EP0450855A2 - Solvent cleaning of articles - Google Patents

Solvent cleaning of articles Download PDF

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Publication number
EP0450855A2
EP0450855A2 EP91302698A EP91302698A EP0450855A2 EP 0450855 A2 EP0450855 A2 EP 0450855A2 EP 91302698 A EP91302698 A EP 91302698A EP 91302698 A EP91302698 A EP 91302698A EP 0450855 A2 EP0450855 A2 EP 0450855A2
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EP
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Prior art keywords
solvent
ether
cleaning
articles
boiling point
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Application number
EP91302698A
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German (de)
French (fr)
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EP0450855B1 (en
EP0450855A3 (en
Inventor
Neil Winterton
David George Mcbeth
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3M Co
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Imperial Chemical Industries Ltd
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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
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/261—Alcohols; Phenols
    • 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
    • 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
    • C11D7/5063—Halogenated hydrocarbons containing heteroatoms, e.g. fluoro alcohols
    • 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
    • C23G5/032—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents containing oxygen-containing 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
    • C11D7/28—Organic compounds containing halogen

Definitions

  • This invention relates to solvent cleaning applications in which contaminated articles such as, for example, metals, textiles, glass, plastics, electronic components and printed circuit boards are cleaned using a solvent or solvent vapour and more particularly to the use of low molecular weight ethers as solvents in solvent cleaning applications.
  • Solvent cleaning applications wherein contaminated articles are immersed in or washed with halogenated hydrocarbon solvents and/or the vapours thereof are well known and are in common use. Applications involving several stages of immersion, rinsing and drying are common and it is well known to use the solvent at ambient temperature (often accompanied by ultrasonic agitation) or at an elevated temperature up to the boiling point of the solvent. Examples of solvents used in these cleaning processes are 1,1,2-trichloro-1,2,2-trifluoroethane, 1,1,1-trichloroethane, trichloroethylene, perchloroethylene and methylene chloride.
  • solvents are used alone or in mixtures with cosolvents such as aliphatic alcohols or other low molecular weight, polar additives and depending to some extent upon the articles to be cleaned are often stabilised against degradation induced by light, heat and the presence of metals.
  • the use of the common cleaning solvents has been regarded as safe practice in that the solvents are stable, of low toxicity, non-flammable materials believed to be environmentally benign.
  • some at least of the common solvents may have a long-term deleterious effect on the stratosphere, the so-called ozone layer, so that a replacement solvent is seen to be desirable.
  • solvent cleaning applications of solvents comprising low molecular weight fluorine-containing ethers of boiling point in the range of about 20°C to about 120°C.
  • the ether has a boiling point in the range 20°C to 120°C, preferably from 25°C to 85°C, such that it may be used in conventional and existing cleaning equipment.
  • an ether may be selected having a boiling point close to that of the solvent the ether is replacing.
  • the ethers can be obtained by reaction of a halogenated aliphatic olefin with an optionally halogenated aliphatic alcohol in known manner and thus contain at least three carbon atoms in the molecule.
  • the ether will contain not more than five carbon atoms although it may contain six or more carbon atoms providing its boiling point is below about 120°C.
  • the ether contains at least one and will usually contain two or more fluorine atoms but will not generally be perfluorinated. In addition to fluorine atoms, the ether may contain chlorine atoms, bromine atoms and hydrogen atoms. Ethers containing chlorine and/or hydrogen may contain one or two chlorine atoms and/or one or two hydrogen atoms.
  • Examples of alcohols which may be used to produce the ethers are methanol, ethanol, propanol and butanol and halogenated derivatives thereof.
  • Alkenes which may be used include tetrafluoroethylene, hexafluoropropene, chlorotrifluoroethylene and the chlorofluoropropenes and hydrogen-containing analogues of these compounds for example trifluoroethylene and chlorodifluoroethylene.
