US20090314015A1 - Method for circulating selected heat transfer fluids through a closed loop cycle - Google Patents

Method for circulating selected heat transfer fluids through a closed loop cycle Download PDF

Info

Publication number
US20090314015A1
US20090314015A1 US12/377,686 US37768607A US2009314015A1 US 20090314015 A1 US20090314015 A1 US 20090314015A1 US 37768607 A US37768607 A US 37768607A US 2009314015 A1 US2009314015 A1 US 2009314015A1
Authority
US
United States
Prior art keywords
hfc
layer
butane
isobutane
trans
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US12/377,686
Inventor
Barbara Haviland Minor
Donald Bernard Bivens
Shailesh Ratilal Doshi
Velliyur Nott Mallikarjuna Rao
Enrico Simonato
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Priority to US12/377,686 priority Critical patent/US20090314015A1/en
Assigned to E. I. DU PONT DE NEMOURS AND COMPANY reassignment E. I. DU PONT DE NEMOURS AND COMPANY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: RAO, VELLIYUR NOTT MALLIKARJUNA, MINOR, BARBARA HAVILAND, BIVENS, DONALD BERNARD, DOSHI, SHAILESH RATILAL, SIMONATO, ENRICO
Publication of US20090314015A1 publication Critical patent/US20090314015A1/en
Abandoned legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F15—FLUID-PRESSURE ACTUATORS; HYDRAULICS OR PNEUMATICS IN GENERAL
    • F15D—FLUID DYNAMICS, i.e. METHODS OR MEANS FOR INFLUENCING THE FLOW OF GASES OR LIQUIDS
    • F15D1/00—Influencing flow of fluids
    • F15D1/02—Influencing flow of fluids in pipes or conduits
    • 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
    • C09K2205/106—Carbon dioxide
    • 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
    • C09K2205/11—Ethers
    • 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
    • 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
    • C09K2205/10—Components
    • C09K2205/134—Components containing sulfur

