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WO2025096365A1 - Compositions comprenant du tétrafluoropropène et leurs utilisations - Google Patents

Compositions comprenant du tétrafluoropropène et leurs utilisations Download PDF

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WO2025096365A1
WO2025096365A1 PCT/US2024/053311 US2024053311W WO2025096365A1 WO 2025096365 A1 WO2025096365 A1 WO 2025096365A1 US 2024053311 W US2024053311 W US 2024053311W WO 2025096365 A1 WO2025096365 A1 WO 2025096365A1
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hfc
hfo
composition
hcc
weight percent
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PCT/US2024/053311
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English (en)
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Sheng Peng
Mary E. Koban
Joshua Hughes
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The Chemours Company Fc, Llc
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Publication of WO2025096365A1 publication Critical patent/WO2025096365A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
    • C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
    • C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
    • C09K5/045—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-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
    • C08J9/14—Working-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
    • C08J9/143—Halogen containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-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
    • C08J9/14—Working-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
    • C08J9/143—Halogen containing compounds
    • C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
    • C08J9/146—Halogen containing compounds containing carbon, halogen and hydrogen only only fluorine as halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
    • C10M171/008—Lubricant compositions compatible with refrigerants
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/16—Unsaturated hydrocarbons
    • C08J2203/162—Halogenated unsaturated hydrocarbons, e.g. H2C=CF2
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/20—Ternary blends of expanding agents
    • C08J2203/202—Ternary blends of expanding agents of physical blowing agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/22—Thermoplastic resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/24—Thermosetting resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2325/02—Homopolymers or copolymers of hydrocarbons
    • C08J2325/04—Homopolymers or copolymers of styrene
    • C08J2325/06—Polystyrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/10—Components
    • C09K2205/12—Hydrocarbons
    • C09K2205/122—Halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/10—Components
    • C09K2205/12—Hydrocarbons
    • C09K2205/126—Unsaturated fluorinated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/22—All components of a mixture being fluoro compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/40—Replacement mixtures
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/40—Replacement mixtures
    • C09K2205/43—Type R22
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/283—Esters of polyhydroxy compounds
    • C10M2207/2835—Esters of polyhydroxy compounds used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/04—Macromolecular 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
    • C10M2209/043—Macromolecular 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/1033—Polyethers, i.e. containing di- or higher polyoxyalkylene groups used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/09—Characteristics associated with water
    • C10N2020/097—Refrigerants
    • C10N2020/101—Containing Hydrofluorocarbons
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/30—Refrigerators lubricants or compressors lubricants

Definitions

  • the present invention is directed to fluoroolefin refrigerant compositions, methods and systems using the same, and systems containing the E-HFO-1234ze refrigerant compositions.
  • HFC refrigerants such as HFC-134a and HFC-125 respectively have global warming potentials (GWP) of 1,430 and 3,500 according to the UN’s IPCC Fourth Assessment Report (AR4).
  • GWP global warming potentials
  • U.S. Patent No. 7,862,742 discloses compositions comprising HFC-1234ze and HFO-1234yf.
  • U.S. Patent No. 9,302,962 discloses methods for making HFO-1234ze.
  • the disclosures of U.S. Patent No. 7,862,742 and U.S. Patent No. 9,302,962 are hereby incorporated by reference in their entireties.
  • HFO-1234ze(E) which has zero ozone depletion and very low global warming potential and with a boiling point of -19.0 °C possesses physical properties that make it an attractive option for refrigeration, air conditioning, and heat pump applications.
  • the present invention solves certain problems associated with conventional refrigerants and provides HFO-1234ze(E)-based compositions which meet the evolving regulatory landscape.
  • HFO-1234ze(E) has been used in refrigerant blends for several years. As a component of blends, it provides the ability to reduce global warming potential and provide environmentally sustainable refrigerant and refrigerant blends to the industry.
  • compositions comprising HFO-1234zeE and HFC-152a.
  • the composition comprises, consists of or consists essentially of HFO-1234ze(E); HFC-152a; and one or more additional compounds or two or more additional compounds or three or more additional compounds selected from HFO-1234yf, HFC-245cb, HFO-1225ye(E), HFO-1225ye(Z), HFO-1225zc, HFC-236fa, HFC-143a, HFC-125, HFC-134a, HFO-1234zc, HFO-1233xf, HFO- 1233zd, CFC-114, HCFC-124, trifluoropropyne, HFO-1234ze(Z), HFC-245fa, HFC- 227ea, HFO-1243zf, HFC-263fb, HFC-134, HFC-161, HCC-40, isobutane, HCO- 1140, HCC-160 and CFC-114a.
  • the composition comprises, consists of or consists essentially of HFO-1234ze(E); HFC-152a; and one or more additional compounds or two or more additional compounds or three or more additional compounds selected from HFO-1234yf, HFC-245cb, H FC- 134, H FC- 134a, H FC- 125, HFO-1225zc, HFO- 1243zf, HFC-161, HCC-40, HCO-1140 and HCC-160.
  • the compositions include refrigerant blends comprising, consisting of or consisting essentially of one of the following: a. HFO-1234ze(E), HFC-152a, HFC-245cb and HFC-161 ; b. HFO-1234ze(E), HFC-152a, HFO-1243zf and HFC-161; c. HFO-1234ze(E), HFC-152a, HFO-1243zf and HCO-1140; d. HFO-1234ze(E), HFC-152a, HFC-134 and HFC-134a; e. HFO-1234ze(E), HFC-152a, HFO-1234yf and HFC-161; f.
  • refrigerant blends comprising, consisting of or consisting essentially of one of the following: a. HFO-1234ze(E), HFC-152a, HFC-245cb and HFC-161 ; b. HFO-1234ze(E), HFC-152a, HFO-1243zf and
  • HFO-1234ze(E), HFC-32, and HFC-152a g. HFO-1234ze(E), HFC-152a and CO 2 ; h. HFO-1234ze(E), HFC-125, HFC-32, and HFC-152a; and i. HFO-1234ze(E), HFC-134a, HCFO-1224yd(Z), and HFC-152a.
  • compositions comprising from about 75 to 85 weight percent HFO-1234ze(E), from about 3 to 7 weight percent HFC-125, and from about 10 to 20 weight percent H FC- 152a.
  • compositions comprising about 60 to 95 weight percent HFO-1234ze(E), about 10 to 30 weight percent HFC-32, and about 5 to 10 weight percent HFC-152a.
  • compositions comprising about 60 weight percent HFO-1234ze(E), about 30 weight percent HFC-32, and about 10 weight percent HFC-152a.
  • compositions comprising from about 75 to 85 weight percent HFO-1234ze(E), from about 3 to 7 weight percent HFC-125, from about 3 to 7 weight percent HFC-32 and from about 5 to 15 weight percent HFC-152a.
  • compositions comprising from about 75 to 85 weight percent HFO-1234ze(E), from about 3 to 7 weight percent HFC-134a, from about 3 to 7 weight percent HCFO- 1224yd(Z), and from about 5 to 15 weight percent HFC-152a.
  • compositions further comprising less than 100 ppm (weight) water, or less than 20 ppm (weight) water, or less than 10 ppm (weight) water.
  • compositions further comprising less than 5 volume percent non-adsorbable gases (NAG) or less than 3 volume percent NAG, or less than 1.5 volume percent NAG.
  • NAG non-adsorbable gases
  • compositions further comprising a stabilizer.
  • compositions further comprising a lubricant selected from polyol ester, polyvinyl ether, and polyalkylene glycol.
  • compositions wherein said composition has global warming potential per IPCC AR4 less than 750, or less than 300, or less than 150.
  • compositions wherein said composition is characterized as flammability class 1 (nonflammable), flammability class 2L (mildly flammable), or flammability class 2.
  • the compositions disclosed herein are characterized as flammability class 2 or 2L.
  • compositions further comprising additional compounds.
  • additional compounds are selected from HFC-23, HFC-32, HFC-125, HFC-143a, HFC-134, HFO-1132a, HFO-1132(E), HFO-1132(Z), HFO-1234ze(Z), HCFO- 1233zd(E), HCFO-1233zd(Z), HFC-245fa, HFO-1336mzz(E), HFO-1336mzz(Z), HCC-1130(E), HCC-1130(Z), CFO-1112(E), CFO-1112(Z), HFC-356mcf, HFC- 356mff, HFO-1234yf, HFC-227ea, HFO-1225ye(E), H CFO-1224yd (Z), HFC-134a, and combinations thereof.
  • compositions further comprising at least one hydrocarbon selected from propane, propylene, cyclopropane, isobutane, n-butane, isobutene, and combinations thereof.
  • compositions wherein the composition is free of or substantially free of Group A Fluorinated Substances.
  • compositions wherein degradation products of the composition are free of or substantially free of Group A Fluorinated Substances.
  • a refrigeration, air conditioning, heat pump, or chiller apparatus containing any of the foregoing compositions.
  • the apparatus comprises an evaporator, a compressor, a condenser, and an expansion device.
  • the apparatus is a chiller.
  • the apparatus is a heat pump.
  • the heat pump is a high temperature heat pump system.
  • the apparatus is an air conditioner or air conditioning system.
  • the apparatus is a medium temperature refrigeration system or a low temperature refrigeration system.
  • the apparatus is a stand-alone refrigeration system, such as a beverage cooler, vending machine or ice machine.
  • the composition comprises, consists of or consists essentially of HFO-1234ze(E), HFC-152a, and two additional compounds of HFO-1234yf and HFC-134.
  • the composition may optionally further comprise one or more additional compounds selected from HFC-245cb, HFO-1225ye(E), HFO- 1225ye(Z), HFO-1225zc, HFC-236fa, HFC-143a, HFC-125, HFC-134a, HFO- 1234zc, HFO-1233xf, HFO-1233zd, CFC-114, HCFC-124, trifluoropropyne, HFO- 1234ze(Z), HFC-245fa, HFC-227ea, HFO-1243zf, HFC-263fb, HFC-161, HCC-40, isobutane, HCO-1140, HCC-160 and CFC-114a, more preferably selected from HFC-245cb, HFC-134a, HFC-
  • the composition comprises, consists of or consists essentially of HFO-1234ze(E), HFC-152a, and four additional compounds of HFO-1225zc, HFO-1243zf, HFO-1234yf and HFC-245cb.
  • composition may optionally further comprise one or more additional compounds selected from HFO- 1225ye(E), HFO-1225ye(Z), HFC-236fa, HFC-143a, HFC-125, HFC-134a, HFO- 1234zc, HFO-1233xf, HFO-1233zd, CFC-114, HCFC-124, trifluoropropyne, HFO- 1234ze(Z), HFC-245fa, HFC-227ea, HFC-263fb, HFC-134, HFC-161 , HCC-40, isobutane, HCO-1140, HCC-160 and CFC-114a, more preferably selected from HFO-1234yf, HFC-245cb, HFC-134, HFC-134a, HFC-125, HFO-1225zc, HFO- 1243zf, HFC-161, HCC-40, HCO-1140 and HCC-160.
  • additional compounds selected from HFO- 1225ye(E), HFO-1225y
  • composition may optionally further comprise one or more additional compounds selected from HFO-1225ye(E), HFO-1225ye(Z), HFO-1225zc, HFC-236fa, H FC- 143a, HFC-125, HFO-1234zc, HFO-1233xf, HFO-1233zd, CFC-114, HCFC-124, trifluoropropyne, HFO-1234ze(Z), HFC-245fa, HFC-227ea, HFO-1243zf, HFC-263fb, HFC-161, HCC-40, isobutane, HCO-1140, HCC-160 and CFC-114a, more preferably selected from HFC-125, HFO- 1225zc, HFO-1243zf, HFC-161 , HCC-40, HCO-1140 and HCC-160.