  • ethers which may be used, and their boiling points, include the following:-
  • ethers including azeotropic mixtures
  • azeotropic mixtures may be used if desired as may mixtures of an ether with one or more cosolvents.
  • the same cosolvents may be used as are used with the principal solvents in known cleaning applications and in particular polar compounds such as alcohols are preferred cosolvents.
  • Cleaning compositions comprising the ether and a cosolvent, notably a lower alkanol cosolvent, are provided according to another feature of the invention.
  • Azeotropic mixtures of ethers and alcohols represent preferred embodiments of the invention. Lower aliphatic alcohols containing 1 to 4 carbon atoms are useful in such mixtures.
  • the ethers used according to the invention tend to be more stable than the commonly-used solvents and generally will not require stabilisation against degradation.
  • stabilisers may be added if desired or if required for particularly onerous cleaning applications and the stabilisers used in the common solvents may be employed, notably nitroalkanes and epoxides.
  • the ethers may be used as replacements for the solvent(s) used in any of the known cleaning applications and have the advantage of being generally more stable towards aluminium than the solvents they replace.
  • the ethers may be used to replace part of the solvent(s) used in known cleaning applications.
  • This Example illustrates the use of 2-chloro-1,1,2-trifluoroethyl methyl ether in cleaning flux residues from copper-coated boards.
  • solder cream A known weight of solder cream was applied to test boards (5 cm x 7 cm) cut from copper-coated FR4 (epoxy/glass fibre laminate) board and the cream was reflowed in a MICRO VPS soldering unit.
  • the solder cream used was a 62% tin/38% lead solder available as Multicore PRAB 3.
  • 2-chloro-1,1,2-trifluoroethyl methyl ether (boiling point 65°C at 630mm Hg) was boiled in a beaker fitted with an upper cooling coil through which cold water was circulated to create a boiling liquid phase and a vapour phase and the contaminated board was dipped into the boiling liquid for 60 seconds and then held in the vapour for 30 seconds.
  • Residual ionic contamination of the test board expressed as mg sodium chloride per square centimetre was determined using a Protonique Contaminometer. The ionic contamination of an unwashed test board was determined and the % removal of ionic contamination was calculated. 61% of the ionic flux residues were removed from the test boards.
  • the ether was heated to 190°C and the vapour pressures above the ether were determined over the range 50 - 190°C. A slight increase in vapour pressure was observed at approximately 120°C but there was no visible evidence of solvent breakdown at this temperature.
  • Example 2 a mixture of 2-chloro-1,1,2-trifluoroethyl methyl ether and methanol was boiled until a constant boiling mixture was obtained. This azeotrope contained 18.5% by weight of methanol and boiled at 56.8°C at normal pressure.
  • the azeotropic mixture was used to remove ionic residues from the test boards as described in Example 1. 66.9% of the ionic resudes were removed.
  • Example 3 the procedure of Example 2 was repeated except that a mixture of the ether (95% by weight) and methanol (5% by weight) was used instead of the azeotropic mixture. 65.1% of the ionic residues were removed.
  • the ether was refluxed in contact with aluminium for 48 hours.
  • the aluminium test piece was partly immersed in the liquid and partly in the vapour above the liquid.
  • This Example illustrates the use of tetrafluoroethyl methyl ether in cleaning flux residues from copper-coated boards.
  • Tetrafluoroethyl methyl ether forms an azeotrope with methanol containing 4% by weight methanol and boiling at 34.5°C.
  • the ether forms an azeotrope with 1,1,2-trichloro-1,2,2 -trifluoroethane containing 39.5% by weight of the haloethane and boiling at about 34.9°C.
  • the ether forms a ternary azeotrope with 1,1,2-trichloro- 1,2,2-trifluoroethane and methanol containing 41% by weight of the haloethane and 3% by weight of methanol and boiling at about 34.5°C.
  • This Example illustrates the use of a ternary azeotropic mixture in the process according to the present invention.
  • Example 8 The ternary azeotropic mixture of tetrafluoroethyl methyl ether, 1,1,2-trichloro-1,2,2-trifluoroethane and methanol prepared in Example 8 was used to remove solder flux residues from circuit boards by the procedure described in Example 1. 48.2% of the ionic flux residues were removed.
  • Tetrafluoroethyl ethyl ether boiling point 56°C and density 1.21 g/ml, forms an azeotrope with methanol containing 10.6% by weight of methanol and boiling at 48.6°C.
  • the ether forms an azeotrope with ethanol containing 38.5% by weight of 1,1,2-trichloro-1,2,2-trifluoroethane and boiling at 46.3°C.

