WO1996015205A1 - Compositions comportant un fluorocarbure cyclique - Google Patents

Compositions comportant un fluorocarbure cyclique Download PDF

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Publication number
WO1996015205A1
WO1996015205A1 PCT/US1995/014426 US9514426W WO9615205A1 WO 1996015205 A1 WO1996015205 A1 WO 1996015205A1 US 9514426 W US9514426 W US 9514426W WO 9615205 A1 WO9615205 A1 WO 9615205A1
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Prior art keywords
weight percent
composition
pentafluorocydopropane
perfluorocyclopropane
hfc
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PCT/US1995/014426
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English (en)
Inventor
Barbara Haviland Minor
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E.I. Du Pont De Nemours And Company
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Publication of WO1996015205A1 publication Critical patent/WO1996015205A1/fr

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    • 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
    • C08J9/149—Mixtures of blowing agents covered by more than one of the groups C08J9/141 - C08J9/143
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
    • A62D1/0028—Liquid extinguishing substances
    • A62D1/0057—Polyhaloalkanes
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
    • A62D1/0071—Foams
    • A62D1/0085—Foams containing perfluoroalkyl-terminated surfactant
    • 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
    • C08J9/127—Mixtures of organic and inorganic blowing agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/143—Halogen containing compounds
    • C—CHEMISTRY; METALLURGY
    • 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
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50—Solvents
    • C11D7/5004—Organic solvents
    • C11D7/5018—Halogenated solvents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50—Solvents
    • C11D7/5036—Azeotropic mixtures containing halogenated solvents
    • C11D7/504—Azeotropic mixtures containing halogenated solvents all solvents being halogenated hydrocarbons
    • C11D7/505—Mixtures of (hydro)fluorocarbons
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50—Solvents
    • C11D7/5036—Azeotropic mixtures containing halogenated solvents
    • C11D7/5068—Mixtures of halogenated and non-halogenated solvents
    • C11D7/509—Mixtures of hydrocarbons and oxygen-containing solvents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
    • C—CHEMISTRY; METALLURGY
    • 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
    • C09K2205/124—Fluorinated cyclic 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
    • C09K2205/132—Components containing nitrogen
    • 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
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/24—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/263—Ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/28—Organic compounds containing halogen