  • additional compounds selected from HFO-1225ye(E), HFO-1225ye(Z), HFO-1225zc, HFC-236fa, H FC- 143a,
  • the composition comprises, consists of or consists essentially of HFO-1234ze(E), HFC-152a, and four additional compounds of HFO-1225zc, HFO-1243zf, HFC-134a and HFC-134.
  • composition may optionally further comprise one or more additional compounds selected from HFO- 1234yf, HFC-245cb, HFO-1225ye(E), HFO-1225ye(Z), HFC-236fa, HFC-143a, HFC- 125, HFO-1234zc, HFO-1233xf, HFO-1233zd, CFC-114, HCFC-124, trifluoropropyne, HFO-1234ze(Z), HFC-245fa, HFC-227ea, HFC-263fb, HFC-161 , HCC-40, isobutane, HCO-1140, HCC-160 and CFC-114a, more preferably selected from HFO-1234yf, HFC-245cb, HFC-125, HFC-161, HCC-40, HCO-1140 and HCC- 160.
  • additional compounds selected from HFO- 1234yf, HFC-245cb, HFO-1225ye(E), HFO-1225ye(Z), HFC-236fa
  • the present disclosure provides compositions comprising HFO-1234zeE, HFC-152a, and at least one compound selected from HFC-23, HFC-32, HFC-125, HFC-143a, HFC-134, HFC-134a, HFC-161 , HFC- 227ca, HCFC-151a, HCFC-22, HCC-40, CFC-114, CFC-115, HCFC-124, HFO- 1132a, HFO-1132(E), HFO-1132(Z), HFO-1234ze(Z), HCFO-1233zd(E), HCFO- 1233zd(Z), HFO-1233xf, HFC-245fa, HFO-1336mzz(E), HFO-1336mzz(Z), HCC- 1130(E), HCC-1130(Z), CFO-1112(E), CFO-1112(Z), HFC-356mcf, HFC-356mff, HFC-356mff, HFC-356mff, HFC-356mf
  • compositions may further comprise one or more additional compounds, two or more additional compounds or three or more additional compounds selected from HFO-1234yf, HFC-245cb, HFO- 1225ye(E), HFO-1225ye(Z), HFO-1225zc, HFC-236fa, HFC-143a, HFC-125, HFC- 134a, HFO-1234zc, HFO-1233xf, HFO-1233zd, CFC-114, HCFC-124, trifluoropropyne, HFO-1234ze(Z), HFC-245fa, HFC-227ea, HFO-1243zf, HFC-263fb, HFC-134, HFC-161, HCC-40, isobutane, HCO-1140, HCC-160 and CFC-114a, more preferably selected from HFO-1234yf, HFC-245cb, HFC-134, HFC-134a, HFC-125, HFO-1225zc, HFO-1243zf, HFC-161,
  • compositions comprising HFO-1234zeE, HFC-152a, and at least one compound selected from HFC-227ea, HFC-134, HFC-125, HFC-32, HFC-134a, HFO-1336mzz(E), HCFO- 1224yd(Z), and combinations thereof.
  • compositions may further comprise one or more additional compounds, two or more additional compounds or three or more additional compounds selected from HFO-1234yf, HFC-245cb, HFO-1225ye(E), HFO-1225ye(Z), HFO-1225zc, HFC-236fa, HFC-143a, HFC-125, HFC-134a, HFO- 1234zc, HFO-1233xf, HFO-1233zd, CFC-114, HCFC-124, trifluoropropyne, HFO- 1234ze(Z), HFC-245fa, HFC-227ea, HFO-1243zf, HFC-263fb, HFC-134, HFC-161 , HCC-40, isobutane, HCO-1140, HCC-160 and CFC-114a, more preferably selected from HFO-1234yf, HFC-245cb, HFC-134, H FC- 134a, HFC-125, HFO-1225zc, HFO- 1243zf,
  • compositions of the present invention provide refrigerant performance that is improved over existing HFC refrigerants and blends and even improved over existing HFO refrigerants and blends. Additionally, the presently disclosed compositions are expected to meet the evolving regulatory landscape in the refrigerants business.
  • E-1,3,3,3-Tetrafluoropropene (HFO-1234ze(E) or R-1234zeE) is available commercially from Honeywell (Charlotte, North Carolina, USA).
  • 1,1-difluoroethane (HFC-152a or R-152a)
  • E-1 ,1 ,1 ,4,4,4-hexafluoro-2-butene (HFO-1336mzzE, or R- 1336mzzE)
  • 1,1 ,2,2-tetrafluoroethane (HFC-134, or R-134)
  • 1,1,1 ,2-tetrafluoroethane (HFC-134a, or R-134a)
  • ChemoursTM Wang, DE, USA).
  • HFC-32 or R-32 Difluoromethane (HFC-32 or R-32), pentafluoroethane (HFC-125, or R- 125), 1 ,1,1 ,2,3,3,3-heptafluoropropane (HFC-227ea, or R-227ea), Z-1-chloro- 2,3,3,3-tetrafluoropropene (HCFO-1224yd(Z), or R-1224yd(Z)) are available commercially from various sources worldwide.
  • compositions comprise, consist of or consist essentially of: a. HFO-1234ze(E), HFC-152a, and HFC-227ea; b. HFO-1234ze(E), HFC-152a, and HFO-1336mzz(E); c. HFO-1234ze(E), HFC-152a, HFO-1336mzz(E), and HFC-227ea; d. HFO-1234ze(E), HFC-152a, and HFC-134; e. HFO-1234ze(E), HFC-152a, and HFC-125; f. HFO-1234ze(E), HFC-152a and CO 2 ; g.
  • any of the above compositions (a) to (i) may further comprise one or more additional compounds, two or more additional compounds or three or more additional compounds selected from HFO-1234yf, HFC-245cb, HFO-1225ye(E), HFO-1225ye(Z), HFO-1225zc, HFC-236fa, HFC-143a, HFC-125, HFC-134a, HFO-1234zc, HFO-1233xf, HFO-1233zd, CFC-114, HCFC-124, trifluoropropyne, HFO-1234ze(Z), HFC-245fa, HFC-227ea, HFO-1243zf, HFC-263fb, HFC-134, HFC-161 , HCC-40, isobutane, HCO-1140, HCC-160 and CFC-114a, more preferably selected from HFO-1234yf, HFC-245cb, HFC-134, HFC-134a, HFC-125
  • composition (a) may further comprise one or more additional compounds selected from HFC-23, FC-1216, HFC-143a, HFC-134a, HCFC-22, HCFC-124, FC-218, HFC-236fa and HFO-1225zc.
  • composition (b) may further comprise one or more additional compounds selected from C-30, HCFC-114, HCFC-114a, HCFC-133, HCFC-133a, HFC-245fa, HFC- 338mee, HFC-338mf, HFC-347mef, HCO-1140, HCFO-1224 isomers, HCFO- 1224yd, HCFO-1224yb, HCFO-1233xf, HCFO-1233zd, HFO-1243zf, HFO-1327mz, HFO-1336ft and HCFO-1326mxz.
  • additional compounds selected from C-30, HCFC-114, HCFC-114a, HCFC-133, HCFC-133a, HFC-245fa, HFC- 338mee, HFC-338mf, HFC-347mef, HCO-1140, HCFO-1224 isomers, HCFO- 1224yd, HCFO-1224yb, HCFO-1233xf, HC
  • composition (c) may further comprise one or more additional compounds selected from C-30, HCFC-114, HCFC-114a, HCFC-133, HCFC-133a, HFC-245fa, HFC- 338mee, HFC-338mf, HFC-347mef, HCO-1140, HCFO-1224 isomers, HCFO- 1224yd, HCFO-1224yb, HCFO-1233xf, HCFO-1233zd, HFO-1243zf, HFO-1327mz, HFO-1336ft, HCFO-1326mxz, HFC-23, FC-1216, HFC-143a, HFC-134a, HCFC-22, HCFC-124, FC-218, HFC-236fa and HFO-1225zc.
  • additional compounds selected from C-30, HCFC-114, HCFC-114a, HCFC-133, HCFC-133a, HFC-245fa, HFC- 338mee, HFC-338mf
  • composition (d) may further comprise one or more additional compounds selected from HFC-134a, HCFC-124, HCFC-124a, HCFO-1122, HFC-143a, HCFC-31, HFC-32, HFC-125, CFC-114, CFC-114a, FCO-1114, HFC-152a, FCO-1318my, HFC-245cb, FC-C318, and HC-161.
  • composition (e) may further comprise one or more additional compounds selected from HFC-23, HFC-32, HFC-143a, HFC-134a, CFC-115, CFCO-1113 and HCC-40.
  • composition (f) may further comprise one or more additional compounds selected from N2, Ar, CO and O2.
  • composition (g) may further comprise one or more additional compounds selected from HFC-143a, HFC-41 , HFC-134a, HCFC-22, CFC-12 and HCC-40.
  • composition (h) may further comprise one or more additional compounds selected from HFC-143a, HFC-41 , HFC-134a, HCFC-22, CFC-12, HCC-40, HFC-23, CFC-115 and CFCO-1113.
  • composition (i) may further comprise one or more additional compounds selected from HFC-143a, HFO-1225zc, HFC-245cb, HFC-134, HFO-1225ye, HFC-161 , HCFC-22, HFO-1243zf, CHFC-124, HCC-40, CHFO-1122, HCFC-31 , CFC-114, CFC-114a, HCO-1140, HFO-1234yf, HFC-263fb, HFC-254eb, HFO-1215yb, HCFC- 244bb, HFO-1224yd(E), HFO-1224 isomer(s), HFO-1112a, HFC-225ca, HFC-225cb and HFC-234bb.
  • additional compounds selected from HFC-143a, HFO-1225zc, HFC-245cb, HFC-134, HFO-1225ye, HFC-161 , HCFC-22, HFO-1243zf, CHFC-124, HCC-40, CHFO-1122,
  • compositions comprising from about 88 to 91 weight percent HFO-1234ze(E), from about 4 to 9 weight percent HFC-227ea, and from about 3 to 5 weight percent HFC-152a.
  • the compositions comprise from about 88 to 91 weight percent HFO- 1234ze(E), from about 4.2 to 9 weight percent HFC-227ea, and from about 3 to 4.8 weight percent HFC-152a.
  • compositions comprising from about 70 to 80 weight percent HFO-1234ze(E), from about 5 to 20 weight percent HFO-1336mzz(E), and from about 5 to 25 weight percent HFC-152a.
  • compositions comprising from about 70 to 80 weight percent HFO-1234ze(E), from about 5 to 20 weight percent HFO-1336mzz(E), from about 5 to 25 weight percent HFC-152a, and from about 1 to 3 weight percent HFC-227ea.
  • compositions comprising from about 75 to 85 weight percent HFO-1234ze(E), from about 2 to 8 weight percent HFC-134, and from about 10 to 20 weight percent HFC-152a.
  • compositions comprising from about 75 to 85 weight percent HFO-1234ze(E), from about 2 to 8 weight percent HFC-125, and from about 10 to 20 weight percent HFC-152a.
  • compositions comprising about 60 weight percent HFO-1234ze(E), about 10 weight percent HFC-32, and about 30 weight percent HFC-152a.
