WO1992016674A2 - A method of cleaning using hydrochlorofluorocarbons having 3 to 5 carbon atoms - Google Patents

A method of cleaning using hydrochlorofluorocarbons having 3 to 5 carbon atoms Download PDF

Info

Publication number
WO1992016674A2
WO1992016674A2 PCT/US1992/002154 US9202154W WO9216674A2 WO 1992016674 A2 WO1992016674 A2 WO 1992016674A2 US 9202154 W US9202154 W US 9202154W WO 9216674 A2 WO9216674 A2 WO 9216674A2
Authority
WO
WIPO (PCT)
Prior art keywords
chloro
cfh
fcf
solvent
commercially available
Prior art date
Application number
PCT/US1992/002154
Other languages
French (fr)
Other versions
WO1992016674A3 (en
Inventor
Chien Chi Li
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
Priority claimed from US07/671,272 external-priority patent/US5152845A/en
Priority claimed from US07/687,342 external-priority patent/US5158617A/en
Application filed by Allied-Signal Inc. filed Critical Allied-Signal Inc.
Publication of WO1992016674A2 publication Critical patent/WO1992016674A2/en
Publication of WO1992016674A3 publication Critical patent/WO1992016674A3/en

Links

Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L1/00—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods
    • D06L1/02—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods using organic 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
    • C11D7/5004—Organic solvents
    • C11D7/5018—Halogenated solvents
    • 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

