WO1998037164A1 - Compositions se comportant comme des melanges azeotropes de pentafluoropropane et de tetrafluoroethane - Google Patents

Compositions se comportant comme des melanges azeotropes de pentafluoropropane et de tetrafluoroethane Download PDF

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Publication number
WO1998037164A1
WO1998037164A1 PCT/US1998/003468 US9803468W WO9837164A1 WO 1998037164 A1 WO1998037164 A1 WO 1998037164A1 US 9803468 W US9803468 W US 9803468W WO 9837164 A1 WO9837164 A1 WO 9837164A1
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WO
WIPO (PCT)
Prior art keywords
compositions
azeotrope
refrigerant
pentafluoropropane
tetrafluoroethane
Prior art date
Application number
PCT/US1998/003468
Other languages
English (en)
Inventor
Hang Thanh Pham
Rajiv Ratna Singh
Original Assignee
Alliedsignal Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Alliedsignal Inc. filed Critical Alliedsignal Inc.
Priority to AU61810/98A priority Critical patent/AU6181098A/en
Publication of WO1998037164A1 publication Critical patent/WO1998037164A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/143—Halogen containing compounds
    • C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
    • C08J9/146—Halogen containing compounds containing carbon, halogen and hydrogen only only fluorine as halogen atoms
    • C—CHEMISTRY; METALLURGY
    • 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
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/30—Materials not provided for elsewhere for aerosols
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
    • C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
    • C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
    • C09K5/045—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2207/00—Foams characterised by their intended use
    • C08J2207/04—Aerosol, e.g. polyurethane foam spray
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/22—All components of a mixture being fluoro compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/32—The mixture being azeotropic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/40—Replacement mixtures
    • C09K2205/42—Type R12