Definitions

  • the present invention relates to the use of flexible hoses capable of handling high pressure fluids and providing a barrier against permeation loss in air conditioning and refrigeration systems. More particularly, the present invention relates to the use of such hoses in air conditioning and refrigeration systems, including mobile air conditioning systems, in which new, low global warming potential (GWP) refrigerant alternatives are used.
  • GWP global warming potential
  • HFC-134a Currently proposed replacement refrigerants for HFC-134a include HFC-152a, pure hydrocarbons such as butane or propane, or “natural” refrigerants such as CO 2 or ammonia. Many of these suggested replacements are toxic, flammable, and/or have low energy efficiency. Therefore, new alternatives are constantly being sought.
  • heat transfer fluids are circulated within a closed loop including a compressor, a condenser and an evaporator.
  • Hoses are typically connected between the outlet of the compressor and the inlet of the condenser; between the outlet of the condenser and the inlet of the evaporator; and between the outlet of the evaporator and the inlet of the compressor.
  • Such hoses must be able to withstand the high pressure of the fluids which are circulated through such systems.
  • Hoses used for these purposes need to be flexible for ease of installation and use, and often must be shaped into curves and bends for connecting components already installed into fixed positions. They must also be able to contain the fluid pressure. These hoses are often made of elastomeric materials such as natural or synthetic rubber or thermoplastic elastomers, and are typically reinforced with braiding to impart high pressure capability.
  • the hoses of such systems offer superior barrier resistance to permeation of the contained fluid through the wall of the hose construction.
  • the hose wall must provide high barrier resistance to ingression of external fluids, such as air or moisture, into the contained fluid.
  • thermoplastic barrier layer on the inside.
  • a typical high pressure barrier hose may thus consist of multiple layers—an inner thermoplastic barrier layer made of a polyamide, a polyester or a suitable thermoplastic material; an over-layer of an elastomeric material to provide flexibility; and a braid layer over the elastomeric layer to provide pressure capability and an outer protective cover layer of an elastomeric material.
  • the present invention relates to transporting a heat transfer fluid within a refrigeration or air conditioning system through a hose, where the hose is able to withstand high-pressure refrigerants, and the hose has improved barrier properties.
  • a further advantage of such hose is its simple and straightforward construction.
  • such hose is especially suitable for use with fluoroolefin compositions which are low GWP refrigerant alternatives.
  • a method of providing transport of a heat transfer fluid composition within a refrigeration or air conditioning system comprising circulating the heat transfer fluid through one or more hoses of said system, wherein said heat transfer fluid comprises a compound selected from the group consisting of: R32, R152a, CF 3 I, 1234yf, 1225ye and trans-1234ze.
  • the composition comprises 1225ye and at least one additional compound selected from the group consisting of HFC-1234ze, HFC-1234yf, HFC-1234ye, HFC-1243zf, HFC-32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethylether, CF 3 SCF 3 , CO 2 , NH 3 , and CF 3 I.
  • the composition comprises HFC-1234ze and at least one additional compound selected from the group consisting of HFC-1234yf, HFC-1234ye, HFC-1243zf, HFC-32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethylether, CF 3 SCF 3 , CO 2 and CF 3 I.
  • the composition comprises HFC-1234yf and at least one additional compound selected from the group consisting of HFC-1234ye, HFC-1243zf, HFC-32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethylether, CF 3 SCF 3 , CO 2 , NH 3 , and CF 3 I.
  • the composition comprises HFC-1243zf and at least one additional compound selected from the group consisting of HFC-1234ye, HFC-32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethylether, CF 3 SCF 3 , CO 2 and CF 3 I.
  • the composition comprises HFC-1234ye and at least one additional compound selected from the group consisting of HFC-1243zf, HFC-32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethylether, CF 3 SCF 3 , CO 2 and CF 3 I.
  • the hose comprises an outer layer comprising a material selected from the group consisting of an elastomer and a polyamide and an inner layer comprising a material selected from the group consisting of an elastomer, a polyamide and a thermoplastic.
  • the hose may further include (a) a tie layer positioned over said inner layer; (b) a metal-polymer laminate positioned over said tie layer and consisting of a layer of polymer compatible with or bondable to said outer surface of said veneer, a thin layer of metallic foil, and another layer of a polymer protecting the metallic foil; (c) a braid under-layer positioned over said metal-polymer laminate and consisting of an elastomeric material; and (d) a reinforcing braid layer positioned over said braid under-layer, wherein the outer layer is positioned on the outside of the reinforcing braid layer.
  • FIG. 1 is a schematic diagram of a refrigeration or air conditioning system including a plurality of hoses according to the present invention.
  • FIG. 2 is a cross-sectional view of a hose of the present invention.
  • a refrigeration or air-conditioning system Such a system, which is a vapor compression system, is shown in FIG. 1 .
  • a vapor-compression system is a closed loop system which re-uses refrigerant in multiple steps producing a cooling effect in one step and a heating effect in a different step.
  • Such a system generally includes an evaporator, a compressor, a condenser and an expansion device, as will be described below in detail with respect to FIG. 1 .
  • gaseous refrigerant from an evaporator ( 42 ) flows through a hose ( 63 ) to the inlet of a compressor ( 12 ), and is then discharged.
  • compressors may be used with the present invention, including reciprocating, rotary, jet, centrifugal, scroll, screw or axial-flow, depending on the mechanical means to compress the fluid, or as positive-displacement (e.g., reciprocating, scroll or screw) or dynamic (e.g., centrifugal or jet).
  • positive-displacement e.g., reciprocating, scroll or screw
  • dynamic e.g., centrifugal or jet
  • the compressed refrigerant gas from the compressor flows through the compressor outlet and through a hose ( 61 ) to a condenser ( 41 ).
  • a pressure regulating valve ( 51 ) in hose ( 61 ) may be used. This valve allows recycle of the refrigerant flow back to the compressor via a hose ( 63 ), thereby providing the ability to control the pressure of the refrigerant reaching the condenser ( 41 ) and if necessary to prevent compressor surge.
  • the compressed refrigerant is condensed in the condenser, thus giving off heat.
  • the liquid refrigerant flows through an expansion device ( 52 ) via a hose ( 62 ) to the evaporator ( 42 ), which is located in the passenger compartment. In the evaporator, the liquid refrigerant is vaporized, providing cooling and the cycle then repeats.
  • the expansion device ( 52 ) may be an expansion valve, a capillary tube or an orifice tube.
  • the closed loop, vapor compression system of the present invention may be used in either stationary or mobile refrigeration or air-conditioning applications.
  • Stationary refrigeration apparatus or stationary air-conditioning apparatus refer to the equipment used for cooling the air in a building, or cooling perishable goods such as foods, pharmaceutical materials, etc, in a conventional, non-mobile, non-vehicle mounted system.
  • These systems may include chillers, ducted and ductless air conditioners and heat pumps, domestic refrigerators and freezers, commercial refrigerators and freezers, supermarket and industrial refrigeration systems.
  • Such stationary refrigeration or air conditioning systems may be associated with CHP (Combined Heat and Power) systems, wherein a stationary internal combustion engine is used to drive an electrical generator.
  • the waste heat produced by the engine may be recovered and used to perform work, by such means as a Rankine Cycle (steam engine) or Organic Rankine cycle (ORC).
  • a Rankine cycle the heat is used to vaporize a liquid (an organic liquid in the case of an ORC), which in turn drives a turbine.
  • the mechanical energy of the turbine may be used to drive an electricity generator, which runs a refrigeration or air-conditioning system.
  • Mobile refrigeration apparatus or mobile air-conditioning apparatus refers to any refrigeration or air-conditioning apparatus incorporated into a mobile transportation unit for the road, rail, sea or air.
  • apparatus which are meant to provide refrigeration or air-conditioning for a system independent of any moving carrier, known as “intermodal” systems, are included in the present invention.
  • intermodal systems include “containers” (combined sea/land transport) as well as “swap bodies” (combined road and rail transport).
  • the present invention is particularly useful for road transport refrigerating or air-conditioning apparatus, such as automobile air-conditioning apparatus or refrigerated road transport equipment.
  • a body to be cooled may be any space, location or object requiring refrigeration or air-conditioning.
  • the body may be the interior of a structure, i.e. residential or commercial, or a storage location for perishables, such as food or pharmaceuticals. Numerous mobile systems are described earlier in defining mobile refrigeration apparatus and mobile air-conditioning apparatus.
  • the refrigeration apparatus or air-conditioning apparatus of the present invention may additionally employ fin and tube heat exchangers, microchannel heat exchangers and vertical or horizontal single pass tube or plate type heat exchangers in the evaporator and/or the condenser.
  • the hose may comprise an outer layer comprising a material selected from the group consisting of an elastomer and a polyamide.
  • the hose may further comprise an inner layer comprising a material selected from the group consisting of an elastomer, a polyamide and a thermoplastic.
  • the inner layer may comprise a thermoplastic veneer, and the outer layer may comprise an elastomer.
  • hoses are constructed in multiple layers such as described below from the innermost to the outermost surface, including:
  • FIG. 2 in which this embodiment is shown.
  • each of the layers of the invention there is shown generally at 10 each of the layers of the invention, numbered and described from the innermost layer to the outermost layer.
  • a thermoplastic veneer 12 having an inner surface 14 and an outer surface 16 .
  • the veneer may incorporate a tie layer 18 positioned at its outer surface 16 .
  • a metal-polymer laminate 20 is positioned over the tie layer and consisting of a layer 22 of polymer compatible with or bondable to the outer surface of the veneer, a thin layer 24 of metallic foil, and another layer 26 of a polymer protecting the metallic foil.
  • a braid under-layer 28 is positioned over the metal-polymer laminate 20 and consisting of an elastomeric material.
  • a reinforcing braid layer 30 is then positioned over the braid under-layer 28 .
  • an outer layer 32 of an elastomeric material positioned over the reinforcing braid layer 30 .
  • the hose of this one embodiment of the present invention is manufactured in multiple steps, sequenced as provided below.
  • Step 1 First a mandrel or a solid rod or other suitable structure is provided that serves as a support through the subsequent manufacturing steps.
  • mandrels are commonly used in the manufacture of hoses made out of thermosetting materials that need to be supported during the extrusion and curing steps. They are made of a variety of thermoplastic or thermosetting materials such as copolyester ethers, copolyamides, polyolefins, TPVs, EPDMs, synthetic rubbers etc. It is desirable to ensure that the mandrel has sufficient flexibility to be spoolable in long lengths.
  • Step 2 A thermoplastic veneer is extruded over the mandrel.
  • the veneer can be in the form of a monolayer or a two layer tube depending on the type of metal foil and polymer laminate to be used in step 3 as explained below. It should not develop adhesion to the mandrel surface so that mandrel can be extracted at the end of hose fabrication. As appropriate, one of skill in the field can apply suitable release agents to the mandrel to facilitate the nonadhesive properties of the mandrel in relation to the inner layer of the veneer and lubricate its extraction at the end of hose fabrication.
  • a monolayer veneer or the inner layer of the two-layer veneer can be made of a polyamide, copolyamide, polyphthalamide, polyester or copolyester that provides chemical and thermal resistance to the contained fluid it is in contact with.
  • the laminate used in step 3 is provided with an adhesive that can bond to the surface of the veneer.
  • the laminates are those where metallic foil is laminated with a pressure sensitive adhesive (PSA) that can adhere to the surface of the veneer.
  • PSA pressure sensitive adhesive
  • Such laminates are available commercially with variety of adhesives such as acrylics, rubber, silicones etc.
  • the outer layer is made of a functionalized polymer to function as a tie layer between the inner thermoplastic veneer and the metal-polymer laminate to be provided over it.
  • a functionalized polyolefin or copolyolefin such as those made by grafting or copolymerizing functional monomers with olefins and copolyolefins.
  • functional monomers include those with acid, anhydride, acrylate, epoxy functionality.
  • the laminate used in step 3 does not need to have an adhesive surface. It is rather sufficient to have a polymeric layer at the surface that is compatible or otherwise bondable to the functionalized tie layer of the veneer.
  • Step 3 A metal foil and polymer laminate consisting of a first polymer layer compatible or bondable to the surface of the veneer, a thin metallic foil and a second polymer layer (which may be identical to or different from the first polymer layer) is then applied over the assembly prepared in step 2.
  • Adhesion can be further promoted by application of heat and/or pressure as warranted. Heating may not be necessary if the first polymer layer of the laminate is a room temperature pressure sensitive adhesive (PSA) type.
  • PSA room temperature pressure sensitive adhesive
  • the assembly of Step 2 is covered by the metal foil laminate and passed through a heated die designed to apply pressure on to the assembly to form the bonding.
  • the veneer supported by the mandrel is first passed through a heating tunnel so as to raise the surface temperature of the veneer. The metal foil laminate is then applied over the veneer, and the assembly is passed through another heated die designed to apply pressure and affect bonding.
  • the laminate is applied over the veneer lengthwise so that it circumferentially wraps around it.
  • the two edges of the foil positioned lengthwise along the tube are bonded tightly together and any excess foil is then trimmed to provide a fully covered assembly.
  • This form of wrapping is preferred over the so-called helical wrap formed by winding a tape over the veneer in a helical fashion at an angle to the axis of the hose because it results in only one seam running along the length of the hose. From barrier perspective, a seam can provide potential site for permeation leak. Hence, it is desirable to minimize it's occurrence in the construction. Lengthwise wrap described above is also easier to apply especially on a small diameter tubing such as that encountered in flexible high pressure hoses.
  • Metallic foil is thin enough to provide flexibility while resist fracture during handling.
  • it can be aluminum foil, in 1-10 micron thickness range to provide very high level of barrier while retaining flexibility. Note that this approach provides a continuous layer of metal over the tube surface unlike vapor deposition techniques which leave gaps in metal coverage resulting in inferior barrier properties.
  • the second layer of polymer over the metallic foil is selected to protect the surface of the metal foil and provide compatibility with the braid under-layer to be provided over it. It can be a polyamide, polyester or a polyolefin, and is selected so as to be compatible with the type of braid underlayer to be used in the next step.
  • Step 4 A braid underlayer is extruded over the assembly of Step 3.
  • the underlayer is an elastomeric material such as a natural or synthetic rubber or a thermoplastic elastomer such as thermoplastic olefin (TPO), thermoplastic ester elastomer (TEE) or a thermoplastic vulcanizate (such as ETPV or TPV, common selections in this field). Its purpose is to provide cushioning and protection against forces imposed during braiding.
  • TPO thermoplastic olefin
  • TEE thermoplastic ester elastomer
  • TPV thermoplastic vulcanizate
  • this braid underlayer bonds to the surface of the laminate applied in step 3. This may be accomplished by several means such as ensuring that the braid underlayer material is compatible with the surface layer of the laminate, extruding a two-layer braid underlayer such that its inner layer acts as a tie layer to bond to the surface of the laminate or sequentially extruding a tie layer over the laminate first and then the braid underlayer.
  • a functionalized polymer such as that used for forming the tie layer of the two-layer veneer of step 2 may be used for this purpose, the functionalization chosen to be compatible with the two layers to be bonded.
  • Step 5 A braided reinforcement layer is provided over the assembly of Step 4.
  • braiding can be made of metallic or polymeric filaments or high performance filaments such as Kevlar® or Nomex®, both commercially available from E.I. du Pont de Nemours and Company of Wilmington, Del.
  • Braid density is determined according to desired pressure capability and filament material selection. Multiple layers of braid and hybrid braids of multiple types of filaments are often used in practice to maximize the degree of reinforcement while optimizing the cost.
  • Step 6 An outer protective layer is extruded over the braided reinforcement layer.
  • This layer can again be made of an elastomeric material such as TPO, TEE or a thermoplastic vulcanizate (ETPV or TPV).
  • ETPV thermoplastic vulcanizate
  • Step 7 If any of the layers in the hose construction are made of a thermosetting material, then the assembly of Step 6 needs to cure. If all the layers are made of thermoplastic materials, then curing is not necessary. Note that one or more outer protective layers can be added at this time as well.
  • Step 8 Finally, the mandrel is extracted from the assembly of Step 6 or Step 7 to produce the finished hose.
  • the mandrel can be extracted by applying hydraulic pressure to one end of the hose or by mechanical means.
  • Hose made this way can be cut to desired length and fittings can be applied as desired.
  • the hose made this way provides flexibility, high pressure capability and very high barrier capability.
  • the heat transfer fluid composition comprises a compound selected from the group consisting of: R32, R152a, CF 3 I, 1234yf, 1225ye and trans-1234ze.
  • the heat transfer fluid composition comprises at least one fluoroolefin.
  • the heat transfer fluid compositions of the present invention may further comprise at least one additional component that may be a second fluoroolefin, hydrofluorocarbon (HFC), hydrocarbon, dimethyl ether, bis(trifluoromethyl)sulfide, CF 3 I, or CO 2 .
  • the heat transfer fluid composition comprises 1225ye and at least one additional compound selected from the group consisting of HFC-1234ze, HFC-1234yf, HFC-1234ye, HFC-1243zf, HFC-32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethylether, CF 3 SCF 3 , CO 2 , NH 3 , and CF 3 I.
  • the heat transfer fluid composition comprises HFC-1234ze and at least one additional compound selected from the group consisting of HFC-1234yf, HFC-1234ye, HFC-1243zf, HFC-32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethylether, CF 3 SCF 3 , CO 2 and CF 3 I.
  • the heat transfer fluid composition comprises HFC-1234yf and at least one additional compound selected from the group consisting of HFC-1234ye, HFC-1243zf, HFC-32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethylether, CF3 s CF 3 , CO 2 , NH 3 , and CF 3 I.
  • the heat transfer fluid composition comprises HFC-1243zf and at least one additional compound selected from the group consisting of HFC-1234ye, HFC-32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethylether, CF 3 SCF 3 , CO 2 and CF 3 I.
  • the heat transfer fluid composition comprises HFC-1234ye and at least one additional compound selected from the group consisting of HFC-1243zf, HFC-32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethylether, CF 3 SCF 3 , CO 2 and CF 3 I.
  • the fluoroolefin and the other components of the heat transfer fluid compositions of the present invention are listed in Table 1.
  • the fluoroolefin compounds used in the compositions of the present invention may exist as different configurational isomers or stereoisomers.
  • the present invention is intended to include all single configurational isomers, single stereoisomers or any combination or mixture thereof.
  • 1,3,3,3-tetra-fluoropropene (HFC-1234ze) is meant to represent the cis-isomer, trans-isomer, or any combination or mixture of both isomers in any ratio.
  • HFC-1225ye by which is represented the cis-isomer, trans-isomer, or any combination or mixture of both isomers in any ratio.
  • the compositions of the present invention contain primarily the cis or Z isomer of HFC-1225ye.
  • the heat transfer fluid compositions of the present invention may be generally useful when the fluoroolefin is present at about 1 weight percent to about 99 weight percent, preferably about 20 weight percent to about 99 weight percent, more preferably about 40 weight percent to about 99 weight percent and still more preferably 50 weight percent to about 99 weight percent.
  • the present invention further provides compositions as listed in Table 2.
  • compositions of the present invention listed in Table 2 are generally expected to maintain the desired properties and functionality when the components are present in the concentrations as listed +/ ⁇ 2 weight percent.
  • compositions containing CO 2 would be expected to maintain the desired properties and functionality when the CO 2 was present at the listed concentration +/ ⁇ 0.2 weight percent.
  • compositions of the present invention may be azeotropic or near-azeotropic compositions.
  • azeotropic composition is meant a constant-boiling mixture of two or more substances that behave as a single substance.
  • One way to characterize an azeotropic composition is that the vapor produced by partial evaporation or distillation of the liquid has the same composition as the liquid from which it is evaporated or distilled, i.e., the mixture distills/refluxes without compositional change.
  • Constant-boiling compositions are characterized as azeotropic because they exhibit either a maximum or minimum boiling point, as compared with that of the non-azeotropic mixture of the same compounds.
  • An azeotropic composition will not fractionate within a refrigeration or air conditioning system during operation, which may reduce efficiency of the system. Additionally, an azeotropic composition will not fractionate upon leakage from a refrigeration or air conditioning system. In the situation where one component of a mixture is flammable, fractionation during leakage could lead to a flammable composition either within the system or outside of the system.
  • a near-azeotropic composition (also commonly referred to as an “azeotrope-like composition”) is a substantially constant boiling liquid admixture of two or more substances that behaves essentially as a single substance.
  • a near-azeotropic composition is that the vapor produced by partial evaporation or distillation of the liquid has substantially the same composition as the liquid from which it was evaporated or distilled, that is, the admixture distills/refluxes without substantial composition change.
  • Another way to characterize a near-azeotropic composition is that the bubble point vapor pressure and the dew point vapor pressure of the composition at a particular temperature are substantially the same.
  • a composition is near-azeotropic if, after 50 weight percent of the composition is removed, such as by evaporation or boiling off, the difference in vapor pressure between the original composition and the composition remaining after 50 weight percent of the original composition has been removed is less than about 10 percent.
  • Azeotropic compositions of the present invention at a specified temperature are shown in Table 3.
  • ternary azeotropes composition have been found as listed in Table 4.
  • Component B (wt % A/wt % B) T (C.) HFC-1234yf HFC-32 1-57/99-43 ⁇ 25 HFC-1234yf HFC-125 1-51/99-49 ⁇ 25 HFC-1234yf HFC-134 1-99/99-1 ⁇ 25 HFC-1234yf HFC-134a 1-99/99-1 ⁇ 25 HFC-1234yf HFC-152a 1-99/99-1 ⁇ 25 HFC-1234yf HFC-161 1-99/99-1 ⁇ 25 HFC-1234yf HFC-143a 1-60/99-40 ⁇ 25 HFC-1234yf HFC-227ea 29-99/71-1 ⁇ 25 HFC-1234yf HFC-236fa 66-99/34-1 ⁇ 25 HFC-1234yf HFC-1225ye 1-99/99-1 ⁇ 25 HFC-1234yf trans-HFC-1234ze 1-99/99-1 ⁇ 25 HFC-1234yf HFC-1243zf 1-
  • compositions of the present invention are non-azeotropic compositions. Those compositions of the present invention falling within the preferred ranges of Table 2, but outside of the near-azeotropic ranges of Table 5 and Table 6 may be considered to be non-azeotropic.
  • a non-azeotropic composition may have certain advantages over azeotropic or near azeotropic mixtures.
  • a non-azeotropic composition is a mixture of two or more substances that behaves as a mixture rather than a single substance.
  • One way to characterize a non-azeotropic composition is that the vapor produced by partial evaporation or distillation of the liquid has a substantially different composition as the liquid from which it was evaporated or distilled, that is, the admixture distills/refluxes with substantial composition change.
  • Another way to characterize a non-azeotropic composition is that the bubble point vapor pressure and the dew point vapor pressure of the composition at a particular temperature are substantially different.
  • a composition is non-azeotropic if, after 50 weight percent of the composition is removed, such as by evaporation or boiling off, the difference in vapor pressure between the original composition and the composition remaining after 50 weight percent of the original composition has been removed is greater than about 10 percent.
  • compositions of the present invention may be prepared by any convenient method to combine the desired amounts of the individual components.
  • a preferred method is to weigh the desired component amounts and thereafter combine the components in an appropriate vessel. Agitation may be used, if desired.
  • An alternative means for making compositions of the present invention may be a method for making a refrigerant blend composition, wherein said refrigerant blend composition comprises a composition as disclosed herein, said method comprising (i) reclaiming a volume of one or more components of a refrigerant composition from at least one refrigerant container, (ii) removing impurities sufficiently to enable reuse of said one or more of the reclaimed components, (iii) and optionally, combining all or part of said reclaimed volume of components with at least one additional refrigerant composition or component.
  • a refrigerant container may be any container in which is stored a refrigerant blend composition that has been used in a refrigeration apparatus, air-conditioning apparatus or heat pump apparatus.
  • Said refrigerant container may be the refrigeration apparatus, air-conditioning apparatus or heat pump apparatus in which the refrigerant blend was used.
  • the refrigerant container may be a storage container for collecting reclaimed refrigerant blend components, including but not limited to pressurized gas cylinders.
  • Residual refrigerant means any amount of refrigerant blend or refrigerant blend component that may be moved out of the refrigerant container by any method known for transferring refrigerant blends or refrigerant blend components.
  • Impurities may be any component that is in the refrigerant blend or refrigerant blend component due to its use in a refrigeration apparatus, air-conditioning apparatus or heat pump apparatus.
  • Such impurities include but are not limited to refrigeration lubricants, being those described earlier herein, particulates including but not limited to metal, metal salt or elastomer particles, that may have come out of the refrigeration apparatus, air-conditioning apparatus or heat pump apparatus, and any other contaminants that may adversely effect the performance of the refrigerant blend composition.
  • Such impurities may be removed sufficiently to allow reuse of the refrigerant blend or refrigerant blend component without adversely effecting the performance or equipment within which the refrigerant blend or refrigerant blend component will be used.
  • refrigerant blend or refrigerant blend component may be necessary to provide additional refrigerant blend or refrigerant blend component to the residual refrigerant blend or refrigerant blend component in order to produce a composition that meets the specifications required for a given product. For instance, if a refrigerant blend has 3 components in a particular weight percentage range, it may be necessary to add one or more of the components in a given amount in order to restore the composition to within the specification limits.
  • the heat transfer fluid compositions of the present invention will have global warming potential (GWP) that are less than many hydrofluorocarbon refrigerants currently in use. Preferably, such compositions will also have zero or low ozone depletion potential.
  • GWP global warming potential
  • One aspect of the present invention is to provide a refrigerant with a global warming potential of less than 1000, less than 500, less than 150, less than 100, or less than 50.
  • Another aspect of the present invention is to reduce the net GWP of refrigerant mixtures by adding fluoroolefins to said mixtures.
  • compositions of the present invention may be useful as low global warming potential (GWP) replacements for currently used refrigerants, including but not limited to R134a (or HFC-134a, 1,1,1,2-tetrafluoroethane), R22 (or HCFC-22, chlorodifluoromethane), R123 (or HFC-123, 2,2-dichloro-1,1,1-trifluoroethane), R11 (CFC-11, fluorotrichloromethane), R12 (CFC-12, dichlorodifluoromethane), R245fa (or HFC-245fa, 1,1,1,3,3-pentafluoropropane), R114 (or CFC-114, 1,2-dichloro-1,1,2,2-tetrafluoroethane), R236fa (or HFC-236fa, 1,1,1,3,3,3-hexafluoropropane), R124 (or HCFC-124, 2-chloro-1,1,1,2-tetrafluor
  • compositions of the present invention may be useful as replacements for R12 (CFC-12, dichlorodifluoromethane) or R502 (ASHRAE designation for a blend of 51.2 weight percent CFC-115 (chloropentafluoroethane) and 48.8 weight percent HCFC-22).
  • compositions of the present invention may be useful as replacements for the above-mentioned refrigerants in original equipment. Additionally, the compositions of the present invention may be useful as replacements for the above mentioned refrigerants in equipment designed to use the above-mentioned refrigerants.
  • compositions of the present invention may further comprise a lubricant.
  • Lubricants of the present invention comprise refrigeration lubricants, i.e. those lubricants suitable for use with refrigeration, air-conditioning, or heat pump apparatus. Among these lubricants are those conventionally used in compression refrigeration apparatus utilizing chlorofluorocarbon refrigerants. Such lubricants and their properties are discussed in the 1990 ASHRAE Handbook, Refrigeration Systems and Applications, chapter 8, titled “Lubricants in Refrigeration Systems”, pages 8.1 through 8.21. Lubricants of the present invention may comprise those commonly known as “mineral oils” in the field of compression refrigeration lubrication. Mineral oils comprise paraffins (i.e.
  • Lubricants of the present invention further comprise those commonly known as “synthetic oils” in the field of compression refrigeration lubrication. Synthetic oils comprise alkylaryls (i.e. linear and branched alkyl alkylbenzenes), synthetic paraffins and napthenes, and poly(alphaolefins).
  • Representative conventional lubricants of the present invention are the commercially available BVM 100 N (paraffinic mineral oil sold by BVA Oils), Suniso® 3GS and Suniso® 5GS (naphthenic mineral oil sold by Crompton Co.), Sontex® 372LT (naphthenic mineral oil sold by Pennzoil), Calumet® RO-30 (naphthenic mineral oil sold by Calumet Lubricants), Zerol® 75, Zerol® 150 and Zerol® 500 (linear alkylbenzenes sold by Scheve Chemicals) and HAB 22 (branched alkylbenzene sold by Nippon Oil).
  • BVM 100 N paraffinic mineral oil sold by BVA Oils
  • Suniso® 3GS and Suniso® 5GS naphthenic mineral oil sold by Crompton Co.
  • Sontex® 372LT naphthenic mineral oil sold by Pennzoil
  • Calumet® RO-30 naphthenic mineral oil sold by Calumet Lubricants
  • Lubricants of the present invention further comprise those that have been designed for use with hydrofluorocarbon refrigerants and are miscible with refrigerants of the present invention under compression refrigeration, air-conditioning, or heat pump apparatus' operating conditions.
  • Such lubricants and their properties are discussed in “Synthetic Lubricants and High-Performance Fluids”, R. L. Shubkin, editor, Marcel Dekker, 1993.
  • Such lubricants include, but are not limited to, polyol esters (POEs) such as Castrol® 100 (Castrol, United Kingdom), polyalkylene glycols (PAGs) such as RL-488A from Dow (Dow Chemical, Midland, Mich.), and polyvinyl ethers (PVEs). These lubricants are readily available from various commercial sources.
  • Lubricants of the present invention are selected by considering a given compressor's requirements and the environment to which the lubricant will be exposed. Lubricants of the present invention preferably have a kinematic viscosity of at least about 5 cs (centistokes) at 40° C.
  • Commonly used refrigeration system additives may optionally be added, as desired, to compositions of the present invention in order to enhance lubricity and system stability.
  • These additives are generally known within the field of refrigeration compressor lubrication, and include anti wear agents, extreme pressure lubricants, corrosion and oxidation inhibitors, metal surface deactivators, free radical scavengers, foaming and antifoam control agents, leak detectants and the like.
  • these additives are present only in small amounts relative to the overall lubricant composition. They are typically used at concentrations of from less than about 0.1% to as much as about 3% of each additive. These additives are selected on the basis of the individual system requirements.
  • additives may include, but are not limited to, lubrication enhancing additives, such as alkyl or aryl esters of phosphoric acid and of thiophosphates.
  • lubrication enhancing additives such as alkyl or aryl esters of phosphoric acid and of thiophosphates.
  • the metal dialkyl dithiophosphates e.g. zinc dialkyl dithiophosphate or ZDDP, Lubrizol 1375
  • Other antiwear additives include natural product oils and assymetrical polyhydroxyl lubrication additives such as Synergol TMS (International Lubricants).
  • stabilizers such as anti oxidants, free radical scavengers, and water scavengers may be employed.
  • Compounds in this category can include, but are not limited to, butylated hydroxy toluene (BHT) and epoxides.
  • compositions of the present invention may further comprise about 0.01 weight percent to about 5 weight percent of an additive such as, for example, a stabilizer, free radical scavenger and/or antioxidant.
  • an additive such as, for example, a stabilizer, free radical scavenger and/or antioxidant.
  • additives include but are not limited to, nitromethane, hindered phenols, hydroxylamines, thiols, phosphites, or lactones. Single additives or combinations may be used.
  • compositions of the present invention may further comprise about 0.01 weight percent to about 5 weight percent of a water scavenger (drying compound).
  • a water scavenger drying compound
  • Such water scavengers may comprise ortho esters such as trimethyl-, triethyl-, or tripropylortho formate.
  • compositions of the present invention may further comprise a tracer selected from the group consisting of hydrofluorocarbons (HFCs), deuterated hydrocarbons, deuterated hydrofluorocarbons, perfluorocarbons, fluoroethers, brominated compounds, iodated compounds, alcohols, aldehydes, ketones, nitrous oxide (N 2 O) and combinations thereof.
  • HFCs hydrofluorocarbons
  • deuterated hydrocarbons deuterated hydrofluorocarbons
  • perfluorocarbons perfluorocarbons
  • fluoroethers brominated compounds
  • iodated compounds alcohols
  • aldehydes aldehydes
  • ketones nitrous oxide
  • Typical tracer compounds for use in the present compositions are listed in Table 7.
  • Single tracer compounds may be used in combination with the heat transfer fluid compositions of the present invention or multiple tracer compounds may be combined in any proportion to serve as a tracer blend.
  • the tracer blend may contain multiple tracer compounds from the same class of compounds or multiple tracer compounds from different classes of compounds.
  • a tracer blend may contain 2 or more deuterated hydrofluorocarbons, or one deuterated hydrofluorocarbon in combination with one or more perfluorocarbons.
  • the tracer compound or tracer blend may be present in the compositions at a total concentration of about 50 parts per million by weight (ppm) to about 1000 ppm.
  • the tracer compound or tracer blend is present at a total concentration of about 50 ppm to about 500 ppm and most preferably, the tracer compound or tracer blend is present at a total concentration of about 100 ppm to about 300 ppm.
  • compositions of the present invention may further comprise a compatibilizer selected from the group consisting of polyoxyalkylene glycol ethers, amides, nitriles, ketones, chlorocarbons, esters, lactones, aryl ethers, fluoroethers and 1,1,1-trifluoroalkanes.
  • the compatibilizer is used to improve solubility of hydrofluorocarbon refrigerants in conventional refrigeration lubricants.
  • Refrigeration lubricants are needed to lubricate the compressor of a refrigeration, air-conditioning or heat pump apparatus. The lubricant must move throughout the apparatus with the refrigerant in particular it must return from the non-compressor zones to the compressor to continue to function as lubricant and avoid compressor failure.
  • Hydrofluorocarbon refrigerants are generally not compatible with convention refrigeration lubricants such as mineral oils, alkylbenzenes, synthetic paraffins, synthetic napthenes and poly(alpha)olefins. Many replacement lubricants have been proposed, however, the polyalkylene glycols, polyol esters and polyvinyl ethers, suggested for use with hydrofluorocarbon refrigerants are expensive and absorb water readily. Water in a refrigeration, air-conditioning system or heat pump can lead to corrosion and the formation of particles that may plug the capillary tubes and other small orifices in the system, ultimately causing system failure. Additionally, in existing equipment, time-consuming and costly flushing procedures are required to change to a new lubricant. Therefore, it is desirable to continue to use the original lubricant if possible.
  • convention refrigeration lubricants such as mineral oils, alkylbenzenes, synthetic paraffins, synthetic napthenes and poly(alpha)olefins.
  • Many replacement lubricants have
  • the compatibilizers of the present invention improve solubility of the hydrofluorocarbon refrigerants in conventional refrigeration lubricants and thus improve oil return to the compressor.
  • Polyoxyalkylene glycol ether compatibilizers of the present invention are represented by the formula R 1 [(OR 2 ) x OR 3 ] y , wherein: x is an integer from 1-3; y is an integer from 1-4; R 1 is selected from hydrogen and aliphatic hydrocarbon radicals having 1 to 6 carbon atoms and y bonding sites; R 2 is selected from aliphatic hydrocarbylene radicals having from 2 to 4 carbon atoms; R 3 is selected from hydrogen and aliphatic and alicyclic hydrocarbon radicals having from 1 to 6 carbon atoms; at least one of R 1 and R 3 is said hydrocarbon radical; and wherein said polyoxyalkylene glycol ethers have a molecular weight of from about 100 to about 300 atomic mass units.
  • bonding sites mean radical sites available to form covalent bonds with other radicals.
  • Hydrocarbylene radicals mean divalent hydrocarbon radicals.
  • preferred polyoxyalkylene glycol ether compatibilizers are represented by R 1 [(OR 2 ) x OR 3 ] y : x is preferably 1-2; y is preferably 1; R 1 and R 3 are preferably independently selected from hydrogen and aliphatic hydrocarbon radicals having 1 to 4 carbon atoms; R 2 is preferably selected from aliphatic hydrocarbylene radicals having from 2 or 3 carbon atoms, most preferably 3 carbon atoms; the polyoxyalkylene glycol ether molecular weight is preferably from about 100 to about 250 atomic mass units, most preferably from about 125 to about 250 atomic mass units.
  • the R 1 and R 3 hydrocarbon radicals having 1 to 6 carbon atoms may be linear, branched or cyclic.
  • Representative R 1 and R 3 hydrocarbon radicals include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, and cyclohexyl.
  • free hydroxyl radicals on the present polyoxyalkylene glycol ether compatibilizers may be incompatible with certain compression refrigeration apparatus materials of construction (e.g.
  • R 1 and R 3 are preferably aliphatic hydrocarbon radicals having 1 to 4 carbon atoms, most preferably 1 carbon atom.
  • the R 2 aliphatic hydrocarbylene radicals having from 2 to 4 carbon atoms form repeating oxyalkylene radicals —(OR 2 ) x — that include oxyethylene radicals, oxypropylene radicals, and oxybutylene radicals.
  • the oxyalkylene radical comprising R 2 in one polyoxyalkylene glycol ether compatibilizer molecule may be the same, or one molecule may contain different R 2 oxyalkylene groups.
  • the present polyoxyalkylene glycol ether compatibilizers preferably comprise at least one oxypropylene radical.
  • R 1 is an aliphatic or alicyclic hydrocarbon radical having 1 to 6 carbon atoms and y bonding sites
  • the radical may be linear, branched or cyclic.
  • Representative R 1 aliphatic hydrocarbon radicals having two bonding sites include, for example, an ethylene radical, a propylene radical, a butylene radical, a pentylene radical, a hexylene radical, a cyclopentylene radical and a cyclohexylene radical.
  • R 1 aliphatic hydrocarbon radicals having three or four bonding sites include residues derived from polyalcohols, such as trimethylolpropane, glycerin, pentaerythritol, 1,2,3-trihydroxycyclohexane and 1,3,5-trihydroxycyclohexane, by removing their hydroxyl radicals.
  • Representative polyoxyalkylene glycol ether compatibilizers include but are not limited to: CH 3 OCH 2 CH(CH 3 )O(H or CH 3 ) (propylene glycol methyl (or dimethyl)ether), CH 3 O[CH 2 CH(CH 3 )O] 2 (H or CH 3 ) (dipropylene glycol methyl (or dimethyl)ether), CH 3 O[CH 2 CH(CH 3 )O] 3 (H or CH 3 ) (tripropylene glycol methyl (or dimethyl)ether), C 2 H 5 OCH 2 CH(CH 3 )O(H or C 2 H 5 ) (propylene glycol ethyl (or diethyl)ether), C 2 H 5 O[CH 2 CH(CH 3 )O] 2 (H or C 2 H 5 ) (dipropylene glycol ethyl (or diethyl)ether), C 2 H 5 O[CH 2 CH(CH 3 )O] 3 (H or C 2 H 5 ) (tripropylene glyco
  • Amide compatibilizers of the present invention comprise those represented by the formulae R 1 C(O)NR 2 R 3 and cyclo-[R 4 C(O)N(R 5 )], wherein R 1 , R 2 , R 3 and R 5 are independently selected from aliphatic and alicyclic hydrocarbon radicals having from 1 to 12 carbon atoms; R 4 is selected from aliphatic hydrocarbylene radicals having from 3 to 12 carbon atoms; and wherein said amides have a molecular weight of from about 100 to about 300 atomic mass units. The molecular weight of said amides is preferably from about 160 to about 250 atomic mass units.
  • R 1 , R 2 , R 3 and R 5 may optionally include substituted hydrocarbon radicals, that is, radicals containing non-hydrocarbon substituents selected from halogens (e.g., fluorine, chlorine) and alkoxides (e.g. methoxy).
  • R 1 , R 2 , R 3 and R 5 may optionally include heteroatom-substituted hydrocarbon radicals, that is, radicals, which contain the atoms nitrogen (aza-), oxygen (oxa-) or sulfur (thia-) in a radical chain otherwise composed of carbon atoms.
  • amide compatibilizers consist of carbon, hydrogen, nitrogen and oxygen.
  • R 1 , R 2 , R 3 and R 5 aliphatic and alicyclic hydrocarbon radicals include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and their configurational isomers.
  • a preferred embodiment of amide compatibilizers are those wherein R 4 in the aforementioned formula cyclo-[R 4 C(O)N(R 5 )—] may be represented by the hydrocarbylene radical (CR 6 R 7 ) n , in other words, the formula: cyclo-[(CR 6 R 7 ) n C(O)N(R 5 )—] wherein: the previously-stated values for molecular weight apply; n is an integer from 3 to 5; R 5 is a saturated hydrocarbon radical containing 1 to 12 carbon atoms; R 6 and R 7 are independently selected (for each n) by the rules previously offered defining R 1-3 .
  • R 6 and R 7 are preferably hydrogen, or contain a single saturated hydrocarbon radical among the n methylene units, and R 5 is a saturated hydrocarbon radical containing 3 to 12 carbon atoms.
  • R 5 is a saturated hydrocarbon radical containing 3 to 12 carbon atoms.
  • amide compatibilizers include but are not limited to: 1-octyl pyrrolidin-2-one, 1-decylpyrrolidin-2-one, 1-octyl-5-methylpyrrolidin-2-one, 1-butylcaprolactam, 1-cyclohexylpyrrolidin-2-one, 1-butyl-5-methylpiperid-2-one, 1-pentyl-5-methylpiperid-2-one, 1-hexylcaprolactam, 1-hexyl-5-methylpyrrolidin-2-one, 5-methyl-1-pentylpiperid-2-one, 1,3-dimethylpiperid-2-one, 1-methylcaprolactam, 1-butyl-pyrrolidin-2-one, 1,5-dimethylpiperid-2-one, 1-decyl-5-methylpyrrolidin-2-one, 1-dodecylpyrrolid-2-one, N,N-dibutylformamide and N,N-diisopropylacetamide.
  • Ketone compatibilizers of the present invention comprise ketones represented by the formula R 1 C(O)R 2 , wherein R 1 and R 2 are independently selected from aliphatic, alicyclic and aryl hydrocarbon radicals having from 1 to 12 carbon atoms, and wherein said ketones have a molecular weight of from about 70 to about 300 atomic mass units.
  • R 1 and R 2 in said ketones are preferably independently selected from aliphatic and alicyclic hydrocarbon radicals having 1 to 9 carbon atoms.
  • the molecular weight of said ketones is preferably from about 100 to 200 atomic mass units.
  • R 1 and R 2 may together form a hydrocarbylene radical connected and forming a five, six, or seven-membered ring cyclic ketone, for example, cyclopentanone, cyclohexanone, and cycloheptanone.
  • R 1 and R 2 may optionally include substituted hydrocarbon radicals, that is, radicals containing non-hydrocarbon substituents selected from halogens (e.g., fluorine, chlorine) and alkoxides (e.g. methoxy).
  • R 1 and R 2 may optionally include heteroatom-substituted hydrocarbon radicals, that is, radicals, which contain the atoms nitrogen (aza-), oxygen (keto-, oxa-) or sulfur (thia-) in a radical chain otherwise composed of carbon atoms.
  • heteroatom-substituted hydrocarbon radicals that is, radicals, which contain the atoms nitrogen (aza-), oxygen (keto-, oxa-) or sulfur (thia-) in a radical chain otherwise composed of carbon atoms.
  • no more than three non-hydrocarbon substituents and heteroatoms, and preferably no more than one, will be present for each 10 carbon atoms in R 1 and R 2 , and the presence of any such non-hydrocarbon substituents and heteroatoms must be considered in applying the aforementioned molecular weight limitations.
  • R 1 and R 2 aliphatic, alicyclic and aryl hydrocarbon radicals in the general formula R 1 C(O)R 2 include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and their configurational isomers, as well as phenyl, benzyl, cumenyl, mesityl, tolyl, xylyl and phenethyl.
  • ketone compatibilizers include but are not limited to: 2-butanone, 2-pentanone, acetophenone, butyrophenone, hexanophenone, cyclohexanone, cycloheptanone, 2-heptanone, 3-heptanone, 5-methyl-2-hexanone, 2-octanone, 3-octanone, diisobutyl ketone, 4-ethylcyclohexanone, 2-nonanone, 5-nonanone, 2-decanone, 4-decanone, 2-decalone, 2-tridecanone, dihexyl ketone and dicyclohexyl ketone.
  • Nitrile compatibilizers of the present invention comprise nitriles represented by the formula R 1 CN, wherein R 1 is selected from aliphatic, alicyclic or aryl hydrocarbon radicals having from 5 to 12 carbon atoms, and wherein said nitriles have a molecular weight of from about 90 to about 200 atomic mass units.
  • R 1 in said nitrile compatibilizers is preferably selected from aliphatic and alicyclic hydrocarbon radicals having 8 to 10 carbon atoms.
  • the molecular weight of said nitrile compatibilizers is preferably from about 120 to about 140 atomic mass units.
  • R 1 may optionally include substituted hydrocarbon radicals, that is, radicals containing non-hydrocarbon substituents selected from halogens (e.g., fluorine, chlorine) and alkoxides (e.g. methoxy).
  • R 1 may optionally include heteroatom-substituted hydrocarbon radicals, that is, radicals, which contain the atoms nitrogen (aza-), oxygen (keto-, oxa-) or sulfur (thia-) in a radical chain otherwise composed of carbon atoms.
  • R 1 aliphatic, alicyclic and aryl hydrocarbon radicals in the general formula R 1 CN include pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and their configurational isomers, as well as phenyl, benzyl, cumenyl, mesityl, tolyl, xylyl and phenethyl.
  • nitrile compatibilizers include but are not limited to: 1-cyanopentane, 2,2-dimethyl-4-cyanopentane, 1-cyanohexane, 1-cyanoheptane, 1-cyanooctane, 2-cyanooctane, 1-cyanononane, 1-cyanodecane, 2-cyanodecane, 1-cyanoundecane and 1-cyanododecane.
  • Chlorocarbon compatibilizers of the present invention comprise chlorocarbons represented by the formula RCl x , wherein; x is selected from the integers 1 or 2; R is selected from aliphatic and alicyclic hydrocarbon radicals having 1 to 12 carbon atoms; and wherein said chlorocarbons have a molecular weight of from about 100 to about 200 atomic mass units.
  • the molecular weight of said chlorocarbon compatibilizers is preferably from about 120 to 150 atomic mass units.
  • R aliphatic and alicyclic hydrocarbon radicals in the general formula RCl x include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and their configurational isomers.
  • Representative chlorocarbon compatibilizers include but are not limited to: 3-(chloromethyl)pentane, 3-chloro-3-methylpentane, 1-chlorohexane, 1,6-dichlorohexane, 1-chloroheptane, 1-chlorooctane, 1-chlorononane, 1-chlorodecane, and 1,1,1-trichlorodecane.
  • Ester compatibilizers of the present invention comprise esters represented by the general formula R 1 CO 2 R 2 , wherein R 1 and R 2 are independently selected from linear and cyclic, saturated and unsaturated, alkyl and aryl radicals.
  • Preferred esters consist essentially of the elements C, H and O, have a molecular weight of from about 80 to about 550 atomic mass units.
  • esters include but are not limited to: (CH 3 ) 2 CHCH 2 OOC(CH 2 ) 2-4 OCOCH 2 CH(CH 3 ) 2 (diisobutyl dibasic ester), ethyl hexanoate, ethyl heptanoate, n-butyl propionate, n-propyl propionate, ethyl benzoate, di-n-propyl phthalate, benzoic acid ethoxyethyl ester, dipropyl carbonate, “Exxate 700” (a commercial C 7 alkyl acetate), “Exxate 800” (a commercial C 8 alkyl acetate), dibutyl phthalate, and tert-butyl acetate.
  • Lactone compatibilizers of the present invention comprise lactones represented by structures [A], [B], and [C]:
  • lactones contain the functional group —CO 2 — in a ring of six (A), or preferably five atoms (B), wherein for structures [A] and [B], R 1 through R 8 are independently selected from hydrogen or linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl radicals. Each R 1 though R 8 may be connected forming a ring with another R 1 through R 8 .
  • the lactone may have an exocyclic alkylidene group as in structure [C], wherein R 1 through R 6 are independently selected from hydrogen or linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl radicals. Each R 1 though R 6 may be connected forming a ring with another R 1 through R 6 .
  • the lactone compatibilizers have a molecular weight range of from about 100 to about 300 atomic mass units, preferred from about 100 to about 200 atomic mass units.
  • lactone compatibilizers include but are not limited to the compounds listed in Table 8.
  • Lactone compatibilizers generally have a kinematic viscosity of less than about 7 centistokes at 40° C. For instance, gamma-undecalactone has kinematic viscosity of 5.4 centistokes and cis-(3-hexyl-5-methyl)dihydrofuran-2-one has viscosity of 4.5 centistokes both at 40° C. Lactone compatibilizers may be available commercially or prepared by methods as described in U.S. patent application Ser. No. 10/910,495 filed Aug. 3, 2004, incorporated herein by reference.
  • Aryl ether compatibilizers of the present invention further comprise aryl ethers represented by the formula R 1 OR 2 , wherein: R 1 is selected from aryl hydrocarbon radicals having from 6 to 12 carbon atoms; R 2 is selected from aliphatic hydrocarbon radicals having from 1 to 4 carbon atoms; and wherein said aryl ethers have a molecular weight of from about 100 to about 150 atomic mass units.
  • R 1 aryl radicals in the general formula R 1 OR 2 include phenyl, biphenyl, cumenyl, mesityl, tolyl, xylyl, naphthyl and pyridyl.
  • R 2 aliphatic hydrocarbon radicals in the general formula R 1 OR 2 include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl.
  • Representative aromatic ether compatibilizers include but are not limited to: methyl phenyl ether (anisole), 1,3-dimethyoxybenzene, ethyl phenyl ether and butyl phenyl ether.
  • Fluoroether compatibilizers of the present invention comprise those represented by the general formula R 1 OCF 2 CF 2 H, wherein R 1 is selected from aliphatic, alicyclic, and aromatic hydrocarbon radicals having from about 5 to about 15 carbon atoms, preferably primary, linear, saturated, alkyl radicals.
  • Representative fluoroether compatibilizers include but are not limited to: C 8 H 17 OCF 2 CF 2 H and C 6 H 13 OCF 2 CF 2 H. It should be noted that if the refrigerant is a fluoroether, then the compatibilizer may not be the same fluoroether.
  • Fluoroether compatibilizers may further comprise ethers derived from fluoroolefins and polyols.
  • the fluoroolefins may be of the type CF 2 ⁇ CXY, wherein X is hydrogen, chlorine or fluorine, and Y is chlorine, fluorine, CF 3 or OR f , wherein R f is CF 3 , C 2 F 5 , or C 3 F 7 .
  • Representative fluoroolefins are tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, and perfluoromethylvinyl ether.
  • the polyols may be linear or branched.
  • Linear polyols may be of the type HOCH 2 (CHOH) x (CRR′) y CH 2 OH, wherein R and R′ are hydrogen, or CH 3 , or C 2 H 5 and wherein x is an integer from 0-4, and y is an integer from 0-4.
  • Representative polyols are trimethylol propane, pentaerythritol, butanediol, and ethylene glycol.
  • 1,1,1-trifluoroalkane compatibilizers of the present invention comprise 1,1,1-trifluoroalkanes represented by the general formula CF 3 R 1 , wherein R 1 is selected from aliphatic and alicyclic hydrocarbon radicals having from about 5 to about 15 carbon atoms, preferably primary, linear, saturated, alkyl radicals.
  • Representative 1,1,1-trifluoroalkane compatibilizers include but are not limited to: 1,1,1-trifluorohexane and 1,1,1-trifluorododecane.
  • effective amount of compatibilizer is meant that amount of compatibilizer that leads to efficient solubilizing of the lubricant in the composition and thus provides adequate oil return to optimize operation of the refrigeration, air-conditioning or heat pump apparatus.
  • compositions of the present invention will typically contain from 0.1 to about 40 weight percent, preferably from about 0.2 to about 20 weight percent, and most preferably from about 0.3 to about 10 weight percent compatibilizer in the compositions of the present invention.
  • the heat transfer fluid of the present invention may be solubilized in a refrigeration lubricant selected from the group consisting of mineral oils, alkylbenzenes, synthetic paraffins, synthetic napthenes, and poly(alpha)olefins, wherein said method comprises contacting said lubricant with said composition in the presence of an effective amount of a compatibilizer, wherein said compatibilizer is selected from the group consisting of polyoxyalkylene glycol ethers, amides, nitriles, ketones, chlorocarbons, esters, lactones, aryl ethers, fluoroethers and 1,1,1-trifluoroalkanes.
  • a refrigeration lubricant selected from the group consisting of mineral oils, alkylbenzenes, synthetic paraffins, synthetic napthenes, and poly(alpha)olefins
  • said method comprises contacting said lubricant with said composition in the presence of an effective amount of a compatibilizer, wherein said compatibilizer is selected from the group consisting of
  • compositions of the present invention may further comprise an ultra-violet (UV) dye and optionally a solubilizing agent.
  • UV dye is a useful component for detecting leaks of the composition by permitting one to observe the fluorescence of the dye in the composition at a leak point or in the vicinity of refrigeration, air-conditioning, or heat pump apparatus. One may observe the fluoroscence of the dye under an ultra-violet light. Solubilizing agents may be needed due to poor solubility of such UV dyes in some compositions.
  • ultra-violet dye is meant a UV fluorescent composition that absorbs light in the ultra-violet or “near” ultra-violet region of the electromagnetic spectrum.
  • the fluorescence produced by the UV fluorescent dye under illumination by a UV light that emits radiation with wavelength anywhere from 10 nanometer to 750 nanometer may be detected. Therefore, if a composition containing such a UV fluorescent dye is leaking from a given point in a refrigeration, air-conditioning, or heat pump apparatus, the fluorescence can be detected at the leak point.
  • UV fluorescent dyes include but are not limited to naphthalimides, perylenes, coumarins, anthracenes, phenanthracenes, xanthenes, thioxanthenes, naphthoxanthenes, fluoresceins, and derivatives or combinations thereof.
  • Solubilizing agents of the present invention comprise at least one compound selected from the group consisting of hydrocarbons, hydrocarbon ethers, dimethylether, polyoxyalkylene glycol ethers, amides, nitriles, ketones, chlorocarbons, esters, lactones, aryl ethers, fluoroethers and 1,1,1-trifluoroalkanes.
  • the polyoxyalkylene glycol ethers, amides, nitriles, ketones, chlorocarbons, esters, lactones, aryl ethers, fluoroethers and 1,1,1-trifluoroalkanes solubilizing agents have been defined previously herein as being compatibilizers for use with conventional refrigeration lubricants.
  • Hydrocarbon solubilizing agents of the present invention comprise hydrocarbons including straight chained, branched chain or cyclic alkanes or alkenes containing 5 or fewer carbon atoms and only hydrogen with no other functional groups.
  • Representative hydrocarbon solubilizing agents comprise propane, propylene, cyclopropane, n-butane, isobutane, 2-methylbutane and n-pentane. It should be noted that if the composition contains a hydrocarbon, then the solubilizing agent may not be the same hydrocarbon.
  • Hydrocarbon ether solubilizing agents of the present invention comprise ethers containing only carbon, hydrogen and oxygen, such as dimethyl ether (DME).
  • DME dimethyl ether
  • Solubilizing agents of the present invention may be present as a single compound, or may be present as a mixture of more than one solubilizing agent. Mixtures of solubilizing agents may contain two solubilizing agents from the same class of compounds, say two lactones, or two solubilizing agents from two different classes, such as a lactone and a polyoxyalkylene glycol ether.
  • compositions comprising refrigerant and UV fluorescent dye, or comprising heat transfer fluid and UV fluorescent dye, from about 0.001 weight percent to about 1.0 weight percent of the composition is UV dye, preferably from about 0.005 weight percent to about 0.5 weight percent, and most preferably from 0.01 weight percent to about 0.25 weight percent.
  • Solubilizing agents such as ketones may have an objectionable odor, which can be masked by addition of an odor masking agent or fragrance.
  • odor masking agents or fragrances may include Evergreen, Fresh Lemon, Cherry, Cinnamon, Peppermint, Floral or Orange Peel all commercially available, as well as d-limonene and pinene.
  • Such odor masking agents may be used at concentrations of from about 0.001% to as much as about 15% by weight based on the combined weight of odor masking agent and solubilizing agent.
  • the UV fluorescent dye could be dissolved in the refrigerant itself thereby not requiring any specialized method for introduction to the refrigeration, air conditioning apparatus, or heat pump.
  • the present invention relates to compositions including UV fluorescent dye, which may be introduced into the system as a solution in the refrigerant.
  • the inventive compositions will allow the storage and transport of dye-containing compositions even at low temperatures while maintaining the dye in solution.
  • compositions comprising refrigerant, UV fluorescent dye and solubilizing agent, or comprising heat transfer fluid and UV fluorescent dye and solubilizing agent, from about 1 to about 50 weight percent, preferably from about 2 to about 25 weight percent, and most preferably from about 5 to about 15 weight percent of the combined composition is solubilizing agent.
  • the UV fluorescent dye is present in a concentration from about 0.001 weight percent to about 1.0 weight percent, preferably from 0.005 weight percent to about 0.5 weight percent, and most preferably from 0.01 weight percent to about 0.25 weight percent.
  • a hose is constructed according to one embodiment of the invention in the following manner.
  • a mandrel is first made in the form of a solid rod with a diameter of 6.4 mm.
  • a veneer consisting of an inner layer of 0.65 mm thick Zytel® 42 (a high MWA 66 commercially available from E.I. du Pont de Nemours and Company) and 0.1 mm thick outer tie layer of Bynel® 4206 (a maleic anhydride grafted polyethylene commercially available from E.I. du Pont de Nemours and Company) is extruded over the mandrel.
  • the assembly is then laminated with a metal-polymer laminate available as BFW 46 and obtained from James Dawson Enterprises Ltd of Lachine, Quebec, Canada.
  • the laminate consists of an inner layer of low density polyethylene, a tie layer of EEA, an aluminum foil (10 micron thick) and an outer layer of polyethylene terephthalate (PET) with a total thickness of 0.1 mm.
  • Lamination is carried out using a heated die with a passage way of appropriate size to pass the assembly through.
  • the assembly of the previous step is uncoiled from a spool and a strip of metal-polymer laminate is wrapped around it such that two long edges of the strip mat against each other.
  • the assembly is passed through the die heated to 140 C to affect the bonding. Excess laminate edge is trimmed off carefully so as not to damage the seal and avoid exposing underlying layer.
  • a layer of TPV is extruded over the assembly. Following that, a braid of PET filaments is applied, and outer protective layer of ETPV is extruded over the top. The mandrel is subsequently extracted to prepare the multi-layer hose.
  • results show hoses permeation for fluoroolefin compositions are at least equivalent to R134a. Since R32 is a small molecule, it contributes the most to hose permeation. The composition containing primarily fluoroolefins and a small amount of R134a had significantly lower permeation than R134a alone indicating, indicating fluoroolefins have overall lower permeation rates.