Definitions

  • the present invention relates to a method of cleaning a surface of a substrate using hydrochlorofluorocarbons having 3 to 5 carbon atoms.
  • 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-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. Final evaporation of solvent from the object leaves behind no residue as would be the case where the object is simply washed in liquid solvent.
  • 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.
  • 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 degreasers comprising a boiling sump, a clean sump, a water separator, and other ancilliary 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 rags or similar objects soaked in solvents.
  • Aerosol products utilize a propellant gas or mixture of propellant gases, preferably in a liquified gas rather than a compressed gas state, to generate sufficient pressure to expel the active ingredients, i.e. product concentrates such as solvents, from the container upon opening of the aerosol valve.
  • the propellants may be in direct contact with the solvent, as in most conventional aerosol systems, or may be isolated from the solvent, as in barrier-type aerosol systems.
  • Chlorofluorocarbon solvents such as trichlorotrifluoroethane
  • 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.
  • Trichlorotrifluoroethane has two iso ers: 1,1,2- trichloro-l,2,2-trifluoroethane (known in the art as CFC-113) and 1,1,1-trichloro-2,2,2-trifluoroethane (known in the art as CFC-113a) .
  • CFC-113 has a boiling point of about 47°C and has been found to have satisfactory solvent power for greases, oils, waxes, and the like.
  • chloroform Another commonly used solvent is chloroform (known in the art as HCC-20) which has a boiling point of about 63°C.
  • Perchloroethylene is a commonly used dry cleaning and vapor degreasing solvent which has a boiling point of about 121°C. These compounds are disadvantageous for use as solvents because they are toxic; also, chloroform causes liver damage when inhaled in excess.
  • CFC-113 Chlorofluorocarbons (CFCs) such as CFC-113 are suspected of causing environmental problems in connection with the ozone layer. Under the Clean Air Act, CFC-113 is being phased-out of production.
  • Solvents should be stabilized against possible changes during storage and use.
  • One problem with CFC-113 is that it hydrolyzes to form HCI.
  • metallic materials such as occurs in many cleaning applications, the problem is worsened because the metal acts as a catalyst and causes the hydrolysis of CFC-113 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 CFC-113.
  • This hydrolysis problem also occurs with hydrochlorofluorocarbon solvents such as 1,1-dichloro-2,2,2-trifluoroethane (known in the art as HCFC-123) because chlorine and hydrogen atoms are on the same carbon or adjacent carbons.
  • the present invention provides a method of cleaning a surface of a substrate which comprises treating the surface with a solvent which is a straight chain or branched hydrochlorofluorocarbon having 3 to 5 carbon atoms.
  • a solvent which is a straight chain or branched hydrochlorofluorocarbon having 3 to 5 carbon atoms.
  • the straight chain hydrochlorofluorocarbons having 3 carbon atoms are listed in Table I below.
  • fluorinated compounds can be modified in order to form the straight chain hydrochlorofluorocarbons having 3 carbon atoms of the present invention.
  • Haszeldine Nature 165. 152 (1950) teaches the reaction of trifluoroiodomethane and acetylene to prepare 3,3,3-trifluoro-l-iodopropene which is then dehydroiodinated to form 3,3,3- trifluoropropyne.
  • CF 3 CFC1CC1H 2 (HCFC-234bb) may be prepared as follows.
  • trifluoromethyl iodide may be reacted with acetylene to prepare 3,3,3-trifluoro-l-iodopropene which is then dehydroiodinated to form 3,3,3-trifluoropropyne.
  • the 3,3,3-trifluoropropyne may then be reacted with commercially available hydrogen fluoride to form 2,3,3,3-tetrafluoro-l-propene which is then chlorinated to form l,2-dichloro-2,3,3,3-tetrafluoropropane.
  • CF 2 C1CFHCC1H 2 (HCFC-243ec) may be prepared as follows.
  • Commercially available 1,1,3-trichloropropene may be dehydrohalogenated to form 1,3-dichloro-l- propyne.
  • the 1,3-dichloro-l-propyne may then be fluorinated to form 1,3-dichloro-l,2-difluoro-l-propene which may then be reacted with commercially available hydrogen fluoride to form 1,3-dichloro-l,1,2- trifluoropropane.
  • CFH 2 CFC1CF 2 H (HCFC-244ba) may be prepared as follows.
  • Commercially available 1,3-difluoro-2- propanol may be dehydrated to form 1,3-difluoro-1- propene which may then be dehydrohalogenated to form 3- fluoro-1-propyne.
  • the 3-fluoro-l-propyne may then be fluorinated, chlorinated, and fluorinated to form 1,1,2,3-tetrafluoro-2-chloropropane.
  • CFH 2 CFHCF 2 C1 (HCFC-2 4ec) may be prepared as follows.
  • Commercially available 1,1,3-trichloropropene may be fluorinated to form 1,l-dichloro-3-fluoro-1- propene which may then be dehydrohalogenated to form 1- chloro-3-fluoro-l-propyne.
  • the l-chloro-3-fluoro-l- propyne may then be fluorinated to form 1-chloro-1,2,3- trifluoro-1-propene which may then be reacted with commercially available hydrogen fluoride to form 1- chloro-1,1,2,3-tetrafluoropropane.
  • CFC1HCH 2 CF 3 (HCFC-244fa) may be prepared as follows.
  • Commercially available 1,1,3-trichloropropene may be fluorinated to form 1,1,1,2,3- pentafluoropropane.
  • the 1,1,1,2,3-pentafluoropropane may then be dehydrohalogenated to form 1,3,3,3- tetrafluoro-1-propene which may then be reacted with commercially available hydrogen chloride to form 1- chloro-1,3,3,3-tetrafluoropropane.
  • CF 2 HCH 2 CF 2 C1 (HCFC-244fb) may be prepared as follows.
  • Commercially available 2,2,3,3-tetrafluoro-1- propanol may be fluorinated to form 1,1,1,2,2,3- hexafluoropropane which may then be dehydrohalogenated to form 1,3,3-trifluoro-l-propyne.
  • the 1,3,3- trifluoro-l-propyne may then be reacted with commercially available hydrogen chloride to form 1- chloro-1,3,3-trifluoro-1-propene which may then be reacted with commercially available hydrogen fluoride to form 1-chloro-1,1,3,3-tetrafluoropropane.
  • CH 3 CFC1CF 2 H (HCFC-253bb) may be prepared as follows.
  • Commercially available 1,2-dibromopropane may be dehydrohalogenated to form propyne.
  • the propyne may then be fluorinated, chlorinated, and fluorinated to form 2-chloro-1,1,2-trifluoropropane.
  • CH 3 CFHCF 2 C1 (HCFC-253ec) may be prepared as follows.
  • Commercially available 1,2-dichloropropane may be dehydrohalogenated to form 1-chloro-1-propene which may then be dehydrogenated to form 1-chloro-1- propyne.
  • the 1-chloro-l-propyne may then be reacted with commercially available hydrogen fluoride to form 1-chloro-1-fluoro-1-propene which may then be fluorinated to form 1-chloro-1,1,2-trifluoropropane.
  • the 1-chloro-3,3,3-trifluoropropane used in the present invention is commercially available from Halocarbon Products Company or may be prepared by reacting commercially available carbon tetrachloride and ethylene at low temperature in the presence of hydrogen fluoride as a catalyst to form 1,1,1,3-tetrachloropropane.
  • the hydrogen fluoride then serves as a fluorination agent to convert the 1,1,1,3-tetrachloropropane to 1-chloro-3,3,3-trifluoropropane.
  • the preferred straight chain hydrochlorofluorocarbons having 3 carbon atoms are CF 2 C1CFHCC1H 2 , CFH 2 CFC1CF 2 H, CFH 2 CFHCF 2 C1, CFC1HCH 2 CF 3 , CF 2 HCH 2 CF 2 C1, CH 3 CFC1CF 2 H, CH 3 CFHCF 2 C1, and CC1H 2 CH 2 CF 3 .
  • fluorinated compounds can be modified in order to form the straight chain hydrochlorofluorocarbons having 4 carbon atoms of the present invention.
  • This known method can be modified to form CF 3 CF 2 CH 2 CC1H 2 (HCFC-355mcf) as follows.
  • Commercially available perfluoroethyl iodide can be reacted with commercially available ethylene to prepare 1,1,1,2,2-pentafluoro-4-iodobutane which is then chlorinated to form l,l,l,2,2-pentafluoro-4- chlorobutane.
  • CH 3 CF 2 CFHCF 2 C1 (HCFC-3551ec) may be prepared as follows.
  • Commercially available l,3-dichloro-2-butene may be fluorinated to form 1-chloro-2,3,3- trifluorobutane which may then be dehydrohalogenated to form l-chloro-3,3-difluoro-l-butene.
  • the l-chloro-3,3- difluoro-1-butene may then be dehydrogenated to form 1- chloro-3,3-difluoro-l-propyne which may then be fluorinated to form l-chloro-l,2,3,3-tetrafluoro-l- butene which may then be reacted with commercially available hydrogen fluoride to form 1-chloro-1,1,2,3,3- pentafluorobutane.
  • CF 3 CH 2 CH 2 CF 2 C1 (HCFC-3551ff) may be prepared as follows.
  • Commercially available 2,3- dichlorohexafluoro-2-butene may be dechlorinated to form hexafluoro-2-butyne.
  • the hexafluoro-2-butyne may be hydrogenated to form 1,1,1,4,4,4-hexafluorobutane which may be chlorinated to form 1-chloro-l,1,4,4,4- pentafluorobutane.
  • CFH 2 CH 2 CFC1CF 3 (HCFC- 355mbf ) may be prepared as follows.
  • Commercially available l,4-dichloro-2-butyne may be reacted with commercially available hydrogen fluoride to form l,4-dichloro-2-fluoro-2-butene which may be fluorinated to form l,2,4-trifluoro-2-butene.
  • the l,2,4-trifluoro-2-butene may be reacted with commercially available hydrogen chloride to form 2- chloro-1,2,4-trifluorobutane which may be dehydrohalogenated, fluorinated, dehydrohalogenated, and fluorinated to form 2-chloro-1,1,1,2,4- pentafluorobutane.
  • CH 3 CF 2 CC1HCF 3 (HCFC-355mdc) may be prepared as follows.
  • Commercially available 3,4-dichloro-l-butene may be dehydrogenated to form 3,4-dichloro-l-butyne which may be reacted with commercially available hydrogen fluoride to form l,2-dichloro-3,3- difluorobutane.
  • the 1,2-dichloro-3,3-difluorobutane may be dehydrogenated to form l,2-dichloro-3,3- difluoro-1-butene which may be reacted with commercially available hydrogen fluoride to form 2- chloro-1,1,3,3-tetrafluorobutane.
  • the 2-chloro- 1,1,3,3-tetrafluorobutane may be dehydrogenated to form 2-chloro-1,1,3,3-tetrafluoro-1-butene which may be reacted with commercially available hydrogen fluoride to form 2-chloro-1,1,1,3,3-pentafluorobutane.
  • CH 3 CFC1CFHCF 3 (HCFC-355meb) may be prepared as follows.
  • Commercially available 1,3-dichloro-2-butene may be fluorinated to form 2-chloro-2,3,4- trifluorobutane which may be dehydrohalogenated to form 3-chloro-1,3-difluoro-1-butene.