  • compositions comprising from about 75 to 85 weight percent HFO-1234ze(E), from about 3 to 7 weight percent HFC-125, from about 3 to 7 weight percent HFC-32 and from about 5 to 15 weight percent HFC-152a.
  • compositions comprising from about 75 to 85 weight percent HFO-1234ze(E), from about 3 to 7 weight percent HFC-134a, from about 3 to 7 weight percent HCFO-1224yd(Z), and from about 5 to 15 weight percent HFC-152a.
  • the one or more additional compounds contained in any of the compositions disclosed herein is/are selected from those compounds which increase cooling capacity (“CAP”) and/or increase coefficient of performance (“COP”) relative to an incumbent composition, and/or reduce flammability of the composition to be, for example, flammability class 2L (mildly flammable), or flammability class 2.
  • the one or more additional compounds contained in any of the compositions disclsoed herein is/are selected from HFO- 1234yf, HFO-1243zf, HFO-1225zc, HFC-161 , HCC-40, HFC-134, HFC-134a and HFC-245cb.
  • the one or more additional compounds contained in any of the compositions disclsoed herein is/are selected from HFO-1234yf, HFO- 1243zf, HFO-1225zc, HFC-161 , HCC-40, HFC-134 and HFC-134a, as such compounds may increase CAP and/or COP of the composition relative to an incumbent composition.
  • the one or more additional compounds contained in any of the compositions disclsoed herein is/are selected from HFO-1225zc, HFC-134, HFC-134a and HFC-245cb, as such compounds may provide for composition which has a flammability classification of 2L or 2.
  • the amount of additional compounds present in any of the compositions disclosed herein can be greater than 0 ppm and less than 5,000 ppm and, in particular, can range from about 5 to about 1,000 ppm, about 5 to about 500 ppm and about 1 to about 100 ppm, based on the total weight of the composition.
  • the amount of additional compounds present in any of the compositions disclosed herein can be greater than 0 and less than 1 wt%, preferably less than 0.5 weight percent, or more preferably less than 0.1 weight percent, based on the total weight of the composition.
  • compositions comprising, consisting essentially of, or consisting of HFO-1234ze(E), HFC-152a, and at least one compound selected from HFC-227ea, HFO-1336mzz(E), HFC-134, HFC-125, HFC-32, HFC-134a, H CFO-1224yd (Z), and combinations thereof, according to the present invention, and the degradation products thereof are preferably free of or substantially free of Group A Fluorinated Substances.
  • Group A Fluorinated Substances include, but are not limited to, trifluoroacetic acid (TFA).
  • TFA trifluoroacetic acid
  • Group A Fluorinated Substances includes any substance that has a Henry’s Law constant ⁇ 250 Pa*m 3 /mol and contains at least one fully fluorinated methyl (-CF3) or methylene (-CF2-) carbon atom (without any H/CI/Br/l attached to it).
  • Group A Fluorinated Substances include, but are not limited to, TFA.
  • the phrase "substantially free of” as used herein with respect to the presence of Group A Fluorinated Substances in the present compositions means that the amount of such substances in the compositions is > 0 wt.% and ⁇ 15 or wt.%, > 0 wt.% and ⁇ 10 wt.%, or > 0 wt.% and
  • gas chromatographic gas chromatographic
  • GO gas chromatography
  • GC/MS gas chromatography/mass spectral
  • IC-MS ion chromatograph
  • HPLC high-performance liquid chromatography
  • HPLC-MS high-performance liquid chromatography mass spectrometry
  • degradation products of such compositions of the present invention which comprise HFO-1234ze(E), as a single fluid or blend are free of or substantially free of Group A Fluorinated Substances, such as TFA.
  • the phrase "free of" as used herein with respect to the formation of Group A Fluorinated Substances by the present compositions means that the theoretical molar yield of such substances in environmental compartments of air, soil/sediment and water produced during tropospheric degradation of the compositions is sufficiently low so as to not be detectable, including but not limited to 0%, when measured by GC techniques, for example GO with a flame ionization or electron-capture detector or GC/MS method, by IC or IC-MS techniques, or by HPLC or HPLC-MS techniques.
  • the phrase "substantially free of” as used herein with respect to the formation of Group A Fluorinated Substances by the present compositions means that the theoretical molar yield of such substances in environmental compartments of air, soil/sediment and water produced during tropospheric degradation of the compositions is > 0% and ⁇ 5%, or > 0% and ⁇ 4%, or > 0% and ⁇ 3%, or > 0% and ⁇ 2%, or > 0% and ⁇ 1%, and all values and ranges therebetween, when measured by GC techniques, for example GC with a flame ionization or electron-capture detector or GC/MS method, by IC or IC-MS techniques, or by HPLC or HPLC-MS techniques.
  • compositions will perform more consistently and be more stable with only minor amounts of water present.
  • the presently claimed compositions may further comprise less than 100 ppm (by weight) water, preferably less than 20 ppm (by weight) water, and even more preferably less than 10 ppm (by weight) water.
  • the presently disclosed compositions will perform more consistently and be more stable with only minor amounts of oxygen or air present. Therefore, the presently claimed compositions may further comprise less than about 5 volume percent non-adsorbable gases (NAG), preferably less than 3 volume percent NAG, and more preferably less than 1.5 volume percent NAG. Further, the presently claimed compositions, due to the presence of air or NAG, will contain less than 1 volume percent oxygen, preferably less than 0.5 volume percent oxygen, and more preferably less than 0.3 volume percent oxygen.
  • NAG non-adsorbable gases
  • the presently disclosed compositions may contain a stabilizer.
  • Such stabilizer compounds are intended to be present in a small amount and prevent decomposition due to the presence of water, air, NAG, or oxygen in a system while in use or while the composition is stored.
  • HFO type refrigerants due to the presence of a double bond, may be subject to thermal instability and decompose under extreme use, handling or storage situations also. Therefore, there may be advantages to adding stabilizers to HFO type refrigerants.
  • Stabilizers may notably include nitromethane, ascorbic acid, terephthalic acid, azoles such as tolutriazole or benzotriazole, phenolic compounds such as tocopherol, hydroquinone, t-butyl hydroquinone, 2,6-di-tertbutyl-4-methylphenol, epoxides (possibly fluorinated or perfluorinated alkyl epoxides or alkenyl or aromatic epoxides) such as n-butyl glycidyl ether, hexanediol diglycidyl ether, allyl glycidyl ether, butylphenylglycidyl ether, cyclic monoterpenes, terpenes, such as d-limonene, a- terpinene, p-terpinene, y-terpinene, a-pinene, or p-pinene
  • Blends may or may not include stabilizers depending on the requirements of the system being used. If the refrigerant blend does include a stabilizer, it may include any amount from 0.001 wt% up to 1 wt%, preferably from about 0.01 to about 0.5 weight percent, more preferably, from about 0.01 to about 0.3 weight percent of any of the stabilizers listed above.
  • compositions further comprise at least one lubricant.
  • Lubricants may be selected from polyol ester, polyvinyl ether, and polyalkylene glycol. Lubricants may also 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 or ring structure saturated hydrocarbons, which may be 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 naphthenes, silicones, and polyalphaolefins.
  • Representative conventional lubricants of the present invention are the commercially available BVM 100 N (paraffinic mineral oil sold by BVA Oils), napthenic mineral oil commercially available under the trademark from Suniso® 3GS and Suniso® 5GS by Crompton Co., naphthenic mineral oil commercially available from Pennzoil under the trademark Sontex® 372LT, naphthenic mineral oil commercially available from Calumet Lubricants under the trademark Calumet® RO-30, linear alkylbenzenes commercially available from Shrieve Chemicals under the trademarks Zerol® 75, Zerol® 150 and Zerol® 500 and branched alkylbenzene, sold by Nippon Oil as HAB 22.
  • BVM 100 N paraffinic mineral oil sold by BVA Oils
  • napthenic mineral oil commercially available under the trademark from Suniso® 3GS and Suniso® 5GS by Crompton Co.
  • naphthenic mineral oil commercially available from Pennzoil under the trademark Sontex® 372LT
  • naphthenic mineral oil commercially
  • Lubricants of the present invention further comprise those which have been designed for use with hydrofluorocarbon refrigerants and are miscible with refrigerants of the present invention under compression refrigeration and air- conditioning apparatus' operating conditions
  • 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, Mich.), and polyvinyl ethers (PVEs) such as PVE-FVC68D.
  • POEs polyol esters
  • PAGs polyalkylene glycols
  • PVEs polyvinyl ethers
  • the foregoing refrigerant compositions are combined with a PAG lubricant or a PVE lubricant or a POE lubricant for usage in an automotive A/C system having an internal combustion engine or an electric or hybrid electric drive train.
  • the lubricant may be present in an amount of less than 80 weight percent of the total composition.
  • the lubricant may further be present in an amount of less than 60 weight percent of the total composition.
  • the amount of lubricant may be between about 0.1 and 50 weight percent of the total composition.
  • the lubricant may also be between about 0.1 and 20 weight percent of the total composition
  • the lubricant may also be between about 0.1 and 5 weight percent of the total composition.
  • the inventive refrigerant composition is used to introduce lubricant into the A/C system as well as or alternatively other additives, such as a) acid scavengers, b) performance enhancers, and c) flame suppressants.
  • the present compositions comprise an acid scavenger.
  • Examples of the acid scavengers that may be included in the present compositions include, but are not limited, the stabilizers and/or the epoxide component of the stabilizers disclosed in U.S. Patent No. 8,535,555 and the acid scavengers disclosed in International Application Publication No. WO 2020/222864, the disclosure of each of which is incorporated herein by reference in its entirety.
  • an acid scavenger may comprise one or more epoxides, one or more amines and/or one or more hindered amines, such as, for example but not limited to, epoxybutane.
  • the acid scavenger e.g., the activated aromatic compound, the siloxane, or both
  • the acid scavenger may be present in any concentration that results in a relatively low total acid number, a relatively low total halides concentration, a relatively low total organic acid concentration, or any combination thereof.
  • the acid scavenger is present at a concentration greater than about 0.0050 wt%, more preferably greater than about 0.05 wt% and even more preferably greater than about 0.1 wt% (e.g. greater than about 0.5 wt%) based on the total weight of the refrigerant composition.
  • the acid scavenger preferably is present in a concentration less than about 5 wt%, less than about 4 wt%, less than about 3 wt%, more preferably less than about 2.5 wt% and most preferably greater than about 2 wt% (e. g. less than about 1.8 wt%) based on the total weight of the refrigerant composition.
  • Preferred additives include those described in U.S. Pat. Nos. 5,152,926; 4,755,316, which are hereby incorporated by reference.
  • the preferred extreme pressure additives include mixtures of (A) tolyltriazole or substituted derivatives thereof, (B) an amine (e.g. Jeffamine M-600) and (C) a third component which is (i) an ethoxylated phosphate ester (e.g. Antara LP-700 type), or (ii) a phosphate alcohol (e.g. ZELEC 3337 type), or (iii) a Zinc dialkyldithiophosphate (e.g.
  • Lubrizol 5139, 5604, 5178, or 5186 type or (iv) a mercaptobenzothiazole, or (v) a 2,5-dimercapto-1 ,3,4-triadiaZole derivative (e. g. Curvan 826) or a mixture thereof.
  • a mercaptobenzothiazole or (v) a 2,5-dimercapto-1 ,3,4-triadiaZole derivative (e. g. Curvan 826) or a mixture thereof.
  • Additional examples of additives which may be used are given in U.S. Pat. No.
