WO1991014020A2 - Compositions stabilisees analogues a l'azeotrope de 1,1-dichloro-1-fluoroethane, de dichlorotrifluoroethane, de nitromethane, et de methanol ou d'ethanol - Google Patents

Compositions stabilisees analogues a l'azeotrope de 1,1-dichloro-1-fluoroethane, de dichlorotrifluoroethane, de nitromethane, et de methanol ou d'ethanol Download PDF

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Publication number
WO1991014020A2
WO1991014020A2 PCT/US1991/001345 US9101345W WO9114020A2 WO 1991014020 A2 WO1991014020 A2 WO 1991014020A2 US 9101345 W US9101345 W US 9101345W WO 9114020 A2 WO9114020 A2 WO 9114020A2
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WO
WIPO (PCT)
Prior art keywords
azeotrope
compositions
weight percent
nitromethane
hcfc
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Application number
PCT/US1991/001345
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English (en)
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WO1991014020A3 (fr
Inventor
Kane David Cook
Alfred A. Riederer
Chien C. Li
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Allied-Signal Inc.
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Application filed by Allied-Signal Inc. filed Critical Allied-Signal Inc.
Publication of WO1991014020A2 publication Critical patent/WO1991014020A2/fr
Publication of WO1991014020A3 publication Critical patent/WO1991014020A3/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G5/00—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents
    • C23G5/02—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents
    • C23G5/028—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents containing halogenated hydrocarbons
    • C23G5/02809—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents containing halogenated hydrocarbons containing chlorine and fluorine
    • C23G5/02825—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents containing halogenated hydrocarbons containing chlorine and fluorine containing hydrogen
    • C23G5/02829—Ethanes
    • C23G5/02832—C2H3Cl2F
    • 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
    • C11D7/5077—Mixtures of only oxygen-containing solvents
    • C11D7/5081—Mixtures of only oxygen-containing solvents the oxygen-containing solvents being alcohols only