Abstract

The present invention relates to the use of flexible hoses capable of handling high pressure fluids and providing a barrier against permeation loss in air conditioning and refrigeration systems. Such hoses are particularly suitable in air conditioning and refrigeration in which new, low global warming potential refrigerant alternatives are used.

Description

    BACKGROUND OF THE INVENTION
  • 1. Field of the Invention
  • The present invention relates to the use of flexible hoses capable of handling high pressure fluids and providing a barrier against permeation loss in air conditioning and refrigeration systems. More particularly, the present invention relates to the use of such hoses in air conditioning and refrigeration systems, including mobile air conditioning systems, in which new, low global warming potential (GWP) refrigerant alternatives are used.
  • 2. Description of Related Art
  • The refrigeration industry has been working for the past few decades to find replacement refrigerants for the ozone depleting chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) being phased out as a result of the Montreal Protocol. The solution for most refrigerant producers has been the commercialization of hydrofluorocarbon (HFC) refrigerants. The new HFC refrigerants, HFC-134a being the most widely used at this time, have zero ozone depletion potential and thus are not affected by the current regulatory phase out as a result of the Montreal Protocol.
  • Further environmental regulations may ultimately cause global phase out of certain HFC refrigerants. Currently, the automobile industry is facing regulations relating to global warming potential (GWP) for refrigerants used in mobile air-conditioning. Therefore, there is a great current need to identify new refrigerants with reduced global warming potential for the automobile air-conditioning market. Should the regulations be more broadly applied in the future, an even greater need will be felt for refrigerants that can be used in all areas of the refrigeration and air-conditioning industry.
  • Currently proposed replacement refrigerants for HFC-134a include HFC-152a, pure hydrocarbons such as butane or propane, or “natural” refrigerants such as CO2 or ammonia. Many of these suggested replacements are toxic, flammable, and/or have low energy efficiency. Therefore, new alternatives are constantly being sought.
  • As is widely understood by those having skill in the field, in a typical refrigeration or air conditioning system heat transfer fluids are circulated within a closed loop including a compressor, a condenser and an evaporator. Hoses are typically connected between the outlet of the compressor and the inlet of the condenser; between the outlet of the condenser and the inlet of the evaporator; and between the outlet of the evaporator and the inlet of the compressor. Such hoses must be able to withstand the high pressure of the fluids which are circulated through such systems.
  • Hoses used for these purposes need to be flexible for ease of installation and use, and often must be shaped into curves and bends for connecting components already installed into fixed positions. They must also be able to contain the fluid pressure. These hoses are often made of elastomeric materials such as natural or synthetic rubber or thermoplastic elastomers, and are typically reinforced with braiding to impart high pressure capability.
  • Moreover, it is essential that the hoses of such systems offer superior barrier resistance to permeation of the contained fluid through the wall of the hose construction. In addition, the hose wall must provide high barrier resistance to ingression of external fluids, such as air or moisture, into the contained fluid.
  • In order to meet barrier requirements, hoses are often provided with a suitable thermoplastic barrier layer on the inside. A typical high pressure barrier hose may thus consist of multiple layers—an inner thermoplastic barrier layer made of a polyamide, a polyester or a suitable thermoplastic material; an over-layer of an elastomeric material to provide flexibility; and a braid layer over the elastomeric layer to provide pressure capability and an outer protective cover layer of an elastomeric material.
  • Attempts to make flexible high pressure high barrier hoses often involve first making a corrugated metallic tube and coating the tube with an elastomeric polymer. Such constructions, however, require complex manufacturing processes, and are expensive for large scale uses. U.S. Pat. No. 7,055,553 describes a fluid transfer hose incorporating a metal barrier layer. The metal barrier layer is bonded using techniques that require use of aggressive chemicals. Also, expensive fluoropolymer layers are incorporated in the hose construction.
  • Moreover, while such hoses provide pressure capability and flexibility, their barrier properties can be improved. With the drive for reduced emissions, this becomes an issue in highly demanding applications such as refrigeration and air conditioning. As low GWP refrigerants are developed it is important to identify barrier hoses which are suitable for these refrigerants.
  • It would be desirable to provide a flexible hose for air conditioning or refrigeration systems which is suitable for use with new, high-pressure, low GWP refrigerants. Ideally, such a hose would not require the use of aggressive chemicals, would be economical to make, and would meet stringent barrier requirements.
    • BRIEF SUMMARY OF THE INVENTION
  • The present invention relates to transporting a heat transfer fluid within a refrigeration or air conditioning system through a hose, where the hose is able to withstand high-pressure refrigerants, and the hose has improved barrier properties. A further advantage of such hose is its simple and straightforward construction. In a particular embodiment, such hose is especially suitable for use with fluoroolefin compositions which are low GWP refrigerant alternatives. These and other objects, features and advantages of the present invention will become better understood upon having reference to the description of the invention herein.
  • Therefore, in accordance with the present invention, there is provided a method of providing transport of a heat transfer fluid composition within a refrigeration or air conditioning system, comprising circulating the heat transfer fluid through one or more hoses of said system, wherein said heat transfer fluid comprises a compound selected from the group consisting of: R32, R152a, CF3I, 1234yf, 1225ye and trans-1234ze.
  • In a particular embodiment, the composition comprises 1225ye and at least one additional compound selected from the group consisting of HFC-1234ze, HFC-1234yf, HFC-1234ye, HFC-1243zf, HFC-32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethylether, CF3SCF3, CO2, NH3, and CF3I.
  • In another particular embodiment, the composition comprises HFC-1234ze and at least one additional compound selected from the group consisting of HFC-1234yf, HFC-1234ye, HFC-1243zf, HFC-32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethylether, CF3SCF3, CO2 and CF3I.
  • In another particular embodiment, the composition comprises HFC-1234yf and at least one additional compound selected from the group consisting of HFC-1234ye, HFC-1243zf, HFC-32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethylether, CF3SCF3, CO2, NH3, and CF3I.
  • In another particular embodiment, the composition comprises HFC-1243zf and at least one additional compound selected from the group consisting of HFC-1234ye, HFC-32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethylether, CF3SCF3, CO2 and CF3I.
  • In another particular embodiment, the composition comprises HFC-1234ye and at least one additional compound selected from the group consisting of HFC-1243zf, HFC-32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethylether, CF3SCF3, CO2 and CF3I.
  • In one particular embodiment of a hose configuration, the hose comprises an outer layer comprising a material selected from the group consisting of an elastomer and a polyamide and an inner layer comprising a material selected from the group consisting of an elastomer, a polyamide and a thermoplastic. The hose may further include (a) a tie layer positioned over said inner layer; (b) a metal-polymer laminate positioned over said tie layer and consisting of a layer of polymer compatible with or bondable to said outer surface of said veneer, a thin layer of metallic foil, and another layer of a polymer protecting the metallic foil; (c) a braid under-layer positioned over said metal-polymer laminate and consisting of an elastomeric material; and (d) a reinforcing braid layer positioned over said braid under-layer, wherein the outer layer is positioned on the outside of the reinforcing braid layer.
    • BRIEF DESCRIPTION OF THE DRAWINGS
  • The present invention may be better understood with reference to the following figure, wherein:
  • FIG. 1 is a schematic diagram of a refrigeration or air conditioning system including a plurality of hoses according to the present invention.
  • FIG. 2 is a cross-sectional view of a hose of the present invention.
    •  DETAILED DESCRIPTION OF THE INVENTION
  • According to the present invention, there is provided a refrigeration or air-conditioning system. Such a system, which is a vapor compression system, is shown in FIG. 1. A vapor-compression system is a closed loop system which re-uses refrigerant in multiple steps producing a cooling effect in one step and a heating effect in a different step. Such a system generally includes an evaporator, a compressor, a condenser and an expansion device, as will be described below in detail with respect to FIG. 1. With reference to FIG. 1, gaseous refrigerant from an evaporator (42) flows through a hose (63) to the inlet of a compressor (12), and is then discharged. Various types of compressors may be used with the present invention, including reciprocating, rotary, jet, centrifugal, scroll, screw or axial-flow, depending on the mechanical means to compress the fluid, or as positive-displacement (e.g., reciprocating, scroll or screw) or dynamic (e.g., centrifugal or jet).
  • The compressed refrigerant gas from the compressor flows through the compressor outlet and through a hose (61) to a condenser (41). A pressure regulating valve (51) in hose (61) may be used. This valve allows recycle of the refrigerant flow back to the compressor via a hose (63), thereby providing the ability to control the pressure of the refrigerant reaching the condenser (41) and if necessary to prevent compressor surge. The compressed refrigerant is condensed in the condenser, thus giving off heat. The liquid refrigerant flows through an expansion device (52) via a hose (62) to the evaporator (42), which is located in the passenger compartment. In the evaporator, the liquid refrigerant is vaporized, providing cooling and the cycle then repeats. The expansion device (52) may be an expansion valve, a capillary tube or an orifice tube.
  • The closed loop, vapor compression system of the present invention may be used in either stationary or mobile refrigeration or air-conditioning applications. Stationary refrigeration apparatus or stationary air-conditioning apparatus refer to the equipment used for cooling the air in a building, or cooling perishable goods such as foods, pharmaceutical materials, etc, in a conventional, non-mobile, non-vehicle mounted system. These systems may include chillers, ducted and ductless air conditioners and heat pumps, domestic refrigerators and freezers, commercial refrigerators and freezers, supermarket and industrial refrigeration systems.
  • Such stationary refrigeration or air conditioning systems may be associated with CHP (Combined Heat and Power) systems, wherein a stationary internal combustion engine is used to drive an electrical generator. The waste heat produced by the engine may be recovered and used to perform work, by such means as a Rankine Cycle (steam engine) or Organic Rankine cycle (ORC). In a Rankine cycle, the heat is used to vaporize a liquid (an organic liquid in the case of an ORC), which in turn drives a turbine. The mechanical energy of the turbine may be used to drive an electricity generator, which runs a refrigeration or air-conditioning system.
  • Mobile refrigeration apparatus or mobile air-conditioning apparatus refers to any refrigeration or air-conditioning apparatus incorporated into a mobile transportation unit for the road, rail, sea or air. In addition, apparatus, which are meant to provide refrigeration or air-conditioning for a system independent of any moving carrier, known as “intermodal” systems, are included in the present invention. Such intermodal systems include “containers” (combined sea/land transport) as well as “swap bodies” (combined road and rail transport). The present invention is particularly useful for road transport refrigerating or air-conditioning apparatus, such as automobile air-conditioning apparatus or refrigerated road transport equipment.
  • A body to be cooled may be any space, location or object requiring refrigeration or air-conditioning. In stationary applications the body may be the interior of a structure, i.e. residential or commercial, or a storage location for perishables, such as food or pharmaceuticals. Numerous mobile systems are described earlier in defining mobile refrigeration apparatus and mobile air-conditioning apparatus.
  • The refrigeration apparatus or air-conditioning apparatus of the present invention may additionally employ fin and tube heat exchangers, microchannel heat exchangers and vertical or horizontal single pass tube or plate type heat exchangers in the evaporator and/or the condenser.
  • In accordance with the present invention, there is provided a method of providing transport of a heat transfer fluid within a refrigeration or air conditioning system, comprising circulating a heat transfer fluid composition through one or more hoses of said system. In one embodiment of the present invention, the hose may comprise an outer layer comprising a material selected from the group consisting of an elastomer and a polyamide. The hose may further comprise an inner layer comprising a material selected from the group consisting of an elastomer, a polyamide and a thermoplastic. In particular, the inner layer may comprise a thermoplastic veneer, and the outer layer may comprise an elastomer.
  • In a particular configuration of the present invention, hoses are constructed in multiple layers such as described below from the innermost to the outermost surface, including:
      • an layer of a thermoplastic veneer;
      • a tie layer;
      • a metal-polymer laminate consisting of a layer of polymer compatible with the tie layer, a thin layer of metallic foil, and another layer of a polymer protecting the metallic foil;
      • a braid under-layer of a thermoplastic or thermosetting elastomer;
      • a braid layer providing reinforcement; and
      • an outer layer of an elastomeric material.
  • Reference is made to FIG. 2, in which this embodiment is shown. In FIG. 2, there is shown generally at 10 each of the layers of the invention, numbered and described from the innermost layer to the outermost layer. Hence, there is first depicted closest to the core (where the mandrel is inserted and then later withdrawn) an innermost layer of a thermoplastic veneer 12 having an inner surface 14 and an outer surface 16. The veneer may incorporate a tie layer 18 positioned at its outer surface 16. A metal-polymer laminate 20 is positioned over the tie layer and consisting of a layer 22 of polymer compatible with or bondable to the outer surface of the veneer, a thin layer 24 of metallic foil, and another layer 26 of a polymer protecting the metallic foil. Thereafter, a braid under-layer 28 is positioned over the metal-polymer laminate 20 and consisting of an elastomeric material. A reinforcing braid layer 30 is then positioned over the braid under-layer 28. Finally, an outer layer 32 of an elastomeric material positioned over the reinforcing braid layer 30.
  • The hose of this one embodiment of the present invention is manufactured in multiple steps, sequenced as provided below.
  • Step 1—First a mandrel or a solid rod or other suitable structure is provided that serves as a support through the subsequent manufacturing steps. Such mandrels are commonly used in the manufacture of hoses made out of thermosetting materials that need to be supported during the extrusion and curing steps. They are made of a variety of thermoplastic or thermosetting materials such as copolyester ethers, copolyamides, polyolefins, TPVs, EPDMs, synthetic rubbers etc. It is desirable to ensure that the mandrel has sufficient flexibility to be spoolable in long lengths.
  • Step 2—A thermoplastic veneer is extruded over the mandrel. The veneer can be in the form of a monolayer or a two layer tube depending on the type of metal foil and polymer laminate to be used in step 3 as explained below. It should not develop adhesion to the mandrel surface so that mandrel can be extracted at the end of hose fabrication. As appropriate, one of skill in the field can apply suitable release agents to the mandrel to facilitate the nonadhesive properties of the mandrel in relation to the inner layer of the veneer and lubricate its extraction at the end of hose fabrication.
  • A monolayer veneer or the inner layer of the two-layer veneer can be made of a polyamide, copolyamide, polyphthalamide, polyester or copolyester that provides chemical and thermal resistance to the contained fluid it is in contact with.
  • When a monolayer veneer is used, the laminate used in step 3 is provided with an adhesive that can bond to the surface of the veneer. Examples of such laminates are those where metallic foil is laminated with a pressure sensitive adhesive (PSA) that can adhere to the surface of the veneer. Such laminates are available commercially with variety of adhesives such as acrylics, rubber, silicones etc.
  • In a two-layer veneer construction, the outer layer is made of a functionalized polymer to function as a tie layer between the inner thermoplastic veneer and the metal-polymer laminate to be provided over it. It can be made of a functionalized polyolefin or copolyolefin such as those made by grafting or copolymerizing functional monomers with olefins and copolyolefins. Some examples of functional monomers include those with acid, anhydride, acrylate, epoxy functionality.
  • When a two-layer veneer is used, the laminate used in step 3 does not need to have an adhesive surface. It is rather sufficient to have a polymeric layer at the surface that is compatible or otherwise bondable to the functionalized tie layer of the veneer.
  • Step 3—A metal foil and polymer laminate consisting of a first polymer layer compatible or bondable to the surface of the veneer, a thin metallic foil and a second polymer layer (which may be identical to or different from the first polymer layer) is then applied over the assembly prepared in step 2.
  • Adhesion can be further promoted by application of heat and/or pressure as warranted. Heating may not be necessary if the first polymer layer of the laminate is a room temperature pressure sensitive adhesive (PSA) type. When a two-layer veneer is used along with a functionalized polyolefin as the tie layer, application of both heat and pressure are needed. In one embodiment, the assembly of Step 2 is covered by the metal foil laminate and passed through a heated die designed to apply pressure on to the assembly to form the bonding. In another embodiment, the veneer supported by the mandrel is first passed through a heating tunnel so as to raise the surface temperature of the veneer. The metal foil laminate is then applied over the veneer, and the assembly is passed through another heated die designed to apply pressure and affect bonding.
  • The laminate is applied over the veneer lengthwise so that it circumferentially wraps around it. The two edges of the foil positioned lengthwise along the tube are bonded tightly together and any excess foil is then trimmed to provide a fully covered assembly. This form of wrapping is preferred over the so-called helical wrap formed by winding a tape over the veneer in a helical fashion at an angle to the axis of the hose because it results in only one seam running along the length of the hose. From barrier perspective, a seam can provide potential site for permeation leak. Hence, it is desirable to minimize it's occurrence in the construction. Lengthwise wrap described above is also easier to apply especially on a small diameter tubing such as that encountered in flexible high pressure hoses.
  • In cases where extremely high barrier is desired, it may be advantageous to provide multiple layers of the laminate in a manner that seams do not overlap thus providing higher level of permeation barrier.
  • Metallic foil is thin enough to provide flexibility while resist fracture during handling. For example, it can be aluminum foil, in 1-10 micron thickness range to provide very high level of barrier while retaining flexibility. Note that this approach provides a continuous layer of metal over the tube surface unlike vapor deposition techniques which leave gaps in metal coverage resulting in inferior barrier properties.
  • The second layer of polymer over the metallic foil is selected to protect the surface of the metal foil and provide compatibility with the braid under-layer to be provided over it. It can be a polyamide, polyester or a polyolefin, and is selected so as to be compatible with the type of braid underlayer to be used in the next step.
  • Step 4—A braid underlayer is extruded over the assembly of Step 3. The underlayer is an elastomeric material such as a natural or synthetic rubber or a thermoplastic elastomer such as thermoplastic olefin (TPO), thermoplastic ester elastomer (TEE) or a thermoplastic vulcanizate (such as ETPV or TPV, common selections in this field). Its purpose is to provide cushioning and protection against forces imposed during braiding.
  • It is preferable if this braid underlayer bonds to the surface of the laminate applied in step 3. This may be accomplished by several means such as ensuring that the braid underlayer material is compatible with the surface layer of the laminate, extruding a two-layer braid underlayer such that its inner layer acts as a tie layer to bond to the surface of the laminate or sequentially extruding a tie layer over the laminate first and then the braid underlayer.
  • A functionalized polymer such as that used for forming the tie layer of the two-layer veneer of step 2 may be used for this purpose, the functionalization chosen to be compatible with the two layers to be bonded.
  • Step 5—A braided reinforcement layer is provided over the assembly of Step 4. Depending on the desired pressure capability, braiding can be made of metallic or polymeric filaments or high performance filaments such as Kevlar® or Nomex®, both commercially available from E.I. du Pont de Nemours and Company of Wilmington, Del. Braid density is determined according to desired pressure capability and filament material selection. Multiple layers of braid and hybrid braids of multiple types of filaments are often used in practice to maximize the degree of reinforcement while optimizing the cost.
  • Step 6—An outer protective layer is extruded over the braided reinforcement layer. This layer can again be made of an elastomeric material such as TPO, TEE or a thermoplastic vulcanizate (ETPV or TPV).
  • Step 7—If any of the layers in the hose construction are made of a thermosetting material, then the assembly of Step 6 needs to cure. If all the layers are made of thermoplastic materials, then curing is not necessary. Note that one or more outer protective layers can be added at this time as well.
  • Step 8—Finally, the mandrel is extracted from the assembly of Step 6 or Step 7 to produce the finished hose. The mandrel can be extracted by applying hydraulic pressure to one end of the hose or by mechanical means.
  • Hose made this way can be cut to desired length and fittings can be applied as desired. The hose made this way provides flexibility, high pressure capability and very high barrier capability.
  • It is readily apparent to those having skill in the art to which this invention pertains that in addition to the materials mentioned herein, a variety of other materials are suitable for each layer as is well known and understood. Likewise, representative thicknesses of each layer and techniques for braiding are already well appreciated by those having skill in the field, and are selected according to the intended application.
  • In accordance with the method of the present invention, the heat transfer fluid composition comprises a compound selected from the group consisting of: R32, R152a, CF3I, 1234yf, 1225ye and trans-1234ze.
  • In certain embodiments of the invention, hereinafter referred to as the fluorolefin embodiment, the heat transfer fluid composition comprises at least one fluoroolefin. The heat transfer fluid compositions of the present invention may further comprise at least one additional component that may be a second fluoroolefin, hydrofluorocarbon (HFC), hydrocarbon, dimethyl ether, bis(trifluoromethyl)sulfide, CF3I, or CO2.
  • According to a particular aspect of the fluoroolefin embodiment, the heat transfer fluid composition comprises 1225ye and at least one additional compound selected from the group consisting of HFC-1234ze, HFC-1234yf, HFC-1234ye, HFC-1243zf, HFC-32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethylether, CF3SCF3, CO2, NH3, and CF3I.
  • According to another particular aspect of the fluoroolefin embodiment, the heat transfer fluid composition comprises HFC-1234ze and at least one additional compound selected from the group consisting of HFC-1234yf, HFC-1234ye, HFC-1243zf, HFC-32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethylether, CF3SCF3, CO2 and CF3I.
  • In another particular aspect of the fluoroolefin embodiment, the heat transfer fluid composition comprises HFC-1234yf and at least one additional compound selected from the group consisting of HFC-1234ye, HFC-1243zf, HFC-32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethylether, CF3sCF3, CO2, NH3, and CF3I.
  • According to another particular aspect of the fluoroolefin embodiment, the heat transfer fluid composition comprises HFC-1243zf and at least one additional compound selected from the group consisting of HFC-1234ye, HFC-32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethylether, CF3SCF3, CO2 and CF3I.
  • In another particular aspect of the fluoroolefin embodiment, the heat transfer fluid composition comprises HFC-1234ye and at least one additional compound selected from the group consisting of HFC-1243zf, HFC-32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethylether, CF3SCF3, CO2 and CF3I.
  • For these particular embodiments, the fluoroolefin and the other components of the heat transfer fluid compositions of the present invention are listed in Table 1.
  • TABLE 1
    Compound Chemical name Chemical formula
    HFC-1225ye 1,2,3,3,3-pentafluoropropene CF3CF═CHF
    HFC-1234ze 1,3,3,3-tetrafluoropropene CF3CH═CHF
