03-04 2006-03-03 COMPOSITION, COOLING PRODUCTION METHOD, HEAT PRODUCTION METHOD, REFRIGERANT REPLACEMENT METHOD, COMPOSITION USING METHOD, FOAM BLOWING AGENT, FOAM FORMATION METHOD, SPRAYABLE COMPOSITION AND AEROSOL PRODUCT MANUFACTURING PROCESS
KR1020077022509A KR101368127B1 (en) 2005-03-04 2006-03-03 Compositions Comprising a Fluoroolefin
EP17198734.0A EP3293242B1 (en) 2005-03-04 2006-03-03 Compositions comprising hfc-1234yf
EP17188278.0A EP3275965B1 (en) 2005-03-04 2006-03-03 Compositions comprising a fluoroolefin
EP19171478.1A EP3543310B2 (en) 2005-03-04 2006-03-03 Compositions comprising hfc-1234yf and hfc-32
MX2007010758A MX2007010758A (en) 2005-03-04 2006-03-03 Compositions comprising a fluoroolefin.
JP2007558341A JP5001181B2 (en) 2005-03-04 2006-03-03 Compositions containing fluoroolefins
PL17198734T PL3293242T3 (en) 2005-03-04 2006-03-03 Compositions comprising hfc-1234yf
PL17179485.2T PL3255116T5 (en) 2005-03-04 2006-03-03 Compositions comprising hfc-1234yf and hfc-32
BR122017022761-0A BR122017022761B1 (en) 2005-03-04 2006-03-03 COMPOSITION, COOLING PRODUCTION METHOD, HEAT PRODUCTION METHOD AND METHOD OF USING THE COMPOSITION
EP19177627.7A EP3553119B1 (en) 2005-03-04 2006-03-03 Compositions comprising trans-hfc-1234ze and isobutane
PL06737345T PL1853679T3 (en) 2005-03-04 2006-03-03 Compositions comprising a fluoroolefin
EP17179485.2A EP3255116B2 (en) 2005-03-04 2006-03-03 Compositions comprising hfc-1234yf and hfc-32
MX2013003225A MX361577B (en) 2005-03-04 2006-03-03 Compositions comprising a fluoroolefin.
EP17208709.0A EP3330339B1 (en) 2005-03-04 2006-03-03 Compositions comprising hfc-1234ze
KR1020127030484A KR101506777B1 (en) 2005-03-04 2006-03-03 Compositions Comprising a Fluoroolefin
EP18169944.8A EP3378919B2 (en) 2005-03-04 2006-03-03 Compositions comprising hfc-1234yf and hfc-32
BR122017022758-0A BR122017022758B1 (en) 2005-03-04 2006-03-03 COMPOSITION, COOLING PRODUCTION METHOD, HEAT PRODUCTION METHOD AND METHOD OF USING THE COMPOSITION
PL17179475T PL3260516T3 (en) 2005-03-04 2006-03-03 Compositions comprising a fluoroolefin
EP18182081.2A EP3425017B1 (en) 2005-03-04 2006-03-03 Compositions comprising hfc-1234ze
PL17179466T PL3255115T3 (en) 2005-03-04 2006-03-03 Compositions consisting of hfc-1234yf and hfc-134a
PL18159202T PL3348624T3 (en) 2005-03-04 2006-03-03 Compositions comprising hfc-1234yf
EP17203942.2A EP3309233B2 (en) 2005-03-04 2006-03-03 Compositions comprising hfc-1234yf and hfc-152a
AU2006218376A AU2006218376B2 (en) 2005-03-04 2006-03-03 Compositions comprising a fluoroolefin
PL17183434T PL3263671T3 (en) 2005-03-04 2006-03-03 Compositions comprising carbon dioxide and a fluoroolefin
EP18180356.0A EP3406685A1 (en) 2005-03-04 2006-03-03 Compositions comprising a pentafluoropropene
PL18202654T PL3461871T3 (en) 2005-03-04 2006-03-03 Compositions comprising trans hfc-1234ze and hfc-1234yf
NO20074989A NO347752B1 (en) 2005-03-04 2007-10-03 Compositions containing a fluoroolefin, and use thereof

Applications Claiming Priority (7)

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US65854305P 2005-03-04 2005-03-04
US60/658,543 2005-03-04
US71043905P 2005-08-23 2005-08-23
US60/710,439 2005-08-23
US73276905P 2005-11-01 2005-11-01
US60/732,769 2005-11-01
US11/369,227 US20060243944A1 (en) 2005-03-04 2006-03-02 Compositions comprising a fluoroolefin

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AR (5) AR053689A1 (en)
AU (1) AU2006218376B2 (en)
BR (6) BR122017022747B1 (en)
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