Definitions

  • This invention relates to stabilized
  • dichlorotrifluoroethane nitromethane
  • methanol or ethanol methanol or ethanol. These mixtures are useful in a variety of vapor degreasing, cold cleaning, dry cleaning, and solvent cleaning applications including defluxing.
  • Vapor degreasing and solvent cleaning with fluorocarbon based solvents have found widespread use in industry for the degreasing and otherwise cleaning of solid surfaces, especially intricate parts and difficult to remove soils.
  • vapor degreasing or solvent cleaning consists of exposing a room
  • the conventional operation of a vapor degreaser consists of immersing the part to be cleaned in a sump of boiling solvent which removes the bulk of the soil, thereafter immersing the part in a sump containing freshly distilled solvent near room temperature, and finally exposing the part to solvent vapors over the boiling sump which condense on the cleaned part.
  • the part can also be sprayed with distilled solvent before final rinsing.
  • Cold cleaning is another application where a number of solvents are used.
  • the soiled part is either immersed in the fluid or wiped with rags or similar objects soaked in solvents and allowed to air dry.
  • Fluorocarbon solvents such as
  • Trichlorotrifluoroethane has been found to have satisfactory solvent power for greases, oils, waxes and the like. It has therefore found widespread use for cleaning electric motors, compressors, heavy metal parts, delicate precision metal parts, printed circuit boards, gyroscopes, guidance systems, aerospace and missile hardware, aluminum parts and the like.
  • compositions including the desired fluorocarbon components such as trichlorotrifluoroethane which include components which contribute additionally desired characteristics, such as polar functionality, increased solvency power, and stabilizers.
  • desired fluorocarbon components such as trichlorotrifluoroethane which include components which contribute additionally desired characteristics, such as polar functionality, increased solvency power, and stabilizers.
  • Azeotropic compositions are desired because they do not
  • the vapor degreasing system acts as a still.
  • the solvent composition exhibits a constant boiling point, i.e., is an
  • azeotrope or is azeotrope-like, fractionation will occur and undesirable solvent distribution may act to upset the cleaning and safety of processing.
  • chlorofluorocarbons are suspected of causing environmental problems in connection with the earth's protective ozone layer.
  • Mathematical models have substantiated that hydrochlorofluorocarbons, such as 1,1-dichloro-1-fluoroethane (HCFC-141b) and dichlorotrifluoroethane (HCFC-123 or HCFC-123a), will not adversely affect atmospheric chemistry, being negligible contributors to ozone depletion and to green-house global warming in comparison to the fully halogenated species.
  • 4,035,258 discloses the azeotropic composition of ethanol with HCFC-141.
  • Commonly assigned U.S. Patent 4,816,174 discloses azeotropic compositions of HCFC-141b, methanol, and nitromethane.
  • Commonly assigned U.S. Patent 4,816,176 discloses azeotropic compositions of 2,2-dichloro-1,1,1-trichloroethane (HCFC-123) or 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a), methanol, and nitromethane.
  • Commonly assigned U.S. Patent 4,816,175 discloses azeotropic compositions of HCFC-123 or HCFC-123a, methanol, nitromethane, and cyclopentane.
  • hydrocarbons hydrocarbons, and esters.
  • Kokai Patent Publication 136,982 published May 30, 1989, discloses a buff-grinding cleaning agent of an azeotropic mixture of 67 weight percent 1,1-dichloro-2,2,2-trifluoroethane and 33 weight percent 1,1-dichloro-1-fluoroethane, plus hydrocarbons, alcohols, ketones, chlorinated
  • hydrocarbons hydrocarbons, and esters.
  • Kokai Patent Publication 137,259 published May 30, 1989, discloses a resist separating agent of an azeotropic composition of 67 weight percent
  • hydrocarbons hydrocarbons, and surfactants. While azeotropic or azeotrope-like
  • compositions are useful as cleaning solvents, the azeotrope-like compositions should be stabilized against possible changes during storage and use.
  • One potential change is due to hydrochlorofluorocarbons hydrolyzing to form HCl.
  • metallic materials When metallic materials are present such as occurs in many cleaning applications, the problem is worsened because the metal acts as a catalyst and causes the hydrolysis of
  • hydrochlorofluorocarbons to increase exponentially.
  • Metallic materials such as Al-2024, copper, cold rolled steel, galvanized steel, and zinc are commonly used in cleaning apparatus. Another potential change is due to ultraviolet light decomposing