    HFC-1234yf 2,3,3,3-tetrafluoropropene CF3CF═CH2
    HFC-1234ye 1,2,3,3-tetrafluoropropene CHF2CF═CHF
    HFC-1243zf 3,3,3-trifluoropropene CF3CH═CH2
    HFC-32 difluoromethane CH2F2
    HFC-125 pentafluoroethane CF3CHF2
    HFC-134 1,1,2,2-tetrafluoroethane CHF2CHF2
    HFC-134a 1,1,1,2-tetrafluoroethane CH2FCF3
    HFC-143a 1,1,1-trifluoroethane CH3CF3
    HFC-152a 1,1-difluoroethane CHF2CH3
    HFC-161 fluoroethane CH3CH2F
    HFC-227ea 1,1,1,2,3,3,3- CF3CHFCF3
    heptafluoropropane
    HFC-236ea 1,1,1,2,3,3-hexafluoropropane CF3CHFCHF2
    HFC-236fa 1,1,1,3,3,3-hexafluoroethane CF3CH2CF3
    HFC-245fa 1,1,1,3,3-pentafluoropropane CF3CH2CHF2
    HFC-365mfc 1,1,1,3,3-pentafluorobutane CF3CH2CH2CHF2
    Propane CH3CH2CH3
    n-butane CH3CH2CH2CH3
    i-butane isobutane CH3CH(CH3)CH3
    2-methylbutane CH3CH(CH3)CH2CH3
    n-pentane CH3CH2CH2CH2CH3
    cyclopentane cyclo-(CH2)5—
    DME dimethylether CH3OCH3
    CO2 carbon dioxide CO2
    CF3SCF3 bis(trifluoromethyl)sulfide CF3SCF3
    iodotrifluoromethane CF3I
    R717 Ammonia NH3
  • The individual components listed in Table 1 may be prepared by methods known in the art.
  • The fluoroolefin compounds used in the compositions of the present invention, HFC-1225ye, HFC-1234ze, and HFC-1234ye, may exist as different configurational isomers or stereoisomers. The present invention is intended to include all single configurational isomers, single stereoisomers or any combination or mixture thereof. For instance, 1,3,3,3-tetra-fluoropropene (HFC-1234ze) is meant to represent the cis-isomer, trans-isomer, or any combination or mixture of both isomers in any ratio. Another example is HFC-1225ye, by which is represented the cis-isomer, trans-isomer, or any combination or mixture of both isomers in any ratio. The compositions of the present invention contain primarily the cis or Z isomer of HFC-1225ye.
  • The heat transfer fluid compositions of the present invention may be generally useful when the fluoroolefin is present at about 1 weight percent to about 99 weight percent, preferably about 20 weight percent to about 99 weight percent, more preferably about 40 weight percent to about 99 weight percent and still more preferably 50 weight percent to about 99 weight percent.
  • The present invention further provides compositions as listed in Table 2.
  • TABLE 2
    Concentration ranges (wt %)
    Components Preferred More preferred Most preferred
    HFC-1225ye/HFC-32 1-99/99-1 30-99/70-1 90-99/10-1;
    95/5/97/3
    HFC-1225ye/HFC-134a 1-99/99-1 40-99/60-1 90/10
    HFC-1225ye/CO2 0.1-99.9/99.9-0.1 70-99.7/30-0.3 99/1
    HFC-1225ye/ammonia 0.1-99.9/0.1-99.9 40-99.9/0.1-60 90/10, 85/15, 80/
    20, 95/5
    HFC-1225ye/HFC-1234yf 1-99/99-1 51-99/49-1 and 60-90/ 60/40, 51/49
    40-10
    HFC-1225ye/HFC-152a/HFC-32 1-98/1-98/1-98 50-98/1-40/1-40 85/10/5
    81/15/4
    82/15/3
    HFC-1225ye/HFC-152a/CO2 1-98/1-98/0.1-98 50-98/1-40/0.3-30 84/15/1
    84/15.5/0.5
    HFC-1225ye/HFC-152a/propane 1-98/1-98/1-98 50-98/1-40/1-20 85/13/2
    HFC-1225ye/HFC-152a/i-butane 1-98/1-98/1-98 50-98/1-40/1-20 85/13/2
    HFC-1225ye/HFC-152a/DME 1-98/1-98/1-98 50-98/1-40/1-20 85/13/2
    HFC-1225ye/HFC-152a/CF3I 1-98/1-98/1-98 20-90/1-50/1-60
    HFC-1225ye/HFC-134a/HFC- 1-98/1-98/1-98 40-98/1-50/1-40 76/9/15
    152a
    HFC-1225ye/HFC-134a/HFC-32 1-98/1-98/1-98 1-80/1-80/1-80 88/9/3
    HFC-1225ye/HFC-134a/HFC-161 1-98/1-98/1-98 40-98/1-50/1-20 86/10/4
    HFC-1225ye/HFC-134a/CO2 1-98/1-98/0.1-98 40-98/1-50/0.3-30 88.5/11/0.5
    HFC-1225ye/HFC-134a/propane 1-98/1-98/1-98 40-98/1-50/1-20 87/10/3
    HFC-1225ye/HFC-134a/i-butane 1-98/1-98/1-98 40-98/1-50/1-20 87/10/3
    HFC-1225ye/HFC-134a/DME 1-98/1-98/1-98 40-98/1-50/1-20 87/10/3
    HFC-1225ye/HFC-134/HFC-32 1-98/1-98/1-98 40-98/1-50/1-40 88/9/3
    trans-HFC-1234ze/HFC-134a 1-99/99-1 30-99/70-1 90/10
    trans-HFC-1234ze/HFC-32 1-99/99-1 40-99/60-1 95/5
    trans-HFC-1234ze/HFC-32/CF3I 1-98/1-98/1-98 20-90/0.1-60/1-70
    trans-HFC-1234ze/HFC-152a 1-99/99-1 40-99/60-1 80/20
    trans-HFC-1234ze/HFC-125 1-99/99-1 30-99/70-1
    HFC-1234yf/HFC-134a 1-99/99-1 30-99/70-1 90/10
    HFC-1234yf/HFC-32 1-99/99-1 40-99/60-1 95/5
    HFC-1234yf/HFC-125 0.1-99/99-0.1 52-99/48-1
    HFC-1234yf/HFC-152a 1-99/99-1 40-99/60-1 80/20
    HFC-1225ye/HFC-134a/HFC- 1-97/1-97/1-97/ 20-97/1-80/1-50/ 74/8/17/1
    152a/HFC-32 0.1-97 0.1-50
    HFC-1225ye/HFC-1234yf/HFC- 1-98/1-98/0.1-98 10-90/10-90/0.1-50 70/20/10 and
    134a 20/70/10
    HFC-1225ye/HFC-1234yf/HFC-32 1-98/1-98/0.1-98 10-90/5-90/0.1-50 25/73/2,
    75/23/2,
    49/49/2, 85/10/5,
    90/5/5
    HFC-1225ye/HFC-1234yf/HFC- 1-97/1-97/0.1-97/ 10-80/10-80/1-60/1-60
    32/CF3I 1-97
    HFC-1225ye/HFC-1234yf/HFC- 1-98/1-98/0.1-98 10-90/10-90/0.1-50 70/25/5 and
    152a 25/70/5
    HFC-1225ye/HFC-1234yf/HFC- 1-98/1-98/0.1-98 10-90/10-90/0.1-50 25/71/4,
    125 75/21/4, 75/24/1
    and 25/74/1
    HFC-1225ye/HFC-1234yf/CF3I 1-98/1-98/1-98 9-90/9-90/1-60 40/40/20 and
    45/45/10
    HFC-32/HFC-125/HFC-1225ye 0.1-98/0.1-98/ 5-70/5-70/5-70 30/30/40 and
    0.1-98 23/25/52
    HFC-32/HFC-125/trans-HFC- 0.1-98/0.1-98/ 5-70/5-70/5-70 30/50/20 and
    1234ze 0.1-98 23/25/52
    HFC-32/HFC-125/HFC-1234yf 0.1-98/0.1-98/ 5-70/5-70/5-70 40/50/10,
    0.1-98 23/25/52,
    15/45/40, and
    10/60/30
    HFC-32/HFC-134a/HFC- 1-97/1-97/1-97/ 1-60/1-60/1-60/1-60
    1225ye/CF3I 1-97
    HFC-32/HFC-134a/HFC- 1-96/1-96/1-96/ 1-50/1-50/1-50/1-50/
    1225ye/HFC-1234yf/CF3I 1-96/1-96 1-50
    HFC-32/HFC-125/HFC- 1-96/1-96/1-96/ 1-50/1-50/1-50/1-50/
    134a/HFC-1225ye/CF3I 1-96/1-96 1-50
    HFC-125/HFC-1225ye/n-butane 0.1-98/0.1-98/ 5-70/5-70/1-20 65/32/3 and
    0.1-98 85.1/11.5/3.4
    HFC-32/NH3/HFC-1225ye 1-98/1-98/1-98 1-60/10-60/10-90
    HFC-32/NH3/HFC-1225ye/CF3I 1-97/1-97/1-97/ 1-60/1-60/10-80/1-60
    1-97
    HFC-32/NH3/HFC-1234yf/CF3I 1-97/1-97/1-97/ 1-60/1-60/10-80/5-80
    1-97
    HFC-125/trans-HFC-1234ze/n- 0.1-98/0.1-98/ 5-70/5-70/1-20 66/32/2 and
    butane 0.1-98 86.1/11.5/2.4
    HFC-125/HFC-1234yf/n-butane 0.1-98/0.1-98/ 5-70/5-70/1-20 67/32/1 and
    0.1-98 87.1/11.5/1.4
    HFC-125/HFC-1225ye/isobutane 0.1-98/0.1-98/ 5-70/5-70/1-20 85.1/11.5/3.4
    0.1-98 and 65/32/3
    HFC-1225ye/HFC-125/ammonia 0.1-98/0.1-98/ 20-98/1-60/0.1-40
    0.1-98
    HFC-1225ye/HFC-32/HFC- 0.1-97/0.1-97/ 20-97/1-60/1-60/
    125/ammonia 0.1-97/0.1-97 0.1-40
    HFC-125/trans-HFC- 0.1-98/0.1-98/ 5-70/5-70/1-20 86.1/11.5/2.4
    1234ze/isobutane 0.1-98 and 66/32/2
    HFC-125/HFC-1234yf/isobutane 0.1-98/0.1-98/ 5-70/5-70/1-20 and 87.1/11.5/1.4
    0.1-98 80-98/1-19/1-10 and 67/32/1
    HFC-1234yf/HFC-32/HFC-143a 1-50/1-98/1-98 15-50/20-80/5-60
    HFC-1234yf/HFC-32/isobutane 1-40/59-98/1-30 10-40/59-90/1-10
    HFC-1234yf/HFC-125/HFC-143a 1-60/1-98/1-98 10-60/20-70/20-70
    HFC-1234yf/HFC-125/isobutane 1-40/59-98/1-20 10-40/59-90/1-10
    HFC-1234yf/HFC-125/CF3I 1-98/0.1-98/1-98 10-80/1-60/1-60
    HFC-1234yf/HFC-134/propane 1-80/1-70/19-90 20-80/10-70/19-50
    HFC-1234yf/HFC-134/DME 1-70/1-98/29-98 20-70/10-70/29-50
    HFC-1234yf/HFC-134a/propane 1-80/1-80/19-98 10-80/10-80/19-50
    HFC-1234yf/HFC-134a/n-butane 1-98/1-98/1-30 10-80/10-80/1-20
    HFC-1234yf/HFC-134a/isobutane 1-98/1-98/1-30 10-80/10-80/1-20
    HFC-1234yf/HFC-134a/DME 1-98/1-98/1-40 10-80/10-80/1-20
    HFC-1234yf/HFC-134a/CF3I 1-98/1-98/1-98 10-80/1-60/1-60
    HFC-1234yf/HFC-143a/propane 1-80/1-98/1-98 10-80/10-80/1-50
    HFC-1234yf/HFC-143a/DME 1-40/59-98/1-20 5-40/59-90/1-10
    HFC-1234yf/HFC-152a/n-butane 1-98/1-98/1-30 10-80/10-80/1-20
    HFC-1234yf/HFC-152a/isobutane 1-98/1-90/1-40 10-80/10-80/1-20
    HFC-1234yf/HFC-152a/DME 1-70/1-98/1-98 10-70/10-80/1-20
    HFC-1234yf/HFC-152a/CF3I 1-98/1-98/1-98 10-80/1-60/1-60
    HFC-1234yf/HFC-227ea/propane 1-80/1-70/29-98 10-60/10-60/29-50
    HFC-1234yf/HFC-227ea/n-butane 40-98/1-59/1-20 50-98/10-49/1-10
    HFC-1234yf/HFC- 30-98/1-69/1-30 50-98/10-49/1-10
    227ea/isobutane
    HFC-1234yf/HFC-227ea/DME 1-98/1-80/1-98 10-80/10-80/1-20
    HFC-1234yf/n-butane/DME 1-98/1-40/1-98 10-80/10-40/1-20
    HFC-1234yf/isobutane/DME 1-98/1-50/1-98 10-90/1-40/1-20
    HFC-1234yf/DME/CF3I 1-98/1-98/1-98 10-80/1-20/10-80
    HFC-1234yf/DME/CF3SCF3 1-98/1-40/1-98 10-80/1-20/10-70
    HFC-1225ye/trans-HFC- 1-98/1-98/1-98 10-80/10-80/10-80
    1234ze/HFC-134
    HFC-1225ye/trans-HFC- 1-98/1-98/1-98 10-80/10-80/10-80
    1234ze/HFC-227ea
    HFC-1225ye/trans-HFC- 1-60/1-60/39-98 10-60/10-60/39-80
    1234ze/propane
    HFC-1225ye/trans-HFC- 1-98/1-98/1-30 10-80/10-80/1-20
    1234ze/n-butane
    HFC-1225ye/trans-HFC- 1-98/1-98/1-98 10-80/10-80/1-30
    1234ze/DME
    HFC-1225ye/trans-HFC-1234ze/ 1-98/1-98/1-98 10-80/10-80/10-80
    CF3SCF3
    HFC-1225ye/HFC-1243zf/HFC- 1-98/1-98/1-98 10-80/10-80/10-80
    134
    HFC-1225ye/HFC-1243zf/n- 1-98/1-98/1-30 10-80/10-80/1-20
    butane
    HFC-1225ye/HFC- 1-98/1-98/1-40 10-80/10-80/1-30
    1243zf/isobutane
    HFC-1225ye/HFC-1243zf/DME 1-98/1-98/1-98 10-80/10-80/1-30
    HFC-1225ye/HFC-1243zf/CF3I 1-98/1-98/1-98 10-80/10-80/10-80
    HFC-1225ye/HFC-134/HFC-152a 1-98/1-98/1-98 10-80/10-80/1-50
    HFC-1225ye/HFC-134/HFC- 1-98/1-98/1-98 10-80/10-80/10-80
    227ea
    HFC-1225ye/HFC-134/n-butane 1-98/1-90/1-40 10-80/10-80/1-30
    HFC-1225ye/HFC-134/isobutane 1-98/1-90/1-40 10-80/10-80/1-30
    HFC-1225ye/HFC-134/DME 1-98/1-98/1-40 10-80/10-80/1-30
    HFC-1225ye/HFC-227ea/DME 40-98/1-59/1-30 50-98/1-49/1-20
    HFC-1225ye/n-butane/DME 1-98/1-30/1-98 60-98/1-20/1-20
    HFC-1225ye/n-butane/CF3SCF3 1-98/1-20/1-98 10-80/1-10/10-80
    HFC-1225ye/isobutane/DME 1-98/1-60/1-98 40-90/1-30/1-30
    HFC-1225ye/isobutane/CF3I 1-98/1-40/1-98 10-80/1-30/10-80
    trans-HFC-1234ze/HFC- 1-98/1-98/1-98 10-80/10-80/10-80
    1243zf/HFC-227ea
    trans-HFC-1234ze/HFC-1243zf/n- 1-98/1-98/1-30 10-80/10-80/1-20
    butane
    trans-HFC-1234ze/HFC- 1-98/1-98/1-40 10-80/10-80/1-30
    1243zf/isobutane
    trans-HFC-1234ze/HFC- 1-98/1-98/1-98 10-80/10-80/1-40
    1243zf/DME
    trans-HFC-1234ze/HFC-32/CF3I 1-98/1-98/1-98 10-80/1-70/1-80
    trans-HFC-1234ze/HFC- 1-98/1-98/1-98 10-80/10-80/1-50
    134/HFC-152a
    trans-HFC-1234ze/HFC- 1-98/1-98/1-98 10-80/10-80/10-80
    134/HFC-227ea
    trans-HFC-1234ze/HFC-134/DME 1-98/1-98/1-40 10-80/10-80/1-30
    trans-HFC-1234ze/HFC- 1-98/1-98/1-98 10-80/10-80/1-50
    134a/HFC-152a
    trans-HFC-1234ze/HFC-152a/n- 1-98/1-98/1-50 10-80/10-80/1-30
    butane
    trans-HFC-1234ze/HFC- 1-98/1-98/1-98 20-90/1-50/1-30
    152a/DME
    trans-HFC-1234ze/HFC-227ea/n- 1-98/1-98/1-40 10-80/10-80/1-30
    butane
    trans-HFC-1234ze/n-butane/DME 1-98/1-40/1-98 10-90/1-30/1-30
    trans-HFC-1234ze/n-butane/CF3I 1-98/1-30/1-98 10-80/1-20/10-80
    trans-HFC- 1-98/1-60/1-98 10-90/1-30/1-30
    1234ze/isobutane/DME
    trans-HFC-1234ze/isobutane/ 1-98/1-40/1-98 10-80/1-20/10-80
    CF3I
    trans-HFC-1234ze/isobutane/ 1-98/1-40/1-98 10-80/1-20/10-80
    CF3SCF3
    HFC-1243zf/HFC-134/HFC- 1-98/1-98/1-98 10-80/10-80/10-80
    227ea
    HFC-1243zf/HFC-134/n-butane 1-98/1-98/1-40 10-80/10-80/1-30
    HFC-1243zf/HFC-134/DME 1-98/1-98/1-98 10-80/10-80/1-30
    HFC-1243zf/HFC-134/CF3I 1-98/1-98/1-98 10-80/10-80/10-80
    HFC-1243zf/HFC-134a/HFC- 1-98/1-98/1-98 10-80/10-80/1-50
    152a
    HFC-1243zf/HFC-134a/n-butane 1-98/1-98/1-40 10-80/10-80/1-30
    HFC-1243zf/HFC-152a/propane 1-70/1-70/29-98 10-70/1-50/29-40
    HFC-1243zf/HFC-152a/n-butane 1-98/1-98/1-30 10-80/1-80/1-20
    HFC-1243zf/HFC-152a/isobutane 1-98/1-98/1-40 10-80/1-80/1-30
    HFC-1243zf/HFC-152a/DME 1-98/1-98/1-98 10-80/1-80/1-30
    HFC-1243zf/HFC-227ea/n-butane 1-98/1-98/1-40 10-80/1-80/1-30
    HFC-1243zf/HFC- 1-98/1-90/1-50 10-80/1-80/1-30
    227ea/isobutane
    HFC-1243zf/HFC-227ea/DME 1-98/1-80/1-90 10-80/1-80/1-30
    HFC-1243zf/n-butane/DME 1-98/1-40/1-98 10-90/1-30/1-30
    HFC-1243zf/isobutane/DME 1-98/1-60/1-98 10-90/1-30/1-30
    HFC-1243zf/isobutane/CF3I 1-98/1-40/1-98 10-80/1-30/10-80
    HFC-1243zf/DME/CF3SCF3 1-98/1-40/1-90 10-80/1-30/10-80
    HFC-1225ye/HFC-32/CF3I 1-98/1-98/1-98 5-80/1-70/1-80
    HFC-1225ye/HFC-1234yf/HFC- 1-97/1-97/1-97/ 1-80/1-70/5-70/5-70
    32/HFC-125 1-97
    HFC-1225ye/HFC-1234yf/HFC- 1-97/1-97/1-97/ 5-80/5-70/5-70/5-70
    32/HFC-134a 1-97
    HFC-1225ye/HFC-1234yf/HFC- 1-96/1-96/1-96/ 1-70/1-60/1-70/1-60/
    32/HFC-125/CF3I 1-96/1-96 1-60
    HFC-1225ye/HFC-32/HFC- 1-97/1-97/1-97/ 10-80/5-70/5-70/5-70
    125/HFC-152a 1-97
    HFC-1225ye/HFC-32/HFC- 1-97/1-97/1-97/ 5-70/5-70/5-70/1-30
    125/isobutane 1-97
    HFC-1225ye/HFC-32/HFC- 1-97/1-97/1-97/ 5-70/5-70/5-70/1-30
    125/propane 1-50
    HFC-1225ye/HFC-32/HFC- 1-97/1-97/1-97/ 5-70/5-70/5-70/1-30
    125/DME 1-50
    HFC-1225ye/HFC-32/CF3I/DME 1-97/1-97/1-97/ 5-70/5-70/5-70/1-30
    1-50
    HFC-1225ye/HFC-32/HFC- 1-97/1-97/1-97/ 10-80/5-70/5-70/1-80
    125/CF3I 1-97
    HFC-1234yf/HFC-32/CF3I 1-98/1-98/1-98 10-80/1-70/1-80
    HFC-1234yf/HFC-32/HFC- 1-97/1-97/1-97/ 5-70/5-80/1-70/5-70
    134a/CF3I 1-97
    HFC-1234yf/HFC-32/HFC-125 1-98/1-98/1-98 10-80/5-80/10-80
    HFC-1234yf/HFC-32/HFC- 1-97/1-97/1-97/ 10-80/5-70/10-80/5-80
    125/CF3I 1-97
  • The most preferred compositions of the present invention listed in Table 2 are generally expected to maintain the desired properties and functionality when the components are present in the concentrations as listed +/−2 weight percent. The compositions containing CO2 would be expected to maintain the desired properties and functionality when the CO2 was present at the listed concentration +/−0.2 weight percent.
  • The compositions of the present invention may be azeotropic or near-azeotropic compositions. By azeotropic composition is meant a constant-boiling mixture of two or more substances that behave as a single substance. One way to characterize an azeotropic composition is that the vapor produced by partial evaporation or distillation of the liquid has the same composition as the liquid from which it is evaporated or distilled, i.e., the mixture distills/refluxes without compositional change. Constant-boiling compositions are characterized as azeotropic because they exhibit either a maximum or minimum boiling point, as compared with that of the non-azeotropic mixture of the same compounds. An azeotropic composition will not fractionate within a refrigeration or air conditioning system during operation, which may reduce efficiency of the system. Additionally, an azeotropic composition will not fractionate upon leakage from a refrigeration or air conditioning system. In the situation where one component of a mixture is flammable, fractionation during leakage could lead to a flammable composition either within the system or outside of the system.
  • A near-azeotropic composition (also commonly referred to as an “azeotrope-like composition”) is a substantially constant boiling liquid admixture of two or more substances that behaves essentially as a single substance. One way to characterize a near-azeotropic composition is that the vapor produced by partial evaporation or distillation of the liquid has substantially the same composition as the liquid from which it was evaporated or distilled, that is, the admixture distills/refluxes without substantial composition change. Another way to characterize a near-azeotropic composition is that the bubble point vapor pressure and the dew point vapor pressure of the composition at a particular temperature are substantially the same. Herein, a composition is near-azeotropic if, after 50 weight percent of the composition is removed, such as by evaporation or boiling off, the difference in vapor pressure between the original composition and the composition remaining after 50 weight percent of the original composition has been removed is less than about 10 percent.
  • Azeotropic compositions of the present invention at a specified temperature are shown in Table 3.
  • TABLE 3
    Wt % Wt % T
    Component A Component B A B Psia kPa (C.)
    HFC-1234yf HFC-32 7.4 92.6 49.2 339 −25
    HFC-1234yf HFC-125 10.9 89.1 40.7 281 −25
    HFC-1234yf HFC-134a 70.4 29.6 18.4 127 −25
    HFC-1234yf HFC-152a 91.0 9.0 17.9 123 −25
    HFC-1234yf HFC-143a 17.3 82.7 39.5 272 −25
    HFC-1234yf HFC-227ea 84.6 15.4 18.0 124 −25
    HFC-1234yf propane 51.5 48.5 33.5 231 −25
    HFC-1234yf n-butane 98.1 1.9 17.9 123 −25
    HFC-1234yf isobutane 88.1 11.9 19.0 131 −25
    HFC-1234yf DME 53.5 46.5 13.1 90 −25
    HFC-1225ye trans-HFC- 63.0 37.0 11.7 81 −25
    1234ze
    HFC-1225ye HFC-1243zf 40.0 60.0 13.6 94 −25
    HFC-1225ye HFC-134 52.2 47.8 12.8 88 −25
    HFC-1225ye HFC-152a 7.3 92.7 14.5 100 −25
    HFC-1225ye propane 29.7 70.3 30.3 209 −25
    HFC-1225ye n-butane 89.5 10.5 12.3 85 −25
    HFC-1225ye isobutane 79.3 20.7 13.9 96 −25
    HFC-1225ye DME 82.1 17.9 10.8 74 −25
    HFC-1225ye CF3SCF3 37.0 63.0 12.4 85 −25
    trans-HFC-1234ze HFC-1243zf 17.0 83.0 13.0 90 −25
    trans-HFC-1234ze HFC-134 45.7 54.3 12.5 86 −25
    trans-HFC-1234ze HFC-134a 9.5 90.5 15.5 107 −25
    trans-HFC-1234ze HFC-152a 21.6 78.4 14.6 101 −25
    trans-HFC-1234ze HFC-227ea 59.2 40.8 11.7 81 −25
    trans-HFC-1234ze propane 28.5 71.5 30.3 209 −25
    trans-HFC-1234ze n-butane 88.6 11.4 11.9 82 −25
    trans-HFC-1234ze isobutane 77.9 22.1 12.9 89 −25
    trans-HFC-1234ze DME 84.1 15.9 10.8 74 −25
    trans-HFC-1234ze CF3SCF3 34.3 65.7 12.7 88 −25
    HFC-1243zf HFC-134 63.0 37.0 13.5 93 −25
    HFC-1243zf HFC-134A 25.1 74.9 15.9 110 −25
    HFC-1243zf HFC-152A 40.7 59.3 15.2 104 −25
    HFC-1243zf HFC-227ea 78.5 21.5 13.1 90 −25
    HFC-1243zf propane 32.8 67.2 31.0 213 −25
    HFC-1243zf n-butane 90.3 9.7 13.5 93 −25
    HFC-1243zf isobutane 80.7 19.3 14.3 98 −25
    HFC-1243zf DME 72.7 27.3 12.0 83 −25
    cis-HFC-1234ze HFC-236ea 20.9 79.1 30.3 209 25
    cis-HFC-1234ze HFC-245fa 76.2 23.8 26.1 180 25
    cis-HFC-1234ze n-butane 51.4 48.6 6.08 42 −25
    cis-HFC-1234ze isobutane 26.2 73.8 8.74 60 −25
    cis-HFC-1234ze 2-methylbutane 86.6 13.4 27.2 188 25
    cis-HFC-1234ze n-pentane 92.9 7.1 26.2 181 25
    HFC-1234ye HFC-236ea 24.0 76.0 3.35 23.1 −25
    HFC-1234ye HFC-245fa 42.5 57.5 22.8 157 25
    HFC-1234ye n-butane 41.2 58.8 38.0 262 25
    HFC-1234ye isobutane 16.4 83.6 50.9 351 25
    HFC-1234ye 2-methylbutane 80.3 19.7 23.1 159 25
    HFC-1234ye n-pentane 87.7 12.3 21.8 150 25
  • Additionally, ternary azeotropes composition have been found as listed in Table 4.
  • TABLE 4
    Pres Pres Temp
    Component A Component B Component C Wt % A Wt % B Wt % C (psi) (kPa) (° C.)
    HFC-1234yf HFC-32 HFC-143A 3.9 74.3 21.8 50.02 345 −25
    HFC-1234yf HFC-32 isobutane 1.1 92.1 6.8 50.05 345 −25
    HFC-1234yf HFC-125 HFC-143A 14.4 43.5 42.1 38.62 266 −25
    HFC-1234yf HFC-125 isobutane 9.7 89.1 1.2 40.81 281 −25
    HFC-1234yf HFC-134 propane 4.3 39.1 56.7 34.30 236 −25
    HFC-1234yf HFC-134 DME 15.2 67.0 17.8 10.38 71.6 −25
    HFC-1234yf HFC-134a propane 24.5 31.1 44.5 34.01 234 −25
    HFC-1234yf HFC-134a n-butane 60.3 35.2 4.5 18.58 128 −25
    HFC-1234yf HFC-134a isobutane 48.6 37.2 14.3 19.86 137 −25
    HFC-1234yf HFC-134a DME 24.0 67.9 8.1 17.21 119 −25
    HFC-1234yf HFC-143a propane 17.7 71.0 11.3 40.42 279 −25
    HFC-1234yf HFC-143a DME 5.7 93.0 1.3 39.08 269 −25
    HFC-1234yf HFC-152a n-butane 86.6 10.8 2.7 17.97 124 −25
    HFC-1234yf HFC-152a isobutane 75.3 11.8 12.9 19.12 132 −25
    HFC-1234yf HFC-152a DME 24.6 43.3 32.1 11.78 81.2 −25
    HFC-1234yf HFC-227ea propane 35.6 17.8 46.7 33.84 233 −25
    HFC-1234yf HFC-227ea n-butane 81.9 16.0 2.1 18.07 125 −25
    HFC-1234yf HFC-227ea isobutane 70.2 18.2 11.6 19.27 133 −25
    HFC-1234yf HFC-227ea DME 28.3 55.6 16.1 15.02 104 −25
    HFC-1234yf n-butane DME 48.9 4.6 46.4 13.15 90.7 −25
    HFC-1234yf isobutane DME 31.2 26.2 42.6 14.19 97.8 −25
    HFC-1234yf DME CF3I 16.3 10.0 73.7 15.65 108 −25
    HFC-1234yf DME CF3SCF3 34.3 10.5 55.2 14.57 100 −25
    HFC-1225ye trans-HFC- HFC-134 47.4 5.6 47.0 12.77 88.0 −25
    1234ze
    HFC-1225ye trans-HFC- HFC-227ea 28.4 52.6 19.0 11.63 80.2 −25
    1234ze
    HFC-1225ye trans-HFC- propane 20.9 9.1 70.0 30.36 209 −25
    1234ze
    HFC-1225ye trans-HFC- n-butane 65.8 24.1 10.1 12.39 85.4 −25
    1234ze
    HFC-1225ye trans-HFC- DME 41.0 40.1 18.9 10.98 75.7 −25
    1234ze
    HFC-1225ye trans-HFC- CF3SCF3 1.0 33.7 65.2 12.66 87.3 −25
    1234ze
    HFC-1225ye HFC-1243zf HFC-134 28.7 47.3 24.1 13.80 95.1 −25
    HFC-1225ye HFC-1243zf n-butane 37.5 55.0 7.5 13.95 96.2 −25
    HFC-1225ye HFC-1243zf isobutane 40.5 43.2 16.3 14.83 102 −25
    HFC-1225ye HFC-1243zf DME 19.1 51.0 29.9 12.15 83.8 −25
    HFC-1225ye HFC-1243zf CF3I 10.3 27.3 62.3 14.05 96.9 −25
    HFC-1225ye HFC-134 HFC-152a 63.6 26.8 9.6 12.38 85.4 −25
    HFC-1225ye HFC-134 HFC-227ea 1.3 52.3 46.4 12.32 84.9 −25
    HFC-1225ye HFC-134 n-butane 18.1 67.1 14.9 14.54 100 −25
    HFC-1225ye HFC-134 isobutane 0.7 74.0 25.3 16.68 115 −25
    HFC-1225ye HFC-134 DME 29.8 52.5 17.8 9.78 67.4 −25
    HFC-1225ye HFC-227ea DME 63.1 31.0 5.8 10.93 75.4 −25
    HFC-1225ye n-butane DME 66.0 13.0 21.1 11.34 78.2 −25
    HFC-1225ye n-butane CF3SCF3 71.3 5.6 23.0 12.25 84.5 −25
    HFC-1225ye isobutane DME 49.9 29.7 20.4 12.83 88.5 −25
    HFC-1225ye isobutane CF3I 27.7 2.2 70.1 13.19 90.9 −25
    Trans-HFC- HFC-1243zf HFC-227ea 7.1 73.7 19.2 13.11 90.4 −25
    1234ze
    Trans-HFC- HFC-1243zf n-butane 9.5 81.2 9.3 13.48 92.9 −25
    1234ze
    Trans-HFC- HFC-1243zf isobutane 3.3 77.6 19.1 14.26 98.3 −25
    1234ze
    Trans-HFC- HFC-1243zf DME 2.6 70.0 27.4 12.03 82.9 −25
    1234ze
    Trans-HFC- HFC-134 HFC-152a 52.0 42.9 5.1 12.37 85.3 −25
    1234ze
    Trans-HFC- HFC-134 HFC-227ea 30.0 43.2 26.8 12.61 86.9 −25
    1234ze
    Trans-HFC- HFC-134 DME 27.7 54.7 17.7 9.76 67.3 −25
    1234ze
    Trans-HFC- HFC-134a HFC-152a 14.4 34.7 51.0 14.42 99.4 −25
    1234ze
    Trans-HFC- HFC-152a n-butane 5.4 80.5 14.1 15.41 106 −25
    1234ze
    Trans-HFC- HFC-152a DME 59.1 16.4 24.5 10.80 74.5 −25
    1234ze
    Trans-HFC- HFC-227ea n-butane 40.1 48.5 11.3 12.61 86.9 −25
    1234ze
    Trans-HFC- n-butane DME 68.1 13.0 18.9 11.29 77.8 −25
    1234ze
    Trans-HFC- n-butane CF3I 81.2 9.7 9.1 11.87 81.8 −25
    1234ze
    Trans-HFC- isobutane DME 55.5 28.7 15.8 12.38 85.4 −25
    1234ze
    Trans-HFC- isobutane CF3I 34.9 6.1 59.0 12.57 86.7 −25
    1234ze
    Trans-HFC- isobutane CF3SCF3 37.7 1.1 61.7 12.66 87.3 −25
    1234ze
    HFC-1243zf HFC-134 HFC-227ea 58.6 34.1 7.3 13.54 93.4 −25
    HFC-1243zf HFC-134 n-butane 27.5 58.7 13.9 14.72 101 −25
    HFC-1243zf HFC-134 DME 18.7 63.5 17.8 10.11 69.7 −25
    HFC-1243zf HFC-134 CF3I 11.4 23.9 64.7 14.45 99.6 −25
    HFC-1243zf HFC-134a HFC-152a 41.5 21.5 37.1 14.95 103 −25
    HFC-1243zf HFC-134A n-butane 7.0 81.4 11.6 17.03 117 −25
    HFC-1243zf HFC-152a propane 2.9 34.0 63.0 31.73 219 −25
    HFC-1243zf HFC-152a n-butane 28.8 60.3 11.0 15.71 108 −25
    HFC-1243zf HFC-152a isobutane 6.2 68.5 25.3 17.05 118 −25
    HFC-1243zf HFC-152a DME 33.1 36.8 30.1 11.41 78.7 −25
    HFC-1243zf HFC-227ea n-butane 62.0 28.4 9.6 13.67 94.3 −25
    HFC-1243zf HFC-227ea isobutane 27.9 51.0 21.1 15.00 103 −25
    HFC-1243zf HFC-227ea DME 48.1 44.8 7.2 12.78 88.1 −25
    HFC-1243zf n-butane DME 60.3 10.1 29.6 12.28 84.7 −25
    HFC-1243zf isobutane DME 47.1 26.9 25.9 13.16 90.7 −25
    HFC-1243zf isobutane CF3I 32.8 1.1 66.1 13.97 96.3 −25
    HFC-1243zf DME CF3SCF3 41.1 2.3 56.6 13.60 93.8 −25
  • The near-azeotropic compositions of the present invention at a specified temperature are listed in Table 5.
  • TABLE 5
    Component A Component B (wt % A/wt % B) T (C.)
    HFC-1234yf HFC-32 1-57/99-43 −25
    HFC-1234yf HFC-125 1-51/99-49 −25
    HFC-1234yf HFC-134 1-99/99-1 −25
    HFC-1234yf HFC-134a 1-99/99-1 −25
    HFC-1234yf HFC-152a 1-99/99-1 −25
    HFC-1234yf HFC-161 1-99/99-1 −25
    HFC-1234yf HFC-143a 1-60/99-40 −25
    HFC-1234yf HFC-227ea 29-99/71-1 −25
    HFC-1234yf HFC-236fa 66-99/34-1 −25
    HFC-1234yf HFC-1225ye 1-99/99-1 −25
    HFC-1234yf trans-HFC-1234ze 1-99/99-1 −25
    HFC-1234yf HFC-1243zf 1-99/99-1 −25
    HFC-1234yf propane 1-80/99-20 −25
    HFC-1234yf n-butane 71-99/29-1 −25
    HFC-1234yf isobutane 60-99/40-1 −25
    HFC-1234yf DME 1-99/99-1 −25
    HFC-1225ye trans-HFC-1234ze 1-99/99-1 −25
    HFC-1225ye HFC-1243zf 1-99/99-1 −25
    HFC-1225ye HFC-134 1-99/99-1 −25
    HFC-1225ye HFC-134a 1-99/99-1 −25
    HFC-1225ye HFC-152a 1-99/99-1 −25
    HFC-1225ye HFC-161 1-84/99-16, 90-99/ −25
    10-1
    HFC-1225ye HFC-227ea 1-99/99-1 −25
    HFC-1225ye HFC-236ea 57-99/43-1 −25
    HFC-1225ye HFC-236fa 48-99/52-1 −25
    HFC-1225ye HFC-245fa 70-99/30-1 −25
    HFC-1225ye propane 1-72/99-28 −25
    HFC-1225ye n-butane 65-99/35-1 −25
    HFC-1225ye isobutane 50-99/50-1 −25
    HFC-1225ye DME 1-99/99-1 −25
    HFC-1225ye CF3I 1-99/99-1 −25
    HFC-1225ye CF3SCF3 1-99/99-1 −25
    trans-HFC-1234ze cis-HFC-1234ze 73-99/27-1 −25
    trans-HFC-1234ze HFC-1243zf 1-99/99-1 −25
    trans-HFC-1234ze HFC-134 1-99/99-1 −25
    trans-HFC-1234ze HFC-134a 1-99/99-1 −25
    trans-HFC-1234ze HFC-152a 1-99/99-1 −25
    trans-HFC-1234ze HFC-161 1-52/99-48, 87-99/ −25
    13-1
    trans-HFC-1234ze HFC-227ea 1-99/99-1 −25
    trans-HFC-1234ze HFC-236ea 54-99/46-1 −25
    trans-HFC-1234ze HFC-236fa 44-99/56-1 −25
    trans-HFC-1234ze HFC-245fa 67-99/33-1 −25
    trans-HFC-1234ze propane 1-71/99-29 −25
    trans-HFC-1234ze n-butane 62-99/38-1 −25
    trans-HFC-1234ze isobutane 39-99/61-1 −25
    trans-HFC-1234ze DME 1-99/99-1 −25
    trans-HFC-1234ze CF3SCF3 1-99/99-1 −25
    trans-HFC-1234ze CF3I 1-99/99-1 −25
    HFC-1243zf HFC-134 1-99/99-1 −25
    HFC-1243zf HFC-134a 1-99/99-1 −25
    HFC-1243zf HFC-152a 1-99/99-1 −25
    HFC-1243zf HFC-161 1-99/99-1 −25
    HFC-1243zf HFC-227ea 1-99/99-1 −25
    HFC-1243zf HFC-236ea 53-99/47-1 −25
    HFC-1243zf HFC-236fa 49-99/51-1 −25
    HFC-1243zf HFC-245fa 66-99/34-1 −25
    HFC-1243zf propane 1-71/99-29 −25
    HFC-1243zf n-butane 62-99/38-1 −25
    HFC-1243zf isobutane 45-99/55-1 −25
    HFC-1243zf DME 1-99/99-1 −25
    cis-HFC-1234ze HFC-236ea 1-99/99-1 25
    cis-HFC-1234ze HFC-236fa 1-99/99-1 25
    cis-HFC-1234ze HFC-245fa 1-99/99-1 25
    cis-HFC-1234ze n-butane 1-80/99-20 −25
    cis-HFC-1234ze isobutane 1-69/99-31 −25
    cis-HFC-1234ze 2-methylbutane 60-99/40-1 25
    cis-HFC-1234ze n-pentane 63-99/37-1 25
    HFC-1234ye HFC-134 38-99/62-1 25
    HFC-1234ye HFC-236ea 1-99/99-1 −25
    HFC-1234ye HFC-236fa 1-99/99-1 25
    HFC-1234ye HFC-245fa 1-99/99-1 25
    HFC-1234ye Cis-HFC-1234ze 1-99/99-1 25
    HFC-1234ye n-butane 1-78/99-22 25
    HFC-1234ye cyclopentane 70-99/30-1 25
    HFC-1234ye isobutane 1-68/99-32 25
    HFC-1234ye 2-methylbutane 47-99/53-1 25
    HFC-1234ye n-pentane 57-99/43-1 25
  • Ternary and higher order near-azeotrope compositions comprising fluoroolefins have also been identified as listed in Table 6.
  • TABLE 6
    Near-azeotrope range Temp
    Components (weight percent) (° C.)
    HFC-1225ye/HFC-134a/HFC-152a 1-98/1-98/1-98 25
    HFC-1225ye/HFC-134a/HFC-161 1-98/1-98/1-98 25
    HFC-1225ye/HFC-134a/isobutane 1-98/1-98/1-40 25
    HFC-1225ye/HFC-134a/DME 1-98/1-98/1-20 25
    HFC-1225ye/HFC-152a/isobutane 1-98/1-98/1-50 25
    HFC-1225ye/HFC-152a/DME 1-98/1-98/1-98 25
    HFC-1225ye/HFC-1234yf/HFC-134a 1-98/1-98/1-98 25
    HFC-1225ye/HFC-1234yf/HFC-152a 1-98/1-98/1-98 25
    HFC-1225ye/HFC-1234yf/HFC-125 1-98/1-98/1-20 25
    HFC-1225ye/HFC-1234yf/CF3I 1-98/1-98/1-98 25
    HFC-1225ye/HFC-134a/HFC- 1-97/1-97/1-97/1-10 25
    152a/HFC-32
    HFC-125/HFC-1225ye/isobutane 80-98/1-19/1-10 25