  • Acid number is measured according to ASTM D664-01 in units of mg KOH/g.
  • the total halides concentration, the fluorine ion concentration, and the total organic acid concentration is measured by ion chromatography.
  • Chemical stability of the refrigerant system is measured according to ASHRAE 97: 2007 (RA 2017) “Sealed Glass Tube Method to Test the Chemical Stability of Materials for Use within Refrigerant Systems”.
  • the viscosity of the lubricant is tested at 40°C according to ASTM D-7042.
  • Mouli et al. (WO 2008/027595 and WO 2009/042847) teach the use of alkyl silanes as a stabilizer in refrigerant compositions containing fluoroolefins.
  • Phosphates, phosphites, epoxides, and phenolic additives also have been employed in certain refrigerant compositions. These are described for example by Kaneko (U.S. patent application Ser. No. 11/575,256, published as U.S. Publication 2007/0290164) and Singh et al. (U.S. patent application Ser. No. 11/250,219, published as U.S. Publication 2006/0116310). All of these aforementioned applications are expressly incorporated herein by reference.
  • Preferred flame suppressants include the flame retardants described in patent application “Refrigerant compositions containing fluorine substituted olefins CA 2557873 A1” and incorporated by reference, as well as fluorinated products such as HFC-125, HFC-227ea, HFC-236fa, and/or Krytox® lubricants, also incorporated by reference and described in patent application “Refrigerant compositions comprising fluoroolefins and uses thereof WO 2009/018117A1.”
  • compositions may further comprise at least one tracer compound or mixture of tracer compounds.
  • Tracers may be used to identify the process by which a refrigerant, or refrigerant mixture is produced.
  • the tracer compounds may be specific to the manner of production or may be added as a single tracer or mixture of tracers in particular amounts in order to detect dilution, adulteration, contamination, or other unauthorized practices.
  • the tracer may be a single compound or two or more tracer compounds from the same class of compounds or from different classes of compounds.
  • the tracer is present in the compositions at a total concentration of about 1 part per million by weight (ppm) to about 5000 ppm, based on the weight of the total composition.
  • the tracer is present at a total concentration of about 1 ppm to about 1000 ppm.
  • the tracer is present at a total concentration of about 2 ppm to about 500 ppm.
  • the tracer is present at a total concentration of about 10 ppm to about 300 ppm.
  • the tracer compound or compounds in amounts up to 100 ppm, 200 ppm, 300, ppm, 400 ppm, 500 ppm, 600 ppm, 700 ppm, 800 ppm and 900 ppm may be selected from hydrofluorocarbons, hydrofluoroolefins, hydrochlorocarbons, hydrochloroolefins, hydrochlorofluorocarbons, hydrochlorofluoroolefins, hydrochlorocarbons, hydrochloroolefins, chlorofluorocarbons, chlorofluoroolefins, hydrocarbons, perfluorocarbons, perfluoroolefins, and combinations thereof.
  • the tracers may include, but are not limited to compounds selected from HFC-23 (trifluoromethane), HCFC-31 (chlorofluoromethane), HFC-41 (fluoromethane), HFC-161 (fluoroethane), H FC- 152a (1 ,1 -difluoromethane), HFC-143a (1 ,1 ,1 -trifluoroethane), HFC-227ca (1 ,1 ,1 ,2,2,3,3-heptafluoropropane), HFC-227ea (1 ,1 ,1 ,2,3,3,3-heptafluoropropane), HFC-236fa (1 , 1 ,1 , 3,3,3- hexafluoropropane), HFC-236cb (1 , 1 ,1 ,2,2,3-hexafluoropropane), HFC-236ea (1 ,1 ,1 ,2,3,3-hexafluoropropane),
  • the tracer is a blend containing two or more hydrofluorocarbons, or one hydrofluorocarbon in combination with one or more perfluorocarbons. In other embodiments, the tracer is a blend of at least one CFC and at least one HCFC, HFC, or PFC.
  • the phrase “effective amount” refers to an amount of inhibitor of the present invention which, when added to a composition comprising at least one fluoroolefin, results in a composition wherein the fluoroolefin will not interact with an initiator, and/or degrade to produce as great a reduction in performance, for example, when in use in a cooling apparatus as compared to the composition without an inhibitor.
  • effective amounts of inhibitor may be determined by way of testing under the conditions of standard test ASHRAE 97-2007 (RA 2017).
  • an effective amount comprises about 1 to about 3,000 ppm by weight, or about 1 to about 2,000 ppm by weight, or about 10 to about 3,000 ppm by weight, or about 10 to about 2,000 ppm by weight, or about 30 ppm to about 3,000 ppm by weight, or about 30 ppm to about 2,000 ppm by weight, or about 5 to about 1,000 ppm and in some cases about 10 to about 500 ppm of at least one inhibitor based on the total weight of the composition.
  • the amount of the inhibitor in the total composition can be reduced if an additional component which is added to an HFO-1234yf blend does not contain an inhibitor.
  • the inventive compositions are substantially free of oligomeric products and polymeric products derived from a hydrofluoroolefin, such as HFO-1234yf, including but not limited to, oligomers and homopolymers.
  • a hydrofluoroolefin such as HFO-1234yf
  • substantially free it is meant that the composition contains less than about 1 wt.%, less than about 0.07 wt.%, less than about 0.03 wt.% and in some cases about 0 ppm of such products when measured by I R or NMR.
  • the at least one inhibitor is selected from hydrocarbons such as cyclic monoterpenes (e.g., limonene, pinene, a-pinene, P-pinene, and terpinene); lipophilic organic compounds such as tocopherols (e.g., a-tocopherol) or butylated hydroxytoluene (BHT); phenols or aromatic organic compounds having at least one chemical moiety -C6H4(OH) (e.g., benzene-1 ,4-diol, 4-methoxyphenol); and mixtures thereof.
  • hydrocarbons such as cyclic monoterpenes (e.g., limonene, pinene, a-pinene, P-pinene, and terpinene); lipophilic organic compounds such as tocopherols (e.g., a-tocopherol) or butylated hydroxytoluene (BHT); phenols or aromatic organic compounds having
  • inhibitor compounds may include at least one member selected from limonene (particularly D-limonene), a-terpinene, pinene, a-pinene, p-pinene, a-tocopherol, butylated hydroxytoluene (BHT), 4-methoxyphenol, benzene-1,4-diol, and mixtures thereof.
  • the inhibitor is limonene, particularly D-limonene.
  • compositions of the present invention may be prepared by any convenient method to combine the desired amount 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.
  • the composition according to the present invention can be prepared by blending HFO-1234zeE and H FC- 152a, and, in some cases, at least one of the additional compounds.
  • any of the foregoing refrigerant compositions can be prepared by blending HFO-1234zeE, HFC-152a, at least one compound selected from HFC-227ea, HFO-1336mzz(E), HFC-134, HFC- 125, HFC-32, HFC-134a, HCFO-1224yd(Z), and, in some cases, at least one of the additional compounds.
  • any of the above-mentioned additives such as stabilizers, acid scavengers, flame suppressants, tracers and the like, may be blended with the HFO-1234zeE and HFC-152a containing compositions.
  • the compositions may be prepared from recycled or reclaimed refrigerant.
  • One or more of the components may be recycled or reclaimed by means of removing contaminants, such as air, water, or residue, which may include lubricant or particulate residue from system components.
  • the means of removing the contaminants may vary widely, but can include distillation, decantation, filtration, and/or drying by use of molecular sieves or other absorbents.
  • the recycled or reclaimed component(s) may be combined with the other component(s) as describe above.
  • compositions disclosed herein relate to any of the compositions disclosed herein.
  • the composition utilized in the method, apparatus and/or system may be a composition comprising, consisting of, or consisting essentially of (i) HFO-1234ze(E) and HFC-152a; or (ii) HFO-1234ze(E), HFC-152a, and one or more additional compounds selected from HFO-1234yf, HFC-245cb, HFO-1225ye(E), HFO-1225ye(Z), HFO-1225zc, HFC-236fa, HFC-143a, HFC-125, HFC-134a, HFO-1234zc, HFO-1233xf, HFO-1233zd, CFC-114, HCFC-124, trifluoropropyne, HFO-1234ze(Z), HFC-245fa, HFC-227ea, HFO-1243zf, HFC-263fb, H
  • compositions disclosed herein are useful in numerous methods and systems that provide cooling (e.g. air-conditioning or refrigeration) and heating.
  • a method of cooling comprising evaporating the inventive composition in the vicinity of a body to be cooled and thereafter condensing said composition, wherein said cooling is provided by a refrigeration system, air-conditioner, heat pump, or chiller.
  • the refrigeration system may be a residential, commercial, or industrial refrigeration system. These may include, but are not limited to, supermarket and convenience store refrigerated cases for beverages, dairy, and produce and prepared foods.
  • the refrigeration system is a low or medium temperature refrigeration system, including supermarket and convenience store refrigerator and freezer cabinets and displays, ice machines, self-contained coolers and freezers, such as beverage coolers, walk-in and reach-in coolers and freezers, supermarket rack and distributed systems, and refrigerated or frozen food transport.
  • the air conditioner may be a residential, commercial, or industrial air-conditioning system. These may include, but are not limited to, window, ducted, ductless, packaged terminal, and those exterior to, but connected to the building, such as rooftop systems. These may also include residential heat pumps that provide comfort air-conditioning and heating.
  • the cooling may be performed in a chiller.
  • Chillers including both flooded evaporator and direct expansion chillers, may be coupled with an air handling and distribution system to provide comfort air conditioning (cooling and dehumidifying the air) to large commercial buildings, including hotels, office buildings, hospitals, universities and the like.
  • chillers most likely air-cooled direct expansion chillers, have found additional utility in naval submarines and surface vessels.
  • Chillers may be characterized by the compressor used.
  • the chiller may comprise a centrifugal compressor.
  • the chiller may comprise a scroll compressor.
  • the chiller may comprise a screw compressor.
  • the chiller may comprise a reciprocating compressor.
  • the present method for cooling may be particularly useful in high ambient temperature regions, due to the high critical temperature of blends comprising, consisting of, or consisting essentially of HFO-1234zeE, HFC-152a, and at least on compounds selected from the group consisting of HFC-227ea, HFO-1336mzz(E), HFC-134, HFC-125, HFC-32, HFC-134a, HCFO-1224yd(Z).
  • the method for producing cooling is particularly useful in regions where the ambient temperature can exceed at least 35°C.
  • R-22 is an ozone depleting substance in the Montreal Protocol to reduce ozone depletion. As such, R-22 has been mandated and legislated for phase out for manufacture for and use in air conditioning and refrigeration. There is interest in finding a refrigerant with the lowest possible direct GWP and also that performs well in hot climate (or high ambient) temperature regions.
  • the body to be cooled may be defined as any space, location, object, or body for which it is desirable to provide cooling. Examples include spaces, open or enclosed, that require cooling such as a residence, such as an apartment or apartment building, university dormitory, townhouse or other attached house, or a single-family home; or the body to be cooled may be any other building, such as an office building, supermarket, college or university classroom or administration buildings.
  • a method for producing air conditioning in high ambient temperatures comprises evaporating the inventive composition and thereafter condensing said composition.
  • the method is particularly useful in regions where ambient temperatures can exceed 35°C or more.
  • a method for replacing HCFC-22 in high ambient air conditioning apparatus comprising providing the inventive composition to said apparatus.
  • the method of replacing HCFC-22 is particularly useful in regions where ambient temperatures can exceed 35°C or more.
