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WO1993016163A1 - Compositions analogues a des azeotropes contenant du 1,1-dichloro-1-fluoroethane, de l'alcane c5 ou c6 ou du cycloalcane, du dichloromethane et eventuellement un alcanol et/ou du nitromethane - Google Patents

Compositions analogues a des azeotropes contenant du 1,1-dichloro-1-fluoroethane, de l'alcane c5 ou c6 ou du cycloalcane, du dichloromethane et eventuellement un alcanol et/ou du nitromethane Download PDF

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Publication number
WO1993016163A1
WO1993016163A1 PCT/US1993/000861 US9300861W WO9316163A1 WO 1993016163 A1 WO1993016163 A1 WO 1993016163A1 US 9300861 W US9300861 W US 9300861W WO 9316163 A1 WO9316163 A1 WO 9316163A1
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WO
WIPO (PCT)
Prior art keywords
weight percent
compositions
dichloro
fluoroethane
dichloromethane
Prior art date
Application number
PCT/US1993/000861
Other languages
English (en)
Inventor
Ellen Louise Swan
Peter Brian Logsdon
Rajat Subhra Basu
Leonard Michael Stachura
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 WO1993016163A1 publication Critical patent/WO1993016163A1/fr

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Classifications

    • 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
    • C11D7/5072—Mixtures of only hydrocarbons
    • 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

Definitions

  • Fluorocarbon based solvents have been used 15 extensively for the degreasing and otherwise cleaning of solid surfaces, especially intricate parts and difficult to remove soils.
  • vapor degreasing or solvent 20 cleaning consists of exposing a room temperature object to be cleaned to the vapors of a boiling solvent.
  • Vapors condensing on the object provide clean distilled solvent to wash away grease or other contamination.
  • a vapor degreaser is used for difficult to remove soils where elevated temperature is necessary to
  • the part can also be sprayed with distilled solvent before final rinsing.
  • Vapor degreasers suitable in the above-described operations are well known in the art.
  • Sherliker et al., in U.S. Patent 3,085,918 disclose such suitable vapor decreasers comprising a boiling sump, a clean sump, a water separator, and other ancillary equipment.
  • Cold cleaning is another application where a number of solvents are used. In most cold cleaning applications, the soiled part is either immersed in the fluid or wiped with cloths soaked in solvents and allowed to air dry.
  • Trichlorotrifluoro ⁇ ethane 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.
  • Azeotropic compositions are desired because they do not fractionate upon boiling. This behavior is desirable because in the previously described vapor degreasing equipment with which these solvents are employed, redistilled material is generated for final rinse-cleaning. Thus, the vapor degreasing system acts as a still. Therefore, unless the solvent composition is essentially constant boiling, fractionation will occur and undesirable solvent distribution may act to upset the cleaning and safety of processing. For example, preferential evaporation of the more volatile components of the solvent mixtures, would result in mixtures with changed compositions which may have less desirable properties, like lower solvency towards soils, less inertness towards metal, plastic or elastomer components, and increased flammability and toxicity.
  • the art has looked towards azeotropic compositions having fluorocarbon components because the fluorocarbon components contribute additionally desired characteristics, such as polar functionality, increased solvency power, and stabilizers.
  • fluorocarbon based azeotrope mixtures or azeotrope-like mixtures which offer alternatives for new and special applications for vapor degreasing and other cleaning applications.
  • fluorocarbon-based azeotrope-like mixtures with minimal or zero amounts of chlorine are of particular interest because they are considered to . be stratospherically safer substitutes than presently used chlorine-containing halogenated fluorocarbons (CFC's). The latter have been implicated in causing environmental problems associated with the depletion of the earth's protective ozone layer.
  • HCFC-141b has a good solvent properties
  • the alkanol, C 5 or C 6 alkane or cycloalkane and dichloro- methane components of the invention also have good solvent capabilities.
  • the alkanol dissolves polar organic materials and amine hydrochlorides while the dichloromethane component enhances the solubility of oils.
  • Nitromethane is a stabilizer. Thus, when these components are combined in effective amounts a stable, efficient azeotrope-like solvent results.
  • compositions of the preferred azeotrope-like compositions of the invention are summarized in the tables which follow. Note that the composition ranges reported are in weight percent and that the composition and boiling point ranges are understood to be prefaced by the term "about”. TABLE I
  • isohexane comprises about 35 to about 75 weight percent 2-methylpentane, about 10 to about 40 weight percent 3-methylpentane, about 7 to about 30 weight percent 2,3-dimethylbutane, about 7 to about 30 weight percent 2,2-dimethylbutane, and about 0.1 to about 10 weight percent n-hexane.
  • ком ⁇ онентs for this purpose are secondary and tertiary amines, olefins and cycloolefins, alkylene oxides, sulfoxides, sulfones, nitrites and nitriles, and acetylenic alcohols or ethers. It is contemplated that such stabilizers as well as other additives may be combined with the azeotrope-like compositions of this invention.
  • 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. 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 slightly. This is contrasted with non-azeotrope-like rl2- compositions in which the liquid composition changes substantially during boiling or evaporation.
  • 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 con ⁇ ventional degreasing apparatus.
  • the azeotrope-like compositions are used to clean solid surfaces by spraying the surfaces with the compositions
  • the azeotrope-like compositions are sprayed onto the surfaces by using a propellant.
  • the propellant is selected from the group consisting of hydrocarbons, chloro- fluorocarbons, hydrochlorofluorocarbons, hydrofluoro- carbons, dimethyl ether, carbon dioxide, nitrogen, nitrous oxide, methylene oxide, air, and mixtures thereof.
  • the HCFC-141b, C 5 or C 6 alkane or cycloalkane, dichloromethane, alkanol and nitromethane components of the invention are known materials. Preferably they should be used in sufficiently high purity so as to avoid the intro-duction of adverse influences upon the solvency properties or constant-boiling properties of the system.
  • the mixture was heated at total reflux for about one hour to ensure equilibration.
  • the distillate was obtained using a 3:1 reflux ratio at a boil-up rate of 250-300 grams per hour. Approximately 150 grams of product were distilled and 4 approximately equivalent sized overhead cuts were collected. The vapor temperature (of the distillate) , pot temperature, and barometric pressure were monitored. A constant boiling fraction was collected and analyzed by gas chromato- graphy to determine the weight percentages of its components.
  • the azeotropic properties of still other compositions of the invention were determined through the use of distillation techniques designed to provide higher rectification of the distillate than found in most vapor degreaser systems.
  • a five-plate Oldenshaw distillation column with a cold water condensed automatic liquid dividing head was used.
  • the distillation column was charged with HCFC-141b, 2-methylpentane, dichloro ⁇ methane and methanol. Then, the composition was heated under total reflux for about an hour to ensure equilibration. A reflux ratio of 5:1 was employed for this distillation. Approximately 50 percent of the original charges were collected in four similar-sized overhead fractions.
  • the composition of the fractions was determined using gas chromatography. 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-1ike.
  • 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.
  • 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.
  • the averages of the distillate fraction 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.
  • Performance studies are conducted wherein metal coupons are cleaned using the present azeotrope-like compositions as solvents.
  • the metal coupons are soiled with various types of oils and heated to 93°C so as to partially simulate the temperature attained while machining and grinding in the presence of these oils.
  • the metal coupons thus treated are degreased in a three-sump vapor phase degreaser machine.
  • condenser coils around the lip of the machine are used to condense the solvent vapor which is then collected in a sump. The condensate overflows into cascading sumps and eventually goes into the boiling sump.
  • the metal coupons are held in the solvent vapor and then vapor rinsed for a period of 15 seconds to 2 minutes depending upon the oils selected.
  • the azeotrope-like compositions of Examples 1 through 27 are used as the solvents. Cleanliness (i.e., the total residual material left after cleaning) of the coupons is determined by measuring the weight change of the coupons using an analytical balance.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne des compositions stables analogues à des azéotropes contenant du 1,1-dichloro-1-fluoroéthane, un alcane C5 ou C6 ou du cycloalcane, du dichlorométhane et éventuellement un alcanol et/ou du nitrométhane, qui sont utilisées dans une grande variété d'applications de nettoyage industriel dont le nettoyage à froid et le décapage de cartes de circuits imprimés.
PCT/US1993/000861 1992-02-05 1993-02-02 Compositions analogues a des azeotropes contenant du 1,1-dichloro-1-fluoroethane, de l'alcane c5 ou c6 ou du cycloalcane, du dichloromethane et eventuellement un alcanol et/ou du nitromethane WO1993016163A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US83221092A 1992-02-05 1992-02-05
US832,210 1992-02-05
US83254392A 1992-02-07 1992-02-07
US832,543 1992-02-07

Publications (1)

Publication Number Publication Date
WO1993016163A1 true WO1993016163A1 (fr) 1993-08-19

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PCT/US1993/000861 WO1993016163A1 (fr) 1992-02-05 1993-02-02 Compositions analogues a des azeotropes contenant du 1,1-dichloro-1-fluoroethane, de l'alcane c5 ou c6 ou du cycloalcane, du dichloromethane et eventuellement un alcanol et/ou du nitromethane

Country Status (2)

Country Link
AU (1) AU3602093A (fr)
WO (1) WO1993016163A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1991018964A1 (fr) * 1990-06-05 1991-12-12 Allied-Signal Inc. Compositions analogues a l'azeotrope de 1,1-dichloro-1-fluoroethane, dichloromethane et facultativement alcanol
US5085798A (en) * 1990-09-11 1992-02-04 Allied-Signal Inc. Azeotrope-like compositions of 1,1-dichloro-1-fluoroethane, cyclopentane and optionally an alkanol
EP0474528A1 (fr) * 1990-08-14 1992-03-11 Elf Atochem S.A. Composition nettoyante à base de 1,1-dichloro-1-fluoroéthane, de chlorure de méthylène et de méthanol
WO1992011351A1 (fr) * 1990-12-19 1992-07-09 Allied-Signal Inc. Compositions de type azeotrope

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1991018964A1 (fr) * 1990-06-05 1991-12-12 Allied-Signal Inc. Compositions analogues a l'azeotrope de 1,1-dichloro-1-fluoroethane, dichloromethane et facultativement alcanol
EP0474528A1 (fr) * 1990-08-14 1992-03-11 Elf Atochem S.A. Composition nettoyante à base de 1,1-dichloro-1-fluoroéthane, de chlorure de méthylène et de méthanol
US5085798A (en) * 1990-09-11 1992-02-04 Allied-Signal Inc. Azeotrope-like compositions of 1,1-dichloro-1-fluoroethane, cyclopentane and optionally an alkanol
WO1992011351A1 (fr) * 1990-12-19 1992-07-09 Allied-Signal Inc. Compositions de type azeotrope

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
DATABASE WPIL Derwent Publications Ltd., London, GB; AN 89-195725 *
DATABASE WPIL Derwent Publications Ltd., London, GB; AN 89-203184 *
DATABASE WPIL Derwent Publications Ltd., London, GB; AN 90-379464 *

Also Published As

Publication number Publication date
AU3602093A (en) 1993-09-03

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