    HFC-125/trans-HFC- 80-98/1-19/1-10 25
    1234ze/isobutane
    HFC-125/HFC-1234yf/isobutane 80-98/1-19/1-10 25
    HFC-32/HFC-125/HFC-1225ye 1-98/1-98/1-4 25
    HFC-32/HFC-125/trans-HFC-1234ze 1-98/1-98/1-50 25
    HFC-32/HFC-125/HFC-1234yf 1-98/1-98/1-55 25
    HFC-125/trans-HFC-1234ze/n-butane 80-98/1-19/1-10 25
    HFC-125/HFC-1234yf/n-butane 80-98/1-19/1-10 25
    HFC-1234yf/HFC-32/HFC-143a 1-50/1-98/1-98 −25
    HFC-1234yf/HFC-32/isobutane 1-40/59-98/1-30 −25
    HFC-1234yf/HFC-125/HFC-143a 1-60/1-98/1-98 −25
    HFC-1234yf/HFC-125/isobutane 1-40/59-98/1-20 −25
    HFC-1234yf/HFC-134/propane 1-80/1-70/19-90 −25
    HFC-1234yf/HFC-134/DME 1-70/1-98/29-98 −25
    HFC-1234yf/HFC-134a/propane 1-80/1-80/19-98 −25
    HFC-1234yf/HFC-134a/n-butane 1-98/1-98/1-30 −25
    HFC-1234yf/HFC-134a/isobutane 1-98/1-98/1-30 −25
    HFC-1234yf/HFC-134a/DME 1-98/1-98/1-40 −25
    HFC-1234yf/HFC-143a/propane 1-80/1-98/1-98 −25
    HFC-1234yf/HFC-143a/DME 1-40/59-98/1-20 −25
    HFC-1234yf/HFC-152a/n-butane 1-98/1-98/1-30 −25
    HFC-1234yf/HFC-152a/isobutane 1-98/1-90/1-40 −25
    HFC-1234yf/HFC-152a/DME 1-70/1-98/1-98 −25
    HFC-1234yf/HFC-227ea/propane 1-80/1-70/29-98 −25
    HFC-1234yf/HFC-227ea/n-butane 40-98/1-59/1-20 −25
    HFC-1234yf/HFC-227ea/isobutane 30-98/1-69/1-30 −25
    HFC-1234yf/HFC-227ea/DME 1-98/1-80/1-98 −25
    HFC-1234yf/n-butane/DME 1-98/1-40/1-98 −25
    HFC-1234yf/isobutane/DME 1-98/1-50/1-98 −25
    HFC-1234yf/DME/CF3I 1-98/1-98/1-98 −25
    HFC-1234yf/DME/CF3SCF3 1-98/1-40/1-80 −25
    HFC-1225ye/trans-HFC- 1-98/1-98/1-98 −25
    1234ze/HFC-134
    HFC-1225ye/trans-HFC- 1-98/1-98/1-98 −25
    1234ze/HFC-227ea
    HFC-1225ye/trans-HFC- 1-60/1-60/1-98 −25
    1234ze/propane
    HFC-1225ye/trans-HFC-1234ze/n- 1-98/1-98/1-30 −25
    butane
    HFC-1225ye/trans-HFC-1234ze/DME 1-98/1-98/1-98 −25
    HFC-1225ye/trans-HFC-1234ze/ 1-98/1-98/1-98 −25
    CF3SCF3
    HFC-1225ye/HFC-1243zf/HFC-134 1-98/1-98/1-98 −25
    HFC-1225ye/HFC-1243zf/n-butane 1-98/1-98/1-30 −25
    HFC-1225ye/HFC-1243zf/isobutane 1-98/1-98/1-40 −25
    HFC-1225ye/HFC-1243zf/DME 1-98/1-98/1-98 −25
    HFC-1225ye/HFC-1243zf/CF3I 1-98/1-98/1-98 −25
    HFC-1225ye/HFC-134/HFC-152a 1-98/1-98/1-98 −25
    HFC-1225ye/HFC-134/HFC-227ea 1-98/1-98/1-98 −25
    HFC-1225ye/HFC-134/n-butane 1-98/1-90/1-40 −25
    HFC-1225ye/HFC-134/isobutane 1-98/1-90/1-40 −25
    HFC-1225ye/HFC-134/DME 1-98/1-98/1-40 −25
    HFC-1225ye/HFC-227ea/DME 40-98/1-59/1-30 −25
    HFC-1225ye/n-butane/DME 1-98/1-30/1-98 −25
    HFC-1225ye/n-butane/CF3SCF3 1-98/1-20/1-98 −25
    HFC-1225ye/isobutane/DME 1-98/1-60/1-98 −25
    HFC-1225ye/isobutane/CF3I 1-98/1-40/1-98 −25
    trans-HFC-1234ze/HFC-1243zf/HFC- 1-98/1-98/1-98 −25
    227ea
    trans-HFC-1234ze/HFC-1243zf/n- 1-98/1-98/1-30 −25
    butane
    trans-HFC-1234ze/HFC- 1-98/1-98/1-40 −25
    1243zf/isobutane
    trans-HFC-1234ze/HFC-1243zf/DME 1-98/1-98/1-98 −25
    trans-HFC-1234ze/HFC-134/HFC- 1-98/1-98/1-98 −25
    152a
    trans-HFC-1234ze/HFC-134/HFC- 1-98/1-98/1-98 −25
    227ea
    trans-HFC-1234ze/HFC-134/DME 1-98/1-98/1-40 −25
    trans-HFC-1234ze/HFC-134a/HFC- 1-98/1-98/1-98 −25
    152a
    trans-HFC-1234ze/HFC-152a/n- 1-98/1-98/1-50 −25
    butane
    trans-HFC-1234ze/HFC-152a/DME 1-98/1-98/1-98 −25
    trans-HFC-1234ze/HFC-227ea/n- 1-98/1-98/1-40 −25
    butane
    trans-HFC-1234ze/n-butane/DME 1-98/1-40/1-98 −25
    trans-HFC-1234ze/n-butane/CF3I 1-98/1-30/1-98 −25
    trans-HFC-1234ze/isobutane/DME 1-98/1-60/1-98 −25
    trans-HFC-1234ze/isobutane/CF3I 1-98/1-40/1-98 −25
    trans-HFC-1234ze/isobutane/ 1-98/1-40/1-98 −25
    CF3SCF3
    HFC-1243zf/HFC-134/HFC-227ea 1-98/1-98/1-98 −25
    HFC-1243zf/HFC-134/n-butane 1-98/1-98/1-40 −25
    HFC-1243zf/HFC-134/DME 1-98/1-98/1-98 −25
    HFC-1243zf/HFC-134/CF3I 1-98/1-98/1-98 −25
    HFC-1243zf/HFC-134a/HFC-152a 1-98/1-98/1-98 −25
    HFC-1243zf/HFC-134a/n-butane 1-98/1-98/1-40 −25
    HFC-1243zf/HFC-152a/propane 1-70/1-70/29-98 −25
    HFC-1243zf/HFC-152a/n-butane 1-98/1-98/1-30 −25
    HFC-1243zf/HFC-152a/isobutane 1-98/1-98/1-40 −25
    HFC-1243zf/HFC-152a/DME 1-98/1-98/1-98 −25
    HFC-1243zf/HFC-227ea/n-butane 1-98/1-98/1-40 −25
    HFC-1243zf/HFC-227ea/isobutane 1-98/1-90/1-50 −25
    HFC-1243zf/HFC-227ea/DME 1-98/1-80/1-90 −25
    HFC-1243zf/n-butane/DME 1-98/1-40/1-98 −25
    HFC-1243zf/isobutane/DME 1-98/1-60/1-98 −25
    HFC-1243zf/isobutane/CF3I 1-98/1-40/1-98 −25
    HFC-1243zf/DME/CF3SCF3 1-98/1-40/1-90 −25
  • Certain of the compositions of the present invention are non-azeotropic compositions. Those compositions of the present invention falling within the preferred ranges of Table 2, but outside of the near-azeotropic ranges of Table 5 and Table 6 may be considered to be non-azeotropic.
  • A non-azeotropic composition may have certain advantages over azeotropic or near azeotropic mixtures. A non-azeotropic composition is a mixture of two or more substances that behaves as a mixture rather than a single substance. One way to characterize a non-azeotropic composition is that the vapor produced by partial evaporation or distillation of the liquid has a substantially different composition as the liquid from which it was evaporated or distilled, that is, the admixture distills/refluxes with substantial composition change. Another way to characterize a non-azeotropic composition is that the bubble point vapor pressure and the dew point vapor pressure of the composition at a particular temperature are substantially different. Herein, a composition is non-azeotropic if, after 50 weight percent of the composition is removed, such as by evaporation or boiling off, the difference in vapor pressure between the original composition and the composition remaining after 50 weight percent of the original composition has been removed is greater than about 10 percent.
  • The compositions of the present invention may be prepared by any convenient method to combine the desired amounts of the individual components. A preferred method is to weigh the desired component amounts and thereafter combine the components in an appropriate vessel. Agitation may be used, if desired.
  • An alternative means for making compositions of the present invention may be a method for making a refrigerant blend composition, wherein said refrigerant blend composition comprises a composition as disclosed herein, said method comprising (i) reclaiming a volume of one or more components of a refrigerant composition from at least one refrigerant container, (ii) removing impurities sufficiently to enable reuse of said one or more of the reclaimed components, (iii) and optionally, combining all or part of said reclaimed volume of components with at least one additional refrigerant composition or component.
  • A refrigerant container may be any container in which is stored a refrigerant blend composition that has been used in a refrigeration apparatus, air-conditioning apparatus or heat pump apparatus. Said refrigerant container may be the refrigeration apparatus, air-conditioning apparatus or heat pump apparatus in which the refrigerant blend was used. Additionally, the refrigerant container may be a storage container for collecting reclaimed refrigerant blend components, including but not limited to pressurized gas cylinders.
  • Residual refrigerant means any amount of refrigerant blend or refrigerant blend component that may be moved out of the refrigerant container by any method known for transferring refrigerant blends or refrigerant blend components.
  • Impurities may be any component that is in the refrigerant blend or refrigerant blend component due to its use in a refrigeration apparatus, air-conditioning apparatus or heat pump apparatus. Such impurities include but are not limited to refrigeration lubricants, being those described earlier herein, particulates including but not limited to metal, metal salt or elastomer particles, that may have come out of the refrigeration apparatus, air-conditioning apparatus or heat pump apparatus, and any other contaminants that may adversely effect the performance of the refrigerant blend composition.
  • Such impurities may be removed sufficiently to allow reuse of the refrigerant blend or refrigerant blend component without adversely effecting the performance or equipment within which the refrigerant blend or refrigerant blend component will be used.
  • It may be necessary to provide additional refrigerant blend or refrigerant blend component to the residual refrigerant blend or refrigerant blend component in order to produce a composition that meets the specifications required for a given product. For instance, if a refrigerant blend has 3 components in a particular weight percentage range, it may be necessary to add one or more of the components in a given amount in order to restore the composition to within the specification limits.
  • The heat transfer fluid compositions of the present invention will have global warming potential (GWP) that are less than many hydrofluorocarbon refrigerants currently in use. Preferably, such compositions will also have zero or low ozone depletion potential. One aspect of the present invention is to provide a refrigerant with a global warming potential of less than 1000, less than 500, less than 150, less than 100, or less than 50. Another aspect of the present invention is to reduce the net GWP of refrigerant mixtures by adding fluoroolefins to said mixtures.
  • The compositions of the present invention may be useful as low global warming potential (GWP) replacements for currently used refrigerants, including but not limited to R134a (or HFC-134a, 1,1,1,2-tetrafluoroethane), R22 (or HCFC-22, chlorodifluoromethane), R123 (or HFC-123, 2,2-dichloro-1,1,1-trifluoroethane), R11 (CFC-11, fluorotrichloromethane), R12 (CFC-12, dichlorodifluoromethane), R245fa (or HFC-245fa, 1,1,1,3,3-pentafluoropropane), R114 (or CFC-114, 1,2-dichloro-1,1,2,2-tetrafluoroethane), R236fa (or HFC-236fa, 1,1,1,3,3,3-hexafluoropropane), R124 (or HCFC-124, 2-chloro-1,1,1,2-tetrafluoroethane), R407c (ASHRAE designation for a blend of 52 weight percent R134a, 25 weight percent R125 (pentafluoroethane), and 23 weight percent R32 (difluoromethane), R410A (ASHRAE designation for a blend of 50 weight percent R125 and 50 weight percent R32), R417A, (ASHRAE designation for a blend of 46.6 weight percent R125, 50.0 weight percent R134a, and 3.4 weight percent n-butane), R422A, R422B, R422c and R422D, (ASHRAE designation for a blend of 85.1 weight percent R125, 11.5 weight percent R134a, and 3.4 weight percent isobutane), R404A, (ASHRAE designation for a blend of 44 weight percent R125, 52 weight percent R143a (1,1,1-trifluoroethane), and 4.0 weight percent R134a) and R507A (ASHRAE designation for a blend of 50 weight percent R125 and 50 weight percent R143a). Additionally, the compositions of the present invention may be useful as replacements for R12 (CFC-12, dichlorodifluoromethane) or R502 (ASHRAE designation for a blend of 51.2 weight percent CFC-115 (chloropentafluoroethane) and 48.8 weight percent HCFC-22).
  • Often replacement refrigerants are most useful if capable of being used in the original refrigeration equipment designed for a different refrigerant. The compositions of the present invention may be useful as replacements for the above-mentioned refrigerants in original equipment. Additionally, the compositions of the present invention may be useful as replacements for the above mentioned refrigerants in equipment designed to use the above-mentioned refrigerants.
  • The compositions of the present invention may further comprise a lubricant. Lubricants of the present invention comprise refrigeration lubricants, i.e. those lubricants suitable for use with refrigeration, air-conditioning, or heat pump apparatus. Among these lubricants are those conventionally used in compression refrigeration apparatus utilizing chlorofluorocarbon refrigerants. Such lubricants and their properties are discussed in the 1990 ASHRAE Handbook, Refrigeration Systems and Applications, chapter 8, titled “Lubricants in Refrigeration Systems”, pages 8.1 through 8.21. Lubricants of the present invention may comprise those commonly known as “mineral oils” in the field of compression refrigeration lubrication. Mineral oils comprise paraffins (i.e. straight-chain and branched-carbon-chain, saturated hydrocarbons), naphthenes (i.e. cyclic paraffins) and aromatics (i.e. unsaturated, cyclic hydrocarbons containing one or more rings characterized by alternating double bonds). Lubricants of the present invention further comprise those commonly known as “synthetic oils” in the field of compression refrigeration lubrication. Synthetic oils comprise alkylaryls (i.e. linear and branched alkyl alkylbenzenes), synthetic paraffins and napthenes, and poly(alphaolefins). Representative conventional lubricants of the present invention are the commercially available BVM 100 N (paraffinic mineral oil sold by BVA Oils), Suniso® 3GS and Suniso® 5GS (naphthenic mineral oil sold by Crompton Co.), Sontex® 372LT (naphthenic mineral oil sold by Pennzoil), Calumet® RO-30 (naphthenic mineral oil sold by Calumet Lubricants), Zerol® 75, Zerol® 150 and Zerol® 500 (linear alkylbenzenes sold by Shrieve Chemicals) and HAB 22 (branched alkylbenzene sold by Nippon Oil).
  • Lubricants of the present invention further comprise those that have been designed for use with hydrofluorocarbon refrigerants and are miscible with refrigerants of the present invention under compression refrigeration, air-conditioning, or heat pump apparatus' operating conditions. Such lubricants and their properties are discussed in “Synthetic Lubricants and High-Performance Fluids”, R. L. Shubkin, editor, Marcel Dekker, 1993. Such lubricants include, but are not limited to, polyol esters (POEs) such as Castrol® 100 (Castrol, United Kingdom), polyalkylene glycols (PAGs) such as RL-488A from Dow (Dow Chemical, Midland, Mich.), and polyvinyl ethers (PVEs). These lubricants are readily available from various commercial sources.
  • Lubricants of the present invention are selected by considering a given compressor's requirements and the environment to which the lubricant will be exposed. Lubricants of the present invention preferably have a kinematic viscosity of at least about 5 cs (centistokes) at 40° C.
  • Commonly used refrigeration system additives may optionally be added, as desired, to compositions of the present invention in order to enhance lubricity and system stability. These additives are generally known within the field of refrigeration compressor lubrication, and include anti wear agents, extreme pressure lubricants, corrosion and oxidation inhibitors, metal surface deactivators, free radical scavengers, foaming and antifoam control agents, leak detectants and the like. In general, these additives are present only in small amounts relative to the overall lubricant composition. They are typically used at concentrations of from less than about 0.1% to as much as about 3% of each additive. These additives are selected on the basis of the individual system requirements. Some typical examples of such additives may include, but are not limited to, lubrication enhancing additives, such as alkyl or aryl esters of phosphoric acid and of thiophosphates. Additionally, the metal dialkyl dithiophosphates (e.g. zinc dialkyl dithiophosphate or ZDDP, Lubrizol 1375) and other members of this family of chemicals may be used in compositions of the present invention. Other antiwear additives include natural product oils and assymetrical polyhydroxyl lubrication additives such as Synergol TMS (International Lubricants). Similarly, stabilizers such as anti oxidants, free radical scavengers, and water scavengers may be employed. Compounds in this category can include, but are not limited to, butylated hydroxy toluene (BHT) and epoxides.
  • The compositions of the present invention may further comprise about 0.01 weight percent to about 5 weight percent of an additive such as, for example, a stabilizer, free radical scavenger and/or antioxidant. Such additives include but are not limited to, nitromethane, hindered phenols, hydroxylamines, thiols, phosphites, or lactones. Single additives or combinations may be used.
  • The compositions of the present invention may further comprise about 0.01 weight percent to about 5 weight percent of a water scavenger (drying compound). Such water scavengers may comprise ortho esters such as trimethyl-, triethyl-, or tripropylortho formate.
  • The compositions of the present invention may further comprise a tracer selected from the group consisting of hydrofluorocarbons (HFCs), deuterated hydrocarbons, deuterated hydrofluorocarbons, perfluorocarbons, fluoroethers, brominated compounds, iodated compounds, alcohols, aldehydes, ketones, nitrous oxide (N2O) and combinations thereof. The tracer compounds are added to the compositions in previously determined quantities to allow detection of any dilution, contamination or other alteration of the composition, as described in U.S. patent application Ser. No. 11/062,044, filed Feb. 18, 2005.
  • Typical tracer compounds for use in the present compositions are listed in Table 7.
  • TABLE 7
    Compound Structure
    Deuterated hydrocarbons and hydrofluorocarbons
    Ethane-d6 CD3CD3
    Propane-d8 CD3CD2CD3
    HFC-32-d2 CD2F2
    HFC-134a-d2 CD2FCF3
    HFC-143a-d3 CD3CF3
    HFC-125-d CDF2CF3
    HFC-227ea-d CF3CDFCF3
    HFC-227ca-d CF3CF2CDF2
    HFC-134-d2 CDF2CDF2
    HFC-236fa-d2 CF3CD2CF3
    HFC-245cb-d3 CF3CF2CD3
    HFC-263fb-d2* CF3CD2CH3
    HFC-263fb-d3 CF2CH2CD3
    Fluoroethers
    HFOC-125E CHF2OCF3
    HFOC-134aE CH2FOCF3
    HFOC-143aE CH3OCF3
    HFOC-227eaE CF3OCHFCF3
    HFOC-236faE CF3OCH2CF3
    HFOC-245faEβγ or CHF2OCH2CF3
    HFOC-245faEαβ (or CHF2CH2OCF3)
    HFOC-245cbEβγ or CH3OCF2CF3
    HFOC-245cbαβ (or CH3CF2OCF3)
    HFE-42-11mcc (or Freon ® E1) CF3CF2CF2OCHFCF3
    Freon ® E2 CF3CF2CF2OCF(CF3) CF2OCHFCF3
    Hydrofluorocarbons
    HFC-23 CHF3
    HFC-161 CH3CH2F
    HFC-152a CH3CHF2
    HFC-134 CHF2CHF2
    HFC-227ea CF3CHFCF3
    HFC-227ca CHF2CF2CF3
    HFC-236cb CH2FCF2CF3
    HFC-236ea CF3CHFCHF2
    HFC-236fa CF3CH2CF3
    HFC-245cb CF3CF2CH3
    HFC-245fa CHF2CH2CF3
    HFC-254cb CHF2CF2CH3
    HFC-254eb CF3CHFCH3
    HFC-263fb CF3CH2CH3
    HFC-272ca CH3CF2CH3
    HFC-281ea CH3CHFCH3
    HFC-281fa CH2FCH2CH3
    HFC-329p CHF2CF2CF2CF3
    HFC-329mmz (CH3)2CHCF3
    HFC-338mf CF3CH2CF2CF3
    HFC-338pcc CHF2CF2CF2CHF2
    HFC-347s CH3CF2CF2CF3
    HFC-43-10mee CF3CHFCHFCF2CF3
    Perfluorocarbons
    PFC-116 CF3CF3
    PFC-C216 Cyclo(—CF2CF2CF2—)
    PFC-218 CF3CF2CF3
    PFC-C318 Cyclo(—CF2CF2CF2CF2—)
    PFC-31-10mc CF3CF2CF2CF3
    PFC-31-10my (CF3)2CFCF3
    PFC-C51-12mycm Cyclo(—CF(CF3)CF2CF(CF3)CF2—)
    PFC-C51-12mym, trans-cyclo(—CF2CF(CF3)CF(CF3)CF2—)
    PFC-C51-12mym, cis-cyclo(—CF2CF(CF3)CF(CF3)CF2—)
    Perfluoromethylcyclo-pentane Cyclo(—CF2CF2(CF3)CF2CF2CF2—)
    Perfluoromethylcyclo-hexane Cyclo(—CF2CF2(CF3)CF2CF2CF2CF2—)
    Perfluorodimethylcyclo-hexane Cyclo(—CF2CF2(CF3)CF2CF2(CF3)CF2—)
    (ortho, meta, or para)
    Perfluoroethylcyclohexane Cyclo(—CF2CF2(CF2CF3)CF2CF2CF2CF2—)
    Perfluoroindan C9F10 (see structure below)
    Figure US20090314015A1-20091224-C00001
    Perfluorotrimethylcyclo-hexane Cyclo(—CF2(CF3)CF2(CF3)CF2CF2(CF3)CF2—)
    (all possible isomers)
    Perfluoroisopropylcyclo-hexane Cyclo(—CF2CF2(CF2(CF3)2)CF2CF2CF2CF2—)
    Perfluorodecalin C10F18 (see structure below)
    (cis or trans, trans shown)
    Figure US20090314015A1-20091224-C00002
    Perfluoromethyldecalin (cis or trans C11F20 (see structure below)
    and all additional possible isomers)
    Figure US20090314015A1-20091224-C00003
    Brominated compounds
    Bromomethane CH3Br
    Bromofluoromethane CH2FBr
    Bromodifluoromethane CHF2Br
    Dibromofluoromethane CHFBr2
    Tribromomethane CHBr3
    Bromoethane CH3CH2Br
    Bromoethene CH2═CHBr
    1,2-dibromoethane CH2BrCH2Br
    1-bromo-1,2-difluoroethene CFBr═CHF
    Iodated compounds
    Iodotrifluoromethane CF3I
    Difluoroiodomethane CHF2I
    Fluoroiodomethane CH2FI
    1,1,2-trifluoro-1-iodoethane CF2ICH2F
    1,1,2,2-tetrafluoro-1-iodoethane CF2ICHF2
    1,1,2,2-tetrafluoro-1,2-diiodoethane CF2ICF2I
    Iodopentafluorobenzene C6F5I
    Alcohols
    Ethanol CH3CH2OH
    n-propanol CH3CH2CH2OH
    Isopropanol CH3CH(OH)CH3
    Aldehydes and Ketones
    Acetone (2-propanone) CH3C(O)CH3
    n-propanal CH3CH2CHO
    n-butanal CH3CH2CH2CHO
    Methyl ethyl ketone (2-butanone) CH3C(O)CH2CH3
    Other
    Nitrous oxide N2O
  • The compounds listed in Table 7 are available commercially (from chemical supply houses) or may be prepared by processes known in the art.
  • Single tracer compounds may be used in combination with the heat transfer fluid compositions of the present invention or multiple tracer compounds may be combined in any proportion to serve as a tracer blend. The tracer blend may contain multiple tracer compounds from the same class of compounds or multiple tracer compounds from different classes of compounds. For example, a tracer blend may contain 2 or more deuterated hydrofluorocarbons, or one deuterated hydrofluorocarbon in combination with one or more perfluorocarbons.
  • Additionally, some of the compounds in Table 7 exist as multiple isomers, structural or optical. Single isomers or multiple isomers of the same compound may be used in any proportion to prepare the tracer compound. Further, single or multiple isomers of a given compound may be combined in any proportion with any number of other compounds to serve as a tracer blend.
  • The tracer compound or tracer blend may be present in the compositions at a total concentration of about 50 parts per million by weight (ppm) to about 1000 ppm. Preferably, the tracer compound or tracer blend is present at a total concentration of about 50 ppm to about 500 ppm and most preferably, the tracer compound or tracer blend is present at a total concentration of about 100 ppm to about 300 ppm.
  • The compositions of the present invention may further comprise a compatibilizer selected from the group consisting of polyoxyalkylene glycol ethers, amides, nitriles, ketones, chlorocarbons, esters, lactones, aryl ethers, fluoroethers and 1,1,1-trifluoroalkanes. The compatibilizer is used to improve solubility of hydrofluorocarbon refrigerants in conventional refrigeration lubricants. Refrigeration lubricants are needed to lubricate the compressor of a refrigeration, air-conditioning or heat pump apparatus. The lubricant must move throughout the apparatus with the refrigerant in particular it must return from the non-compressor zones to the compressor to continue to function as lubricant and avoid compressor failure.
  • Hydrofluorocarbon refrigerants are generally not compatible with convention refrigeration lubricants such as mineral oils, alkylbenzenes, synthetic paraffins, synthetic napthenes and poly(alpha)olefins. Many replacement lubricants have been proposed, however, the polyalkylene glycols, polyol esters and polyvinyl ethers, suggested for use with hydrofluorocarbon refrigerants are expensive and absorb water readily. Water in a refrigeration, air-conditioning system or heat pump can lead to corrosion and the formation of particles that may plug the capillary tubes and other small orifices in the system, ultimately causing system failure. Additionally, in existing equipment, time-consuming and costly flushing procedures are required to change to a new lubricant. Therefore, it is desirable to continue to use the original lubricant if possible.
  • The compatibilizers of the present invention improve solubility of the hydrofluorocarbon refrigerants in conventional refrigeration lubricants and thus improve oil return to the compressor.
  • Polyoxyalkylene glycol ether compatibilizers of the present invention are represented by the formula R1[(OR2)xOR3]y, wherein: x is an integer from 1-3; y is an integer from 1-4; R1 is selected from hydrogen and aliphatic hydrocarbon radicals having 1 to 6 carbon atoms and y bonding sites; R2 is selected from aliphatic hydrocarbylene radicals having from 2 to 4 carbon atoms; R3 is selected from hydrogen and aliphatic and alicyclic hydrocarbon radicals having from 1 to 6 carbon atoms; at least one of R1 and R3 is said hydrocarbon radical; and wherein said polyoxyalkylene glycol ethers have a molecular weight of from about 100 to about 300 atomic mass units. As used herein, bonding sites mean radical sites available to form covalent bonds with other radicals. Hydrocarbylene radicals mean divalent hydrocarbon radicals. In the present invention, preferred polyoxyalkylene glycol ether compatibilizers are represented by R1[(OR2)xOR3]y: x is preferably 1-2; y is preferably 1; R1 and R3 are preferably independently selected from hydrogen and aliphatic hydrocarbon radicals having 1 to 4 carbon atoms; R2 is preferably selected from aliphatic hydrocarbylene radicals having from 2 or 3 carbon atoms, most preferably 3 carbon atoms; the polyoxyalkylene glycol ether molecular weight is preferably from about 100 to about 250 atomic mass units, most preferably from about 125 to about 250 atomic mass units. The R1 and R3 hydrocarbon radicals having 1 to 6 carbon atoms may be linear, branched or cyclic. Representative R1 and R3 hydrocarbon radicals include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, and cyclohexyl. Where free hydroxyl radicals on the present polyoxyalkylene glycol ether compatibilizers may be incompatible with certain compression refrigeration apparatus materials of construction (e.g. Mylar®), R1 and R3 are preferably aliphatic hydrocarbon radicals having 1 to 4 carbon atoms, most preferably 1 carbon atom. The R2 aliphatic hydrocarbylene radicals having from 2 to 4 carbon atoms form repeating oxyalkylene radicals —(OR2)x— that include oxyethylene radicals, oxypropylene radicals, and oxybutylene radicals. The oxyalkylene radical comprising R2 in one polyoxyalkylene glycol ether compatibilizer molecule may be the same, or one molecule may contain different R2oxyalkylene groups. The present polyoxyalkylene glycol ether compatibilizers preferably comprise at least one oxypropylene radical. Where R1 is an aliphatic or alicyclic hydrocarbon radical having 1 to 6 carbon atoms and y bonding sites, the radical may be linear, branched or cyclic. Representative R1 aliphatic hydrocarbon radicals having two bonding sites include, for example, an ethylene radical, a propylene radical, a butylene radical, a pentylene radical, a hexylene radical, a cyclopentylene radical and a cyclohexylene radical. Representative R1 aliphatic hydrocarbon radicals having three or four bonding sites include residues derived from polyalcohols, such as trimethylolpropane, glycerin, pentaerythritol, 1,2,3-trihydroxycyclohexane and 1,3,5-trihydroxycyclohexane, by removing their hydroxyl radicals.