  • the 3-chloro-1,3- difluoro-1-butene may be fluorinated to form 2-chloro- 2,3,4, -tetrafluorobutane which may be dehydrohalogenated to form 3-chloro-1,1,3-trifluoro-1- butene.
  • the 3-chloro-l,l,3-trifluoro-l-butene may be fluorinated to form 2-chloro-2,3,4,4,4- pentafluorobutane.
  • CH 3 CFC1CF 2 CF 2 H (HCFC-355pcb) may be prepared as follows.
  • Commercially available 1,3-dichloro-2-butene may be fluorinated to form 2-chloro-2,3,4- trifluorobutane which may be dehydrogenated to form 3- chloro-1,2,3-trifluoro-1-butene.
  • the 3-chloro-1,2,3- trifluoro-1-butene may be fluorinated to form 2-chloro- 2,3,3,4,4-pentafluorobutane.
  • CH 3 CF 2 CF 2 CFC1H (HCFC-355rcc) may be prepared as follows.
  • Commercially available 1,3-dichloro-2-butene may be fluorinated to form 1-chloro-2,3,3- trifluorobutane which may be dehydrogenated to form 1- chloro-2,3,3-trifluoro-l-butene.
  • the l-chloro-2,3,3- trifluoro-1-butene may be fluorinated to form 1-chloro- 1,2,2,3,3-pentafluorobutane.
  • CH 3 CC1HCFHCF 3 (HCFC-364med) may be prepared as follows.
  • Commercially available 1,3-dichloro-2-butene may be reacted with commercially available hydrogen fluoride to form 1,3-dichloro-2-fluorobutane which may be dehydrohalogenated to form 1,3-dichloro-1-butene.
  • the 1,3-dichloro-1-butene may be fluorinated to form 2- chloro-3,4,4-trifluorobutane which may be dehydrohalogenated to form 3-chloro-1,1-difluoro-1- butene.
  • the 3-chloro-1,1-difluoro-1-butene may be fluorinated to form 2-chloro-3,4,4,4-tetrafluorobutane.
  • the preferred straight chain hydrochlorofluorocarbons having 4 carbon atoms are CH 3 CF 2 CFHCF 2 C1, CF 3 CH 2 CH 2 CF 2 C1, CFH 2 CH 2 CFC1CF 3 , CH 3 CF 2 CC1HCF 3 , CH 3 CFC1CFHCF 3 , CH 3 CFC1CF 2 CF 2 H, CH 3 CF 2 CF 2 CFC1H, and CH 3 CC1HCFHCF 3 .
  • fluorinated compounds can be modified in order to form the branched hydrochlorofluorocarbons having 4 carbon atoms of the present invention.
  • CH 3 C(CF 3 )HCF 2 C1 (HCFC-3551ms) may be prepared as follows.
  • Commercially available 1-chloro-2- methylpropene may be fluorinated to form 1-chloro-1,2- difluoro-2-methylpropane which may be dehydrohalogenated to form l-chloro-l-fluoro-2- methylpropene.
  • the l-chloro-l-fluoro-2-methylpropene may be fluorinated to form 1-chloro-1,1,2-trifluoro-2- methylpropane which may be dehydrohalogenated to form 3-chloro-3,3-difluoro-2-methylpropene.
  • the 3-chlor ⁇ - 3,3-difluoro-2-methylpropene may be fluorinated to form 1-chloro-1,1,2,3-tetrafluoro-2-methylpropane which may be dehydrogenated to form 3-chloro-1,3,3-trifluoro-2- methylpropene.
  • the 3-chloro-l,3,3-trifluoro-2- methylpropene may be fluorinated to form l-chloro- 1,1,2,3,3-pentafluoro-2-methylpropane which may be dehydrohalogenated to form 3-chloro-1,1,3,3- tetrafluoro-2-methylpropene.
  • the 3-chloro-1,1,3,3- tetrafluoro-2-methylpropene may be fluorinated to form 1-chloro-1,1,3,3,3-pentafluoro-2-methylpropane.
  • CH 3 C(CF 2 H)C1CF 3 (HCFC-355mps) may be prepared as follows.
  • Commercially available 1-chloro-2- methylpropene may be fluorinated to form 1,1,2- trifluoro-2-methylpropane which may be dehydrohalogenated to form 3,3-difluoro-2- methylpropene.
  • the 3,3-difluoro-2-methylpropene may be fluorinated to form 1,1,2,3-tetrafluoro-2-methylpropane which may be dehydrohalogenated to form 1,3,3- trifluoro-2-methylpropene.
  • the l,3,3-trifluoro-2- methylpropene may be fluorinated to form 1,1,2,3,3- pentafluoro-2-methylpropane which may be dehydrohalogenated to form 1,1,3,3-tetrafluoro-2- methylpropene.
  • the 1,1,3,3-tetrafluoro-2-methylpropene may be chlorinated to form 1,2-dichloro-l,1,4,4- tetrafluoro-2-methylpropane which may be fluorinated to form 2-chloro-1,1,1,3,3-pentafluoro-2-methylpropane.
  • CH 3 C(CFC1H)FCF 3 (HCFC-355mrs) may be prepared as follows.
  • Commercially available l-chloro-2- methylpropene may be fluorinated to form 1-chloro-1,2- difluoro-2-methylpropane which may be dehydrohalogenated to form 3-chloro-3-fluoro-2- methylpropene.
  • the 3-chloro-3-fluoro-2-methylpropene may be fluorinated to form 1-chloro-1,2,3-trifluoro-2- methylpropane which may be dehydrohalogenated to form 3-chloro-l,3-difluoro-2-methylpropene.
  • the 3-chloro- 1,3-difluoro-2-methylpropene may be fluorinated to form l-chloro-l,2,3,3-tetrafluoro-2-methylpropane which may be dehydrohalogenated to form 3-chloro-1,1,3-trifluoro- 2-methylpropene.
  • the 3-chloro-1,1,3-trifluoro-2- methylpropene may be fluorinated to form 1-chloro- 1,2,3,3,3-pentafluoro-2-methylpropane.
  • the preferred branched hydrochlorofluorocarbons having 4 carbon atoms are CH 3 C(CF 3 )HCF 2 C1, CH 3 C(CF 2 H)C1CF 3 , and CH 3 C(CFC1H)FCF 3 .
  • CFH 2 CH 2 C(CF 2 C1)FCF 3 (HCFC-356mlfq) may be prepared as follows.
  • Commercially available l,4-dichloro-2- butene may be reacted with commercially available trifluoromethyl iodide to form l,4-dichloro-2- trifluoromethyl-3-iodobutane which may be dehydrohalogenated to form l,4-dichloro-3- trifluoromethyl-1-butene.
  • the l,4-dichloro-3- trifluoromethyl-1-butene may be hydrogenated to form l,4-dichloro-2-trifluoromethylbutane which may be fluorinated to form 1-chloro-2-trifluoromethyl-4- fluorobutane.
  • the 1-chloro-2-trifluoromethyl-4- fluorobutane may be dehydrogenated to form 1-chloro-2- trifluoromethyl-4-fluoro-1-butene which may be fluorinated to form 1-chloro-2-trifluoromethyl-1,2,4- trifluorobutane.
  • the l-chloro-2-trifluoromethyl-l,2,4- trifluorobutane may be dehydrohalogenated to form 1- chloro-2-trifluoromethyl-1,4-difluoro-1-butene which may be fluorinated to form 1-chloro-2-trifluoromethyl- 1,1,2,4-tetrafluorobutane.
  • CH 3 C(CF 3 ) (CF 2 H)CF 2 C1 (HCFC-3571mps) may be prepared as follows.
  • Commercially available 1,1-dichloropropene may be reacted with commercially available trifluoromethyl iodide to form 1,l-dichloro-l-iodo-2- trifluoromethylpropane which may be dehydrohalogenated to form 1,1-dichloro-2-trifluoromethyl-l-propene.
  • the 1,l-dichloro-2-trifluoromethyl-l-propene may be hydrogenated to form 1,l-dichloro-2- trifluoromethylpropane which may be fluorinated to form 1,1-difluoro-2-trifluoromethylpropane.
  • the 1,1- difluoro-2-trifluoromethylpropane may be dehydrogenated to form 1,1-difluoro-2-trifluoromethy-1-propene which may be reacted with commercially available trifluoromethyl iodide to form 1,l-difluoro-l-iodo-2,2- trifluoromethylpropane.
  • the 1,l-difluoro-l-iodo-2,2- trifluoromethylpropane may be chlorinated to form 1- chloro-1,1-difluoro-2,2-trifluoromethylpropane which may be hydrogenated to form 1-chloro-1,1-difluoro-2- difluoromethyl-2-trifluoromethylpropane.
  • CF 3 CFHC(CH 3 )FCF 2 C1 (HCFC-3571sem) may be prepared as follows.
  • Commercially available l,4-dichloro-2- butene may be reacted with commercially available iodomethane to form 1,4-dichloro-3-iodo-2-methylbutane which may be dehydrohalogenated to form 1,4-dichloro-3- methyl-1-butene.
  • the l,4-dichloro-3-methyl-l-butene may be fluorinated to form l-chloro-2-methyl-3,4,4- trifluorobutane which may be dehydrohalogenated to form l,l-difluoro-3-methyl-4-chloro-l-butene.
  • the 1,1- difluoro-3-methyl-4-chloro-l-butene may be fluorinated to form 1-chloro-2-methyl-3,4,4,4-tetrafluorobutane which may be dehydrogenated to form 1-chloro-2-methyl- 3,4, ,4-tetrafluoro-1-butene.
  • the 1-chloro-2-methyl- 3,4,4,4-tetrafluoro-1-butene may be fluorinated to form l-chloro-2-methyl-l,2,3,4,4,4-hexafluorobutane which may be dehydrohalogenated to form 1-chloro-2-methyl- 1,3,4,4,4-pentafluoro-1-butene.
  • the 1-chloro-2-methyl- 1,3,4, ,4-pentafluoro-1-butene may be fluorinated to form 1-chloro-2-methyl-1,1,2,3,4,4,4-heptafluorobutane.
  • CF 3 CFC1C(CH 3 )FCF 2 H (HCFC-357mbsp) may be prepared as follows.
  • Commercially available 2,3- dichlorohexafluoro-2-butene may be reacted with commercially available iodomethane to form 2,3- dichloro-3-iodo-2-methyl-1,1,1,4,4,4-hexafluoropropane which may be fluorinated to form 2-methyl-3-chloro- 1,1,1,2,3,4,4-heptafluorobutane.
  • the 2-methyl-3- chloro-1,1,1,2,3,4,4-heptafluorobutane may be dehalogenated to form 3-chloro-2-methyl-1,1,3,4,4,4- hexafluoro-1-butene which may be reacted with commercially available hydrogen fluoride to form 3- chloro-2-methyl-1,1,2,3,4,4,4-heptafluorobutane.
  • CF 3 CF 2 C (CH 3 ) C1CF 2 H (HCFC- 357mcsp) may be prepared as follows .
  • Commercially available 2 , 3 - dichlorohexafluoro-2-butene may be reacted with iodomethane to form 2-methyl-2,3-dichloro-3-iodo- 1,1,1,4,4,4-hexafluorobutane which may be fluorinated to form 2-methyl-1,1,1,2,3,3,4,4,4-nonafluorobutane.
  • the 2-methyl-1,1,1,2,3,3,4,4,4-nonafluorobutane may be dehalogenated to form 2-methyl-l,1,3,3,4,4,4- heptafluoro-1-butene which may be reacted with commercially available hydrogen chloride to form 2- chloro-2-methyl-1,1,3,3,4,4,4-heptafluorobutane.
  • CH 3 CF 2 C(CF 2 C1)HCF 3 (HCFC-357mlcs) may be prepared as follows.
  • Commercially available 1,3-dichloro-2-butene may be reacted with commercially available trifluoromethyl iodide to form 1,3-dichloro-2- trifluoromethyl-3-iodobutane which may be fluorinated to form 1,3,3-trifluoro-2-trifluoromethylbutane.
  • the l,3,3-trifluoro-2-trifluoromethylbutane may be dehydrogenated to form 1,3,3-trifluoro-2- trifluoromethyl-1-butene which may be fluorinated to form 1,l,2,3,3-pentafluoro-2-trifluoromethylbutane.
  • the l,l,2,3,3-pentafluoro-2-trifluoromethylbutane may be dehydrohalogenated to form 1,1,3,3-tetrafluoro-2- trifluoromethyl-1-butene which may be reacted with commercially available hydrogen chloride to form 1- chloro-l,1,3,3-tetrafluoro-2-trifluoromethylbutane.
  • CH 3 CFC1C(CF 3 )HCF 3 (HCFC-357mmbs) may be prepared as follows.
  • Commercially available 2,3- dichlorohexafluoro-2-butene may be reacted with commercially available trifluoromethyl iodide to form 2,3-dichloro-3-iodo-2-trifluoromethyl-1,1,1,4,4,4- hexafluorobutane which may be fluorinated to form 2- trifluoromethyl-1,1,1,2,3,3,4,4,4-nonafluorobutane.
  • the 2-trifluoromethyl-1,1,1,2,3,3,4,4,4- nonafluorobutane may be dehalogenated to form 3- trifluoromethyl-1,1,2,3,4,4,4-heptafluoro-1-butene which may be hydrogenated to form 2-trifluoromethyl- 1,1,1,2,3,4,4-heptafluorobutane.
  • the 2- trifluoromethyl-1,1,1,2,3,4,4-heptafluorobutane may be dehydrohalogenated to form 3-trifluoromethyl- 1,2,3,4,4,4-hexafluoro-l-butene which may be hydrogenated to form 3-trifluoromethyl-1,2,3,4,4, - hexafluorobutane.