Definitions

  • compositions that include a cyclic fluorocarbon.
  • compositions are useful as refrigerants, cleaning agents, expansion agents for polyolefins and polyurethanes, aerosol propellants, refrigerants, heat transfer media, gaseous dielectrics, fire extinguishing agents, power cycle working fluids, polymerization media, paniculate removal fluids, carrier fluids, buffing abrasive agents, and displacement drying agents.
  • Fluorinated hydrocarbons have many uses, one of which is as a refrigerant.
  • refrigerants include dichlorodifluoromethane (CFC-12) and chlorodifluoromethane (HCFC-22).
  • HFCs Hydrofluorocarbons
  • fluorocarbons have been suggested as replacements for CFCs and HCFCs since HFCs have no chlorine and therefore have zero ozone depletion potential.
  • a refrigerant In refrigeration applications, a refrigerant is often lost during operation through leaks in shaft seals, hose connections, soldered joints and broken lines. In addition, the refrigerant may be released to the atmosphere during maintenance procedures on refrigeration equipment. If the refrigerant is not a pure component or an azeotropic or azeotrope-like composition, the refrigerant composition may change when leaked or discharged to the atmosphere from the refrigeration equipment, which may cause the refrigerant to become flammable or to have poor refrigeration performance.
  • a single fluorinated cyclic hydrocarbon or an azeotropic or azeotrope-like composition that includes one or more cyclic fluorinated hydrocarbons.
  • a cyclic fluorinated hydrocarbon may also be used as a cleaning agent o solvent to clean, for example, electronic circuit boards. It is desirable that the cleanin agents be azeotropic or azeotrope-like because in vapor degreasing operations the cleaning agent is generally redistilled and reused for final rinse cleaning.
  • Azeotropic or azeotrope-like compositions that include a cyclic fluorina hydrocarbon are also useful as blowing agents in the manufacture of closed-cell polyurethane, phenolic and thermoplastic foams, as propellants in aerosols, as heat transfer media, gaseous dielectrics, fire extinguishing agents, power cycle working flui such as for heat pumps, inert media for polymerization reactions, fluids for removing particulates from metal surfaces, as carrier fluids that may be used, for example, to pl a fine film of lubricant on metal parts, as buffing abrasive agents to remove buffing abrasive compounds from polished surfaces such as metal, as displacement drying age for removing water, such as from jewelry or metal parts, as resist developers in conventional circuit manufacturing techniques including chlorine-type developing age or as strippers for photoresists when used with, for example, a chlorohydrocarbon such 1,1, 1-trichloroethane or trichloroethylene.
  • a chlorohydrocarbon such
  • compositions are useful as refrigerants, cleaning agents, expansio agents for polyolefins and polyurethanes, aerosol propellants, heat transfer media, gaseous dielectrics, fire extinguishing agents, power cycle working fluids, polymerizatio media, paniculate removal fluids, carrier fluids, buffing abrasive agents, and displacement drying agents.
  • the invention relates to the discovery of binary azeotropic or azeotrope-like compositions comprising effective amounts of perfluorocyclopropane and at least one of 1,1,1,2-tetrafluoroethane, 1,1-difluoroethan fluoroethane, 1,1,1,2,3,3,3-heptafluoropropane, 1,2-difluoropropane, 2-fluoropropane, fluoropropane, butane, cyclopropane, dimethylether, ammonia or propane; pentafluorocyclopropane and at least one of 1,1,2-trifluoroethane, 1,1,1,2,2,3,3- heptafluoropropane, 1,1, 1,3,3,3-hexafluoropropane, 1, 1, 1,2,2-pentafluoropropane, 1,1,1,3,3-pentafluoropropane, 1,1,2,2-tetrafluoropropane, 1,1,1-triflu
  • Figure 1 is a graph of the vapor/liquid equilibrium curve for mixtures of c216 and HFC-134a at 25°C;
  • Figure 2 is a graph of the vapor/liquid equilibrium curve for mixtures of c216 and HFC-152a at 25°C
  • Figure 3 is a graph of the vapor/liquid equilibrium curve for mixtures of c216 and HFC-161 at 25°C;
  • Figure 4 is a graph of the vapor/liquid equilibrium curve for mixtures of c216 and HFC-227ea at 25°C;
  • Figure 5 is a graph of the vapor/liquid equilibrium curve for mixtures of c216 and HFC-272ea at 25°C;
  • Figure 6 is a graph of the vapor/liquid equilibrium curve for mixtures of c216 and HFC-281ea at 25°C;
  • Figure 7 is a graph of the vapor/liquid equilibrium curve for mixtures of c216 and HFC-281fa at 25°C
  • Figure 8 is a graph of the vapor/liquid equilibrium curve for mixtures of c216 and butane at 25°C;
  • Figure 9 is a graph of the vapor/liquid equilibrium curve for mixtures of c216 and cyclopropane at 25°C;
  • Figure 10 is a graph of the vapor/liquid equilibrium curve for mixtures of c216 and DME at 25°C;
  • Figure 11 is a graph of the vapor/liquid equilibrium curve for mixtures of c216 and propane at 25°C;
  • Figure 12 is a graph of the vapor/Uquid equilibrium curve for mixtures of c225 and HFC-143 at 25°C
  • Figure 13 is a graph of the vapor/liquid equilibrium curve for mixtures of c225 and HFC-227ca at 25°C;
  • Figure 14 is a graph of the vapor/liquid equilibrium curve for mixtures of c225 and HFC-236fa at 25°C;
  • Figure 15 is a graph of the vapor/liquid equilibrium curve for mixtures of c225 and HFC-245cb at 25°C;
  • Figure 16 is a graph of the vapor/liquid equilibrium curve for mixtures of c225 and HFC-245fa at 25°C;
  • Figure 17 is a graph of the vapor/liquid equilibrium curve for mixtures of c225 and HFC-254cb at 25°C
  • Figure 18 is a graph of the vapor/liquid equilibrium curve for mixtures of c225 and HFC-263fb at 25°C;
  • Figure 19 is a graph of the vapor/liquid equilibrium curve for mixtures c225 and HFC-272ca at 25°C;
  • Figure 20 is a graph of the vapor/liquid equilibrium curve for mixtures c225 and butane at 25°C
  • Figure 21 is a graph of the vapor/liquid equilibrium curve for mixtures c225 and DME at 25°C;
  • Figure 22 is a graph of the vapor/liquid equilibrium curve for mixtures c225 and isobutane at 25°C;
  • Figure 23 is a graph of the vapor/liquid equilibrium curve for mixtures c225 and propane at 25°C.
  • the present invention also relates to the discovery of azeotropic 1-99 wt.% of each of the components of the compositions can be used as refrigerants. Further, the present invention also relates to the discovery of azeotropic or azeotrope-like compositions of effective amounts of each of the above mixtures to form an azeotropic or azeotrope-like composition.
  • Hexafluorocyclopropane (C-216, cyclo-C3F6, CAS Reg. No. [931-91-9]) has been prepared by the thermal decomposition of hexafluoropropylene oxide as reported by Sargeant in Journal of Organic Chemistry, Vol.35, pages 678-682 (1970).
  • Pentafluorocyclopropane (C-225, cyclo-C3HF5, CAS Reg. No. [872-58-2]) has been prepared by the reaction of hexafluoropropylene oxide with trifluoroethylene as reported by Sargeant and Krespan in Journal of the American Chemical Society, Vol. 91, pages 415-419 (1969).
  • the present invention also relates to the discovery of azeotropic or azeotrope-like compositions of effective amounts of c216 and HFC- 134a, HFC- 152a, HFC-161, HFC-227ea, HFC-272ea, HFC-281ea, HFC-281fa, butane, cyclopropane, DME, NH 3 or propane; c225 and HFC-143, HFC-227ca, HFC-236fa, HFC-245cb, HFC- 245fa, HFC-254cb, HFC-263fb, HFC-272ca, butane, DME, NH3, isobutane or propane.
  • azeotropic composition is meant a constant boiling liquid admixture of two or more substances that behaves 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 was evaporated or distilled, that is, the admixture 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 mixtures of the same components.
  • azeotrope-like composition is meant a constant boiling, or substantially constant boiling, liquid admixture of two or more substances that behaves as a single substance.
  • One way to characterize an azeotrope-like 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.
  • azeotrope-like composition is meant a constant boiling, or substantially constant boiling, liquid admixture of two or more substances that beha as a single substance.
  • azeotrope-like composition One way to characterize an azeotrope-like composition is that vapor produced by partial evaporation or distillation of the liquid has substantially th same composition as the liquid from which it was evaporated or distilled, that is, the admixture distills/refluxes without substantial composition change.
  • a composition is azeotrope-like if, after weight percent of the composition is removed such as by evaporation or boiling off, t difference in vapor pressure between the original composition and the composition remaining after 50 weight percent of the original composition has been removed is le than 10 percent, when measured in absolute units.
  • absolute units it is meant measurements of pressure and, for example, psia, atmospheres, bars, torr, dynes per square centimeter, millimeters of mercury, inches of water and other equivalent term well known in the art. If an azeotrope is present, there is no difference in vapor pres between the original composition and the composition remaining after 50 weight per of the original composition has been removed.
  • compositions that are azeotropic there is usually some range of compositions around the azeotrope point that, for a maximum boiling azeotrope, hav boiling points at a particular pressure higher than the pure components of the composition at that pressure and have vapor pressures at a particular temperature lo than the pure components of the composition at that temperature, and that, for a minimum boiling azeotrope, have boiling points at a particular pressure lower than th pure components of the composition at that pressure and have vapor pressures at a particular temperature higher than the pure components of the composition at that temperature.
  • Boiling temperatures and vapor pressures above or below that of the p components are caused by unexpected intermolecular forces between and among the molecules of the compositions, which can be a combination of repulsive and attractiv forces such as van der Waals forces and hydrogen bonding.
  • the range of compositions that have a maximum or minimum boiling point at a particular pressure, or a maximum or minimum vapor pressure at a particular temperature may or may not be coextensive with the range of compositions that have a change in vapor pressure of less than about 10% when 50 weight percent of the composition is evaporated.
  • compositions of this invention have the following vapor pressures at 25°C.
  • compositions of this invention comprise the following (all compositions are measured at 25°C):
  • effective amount is defined as the amo of each component of the inventive compositions which, when combined, results in th formation of an azeotropic or azeotrope-like composition.
  • This definition includes th amounts of each component, which amounts may vary depending on the pressure app to the composition so long as the azeotropic or azeotrope-like compositions continue exist at the different pressures, but with possible different boiling points. Therefore, effective amount includes the amounts, such as may be expressed in weight percentages, of each component of the compositions of the instant invention which form azeotropic or azeotrope-like compositions at temperatures or pressures other than as described herein.
  • azeotropic or constant-boiling is intended to mean also essentially azeotropic or essentially-constant boiling.
  • included within the meaning of these terms are not only the true azeotropes described above, but also other compositions containing the same components in different proportions, which are true azeotropes at other temperatures and pressures, as well as those equivalent compositions which are part of the same azeotropic system and are azeotrope-like in their properties.
  • compositions which contain the same components as the azeotrope, which will not only exhibit essentially equivalent properties for refrigeration and other applications, but which will also exhibit essentially equivalent properties to the true azeotropic composition in terms of constant boiling characteristics or tendency not to segregate or fractionate on boiling.
  • composition can be defined as an azeotrope of A, B, C (and D%) since the very term "azeotrope" is at once both definitive and limitative, and requires that effective amounts of A, B, C (and D%) for this unique composition of matter which is a constant boiling composition.
  • composition can be defined as a particular weight percent relationship or mole percent relationship of A, B, C (and D%), while recognizing that such specific values point out only one particular relationship and that in actuality, a series of such relationships, represented by A, B, C (and D%) actually exist for a given azeotrope, varied by the influence of pressure.
  • An azeotrope of A, B, C (and D%) can be characterized by defining the compositions as an azeotrope characterized by a boiling point at a given pressure, thus giving identifying characteristics without unduly limiting t scope of the invention by a specific numerical composition, which is limited by and is only as accurate as the analytical equipment available.
  • the azeotrope or azeotrope-like compositions of the present invention be prepared by any convenient method including mixing or combining the desired amounts. A preferred method is to weigh the desired component amounts and thereafter combine them in an appropriate container.
  • compositions are azeotropic (all amounts of components are weight percent).
  • a vessel is charged with an initial liquid composition at 25°C.
  • the liquid, and the vapor above the liquid, are allowed to come to equilibrium, and the vapor pressure in the vessel is measured.
  • Vapor is allowed to leak from the vessel, while the temperature is held constant at 25°C, until 50 weight percent of the initial charge is removed, at which time the vapor pressure of the composition remaining in the vessel is measured.
  • Compressor efficiency is 75%.
  • the refrigeration capacity is based on a compressor with a fixed displacement of 3.5 cubic feet per minute and 75% volumetric efficiency.
  • Capacity is intended to mean the change in enthalpy of the refrigerant in the evaporator per pound of refrigerant circulated, i.e. the heat removed by the refrigerant in the evaporator per time.
  • Coefficient of performance (COP) is intended to mean the ratio of the capacity to compressor work. It is a measure of refrigerant energy efficiency.
  • This Example is directed to measurements of the liquid/vapor equilibrium curves for the mixtures in Figures 1-23.
  • the upper curve represents the composition of the liquid
  • the lower curve represents the composition of the vapor
  • the data for the compositions of the liquid in Figure 1 are obtained as follows. A stainless steel cylinder is evacuated, and a weighed amount of c216 is added to the cylinder. The cylinder is cooled to reduce the vapor pressure of c216, and then a weighed amount of HFC- 134a is added to the cylinder. The cylinder is agitated to mix the c216 and HFC- 134a, and then the cylinder is placed in a constant temperature bath until the temperature comes to equilibrium at 25°C, at which time the vapor pressure o the c216 and HFC- 134a in the cylinder is measured. Additional samples of liquid are measured the same way, and the results are plotted in Figure 1.
  • the curve which shows the composition of the vapor is calculated using a ideal gas equation of state.
  • Vapor/liquid equilibrium data are obtained in the same way for the mixtures shown in Figures 2-23.
  • the data in Figures 1-11, 14, 15 and 18-23 show that at 25°C, there are ranges of compositions that have vapor pressures higher than the vapor pressures of the pure components of the composition at that same temperature.
  • the higher than expected pressures of these compositions may result in an unexpected increase in the refrigeration capacity and efficiency for these compositions versus the pure components of the compositions.
  • novel compositions of this invention may be used to produce refrigeration by condensing the compositions and thereafter evaporating the condensate in the vicinity of a body to be cooled.
  • the novel compositions may also be used to produce heat by condensing the refrigerant in the vicinity of the body to be heated and thereafter evaporating the refrigerant.
  • compositions of the present inventions are useful as blowing agents i the production of thermoset foams, which include polyurethane and phenolic foams, an thermoplastic foams, which include polystyrene or polyolefin foams.
  • a polyurethane foam may be made by combining a composition of the present invention, which functions as a blowing agent, together with an isocyanate, a polyol, and appropriate catalysts or surfactants to form a poylurethane or polyisocyanurate reaction formulation. Water may be added to the formulation raction to modify the foam polymer as well as to generate carbon dioxide as an in-situ blowing agent.
  • a phenolic foam may be produced by combining a phenolic resin or resole, acid catalysts, a blowing agent of the present invention and appropriate surfactants to form a phenolic reaction formulation.
  • the formulation may be chosen such that either an open cell or closed cell phenolic foam is produced.
  • Polystyrene or polyolefin foams may be made by extruing a molten mixure of a polymer, such as polystyrere, polyethylene or polypropylene), a nucleating agent and a blowing agent of the present invention through an extrusion die that yields the desired foam product profile.
  • novel compositions of this invention may be used as cleaning agents to clean, for example, electronic circuit boards.
  • Electronic components are soldered to circuit boards by coating the entire circuit side of the board with flux and thereafter passing the flux- coated board over preheaters and through molten solder.
  • the flux cleans the conductive metal parts and promotes solder fusion, but leave residues on the circuit boards that must be removed with a cleaning agent.
  • azeotropic mixtures of this invention can be used in cleaning processes such as described in U.S. Patent No. 3,881,949, or as a buffing abrasive detergent.
  • the cleaning agents be azeotropic or azeotrope-like so that they do not tend to fractionate upon boiling or evaporation. This behavior is desirable because if the cleaning agent were not azeotropic or azeotrope-like, the more volatile components of the cleaning agent would preferentially evaporate, and would result in a cleaning agent with a changed composition that may become flammable and that may have less-desirable solvency properties, such as lower rosin flux solvency and lower inertness toward the electrical components being cleaned.
  • the azeotropic character is also desirable in vapor degreasing operations because the cleaning agent is generally redistilled and employed for final rinse cleaning.
  • the novel compositions of this invention are also useful as fire extinguishing agents, heat transfer media, gaseous dielectrics, and power cycle working
  • ADDITIONAL COMPOUNDS Other components, such as aliphatic hydrocarbons having a boiling point of -60 to + 60°C, hydrofluorocarbonalkanes having a boiling point of -60 to + 60°C, hydrofluoropropanes having a boiling point of between -60 to + 60°C, hydrocarbon este having a boiling point between -60 to + 60°C, hydrochlorofluorocarbons having a boilin point between -60 to + 60°C, hydrofluorocarbons having a boiling point of -60 to + 60°C hydrochlorocarbons having a boiling point between -60 to +60°C, chlorocarbons and perfluorinated compounds, can be added to the azeotropic or azeotrope-like compositions described above.
  • Additives such as lubricants, corrosion inhibitors, surfactants, stabilizers, dyes and other appropriate materials may be added to the novel compositions of the invention for a variety of purposes provides they do not have an adverse influence on th composition for its intended application.
  • Preferred lubricants include esters having a molecular weight greater than 250.

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  • Chemical & Material Sciences (AREA)
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  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • Detergent Compositions (AREA)

Abstract

L'invention présente des compositions comportant un cycle C3FxHy (cyclique) où 1≤x≤6 et x + y = 6 et CnFmH2n + 2-m dans lequel n = 2 ou 3 et 1≤m≤8; un hydrocarbure ayant de 1 à 5 atomes de carbone; de l'ammoniac ou de l'éther méthylique. Dans des exemples de ces compostions figurent les perfluorocyclopropane et 1, 1, 1, 2-tétrafluoroéthane, 1, 1-difluoroéthane, fluoroéthane, 1, 1, 1, 2, 3, 3, 3-heptafluoropropane, 1, 2-difluoropropane, 2-fluoropropane, 1-fluoropropane, ainsi que du butane, du cyclopropane, de l'éther méthylique, de l'ammoniac ou du propane; les pentafluorocyclopropane et 1, 1, 2-trifluoroéthane, 1, 1, 1, 2, 2, 3, 3-heptafluoropropane, 1, 1, 1, 3, 3, 3-hexafluoropropane, 1, 1, 1, 2, 2-pentafluoropropane, 1, 1, 1, 3, 3-pentafluoropropane, 1, 1, 2, 2-tétrafluoropropane, 1, 1, 1-trifluoropropane, 2, 2-difluoropropane, ainsi que du butane, de l'éther méthylique, de l'ammoniac, de l'isobutane ou du propane.
PCT/US1995/014426 1994-11-16 1995-11-08 Compositions comportant un fluorocarbure cyclique WO1996015205A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US34104594A 1994-11-16 1994-11-16
US08/341,045 1994-11-16

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WO1996015205A1 true WO1996015205A1 (fr) 1996-05-23