  • Representative polyoxyalkylene glycol ether compatibilizers include but are not limited to: CH3OCH2CH(CH3)O(H or CH3) (propylene glycol methyl (or dimethyl)ether), CH3O[CH2CH(CH3)O]2(H or CH3) (dipropylene glycol methyl (or dimethyl)ether), CH3O[CH2CH(CH3)O]3(H or CH3) (tripropylene glycol methyl (or dimethyl)ether), C2H5OCH2CH(CH3)O(H or C2H5) (propylene glycol ethyl (or diethyl)ether), C2H5O[CH2CH(CH3)O]2(H or C2H5) (dipropylene glycol ethyl (or diethyl)ether), C2H5O[CH2CH(CH3)O]3(H or C2H5) (tripropylene glycol ethyl (or diethyl)ether), C3H7OCH2CH(CH3)O(H or C3H7) (propylene glycol n-propyl (or di-n-propyl)ether), C3H7O[CH2CH(CH3)O]2(H or C3H7) (dipropylene glycol n-propyl (or di-n-propyl)ether), C3H7O[CH2CH(CH3)O]3(H or C3H7) (tripropylene glycol n-propyl (or di-n-propyl)ether), C4H9OCH2CH(CH3)OH (propylene glycol n-butyl ether), C4H9O[CH2CH(CH3)O]2(H or C4H9) (dipropylene glycol n-butyl (or di-n-butyl)ether), C4H9O[CH2CH(CH3)O]3(H or C4H9) (tripropylene glycol n-butyl (or di-n-butyl)ether), (CH3)3COCH2CH(CH3)OH (propylene glycol t-butyl ether), (CH3)3CO[CH2CH(CH3)O]2(H or (CH3)3) (dipropylene glycol t-butyl (or di-t-butyl)ether), (CH3)3CO[CH2CH(CH3)O]3(H or (CH3)3) (tripropylene glycol t-butyl (or di-t-butyl)ether), C5H11OCH2CH(CH3)OH (propylene glycol n-pentyl ether), C4H9OCH2CH(C2H5)OH (butylene glycol n-butyl ether), C4H9O[CH2CH(C2H5)O]2H (dibutylene glycol n-butyl ether), trimethylolpropane tri-n-butyl ether (C2H5C(CH2—O—(CH2)3CH3)3) and trimethylolpropane di-n-butyl ether (C2H5C(CH2OC(CH2)3CH3)2CH2OH).
  • Amide compatibilizers of the present invention comprise those represented by the formulae R1C(O)NR2R3 and cyclo-[R4C(O)N(R5)], wherein R1, R2, R3 and R5 are independently selected from aliphatic and alicyclic hydrocarbon radicals having from 1 to 12 carbon atoms; R4 is selected from aliphatic hydrocarbylene radicals having from 3 to 12 carbon atoms; and wherein said amides have a molecular weight of from about 100 to about 300 atomic mass units. The molecular weight of said amides is preferably from about 160 to about 250 atomic mass units. R1, R2, R3 and R5 may optionally include substituted hydrocarbon radicals, that is, radicals containing non-hydrocarbon substituents selected from halogens (e.g., fluorine, chlorine) and alkoxides (e.g. methoxy). R1, R2, R3 and R5 may optionally include heteroatom-substituted hydrocarbon radicals, that is, radicals, which contain the atoms nitrogen (aza-), oxygen (oxa-) or sulfur (thia-) in a radical chain otherwise composed of carbon atoms. In general, no more than three non-hydrocarbon substituents and heteroatoms, and preferably no more than one, will be present for each 10 carbon atoms in R1-3, and the presence of any such non-hydrocarbon substituents and heteroatoms must be considered in applying the aforementioned molecular weight limitations. Preferred amide compatibilizers consist of carbon, hydrogen, nitrogen and oxygen. Representative R1, R2, R3 and R5 aliphatic and alicyclic hydrocarbon radicals include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and their configurational isomers. A preferred embodiment of amide compatibilizers are those wherein R4 in the aforementioned formula cyclo-[R4C(O)N(R5)—] may be represented by the hydrocarbylene radical (CR6R7)n, in other words, the formula: cyclo-[(CR6R7)nC(O)N(R5)—] wherein: the previously-stated values for molecular weight apply; n is an integer from 3 to 5; R5 is a saturated hydrocarbon radical containing 1 to 12 carbon atoms; R6 and R7 are independently selected (for each n) by the rules previously offered defining R1-3. In the lactams represented by the formula: cyclo-[(CR6R7)nC(O)N(R5)—], all R6 and R7 are preferably hydrogen, or contain a single saturated hydrocarbon radical among the n methylene units, and R5 is a saturated hydrocarbon radical containing 3 to 12 carbon atoms. For example, 1-(saturated hydrocarbon radical)-5-methylpyrrolidin-2-ones.
  • Representative amide compatibilizers include but are not limited to: 1-octyl pyrrolidin-2-one, 1-decylpyrrolidin-2-one, 1-octyl-5-methylpyrrolidin-2-one, 1-butylcaprolactam, 1-cyclohexylpyrrolidin-2-one, 1-butyl-5-methylpiperid-2-one, 1-pentyl-5-methylpiperid-2-one, 1-hexylcaprolactam, 1-hexyl-5-methylpyrrolidin-2-one, 5-methyl-1-pentylpiperid-2-one, 1,3-dimethylpiperid-2-one, 1-methylcaprolactam, 1-butyl-pyrrolidin-2-one, 1,5-dimethylpiperid-2-one, 1-decyl-5-methylpyrrolidin-2-one, 1-dodecylpyrrolid-2-one, N,N-dibutylformamide and N,N-diisopropylacetamide.
  • Ketone compatibilizers of the present invention comprise ketones represented by the formula R1C(O)R2, wherein R1 and R2 are independently selected from aliphatic, alicyclic and aryl hydrocarbon radicals having from 1 to 12 carbon atoms, and wherein said ketones have a molecular weight of from about 70 to about 300 atomic mass units. R1 and R2 in said ketones are preferably independently selected from aliphatic and alicyclic hydrocarbon radicals having 1 to 9 carbon atoms. The molecular weight of said ketones is preferably from about 100 to 200 atomic mass units. R1 and R2 may together form a hydrocarbylene radical connected and forming a five, six, or seven-membered ring cyclic ketone, for example, cyclopentanone, cyclohexanone, and cycloheptanone. R1 and R2 may optionally include substituted hydrocarbon radicals, that is, radicals containing non-hydrocarbon substituents selected from halogens (e.g., fluorine, chlorine) and alkoxides (e.g. methoxy). R1 and R2 may optionally include heteroatom-substituted hydrocarbon radicals, that is, radicals, which contain the atoms nitrogen (aza-), oxygen (keto-, oxa-) or sulfur (thia-) in a radical chain otherwise composed of carbon atoms. In general, no more than three non-hydrocarbon substituents and heteroatoms, and preferably no more than one, will be present for each 10 carbon atoms in R1 and R2, and the presence of any such non-hydrocarbon substituents and heteroatoms must be considered in applying the aforementioned molecular weight limitations. Representative R1 and R2 aliphatic, alicyclic and aryl hydrocarbon radicals in the general formula R1C(O)R2 include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and their configurational isomers, as well as phenyl, benzyl, cumenyl, mesityl, tolyl, xylyl and phenethyl.
  • Representative ketone compatibilizers include but are not limited to: 2-butanone, 2-pentanone, acetophenone, butyrophenone, hexanophenone, cyclohexanone, cycloheptanone, 2-heptanone, 3-heptanone, 5-methyl-2-hexanone, 2-octanone, 3-octanone, diisobutyl ketone, 4-ethylcyclohexanone, 2-nonanone, 5-nonanone, 2-decanone, 4-decanone, 2-decalone, 2-tridecanone, dihexyl ketone and dicyclohexyl ketone.
  • Nitrile compatibilizers of the present invention comprise nitriles represented by the formula R1CN, wherein R1 is selected from aliphatic, alicyclic or aryl hydrocarbon radicals having from 5 to 12 carbon atoms, and wherein said nitriles have a molecular weight of from about 90 to about 200 atomic mass units. R1 in said nitrile compatibilizers is preferably selected from aliphatic and alicyclic hydrocarbon radicals having 8 to 10 carbon atoms. The molecular weight of said nitrile compatibilizers is preferably from about 120 to about 140 atomic mass units. R1 may optionally include substituted hydrocarbon radicals, that is, radicals containing non-hydrocarbon substituents selected from halogens (e.g., fluorine, chlorine) and alkoxides (e.g. methoxy). R1 may optionally include heteroatom-substituted hydrocarbon radicals, that is, radicals, which contain the atoms nitrogen (aza-), oxygen (keto-, oxa-) or sulfur (thia-) in a radical chain otherwise composed of carbon atoms. In general, no more than three non-hydrocarbon substituents and heteroatoms, and preferably no more than one, will be present for each 10 carbon atoms in R1, and the presence of any such non-hydrocarbon substituents and heteroatoms must be considered in applying the aforementioned molecular weight limitations. Representative R1 aliphatic, alicyclic and aryl hydrocarbon radicals in the general formula R1CN include pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and their configurational isomers, as well as phenyl, benzyl, cumenyl, mesityl, tolyl, xylyl and phenethyl.
  • Representative nitrile compatibilizers include but are not limited to: 1-cyanopentane, 2,2-dimethyl-4-cyanopentane, 1-cyanohexane, 1-cyanoheptane, 1-cyanooctane, 2-cyanooctane, 1-cyanononane, 1-cyanodecane, 2-cyanodecane, 1-cyanoundecane and 1-cyanododecane.
  • Chlorocarbon compatibilizers of the present invention comprise chlorocarbons represented by the formula RClx, wherein; x is selected from the integers 1 or 2; R is selected from aliphatic and alicyclic hydrocarbon radicals having 1 to 12 carbon atoms; and wherein said chlorocarbons have a molecular weight of from about 100 to about 200 atomic mass units. The molecular weight of said chlorocarbon compatibilizers is preferably from about 120 to 150 atomic mass units. Representative R aliphatic and alicyclic hydrocarbon radicals in the general formula RClx include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and their configurational isomers.
  • Representative chlorocarbon compatibilizers include but are not limited to: 3-(chloromethyl)pentane, 3-chloro-3-methylpentane, 1-chlorohexane, 1,6-dichlorohexane, 1-chloroheptane, 1-chlorooctane, 1-chlorononane, 1-chlorodecane, and 1,1,1-trichlorodecane.
  • Ester compatibilizers of the present invention comprise esters represented by the general formula R1CO2R2, wherein R1 and R2 are independently selected from linear and cyclic, saturated and unsaturated, alkyl and aryl radicals. Preferred esters consist essentially of the elements C, H and O, have a molecular weight of from about 80 to about 550 atomic mass units.
  • Representative esters include but are not limited to: (CH3)2CHCH2OOC(CH2)2-4OCOCH2CH(CH3)2 (diisobutyl dibasic ester), ethyl hexanoate, ethyl heptanoate, n-butyl propionate, n-propyl propionate, ethyl benzoate, di-n-propyl phthalate, benzoic acid ethoxyethyl ester, dipropyl carbonate, “Exxate 700” (a commercial C7 alkyl acetate), “Exxate 800” (a commercial C8 alkyl acetate), dibutyl phthalate, and tert-butyl acetate.
  • Lactone compatibilizers of the present invention comprise lactones represented by structures [A], [B], and [C]:
  • Figure US20090314015A1-20091224-C00004
  • These lactones contain the functional group —CO2— in a ring of six (A), or preferably five atoms (B), wherein for structures [A] and [B], R1 through R8 are independently selected from hydrogen or linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl radicals. Each R1 though R8 may be connected forming a ring with another R1 through R8. The lactone may have an exocyclic alkylidene group as in structure [C], wherein R1 through R6 are independently selected from hydrogen or linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl radicals. Each R1 though R6 may be connected forming a ring with another R1 through R6. The lactone compatibilizers have a molecular weight range of from about 100 to about 300 atomic mass units, preferred from about 100 to about 200 atomic mass units.
  • Representative lactone compatibilizers include but are not limited to the compounds listed in Table 8.
  • TABLE 8
    Molecular
    Molecular Weight
    Additive Molecular Structure Formula (amu)
    (E,Z)-3-ethylidene-5- methyl-dihydro-furan-2- one
    Figure US20090314015A1-20091224-C00005
         		C7H10O2 126
    (E,Z)-3-propylidene-5- methyl-dihydro-furan-2- one
    Figure US20090314015A1-20091224-C00006
         		C8H12O2 140
    (E,Z)-3-butylidene-5- methyl-dihydro-furan-2- one
    Figure US20090314015A1-20091224-C00007
         		C9H14O2 154
    (E,Z)-3-pentylidene-5- methyl-dihydro-furan-2- one
    Figure US20090314015A1-20091224-C00008
         		C10H16O2 168
    (E,Z)-3-Hexylidene-5- methyl-dihydro-furan-2- one
    Figure US20090314015A1-20091224-C00009
         		C11H18O2 182
    (E,Z)-3-Heptylidene-5- methyl-dihydro-furan-2- one
    Figure US20090314015A1-20091224-C00010
         		C12H20O2 196
    (E,Z)-3-octylidene-5- methyl-dihydro-furan-2- one
    Figure US20090314015A1-20091224-C00011
         		C13H22O2 210
    (E,Z)-3-nonylidene-5- methyl-dihydro-furan-2- one
    Figure US20090314015A1-20091224-C00012
         		C14H24O2 224
    (E,Z)-3-decylidene-5- methyl-dihydro-furan-2- one
    Figure US20090314015A1-20091224-C00013
         		C15H26O2 238
    (E,Z)-3-(3,5,5- trimethylhexylidene)-5- methyl-dihydrofuran-2- one
    Figure US20090314015A1-20091224-C00014
         		C14H24O2 224
    (E,Z)-3- cyclohexylmethylidene- 5-methyl-dihydrofuran- 2-one
    Figure US20090314015A1-20091224-C00015
         		C12H18O2 194
    gamma-octalactone
    Figure US20090314015A1-20091224-C00016
         		C8H14O2 142
    gamma-nonalactone
    Figure US20090314015A1-20091224-C00017
         		C9H16O2 156
    gamma-decalactone
    Figure US20090314015A1-20091224-C00018
         		C10H18O2 170
    gamma-undecalactone
    Figure US20090314015A1-20091224-C00019
         		C11H20O2 184
    gamma-dodecalactone
    Figure US20090314015A1-20091224-C00020
         		C12H22O2 198
    3-hexyldihydro-furan-2- one
    Figure US20090314015A1-20091224-C00021
         		C10H18O2 170
    3-heptyldihydro-furan- 2-one
    Figure US20090314015A1-20091224-C00022
         		C11H20O2 184
    cis-3-ethyl-5-methyl- dihydro-furan-2-one
    Figure US20090314015A1-20091224-C00023
         		C7H12O2 128
    cis-(3-propyl-5-methyl)- dihydro-furan-2-one
    Figure US20090314015A1-20091224-C00024
         		C8H14O2 142
    cis-(3-butyl-5-methyl)- dihydro-furan-2-one
    Figure US20090314015A1-20091224-C00025
         		C9H16O2 156
    cis-(3-pentyl-5-methyl)- dihydro-furan-2-one
    Figure US20090314015A1-20091224-C00026
         		C10H18O2 170
    cis-3-hexyl-5-methyl- dihydro-furan-2-one
    Figure US20090314015A1-20091224-C00027
         		C11H20O2 184
    cis-3-heptyl-5-methyl- dihydro-furan-2-one
    Figure US20090314015A1-20091224-C00028
         		C12H22O2 198
    cis-3-octyl-5-methyl- dihydro-furan-2-one
    Figure US20090314015A1-20091224-C00029
         		C13H24O2 212
    cis-3-(3,5,5- trimethylhexyl)-5- methyl-dihydro-furan-2- one
    Figure US20090314015A1-20091224-C00030
         		C14H26O2 226
    cis-3-cyclohexylmethyl- 5-methyl-dihydro-furan- 2-one
    Figure US20090314015A1-20091224-C00031
         		C12H20O2 196
    5-methyl-5-hexyl- dihydro-furan-2-one
    Figure US20090314015A1-20091224-C00032
         		C11H20O2 184
    5-methyl-5-octyl- dihydro-furan-2-one
    Figure US20090314015A1-20091224-C00033
         		C13H24O2 212
    Hexahydro- isobenzofuran-1-one
    Figure US20090314015A1-20091224-C00034
         		C8H12O2 140
    delta-decalactone
    Figure US20090314015A1-20091224-C00035
         		C10H18O2 170
    delta-undecalactone
    Figure US20090314015A1-20091224-C00036
         		C11H20O2 184
    delta-dodecalactone
    Figure US20090314015A1-20091224-C00037
         		C12H22O2 198
    mixture of 4-hexyl- dihydrofuran-2-one and 3-hexyl-dihydro-furan- 2-one
    Figure US20090314015A1-20091224-C00038
         		C10H18O2 170
  • Lactone compatibilizers generally have a kinematic viscosity of less than about 7 centistokes at 40° C. For instance, gamma-undecalactone has kinematic viscosity of 5.4 centistokes and cis-(3-hexyl-5-methyl)dihydrofuran-2-one has viscosity of 4.5 centistokes both at 40° C. Lactone compatibilizers may be available commercially or prepared by methods as described in U.S. patent application Ser. No. 10/910,495 filed Aug. 3, 2004, incorporated herein by reference.
  • Aryl ether compatibilizers of the present invention further comprise aryl ethers represented by the formula R1OR2, wherein: R1 is selected from aryl hydrocarbon radicals having from 6 to 12 carbon atoms; R2 is selected from aliphatic hydrocarbon radicals having from 1 to 4 carbon atoms; and wherein said aryl ethers have a molecular weight of from about 100 to about 150 atomic mass units. Representative R1 aryl radicals in the general formula R1OR2 include phenyl, biphenyl, cumenyl, mesityl, tolyl, xylyl, naphthyl and pyridyl. Representative R2 aliphatic hydrocarbon radicals in the general formula R1OR2 include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl. Representative aromatic ether compatibilizers include but are not limited to: methyl phenyl ether (anisole), 1,3-dimethyoxybenzene, ethyl phenyl ether and butyl phenyl ether.
  • Fluoroether compatibilizers of the present invention comprise those represented by the general formula R1OCF2CF2H, wherein R1 is selected from aliphatic, alicyclic, and aromatic hydrocarbon radicals having from about 5 to about 15 carbon atoms, preferably primary, linear, saturated, alkyl radicals. Representative fluoroether compatibilizers include but are not limited to: C8H17OCF2CF2H and C6H13OCF2CF2H. It should be noted that if the refrigerant is a fluoroether, then the compatibilizer may not be the same fluoroether.
  • Fluoroether compatibilizers may further comprise ethers derived from fluoroolefins and polyols. The fluoroolefins may be of the type CF2═CXY, wherein X is hydrogen, chlorine or fluorine, and Y is chlorine, fluorine, CF3 or ORf, wherein Rf is CF3, C2F5, or C3F7. Representative fluoroolefins are tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, and perfluoromethylvinyl ether. The polyols may be linear or branched. Linear polyols may be of the type HOCH2(CHOH)x(CRR′)yCH2OH, wherein R and R′ are hydrogen, or CH3, or C2H5 and wherein x is an integer from 0-4, and y is an integer from 0-4. Branched polyols may be of the type C(OH)t(R)u(CH2OH)v[(CH2)mCH2OH]w, wherein R may be hydrogen, CH3 or C2H5, m may be an integer from 0 to 3, t and u may be 0 or 1, v and w are integers from 0 to 4, and also wherein t+u+v+w=4. Representative polyols are trimethylol propane, pentaerythritol, butanediol, and ethylene glycol.
  • 1,1,1-trifluoroalkane compatibilizers of the present invention comprise 1,1,1-trifluoroalkanes represented by the general formula CF3R1, wherein R1 is selected from aliphatic and alicyclic hydrocarbon radicals having from about 5 to about 15 carbon atoms, preferably primary, linear, saturated, alkyl radicals. Representative 1,1,1-trifluoroalkane compatibilizers include but are not limited to: 1,1,1-trifluorohexane and 1,1,1-trifluorododecane.
  • By effective amount of compatibilizer is meant that amount of compatibilizer that leads to efficient solubilizing of the lubricant in the composition and thus provides adequate oil return to optimize operation of the refrigeration, air-conditioning or heat pump apparatus.
  • The compositions of the present invention will typically contain from 0.1 to about 40 weight percent, preferably from about 0.2 to about 20 weight percent, and most preferably from about 0.3 to about 10 weight percent compatibilizer in the compositions of the present invention.
  • The heat transfer fluid of the present invention may be solubilized in a refrigeration lubricant selected from the group consisting of mineral oils, alkylbenzenes, synthetic paraffins, synthetic napthenes, and poly(alpha)olefins, wherein said method comprises contacting said lubricant with said composition in the presence of an effective amount of a compatibilizer, wherein said compatibilizer is selected from the group consisting of polyoxyalkylene glycol ethers, amides, nitriles, ketones, chlorocarbons, esters, lactones, aryl ethers, fluoroethers and 1,1,1-trifluoroalkanes.
  • The compositions of the present invention may further comprise an ultra-violet (UV) dye and optionally a solubilizing agent. The UV dye is a useful component for detecting leaks of the composition by permitting one to observe the fluorescence of the dye in the composition at a leak point or in the vicinity of refrigeration, air-conditioning, or heat pump apparatus. One may observe the fluoroscence of the dye under an ultra-violet light. Solubilizing agents may be needed due to poor solubility of such UV dyes in some compositions.
  • By “ultra-violet” dye is meant a UV fluorescent composition that absorbs light in the ultra-violet or “near” ultra-violet region of the electromagnetic spectrum. The fluorescence produced by the UV fluorescent dye under illumination by a UV light that emits radiation with wavelength anywhere from 10 nanometer to 750 nanometer may be detected. Therefore, if a composition containing such a UV fluorescent dye is leaking from a given point in a refrigeration, air-conditioning, or heat pump apparatus, the fluorescence can be detected at the leak point. Such UV fluorescent dyes include but are not limited to naphthalimides, perylenes, coumarins, anthracenes, phenanthracenes, xanthenes, thioxanthenes, naphthoxanthenes, fluoresceins, and derivatives or combinations thereof.
  • Solubilizing agents of the present invention comprise at least one compound selected from the group consisting of hydrocarbons, hydrocarbon ethers, dimethylether, polyoxyalkylene glycol ethers, amides, nitriles, ketones, chlorocarbons, esters, lactones, aryl ethers, fluoroethers and 1,1,1-trifluoroalkanes. The polyoxyalkylene glycol ethers, amides, nitriles, ketones, chlorocarbons, esters, lactones, aryl ethers, fluoroethers and 1,1,1-trifluoroalkanes solubilizing agents have been defined previously herein as being compatibilizers for use with conventional refrigeration lubricants.
  • Hydrocarbon solubilizing agents of the present invention comprise hydrocarbons including straight chained, branched chain or cyclic alkanes or alkenes containing 5 or fewer carbon atoms and only hydrogen with no other functional groups. Representative hydrocarbon solubilizing agents comprise propane, propylene, cyclopropane, n-butane, isobutane, 2-methylbutane and n-pentane. It should be noted that if the composition contains a hydrocarbon, then the solubilizing agent may not be the same hydrocarbon.
  • Hydrocarbon ether solubilizing agents of the present invention comprise ethers containing only carbon, hydrogen and oxygen, such as dimethyl ether (DME).
  • Solubilizing agents of the present invention may be present as a single compound, or may be present as a mixture of more than one solubilizing agent. Mixtures of solubilizing agents may contain two solubilizing agents from the same class of compounds, say two lactones, or two solubilizing agents from two different classes, such as a lactone and a polyoxyalkylene glycol ether.
  • In the present compositions comprising refrigerant and UV fluorescent dye, or comprising heat transfer fluid and UV fluorescent dye, from about 0.001 weight percent to about 1.0 weight percent of the composition is UV dye, preferably from about 0.005 weight percent to about 0.5 weight percent, and most preferably from 0.01 weight percent to about 0.25 weight percent.
  • Solubilizing agents such as ketones may have an objectionable odor, which can be masked by addition of an odor masking agent or fragrance. Typical examples of odor masking agents or fragrances may include Evergreen, Fresh Lemon, Cherry, Cinnamon, Peppermint, Floral or Orange Peel all commercially available, as well as d-limonene and pinene. Such odor masking agents may be used at concentrations of from about 0.001% to as much as about 15% by weight based on the combined weight of odor masking agent and solubilizing agent.
  • Solubility of these UV fluorescent dyes in the compositions of the present invention may be poor. Therefore, methods for introducing these dyes into the refrigeration, air-conditioning, or heat pump apparatus have been awkward, costly and time consuming. U.S. Pat. No. RE 36,951 describes a method, which utilizes a dye powder, solid pellet or slurry of dye that may be inserted into a component of the refrigeration, air-conditioning, or heat pump apparatus. As refrigerant and lubricant are circulated through the apparatus, the dye is dissolved or dispersed and carried throughout the apparatus. Numerous other methods for introducing dye into a refrigeration or air conditioning apparatus are described in the literature.
  • Ideally, the UV fluorescent dye could be dissolved in the refrigerant itself thereby not requiring any specialized method for introduction to the refrigeration, air conditioning apparatus, or heat pump. The present invention relates to compositions including UV fluorescent dye, which may be introduced into the system as a solution in the refrigerant. The inventive compositions will allow the storage and transport of dye-containing compositions even at low temperatures while maintaining the dye in solution.
  • In the present compositions comprising refrigerant, UV fluorescent dye and solubilizing agent, or comprising heat transfer fluid and UV fluorescent dye and solubilizing agent, from about 1 to about 50 weight percent, preferably from about 2 to about 25 weight percent, and most preferably from about 5 to about 15 weight percent of the combined composition is solubilizing agent. In the compositions of the present invention the UV fluorescent dye is present in a concentration from about 0.001 weight percent to about 1.0 weight percent, preferably from 0.005 weight percent to about 0.5 weight percent, and most preferably from 0.01 weight percent to about 0.25 weight percent.
    • EXAMPLES Example 1
  • A hose is constructed according to one embodiment of the invention in the following manner. A mandrel is first made in the form of a solid rod with a diameter of 6.4 mm. A veneer consisting of an inner layer of 0.65 mm thick Zytel® 42 (a high MWA 66 commercially available from E.I. du Pont de Nemours and Company) and 0.1 mm thick outer tie layer of Bynel® 4206 (a maleic anhydride grafted polyethylene commercially available from E.I. du Pont de Nemours and Company) is extruded over the mandrel. The assembly is then laminated with a metal-polymer laminate available as BFW 46 and obtained from James Dawson Enterprises Ltd of Lachine, Quebec, Canada. The laminate consists of an inner layer of low density polyethylene, a tie layer of EEA, an aluminum foil (10 micron thick) and an outer layer of polyethylene terephthalate (PET) with a total thickness of 0.1 mm. Lamination is carried out using a heated die with a passage way of appropriate size to pass the assembly through. The assembly of the previous step is uncoiled from a spool and a strip of metal-polymer laminate is wrapped around it such that two long edges of the strip mat against each other. The assembly is passed through the die heated to 140 C to affect the bonding. Excess laminate edge is trimmed off carefully so as not to damage the seal and avoid exposing underlying layer. A layer of TPV is extruded over the assembly. Following that, a braid of PET filaments is applied, and outer protective layer of ETPV is extruded over the top. The mandrel is subsequently extracted to prepare the multi-layer hose.
    • Example 2
  • Samples of hoses as described Example 1 were tested for hose permeation following the procedure outlined in Standard SAE J2064. Lengths of hose were cut and fitted at the ends to contain refrigerant. Hoses were charged with refrigerant to 70% by volume. Hoses were then placed in an oven and held at 80 C for 28 days. Hoses were periodically removed and weighed to determine refrigerant loss. An overall loss or permeation rate was then determined in kg/m2/yr. Results are shown in Table 9.
  • TABLE 9
    Hose Permeation Rate
    Refrigerant Composition (kg/m2/yr)
    R134a 0.44
    1225ye/R32 (95/5 wt %) 0.45
    1225ye/1234yf/134a (45/45/10 wt %) 0.07
  • Results show hoses permeation for fluoroolefin compositions are at least equivalent to R134a. Since R32 is a small molecule, it contributes the most to hose permeation. The composition containing primarily fluoroolefins and a small amount of R134a had significantly lower permeation than R134a alone indicating, indicating fluoroolefins have overall lower permeation rates.