  • a method of heating comprising evaporating the inventive composition and thereafter condensing said composition in the vicinity of a body to be heated.
  • the heating is accomplished by a heat pump, which may be a residential, light commercial, commercial, or industrial heat pump system.
  • a heat pump which may include, but are not limited to, residential heat pumps that provide comfort air-conditioning and heating, hot water heat pumps for heating air (by secondary loop) or for heating water for residential or commercial use, heat pumps for heating manufacturing process equipment, and high temperature heat pumps (with condensing temperature of 50 deg C or higher).
  • a system for cooling or heating comprising the inventive composition.
  • the system comprises an evaporator, compressor, condenser, and expansion device, each operably connected to perform a vapor compression cycle.
  • the system may further comprise a lubricant.
  • the lubricant may be selected from the group consisting of polyalkylene glycol, polyol ester, poly-a-olefin, and polyvinyl ether.
  • the lubricant is selected from POE or PVE.
  • the system for cooling or heating may be a refrigeration system, airconditioner, heat pump, or chiller.
  • the refrigeration system may be a residential, commercial, or industrial refrigeration system. These may include, but are not limited to, supermarket and convenience store refrigerated cases for beverages, dairy, and produce and prepared foods.
  • the refrigeration system is a low or medium temperature refrigeration system, including supermarket and convenience store refrigerator and freezer cabinets and displays, ice machines, self-contained coolers and freezers, such as beverage coolers, walk-in and reach-in coolers and freezers, supermarket rack and distributed systems, and refrigerated or frozen food transport.
  • the air conditioner may be a residential, commercial, or industrial air-conditioning system. These may include, but are not limited to, window, ducted, ductless, packaged terminal, and those exterior to, but connected to the building, such as rooftop systems. These may also include residential heat pumps that provide comfort air-conditioning and heating.
  • the system is a chiller.
  • Chillers including both flooded evaporator and direct expansion chillers, may be coupled with an air handling and distribution system to provide comfort air conditioning (cooling and dehumidifying the air) to large commercial buildings, including hotels, office buildings, hospitals, universities and the like.
  • chillers most likely air-cooled direct expansion chillers, have found additional utility in naval submarines and surface vessels.
  • Chillers may be characterized by the compressor used.
  • the chiller may comprise a centrifugal compressor.
  • the chiller may comprise a scroll compressor.
  • the chiller may comprise a screw compressor.
  • the chiller may comprise a reciprocating compressor.
  • the compressor often designed for the refrigerant to be used, may need modification. Therefore, for centrifugal chillers, the impeller diameter or impeller tip speed for the new refrigerant must be similar or match that for the original refrigerant to be used as a drop-in replacement.
  • the system containing the inventive composition may be an automobile heat pump for cooling and heating the passenger compartment of an electric or hybrid vehicle.
  • Electric or hybrid vehicles include automobiles with no internal combustion engine (ICE) or those that maintain an ICE but also use electric power and are therefore hybrid electric vehicles (HEV) or plug-in hybrid electric vehicles (PHEV) or mild hybrid electric vehicles (MHEV). Additionally, electric or hybrid vehicles include full electric vehicles (EV), such as battery electric vehicles (BEV). All of these electric or hybrid vehicles use at least one electric motor, wherein the electric motor provides some form of propulsion for the vehicles normally provided by the ICE found in gasoline/diesel powered vehicles.
  • the automobile heat pump is a secondary loop system.
  • the secondary loop allows the separation of a flammable refrigerant from the passenger compartment, using a heat transfer fluid to produce cooling or heating in the passenger compartment.
  • the automobile heat pump does not include a positive temperature coefficient (PTC) heater.
  • PTC positive temperature coefficient
  • the PTC heater often used in electric vehicles is needed in the absence of an ICE to provide adequate heating to the passenger compartment.
  • the inventive composition may be used in a method of replacing at least one of R-22, HFC-134a, propane, HFO-1234yf, R-407C, R-404A, R-410A, R-513A, R-454A, R-454B, R-454C, R-448A, R-449A, R-449B, R- 449C, R-1234zeE, R-515B, R471A, R-476A, R-482A, R-452A, or R-452C, in refrigeration, air-conditioning, heat pump, or chiller systems comprising providing any of the compositions disclosed herein to the system in place of R-22, HFC-134a, propane, HFO-1234yf, R-407C, R-404A, R-410A, R-513A, R-454A, R-454B, R- 454C, R-448A, R-449A, R-449B, R-449C, R-1234zeE, R-515B, R471
  • the method for replacement may be a retrofit for existing equipment. Therefore, the method is specific to replacing a refrigerant in equipment that was designed for, or originally contained R-22, HFC-134a, propane, HFO-1234yf, R-407C, R-404A, R-410A, R-513A, R-454A, R-454B, R-454C, R-448A, R-449A, R-449B, R-449C, R-452A, or R-452C.
  • the replacement is simply providing a new refrigerant for an application or use, wherein the new refrigerant can provide improved performance, or meet regulatory requirements that are not met by the incumbent refrigerant.
  • inventive compositions and particularly the compositions comprising, consisting of, or consisting essentially of HFO-1234zeE, HFC-152a, and at least one compound selected from HFC-227ea, HFO-1336mzz(E), HFC-134, HFC-125, HFC-32, HFC-134a, and HCFO-1224yd(Z), and optionally one or more additional compounds, provide performance that would allow replacement of R-22, HFC-134a, propane, HFO-1234yf, R-407C, R-404A, R-410A, R-513A, R-454A, R-454B, R- 454C, R-448A, R-449A, R-449B, R-449C, R-1234zeE, R-515B, R471A, R-476A, R-482A, R-452A, or R-452C.
  • the inventive compositions provide performance that enables the use as refrigerant in refrigeration, air-conditioning, heat pump, or chiller systems.
  • the refrigeration, air-conditioning, heat pump, or chiller systems comprise mobile or stationary air conditioning, mobile or stationary heat pumps, residential, light commercial, commercial, or industrial air-conditioner, residential, light commercial, commercial, or industrial heat pump, centrifugal chiller, screw chiller, scroll chiller, flooded evaporator chiller, direct expansion chiller, medium or low temperature refrigeration system, beverage cooler, supermarket display case, ice machine, or transport refrigeration or freezer system.
  • the compositions are useful wherein the system is an automobile heat pump for cooling and heating the passenger compartment of an electric or hybrid vehicle.
  • compositions may be useful in replacing refrigerants such as R-22, HFC-134a, propane, HFO-1234yf, R-407C, R-404A, R-410A, R-513A, R-454A, R-454B, R-454C, R-448A, R-449A, R-449B, R-449C, R-1234zeE, R-515B, R471A, R-476A, R-482A, R-452A, or R-452C.
  • refrigerants such as R-22, HFC-134a, propane, HFO-1234yf, R-407C, R-404A, R-410A, R-513A, R-454A, R-454B, R-454C, R-448A, R-449A, R-449B, R-449C, R-1234zeE, R-515B, R471A, R-476A, R-482A, R-452A, or R-452C.
  • compositions disclosed herein may be useful in air conditioning, heat pumps, chillers, and refrigeration systems.
  • the compositions may be used in residential air conditioning, industrial air conditioning, residential heat pumps, industrial heat pumps, water heating heat pumps, high temperature heat pumps (with condenser temperature above about 55 degrees C), flooded evaporator chillers, screw chillers, scroll chillers, centrifugal chillers, residential refrigerators, supermarket refrigeration systems, ice machines, beverage coolers, vending machines, medium temperature refrigeration, low temperature refrigeration, transport refrigeration, among others.
  • compositions disclosed herein may also be useful in methods for replacing existing or conventional refrigerants that for reasons of environmental concern are in need of replacement.
  • the replacement may mean that the composition of the present invention is used in place of the existing refrigerant in new equipment for a specific application or use.
  • the replacement may also mean that the composition of the invention is used in existing equipment after the original refrigerant is removed. This type of replacement may be referred to as drop-in replacement or retrofit.
  • the retrofit may require adjustment of existing equipment or even changing out certain pieces of equipment to allow use of the new refrigerant.
  • compositions disclosed herein are useful in methods of replacing R- 134a, R-1234zeE, R-515B, R471A, R-476A, R-482A, R-454C, R-404A, and R-449A.
  • the method comprises providing the composition of the present invention comprising, consisting essentially of, or consisting of HFO-1234zeE and HFC-152a; or HFO-1234zeE, HFC-152a and one or more additional compounds as disclsoed above; or HFO-1234zeE, HFC-152a, and at least one compound selected from HFC-227ea, HFO-1336mzz(E), HFC-134, HFC-125, HFC-32, HFC-134a, and H CFO-1224yd (Z); or HFO-1234zeE, HFC-152a, at least one compound selected from HFC-227ea, HFO-1336mzz(E), HFC-134, HFC-125, HFC-32, HFC-134a, and H CFO-1224yd (Z), and one or more additional compounds as disclosed above, in place of the refrigerant to be replaced.
  • the method may also comprise, first removing the refrigerant in need of replacement from existing equipment, then charging the composition of the present
  • the present invention includes methods and systems which include using the inventive composition as a blowing agent, optionally with one or more of the additional compounds which include, but are not limited to, other compounds which also act as blowing agents (hereinafter referred to for convenience but not by way of limitation as co-blowing agents), and optionally with one or more additives such as surfactants, polyols, catalysts, flame retardants, polymer modifiers, colorants, dyes, solubility enhancers, rheology modifiers, plasticizing agents, fillers, nucleating agents, viscosity reduction agents, vapor pressure modifiers, stabilizers, and the like.
  • the additional compounds which include, but are not limited to, other compounds which also act as blowing agents (hereinafter referred to for convenience but not by way of limitation as co-blowing agents)
  • additives such as surfactants, polyols, catalysts, flame retardants, polymer modifiers, colorants, dyes, solubility enhancers, rheology modifiers, plasticizing agents, fillers,
  • Preferred blends for blowing agents used for foams, especially spray foams and panel foams include blends of HFO- 1234ze(E) and HFC-152a, more preferably HFO-1234ze(E), HFC-152a and one or more additional compounds or two or more additional compounds or three or more additional compounds selected from HFO-1234yf, HFC-245cb, HFO-1225ye(E), HFO-1225ye(Z), HFO-1225zc, HFC-236fa, H FC- 143a, HFC-125, H FC- 134a, HFO-1234zc, HFO-1233xf, HFO-1233zd, CFC-114, HCFC-124, trifluoropropyne, HFO-1234ze(Z), HFC-245fa, HFC-227ea, HFO-1243zf, HFC-263fb, HFC-134, HFC-161 , HCC-40, isobutane, HCO-1140, HCC-160 and CFC-114
  • blowing agent compositions comprise from about 70 wt% to 30 wt% HFO-1234ze(E) and from about 30 wt.% to 70 wt% H FC- 152a.
  • the blowing agent composition may optionally contain one or more of the additional compounds in an amount greater than 0 ppm and less than 5,000 ppm, or from about 5 to about 1 ,000 ppm, or from about 5 to about 500 ppm, or from about 1 to about 100 ppm, based on the total weight of the composition.
  • blowing agent compositions according to the present invention comprise from about 60 wt% to 40 wt% HFO-1234ze(E) and from about 40 wt.% to 60 wt% H FC- 152a.
  • the blowing agent composition may optionally contain one or more of the additional compounds in an amount greater than 0 ppm and less than 5,000 ppm, or from about 5 to about 1 ,000 ppm, or from about 5 to about 500 ppm, or from about 1 to about 100 ppm, based on the total weight of the composition.