  • the 3-trifluoromethyl-1,2,3, ,4, - hexafluorobutane may be dehydrohalogenated to form 3- trifluoromethyl-2,3,4, ,4-pentafluoro-1-butene which may be reacted with commercially available hydrogen chloride to form 3-chloro-2-trifluoromethyl-1,1,1,2,3- pentafluorobutane.
  • the 3-chloro-2-trifluoromethyl- 1,1,1,2,3-pentafluorobutane may be dehalogenated to form 3-chloro-2-trifluoromethyl-1,1,3-trifluoro-1- butene which may be reacted with commercially available hydrogen fluoride to form 3-chloro-2-trifluoromethyl- 1,1,1,3-tetrafluorobutane.
  • CF 2 C1CHFC(CH 3 )FCF 3 (HCFC-357mmel) may be prepared as follows.
  • Commercially available 2,3- dichlorohexafluoro-2-butene may be reacted with commercially available iodomethane to form 2,3- dichloro-3-iodo-1,1,1,4,4,4-hexafluoro-2- ethylbutane which may be fluorinated to form 2- methylperfluorobutane.
  • the 2-methylperfluorobutane may be dehalogenated to form 1,1,2,3,4,4,4-heptafluoro-3- methyl-1-butene which may be reacted with commercially available hydrogen chloride to form 4-chloro- 1,1,1,2,3,4,4-heptafluoro-2-methylbutane.
  • the method of R.N. Haszeldine et al., supra, can be modified to form CH 2 C1CH 2 C(CF 3 )FCF 3 (HCFC-357 mmfo) as follows.
  • perfluoroisopropyl iodide may be reacted with commercially available ethylene to prepare 2-trifluoromethyl-1,1,1,2- tetrafluoro-4-iodobutane which may then be chlorinated to form 2-trifluoromethyl-1,1,1,2-tetrafluoro-4- chlorobutane.
  • CFH 2 CH 2 C(CF 3 )C1CF 3 (HCFC-357mmfq) may be prepared as follows.
  • Commercially available 2,3- dichlorohexafluoro-2-butene may be reacted with commercially available trifluoromethyl iodide to form 2,3-dichloro-3-iodo-1,1,1,4,4,4-hexafluoro-2- trifluoromethylbutane which may be fluorinated to form 2-chloro-2-trifluoromethyl-perfluorobutane.
  • the 2- chloro-2-trifluoromethyl-perfluorobutane may be dehalogenated to form 3-chloro-3- rifluoromethyl- 1,1,2,4,4,4-hexafluoro-l-butene which may be hydrogenated to form 2-chloro-2-trifluoromethyl- 1,1,1,3,4,4-hexafluorobutane.
  • the 2-chloro-2- trifluoromethyl-1,1,1,3,4,4-hexafluorobutane may be fluorinated to form 3-chloro-3-trifluoromethyl-1,4,4,4- tetrafluoro-1-butene which may then be hydrogenated to form 2-chloro-2-trifluoromethyl-1,1,1,4- tetrafluorobutane.
  • CF 3 CFHC(CH 3 )C1CF 3 (HCFC-357msem) may be prepared as follows.
  • Commercially available 2,3- dichlorohexafluoro-2-butene may be reacted with commercially available iodomethane to form 2,3- dichloro-3-iodo-1,1,1,4,4,4-hexafluoro-2-methylbutane which may be chlorinated to form 2,3,3-trichloro- 1,1,1,4,4,4-hexafluoro-2-methylbutane.
  • the 2,3,3- trichloro-1,1,1,4,4,4-hexafluoro-2-methylbutane may be dehalogenated to form 3-chloro-l,l,l,4,4,4-hexafluoro- 2-methyl-2-butene which may be reacted with commercially available hydrogen fluoride to form 3- chloro-1,1,1,3,4,4,4-heptafluoro-2-methylbutane.
  • the 3-chloro-1,1,1,3,4,4,4-heptafluoro-2-methylbutane may be dehydrohalogenated to form l,l,l,4,4,4-hexafluoro-2- ethyl-2-butene which may be reacted with commercially available hydrogen chloride to form 2-chloro- 1,1,1,3,4,4,4-heptafluoro-2-methylbutane.
  • CF 3 CF 2 C(CH 3 )FCC1FH (HCFC-358mcsr) may be prepared as follows.
  • Commercially available 2,3- dichlorohexafluoro-2-butene may be reacted with commercially available trifluoromethyl iodide to form 2,3-dichloro-3-iodo-1,1,1,4,4,4-hexafluoro-2- methylbutane which may be fluorinated to form 2-methyl- perfluorobutane.
  • the 2-methyl-perfluorobutane may be dehalogenated to form 2-methyl-perfluoro-1-butene which may be reacted with commercially available hydrogen fluoride to form l,l,2,3,3,4,4,4-octafluoro-2- methylbutane.
  • the l,l,2,3 r 3,4,4,4-octafluoro-2- methylbutane may be dehalogenated to form 1,3,3,4,4,4- hexafluoro-2-methyl-1-butene which may be chlorinated to form l,2-dichloro-l,3,3,4,4,4-hexafluoro-2- methylbutane.
  • the l,2-dichloro-l,3,3,4,4,4-hexafluoro- 2-methylbutane may be dehydrohalogenated to form 1- chloro-l,3,3,4,4,4-hexafluoro-2-methyl-l-butene which may be reacted with commercially available hydrogen fluoride to form l-chloro-l,2,3,3,4,4,4-heptafluoro-2- methylbutane.
  • CH 3 CC1HC(CF 3 )HCF 3 (HCFC-366mmds) may be prepared as follows.
  • Commercially available 2,3- dichlorohexafluoro-2-butene may be reacted with trifluoromethyl iodide to form 2,3-dichloro-3-iodo- 1,1,1,4,4,4-hexafluoro-2-trifluoromethylbutane which may be chlorinated to form 3-iodo-l,1,1,4,4,4- hexafluoro-2-methyl-2-butene.
  • the 3-iodo-1,1,1,4,4,4- hexafluoro-2-trifluoromethyl-2-butene may be hydrogenated to form 3-iodo-l,1,1,4,4,4-hexafluoro-2- trifluoromethylbutane which may be dehydrohalogenated to form 2-iodo-1,1,4,4,4-pentafluoro-3-trifluoromethyl- 1-butene.
  • the 2-iodo-l,1,4,4,4-pentafluoro-3- trifluoromethyl-1-butene may be hydrogenated to form 3- iodo-1,1,1,4,4-pentafluoro-2-trifluoromethylbutane which may be chlorinated to form 3-chloro-1,1,1,4,4- pentafluoro-2-trifluoromethylbutane.
  • the 3-chloro- 1,1,1,4,4-pentafluoro-2-trifluoromethylbutane may be dehydrohalogenated to form 2-chloro-1,4,4,4- tetrafluoro-3-trifluoromethyl-1-butene which may be hydrogenated to form 3-chloro-1,1,1,4-tetrafluoro-2- trifluoromethylbutane.
  • the 3-chloro-1,1,1,4- tetrafluoro-2-trifluoromethylbutane may be dehydrohalogenated to form 2-chloro-4,4,4-trifluoro-3- trifluoromethyl-1-butene which may be hydrogenated to form 3-chloro-1,1,1-trifluoro-2-trifluoromethylbutane.
  • the preferred branched hydrochlorofluorocarbons having 5 carbon atoms are CFH 2 CH 2 C(CF 2 C1)FCF 3 , CH 3 C(CF 3 ) (CF 2 H)CF 2 C1, CF 3 CFHC(CH 3 )FCF 2 C1,
  • the present method is advantageous because the solvents have low atmospheric lifetimes.
  • Known solvents may be blended with the solvents of the present method. Examples of useful known solvents are listed in Table V below.
  • HCFC-234cc may be formed by any known method such as the reaction of 1,1,1,2,2,3-hexachloropropane with antimony pentachloride and hydrogen fluoride at 100°C.
  • HCFC-234cd may be formed by any known method such as the reaction of 1,1,1-trichloro-2,2, 3-trifluoropropane with antimony pentachloride and hydrogen fluoride at 120°C.
  • HCFC-244ca may be formed by any known method such as the reaction of 1,1,2,2,3-pentachloropropane with antimony pentachloride and hydrogen fluoride at 100°C.
  • HCFC-244cb may be formed by any known method such as the reaction of 1-chloro-1,1,2,2-tetra luoropropane with cesium fluoride and tetrabutylammonium bromide at 150°C.
  • HCFC-253ca may be formed by any known method such as the reaction of 1,2,3-trichloro-2-fluoropropane with niobium pentachloride and hydrogen fluoride at 100°C.
  • HCFC-253cb may be formed by any known method such as the reaction of 1,1,2,2-tetrachloropropane with tantalum pentafluoride and hydrogen fluoride at 130°C.
  • the present method removes most contaminants from the surface of a substrate.
  • the present method removes organic contaminants such as mineral oils from the surface of a substrate.
  • mineral oils both petroleum-based and petroleum- derived oils are included.
  • Lubricants such as engine oil, machine oil, and cutting oil are examples of petroleum-derived oils.
  • the present method also removes water from surface of a substrate.
  • the method may be used in the single- stage or multi-stage drying of objects.
  • the present method may be used to clean the surface of inorganic substrates and some organic substrates.
  • inorganic substrates include metallic substrates, ceramic substrates, and glass substrates.
  • organic substrates include polymeric substrates such as polycarbonate, polystyrene, and acrylonitrile-butadiene-styrene.
  • the method also may be used to clean the surface of natural fabrics such as cotton, silk, fur, suede, leather, linen, and wool.
  • the method also may be used to clean the surface of synthetic fabrics such as polyester, rayon, acrylics, nylon, and blends thereof, and blends of synthetic and natural fabrics. It should also be understood that composites of the foregoing materials may be cleaned by the present method.
  • the present method may be used in vapor degreasing, solvent cleaning, cold cleaning, dewatering, and dry cleaning.
  • the object to be cleaned is immersed in one or more stages in the liquid and/or vaporized solvent or is sprayed with the liquid solvent. Elevated temperatures, ultrasonic energy, and/or agitation may be used to intensify the cleaning effect.
  • CFC-113 was saturated with water at room temperature. 125 ml of CFC-113 was transferred into a 250 ml Pyrex flask which was connected to a water/glycol cooled condenser.
  • a "Drierite” desiccant was provided to prevent ambient moisture leaking into the solvent.
  • a metal coupon was situated in the middle of the liquid-vapor phase.
  • a total of eight common metal alloys were investigated. They are: Aluminum-2024(hereinafter Al-2024) , Copper(hereinafter Cu) , Cold Rolled steel(hereinafter CRS) , and Galvanized Steel(hereinafter GS) , SS 304, SS 304L, SS 316, and SS 316L.
  • the solvent then was under total reflux at its boiling temperature for seven days. Observation was made daily on the change of the metal surface including the loss of luster of the metal surface and stain or corrosion on the metal surface, if any and the solvent including coloration of the solvent, increased viscosity of the solvent and most importantly, the rate of change of the viscosity.
  • the pH values were determined for each solvent before and after the test.
  • the Cl ion concentration in the solvent was determined by ion chromatography.
  • Comparative A was repeated except that HCFC-123 was used instead of CFC-113.
  • the pH was about 4.8 in the presence of Al-2024 and was about 3.5 in the presence of the other metals.
  • S means stained
  • SC means slightly corroded
  • C means corroded
  • VC means very corroded
  • CL means colorless
  • G means gray with suspended particles.
  • Each solvent listed in Tables I through IV is added to mineral oil in a weight ratio of 50:50 at 27°C. Each solvent is miscible in the mineral oil.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Textile Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Detergent Compositions (AREA)