  • 1,1-dichloro-1-fluoroethane 1,1-dichloro-1-fluoroethane; dichlorotrifluoroethane; nitromethane; and methanol or ethanol; and effective stabilizing amounts of 1,2-epoxyalkane having 3 to 7 carbon atoms.
  • novel azeotrope-like compositions comprising HCFC-141b, dichlorotrifluoroethane, nitromethane, and methanol or ethanol.
  • dichlorotrifluoroethane component can be either of its isorners 1,1-dichloro-2,2,2-trifluoroethane
  • HCFC-123 1,2-dichloro-1,2,2-trifluoroethane
  • HCFC-123a 1,2-dichloro-1,2,2-trifluoroethane
  • the preferred isomer is HCFC-123.
  • Dichlorotrifluoroethane and HCFC-141b do not form binary azeotrope systems.
  • compositions of the invention comprise from about 62.5 to about 97.9 weight percent of HCFC-141b, from about 2.0 to about 35.5 weight percent of
  • dichlorotrifluoroethane from about 0.02 to about 0.3 weight percent of nitromethane, and from about 0.1 to about 3.0 weight percent ethanol.
  • the azeotrope-like compositions of the invention comprise from about 72.0 to about 94.7 weight percent of HCFC-141b, from about 3.0 to about 26.0 weight percent of dichlorotrifluoroethane, from about 0.05 to about 0.3 weight percent of nitromethane, and from about 0.3 to about 2.0 weight percent ethanol.
  • the azeotrope-like compositions of the invention comprise from about 75.0 to about 90.0 weight percent of HCFC-141b, from about 5.0 to about 24.7 weight percent of dichlorotrifluoroethane, from about 0.05 to about 0.2 weight percent of
  • nitromethane and from about 0.3 to about 1.8 weight percent ethanol.
  • the azeotrope-like compositions of the invention comprise from about 77.2 to about 90.0 weight percent of HCFC-141b, from about 5.0 to about 21.7 weight percent of dichlorotrifluoroethane, from about 0.05 to about 0.2 weight percent of nitromethane, and from about 0.3 to about 1.5 weight percent ethanol which exhibits a boiling point of about 33.0°C at 760 mm Hg.
  • azeotrope-like is also used herein for a composition of HCFC-141b,
  • the azeotrope-like compositions of the invention comprise from about 60 to about 97 weight percent of HCFC-141b, from about 2.0 to about 35.5 weight percent of
  • the constant-boiling compositions of the invention comprise from about 70 to about 94 weight percent of HCFC-141b, from about 5 to about 26.0 weight percent of dichlorotrifluoroethane, from about 1.0 to about 4.0 weight percent of methanol, and from about 0.02 to about 1.0 weight percent nitromethane.
  • the constant-boiling compositions of the invention comprise from about 75 to about 90 weight percent of HCFC-141b, from about 7.5 to about 21.0 weight percent of dichlorotrifluoroethane, from about 2.0 to about 3.8 weight percent of methanol, and from about 0.02 to about 0.5 weight percent nitromethane.
  • the constant-boiling compositions of the invention comprise from about 80.0 to about 90.0 weight percent HCFC-141b, about 7.5 to about 16.0 weight percent dichlorotrifluoroethane, about 0.02 to about 0.2 weight percent nitromethane, and about 2.5 to about 3.8 weight percent methanol which exhibits a boiling point of about 30.2°C at 760 mm Hg.
  • compositions of the invention containing a mixture of HCFC-123 and
  • HCFC-123a behave as an azeotrope-like composition because the separate quaternary azeotropic
  • compositions with HCFC-123 and HCFC-123a have boiling points so close to one another as to be
  • thermodynamic state of a fluid is defined by four variables:
  • An azeotrope is a unique characteristic of a system of two or more components where X and Y are equal at the stated P and T. In practice, this means that the components of a mixture cannot be separated during distillation, and therefore are useful in vapor phase solvent cleaning as described above.
  • 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
  • Such composition may or may not be a true azeotrope.
  • the composition of the vapor formed during boiling or evaporation is identical or substantially identical to the original liquid composition.
  • the liquid composition if it changes at all, changes only to a minimal or negligible extent. This is to be contrasted with non-azeotrope-like compositions in which during boiling or evaporation, the liquid composition changes to a substantial degree.
  • one way to determine whether a candidate mixture is "azeotrope-like" within the meaning of this invention is to distill a sample thereof under conditions (i.e. resolution - number of plates) which would be expected to separate the mixture into its separate components. If the mixture is
  • the mixture will fractionate, i.e. separate into its various components with the lowest boiling component