Abstract

Low molecular weight, fluorine-containing ethers of boiling point 20°C to 120°C are used in solvent cleaning applications.

Description

  • This invention relates to solvent cleaning applications in which contaminated articles such as, for example, metals, textiles, glass, plastics, electronic components and printed circuit boards are cleaned using a solvent or solvent vapour and more particularly to the use of low molecular weight ethers as solvents in solvent cleaning applications.
  • Solvent cleaning applications wherein contaminated articles are immersed in or washed with halogenated hydrocarbon solvents and/or the vapours thereof are well known and are in common use. Applications involving several stages of immersion, rinsing and drying are common and it is well known to use the solvent at ambient temperature (often accompanied by ultrasonic agitation) or at an elevated temperature up to the boiling point of the solvent. Examples of solvents used in these cleaning processes are 1,1,2-trichloro-1,2,2-trifluoroethane, 1,1,1-trichloroethane, trichloroethylene, perchloroethylene and methylene chloride. These solvents are used alone or in mixtures with cosolvents such as aliphatic alcohols or other low molecular weight, polar additives and depending to some extent upon the articles to be cleaned are often stabilised against degradation induced by light, heat and the presence of metals.
  • In the known common solvent cleaning applications and especially in those applications where the solvent is used at an elevated temperature, there is a tendency for solvent vapour to be lost from the cleaning system into the atmosphere. Further losses may occur in loading and unloading the solvents into cleaning plant and in recovering used solvent by distillation. Whilst care is usually exercised to minimize losses of solvent into the atmosphere, for instance by improved plant design and vapour recovery systems, the expense of totally preventing losses is exhorbitant and most practical cleaning applications result in some loss of solvent vapour into the atmosphere.
  • Until recently, the use of the common cleaning solvents has been regarded as safe practice in that the solvents are stable, of low toxicity, non-flammable materials believed to be environmentally benign. However recent evidence suggests that some at least of the common solvents may have a long-term deleterious effect on the stratosphere, the so-called ozone layer, so that a replacement solvent is seen to be desirable.
  • According to the invention there is provided the use in solvent cleaning applications of solvents comprising low molecular weight fluorine-containing ethers of boiling point in the range of about 20°C to about 120°C.
  • The ether has a boiling point in the range 20°C to 120°C, preferably from 25°C to 85°C, such that it may be used in conventional and existing cleaning equipment. For any particular cleaning application, an ether may be selected having a boiling point close to that of the solvent the ether is replacing.
  • The ethers can be obtained by reaction of a halogenated aliphatic olefin with an optionally halogenated aliphatic alcohol in known manner and thus contain at least three carbon atoms in the molecule. Usually the ether will contain not more than five carbon atoms although it may contain six or more carbon atoms providing its boiling point is below about 120°C.
  • The ether contains at least one and will usually contain two or more fluorine atoms but will not generally be perfluorinated. In addition to fluorine atoms, the ether may contain chlorine atoms, bromine atoms and hydrogen atoms. Ethers containing chlorine and/or hydrogen may contain one or two chlorine atoms and/or one or two hydrogen atoms.
  • Examples of alcohols which may be used to produce the ethers are methanol, ethanol, propanol and butanol and halogenated derivatives thereof. Alkenes which may be used include tetrafluoroethylene, hexafluoropropene, chlorotrifluoroethylene and the chlorofluoropropenes and hydrogen-containing analogues of these compounds for example trifluoroethylene and chlorodifluoroethylene.
  • Examples of ethers which may be used, and their boiling points, include the following:-
    Figure imgb0001
  • Mixtures of ethers, including azeotropic mixtures, may be used if desired as may mixtures of an ether with one or more cosolvents. The same cosolvents may be used as are used with the principal solvents in known cleaning applications and in particular polar compounds such as alcohols are preferred cosolvents. Cleaning compositions comprising the ether and a cosolvent, notably a lower alkanol cosolvent, are provided according to another feature of the invention. Azeotropic mixtures of ethers and alcohols represent preferred embodiments of the invention. Lower aliphatic alcohols containing 1 to 4 carbon atoms are useful in such mixtures.
  • The ethers used according to the invention tend to be more stable than the commonly-used solvents and generally will not require stabilisation against degradation. However, stabilisers may be added if desired or if required for particularly onerous cleaning applications and the stabilisers used in the common solvents may be employed, notably nitroalkanes and epoxides.