Abstract

A method of cleaning a surface of a substrate is provided. The solvent is selected from a group consisting of hydrochlorofluorocarbons having 3 to 5 carbon atoms and a maximum of two chlorine atoms. The environmental lifetime of the solvent is expected to be less than one year.

Description

A METHOD OF CLEANING USING HYDROCHLOROFLUOROCARBONS HAVING 3 TO 5 CARBON ATOMS
BACKGROUND OF THE INVENTION
The present invention relates to a method of cleaning a surface of a substrate using hydrochlorofluorocarbons having 3 to 5 carbon atoms.
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.
In its simplest form, vapor degreasing or solvent 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. Final evaporation of solvent from the object leaves behind no residue as would be the case where the object is simply washed in liquid solvent.
For soils which are difficult to remove, where elevated temperature is necessary to improve the cleaning action of the solvent, or for large volume assembly line operations where the cleaning of metal parts and assemblies must be done efficiently and quickly, 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. In addition, 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. For example, Sherliker et al. in U.S. Patent 3,085,918 disclose such suitable vapor degreasers comprising a boiling sump, a clean sump, a water separator, and other ancilliary 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 rags or similar objects soaked in solvents.
In cold cleaning applications, the use of the aerosol packaging concept has long been found to be a convenient and cost effective means of dispensing solvents. Aerosol products utilize a propellant gas or mixture of propellant gases, preferably in a liquified gas rather than a compressed gas state, to generate sufficient pressure to expel the active ingredients, i.e. product concentrates such as solvents, from the container upon opening of the aerosol valve. The propellants may be in direct contact with the solvent, as in most conventional aerosol systems, or may be isolated from the solvent, as in barrier-type aerosol systems.
Chlorofluorocarbon solvents, such as trichlorotrifluoroethane, have attained widespread use in recent years as effective, nontoxic, and nonflammable agents useful in degreasing applications and other solvent cleaning applications. 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. Trichlorotrifluoroethane has two iso ers: 1,1,2- trichloro-l,2,2-trifluoroethane (known in the art as CFC-113) and 1,1,1-trichloro-2,2,2-trifluoroethane (known in the art as CFC-113a) . CFC-113 has a boiling point of about 47°C and has been found to have satisfactory solvent power for greases, oils, waxes, and the like.
Another commonly used solvent is chloroform (known in the art as HCC-20) which has a boiling point of about 63°C. Perchloroethylene is a commonly used dry cleaning and vapor degreasing solvent which has a boiling point of about 121°C. These compounds are disadvantageous for use as solvents because they are toxic; also, chloroform causes liver damage when inhaled in excess.
Although chlorine is known to contribute to the solvency capability of a compound, fully halogenated chlorofluorocarbons and hydrochlorofluorocarbons are suspected of causing environmental problems in connection with the earth's protective ozone layer. Thus, the art is seeking new compounds which do not contribute to environmental problems but yet provide the solvency properties of CFC-113. Chlorofluorocarbons (CFCs) such as CFC-113 are suspected of causing environmental problems in connection with the ozone layer. Under the Clean Air Act, CFC-113 is being phased-out of production.
In response to the need for stratospherically safe materials, substitutes have been developed and continue to be developed. Research Disclosure 14623 (June 1978) reports that l,l-dichloro-2,2,2-trifluoroethane (known in the art as HCFC-123) is a useful solvent for degreasing and defluxing substrates. In the EPA "Findings of the Chlorofluorocarbon Chemical Substitutes International Committee", EPA-600/9-88-009 (April 1988), it was reported that HCFC-123 and 1,1- dichloro-1-fluoroethane (known in the art as HCFC-141b) have potential as replacements for CFC-113 as cleaning agents.
Commonly assigned U.S. Patent 4,947,881 teaches a method of cleaning using hydrochlorofluoropropanes having 2 chlorine atoms and a difluoromethylene group. European Publication 347,924 published December 27, 1989 teaches hydrochlorofluoropropanes having a difluoromethylene group. International Publication Number WO 90/08814 published August 9, 1990 teaches azeotropes having at least one hydrochlorofluoropropane having a difluoromethylene group.
A wide variety of consumer parts is produced on an annual basis in the United States and abroad. Many of these parts have to be cleaned during various manufacturing stages in order to remove undesirable contaminants. These parts are produced in large quantities and as a result, substantial quantities of solvents are used to clean them. It is apparent that the solvent used must be compatible with the material to be cleaned.
Solvents should be stabilized against possible changes during storage and use. One problem with CFC-113 is that it hydrolyzes to form HCI. 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 CFC-113 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 CFC-113. This hydrolysis problem also occurs with hydrochlorofluorocarbon solvents such as 1,1-dichloro-2,2,2-trifluoroethane (known in the art as HCFC-123) because chlorine and hydrogen atoms are on the same carbon or adjacent carbons.
SUMMARY OF THE INVENTION
The present invention provides a method of cleaning a surface of a substrate which comprises treating the surface with a solvent which is a straight chain or branched hydrochlorofluorocarbon having 3 to 5 carbon atoms. The straight chain hydrochlorofluorocarbons having 3 carbon atoms are listed in Table I below.
Figure imgf000008_0001
Known methods for making fluorinated compounds can be modified in order to form the straight chain hydrochlorofluorocarbons having 3 carbon atoms of the present invention.
For example, Haszeldine, Nature 165. 152 (1950) teaches the reaction of trifluoroiodomethane and acetylene to prepare 3,3,3-trifluoro-l-iodopropene which is then dehydroiodinated to form 3,3,3- trifluoropropyne. By using 3,3,3-trifluoropropyne as a starting material, CF3CFC1CC1H2 (HCFC-234bb) may be prepared as follows. Commercially available trifluoromethyl iodide may be reacted with acetylene to prepare 3,3,3-trifluoro-l-iodopropene which is then dehydroiodinated to form 3,3,3-trifluoropropyne. The 3,3,3-trifluoropropyne may then be reacted with commercially available hydrogen fluoride to form 2,3,3,3-tetrafluoro-l-propene which is then chlorinated to form l,2-dichloro-2,3,3,3-tetrafluoropropane.
E.T. McBee et al., "Fluorinated Derivatives of Propane", J. of Amer. Chem Soc. 69. 944 (1947) teach a method for the preparation of CC1F2CHC1CH3 (HCFC-252dc) . Commercially available 1,1-dichloropropene is reacted with commercially available commercially available hydrogen chloride to form 1,1,1-trichloropropane. The 1,1,1-trichloropropane is then reacted with commercially available hydrogen fluoride to form 1- chloro-1,1-difluoropropane which is then chlorinated to form 1,2-dichloro-l,1-difluoropropane.
CF2C1CFHCC1H2 (HCFC-243ec) may be prepared as follows. Commercially available 1,1,3-trichloropropene may be dehydrohalogenated to form 1,3-dichloro-l- propyne. The 1,3-dichloro-l-propyne may then be fluorinated to form 1,3-dichloro-l,2-difluoro-l-propene which may then be reacted with commercially available hydrogen fluoride to form 1,3-dichloro-l,1,2- trifluoropropane.
CFH2CFC1CF2H (HCFC-244ba) may be prepared as follows. Commercially available 1,3-difluoro-2- propanol may be dehydrated to form 1,3-difluoro-1- propene which may then be dehydrohalogenated to form 3- fluoro-1-propyne. The 3-fluoro-l-propyne may then be fluorinated, chlorinated, and fluorinated to form 1,1,2,3-tetrafluoro-2-chloropropane.
CFH2CFHCF2C1 (HCFC-2 4ec) may be prepared as follows. Commercially available 1,1,3-trichloropropene may be fluorinated to form 1,l-dichloro-3-fluoro-1- propene which may then be dehydrohalogenated to form 1- chloro-3-fluoro-l-propyne. The l-chloro-3-fluoro-l- propyne may then be fluorinated to form 1-chloro-1,2,3- trifluoro-1-propene which may then be reacted with commercially available hydrogen fluoride to form 1- chloro-1,1,2,3-tetrafluoropropane.
CFC1HCH2CF3 (HCFC-244fa) may be prepared as follows. Commercially available 1,1,3-trichloropropene may be fluorinated to form 1,1,1,2,3- pentafluoropropane. The 1,1,1,2,3-pentafluoropropane may then be dehydrohalogenated to form 1,3,3,3- tetrafluoro-1-propene which may then be reacted with commercially available hydrogen chloride to form 1- chloro-1,3,3,3-tetrafluoropropane.
CF2HCH2CF2C1 (HCFC-244fb) may be prepared as follows. Commercially available 2,2,3,3-tetrafluoro-1- propanol may be fluorinated to form 1,1,1,2,2,3- hexafluoropropane which may then be dehydrohalogenated to form 1,3,3-trifluoro-l-propyne. The 1,3,3- trifluoro-l-propyne may then be reacted with commercially available hydrogen chloride to form 1- chloro-1,3,3-trifluoro-1-propene which may then be reacted with commercially available hydrogen fluoride to form 1-chloro-1,1,3,3-tetrafluoropropane. CH3CFC1CF2H (HCFC-253bb) may be prepared as follows. Commercially available 1,2-dibromopropane may be dehydrohalogenated to form propyne. The propyne may then be fluorinated, chlorinated, and fluorinated to form 2-chloro-1,1,2-trifluoropropane.
CH3CFHCF2C1 (HCFC-253ec) may be prepared as follows. Commercially available 1,2-dichloropropane may be dehydrohalogenated to form 1-chloro-1-propene which may then be dehydrogenated to form 1-chloro-1- propyne. The 1-chloro-l-propyne may then be reacted with commercially available hydrogen fluoride to form 1-chloro-1-fluoro-1-propene which may then be fluorinated to form 1-chloro-1,1,2-trifluoropropane.
The 1-chloro-3,3,3-trifluoropropane used in the present invention is commercially available from Halocarbon Products Company or may be prepared by reacting commercially available carbon tetrachloride and ethylene at low temperature in the presence of hydrogen fluoride as a catalyst to form 1,1,1,3-tetrachloropropane. The hydrogen fluoride then serves as a fluorination agent to convert the 1,1,1,3-tetrachloropropane to 1-chloro-3,3,3-trifluoropropane.
Because CFC-113 and HCFC-123 readily hydrolyze, I was surprised to find that 1-chloro-3,3,3-trifluoropropane, a hydrochlorofluorocarbon, undergoes no hydrolysis when saturated with water. I believe that HCFC-253fb will be a better solvent than CFC-113 because HCFC-253fb contains -Cl and -H. The preferred straight chain hydrochlorofluorocarbons having 3 carbon atoms are CF2C1CFHCC1H2, CFH2CFC1CF2H, CFH2CFHCF2C1, CFC1HCH2CF3, CF2HCH2CF2C1, CH3CFC1CF2H, CH3CFHCF2C1, and CC1H2CH2CF3.
The straight chain hydrochlorofluorocarbons having 4 carbon atoms are listed in Table II below.
TABLE II
Figure imgf000013_0001
Known methods for making fluorinated compounds can be modified in order to form the straight chain hydrochlorofluorocarbons having 4 carbon atoms of the present invention.
For example, R. N. Haszeldine et al., "Addition of Free Radicals to Unsaturated Systems. Part XIII. Direction of Radical Addition to Chloro-1:1- difluoroethylene", J. of Amer. Chem. Soc. , 2193 (1957) teach the reaction of trifluoroiodomethane with chloro- l:l-difluoroethylene to prepare 3-chloro-1:1:1:2:2- pentafluoro-3-iodopropane which is then chlorinated to form 1,1-dichloro-2,2,3,3,3-pentafluoropropane (known in the art as HCFC-225ca) . This known method can be modified to form CF3CF2CH2CC1H2 (HCFC-355mcf) as follows. Commercially available perfluoroethyl iodide can be reacted with commercially available ethylene to prepare 1,1,1,2,2-pentafluoro-4-iodobutane which is then chlorinated to form l,l,l,2,2-pentafluoro-4- chlorobutane.
CH3CF2CFHCF2C1 (HCFC-3551ec) may be prepared as follows. Commercially available l,3-dichloro-2-butene may be fluorinated to form 1-chloro-2,3,3- trifluorobutane which may then be dehydrohalogenated to form l-chloro-3,3-difluoro-l-butene. The l-chloro-3,3- difluoro-1-butene may then be dehydrogenated to form 1- chloro-3,3-difluoro-l-propyne which may then be fluorinated to form l-chloro-l,2,3,3-tetrafluoro-l- butene which may then be reacted with commercially available hydrogen fluoride to form 1-chloro-1,1,2,3,3- pentafluorobutane.