Definitions

  • the present invention relates to mixtures of 1, 1, 1,2,2-pentafluoropropane ("HFC-245cb”) and 1, 1,1,2-tetrafluoroethane ("HFC- 134a”). More particularly, the invention provides compositions of HFC-245cb and HFC-134a that are environmentally desirable for use as refrigerants, including in centrifugal chillers, and as aerosol propellants, blowing agents for polymer foam, heat transfer media, and gaseous dielectrics
  • Fluorocarbon based fluids have found widespread use in industry in a number of applications, including as refrigerants, aerosol propellants, blowing agents, heat transfer media, and gaseous dielectrics. Certain of these fluids, such as the chlorofluorocarbons (“CFC's”) and the hydrochlorofluorocarbons (“HCFC's”) are suspected of causing environmental problems in connection with the earth's protective ozone layer. For example, chlorodifluoromethane (“HCFC-22”) is an ozone depleting mixture.
  • This invention provides azeotrope-like and nonazeotrope-like compositions of HFC-245cb and HFC- 134a that are environmentally desirable replacements for some of the currently used CFC's and HCFC's. Additionally, the compositions of the invention exhibit characteristics that make the compositions better CFC and HCFC substitutes than either HFC-245cb or HFC- 134a alone.
  • One embodiment of the invention provides azeotrope-like compositions comprising effective amounts of HFC-245cb and HFC- 134a.
  • effective amounts is meant the amount of each component that, on combination with the other component, results in the formation of an azeotrope-like composition.
  • the invention provides azeotrope-like compositions preferably of from about 1 to about 50 weight percent HFC-245cb and from about 99 to about 50 weight percent HFC- 134a having a boiling point of -25° C ⁇ 2, preferably ⁇ 1° C, at 760 mm Hg.
  • the preferred, more preferred, and most preferred compositions of the invention are set forth in Table 1. The numerical ranges in Table 1 are to be understood to be prefaced by the term "about”.
  • azeotrope-like compositions are compositions that behave like azeotropic mixtures. From fundamental principles, the thermodynamic state of a fluid is defined by pressure and temperature as well as liquid composition and vapor composition.
  • An azeotropic mixture is a system of two or more components in which the liquid composition and vapor composition are equal at the state pressure and temperature. In practice, this means that the components of an azeotropic mixture are constant boiling and cannot be separated during a phase change.
  • Azeotrope-like compositions behave like azeotropic mixtures, Le ⁇ , or are constant boiling or essentially constant boiling.
  • the composition of the vapor formed during boiling or evaporation is identical, or substantially identical, to the original liquid composition.
  • the liquid composition changes, if at all, only to a minimal or negligible extent.
  • non-azeotrope-like compositions in which, during boiling or evaporation, the liquid composition changes to a substantial degree. All azeotrope-like compositions of the invention within the indicated ranges as well as certain compositions outside these ranges are azeotrope-like.
  • the azeotrope-like compositions of the invention may include additional components that do not form new azeotropic or azeotrope-like systems, or additional components that are not in the first distillation cut.
  • the first distillation cut is the first cut taken after the distillation column displays steady state operation under total reflux conditions.
  • One way to determine whether the addition of a component forms a new azeotropic or azeotrope-like system so as to be outside of this invention is to distill a sample of the composition with the component under conditions that would be expected to separate a nonazeotropic mixture into its separate components. If the mixture containing the additional component is nonazeotropic or nonazeotrope-like, the additional component will fractionate from the azeotropic or azeotrope-like components.
  • azeotrope-like compositions there is a range of compositions containing the same components in varying proportions that are azeotrope-like, or constant boiling. All such compositions are intended to be covered by the terms "azeotrope-like" and "constant boiling". As an example, it is well known that at differing pressures, the composition of a given azeotrope will vary at least slightly as does the boiling point of the composition.
  • an azeotrope of A and B represents a unique type of relationship, but with a variable composition depending on temperature and/or pressure. It follows that, for azeotrope- like compositions, there is a range of compositions containing the same components in varying proportions that are azeotrope-like. All such compositions are intended to be covered by the term azeotrope-like as used herein.
  • nonazeotrope-like compositions which compositions comprise HFC-245cb and HFC- 134a and which have a vapor pressure of about 43 psia to about 38 psia at 0° C.
  • the compositions of the invention comprise from about 1 to about 50 weight percent HFC-245cb and from about 99 to about 50 weight percent HFC- 134a.
  • the preferred, more preferred, and most preferred compositions of this embodiment are set forth in Table 2. The numerical ranges in Table 2 are to be understood to be prefaced by the term "about.”
  • the azeotrope-like and nonazeotrope-like compositions of the invention meet the need in the art for CFC and HCFC substitutes that have a low ozone depletion potential and are a negligible contributor to greenhouse global warming, are nonflammable, and have an appropriate compressor discharge temperature. Additionally, the compositions of the invention offer superior efficiency and capacity when compared to such fluids as HFC-245cb or HFC- 134a alone. Further, because the azeotrope-like compositions of the invention exhibit constant vapor pressure characteristics and relatively minor composition shifts as the liquid mixture is evaporated, the azeotrope-like composition of the invention are comparable to a constant boiling single component refrigerant or an azeotropic mixture refrigerant.
  • the compositions of the invention may be used in a method for producing refrigeration that comprises condensing a refrigerant comprising the azeotrope-like or nonazeotrope-like compositions of this invention and thereafter evaporating the refrigerant in the vicinity of a body to be cooled.
  • the compositions of the invention may be used in a method for heating that comprises condensing a refrigerant comprising the azeotrope-like or nonazeotrope-like compositions of the invention in the vicinity of a body to be heated and thereafter evaporating the refrigerant.
  • compositions of the invention may be used in centrifugal chillers.
  • centrifugal chillers is meant refrigeration equipment that uses centrifugal compression to compress the refrigerant.
  • the invention provides a method for producing refrigeration using a centrifugal compressor comprising compressing a refrigerant comprising the azeotrope-like or nonazeotrope-like compositions of the invention and thereafter evaporating the refrigerant in the vicinity of a body to be cooled
  • compositions of the invention may be used in a method for producing foam comprising blending a heat plasticized resin with a volatile bowing agent comprising the azeotrope-like or nonazeotrope-like compositions of the invention and introducing the resin/volatile blowing agent blend into a zone of lower pressure to cause foaming.
  • the compositions of the invention are used in a method for producing polyurethane and polyisocyanurate foams.
  • the method comprises reacting and foaming a mixture of ingredients that forms the polyurethane and polyisocyanurate foams in the presence of a volatile blowing agent comprising the azeotrope-like or nonazeotrope-like compositions of the present invention.
  • azeotrope-like or nonazeotrope-like compositions of the invention may be used in a premix of polyol and blowing agent, which premix comprises the azeotrope-like compositions of the invention prior to reaction and foaming of the ingredients forming polyurethane and polyisocyanurate foams.
  • the blowing agents of the invention may be used alone or in premix with a polyol.
  • thermoplastic foams using the compositions of the invention.
  • conventional foam polyurethanes and isocyanurate formulations may be combined with the azeotrope-like or nonazeotrope-like composition in a conventional manner to produce rigid foams.
  • compositions of the invention may also be used as heat transfer fluids.
  • a secondary heating loop containing an appropriate heat transfer fluid may be added.
  • the heat transfer fluid absorbs heat in one part of the cycle and transfers the heat to another part of the cycle without changing state, when the heat transferred is sensible, or by changing state, when the heat transferred is latent.
  • compositions of the invention may also be used as propellants for aerosol sprays.
  • aerosol compositions typically contain one or more propellants along with one or more active ingredients, inert ingredient, or solvents.
  • the components of the composition of the invention are known materials that are commercially available or may be prepared by known methods. Preferably, the components are of sufficiently high purity so as to avoid the introduction of adverse influences on the properties of the system. Additional components may be added to tailor the properties of the compositions of the invention as needed. By way of example, oil solubility aids may be added in the case in which the compositions of the invention are used as refrigerants.
  • Example 2 This example demonstrates that constant-boiling blends of HFC-245cb and HFC- 134a have certain advantages compared to other refrigerants currently used.
  • the theoretical performance of a refrigerant at specific operating conditions can be estimated from the thermodynamic properties of the refrigerant using standard refrigeration cycle analysis techniques. See, e.g.. R.C. Downing Fluorocarbon Refrigerants Handbook. Prentice Hall (1988).
  • the coefficient of performance, COP is a universally accepted measure especially useful in representing the relative thermodynamic efficiency of a refrigerant in a specific heating or cooling cycle involving evaporation or condensation of a refrigerant. This term expresses the ratio of useful refrigeration to the energy applied by the compressor in compressing the PCT/US98/03468
  • the capacity of a refrigerant represents the volumetric efficiency of the refrigerant. This value expresses the capability of a compressor to pump quantities of heat for a given volumetric flow rate of refrigerant. In other words, given a specific compressor, a refrigerant with a higher capacity will deliver more cooling or heating power.
  • the azeotrope-like compositions of the invention are good CFC- 12 and F£FC-134a alternatives and are better than HFC-245cb alone in energy efficiency (COP) and refrigeration capacity.
  • Example 3 40 g of the azeotrope-like composition of Example 1 are charged into a 200 cc sealed vessel containing 3 g on Dow styrene 685D. The vessel is placed in a 250° F oven overnight. Twenty-four hours later, the vessel is removed from the oven and rapidly depressurized. The resulting foam is inspected and found to be of good quality.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Combustion & Propulsion (AREA)
  • Thermal Sciences (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