Claims (13)

1. A method of providing transport of a heat transfer fluid composition within a refrigeration or air conditioning system, comprising circulating a heat transfer fluid through one or more hoses of said system, wherein said heat transfer fluid composition comprises a compound selected from the group consisting of: R32, R152a, CF3I, 1234yf, 1225ye and trans-1234ze.
2. The method of claim 1, wherein the method comprises the steps of circulating the heat transfer fluid composition from a hose connected between the outlet of a compressor and the inlet of a condenser.
3. The method of claim 2, further comprising the step of circulating the heat transfer fluid composition through a hose connected between an outlet of the condenser and an inlet of an evaporator.
4. The method of claim 3, further comprising the step of circulating the heat transfer fluid composition through a hose connected between an outlet of the evaporator and an inlet of the compressor.
5. The method of claim 3, wherein the hose comprises an outer layer comprising a material selected from the group consisting of an elastomer and a polyamide and an inner layer comprising a material selected from the group consisting of an elastomer, a polyamide and a thermoplastic.
6. The method of claim 5, wherein the inner layer comprises a thermoplastic veneer and the outer layer comprises an elastomer.
7. The method of claim 6, further including:
(a) a tie layer positioned over said inner layer;
(b) a metal-polymer laminate positioned over said tie layer and consisting of a layer of polymer compatible with or bondable to said outer surface of said veneer, a thin layer of metallic foil, and another layer of a polymer protecting the metallic foil;
(c) a braid under-layer positioned over said metal-polymer laminate and consisting of an elastomeric material; and
(d) a reinforcing braid layer positioned over said braid under-layer, wherein the outer layer is positioned on the outside of the reinforcing braid layer.
8. The method of claim 7, further comprising one or more additional reinforcing braid layers (d) and/or one or more additional outer layers.
9. The method of claim 1, wherein the heat transfer fluid composition comprises HFC-1225ye and at least one additional compound selected from the group consisting of HFC-1234ze, HFC-1234yf, HFC-1234ye, HFC-1243zf, HFC-32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethylether, CF3SCF3, CO2, NH3, and CF3I.
10. The method of claim 1, wherein the heat transfer fluid composition comprises HFC-1234ze and at least one additional compound selected from the group consisting of HFC-1234yf, HFC-1234ye, HFC-1243zf, HFC-32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethylether, CF3SCF3, CO2 and CF3I.
11. The method of claim 1, wherein the heat transfer fluid composition comprises HFC-1234yf and at least one additional compound selected from the group consisting of HFC-1234ye, HFC-1243zf, HFC-32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethylether, CF3SCF3, CO2, NH3, and CF3I.
12. The method of claim 1, wherein the heat transfer fluid composition comprises HFC-1243zf and at least one additional compound selected from the group consisting of HFC-1234ye, HFC-32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethylether, CF3SCF3, CO2 and CF3I.
13. The method of claim 1, wherein the heat transfer fluid composition comprises HFC-1234ye and at least one additional compound selected from the group consisting of HFC-1243zf, HFC-32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethylether, CF3SCF3, CO2 and CF3I.
US12/377,686 2006-09-01 2007-08-31 Method for circulating selected heat transfer fluids through a closed loop cycle Abandoned US20090314015A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US12/377,686 US20090314015A1 (en) 2006-09-01 2007-08-31 Method for circulating selected heat transfer fluids through a closed loop cycle

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US84171306P 2006-09-01 2006-09-01
US12/377,686 US20090314015A1 (en) 2006-09-01 2007-08-31 Method for circulating selected heat transfer fluids through a closed loop cycle
PCT/US2007/019205 WO2008027555A2 (en) 2006-09-01 2007-08-31 Method for circulating selected heat transfer fluids through a closed loop cycle

Publications (1)

Publication Number Publication Date
US20090314015A1 true US20090314015A1 (en) 2009-12-24

Family

ID=39136628

Family Applications (1)

Application Number Title Priority Date Filing Date
US12/377,686 Abandoned US20090314015A1 (en) 2006-09-01 2007-08-31 Method for circulating selected heat transfer fluids through a closed loop cycle

Country Status (9)

Country Link
US (1) US20090314015A1 (en)
EP (2) EP2602299A2 (en)
JP (1) JP2010513827A (en)
KR (1) KR20090049617A (en)
CN (1) CN101827912A (en)
BR (1) BRPI0714896A2 (en)
CA (1) CA2661007A1 (en)
RU (1) RU2009111881A (en)
WO (1) WO2008027555A2 (en)

Cited By (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090075439A1 (en) * 2006-01-31 2009-03-19 International Business Machines Corporation Microelectronic structure by selective deposition
US20100044619A1 (en) * 2003-10-27 2010-02-25 Honeywell International Inc. Compositions Containing Difluoromethane and Fluorine Substituted Olefins
US20110108757A1 (en) * 2008-07-01 2011-05-12 Daikin Industries, Ltd. REFRIGERANT COMPOSITION COMPRISING 1,1,1,2-TETRAFLUOROETHANE (HFC134a) AND 2,3,3,3-TETRAFLUOROPROPENE (HFO1234yf)
US20110186772A1 (en) * 2008-10-08 2011-08-04 Arkerna France Heat transfer fluid
WO2011107698A2 (en) * 2010-03-02 2011-09-09 Arkema France Heat-transfer fluid for a centrifugal compressor
CN102782076A (en) * 2010-02-16 2012-11-14 墨西哥化学阿玛科股份有限公司 Heat transfer compositions
US20130025733A1 (en) * 2009-08-12 2013-01-31 Kazuto Yamakawa Hose for refrigerant transport use
WO2013012563A3 (en) * 2011-07-20 2013-06-13 Honeywell International Inc. Low gwp heat transfer compositions containing difluoromethane and 1,3,3,3-tetrafluoropropene
US20140248706A1 (en) * 2009-02-26 2014-09-04 Daikin Industries, Ltd. Refrigerant composition containing hydrofluoropropene with low-global warming potential
US8940180B2 (en) 2012-11-21 2015-01-27 Honeywell International Inc. Low GWP heat transfer compositions
US8951432B2 (en) 2011-06-07 2015-02-10 Arkema France Binary compositions of 1,3,3,3-tetrafluoropropene and ammonia
US8980118B2 (en) 2009-05-08 2015-03-17 Honeywell International Inc. Heat transfer compositions and methods
US9005468B2 (en) 2010-05-11 2015-04-14 Arkema France Heat-transfer fluids and use thereof in countercurrent heat exchangers
US9039922B2 (en) 2009-09-11 2015-05-26 Arkema France Low-temperature and average-temperature refrigeration
US9039923B2 (en) 2012-02-14 2015-05-26 United Technologies Corporation Composition of zeotropic mixtures having predefined temperature glide
US20150240668A1 (en) * 2012-09-11 2015-08-27 Amovis Gmbh Working medium mixture for steam engines
US9133379B2 (en) 2009-09-11 2015-09-15 Arkema France Binary refrigerating fluid
US9315706B2 (en) 2010-09-20 2016-04-19 Arkema France 3,3,3-trifluoropropene compositions
US9683157B2 (en) 2009-09-11 2017-06-20 Arkema France Heat transfer method
US9783721B2 (en) 2012-08-20 2017-10-10 Honeywell International Inc. Low GWP heat transfer compositions
US9982180B2 (en) 2013-02-13 2018-05-29 Honeywell International Inc. Heat transfer compositions and methods
US10035938B2 (en) 2009-09-11 2018-07-31 Arkema France Heat transfer fluid replacing R-134a
US20190016937A1 (en) * 2009-12-18 2019-01-17 Arkema France Heat-transfer fluids having reduced flammability
US10308854B2 (en) 2010-05-11 2019-06-04 Arkema France Heat-transfer fluids and use thereof in countercurrent heat exchangers
US20200165500A1 (en) * 2016-02-29 2020-05-28 The Chemours Company Fc, Llc Refrigerant mixtures comprising difluoromethane, pentafluoroethane, tetrafluoroethane, tetrafluoropropene, and carbon dioxide and uses thereof
US10767091B2 (en) 2017-11-30 2020-09-08 Honeywell International Inc. Heat transfer compositions, methods, and systems
US10808157B2 (en) 2008-11-03 2020-10-20 Arkema France Vehicle heating and/or air conditioning method
US11028300B1 (en) 2020-09-16 2021-06-08 David L. Couchot Environmentally friendly refrigerant compositions
EP3717589A4 (en) * 2017-11-30 2021-08-18 Honeywell International Inc. Heat transfer compositions, methods, and systems
US11306235B2 (en) 2009-07-29 2022-04-19 Honeywell International Inc. Compositions containing difluoromethane and fluorine substituted olefins
EP3794088A4 (en) * 2018-05-15 2022-04-20 Srf Limited Azeotrope or azeotrope like compositions comprising 1234yf
US11359122B2 (en) 2017-03-21 2022-06-14 Arkema France Method for heating and/or air-conditioning in a vehicle
US11370948B2 (en) 2017-03-21 2022-06-28 Arkema France Tetrafluoropropene-based composition
US11624534B2 (en) 2007-05-11 2023-04-11 The Chemours Company Fc, Llc Method for exchanging heat in vapor compression heat transfer systems and vapor compression heat transfer systems comprising intermediate heat exchangers with dual-row evaporators or condensers
US11885561B2 (en) * 2012-12-04 2024-01-30 Conocophillips Company Low global-warming refrigerants in LNG processing