  • distillation cut will be obtained which contains all of the mixture components and which is constant boiling or behaves as a single substance. This phenomenon cannot occur if the mixture is not
  • azeotrope-like i.e., it is not part of an azeotropic system. If the degree of fractionation of the candidate mixture is unduly great, then a composition closer to the true azeotrope must be selected to minimize fractionation. Of course, upon distillation of an azeotrope-like composition such as in a vapor degreaser, the true azeotrope will form and tend to concentrate.
  • azeotrope-like All such compositions are intended to be covered by the term azeotrope-like as used herein.
  • azeotrope-like 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. Thus, an azeotrope of A and B represents a unique type of relationship but with a variable composition depending on
  • azeotrope-like within the meaning of this invention is to state that such mixtures boil within about ⁇ 0.8°C. (at about 760 mm Hg) of the boiling point of the most preferred compositions disclosed herein.
  • the azeotrope-like compositions of the invention may be used to clean solid surfaces by treating said surfaces with said compositions in any manner well known to the art such as by dipping or spraying or use of conventional degreasing apparatus.
  • the HCFC-141b, dichlorotrifluoroethane, nitromethane, methanol, and ethanol components of the novel solvent 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 solvency properties or constant-boiling properties of the system. Of the possible six binary combinations of the four components which form the azeotrope-like
  • HCFC-141b and ethanol (31.9°C boiling point at 765 mm Hg), a minimum boiling azeotrope and nitromethane and ethanol (76.0°C boiling point at 760 mm Hg), a minimum boiling azeotrope.
  • HCFC-141b dichlorotrifluoroethane, and ethanol (for HCFC-123, 31.6oC boiling point at 760 mm Hg; for HCFC-123a, 32.0°C boiling point at 760 mm Hg), a minimum boiling azeotrope.
  • HCFC-141b dichlorotrifluoroethane, and ethanol (for HCFC-123, 31.6oC boiling point at 760 mm Hg; for HCFC-123a, 32.0°C boiling point at 760 mm Hg), a minimum boiling azeotrope.
  • dichlorotrifluoroethane, nitromethane, and ethanol are not known to form ternary azeotropes.
  • HCFC-141b/ethanol/dichlorotrifluoroethane is their ability to inhibit corrosion in metals.
  • HCFC-141b/ethanol/dichlorotrifluoroethane is their ability to inhibit corrosion in metals.
  • HCFC-141b and methanol 29.8°C boiling point at 765 mm Hg
  • a minimum boiling azeotrope a minimum boiling azeotrope
  • methanol and nitromethane 64.4°C boiling point at 760 mm Hg
  • nitromethane are not known to form binary azeotropes.
  • HCFC-141b dichlorotrifluoroethane, nitromethane, and methanol, three are known to form azeotropes:
  • compositions may include additional components so as to form new azeotrope-like compositions. Any such compositions are considered to be within the scope of the present invention as long as the compositions are constant-boiling or essentially constant-boiling and contain all of the essential components described herein. Although the azeotrope-like composition alone is stable, the addition of 1,2-epoxyalkane having 3 to 7 carbon atoms forms the present "stabilized azeotrope-like composition".
  • Examples of useful 1,2-epoxyalkanes having 3 to 7 carbon atoms include 1,2-epoxypropane;
  • 1,2-epoxybutane 1,2-e ⁇ oxypentane; 1,2-epoxyhexane; and 1,2-epoxyheptane.
  • the preferred 1,2-epoxyalkanes are 1,2-epoxybutane and 1,2-epoxyhexane.
  • composition of 1,1-dichloro-1-fluoroethane 1,1-dichloro-1-fluoroethane
  • 1,1-dichloro-2,2,2-trifluoroethane 1,1-dichloro-2,2,2-trifluoroethane; nitromethane; and methanol or ethanol allow the composition to be used and stored without loss of acceptable properties.
  • the preferred stabilized azeotrope-like composition of the present invention contains 1,2-epoxyalkane having 3 to 7 carbon atoms in an amount of from about 0.2 to about 1.0 percent by weight. More preferably, the stabilized azeotrope-like composition of the present invention contains 1,2-epoxyalkane having 3 to 7 carbon atoms in an amount of from about 0.3 to about 0.8 percent by weight.
  • the stabilizers are effective in preventing the hydrolysis of the azeotrope-like composition in the presence of Aluminum-2024, copper, cold rolled steel, galvanized steel, SS 304, SS 304L, SS 316, and SS 316L.
  • the Cl- concentration is less than 0.05 parts per million. Also, the metallic surface remains shiny.
  • the stabilized azeotrope-like composition of the present invention may be prepared in any known manner including weighing each component and then mixing said components.
  • the present invention is more fully
  • Example 1 A 5-plate Oldershaw distillation column with a cold water condensed automatic liquid dividing head was used for these examples.
  • the distillation column was charged with approximately 360 grams of 89.9 weight percent HCFC-141b, 8.1 weight percent HCFC-123, 2.0 weight percent ethanol and 0.2 weight percent nitromethane which was heated under total reflux for about an hour to ensure equilibration.
  • a reflux ratio of 2:1 was employed for this particular distillation. Approximately 50 percent of the original charges were collected in four similar-sized overhead fractions. The
  • compositions of these fractions were analyzed using gas chromatography. Table I shows the compositions of the starting materials. The averages of the distillate fractions and the overhead temperatures are quite constant within the uncertainty associated with determining the compositions, indicating that the mixtures are constant boiling or azeotrope-like.
  • compositions of the invention are useful as solvents in a variety of vapor degreasing, cold cleaning and solvent cleaning applications including defluxing.
  • HCFC-141b about 9.6 weight percent HCFC-123, about 3.1 weight percent methanol, and 0.3 weight percent nitromethane.
  • the mixture was evaluated for its constant boiling or non-segregating characteristics.
  • the vapor phase degreasing machine utilized was a small water-cooled, three-sump vapor phase degreaser, which represents a type of system configuration comparable to machine types in the field today which would present the most rigorous test of solvent segregating behavior.
  • the degreaser employed to demonstrate the invention contained two overflowing rinse-sumps and a boil-sump. The
  • boil-sump was electrically heated, and contained a low-level shut-off switch. Solvent vapors in the degreaser were condensed on water-cooled stainless-steel coils. The capacity of the unit was approximately 1.2 gallons. This degreaser was very similar to Baron Blakeslee 2 LLV 3-sump degreasers which are quite commonly used in commercial
  • the solvent charge was brought to reflux and the compositions in the rinse sump and the boil sump where the overflow from the work sump was brought to the mixture boiling point, were determined with a Perkin Elmer 8500 gas chromatograph.
  • the temperature of the liquid in the boil sump was monitored with a thermocouple temperature sensing device accurate to ⁇ 0.2°C. Refluxing was continued for 48 hours and sump compositions were monitored throughout this time. A mixture was considered constant boiling or
  • compositions of this invention will not segregate in any types of large-scale commercial vapor
  • Example 3 was repeated for Example 4 except that the composition was a constant-boiling mixture of 70.1 weight percent HCFC-141b, 26.8 weight percent HCFC-123, 0.2 weight percent nitromethane, and 2.9 weight percent methanol. The results are shown in Table 2 below.
  • azeotrope-like compositions comprising 86.1 percent by weight 1,1-dichloro-1-fluoroethane; 10 percent by weight
  • Al-2024 (hereinafter Al-2024),
  • Cu Copper(hereinafter Cu), Cold Rolled Steel(hereinafter CRS), Galvanized Steel(hereinafter GS), SS 304, SS 304L, SS 316, and SS 316L.
  • the stabilized azeotrope-like composition was oversaturated with water in order to create the worse possible scenario.
  • About 125 milliliters of the water saturated five component mixture were then transferred into a 250 milliliter pyrex flask which connected to a water/glycol cooled condenser.
  • a Drierite desiccant tube was installed to prevent ambient moisture from leaking into the system.
  • a metal strip was placed in the middle of the liquid-vapor phases because corrosion tends to begin at the liquid-vapor interface.
  • the water saturated five component mixture with the metal strip therein was under total reflux at its boiling temperature for seven days.
  • Example 5-20 The metallic materials and methods of Examples 5-20 are used.
  • Example 21, 23, 25, 27, 29, 31, 33, and 35 stabilized azeotrope-like compositions comprising 89.9 percent by weight
  • 1,1-dichloro-1-fluoroethane 8.1 percent by weight 1,1-dichloro-2,2,2-trifluoroethane; 0.2 percent by weight nitromethane; 2.0 percent by weight ethanol; and 0.4 percent by weight 1,2-epoxyhexane are tested for stability in the presence of metallic materials.
  • stabilized azeotrope-like compositions comprising 89.9 percent by weight 1,1-dichloro-1-fluoroethane; 8.1 percent by weight
  • 1,1-dichloro-2,2,2-trifluoroethane 0.2 percent by weight nitromethane; 2.0 percent by weight ethanol; and 0.4 percent by weight 1,2-epoxybutane are tested for stability in the presence of metallic materials.