  • The ethers may be used as replacements for the solvent(s) used in any of the known cleaning applications and have the advantage of being generally more stable towards aluminium than the solvents they replace. The ethers may be used to replace part of the solvent(s) used in known cleaning applications.
  • The invention is illustrated by the following examples.
    • EXAMPLE 1
  • This Example illustrates the use of 2-chloro-1,1,2-trifluoroethyl methyl ether in cleaning flux residues from copper-coated boards.
  • A known weight of solder cream was applied to test boards (5 cm x 7 cm) cut from copper-coated FR4 (epoxy/glass fibre laminate) board and the cream was reflowed in a MICRO VPS soldering unit. The solder cream used was a 62% tin/38% lead solder available as Multicore PRAB 3.
  • 2-chloro-1,1,2-trifluoroethyl methyl ether (boiling point 65°C at 630mm Hg) was boiled in a beaker fitted with an upper cooling coil through which cold water was circulated to create a boiling liquid phase and a vapour phase and the contaminated board was dipped into the boiling liquid for 60 seconds and then held in the vapour for 30 seconds.
  • Residual ionic contamination of the test board, expressed as mg sodium chloride per square centimetre was determined using a Protonique Contaminometer. The ionic contamination of an unwashed test board was determined and the % removal of ionic contamination was calculated. 61% of the ionic flux residues were removed from the test boards.
  • The ether was heated to 190°C and the vapour pressures above the ether were determined over the range 50 - 190°C. A slight increase in vapour pressure was observed at approximately 120°C but there was no visible evidence of solvent breakdown at this temperature.
  • In a Comparative Test, using
    1,1,2-trichloro-1,2,2-trifluoroethane as the solvent, 45% of the ionic flux residues were removed.
    • EXAMPLE 2-3
  • These Examples illustrate the use of mixtures of 2-chloro-1,1,2-trifluoroethyl methyl ether and methanol for cleaning flux residues from copper coated printed circuit boards.
  • In Example 2, a mixture of 2-chloro-1,1,2-trifluoroethyl methyl ether and methanol was boiled until a constant boiling mixture was obtained. This azeotrope contained 18.5% by weight of methanol and boiled at 56.8°C at normal pressure.
  • The azeotropic mixture was used to remove ionic residues from the test boards as described in Example 1. 66.9% of the ionic resudes were removed.
  • In Example 3, the procedure of Example 2 was repeated except that a mixture of the ether (95% by weight) and methanol (5% by weight) was used instead of the azeotropic mixture. 65.1% of the ionic residues were removed.
    • EXAMPLE 4
  • This Example demonstrates the stability of 2-chloro-1,1,2- trifluoroethyl methyl ether in the presence of aluminium.
  • The ether was refluxed in contact with aluminium for 48 hours. The aluminium test piece was partly immersed in the liquid and partly in the vapour above the liquid.
  • In the test, no increase in chloride ion or fluoride ion was observed in the liquid phase and the GC trace of the solvent after the test showed no change. There was no significant weight change in the metal test piece which emerged from the test clean and bright with no evidence of corrosion.
  • The results demonstrate that the ether has high stability in the presence of aluminium and is suitable for use in aluminium cleaning applications. Stabilisers may be added to inhibit the build up of acidity in the ether when it is used to clean metals.
    • EXAMPLE 5
  • This Example illustrates the use of tetrafluoroethyl methyl ether in cleaning flux residues from copper-coated boards.
  • Tetrafluoroethyl methyl ether, boiling point 33-35°C (630 mm Hg) and density (25°C) 1.28g/ml, was used to clean flux residues from copper coated boards as described in Example 1. 62% of the ionic flux residues were removed.
    • EXAMPLE 6-8
  • These Examples illustrate certain azeotropic mixtures suitable for use in the process according to the present invention.
  • Tetrafluoroethyl methyl ether forms an azeotrope with methanol containing 4% by weight methanol and boiling at 34.5°C.
  • The ether forms an azeotrope with 1,1,2-trichloro-1,2,2 -trifluoroethane containing 39.5% by weight of the haloethane and boiling at about 34.9°C.
  • The ether forms a ternary azeotrope with 1,1,2-trichloro- 1,2,2-trifluoroethane and methanol containing 41% by weight of the haloethane and 3% by weight of methanol and boiling at about 34.5°C.
    • EXAMPLE 9
  • This Example illustrates the use of a ternary azeotropic mixture in the process according to the present invention.
  • The ternary azeotropic mixture of tetrafluoroethyl methyl ether, 1,1,2-trichloro-1,2,2-trifluoroethane and methanol prepared in Example 8 was used to remove solder flux residues from circuit boards by the procedure described in Example 1. 48.2% of the ionic flux residues were removed.
    • EXAMPLE 10-11
  • These Examples illustrate further azeotropic mixtures for use in the process according to the present invention.
  • Tetrafluoroethyl ethyl ether, boiling point 56°C and density 1.21 g/ml, forms an azeotrope with methanol containing 10.6% by weight of methanol and boiling at 48.6°C.
  • The ether forms an azeotrope with ethanol containing 38.5% by weight of 1,1,2-trichloro-1,2,2-trifluoroethane and boiling at 46.3°C.