Families Citing this family (69)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2156158A1 (en) 2007-06-21 2010-02-24 E. I. Du Pont de Nemours and Company Method for leak detection in heat transfer system
EP2171012A1 (en) * 2007-07-27 2010-04-07 E. I. du Pont de Nemours and Company Compositions comprising fluoroolefins and uses thereof
US8628681B2 (en) 2007-10-12 2014-01-14 Mexichem Amanco Holding S.A. De C.V. Heat transfer compositions
US8512591B2 (en) 2007-10-12 2013-08-20 Mexichem Amanco Holding S.A. De C.V. Heat transfer compositions
US8333901B2 (en) 2007-10-12 2012-12-18 Mexichem Amanco Holding S.A. De C.V. Heat transfer compositions
GB2457345B (en) * 2007-10-12 2012-02-08 Ineos Fluor Holdings Ltd Heat transfer compositions
GB201002625D0 (en) * 2010-02-16 2010-03-31 Ineos Fluor Holdings Ltd Heat transfer compositions
JP2009257742A (en) * 2008-03-25 2009-11-05 Daikin Ind Ltd Refrigerating device and manufacturing method therefor
JP2009270727A (en) 2008-04-30 2009-11-19 Sanden Corp Refrigerating circuit
WO2010002016A1 (en) * 2008-07-01 2010-01-07 Daikin Industries, Ltd. REFRIGERANT COMPOSITION COMPRISING DIFLUOROMETHANE (HFC32) AND 2,3,3,3-TETRAFLUOROPROPENE (HFO1234yf)
WO2010002023A1 (en) * 2008-07-01 2010-01-07 Daikin Industries, Ltd. REFRIGERANT COMPOSITION COMPRISING DIFLUOROMETHANE (HFC32), 2,3,3,3-TETRAFLUOROPROPENE (HFO1234yf) AND 1,1,1,2-TETRAFLUOROETHANE (HFC134a)
US8496845B2 (en) 2008-07-01 2013-07-30 Daikin Industries, Ltd. Refrigerant composition comprising difluoromethane (HFC32), pentafluoroethane (HFC125) and 2, 3, 3, 3-tetrafluoropropene (HFO1234yf)
WO2010002022A1 (en) * 2008-07-01 2010-01-07 Daikin Industries, Ltd. REFRIGERANT COMPOSITION COMPRISING PENTAFLUOROETHANE (HFC125), 2,3,3,3-TETRAFLUOROPROPENE (HFO1234yf) AND 1,1,1,2-TETRAFLUOROETHANE (HFC134a)
ES2581933T3 (en) * 2008-07-30 2016-09-08 Honeywell International Inc. Compositions containing olefins substituted with difluoromethane and fluorine
CA2674256C (en) * 2008-07-30 2019-02-12 Honeywell International Inc. Compositions containing difluoromethane and fluorine substituted olefins
JP2010060262A (en) * 2008-08-04 2010-03-18 Sanden Corp Resin material for refrigeration circuit
FR2937906B1 (en) 2008-11-03 2010-11-19 Arkema France METHOD FOR HEATING AND / OR AIR CONDITIONING A VEHICLE
DE202009019199U1 (en) * 2008-11-19 2018-10-15 The Chemours Company Fc, Llc Tetrafluoropropene compositions and their uses
FR2938550B1 (en) * 2008-11-20 2010-11-12 Arkema France COMPOSITION COMPRISING 2,3,3,3-TETRAFLUOROPROPENE METHOD FOR HEATING AND / OR AIR CONDITIONING A VEHICLE
BRPI0921128A2 (en) * 2008-12-02 2016-02-16 Mexichem Amanco Holding Sa heat transfer composition and device, use of a composition, whey agent, foamable composition, foam, sprayable composition, methods for cooling, heating and cleaning an article, to extract a substance from biomass, a material from an aqueous solution , and a particulate solid matrix material, for retrofitting a heat transfer device, for reducing the environmental impact arising from the operation of a product, for preparing a composition, and for generating heat transfer composition and device. , use of a composition, whey agent, foamable composition, foam, sprayable composition, methods for cooling, heating and cleaning an article, for extracting a substance from biomass, a material from an aqueous solution, and a particulate solid matrix material , to retrofit a heat transfer device, to reduce the environmental impact arising from the operation of a product, to prepare a composition and, to generate greenhouse gas emission credit, and mechanical power generation device.
FR2942237B1 (en) * 2009-02-13 2013-01-04 Arkema France METHOD FOR HEATING AND / OR AIR CONDITIONING A VEHICLE
US9074115B2 (en) 2009-08-28 2015-07-07 Mexichem Amanco Holding S.A. De C.V. Heat transfer compositions
GB0915004D0 (en) * 2009-08-28 2009-09-30 Ineos Fluor Holdings Ltd Heat transfer composition
FR2950071B1 (en) * 2009-09-11 2012-02-03 Arkema France TERNARY COMPOSITIONS FOR LOW CAPACITY REFRIGERATION
FR2950070B1 (en) * 2009-09-11 2011-10-28 Arkema France TERNARY COMPOSITIONS FOR HIGH CAPACITY REFRIGERATION
CN102925110A (en) * 2009-10-13 2013-02-13 天津大学 Organic Rankine cycle mixed refrigerant containing HFC-143(1,1,2-halothane)
CN102732220A (en) * 2009-10-13 2012-10-17 天津大学 Organic Rankine cycle mixed refrigerant containing HFO-1234yf(CF3CF=CH2)
CN102311719A (en) * 2009-10-13 2012-01-11 天津大学 Organic Rankine cycle mixed working fluid containing HFO-1234yf(CF3CF=CH2)
US20110100605A1 (en) * 2009-11-05 2011-05-05 Wanlie Zheng Cooling device and system
RU2012131163A (en) 2009-12-21 2014-01-27 Е.И.Дюпон Де Немур Энд Компани COMPOSITIONS CONTAINING TETRAFluoropropene and difluoromethane, AND THEIR APPLICATION
GB201002616D0 (en) * 2010-02-16 2010-03-31 Ineos Fluor Holdings Ltd Heat transfer compositions
GB201002618D0 (en) * 2010-02-16 2010-03-31 Ineos Fluor Ltd Heat transfet compositions
GB201002622D0 (en) 2010-02-16 2010-03-31 Ineos Fluor Holdings Ltd Heat transfer compositions
CN102844400B (en) 2010-04-16 2016-10-12 纳幕尔杜邦公司 Comprise 2,3,3,3-tetrafluoropropenes and the compositions of HFA 134a, the cooler comprising them and the method producing cooling wherein
EP2957617A1 (en) * 2010-05-20 2015-12-23 Mexichem Fluor S.A. de C.V. Heat transfer compositions
GB2480517B (en) * 2010-05-20 2013-03-06 Mexichem Amanco Holding Sa Heat transfer compositions
ES2565088T3 (en) 2010-05-20 2016-03-31 Mexichem Fluor S.A. De C.V. Heat transfer compositions
CN101864276A (en) * 2010-06-03 2010-10-20 集美大学 Environment-friendly refrigerant
CN101851490B (en) * 2010-06-04 2012-10-24 集美大学 Refrigerant composition capable of replacing HFC-134a
GB2481443B (en) 2010-06-25 2012-10-17 Mexichem Amanco Holding Sa Heat transfer compositions
FR2962130B1 (en) 2010-06-30 2012-07-20 Arkema France COMPOSITION BASED ON 2,3,3,3-TETRAFLUOROPROPENE
EP2652065B2 (en) 2010-12-14 2019-05-15 The Chemours Company FC, LLC Use of refrigerants comprising e-1,3,3,3-tetrafluoropropene and at least one tetrafluoroethane for cooling
FR2971512B1 (en) 2011-02-10 2013-01-18 Arkema France BINARY COMPOSITIONS OF 2,3,3,3-TETRAFLUOROPROPENE AND AMMONIA
FR2973805B1 (en) * 2011-04-08 2013-04-12 Arkema France COMPOSITIONS COMPRISING 3,3,3-TRIFLUOROPROPENE AND AMMONIA
JP2014141537A (en) * 2011-05-19 2014-08-07 Asahi Glass Co Ltd Working medium and heat cycle system
JP2014141538A (en) * 2011-05-19 2014-08-07 Asahi Glass Co Ltd Working medium and heat cycle system
KR20130017040A (en) * 2011-08-09 2013-02-19 현대자동차주식회사 Multilayer tube for transmission oil cooler
CN102676119B (en) * 2012-05-24 2014-01-29 浙江大学 Refrigerant with low GWP (global warming potential) and preparation method thereof
CN104955916A (en) * 2012-12-04 2015-09-30 霍尼韦尔国际公司 Low GWP heat transfer compositions
FR3008419B1 (en) 2013-07-11 2015-07-17 Arkema France 2,3,3,3-TETRAFLUOROPROPENE-BASED COMPOSITIONS HAVING IMPROVED MISCIBILITY
US10330364B2 (en) 2014-06-26 2019-06-25 Hudson Technologies, Inc. System and method for retrofitting a refrigeration system from HCFC to HFC refrigerant
RU2661418C1 (en) * 2017-01-24 2018-07-16 Сергей Вячеславович Поспелов Turbocharger thermal machine operating on a closed thermodynamic cycle with internal heat recovery
JP7287958B2 (en) * 2017-11-17 2023-06-06 ハネウェル・インターナショナル・インコーポレーテッド Heat transfer composition, method and system
US11078392B2 (en) 2017-12-29 2021-08-03 Trane International Inc. Lower GWP refrigerant compositions
US20200325373A1 (en) * 2018-01-15 2020-10-15 Mitsubishi Electric Corporation Air-conditioning apparatus
CN110343510B (en) * 2018-04-02 2021-06-04 江西天宇化工有限公司 Non-flammable mixed refrigerant with low-temperature chamber effect and application thereof
EP3814446A1 (en) * 2018-06-28 2021-05-05 The Chemours Company FC, LLC Refrigerant blends having low global warming potential
CN109971433B (en) * 2019-04-08 2021-04-13 中国科学院理化技术研究所 Multi-component mixed refrigerant
CN110628390B (en) * 2019-09-12 2020-12-15 珠海格力电器股份有限公司 Environment-friendly mixed refrigerant, composition and heat exchange system
CN110746936B (en) * 2019-10-11 2021-05-04 金华永和氟化工有限公司 Environment-friendly mixed refrigerant
CN110878194B (en) * 2019-10-16 2020-11-17 珠海格力电器股份有限公司 R13I 1-containing environment-friendly mixed refrigerant and heat exchange system
CN110845997B (en) * 2019-10-16 2020-12-22 珠海格力电器股份有限公司 Heat transfer medium and composition suitable for cooler
CN111592858B (en) * 2020-05-21 2022-01-11 冰山松洋生物科技(大连)有限公司 Mixed refrigerant, refrigeration system and refrigeration device
CN112111249B (en) * 2020-09-28 2021-07-13 珠海格力电器股份有限公司 Mixed refrigerant, heat exchange system and household appliance
CN113046029B (en) * 2021-02-09 2022-06-28 浙江衢化氟化学有限公司 Composition containing fluoroolefin and preparation method thereof
CN113388371B (en) * 2021-06-07 2022-06-24 湖北瑞能华辉能源管理有限公司 Quaternary mixed refrigerant capable of replacing R22 or R410a and application thereof
CN113980649B (en) * 2021-11-09 2022-07-15 珠海格力电器股份有限公司 Mixed refrigerant and air conditioning system
CN114716975B (en) * 2022-04-08 2023-04-14 大连理工大学 Heat transfer working medium suitable for reverse Carnot circulation system
JP2024002978A (en) * 2022-06-23 2024-01-11 ダイキン工業株式会社 Transport method, refrigeration method, refrigeration system, and hose for refrigeration system

Citations (36)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3159183A (en) * 1961-07-17 1964-12-01 Moore & Co Samuel Composite tubing product, and apparatus and method for manufacturing same
US4510974A (en) * 1980-08-21 1985-04-16 Hitachi Cable Ltd. Fluid conveying hose
US5957164A (en) * 1998-09-10 1999-09-28 Aeroquip Corporation Refrigerant hose
USRE36951E (en) * 1994-08-29 2000-11-14 Spectronics Corporation Method of introducing leak detection dye into an air conditioning or refrigeration system including solid or semi-solid fluorescent dyes
US20010006712A1 (en) * 1999-12-27 2001-07-05 Motoshige Hibino Hose of impermeability and a process for manufacturing the same
US6261473B1 (en) * 1998-06-26 2001-07-17 Kabushiki Kaisha Sanai Working fluid containing 1,1-difluoroethane, 1,1,2,2-tetrafluoroethane and carbon dioxide
US20010013374A1 (en) * 2000-02-16 2001-08-16 Nobuaki Niki Fluid-impermeable composite hose
US20010023713A1 (en) * 2000-03-21 2001-09-27 Nobuaki Niki Fluid-impermeable composite hose
US20010045237A1 (en) * 2000-02-03 2001-11-29 Hisanobu Monobe Refrigerant transporting rubber hose
US6328075B1 (en) * 1999-01-11 2001-12-11 Tokai Rubber Industries, Ltd. Hose for transporting carbon dioxide refrigerant
US6345647B2 (en) * 2000-03-21 2002-02-12 Tokai Rubber Industries, Ltd. Fluid-impermeable composite hose
US20020056481A1 (en) * 2000-09-26 2002-05-16 The Yokohama Rubber Co., Ltd. Low permeable hose and method for producing the same
US20020056284A1 (en) * 2000-11-13 2002-05-16 Tetsuji Nobuta Refrigeration system
US6532994B1 (en) * 1998-08-13 2003-03-18 Aeroquip-Vickers International Gmbh Hollow body in the form of a flexible bar
US20030172982A1 (en) * 1998-08-12 2003-09-18 Silvia Enders Flexible cord-like hollow object
US20040040609A1 (en) * 2002-08-30 2004-03-04 The Yokohama Rubber Co., Ltd. Ultra-low permeation hose and method of manufacture
US20040089839A1 (en) * 2002-10-25 2004-05-13 Honeywell International, Inc. Fluorinated alkene refrigerant compositions
US20040119047A1 (en) * 2002-10-25 2004-06-24 Honeywell International, Inc. Compositions containing fluorine substituted olefins
US20040256594A1 (en) * 2002-10-25 2004-12-23 Honeywell International, Inc. Compositions containing fluorine substituted olefins
US20050011571A1 (en) * 2003-07-11 2005-01-20 Wilson Reji Paul Refrigerant hose
US20050211326A1 (en) * 2004-03-29 2005-09-29 Motoshige Hibino Composite hose with a corrugated metal tube and method for making the same
US20050233923A1 (en) * 2004-04-16 2005-10-20 Honeywell International, Inc. Azeotrope-like trifluoroiodomethane compositions
US20060011250A1 (en) * 2004-07-15 2006-01-19 Tokai Rubber Industries, Ltd. Refrigerant transportation hose
US20060030719A1 (en) * 2004-08-03 2006-02-09 Fagan Paul J Cis-3,5-disubstituted-dihydro-furan-2-ones and the preparation and use thereof
US7055553B2 (en) * 2003-02-27 2006-06-06 Titeflex Corporation Laminated hose construction having one or more intermediate metal barrier layers
US20060243945A1 (en) * 2005-03-04 2006-11-02 Minor Barbara H Compositions comprising a fluoroolefin
US20060243944A1 (en) * 2005-03-04 2006-11-02 Minor Barbara H Compositions comprising a fluoroolefin
US20070108403A1 (en) * 2005-11-01 2007-05-17 Sievert Allen C Compositions comprising fluoroolefins and uses thereof
US20080017266A1 (en) * 2006-07-24 2008-01-24 Doshi Shailesh R High pressure barrier hose and method of manufacture
US20080053553A1 (en) * 2006-09-01 2008-03-06 Doshi Shailesh R Method for circulating select heat transfer fluids through closed loop cycles, incorporating high pressure barrier hoses
US20080230738A1 (en) * 2005-03-04 2008-09-25 Barbara Haviland Minor Compositions comprising a fluoroolefin
US20100012302A1 (en) * 2006-12-19 2010-01-21 E. I. Du Pont De Nemours And Company Dual row heat exchanger and automobile bumper incorporating the same
US20110197604A1 (en) * 2007-12-20 2011-08-18 E.I. Dupont De Nemours And Company Secondary loop cooling system having a bypass and a method for bypassing a reservoir in the system
US8024937B2 (en) * 2007-06-21 2011-09-27 E. I. Du Pont De Nemours And Company Method for leak detection in heat transfer systems
US8058070B2 (en) * 2006-09-15 2011-11-15 E. I. Du Pont De Nemours And Company Method of determining the components of a fluoroolefin composition, method of recharging a fluid system in response thereto, and sensors used therefor
US8070355B2 (en) * 2006-09-15 2011-12-06 E. I. Du Pont De Nemours And Company Method of detecting leaks of fluoroolefin compositions and sensors used therefor

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000179758A (en) 1998-12-16 2000-06-27 Tokai Rubber Ind Ltd Coolant hose for electric compressor
JP4496629B2 (en) * 1999-09-27 2010-07-07 横浜ゴム株式会社 Low permeability hose and method for manufacturing the same
US6204405B1 (en) 1999-12-22 2001-03-20 Sigma-Aldrich Co. Economical and convenient procedures for the synthesis of catecholborane
AU2005236038B2 (en) * 2004-04-16 2008-10-02 Honeywell International Inc. Azeotrope-like compositions of difluoromethane and trifluoroiodomethane

Patent Citations (41)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3159183A (en) * 1961-07-17 1964-12-01 Moore & Co Samuel Composite tubing product, and apparatus and method for manufacturing same
US4510974A (en) * 1980-08-21 1985-04-16 Hitachi Cable Ltd. Fluid conveying hose
USRE36951E (en) * 1994-08-29 2000-11-14 Spectronics Corporation Method of introducing leak detection dye into an air conditioning or refrigeration system including solid or semi-solid fluorescent dyes
US6261473B1 (en) * 1998-06-26 2001-07-17 Kabushiki Kaisha Sanai Working fluid containing 1,1-difluoroethane, 1,1,2,2-tetrafluoroethane and carbon dioxide
US20030172982A1 (en) * 1998-08-12 2003-09-18 Silvia Enders Flexible cord-like hollow object
US6807989B2 (en) * 1998-08-12 2004-10-26 Aeroquip-Vickers International Gmbh Flexible cord-like hollow object
US6532994B1 (en) * 1998-08-13 2003-03-18 Aeroquip-Vickers International Gmbh Hollow body in the form of a flexible bar
US5957164A (en) * 1998-09-10 1999-09-28 Aeroquip Corporation Refrigerant hose
US6328075B1 (en) * 1999-01-11 2001-12-11 Tokai Rubber Industries, Ltd. Hose for transporting carbon dioxide refrigerant
US20050268979A1 (en) * 1999-12-27 2005-12-08 Tokai Rubber Industries, Ltd. Hose of impermeability and a process for manufacturing the same
US20010006712A1 (en) * 1999-12-27 2001-07-05 Motoshige Hibino Hose of impermeability and a process for manufacturing the same
US20010045237A1 (en) * 2000-02-03 2001-11-29 Hisanobu Monobe Refrigerant transporting rubber hose
US20010013374A1 (en) * 2000-02-16 2001-08-16 Nobuaki Niki Fluid-impermeable composite hose
US6390140B2 (en) * 2000-02-16 2002-05-21 Tokai Rubber Industries, Ltd. Fluid-impermeable composite hose
US6345647B2 (en) * 2000-03-21 2002-02-12 Tokai Rubber Industries, Ltd. Fluid-impermeable composite hose
US20010023713A1 (en) * 2000-03-21 2001-09-27 Nobuaki Niki Fluid-impermeable composite hose
US20040079430A1 (en) * 2000-09-26 2004-04-29 The Yokohama Rubber Co., Ltd. Low permeable hose and method for producing the same
US20020056481A1 (en) * 2000-09-26 2002-05-16 The Yokohama Rubber Co., Ltd. Low permeable hose and method for producing the same
US20020056284A1 (en) * 2000-11-13 2002-05-16 Tetsuji Nobuta Refrigeration system
US20040040609A1 (en) * 2002-08-30 2004-03-04 The Yokohama Rubber Co., Ltd. Ultra-low permeation hose and method of manufacture
US6988515B2 (en) * 2002-08-30 2006-01-24 The Yokohama Rubber Co., Ltd. Ultra-low permeation hose and method of manufacture
US20040256594A1 (en) * 2002-10-25 2004-12-23 Honeywell International, Inc. Compositions containing fluorine substituted olefins
US20040119047A1 (en) * 2002-10-25 2004-06-24 Honeywell International, Inc. Compositions containing fluorine substituted olefins
US20040089839A1 (en) * 2002-10-25 2004-05-13 Honeywell International, Inc. Fluorinated alkene refrigerant compositions
US7055553B2 (en) * 2003-02-27 2006-06-06 Titeflex Corporation Laminated hose construction having one or more intermediate metal barrier layers
US20050011571A1 (en) * 2003-07-11 2005-01-20 Wilson Reji Paul Refrigerant hose
US20050211326A1 (en) * 2004-03-29 2005-09-29 Motoshige Hibino Composite hose with a corrugated metal tube and method for making the same
US20050233923A1 (en) * 2004-04-16 2005-10-20 Honeywell International, Inc. Azeotrope-like trifluoroiodomethane compositions
US20060011250A1 (en) * 2004-07-15 2006-01-19 Tokai Rubber Industries, Ltd. Refrigerant transportation hose
US20060030719A1 (en) * 2004-08-03 2006-02-09 Fagan Paul J Cis-3,5-disubstituted-dihydro-furan-2-ones and the preparation and use thereof
US20060243945A1 (en) * 2005-03-04 2006-11-02 Minor Barbara H Compositions comprising a fluoroolefin
US20060243944A1 (en) * 2005-03-04 2006-11-02 Minor Barbara H Compositions comprising a fluoroolefin
US20080230738A1 (en) * 2005-03-04 2008-09-25 Barbara Haviland Minor Compositions comprising a fluoroolefin
US20070108403A1 (en) * 2005-11-01 2007-05-17 Sievert Allen C Compositions comprising fluoroolefins and uses thereof
US20080017266A1 (en) * 2006-07-24 2008-01-24 Doshi Shailesh R High pressure barrier hose and method of manufacture
US20080053553A1 (en) * 2006-09-01 2008-03-06 Doshi Shailesh R Method for circulating select heat transfer fluids through closed loop cycles, incorporating high pressure barrier hoses
US8058070B2 (en) * 2006-09-15 2011-11-15 E. I. Du Pont De Nemours And Company Method of determining the components of a fluoroolefin composition, method of recharging a fluid system in response thereto, and sensors used therefor
US8070355B2 (en) * 2006-09-15 2011-12-06 E. I. Du Pont De Nemours And Company Method of detecting leaks of fluoroolefin compositions and sensors used therefor
US20100012302A1 (en) * 2006-12-19 2010-01-21 E. I. Du Pont De Nemours And Company Dual row heat exchanger and automobile bumper incorporating the same
US8024937B2 (en) * 2007-06-21 2011-09-27 E. I. Du Pont De Nemours And Company Method for leak detection in heat transfer systems
US20110197604A1 (en) * 2007-12-20 2011-08-18 E.I. Dupont De Nemours And Company Secondary loop cooling system having a bypass and a method for bypassing a reservoir in the system

Cited By (62)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100044619A1 (en) * 2003-10-27 2010-02-25 Honeywell International Inc. Compositions Containing Difluoromethane and Fluorine Substituted Olefins
US8138100B2 (en) * 2006-01-31 2012-03-20 International Business Machines Corporation Microelectronic structure by selective deposition
US20090075439A1 (en) * 2006-01-31 2009-03-19 International Business Machines Corporation Microelectronic structure by selective deposition
US8697561B2 (en) 2006-01-31 2014-04-15 International Business Machines Corporation Microelectronic structure by selective deposition
US11867436B2 (en) 2007-05-11 2024-01-09 The Chemours Company Fc, Llc Method for exchanging heat in vapor compression heat transfer systems and vapor compression heat transfer systems comprising intermediate heat exchangers with dual-row evaporators or condensers
US11624534B2 (en) 2007-05-11 2023-04-11 The Chemours Company Fc, Llc Method for exchanging heat in vapor compression heat transfer systems and vapor compression heat transfer systems comprising intermediate heat exchangers with dual-row evaporators or condensers
US20110108757A1 (en) * 2008-07-01 2011-05-12 Daikin Industries, Ltd. REFRIGERANT COMPOSITION COMPRISING 1,1,1,2-TETRAFLUOROETHANE (HFC134a) AND 2,3,3,3-TETRAFLUOROPROPENE (HFO1234yf)
US8318039B2 (en) * 2008-07-01 2012-11-27 Daikin Industries, Ltd. Refrigerant composition comprising 1,1,1,2-tetrafluoroethane (HFC134a) and 2,3,3,3-tetrafluoropropene (HFO1234yf)
US20110186772A1 (en) * 2008-10-08 2011-08-04 Arkerna France Heat transfer fluid
US9599381B2 (en) 2008-10-08 2017-03-21 Arkema France Heat transfer fluid
US11130893B2 (en) 2008-10-08 2021-09-28 Arkema France Heat transfer fluid
US10808157B2 (en) 2008-11-03 2020-10-20 Arkema France Vehicle heating and/or air conditioning method
US20140248706A1 (en) * 2009-02-26 2014-09-04 Daikin Industries, Ltd. Refrigerant composition containing hydrofluoropropene with low-global warming potential
US9303198B2 (en) * 2009-02-26 2016-04-05 Daikin Industries, Ltd. Hydrofluoropropene refrigerant composition comprising phthalates
US8980118B2 (en) 2009-05-08 2015-03-17 Honeywell International Inc. Heat transfer compositions and methods
US11306235B2 (en) 2009-07-29 2022-04-19 Honeywell International Inc. Compositions containing difluoromethane and fluorine substituted olefins
US9845419B2 (en) * 2009-07-29 2017-12-19 Honeywell International Inc. Low GWP heat transfer compositions containing difluoromethane and 1,3,3,3-tetrafluoropropene
US8580366B2 (en) * 2009-08-12 2013-11-12 The Yokohama Rubber Co., Ltd. Hose for refrigerant transport use
US20130025733A1 (en) * 2009-08-12 2013-01-31 Kazuto Yamakawa Hose for refrigerant transport use
US10858562B2 (en) 2009-09-11 2020-12-08 Arkema France Binary refrigerating fluid
US9039922B2 (en) 2009-09-11 2015-05-26 Arkema France Low-temperature and average-temperature refrigeration
US9683157B2 (en) 2009-09-11 2017-06-20 Arkema France Heat transfer method
US9133379B2 (en) 2009-09-11 2015-09-15 Arkema France Binary refrigerating fluid
US9884984B2 (en) 2009-09-11 2018-02-06 Arkema France Binary refrigerating fluid
US10035938B2 (en) 2009-09-11 2018-07-31 Arkema France Heat transfer fluid replacing R-134a
US10125296B2 (en) 2009-09-11 2018-11-13 Arkema France Binary refrigerating fluid
US10316231B2 (en) 2009-09-11 2019-06-11 Arkema France Low-temperature and average-temperature refrigeration
US11352533B2 (en) * 2009-12-18 2022-06-07 Arkema France Heat-transfer fluids having reduced flammability
US20190016937A1 (en) * 2009-12-18 2019-01-17 Arkema France Heat-transfer fluids having reduced flammability
CN102782076A (en) * 2010-02-16 2012-11-14 墨西哥化学阿玛科股份有限公司 Heat transfer compositions
WO2011107698A3 (en) * 2010-03-02 2011-11-10 Arkema France Heat-transfer fluid for a centrifugal compressor
US9574124B2 (en) 2010-03-02 2017-02-21 Arkema France Heat-transfer fluid for a centrifugal compressor
EP3241877A1 (en) * 2010-03-02 2017-11-08 Arkema France Heat-transfer fluid for centrifugal compressor
US10450489B2 (en) 2010-03-02 2019-10-22 Arkema France Heat-transfer fluid for a centrifugal compressor
WO2011107698A2 (en) * 2010-03-02 2011-09-09 Arkema France Heat-transfer fluid for a centrifugal compressor
CN102782078A (en) * 2010-03-02 2012-11-14 阿克马法国公司 Heat-transfer fluid for a centrifugal compressor
US10858564B2 (en) 2010-05-11 2020-12-08 Arkema France Heat-transfer fluids and use thereof in countercurrent heat exchangers
US9683154B2 (en) 2010-05-11 2017-06-20 Arkema France Heat-transfer fluids and use thereof in countercurrent heat exchangers
US10308854B2 (en) 2010-05-11 2019-06-04 Arkema France Heat-transfer fluids and use thereof in countercurrent heat exchangers
US9005468B2 (en) 2010-05-11 2015-04-14 Arkema France Heat-transfer fluids and use thereof in countercurrent heat exchangers
US9315706B2 (en) 2010-09-20 2016-04-19 Arkema France 3,3,3-trifluoropropene compositions
US8951432B2 (en) 2011-06-07 2015-02-10 Arkema France Binary compositions of 1,3,3,3-tetrafluoropropene and ammonia
WO2013012563A3 (en) * 2011-07-20 2013-06-13 Honeywell International Inc. Low gwp heat transfer compositions containing difluoromethane and 1,3,3,3-tetrafluoropropene
US9039923B2 (en) 2012-02-14 2015-05-26 United Technologies Corporation Composition of zeotropic mixtures having predefined temperature glide
US9783721B2 (en) 2012-08-20 2017-10-10 Honeywell International Inc. Low GWP heat transfer compositions
US9856756B2 (en) * 2012-09-11 2018-01-02 Mahle International Gmbh Working medium mixture for steam engines
US20150240668A1 (en) * 2012-09-11 2015-08-27 Amovis Gmbh Working medium mixture for steam engines
US8940180B2 (en) 2012-11-21 2015-01-27 Honeywell International Inc. Low GWP heat transfer compositions
US11885561B2 (en) * 2012-12-04 2024-01-30 Conocophillips Company Low global-warming refrigerants in LNG processing
US9982180B2 (en) 2013-02-13 2018-05-29 Honeywell International Inc. Heat transfer compositions and methods
CN112391146A (en) * 2016-02-29 2021-02-23 科慕埃弗西有限公司 Refrigerant mixtures comprising difluoromethane, pentafluoroethane, tetrafluoroethane, tetrafluoropropene and carbon dioxide and uses thereof
US20200165500A1 (en) * 2016-02-29 2020-05-28 The Chemours Company Fc, Llc Refrigerant mixtures comprising difluoromethane, pentafluoroethane, tetrafluoroethane, tetrafluoropropene, and carbon dioxide and uses thereof
US10836944B1 (en) * 2016-02-29 2020-11-17 The Chemours Company Fc, Llc Refrigerant mixtures comprising difluoromethane, pentafluoroethane, tetrafluoroethane, tetrafluoropropene, and carbon dioxide and uses thereof
US11312891B2 (en) * 2016-02-29 2022-04-26 The Chemours Company Fc, Llc Refrigerant mixtures comprising difluoromethane, pentafluoroethane, tetrafluoroethane, tetrafluoropropene, and carbon dioxide and uses thereof
US10836942B2 (en) * 2016-02-29 2020-11-17 The Chemours Company Fc, Llc Refrigerant mixtures comprising difluoromethane, pentafluoroethane, tetrafluoroethane, tetrafluoropropene, and carbon dioxide and uses thereof
US11359122B2 (en) 2017-03-21 2022-06-14 Arkema France Method for heating and/or air-conditioning in a vehicle
US11370948B2 (en) 2017-03-21 2022-06-28 Arkema France Tetrafluoropropene-based composition
EP3717588A4 (en) * 2017-11-30 2021-08-11 Honeywell International Inc. Heat transfer compositions, methods, and systems
EP3717589A4 (en) * 2017-11-30 2021-08-18 Honeywell International Inc. Heat transfer compositions, methods, and systems
US10767091B2 (en) 2017-11-30 2020-09-08 Honeywell International Inc. Heat transfer compositions, methods, and systems
EP3794088A4 (en) * 2018-05-15 2022-04-20 Srf Limited Azeotrope or azeotrope like compositions comprising 1234yf
US11028300B1 (en) 2020-09-16 2021-06-08 David L. Couchot Environmentally friendly refrigerant compositions

Also Published As

Publication number Publication date
EP2602299A2 (en) 2013-06-12
JP2010513827A (en) 2010-04-30
WO2008027555A2 (en) 2008-03-06
RU2009111881A (en) 2010-10-10
CN101827912A (en) 2010-09-08
WO2008027555A3 (en) 2010-03-11
CA2661007A1 (en) 2008-03-06
BRPI0714896A2 (en) 2013-05-21
KR20090049617A (en) 2009-05-18
EP2118229A2 (en) 2009-11-18

Similar Documents

Publication Publication Date Title
US20090314015A1 (en) Method for circulating selected heat transfer fluids through a closed loop cycle
US11034872B2 (en) Compositions comprising a fluoroolefin
JP5001181B2 (en) Compositions containing fluoroolefins
EP3425017B1 (en) Compositions comprising hfc-1234ze
US20060243945A1 (en) Compositions comprising a fluoroolefin
US20230265330A1 (en) Compositions comprising a fluoroolefin

Legal Events

Date Code Title Description
AS Assignment

Owner name: E. I. DU PONT DE NEMOURS AND COMPANY, DELAWARE

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:MINOR, BARBARA HAVILAND;RAO, VELLIYUR NOTT MALLIKARJUNA;BIVENS, DONALD BERNARD;AND OTHERS;REEL/FRAME:023027/0337;SIGNING DATES FROM 20090130 TO 20090211

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION