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WO1994004628A1 - Compositions de difluoromethane et de 1,1,1-trifluoroethane du type azeotrope - Google Patents

Compositions de difluoromethane et de 1,1,1-trifluoroethane du type azeotrope Download PDF

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Publication number
WO1994004628A1
WO1994004628A1 PCT/US1993/007390 US9307390W WO9404628A1 WO 1994004628 A1 WO1994004628 A1 WO 1994004628A1 US 9307390 W US9307390 W US 9307390W WO 9404628 A1 WO9404628 A1 WO 9404628A1
Authority
WO
WIPO (PCT)
Prior art keywords
compositions
azeotrope
composition
hfc
weight percent
Prior art date
Application number
PCT/US1993/007390
Other languages
English (en)
Inventor
Kenneth Harris
Earl August Eugene Lund
Ian Robert Shankland
Rajiv Ratha Singh
Original Assignee
Allied-Signal 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 Allied-Signal Inc. filed Critical Allied-Signal Inc.
Publication of WO1994004628A1 publication Critical patent/WO1994004628A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C19/00—Acyclic saturated compounds containing halogen atoms
    • C07C19/08—Acyclic saturated compounds containing halogen atoms containing fluorine
    • 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
    • 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
    • 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

Definitions

  • Fluorocarbon based fluids have found widespread use in industry for refrigeration, air conditioning and heat pump applications.
  • Vapor compression is one form of refrigeration.
  • vapor compression involves changing the refrigerant from the liquid to the vapor phase through heat absorption at a low pressure and then from the vapor to the liquid phase through heat removal at an elevated pressure.
  • While the primary purpose of refrigeration is to remove energy at low temperature, the primary purpose of a heat pump is to add energy at higher temperature.
  • Heat pumps are considered reverse cycle systems because for heating, the operation of the condenser is inter ⁇ changed with that of the refrigeration evaporator.
  • Certain chlorofluorocarbons have gained widespread use in refrigeration applications including air conditioning and heat pump applications owing to their unique combination of chemical and physical properties.
  • the majority of refrigerants utilized in vapor compression systems are either single component fluids or azeotropic mixtures. Single component fluids and azeotropic mixtures are characterized as constant- boiling because they exhibit isothermal and isobaric evaporation and condensation.
  • the use of azeotropic mixtures as refrigerants is known in the art. See, for example, R.C. Downing, "Fluorocarbon Refrigerants Handbook", pp. 139-158, Prentice-Hall, 1988, and U.S. Patents 2,101,993 and 2,641,579.
  • Azeotropic or azeotrope-like compositions are desired because they do not fractionate upon boiling or evaporation. This behavior is desirable because in the previously described vapor compression equipment with which these refrigerants are employed, condensed material is generated in preparation for cooling or for heating purposes, and unless the refrigerant composition is constant boiling, i.e., is azeotrope- like, fractionation and segregation will occur upon evaporation and condensation and undesirable refrigerant distribution may act to upset cooling or heating.
  • fluorocarbon based azeotrope-like mixtures which offer alternatives for refrigeration and heat pump applications.
  • fluorocarbon and hydrofluorocarbon based refrigerants are of particular interest because they are considered to be environmentally acceptable substitutes for the fully halogenated chlorofluorocarbons which are suspected of causing environmental problems associated with the depletion of the earth's protective ozone layer.
  • HFC-32 has been proposed as an environmentally acceptable refrigerant however, it is not a particularly efficient refrigerant especially at higher condensing temperatures because it has a relatively low critical temperature.
  • HFC-143a is a good refrigerant on a thermodynamic basis but has a lower vapor pressure than HFC-32. This results in a lower refrigeration capacity than HFC-32.
  • Applicants have discovered, however, that when these compounds are combined in effective amounts, surprisingly an azeotrope-like composition results which has a higher refrigeration capacity than both HFC-32 and HFC-143a.
  • compositions of the invention are useful as blowing agents for extruded thermal plastic foams such as polyethylene and polystyrene foams and for certain polyurethane type foams.
  • compositions of the invention may be used alone or in combination with another liquid blowing agent such as 1,1-dichloro-l-fluoroethane (HCFC-l41b) or other hydrochlorofluorocarbon or hydrofluorocarbon liquids.
  • compositions of the more preferred and most preferred azeotrope-like compositions of the invention are summarized in Table I below. Note that the composition ranges reported are in weight percent.
  • compositions within the indicated ranges, as well as certain compositions outside the indicated ranges, are azeotrope-like, as defined more particularly below.
  • azeotrope-like composition is intended to mean that the composition behaves like a true azeotrope in terms of its constant boiling characteristics or tendency not to fractionate upon boiling or evaporation.
  • the composition of the vapor formed during evaporation is identical or substantially identical to the original liquid composition.
  • the liquid composition if it changes at all, changes only slightly. This is contrasted with non-azeotrope-like compositions in which the liquid and vapor compositions change substantially during evaporation or condensation.
  • the azeotrope-like compositions of the invention may be used in a method for producing refrigeration which comprises condensing a refrigerant comprising the azeotrope-like compositions and thereafter evaporating the refrigerant in the vicinity of the body to be cooled.
  • the azeotrope-like compositions of the invention may be used in a method for producing heating which comprises condensing a refrigerant in the vicinity of the body to be heated and thereafter evaporating the refrigerant.
  • the azeotrope-like compositions of the invention may besused as a blowing agent in a process for making extruded thermal plastic foams comprising blending heat plasticized polyolefin resin with a blowing agent and introducing the resin/blowing agent blend into a zone of lower pressure to cause foaming.
  • blowing agent Generally, about 1 - 15 parts of blowing agent are utilized per 100 parts resin.
  • the azeotrope-like compositions of the invention may be used as a blowing agent in a process for preparing polyurethane foams comprising reacting and foaming a mixture of ingredients which will form the polymeric foam in the presence of a blowing agent.
  • a blowing agent approximately 30 parts of blowing agent is used per 100 parts of polyol.
  • the difluoromethane and 1,1,1-trifluoroethane components of the novel azeotrope-like compositions of the invention are known materials. Preferably they should be used in sufficiently high purity so as to avoid the introduction of adverse influences upon the constant boiling properties of the system.
  • the ebulliometer was first charged with a weighed amount of HFC-32. The system was brought to total reflux by gently warming the lower part of the ebulliometer. A carbon dioxide ice/methanol mixture was used to cool the condenser. The temperature of the boiling liquid was measured using a precision 25 ohm platinum resistance thermometer. The thermometer recorded the boiling point measurements with a precision of + 0.01'C. Boiling temperature and atmospheric pressure were recorded after steady-state had been attained. A weighed aliquot of HFC-143a was then introduced into the ebulliometer and the temperature and pressure recorded again after the attainment of steady-state. This process was repeated with additional aliquots of HFC-143a.
  • mixtures comprising from about 10 to about 99 weight percent HFC-32 and from about 1 to about 90 weight percent HFC-143a are constant boiling at about -51 * C + 5*C at 760 mm Hg.
  • 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, for example, "Fluorocarbons Refrigerants Handbook", ch. 3, Prentice-Hall, (1988) by R.C. Downing.
  • 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 the refrigerant. In refrigeration engineering this term expresses the ratio of useful refrigeration to the energy applied by the compressor in compressing the vapor.
  • 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.
  • a refrigerant with a higher capacity will deliver more cooling or heating power.
  • the COP of the 95/5 weight percent HFC-32/HFC-143a blend was 1.52 and that of HFC-32 alone was 1.5.
  • the energy efficiency of the mixture was higher than that of pure HFC-32.
  • the capacity of the azeotropic blend was higher than that of HFC-32 and HFC-143a by 3%.
  • Another important parameter for refrigeration is the compressor discharge temperature. High discharge temperatures cause a decrease in compressor reliability and are therefore preferably avoided.
  • the discharge temperature for the 95/5 weight percent HFC-32/HFC-143a blend was 406 ⁇ F. This is lower than the discharge temperature for HFC-32 which, under the conditions specified above, was determined to be 416'F.
  • Free-rise rigid polyurethane foams are prepared using the formulations specified in Table II below using a Martin Sweets Co. Modern Module III urethane foam machine at a delivery rate of 15 lbs./min. This formulation is an example of a pour-in-place rigid polyurethane formulation which might be used as appliance insulation.
  • the HFC-32/HFC-143a composition of Example 1 is metered into the Martin Sweets machine as a third stream. Alternately, it may be preblended with the polyol and held in solution under pressure and a two stream foam machine used.
  • P uraco 11141 s a polyether polyol manufactured by
  • Silicone L-5340 is a silicone surfactant manufactured by Union Carbide Corp.
  • Thancat TD-33 is 33% triethylenediamine in propylene glycol manufactured by Texaco Inc.
  • Tehancat DME is N,N-dimethylethanolamine manufactured by Texaco Inc.
  • Catalyst T-12 is dibutyl dilaurate manufactured by
  • Lupranate M20S is polyethylene polyphenylisocyanate manufactured by BASF Wandotte Corp.
  • Example 4 The froth foams produced using the above formulation are closed-cell, low density foams with good insulation characteristics indicating that the composition of Example 1 is a good blowing agent for polyurethane foams.
  • Example4
  • a small 304 grade stainless steel pressure vessel is constructed using schedule 40 pipe which is 4 inches in length and 2 inches in diameter.
  • the vessel has top and bottom flanges which are used to close the ends of the cell.
  • a pressure tight seal is maintained between the ends of the pipe and the flanges using Teflon o- rings.
  • the vessel is closed by tightening 4 bolts which run the length of the cell through the top and bottom flanges.
  • the design pressure limit for the apparatus is 1700 psi at 200°C; the operational limit is set at 1000 psi.
  • Example 1 Twenty two and one half grams of the composition of Example 1 is charged into the sealed vessel. The vessel is placed in a 250°F oven overnight. The vessel is removed from the oven, rapidly depressurized and then immersed in water. The glass jar is removed from the vessel. The resulting foam has a density of 3 - 4 lbs/ft 3 indicating that the composition of Example 1 is a good blowing agent for thermal plastic foam.
  • compositions of HFC-32 and HFC-143a are azeotrope-like, useful as blowing agents for thermal plastic foam and polyurethane foam and exhibit improved refrigeration properties.

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

Abstract

L'invention concerne des compositions de difluorométhane et de 1,1,1-trifluoroéthane du type azéotrope qui sont utilisées en tant que réfrigérants pour le chauffage ou le refroidissement et en tant qu'agents gonflants pour la préparation de mousse thermoplastique et de mousse de polyuréthane.
PCT/US1993/007390 1992-08-19 1993-08-05 Compositions de difluoromethane et de 1,1,1-trifluoroethane du type azeotrope WO1994004628A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US93286292A 1992-08-19 1992-08-19
US932,862 1992-08-19

Publications (1)

Publication Number Publication Date
WO1994004628A1 true WO1994004628A1 (fr) 1994-03-03

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996023752A1 (fr) * 1995-02-01 1996-08-08 E.I. Du Pont De Nemours And Company SEPARATION ET ELIMINATION DES IMPURETES DE 1,1,1-TRIFLUOROETHANE (HFC-143a) PAR DISTILLATION EXTRACTIVE

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993007232A1 (fr) * 1991-09-30 1993-04-15 E.I. Du Pont De Nemours And Company Compositions de difluoromethane et de trifluoroethane ou perfluoroethane a point d'ebullition sensiblement constant

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993007232A1 (fr) * 1991-09-30 1993-04-15 E.I. Du Pont De Nemours And Company Compositions de difluoromethane et de trifluoroethane ou perfluoroethane a point d'ebullition sensiblement constant

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 9136, Derwent Publications Ltd., London, GB; AN 91-262357 *
DATABASE WPI Week 9136, Derwent Publications Ltd., London, GB; AN 91-262359 *
DATABASE WPI Week 9136, Derwent Publications Ltd., London, GB; AN 91-262362 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996023752A1 (fr) * 1995-02-01 1996-08-08 E.I. Du Pont De Nemours And Company SEPARATION ET ELIMINATION DES IMPURETES DE 1,1,1-TRIFLUOROETHANE (HFC-143a) PAR DISTILLATION EXTRACTIVE
US5830325A (en) * 1995-02-01 1998-11-03 E. I. Du Pont De Nemours And Company Separating and removing 1, 1, 1-trifluoroethane by using azeotropic distillation

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