Claims (10)

  1. A process for cleaning articles which comprises contacting the articles with a solvent composition comprising a low molecular weight fluorine-containing ether of boiling point in the range of about 20°C to about 120°C, or the vapour thereof or both
  2. A process for cleaning article/s as claimed in Claim 1 wherein the ether contains at least 3 carbon atoms.
  3. A process for cleaning articles as claimed in Claim 1 carried out at elevated temperature.
  4. A process for cleaning articles as claimed in Claim 1 wherein the said ether has a boiling point in the range of from 25°C to 80°C.
  5. A process as claimed in Claim 1 wherein the solvent composition further comprises a co-solvent.
  6. A process as claimed in Claim 5 wherein the co-solvent is a lower alkanol having up to 4 carbon atoms.
  7. A process as claimed in Claim 6 wherein the ether and the alcohol form an azeotropic mixture.
  8. A solvent composition as defined in any one of Claims 5-7.
  9. A solvent cleaning composition is claimed in Claim 8 wherein the low molecular weight fluorine containing ether of boiling point in the range of about 20°C to about 120°C is at least
    2-chloro-1,1,12-trifluoroethyl methyl ether, tetrafluoroethyl methyl ether, or tetrafluoroethyl ethyl ether.
  10. A solvent cleaning composition as claimed in Claim 9 in the form of an azeotrope wherein the co-solvent is at least one of methanol, ethanol or 1,1,2-trichloro-1,2,2-trifluoroethane.
EP91302698A 1990-04-04 1991-03-27 Solvent cleaning of articles Expired - Lifetime EP0450855B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9007645 1990-04-04
GB909007645A GB9007645D0 (en) 1990-04-04 1990-04-04 Solvent cleaning of articles

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EP0450855A2 true EP0450855A2 (en) 1991-10-09
EP0450855A3 EP0450855A3 (en) 1992-01-15
EP0450855B1 EP0450855B1 (en) 1999-10-27

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JP (1) JP2961924B2 (en)
KR (1) KR100205296B1 (en)
AT (1) ATE186071T1 (en)
AU (1) AU640760B2 (en)
CA (1) CA2039828C (en)
DE (1) DE69131737T2 (en)
ES (1) ES2140382T3 (en)
GB (1) GB9007645D0 (en)
IE (1) IE911028A1 (en)
NZ (1) NZ237628A (en)

Cited By (26)