  • blowing agent compositions according to the present invention comprise about 50 wt% HFO-1234ze(E) and about 50 wt% HFC-152a.
  • the blowing agent composition may optionally contain one or more of the additional compounds in an amount greater than 0 ppm and less than 5,000 ppm, or from about 5 to about 1 ,000 ppm, or from about 5 to about 500 ppm, or from about 1 to about 100 ppm, based on the total weight of the composition.
  • dispersing agents may also be incorporated into the blowing agent compositions of the present invention.
  • Certain surfactants are optionally but preferably added to serve as cell stabilizers.
  • Some representative materials are sold under the names of DC-193, B-8404, and L-5340 which are, generally, polysiloxane polyoxyalkylene block co-polymers such as those disclosed in U.S. Pat. Nos. 2,834,748, 2,917,480, and 2,846,458, each of which is incorporated herein by reference.
  • blowing agent mixture may include flame retardants such as tris(2-chloroethyl)phosphate, tris(2-chloropropyl)phosphate, tris(2,3-dibromopropyl)-phosphate, tris(1 ,3-dichloro-propyl)phosphate, diammonium phosphate, various halogenated aromatic compounds, antimony oxide, aluminum trihydrate, polyvinyl chloride, and the like.
  • flame retardants such as tris(2-chloroethyl)phosphate, tris(2-chloropropyl)phosphate, tris(2,3-dibromopropyl)-phosphate, tris(1 ,3-dichloro-propyl)phosphate, diammonium phosphate, various halogenated aromatic compounds, antimony oxide, aluminum trihydrate, polyvinyl chloride, and the like.
  • nucleating agents all known compounds and materials having nucleating functionality are available for use in the present invention, including particularly talc
  • the co-blowing agent in accordance with the present invention can comprise a physical blowing agent, a chemical blowing agent (which preferably in certain embodiments comprises water) or a blowing agent having a combination of physical and chemical blowing agent properties.
  • blowing agent compositions of the present invention include one or more HFCs as co-blowing agents, more preferably one or more C1-C4 HFCs, and/or one or more hydrocarbons, more preferably C4-C6 hydrocarbons.
  • the present blowing agent compositions may include one or more of 1 ,1-difluoroethane (HFC-152a), difluoromethane (HFC-32), fluoroethane (HFC-161), difluoroethane (HFC-152), trifluoroethane (HFC-143), tetrafluoroethane (HFC-134), pentafluoroethane (HFC-125), pentafluoropropane (HFC-245), hexafluoropropane (HFC-236), heptafluoropropane (HFC-227), pentafluorobutane (HFC-365), hexafluorobutane (HFC-356) and all isomers of all such HFCs.
  • HFC-152a 1 ,1-difluoroethane
  • HFC-32 difluoromethane
  • fluoroethane HFC-161
  • the present blowing agent compositions may include in certain preferred embodiments, for example, iso, normal and/or cyclopentane for thermoset foams and butane or isobutane for thermoplastic foams.
  • other materials such as water, CO2, CFCs (such as trichlorofluoromethane (CFC-11) and dichlorodifluoromethane (CFC-12), hydrochlorocarbons (HCCs such as dichloroethylene (preferably trans-1 ,2- dichloroethylene), ethyl chloride and chloropropane), HCFCs, C1-C5 alcohols (such as, for example, ethanol and/or propanol and/or butanol), C1-C4 aldehydes, C1-C4 ketones, C1-C4 ethers (including ethers (such as dimethyl ether and diethyl ether), diethers (such as dimethoxy methane and diethoxy methan
  • blowing agent compositions of the present invention comprise at least one co-blowing agent and an amount of HFO-1234ze(E) and HFC-152a sufficient to produce a blowing agent composition which is overall nonflammable.
  • the HFC coblowing agent preferably C2, C3, C4 and/or C5 HFC
  • HFC-152a being particularly preferred for extruded thermoplastics
  • pentafluoropropane HFC-245
  • the HFC is preferably C2-C4 HFC, and even more preferably C3 HFC, with penta-fluorinated C3 HFC, such as HFC-245fa, being highly preferred in certain embodiments.
  • foamable compositions generally include one or more components capable of forming foam.
  • foam foaming agent is used to refer to a component, or a combination on components, which are capable of forming a foam structure, preferably a generally cellular foam structure.
  • the foamable compositions of the present invention include such component(s) and the blowing agent composition of the present invention (e.g., composition comprising at least HFO-1234ze(E) and HFC-152a).
  • the one or more components capable of forming foam comprise a thermosetting composition capable of forming foam and/or foamable compositions.
  • thermosetting compositions include polyurethane and polyisocyanurate foam compositions, and also phenolic foam compositions.
  • This reaction and foaming process may be enhanced through the use of various additives such as catalysts and surfactant materials that serve to control and adjust cell size and to stabilize the foam structure during formation.
  • any one or more of the additional components described above with respect to the blowing agent compositions of the present invention could be incorporated into the foamable composition of the present invention.
  • one or more of the present compositions are included as or part of a blowing agent in a foamable composition, or as a part of a two or more part foamable composition, which preferably includes one or more of the components capable of reacting and/or foaming under the proper conditions to form a foam or cellular structure.
  • the one or more components capable of foaming comprise thermoplastic materials, particularly thermoplastic polymers and/or resins.
  • PS polystyrene
  • suitable polyolefin resins in accordance with the invention include the various ethylene resins including the ethylene homopolymers such as polyethylene and ethylene copolymers, polypropylene (PP) and polyethylene-terephthalate (PET).
  • the thermoplastic foamable composition is an extrudable composition.
  • the methods of the present invention generally require incorporating a blowing agent in accordance with the present invention into a foamable or foam forming composition and then foaming the composition, preferably by a step or series of steps which include causing volumetric expansion of the blowing agent in accordance with the present invention.
  • blowing agent in general, it is contemplated that the presently used systems and devices for incorporation of blowing agent and for foaming are readily adaptable for use in accordance with the present invention.
  • one advantage of the present invention is the provision of an improved blowing agent which is generally compatible with existing foaming methods and systems.
  • the present invention comprises methods and systems for foaming all types of foams, including thermosetting foams, thermoplastic foams and formed-in-place foams.
  • one aspect of the present invention is the use of the present blowing agents in connection with conventional foaming equipment, such as polyurethane foaming equipment, at conventional processing conditions.
  • the present methods therefore include polyol premix type operations, blending type operations, third stream blowing agent addition, and blowing agent addition at the foam head.
  • One embodiment of the present invention relates to methods of forming foams, especially panel foams and spray foams, and preferably such foams made from polyurethane and polyisocyanurate.
  • the methods generally comprise providing a blowing agent composition of the present inventions, adding (directly or indirectly) the blowing agent composition to a foamable composition, and reacting the foamable composition under the conditions effective to form a foam or cellular structure, as is well known in the art.
  • such preferred methods comprise preparing polyurethane or polyisocyanurate foams by combining an isocyanate, a polyol or mixture of polyols, a blowing agent or mixture of blowing agents comprising one or more of the present compositions, and other materials such as catalysts, surfactants, and optionally, flame retardants, colorants, or other additives.
  • a blowing agent or mixture of blowing agents comprising one or more of the present compositions
  • other materials such as catalysts, surfactants, and optionally, flame retardants, colorants, or other additives.
  • the isocyanate and optionally certain surfactants and blowing agents comprise the first component, commonly referred to as the “A” component.
  • polyol or polyol mixture, surfactant, catalysts, blowing agents, flame retardant, and other isocyanate reactive components comprise the second component, commonly referred to as the “B” component.
  • B component the second component
  • polyurethane or polyisocyanurate foams are readily prepared by bringing together the A and B side components either by hand mix for small preparations and, preferably, machine mix techniques to form blocks, slabs, laminates, pour-in-place panels and other items, spray applied foams, froths, and the like.
  • other ingredients such as fire retardants, colorants, auxiliary blowing agents, and even other polyols can be added as one or more additional streams to the mix head or reaction site. Most preferably, however, they are all incorporated into one B-component as described above.
  • the present methods and systems also include forming a one component foam, preferably polyurethane foam, containing a blowing agent in accordance with the present invention.
  • a portion of the blowing agent is contained in the foam forming agent, preferably by being dissolved in a foam forming agent which is liquid at the pressure within the container, a second portion of the blowing agent is present as a separate gas phase.
  • the contained/dissolved blowing agent performs, in large part, to cause the expansion of the foam, and the separate gas phase operates to impart propulsive force to the foam forming agent.
  • Such one component systems are typically and preferably packaged in a container, such as an aerosol type can, and the blowing agent of the present invention thus preferably provides for expansion of the foam and/or the energy to transport the foam/foamable material from the package, and preferably both.
  • such systems and methods comprise charging the package with a fully formulated system (preferably isocyanate/polyol system) and incorporating a gaseous blowing agent in accordance with the present invention into the package, preferably an aerosol type can.
  • a fully formulated system preferably isocyanate/polyol system
  • a gaseous blowing agent in accordance with the present invention into the package, preferably an aerosol type can.
  • the present invention also relates to all foams, including but not limited to closed cell foam, open cell foam, spray foams, panel foams, rigid foam, flexible foam, integral skin and the like, prepared from a polymer foam formulation containing a blowing agent composition, such as a composition comprising HFO-1234ze(E) and HFC-152a, either alone or in combination with one or more other compounds.
  • a blowing agent composition such as a composition comprising HFO-1234ze(E) and HFC-152a, either alone or in combination with one or more other compounds.
  • compositions of the present invention were calculated using conditions for a heat pump in cooling mode.
  • Compositions containing HFO-1234zeE, HFC-227ea, and HFC-152a were compared to results for R-515A (ASHRAE designation for refrigerant mixtures containing 88 wt% HFO- 1234zeE and 12 wt% HFC-227ea) and R-515B (ASHRAE designation for refrigerant mixtures containing 91.1 wt% HFO-1234zeE and 8.9 wt% HFC-227ea).
  • the conditions for the comparisons are as follows:
  • HFO-1234ze(E), HFC- 152a and HFC-227ea may be less than 100 wt%
  • the ternary composition of HFO-1234ze(E), HFC-152a and HFC-227ea may further comprise one or more additional compounds selected from HFO-1234yf, HFC-245cb, HFO-1225ye(E), HFO-1225ye(Z), HFO-1225zc, HFC-236fa, HFC-143a, HFC-125, HFC-134a, HFO- 1234zc, HFO-1233xf, HFO-1233zd, CFC-114, HCFC-124, trifluoropropyne, HFO- 1234ze(Z), HFC-245fa, HFO-1243zf, HFC-263fb, HFC-134, HFC-161, HCC-40, isobutane, HCO-11
  • compositions of the present invention were calculated using conditions for a heat pump in cooling mode.
  • Compositions containing HFO-1234zeE, HFO-1336mzzE, and HFC-152a or HFO-1234zeE, HFO- 1336mzzE, HFC-152a, and HFC-227ea or HFO-1234zeE, HFC-134a, and HFC- 152a were compared to results for R-471A (ASHRAE designation for refrigerant mixtures containing 78.7 wt% HFO-1234zeE, 17 wt% HFO-1336mzzE, and 4.3 wt% HFC-227ea) and R-476A (ASHRAE designation for refrigerant mixtures containing 78 wt% HFO-1234zeE, 12 wt% HFO-1336mzzE, and 10 wt% HFC-134a).