L'invention concerne des compositions de 1,1,1,2,2-pentafluoropropane et de 1,1,1,2-tétrafluoroéthane. Les compositions de l'invention sont souhaitables du point de vue écologique et ce, dans le but d'une utilisation en tant que réfrigérants, propulseurs, gonflants pour mousse polymère, fluides de transfert de chaleur et diélectriques gazeux.
PCT/US1998/003468 1997-02-24 1998-02-23 Compositions se comportant comme des melanges azeotropes de pentafluoropropane et de tetrafluoroethane WO1998037164A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU61810/98A AU6181098A (en) 1997-02-24 1998-02-23 Azeotrope-like compositions of pentafluoropropane and tetrafluoroethane

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US80487397A 1997-02-24 1997-02-24
US08/804,873 1997-02-24

Publications (1)

Publication Number Publication Date
WO1998037164A1 true WO1998037164A1 (fr) 1998-08-27

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PCT/US1998/003468 WO1998037164A1 (fr) 1997-02-24 1998-02-23 Compositions se comportant comme des melanges azeotropes de pentafluoropropane et de tetrafluoroethane

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AU (1) AU6181098A (fr)
WO (1) WO1998037164A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994002563A1 (fr) * 1992-07-15 1994-02-03 E.I. Du Pont De Nemours And Company Compositions de refrigerant comprenant du 1,1,2,2-tetrafluoroethane
WO1995008603A1 (fr) * 1993-09-24 1995-03-30 E.I. Du Pont De Nemours And Company Associations de deux hydrofluorocarbures
WO1996018384A1 (fr) * 1994-12-10 1996-06-20 Glaxo Group Limited Melange propulseur pour formulation d'aerosol
WO1997034961A1 (fr) * 1996-03-22 1997-09-25 Goble George H REFRIGERANTS INTRODUITS DANS UN SYSTEME DE REFRIGERATION POUR SUBSTITUER LE REFRIGERANT 1,1,1,2-TETRAFLUOROETHANE (R-134a)

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994002563A1 (fr) * 1992-07-15 1994-02-03 E.I. Du Pont De Nemours And Company Compositions de refrigerant comprenant du 1,1,2,2-tetrafluoroethane
WO1995008603A1 (fr) * 1993-09-24 1995-03-30 E.I. Du Pont De Nemours And Company Associations de deux hydrofluorocarbures
WO1996018384A1 (fr) * 1994-12-10 1996-06-20 Glaxo Group Limited Melange propulseur pour formulation d'aerosol
WO1997034961A1 (fr) * 1996-03-22 1997-09-25 Goble George H REFRIGERANTS INTRODUITS DANS UN SYSTEME DE REFRIGERATION POUR SUBSTITUER LE REFRIGERANT 1,1,1,2-TETRAFLUOROETHANE (R-134a)

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Publication number Publication date
AU6181098A (en) 1998-09-09

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