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WO1993009272A1 (en) * 1991-11-01 1993-05-13 Allied-Signal Inc. A method of cleaning using partially fluorinated ethers having a tertiary structure
US5278342A (en) * 1992-03-25 1994-01-11 Hampshire Chemical Corp. Vapor phase chlorination of difluoromethyl methyl ether
US5304320A (en) * 1991-08-19 1994-04-19 Solvay (Societe Anonyme) Compositions comprising a fluoro ether and use of these compositions
EP0600538A1 (en) * 1992-12-03 1994-06-08 SOLVAY (Société Anonyme) Compositions containing a fluorinated ether and use thereof
US5484546A (en) * 1993-05-19 1996-01-16 E. I. Du Pont De Nemours And Company Refrigerant compositions including an acylic fluoroether
WO1996022356A1 (en) * 1995-01-20 1996-07-25 Minnesota Mining And Manufacturing Company Cleaning process and composition
US5543055A (en) * 1995-06-06 1996-08-06 Hampshire Chemical Corp. Purifications of flourinated dimethyl ethers
US5562854A (en) * 1994-09-29 1996-10-08 E. I. Du Pont De Nemours And Company Octafluorobutane compositions
WO1996036689A1 (en) * 1995-05-16 1996-11-21 Minnesota Mining And Manufacturing Company Azeotrope-like compositions and their use
WO1996036688A1 (en) * 1995-05-16 1996-11-21 Minnesota Mining And Manufacturing Company Azeotrope-like compositions and their use
US5605882A (en) * 1992-05-28 1997-02-25 E. I. Du Pont De Nemours And Company Azeotrope(like) compositions of pentafluorodimethyl ether and difluoromethane
WO1997022683A1 (en) * 1995-12-15 1997-06-26 Minnesota Mining And Manufacturing Company Cleaning process and composition
US5650089A (en) * 1991-12-03 1997-07-22 The United States Of America, As Represented By The Administrator Of The U.S. Environmental Protection Agency Refrigerant compositions with fluorinated dimethyl ether and either difluoroethane or cyclopropane, and use thereof
US5718293A (en) * 1995-01-20 1998-02-17 Minnesota Mining And Manufacturing Company Fire extinguishing process and composition
US5888418A (en) * 1992-03-20 1999-03-30 The United States Of America As Represented By The Secretary Of Commerce Azeotropic refrigerant comprising bis-(difluoromethyl)ether and 1,1,2-trifluoroethane
US6008179A (en) * 1995-05-16 1999-12-28 3M Innovative Properties Company Azeotrope-like compositions and their use
US6022842A (en) * 1998-02-11 2000-02-08 3M Innovative Properties Company Azeotrope-like compositions including perfluorobutyl methyl ether, 1- bromopropane and alcohol
US6030934A (en) * 1997-02-19 2000-02-29 3M Innovative Properties Company Azeotropic compositions of methoxy-perfluoropropane and their use
US6127430A (en) * 1998-12-16 2000-10-03 3M Innovative Properties Company Microemulsions containing water and hydrofluroethers
US6149980A (en) * 1997-09-15 2000-11-21 3M Innovative Properties Company Perfluoroalkyl haloalkyl ethers and compositions and applications thereof
US6159917A (en) * 1998-12-16 2000-12-12 3M Innovative Properties Company Dry cleaning compositions containing hydrofluoroether
US6355113B1 (en) 1991-12-02 2002-03-12 3M Innovative Properties Company Multiple solvent cleaning system
US6506459B2 (en) 1995-01-20 2003-01-14 3M Innovative Properties Company Coating compositions containing alkoxy substituted perfluoro compounds
US6548471B2 (en) 1995-01-20 2003-04-15 3M Innovative Properties Company Alkoxy-substituted perfluorocompounds
GB2385272A (en) * 2002-02-13 2003-08-20 Stephen Rodger Henly Method of sterilising an article
US6863211B2 (en) 1994-05-20 2005-03-08 3M Innovative Properties Company Omega-hydrofluoroalkyl ethers, precursor carboxylic acids and derivatives thereof, and their preparation and application

Families Citing this family (4)

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US5607616A (en) * 1993-05-19 1997-03-04 E. I. Du Pont De Nemours And Company Azeotrope(like) compositions with fluoromethyl trifluoromethyl ether and dimethyl ether
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AU640760B2 (en) 1993-09-02
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EP0450855B1 (en) 1999-10-27
KR100205296B1 (en) 1999-07-01
ATE186071T1 (en) 1999-11-15
CA2039828A1 (en) 1991-10-05
AU7391391A (en) 1991-10-10
DE69131737T2 (en) 2000-06-08
CA2039828C (en) 2001-01-23
JP2961924B2 (en) 1999-10-12
EP0450855A3 (en) 1992-01-15
KR910018532A (en) 1991-11-30
GB9007645D0 (en) 1990-05-30
JPH05271692A (en) 1993-10-19
ES2140382T3 (en) 2000-03-01

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