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
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Abstract

Des compositions stabilisées analogues à l'azéotrope comprenant du 1,1-dichloro-1-fluoroéthane, du dichlorotrifluoroéthane, du nitrométhane, et de l'éthanol et du méthanol ainsi que de quantités appropriées de 1,2-alcane époxyde ayant de 3 à 7 atomes de carbone sont utiles en tant qu'éléments de dégraissage et comme solvants dans une variété d'utilisations concernant le nettoyage industriel, y compris le nettoyage à froid, le nettoyage à sec, et le décapage de plaquettes de circuits imprimés.
PCT/US1991/001345 1990-03-14 1991-02-26 Compositions stabilisees analogues a l'azeotrope de 1,1-dichloro-1-fluoroethane, de dichlorotrifluoroethane, de nitromethane, et de methanol ou d'ethanol WO1991014020A2 (fr)

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US49326890A 1990-03-14 1990-03-14
US493,268 1990-03-14

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992007059A1 (fr) * 1990-10-12 1992-04-30 Baxter International Inc. Stabilisation de compositions de chlorofluorocarbone
US5366946A (en) * 1992-09-29 1994-11-22 Solvay (Societe Anonyme) Stabilized 1,1-dichloro-1-fluoroethane, premixtures intended for the preparation of polymeric foams and polymeric foams obtained by the use thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4863630A (en) * 1989-03-29 1989-09-05 Allied-Signal Inc. Azeotrope-like compositions of 1,1-dichloro-1-fluoroethane, dichlorotrifluoroethane and ethanol
US4894176A (en) * 1988-12-27 1990-01-16 Allied-Signal Inc. Azeotrope-like compositions of 1,1-dichloro-1-fluoroethane, dichlorotrifluoroethane and methanol
WO1990007568A1 (fr) * 1988-12-27 1990-07-12 Allied-Signal Inc. Compositions semblables a l'azeotrope contenant du 1,1-dichloro-1-fluoroethane, du dichlorotrifluoroethane et du methanol ou de l'ethanol

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4894176A (en) * 1988-12-27 1990-01-16 Allied-Signal Inc. Azeotrope-like compositions of 1,1-dichloro-1-fluoroethane, dichlorotrifluoroethane and methanol
WO1990007568A1 (fr) * 1988-12-27 1990-07-12 Allied-Signal Inc. Compositions semblables a l'azeotrope contenant du 1,1-dichloro-1-fluoroethane, du dichlorotrifluoroethane et du methanol ou de l'ethanol
US4863630A (en) * 1989-03-29 1989-09-05 Allied-Signal Inc. Azeotrope-like compositions of 1,1-dichloro-1-fluoroethane, dichlorotrifluoroethane and ethanol

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992007059A1 (fr) * 1990-10-12 1992-04-30 Baxter International Inc. Stabilisation de compositions de chlorofluorocarbone
US5366946A (en) * 1992-09-29 1994-11-22 Solvay (Societe Anonyme) Stabilized 1,1-dichloro-1-fluoroethane, premixtures intended for the preparation of polymeric foams and polymeric foams obtained by the use thereof

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CS64391A2 (en) 1991-09-15
WO1991014020A3 (fr) 1991-10-31

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