  • the conditions for the comparisons are as follows:
  • the performance of the presently claimed compositions is an improvement over the existing R-471A and R-476A compositions, providing higher capacity in most cases and higher COP with essentially equivalent compressor discharge temperature and average glide.
  • HFO-1234ze(E), HFO- 1336mzz(E) and HFC-152a may be less than 100 wt%
  • the ternary composition of HFO-1234ze(E), HFO-1336mzz(E) and HFC-152a may further comprise one or more additional compounds selected from HFO-1234yf, HFC-245cb, HFO- 1225ye(E), HFO-1225ye(Z), HFO-1225zc, HFC-236fa, HFC-143a, HFC-125, HFC- 134a, HFO-1234zc, HFO-1233xf, HFO-1233zd, CFC-114, HCFC-124, trifluoropropyne, HFO-1234ze(Z), HFC-245fa, HFC-227ea, HFO-1243zf, HFC-263fb, HFC-134, HFC-161,
  • HFO-1234ze(E), HFO- 1336mzz(E), HFC-152a and HFC-227ea may be less than 100 wt%
  • the quaternary composition of HFO-1234ze(E), HFO-1336mzz(E), HFC-152a and HFC- 227ea may further comprise one or more additional compounds selected from HFO- 1234yf, HFC-245cb, HFO-1225ye(E), HFO-1225ye(Z), HFO-1225zc, HFC-236fa, HFC-143a, HFC-125, HFC-134a, HFO-1234zc, HFO-1233xf, HFO-1233zd, CFC- 114, HCFC-124, trifluoropropyne, HFO-1234ze(Z), HFC-245fa, HFC-227ea, HFO- 1243zf, H
  • HFO-1234ze(E), HFC- 134a and HFC-152a may be less than 100 wt%
  • the ternary composition of HFO-1234ze(E), HFC-134a and HFC-152a may further comprise one or more additional compounds selected from HFO-1234yf, HFC-245cb, HFO-1225ye(E), HFO-1225ye(Z), HFO-1225zc, HFC-236fa, HFC-143a, HFC-125, HFC-134a, HFO- 1234zc, HFO-1233xf, HFO-1233zd, CFC-114, HCFC-124, trifluoropropyne, HFO- 1234ze(Z), HFC-245fa, HFC-227ea, HFO-1243zf, HFC-263fb, HFC-134, HFC-161 , HCC-40, iso
  • compositions of the present invention were calculated using conditions for a heat pump in cooling mode.
  • Compositions containing HFO-1234zeE, HFC-134, and HFC-152a were compared to results for a composition containing only HFO-1234zeE and HFC-134.
  • the conditions for the comparisons are as follows: Temperature of the condenser 65 C
  • HFO-1234ze(E), HFC- 152a and HFC-134 may be less than 100 wt%
  • the ternary composition of HFO- 1234ze(E), HFC-152a and HFC-134 may further comprise one or more additional compounds selected from HFO-1234yf, HFC-245cb, HFO-1225ye(E), HFO- 1225ye(Z), HFO-1225zc, HFC-236fa, HFC-143a, HFC-125, HFC-134a, HFO- 1234zc, HFO-1233xf, HFO-1233zd, CFC-114, HCFC-124, trifluoropropyne, HFO- 1234ze(Z), HFC-245fa, HFC-227ea, HFO-1243zf, HFC-263fb, HFC-161, HCC-40, isobutane, HCO-11
  • compositions of the present invention were calculated using conditions for a heat pump in cooling mode.
  • Compositions containing HFO-1234zeE, HFC-125, and HFC-152a were compared to results for a composition containing only HFO-1234zeE and HFC-125.
  • the conditions for the comparisons are as follows:
  • the performance of the presently claimed compositions is an improvement over the prior art composition containing 96 wt% HFO-1234zeE and 4 wt% HFC-125, providing higher capacity and higher COP with essentially equivalent compressor discharge temperature and average glide.
  • the capacity is lower, but the GWP is significantly reduced and the COP is also improved making it applicable to certain applications.
  • HFO-1234ze(E), HFC- 152a and HFC-125 may be less than 100 wt%
  • the ternary composition of HFO- 1234ze(E), HFC-152a and HFC-125 may further comprise one or more additional compounds selected from HFO-1234yf, HFC-245cb, HFO-1225ye(E), HFO- 1225ye(Z), HFO-1225zc, HFC-236fa, HFC-143a, HFC-134a, HFC-134, HFO- 1234zc, HFO-1233xf, HFO-1233zd, CFC-114, HCFC-124, trifluoropropyne, HFO- 1234ze(Z), HFC-245fa, HFC-227ea, HFO-1243zf, HFC-263fb, HFC-161, HCC-40, isobutane, HCO-11
  • compositions of the present invention were calculated using conditions for a heat pump in cooling mode.
  • Compositions containing HFO-1234zeE, HFC-32, HFC-125, and HFC-152a were compared to results for R-447A (ASHRAE designation for refrigerant mixtures containing 28.5 wt% HFO-1234zeE, 68 wt% HFC-32, and 3.5 wt% HFC-125) and R-447B (ASHRAE designation for refrigerant mixtures containing 24 wt% HFO-1234zeE, 68 wt% HFC- 32, and 8 wt% HFC-125).
  • the conditions for the comparisons are as follows:
  • Evaporator temperature -20 C [0260] *lt will be understood by those skilled in the art that weight percentage of each component is approximate such that the total amount of HFO-1234ze(E), HFC- 152a, HFC-32 and HFC-125 may be less than 100 wt%, and the quaternary composition of HFO-1234ze(E), HFC-152a, HFC-32 and HFC-125 may further comprise one or more additional compounds selected from HFO-1234yf, HFC- 245cb, HFO-1225ye(E), HFO-1225ye(Z), HFO-1225zc, HFC-236fa, HFC-143a, HFC-134a, HFC-134, HFO-1234zc, HFO-1233xf, HFO-1233zd, CFC-114, HCFC- 124, trifluoropropyne, HFO-1234ze(Z), HFC-245fa, HFC-227ea, HFO-1243zf, HFC
  • compositions of the present invention were calculated using conditions for a heat pump in cooling mode.
  • Compositions containing HFO-1234zeE, HCFO-1224ydZ, HFC-134, and HFC-152a were compared to results for R-482A (ASHRAE designation for refrigerant mixtures containing 83.5 wt% HFO-1234zeE, 6.5 wt% HCFO-1224ydZ, and 10 wt% HFC- 134a).
  • the conditions for the comparisons are as follows:
  • HFO-1234ze(E), HFC- 152a, HFC-134 and HFO-1224yd(Z) may be less than 100 wt%
  • the quaternary composition of HFO-1234ze(E), HFC-152a, HFC-134 and HFO-1224yd(Z) may further comprise one or more additional compounds selected from HFO-1234yf, HFC-245cb, HFO-1225ye(E), HFO-1225ye(Z), HFO-1225zc, HFC-236fa, HFC-143a, HFC-125, HFC-134a, HFO-1234zc, HFO-1233xf, HFO-1233zd, CFC-114, HCFC- 124, trifluoropropyne, HFO-1234ze(Z), HFC-245fa, HFC-227ea, HFO-1243zf, HFC- 263f
  • compositions of the present invention were calculated using conditions for a chiller.
  • Compositions containing HFO-1234zeE, HFC-152a, and HFC-227ea were compared to results for R-515A (ASHRAE designation for refrigerant mixtures containing 88 wt% HFO-1234zeE and 12 wt% HFC-227ea), R-515B (ASHRAE designation for refrigerant mixtures containing 91.1 wt% HFO-1234zeE and 8.9 wt% HFC-227ea), R-471A (ASHRAE designation for refrigerant mixtures containing 78.7 wt% HFO-1234zeE, 17 wt% HFO-1336mzzE, and 4.3 wt% HFC-227ea), R-476A (ASHRAE designation for refrigerant mixtures containing HFO-1234zeE, HFO-1336mzzE, and HFC-134a), and 134a.
  • compositions provide higher capacity and similar or improved COP, with low average glide and similar compressor discharge temperatures as compared to R-515A, R-515B, and R-471A.
  • capacity is lower but COP essentially equivalent, discharge temperature lower, average glide is acceptable, and GWP is significantly reduced.
  • HFO-1234ze(E), HFC- 152a and HFC-227ea may be less than 100 wt%
  • the ternary composition of HFO-1234ze(E), HFC-152a, and HFC-227ea may further comprise one or more additional compounds selected from HFO-1234yf, HFC-245cb, HFO-1225ye(E), HFO-1225ye(Z), HFO-1225zc, HFC-236fa, HFC-143a, HFC-125, HFC-134a, HFC- 134, HFO-1234zc, HFO-1233xf, HFO-1233zd, CFC-114, HCFC-124, trifluoropropyne, HFO-1234ze(Z), HFC-245fa, HFO-1243zf, HFC-263fb, HFC-161 , HCC-40, isobutane, H
  • compositions of the present invention were calculated using conditions for low temperature refrigeration.
  • Compositions containing HFO-1234zeE, HFC-152a, and HFC-32 were compared to results for R- 404A (ASHRAE designation for refrigerant mixtures containing 44 wt% HFC-125, 52 wt% HFC-143a, and 4 wt% FC-134a), R-454C (ASHRAE designation for refrigerant mixtures containing 78.5 wt% HFO-1234yf and 21.5 wt% HFC-32), and R-449A (ASHRAE designation for refrigerant mixtures containing 25.3 wt% HFO-1234yf, 24.3 wt% HFC-32, 24.7 wt% HFC-125, and 25.7 wt% HFC-134a).
  • the conditions for the comparisons are as follows:
  • HFO-1234ze(E), HFC- 152a and HFC-32 may be less than 100 wt%
  • the ternary composition of HFO- 1234ze(E), HFC-152a, and HFC-32 may further comprise one or more additional compounds selected from HFO-1234yf, HFC-245cb, HFO-1225ye(E), HFO- 1225ye(Z), HFO-1225zc, HFC-236fa, HFC-143a, HFC-125, HFC-134a, HFC-134, HFC-227ea, HFO-1234zc, HFO-1233xf, HFO-1233zd, CFC-114, HCFC-124, trifluoropropyne, HFO-1234ze(Z), HFC-245fa, HFO-1243zf, HFC-263fb, HFC-161 , HCC-40, isobut
  • Embodiment 1 A composition comprising HFO-1234ze(E), HFC-152a, and at least one compound selected from the group consisting of HFC-227ea, HFO- 1336mzz(E), HFC-134, HFC-125, HFC-32, HFC-134a, HCFO-1224yd(Z), CO2, and combinations thereof.
  • Embodiment 2 The composition of Embodiment 1, wherein said composition comprises one of: a. HFO-1234ze(E), HFC-152a, and HFC-227ea; b. HFO-1234ze(E), HFC-152a, and HFO-1336mzz(E); c. HFO-1234ze(E), HFC-152a, HFO-1336mzz(E), and HFC-227ea; d. HFO-1234ze(E), HFC-134, and HFC-152a; e. HFO-1234ze(E), HFC-125, and HFC-152a; f. HFO-1234ze(E), HFC-32, and HFC-152a; g.
  • Embodiment 3 The composition of Embodiment 1 or 2, comprising from about 88 to 91 weight percent HFO-1234ze(E), from about 4 to 9 weight percent HFC-227ea, and from about 3 to 5 weight percent HFC-152a.
  • Embodiment 4 The composition of Embodiment 1 or 2, comprising from about 70 to 80 weight percent HFO-1234ze(E), from about 5 to 20 weight percent HFO-1336mzz(E), from about 5 to 25 weight percent HFC-152a, and from about 1 to 3 weight percent HFC-227ea.