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999003947A1 (fr) * 1997-07-15 1999-01-28 Rhodia Limited Compositions refrigerantes
EP1179579A2 (fr) * 1996-11-04 2002-02-13 E.I. Du Pont De Nemours And Company Compositions d'hydrofluorocarbones
EP1195421A2 (fr) * 1997-07-15 2002-04-10 Rhodia Limited Compositions réfrigérantes
KR100398093B1 (ko) * 2000-12-20 2003-09-19 주식회사 제이오 냉장고/에어컨용 혼합냉매
US7258813B2 (en) 1999-07-12 2007-08-21 E.I. Du Pont De Nemours And Company Refrigerant composition
WO2007144623A1 (fr) * 2006-06-14 2007-12-21 Ineos Fluor Holdings Limited Compositions réfrigérantes
US7641810B2 (en) 2002-11-29 2010-01-05 Neil Andre Roberts Refrigerant compositions

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US4997706A (en) * 1990-02-09 1991-03-05 The Dow Chemical Company Foaming system for closed-cell rigid polymer foam
JPH0393881A (ja) * 1989-09-06 1991-04-18 Daikin Ind Ltd 作動流体
WO1992001762A1 (fr) * 1990-07-26 1992-02-06 E.I. Du Pont De Nemours And Company Melanges quasi-azeotropes destines a etre utilises en tant que refrigerants
EP0485979A2 (fr) * 1990-11-16 1992-05-20 Hitachi, Ltd. Appareil frigorifique et compresseur pour réfrigérant
US5135054A (en) * 1990-10-05 1992-08-04 University Of New Mexico Fire extinguishing agents for flooding applications
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
JPH06220432A (ja) * 1993-01-26 1994-08-09 Showa Denko Kk 冷媒組成物

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Publication number Priority date Publication date Assignee Title
JPH0393881A (ja) * 1989-09-06 1991-04-18 Daikin Ind Ltd 作動流体
US4997706A (en) * 1990-02-09 1991-03-05 The Dow Chemical Company Foaming system for closed-cell rigid polymer foam
WO1992001762A1 (fr) * 1990-07-26 1992-02-06 E.I. Du Pont De Nemours And Company Melanges quasi-azeotropes destines a etre utilises en tant que refrigerants
US5135054A (en) * 1990-10-05 1992-08-04 University Of New Mexico Fire extinguishing agents for flooding applications
EP0485979A2 (fr) * 1990-11-16 1992-05-20 Hitachi, Ltd. Appareil frigorifique et compresseur pour réfrigérant
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
JPH06220432A (ja) * 1993-01-26 1994-08-09 Showa Denko Kk 冷媒組成物

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DATABASE WPI Week 9122, Derwent World Patents Index; AN 91-159420 *
PATENT ABSTRACTS OF JAPAN vol. 18, no. 591 (C - 1272) *

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1179579A3 (fr) * 1996-11-04 2004-01-07 E.I. Du Pont De Nemours And Company Compositions d'hydrofluorocarbones
EP1179579A2 (fr) * 1996-11-04 2002-02-13 E.I. Du Pont De Nemours And Company Compositions d'hydrofluorocarbones
US7229567B2 (en) 1997-07-15 2007-06-12 E.I. Dupont De Nemours And Company Refrigerant compositions
US6428720B1 (en) 1997-07-15 2002-08-06 Rhodia Limited Refrigerant compositions
EP1195421A2 (fr) * 1997-07-15 2002-04-10 Rhodia Limited Compositions réfrigérantes
WO1999003947A1 (fr) * 1997-07-15 1999-01-28 Rhodia Limited Compositions refrigerantes
EP1195421A3 (fr) * 1997-07-15 2008-02-27 E.I.Du pont de nemours and company Compositions réfrigérantes
US7258813B2 (en) 1999-07-12 2007-08-21 E.I. Du Pont De Nemours And Company Refrigerant composition
KR100398093B1 (ko) * 2000-12-20 2003-09-19 주식회사 제이오 냉장고/에어컨용 혼합냉매
US7641810B2 (en) 2002-11-29 2010-01-05 Neil Andre Roberts Refrigerant compositions
US7713434B2 (en) 2002-11-29 2010-05-11 E.I. Du Pont De Nemours And Company Refrigerant compositions
US7771610B2 (en) 2002-11-29 2010-08-10 E.I. Du Pont De Nemours And Company Refrigerant compositions
US8246851B2 (en) 2002-11-29 2012-08-21 Roberts Neil Andre Chiller refrigerants
WO2007144623A1 (fr) * 2006-06-14 2007-12-21 Ineos Fluor Holdings Limited Compositions réfrigérantes

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