CF3CH2CH2CF2C1 (HCFC-3551ff) may be prepared as follows. Commercially available 2,3- dichlorohexafluoro-2-butene may be dechlorinated to form hexafluoro-2-butyne. The hexafluoro-2-butyne may be hydrogenated to form 1,1,1,4,4,4-hexafluorobutane which may be chlorinated to form 1-chloro-l,1,4,4,4- pentafluorobutane.
CFH2CH2CFC1CF3 (HCFC- 355mbf ) may be prepared as follows. Commercially available l,4-dichloro-2-butyne may be reacted with commercially available hydrogen fluoride to form l,4-dichloro-2-fluoro-2-butene which may be fluorinated to form l,2,4-trifluoro-2-butene. The l,2,4-trifluoro-2-butene may be reacted with commercially available hydrogen chloride to form 2- chloro-1,2,4-trifluorobutane which may be dehydrohalogenated, fluorinated, dehydrohalogenated, and fluorinated to form 2-chloro-1,1,1,2,4- pentafluorobutane.
CH3CF2CC1HCF3 (HCFC-355mdc) may be prepared as follows. Commercially available 3,4-dichloro-l-butene may be dehydrogenated to form 3,4-dichloro-l-butyne which may be reacted with commercially available hydrogen fluoride to form l,2-dichloro-3,3- difluorobutane. The 1,2-dichloro-3,3-difluorobutane may be dehydrogenated to form l,2-dichloro-3,3- difluoro-1-butene which may be reacted with commercially available hydrogen fluoride to form 2- chloro-1,1,3,3-tetrafluorobutane. The 2-chloro- 1,1,3,3-tetrafluorobutane may be dehydrogenated to form 2-chloro-1,1,3,3-tetrafluoro-1-butene which may be reacted with commercially available hydrogen fluoride to form 2-chloro-1,1,1,3,3-pentafluorobutane.
CH3CFC1CFHCF3 (HCFC-355meb) may be prepared as follows. Commercially available 1,3-dichloro-2-butene may be fluorinated to form 2-chloro-2,3,4- trifluorobutane which may be dehydrohalogenated to form 3-chloro-1,3-difluoro-1-butene. The 3-chloro-1,3- difluoro-1-butene may be fluorinated to form 2-chloro- 2,3,4, -tetrafluorobutane which may be dehydrohalogenated to form 3-chloro-1,1,3-trifluoro-1- butene. The 3-chloro-l,l,3-trifluoro-l-butene may be fluorinated to form 2-chloro-2,3,4,4,4- pentafluorobutane.
CH3CFC1CF2CF2H (HCFC-355pcb) may be prepared as follows. Commercially available 1,3-dichloro-2-butene may be fluorinated to form 2-chloro-2,3,4- trifluorobutane which may be dehydrogenated to form 3- chloro-1,2,3-trifluoro-1-butene. The 3-chloro-1,2,3- trifluoro-1-butene may be fluorinated to form 2-chloro- 2,3,3,4,4-pentafluorobutane.
CH3CF2CF2CFC1H (HCFC-355rcc) may be prepared as follows. Commercially available 1,3-dichloro-2-butene may be fluorinated to form 1-chloro-2,3,3- trifluorobutane which may be dehydrogenated to form 1- chloro-2,3,3-trifluoro-l-butene. The l-chloro-2,3,3- trifluoro-1-butene may be fluorinated to form 1-chloro- 1,2,2,3,3-pentafluorobutane.
CH3CC1HCFHCF3 (HCFC-364med) may be prepared as follows. Commercially available 1,3-dichloro-2-butene may be reacted with commercially available hydrogen fluoride to form 1,3-dichloro-2-fluorobutane which may be dehydrohalogenated to form 1,3-dichloro-1-butene. The 1,3-dichloro-1-butene may be fluorinated to form 2- chloro-3,4,4-trifluorobutane which may be dehydrohalogenated to form 3-chloro-1,1-difluoro-1- butene. The 3-chloro-1,1-difluoro-1-butene may be fluorinated to form 2-chloro-3,4,4,4-tetrafluorobutane. The preferred straight chain hydrochlorofluorocarbons having 4 carbon atoms are CH3CF2CFHCF2C1, CF3CH2CH2CF2C1, CFH2CH2CFC1CF3, CH3CF2CC1HCF3, CH3CFC1CFHCF3, CH3CFC1CF2CF2H, CH3CF2CF2CFC1H, and CH3CC1HCFHCF3.
The branched chain hydrochlorofluorocarbons having 4 carbon atoms are listed in Table III below.
TABLE III
Number Chemical Formula
HCFC-345kms CH3C(CF3) FCFC12
HCFC-34511s CH3C(CF2C1) FCF2C1
HCFC-3551ms CH3C(CF3)HCF2C1
HCFC-355mop CF2HC(CC1H2)HCF3
HCFC-355mps CH3C(CF2H) C1CF3 HCFC-355mrs CH3C (CFC1H) FCF3
HCFC-373mss CH3C(CH3) C1CF3
Known methods for making fluorinated compounds can be modified in order to form the branched hydrochlorofluorocarbons having 4 carbon atoms of the present invention.
CH3C(CF3)HCF2C1 (HCFC-3551ms) may be prepared as follows. Commercially available 1-chloro-2- methylpropene may be fluorinated to form 1-chloro-1,2- difluoro-2-methylpropane which may be dehydrohalogenated to form l-chloro-l-fluoro-2- methylpropene. The l-chloro-l-fluoro-2-methylpropene may be fluorinated to form 1-chloro-1,1,2-trifluoro-2- methylpropane which may be dehydrohalogenated to form 3-chloro-3,3-difluoro-2-methylpropene. The 3-chlorσ- 3,3-difluoro-2-methylpropene may be fluorinated to form 1-chloro-1,1,2,3-tetrafluoro-2-methylpropane which may be dehydrogenated to form 3-chloro-1,3,3-trifluoro-2- methylpropene. The 3-chloro-l,3,3-trifluoro-2- methylpropene may be fluorinated to form l-chloro- 1,1,2,3,3-pentafluoro-2-methylpropane which may be dehydrohalogenated to form 3-chloro-1,1,3,3- tetrafluoro-2-methylpropene. The 3-chloro-1,1,3,3- tetrafluoro-2-methylpropene may be fluorinated to form 1-chloro-1,1,3,3,3-pentafluoro-2-methylpropane.
CH3C(CF2H)C1CF3 (HCFC-355mps) may be prepared as follows. Commercially available 1-chloro-2- methylpropene may be fluorinated to form 1,1,2- trifluoro-2-methylpropane which may be dehydrohalogenated to form 3,3-difluoro-2- methylpropene. The 3,3-difluoro-2-methylpropene may be fluorinated to form 1,1,2,3-tetrafluoro-2-methylpropane which may be dehydrohalogenated to form 1,3,3- trifluoro-2-methylpropene. The l,3,3-trifluoro-2- methylpropene may be fluorinated to form 1,1,2,3,3- pentafluoro-2-methylpropane which may be dehydrohalogenated to form 1,1,3,3-tetrafluoro-2- methylpropene. The 1,1,3,3-tetrafluoro-2-methylpropene may be chlorinated to form 1,2-dichloro-l,1,4,4- tetrafluoro-2-methylpropane which may be fluorinated to form 2-chloro-1,1,1,3,3-pentafluoro-2-methylpropane.
CH3C(CFC1H)FCF3 (HCFC-355mrs) may be prepared as follows. Commercially available l-chloro-2- methylpropene may be fluorinated to form 1-chloro-1,2- difluoro-2-methylpropane which may be dehydrohalogenated to form 3-chloro-3-fluoro-2- methylpropene. The 3-chloro-3-fluoro-2-methylpropene may be fluorinated to form 1-chloro-1,2,3-trifluoro-2- methylpropane which may be dehydrohalogenated to form 3-chloro-l,3-difluoro-2-methylpropene. The 3-chloro- 1,3-difluoro-2-methylpropene may be fluorinated to form l-chloro-l,2,3,3-tetrafluoro-2-methylpropane which may be dehydrohalogenated to form 3-chloro-1,1,3-trifluoro- 2-methylpropene. The 3-chloro-1,1,3-trifluoro-2- methylpropene may be fluorinated to form 1-chloro- 1,2,3,3,3-pentafluoro-2-methylpropane.
The preferred branched hydrochlorofluorocarbons having 4 carbon atoms are CH3C(CF3)HCF2C1, CH3C(CF2H)C1CF3, and CH3C(CFC1H)FCF3.
The branched hydrochlorofluorocarbons having 5 carbon atoms are listed in Table IV below.
TABLE IV
N mber Chemical Formula
Figure imgf000020_0001
Known methods for making fluorinated compounds can be modified in order to form the branched hydrochlorofluorocarbons having 5 carbon atoms of the present invention. CFH2CH2C(CF2C1)FCF3 (HCFC-356mlfq) may be prepared as follows. Commercially available l,4-dichloro-2- butene may be reacted with commercially available trifluoromethyl iodide to form l,4-dichloro-2- trifluoromethyl-3-iodobutane which may be dehydrohalogenated to form l,4-dichloro-3- trifluoromethyl-1-butene. The l,4-dichloro-3- trifluoromethyl-1-butene may be hydrogenated to form l,4-dichloro-2-trifluoromethylbutane which may be fluorinated to form 1-chloro-2-trifluoromethyl-4- fluorobutane. The 1-chloro-2-trifluoromethyl-4- fluorobutane may be dehydrogenated to form 1-chloro-2- trifluoromethyl-4-fluoro-1-butene which may be fluorinated to form 1-chloro-2-trifluoromethyl-1,2,4- trifluorobutane. The l-chloro-2-trifluoromethyl-l,2,4- trifluorobutane may be dehydrohalogenated to form 1- chloro-2-trifluoromethyl-1,4-difluoro-1-butene which may be fluorinated to form 1-chloro-2-trifluoromethyl- 1,1,2,4-tetrafluorobutane.
CH3C(CF3) (CF2H)CF2C1 (HCFC-3571mps) may be prepared as follows. Commercially available 1,1-dichloropropene may be reacted with commercially available trifluoromethyl iodide to form 1,l-dichloro-l-iodo-2- trifluoromethylpropane which may be dehydrohalogenated to form 1,1-dichloro-2-trifluoromethyl-l-propene. The 1,l-dichloro-2-trifluoromethyl-l-propene may be hydrogenated to form 1,l-dichloro-2- trifluoromethylpropane which may be fluorinated to form 1,1-difluoro-2-trifluoromethylpropane. The 1,1- difluoro-2-trifluoromethylpropane may be dehydrogenated to form 1,1-difluoro-2-trifluoromethy-1-propene which may be reacted with commercially available trifluoromethyl iodide to form 1,l-difluoro-l-iodo-2,2- trifluoromethylpropane. The 1,l-difluoro-l-iodo-2,2- trifluoromethylpropane may be chlorinated to form 1- chloro-1,1-difluoro-2,2-trifluoromethylpropane which may be hydrogenated to form 1-chloro-1,1-difluoro-2- difluoromethyl-2-trifluoromethylpropane.
CF3CFHC(CH3)FCF2C1 (HCFC-3571sem) may be prepared as follows. Commercially available l,4-dichloro-2- butene may be reacted with commercially available iodomethane to form 1,4-dichloro-3-iodo-2-methylbutane which may be dehydrohalogenated to form 1,4-dichloro-3- methyl-1-butene. The l,4-dichloro-3-methyl-l-butene may be fluorinated to form l-chloro-2-methyl-3,4,4- trifluorobutane which may be dehydrohalogenated to form l,l-difluoro-3-methyl-4-chloro-l-butene. The 1,1- difluoro-3-methyl-4-chloro-l-butene may be fluorinated to form 1-chloro-2-methyl-3,4,4,4-tetrafluorobutane which may be dehydrogenated to form 1-chloro-2-methyl- 3,4, ,4-tetrafluoro-1-butene. The 1-chloro-2-methyl- 3,4,4,4-tetrafluoro-1-butene may be fluorinated to form l-chloro-2-methyl-l,2,3,4,4,4-hexafluorobutane which may be dehydrohalogenated to form 1-chloro-2-methyl- 1,3,4,4,4-pentafluoro-1-butene. The 1-chloro-2-methyl- 1,3,4, ,4-pentafluoro-1-butene may be fluorinated to form 1-chloro-2-methyl-1,1,2,3,4,4,4-heptafluorobutane.
CF3CFC1C(CH3)FCF2H (HCFC-357mbsp) may be prepared as follows. Commercially available 2,3- dichlorohexafluoro-2-butene may be reacted with commercially available iodomethane to form 2,3- dichloro-3-iodo-2-methyl-1,1,1,4,4,4-hexafluoropropane which may be fluorinated to form 2-methyl-3-chloro- 1,1,1,2,3,4,4-heptafluorobutane. The 2-methyl-3- chloro-1,1,1,2,3,4,4-heptafluorobutane may be dehalogenated to form 3-chloro-2-methyl-1,1,3,4,4,4- hexafluoro-1-butene which may be reacted with commercially available hydrogen fluoride to form 3- chloro-2-methyl-1,1,2,3,4,4,4-heptafluorobutane.
CF3CF2C (CH3) C1CF2H (HCFC- 357mcsp) may be prepared as follows . Commercially available 2 , 3 - dichlorohexafluoro-2-butene may be reacted with iodomethane to form 2-methyl-2,3-dichloro-3-iodo- 1,1,1,4,4,4-hexafluorobutane which may be fluorinated to form 2-methyl-1,1,1,2,3,3,4,4,4-nonafluorobutane. The 2-methyl-1,1,1,2,3,3,4,4,4-nonafluorobutane may be dehalogenated to form 2-methyl-l,1,3,3,4,4,4- heptafluoro-1-butene which may be reacted with commercially available hydrogen chloride to form 2- chloro-2-methyl-1,1,3,3,4,4,4-heptafluorobutane.
CH3CF2C(CF2C1)HCF3 (HCFC-357mlcs) may be prepared as follows. Commercially available 1,3-dichloro-2-butene may be reacted with commercially available trifluoromethyl iodide to form 1,3-dichloro-2- trifluoromethyl-3-iodobutane which may be fluorinated to form 1,3,3-trifluoro-2-trifluoromethylbutane. The l,3,3-trifluoro-2-trifluoromethylbutane may be dehydrogenated to form 1,3,3-trifluoro-2- trifluoromethyl-1-butene which may be fluorinated to form 1,l,2,3,3-pentafluoro-2-trifluoromethylbutane.
The l,l,2,3,3-pentafluoro-2-trifluoromethylbutane may be dehydrohalogenated to form 1,1,3,3-tetrafluoro-2- trifluoromethyl-1-butene which may be reacted with commercially available hydrogen chloride to form 1- chloro-l,1,3,3-tetrafluoro-2-trifluoromethylbutane.