  • Embodiment 5 The composition of Embodiment 1 or 2, comprising from about 75 to 85 weight percent HFO-1234ze(E), from about 2 to 8 weight percent HFC-134, and from about 10 to 20 weight percent HFC-152a.
  • Embodiment 6 The composition of Embodiment 1 or 2, comprising from about 75 to 85 weight percent HFO-1234ze(E), from about 3 to 7 weight percent HFC-125, and from about 10 to 20 weight percent HFC-152a.
  • Embodiment 7 The composition of Embodiment 1 or 2, comprising from about 75 to 85 weight percent HFO-1234ze(E), from about 3 to 7 weight percent HFC-125, from about 3 to 7 weight percent HFC-32, and from about 5 to 15 weight percent HFC-152a.
  • the composition of Embodiment 1 or 2 comprising from about 75 to 85 weight percent HFO-1234ze(E), from about 3 to 7 weight percent HFC-134a, from about 3 to 7 weight percent HCFO-1224yd(Z), and from about 5 to 15 weight percent HFC-152a.
  • Embodiment 8 The composition of Embodiment 1 or 2, comprising about 60 weight percent HFO-1234ze(E), about 10 weight percent HFC-32, and about 30 weight percent HFC-152a.
  • Embodiment 9 The composition of any of Embodiments 1 to 8, further comprising at least one additional compound selected from the group consisting of HFO-1234yf, HFC-245cb, HFO-1225ye(E), HFO-1225ye(Z), HFO-1225zc, HFC- 236fa, HFC-152a, HFC-143a, HFC-125, HFC-134a, HFO-1234zc, HCFO-1233xf, HCFO-1233zd, CFC-114, HCFC-124, HFO-2223, HFO-1234ze(Z), HFC-245fa, HFC- 227ea, HFO-1243zf, and HFC-263fb.
  • Embodiment 10 The composition of any of Embodiments 1 to 9, further comprising one or more additional compounds selected from the group consisting of HFO-1234yf, HFC-245cb, HFO-1225ye(E), HFO-1225ye(Z), HFO-1225zc, HFC- 236fa, HFC-143a, HFC-125, HFC-134a, HFO-1234zc, HFO-1233xf, HFO-1233zd, CFC-114, HCFC-124, trifluoropropyne, HFO-1234ze(Z), HFC-245fa, HFC-227ea, HFO-1243zf, HFC-263fb, HFC-134, HFC-161, HCC-40, isobutane, HCO-1140, HCC- 160 and CFC-114a, preferably two or more compounds or preferably three or more compounds.
  • additional compounds selected from the group consisting of HFO-1234yf, HFC-245cb, HFO-1225ye(
  • Embodiment 11 The composition of any of Embodiments 1 to 9, further comprising one or more additional compounds selected from the group consisting of HFO-1234yf, HFC-245cb, HFC-134, HFC-134a, HFC-125, HFO-1225zc, HFO- 1243zf, HFC-161 , HCC-40, HCO-1140 and HCC-160, preferably two or more compounds or preferably three or more compounds.
  • Embodiment 12 A composition comprising HFO-1234ze(E), HFC-152a, and one or more additional compounds selected from the group consisting of HFO- 1234yf, HFC-245cb, HFO-1225ye(E), HFO-1225ye(Z), HFO-1225zc, HFC-236fa, HFC-143a, HFC-125, HFC-134a, HFO-1234zc, HFO-1233xf, HFO-1233zd, CFC- 114, HCFC-124, trifluoropropyne, HFO-1234ze(Z), HFC-245fa, HFC-227ea, HFO- 1243zf, HFC-263fb, HFC-134, HFC-161, HCC-40, isobutane, HCO-1140, HCC-160 and CFC-114a, preferably two or more compounds or preferably three or more compounds.
  • Embodiment 13 A composition comprising HFO-1234ze(E), HFC-152a, and one or more additional compounds selected from the group consisting of HFO- 1234yf, HFC-245cb, HFC-134, HFC-134a, HFC-125, HFO-1225zc, HFO-1243zf, HFC-161 , HCC-40, HCO-1140 and HCC-160, preferably two or more compounds or preferably three or more compounds.
  • Embodiment 14 The composition of Embodiment 12 or 13, the composition comprising one of: a. HFO-1234ze(E), HFC-152a, HFC-245cb and HFC-161 ; b. HFO-1234ze(E), HFC-152a, HFO-1243zf and HFC-161; c. HFO-1234ze(E), HFC-152a, HFO-1243zf and HCO-1140; d. HFO-1234ze(E), HFC-152a, HFC-134 and HFC-134a; e. HFO-1234ze(E), HFC-152a, HFO-1234yf and HFC-161; f.
  • Embodiment 15 The composition of Embodiment 12 or 13, the composition comprising one of: a. HFO-1234ze(E), HFC-152a, HFC-245cb, HFO-1234yf and HFC-161 ; b. HFO-1234ze(E), HFC-152a, HFC-245cb, HFO-1234yf and HCO-1140; c. HFO-1234ze(E), HFC-152a, HFC-245cb, HFO-1234yf and HCC-160; d. HFO-1234ze(E), HFC-152a, HFC-245cb, HFO-1234yf and HCC-40; e.
  • Embodiment 16 The composition of any of Embodiments 1 to 15, further comprising less than 100 ppm wt water, preferably less than 20 ppm wt water, and more preferably less than 10 ppm wt water.
  • Embodiment 17 The composition of any of Embodiments 1 to 16, further comprising less than 5 volume percent non-adsorbable gases (NAG), preferably less than 3 volume percent NAG, and more preferably less than 1 .5 volume percent NAG.
  • NAG non-adsorbable gases
  • Embodiment 18 The composition of any of Embodiments 1 to 17, further comprising less than 0.35 volume percent oxygen.
  • Embodiment 19 The composition of any of Embodiments 1 to 18, further comprising at least one stabilizer.
  • Embodiment 20 The composition of any of Embodiments 1 to 19, further comprising at least one lubricant selected from the group consisting of polyol ester, polyvinyl ether, and polyalkylene glycol.
  • Embodiment 21 The composition of any of Embodiments 1 to 20, wherein said composition has GWP(AR4) less than 750, preferably GWP less than 300, and more preferably less than 150.
  • Embodiment 22 The composition of any of Embodiments 1 to 21 , wherein said composition is characterized as flammability class 1 (non-flammable), flammability class 2L (mildly flammable), or flammability class 2.
  • Embodiment 23 The composition of any of Embodiments 1 to 22, further comprising a hydrocarbon selected from the group consisting of propane, propylene, cyclopropane, isobutane, n-butane, isobutene, and combinations thereof.
  • a hydrocarbon selected from the group consisting of propane, propylene, cyclopropane, isobutane, n-butane, isobutene, and combinations thereof.
  • Embodiment 24 The composition of any of Embodiments 1 to 23, wherein the composition is free of or substantially free of Group A Fluorinated Substances, and wherein degradation products of the composition are free of or substantially free of Group A Fluorinated Substances.
  • Embodiment 25 A process for producing cooling comprising condensing the composition of any of Embodiments 1 to 24 and thereafter evaporating said composition in the vicinity of a body to be cooled.
  • Embodiment 26 A process for producing heating comprising evaporating the composition of any of Embodiments 1 to 24 and thereafter condensing said composition in the vicinity of a body to be heated.
  • Embodiment 28 The apparatus of Embodiment 27 comprising an evaporator, a compressor, a condenser, and an expansion device.
  • Embodiment 29 The apparatus of Embodiment 27 or 28 comprising a chiller.
  • Embodiment 30 The apparatus of Embodiment 27 or 28 comprising a heat pump.
  • Embodiment 31 The apparatus of Embodiment 27 or 28 comprising an air conditioner or air conditioning system.
  • Embodiment 32 The apparatus of Embodiment 27 or 28 comprising a refrigerator or refrigeration system.
  • Embodiment 33 The apparatus of Embodiment 27, 28 or 32 comprising a low temperature refrigeration system.
  • Embodiment 34 The apparatus of Embodiment 27, 28 or 32 comprising a medium temperature refrigeration system.
  • Embodiment 35 The apparatus of Embodiment 27, 28 or 32 comprising a transport refrigeration system.
  • Embodiment 36 The apparatus of Embodiment 27, 28 or 30 comprising a high temperature heat pump system.
  • Embodiment 37 The apparatus of Embodiment 27, 28 or 30 comprising an automobile heat pump system.
  • Embodiment 38 The apparatus of Embodiment 37 comprising a secondary loop system.
  • Embodiment 39 A method for replacing a first refrigerant in a refrigeration, air conditioning, heat pump, or chiller apparatus, the first refrigerant being selected from the group consisting of R-22, HFC-134a, propane, HFO-1234yf, R-407C, R- 404A, R-410A, R-513A, R-454A, R-454B, R-454C, R-448A, R-449A, R-449B, R- 449C, R-1234zeE, R-515B, R471A, R-476A, R-482A, R-452A, and R-452C, the method comprising providing the composition of any of Embodiments 1 to 24 to the refrigeration, air conditioning, heat pump, or chiller apparatus.
  • the first refrigerant being selected from the group consisting of R-22, HFC-134a, propane, HFO-1234yf, R-407C, R- 404A, R-410A, R-513A, R-454A, R-454B
  • Embodiment 40 A composition comprising HFO-1234ze(E) and: a. at least one compound selected from the group consisting of HFC-23, HFC- 32, HFC-125, HFC-143a, HFC-134, HFC-152a, HFO-1132a, HFO-1132(E), HFO-1132(Z), HFO-1234ze(Z), HCFO-1233zd(E), HCFO-1233zd(Z), HFC- 245fa, HFO-1336mzz(E), HFO-1336mzz(Z), HCC-1130(E), HCC-1130(Z), CFO-1112(E), CFO-1112(Z), HFC-356mcf, HFC-356mff and combinations thereof; or b.
  • HFO-1234yf at least one compound selected from the group consisting of HFO-1234yf, HFC-227ea, HFO-1225ye(E), HCFO-1224yd(Z), HFC-134a; and combinations thereof; and c. optionally at least one compound selected from the group consisting of propane, propylene, cyclopropane, isobutane, n-butane, and isobutene.
  • Embodiment 41 Use of the composition according to any of Embodiments 1 to 24, preferably any of Embodiments 12 to 24, as a blowing agent for formation of a foam.
  • Embodiment 42 A process of forming a foam comprising: adding a foamable composition to a blowing agent; and
  • blowing agent comprises the composition according to any of Embodiments 1 to 24, preferably any of Embodiments 12 to 24.
  • Embodiment 43 A foam formed by the process according to Embodiment 42.
  • Embodiment 43 A foam formed by the process according to Embodiment 42.

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Abstract

L'invention concerne des compositions contenant du HFO-1234 ze(E), du HFC-152a, et au moins un composé choisi parmi le HFC-227ea, le HFO-1336mzz(E), le HFC-134, le HFC-125, le HFC-32, le HFC-134a, le HCFO-1224yd(Z), le CO2, et des combinaisons de ceux-ci. Ces compositions sont utiles en tant que fluides frigorigènes dans la climatisation, les pompes à chaleur, la réfrigération et les refroidisseurs.
PCT/US2024/053311 2023-10-30 2024-10-29 Compositions comprenant du tétrafluoropropène et leurs utilisations WO2025096365A1 (fr)

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