CH3CFC1C(CF3)HCF3 (HCFC-357mmbs) may be prepared as follows. Commercially available 2,3- dichlorohexafluoro-2-butene may be reacted with commercially available trifluoromethyl iodide to form 2,3-dichloro-3-iodo-2-trifluoromethyl-1,1,1,4,4,4- hexafluorobutane which may be fluorinated to form 2- trifluoromethyl-1,1,1,2,3,3,4,4,4-nonafluorobutane. The 2-trifluoromethyl-1,1,1,2,3,3,4,4,4- nonafluorobutane may be dehalogenated to form 3- trifluoromethyl-1,1,2,3,4,4,4-heptafluoro-1-butene which may be hydrogenated to form 2-trifluoromethyl- 1,1,1,2,3,4,4-heptafluorobutane. The 2- trifluoromethyl-1,1,1,2,3,4,4-heptafluorobutane may be dehydrohalogenated to form 3-trifluoromethyl- 1,2,3,4,4,4-hexafluoro-l-butene which may be hydrogenated to form 3-trifluoromethyl-1,2,3,4,4, - hexafluorobutane. The 3-trifluoromethyl-1,2,3, ,4, - hexafluorobutane may be dehydrohalogenated to form 3- trifluoromethyl-2,3,4, ,4-pentafluoro-1-butene which may be reacted with commercially available hydrogen chloride to form 3-chloro-2-trifluoromethyl-1,1,1,2,3- pentafluorobutane. The 3-chloro-2-trifluoromethyl- 1,1,1,2,3-pentafluorobutane may be dehalogenated to form 3-chloro-2-trifluoromethyl-1,1,3-trifluoro-1- butene which may be reacted with commercially available hydrogen fluoride to form 3-chloro-2-trifluoromethyl- 1,1,1,3-tetrafluorobutane.
CF2C1CHFC(CH3)FCF3 (HCFC-357mmel) may be prepared as follows. Commercially available 2,3- dichlorohexafluoro-2-butene may be reacted with commercially available iodomethane to form 2,3- dichloro-3-iodo-1,1,1,4,4,4-hexafluoro-2- ethylbutane which may be fluorinated to form 2- methylperfluorobutane. The 2-methylperfluorobutane may be dehalogenated to form 1,1,2,3,4,4,4-heptafluoro-3- methyl-1-butene which may be reacted with commercially available hydrogen chloride to form 4-chloro- 1,1,1,2,3,4,4-heptafluoro-2-methylbutane. The method of R.N. Haszeldine et al., supra, can be modified to form CH2C1CH2C(CF3)FCF3 (HCFC-357 mmfo) as follows. Commercially available perfluoroisopropyl iodide may be reacted with commercially available ethylene to prepare 2-trifluoromethyl-1,1,1,2- tetrafluoro-4-iodobutane which may then be chlorinated to form 2-trifluoromethyl-1,1,1,2-tetrafluoro-4- chlorobutane.
CFH2CH2C(CF3)C1CF3 (HCFC-357mmfq) may be prepared as follows. Commercially available 2,3- dichlorohexafluoro-2-butene may be reacted with commercially available trifluoromethyl iodide to form 2,3-dichloro-3-iodo-1,1,1,4,4,4-hexafluoro-2- trifluoromethylbutane which may be fluorinated to form 2-chloro-2-trifluoromethyl-perfluorobutane. The 2- chloro-2-trifluoromethyl-perfluorobutane may be dehalogenated to form 3-chloro-3- rifluoromethyl- 1,1,2,4,4,4-hexafluoro-l-butene which may be hydrogenated to form 2-chloro-2-trifluoromethyl- 1,1,1,3,4,4-hexafluorobutane. The 2-chloro-2- trifluoromethyl-1,1,1,3,4,4-hexafluorobutane may be fluorinated to form 3-chloro-3-trifluoromethyl-1,4,4,4- tetrafluoro-1-butene which may then be hydrogenated to form 2-chloro-2-trifluoromethyl-1,1,1,4- tetrafluorobutane.
CF3CFHC(CH3)C1CF3 (HCFC-357msem) may be prepared as follows. Commercially available 2,3- dichlorohexafluoro-2-butene may be reacted with commercially available iodomethane to form 2,3- dichloro-3-iodo-1,1,1,4,4,4-hexafluoro-2-methylbutane which may be chlorinated to form 2,3,3-trichloro- 1,1,1,4,4,4-hexafluoro-2-methylbutane. The 2,3,3- trichloro-1,1,1,4,4,4-hexafluoro-2-methylbutane may be dehalogenated to form 3-chloro-l,l,l,4,4,4-hexafluoro- 2-methyl-2-butene which may be reacted with commercially available hydrogen fluoride to form 3- chloro-1,1,1,3,4,4,4-heptafluoro-2-methylbutane. The 3-chloro-1,1,1,3,4,4,4-heptafluoro-2-methylbutane may be dehydrohalogenated to form l,l,l,4,4,4-hexafluoro-2- ethyl-2-butene which may be reacted with commercially available hydrogen chloride to form 2-chloro- 1,1,1,3,4,4,4-heptafluoro-2-methylbutane.
CF3CF2C(CH3)FCC1FH (HCFC-358mcsr) may be prepared as follows. Commercially available 2,3- dichlorohexafluoro-2-butene may be reacted with commercially available trifluoromethyl iodide to form 2,3-dichloro-3-iodo-1,1,1,4,4,4-hexafluoro-2- methylbutane which may be fluorinated to form 2-methyl- perfluorobutane. The 2-methyl-perfluorobutane may be dehalogenated to form 2-methyl-perfluoro-1-butene which may be reacted with commercially available hydrogen fluoride to form l,l,2,3,3,4,4,4-octafluoro-2- methylbutane. The l,l,2,3r3,4,4,4-octafluoro-2- methylbutane may be dehalogenated to form 1,3,3,4,4,4- hexafluoro-2-methyl-1-butene which may be chlorinated to form l,2-dichloro-l,3,3,4,4,4-hexafluoro-2- methylbutane. The l,2-dichloro-l,3,3,4,4,4-hexafluoro- 2-methylbutane may be dehydrohalogenated to form 1- chloro-l,3,3,4,4,4-hexafluoro-2-methyl-l-butene which may be reacted with commercially available hydrogen fluoride to form l-chloro-l,2,3,3,4,4,4-heptafluoro-2- methylbutane.
CH3CC1HC(CF3)HCF3 (HCFC-366mmds) may be prepared as follows. Commercially available 2,3- dichlorohexafluoro-2-butene may be reacted with trifluoromethyl iodide to form 2,3-dichloro-3-iodo- 1,1,1,4,4,4-hexafluoro-2-trifluoromethylbutane which may be chlorinated to form 3-iodo-l,1,1,4,4,4- hexafluoro-2-methyl-2-butene. The 3-iodo-1,1,1,4,4,4- hexafluoro-2-trifluoromethyl-2-butene may be hydrogenated to form 3-iodo-l,1,1,4,4,4-hexafluoro-2- trifluoromethylbutane which may be dehydrohalogenated to form 2-iodo-1,1,4,4,4-pentafluoro-3-trifluoromethyl- 1-butene. The 2-iodo-l,1,4,4,4-pentafluoro-3- trifluoromethyl-1-butene may be hydrogenated to form 3- iodo-1,1,1,4,4-pentafluoro-2-trifluoromethylbutane which may be chlorinated to form 3-chloro-1,1,1,4,4- pentafluoro-2-trifluoromethylbutane. The 3-chloro- 1,1,1,4,4-pentafluoro-2-trifluoromethylbutane may be dehydrohalogenated to form 2-chloro-1,4,4,4- tetrafluoro-3-trifluoromethyl-1-butene which may be hydrogenated to form 3-chloro-1,1,1,4-tetrafluoro-2- trifluoromethylbutane. The 3-chloro-1,1,1,4- tetrafluoro-2-trifluoromethylbutane may be dehydrohalogenated to form 2-chloro-4,4,4-trifluoro-3- trifluoromethyl-1-butene which may be hydrogenated to form 3-chloro-1,1,1-trifluoro-2-trifluoromethylbutane.
The preferred branched hydrochlorofluorocarbons having 5 carbon atoms are CFH2CH2C(CF2C1)FCF3, CH3C(CF3) (CF2H)CF2C1, CF3CFHC(CH3)FCF2C1,
CF3CFC1C(CH3)FCF2H, CF3CF2C(CH3)C1CF2H, CH3CF2C(CF2C1)HCF3, CH3CFC1C(CF3)HCF3, CF2C1CHFC(CH3)FCF3, CH2C1CH2C(CF3)FCF3, CFH2CH2C(CF3)C1CF3, CF3CFHC(CH3)C1CF3, CF3CF2C(CH3)FCC1FH, and CH3CC1HC(CF3)HCF3.
The present method is advantageous because the solvents have low atmospheric lifetimes. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Known solvents may be blended with the solvents of the present method. Examples of useful known solvents are listed in Table V below.
TABLE V
Number Chemical Formula
HCFC-234CC CF2C1CF2CC1H2
HCFC-234cd CH2FCF2CFC12
HCFC-244ca CF2HCF2CC1H2
HCFC-244cb CFH2CF2CFC1H HCFC-253ca CFH2CF2CC1H2
HCFC-253cb CH3CF2CFC1H
HCFC-234cc may be formed by any known method such as the reaction of 1,1,1,2,2,3-hexachloropropane with antimony pentachloride and hydrogen fluoride at 100°C. HCFC-234cd may be formed by any known method such as the reaction of 1,1,1-trichloro-2,2, 3-trifluoropropane with antimony pentachloride and hydrogen fluoride at 120°C.
HCFC-244ca may be formed by any known method such as the reaction of 1,1,2,2,3-pentachloropropane with antimony pentachloride and hydrogen fluoride at 100°C. HCFC-244cb may be formed by any known method such as the reaction of 1-chloro-1,1,2,2-tetra luoropropane with cesium fluoride and tetrabutylammonium bromide at 150°C.
HCFC-253ca may be formed by any known method such as the reaction of 1,2,3-trichloro-2-fluoropropane with niobium pentachloride and hydrogen fluoride at 100°C. HCFC-253cb may be formed by any known method such as the reaction of 1,1,2,2-tetrachloropropane with tantalum pentafluoride and hydrogen fluoride at 130°C.
The present method removes most contaminants from the surface of a substrate. For example, the present method removes organic contaminants such as mineral oils from the surface of a substrate. Under the term "mineral oils", both petroleum-based and petroleum- derived oils are included. Lubricants such as engine oil, machine oil, and cutting oil are examples of petroleum-derived oils.
The present method also removes water from surface of a substrate. The method may be used in the single- stage or multi-stage drying of objects.
The present method may be used to clean the surface of inorganic substrates and some organic substrates. Examples of inorganic substrates include metallic substrates, ceramic substrates, and glass substrates. Examples of organic substrates include polymeric substrates such as polycarbonate, polystyrene, and acrylonitrile-butadiene-styrene. The method also may be used to clean the surface of natural fabrics such as cotton, silk, fur, suede, leather, linen, and wool. The method also may be used to clean the surface of synthetic fabrics such as polyester, rayon, acrylics, nylon, and blends thereof, and blends of synthetic and natural fabrics. It should also be understood that composites of the foregoing materials may be cleaned by the present method. The present method may be used in vapor degreasing, solvent cleaning, cold cleaning, dewatering, and dry cleaning. In these uses, the object to be cleaned is immersed in one or more stages in the liquid and/or vaporized solvent or is sprayed with the liquid solvent. Elevated temperatures, ultrasonic energy, and/or agitation may be used to intensify the cleaning effect.
COMPARATIVE A
Seven day stability tests were done with commercial grade CFC-113 as follows:
Commercial grade CFC-113 was saturated with water at room temperature. 125 ml of CFC-113 was transferred into a 250 ml Pyrex flask which was connected to a water/glycol cooled condenser.
On top of the condenser, a "Drierite" desiccant was provided to prevent ambient moisture leaking into the solvent. A metal coupon was situated in the middle of the liquid-vapor phase. A total of eight common metal alloys were investigated. They are: Aluminum-2024(hereinafter Al-2024) , Copper(hereinafter Cu) , Cold Rolled steel(hereinafter CRS) , and Galvanized Steel(hereinafter GS) , SS 304, SS 304L, SS 316, and SS 316L.
The solvent then was under total reflux at its boiling temperature for seven days. Observation was made daily on the change of the metal surface including the loss of luster of the metal surface and stain or corrosion on the metal surface, if any and the solvent including coloration of the solvent, increased viscosity of the solvent and most importantly, the rate of change of the viscosity.
The pH values were determined for each solvent before and after the test. The Cl ion concentration in the solvent was determined by ion chromatography.
The pH was about 6 in the presence of Al-2024 and was about 5.9 in the presence of the other metals. The results are in Table VI below. In Table VI, NC means No Change, C means corroded, WD means White Deposit, CL means colorless, and SY means Slightly Yellow.
TABLE VI
Al-2024 £u CRS £S
Cl" 5.7 5.8 4.9 11 (ppm)
Metal NC NC C WD
Solvent CL CL SY CL
The results indicate that in the presence of Al-2024, Cu, CRS, or GS, CFC-113 undergoes hydrolyzes to form HCI.
COMPARATIVE B
Comparative A was repeated except that HCFC-123 was used instead of CFC-113. The pH was about 4.8 in the presence of Al-2024 and was about 3.5 in the presence of the other metals. The results are in Table VII below. In Table VII, S means stained, SC means slightly corroded, C means corroded, VC means very corroded, CL means colorless, and G means gray with suspended particles.
TABLE VII
Al-2024 Cu CRS GS
(ppm)
Metal S SC C VC
Solvent CL CL CL G
The results indicate that in the presence of Al-2024, Cu, CRS, or GS, HCFC-123 undergoes hydrolyzes to form HCI. Compared with CFC-113, HCFC-123 hydrolyzes to a greater extent.
EXAMPLE 1
Comparative A was repeated except that 1-chloro-3,3,3-trifluoropropane was used instead of CFC-113.
The pH was about 6.9 in the presence of Al-2024 and was about 6.9 in the presence of the other metals. The results are in Table VIII below. In Table VIII, NC means No Change, CL means colorless.
TABLE VIII
Figure imgf000033_0001
Metal NC NC NC NC
Solvent CL CL CL CL
The results indicate that in the presence of Al-2024, Cu, CRS, and GS, HCFC-253fb undergoes substantially no hydrolysis and any hydrolysis which HCFC-253fb undergoes is minimal compared with the hydrolysis which CFC-113 or HCFC-123 undergoes under the same conditions. Considering that HCFC-123 and HCFC-253fb differ by only a -CH2 and -Cl, this result is unexpected.
EXAMPLE 2
1-chloro-3,3,3-trifluoropropane was added to mineral oil in a weight ratio of 50:50 at 27°C. The l-chloro-3,3,3-trifluoropropane was completely miscible in the mineral oil. EXAMPLES 3 - 87
Each solvent listed in Tables I through IV is added to mineral oil in a weight ratio of 50:50 at 27°C. Each solvent is miscible in the mineral oil.

Claims

What is claimed is :
1 . A method of cleaning a surface of a substrate which comprises treating said surface with a solvent comprising a solvent selected from the group consisting of CFH2CC12CF3 , CF3CFC1CC1H2, CFH2CFC1CF2C1 , CF2C1CH2CF2C1 , CF3CH2CFC12 , CH3CFC1CF2H , CF2C1CFHCC1H2, CFH2CFC1CF2H , CF2HCC1HCF2H, CF2HCFHCFC1H, CFH2CFHCF2C1 , CFC1HCH2CF3 , CF2HCH2CF2C1 , CH3CC1HCF2C1 , CF2HCFHCC1H2 , CH3CFHCF2C1 , CF2HCH2CFC1H, CC1H2CH2CF3 , CFH2CH2CF2C1 , CF2HCH2CC1H2 ,
CH3CFC1CH3 , CH3CH2CFC1H, CH3CC1HCF2CF2C1 , CH3CHFCC1FCF2C1 , CH3CC1HCFC1CF3 , CFH2CH2CF2CF2C1 , CH3CF2CFHCF2C1 , CF2HCH2CFHCF2C1 , CF3CH2CH2CF2C1 , CFH2CH2CFC1 CF3 , CF3CF2CH2CC1H2, CH3CF2CC1HCF3 , CF2HCH2CC1HCF3 , CH3CFC1CFHCF3 , CFH2CC1HCFHCF3 , CFH2CFC1CH2CF3 ,
CF3CH2CF2CC1H2, CF2HCC1HCH2CF3 , CFC1HCFHCH2CF3, CH3CFC1CF2CF2H, CH3CF2CF2CFC1H, CH3CC1HCFHCF3 , CFC1HCH2CH2CF3 , CH3CH2CFHCF2C1 , CH3CC1HCH2CF3 , CF3CH2CH2CC1H2 , CH3CH2CH2CFC1H, CH3CH2CFC1CH3 , and mixtures thereof .
2. The method of claim 1 wherein said solvent additionally comprises a solvent selected from the group consisting of CF2C1CF2CC1H2, CH2FCF2CFC12, CF2HCF2CC1H2, CFH2CF2CFC1H, CFH2CF2CC1H2, CH3CF2CFC1H, and mixtures thereof.
3. The method of claim 1 wherein said solvent is selected from the group consisting of CH3CFC1CF2H, CF2C1CFHCC1H2, CFH2CFC1CF2H, CFH2CFHCF2C1, CFC1HCH2CF3, CF2HCH2CF2C1, CH3CFHCF2C1, CF3CH2CC1H2, CC1H2CH2CF3 and mixtures thereof.
4. The method of claim 1 wherein said method removes organic contaminants from said surface.
5. The method of claim 1 wherein said method cleans the surface of an organic substrate.
6. The method of claim l wherein said solvent is CC1H2CH2CF3.
7. The method of claim 1 wherein said solvent is selected from the group consisting of CH3CF2CFHCF2C1 , CF3CH2CH2CF2C1, CFH2CH2CFC1CF3 , CH3CF2CC1HCF3 , CH3CFC1CFHCF3, CH3CFC1CF2CF2H, CH3CF2CF2CFC1H, CH3CC1HCFHCF3 , and mixtures thereof .
8. A method of cleaning a surface of a substrate which comprises treating said surface with a solvent comprising a solvent selected from the group consisting Of CH3C(CF3)FCFC12, CH3C ( CF2C1 ) FCF2C1 , CH3C ( CF3 ) HCF2C1 , CF2HC ( CC1H2) HCF3 , CH3C ( CF2H) C1CF3 , CH3C ( CFC1H) FCF3 , CH3C(CH3)C1CF3, CFH2CH2C(CF2C1)FCF3, CF2C1CF2C (CH3) FCF2H, CH3C(CF3) (CF2H)CF2C1, CF3CFHC (CH3) FCF2C1, CF3CFC1C(CH3)FCF2H, CF3CF2C (CF2H) HCC1H2, CF3CF2C (CH3) C1CF2H, CF3CF2C (CH3) FCFC1H, CH3CF2C (CF2C1) HCF3, CH3CFC1C (CF3) HCF3, CF2C1CHFC (CH3) FCF3, CH2C1CH2C (CF3) FCF3, CFH2CH2C (CF3) C1CF3, CFC1HCH2C(CF3)HCF3, CF3CH2C(CC1H2) FCF3, CF3CFHC(CH3) C1CF3, CF3CF2C ( CH3 ) FCC1FH , CH3CC1HC ( CF3 ) HCF3 , CC1H2CH2C ( CF3 ) HCF3 , CF2C1CF2C(CH3)FCH3, CF3CFC1C (CH3) FCH3, CF2C1CFHC (CH3)HCH3, CF3CC1HC (CH3) HCH3, CH3CH2C (CF3) C1CH3, CFC1HCH2C(CH3)HCH3, and mixtures thereof.
9. The method of claim 8 wherein said solvent is selected from the group consisting of CH3C(CF3)HCF2C1,
CH3C(CF2H)C1CF3, CH3C (CFC1H) FCF3, and mixtures thereof.
10. The method of claim 8 wherein said solvent is selected from the group consisting of CFH2CH2C ( CF2C1 ) FCF3 , CH3C ( CF3 ) ( CF2H) CF2C1 , CF3CFHC (CH3) FCF2C1 , CF3CFC1C (CH3) FCF2H, CF3CF2C (CH3) C1CF2H, CH3CF2C(CF2C1)HCF3, CH3CFC1C (CF3) HCF3, CF2C1CHFC (CH3) FCF3, CH2C1CH2C(CF3)FCF3, CFHjC^C (CF3) C1CF3, CF3CFHC (CH3) C1CF3, CF3CF2C(CH3)FCC1FH, and CH3CC1HC(CF3)HCF3.
PCT/US1992/002154 1991-03-18 1992-03-18 A method of cleaning using hydrochlorofluorocarbons having 3 to 5 carbon atoms WO1992016674A2 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US671,272 1991-03-18
US07/671,272 US5152845A (en) 1991-03-18 1991-03-18 Method of cleaning using 1-chloro-3,3,3-trifluoropropane
US687,342 1991-04-18
US07/687,342 US5158617A (en) 1991-04-18 1991-04-18 Method of cleaning using hydrochlorofluorocarbons having 3 to 5 carbon atoms

Publications (2)

Publication Number Publication Date
WO1992016674A2 true WO1992016674A2 (en) 1992-10-01
WO1992016674A3 WO1992016674A3 (en) 1993-03-18

Family

ID=27100511

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1992/002154 WO1992016674A2 (en) 1991-03-18 1992-03-18 A method of cleaning using hydrochlorofluorocarbons having 3 to 5 carbon atoms

Country Status (2)

Country Link
AU (1) AU1786892A (en)
WO (1) WO1992016674A2 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013062733A1 (en) * 2011-10-24 2013-05-02 E. I. Du Pont De Nemours And Company Catalytic processes for making hydromonochlorofluorobutane and hydromonochlorofluoropentane compounds

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0374780A1 (en) * 1988-12-20 1990-06-27 Daikin Industries, Limited Solvents containing dichlorotetrafluoropropane
EP0381216A1 (en) * 1989-02-01 1990-08-08 Asahi Glass Company Ltd. Hydrochlorofluorocarbon azeotropic or azeotropic-like mixture
JPH02207031A (en) * 1989-02-06 1990-08-16 Asahi Glass Co Ltd Azeotropic composition and pseudo-azeotropic composition of dichloropentafluoropropane
JPH02221386A (en) * 1989-02-23 1990-09-04 Asahi Glass Co Ltd Chlorofluorohydrocarbon-based degreasing detergent
EP0394992A2 (en) * 1989-04-27 1990-10-31 Daikin Industries, Limited Solvent composition
JPH03123743A (en) * 1989-10-06 1991-05-27 Asahi Glass Co Ltd 1,3-dichloro-1,1,2,2,3-pentafluoropropane composition
US5034149A (en) * 1990-03-21 1991-07-23 E. I. Du Pont De Nemours And Company Binary azeotropic compositions of 3-chloro-1,1,1-trifluoropropane with methanol or ethanol, or trans-1,2-dichloroethylene

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0374780A1 (en) * 1988-12-20 1990-06-27 Daikin Industries, Limited Solvents containing dichlorotetrafluoropropane
EP0381216A1 (en) * 1989-02-01 1990-08-08 Asahi Glass Company Ltd. Hydrochlorofluorocarbon azeotropic or azeotropic-like mixture
JPH02207031A (en) * 1989-02-06 1990-08-16 Asahi Glass Co Ltd Azeotropic composition and pseudo-azeotropic composition of dichloropentafluoropropane
JPH02221386A (en) * 1989-02-23 1990-09-04 Asahi Glass Co Ltd Chlorofluorohydrocarbon-based degreasing detergent
EP0394992A2 (en) * 1989-04-27 1990-10-31 Daikin Industries, Limited Solvent composition
JPH03123743A (en) * 1989-10-06 1991-05-27 Asahi Glass Co Ltd 1,3-dichloro-1,1,2,2,3-pentafluoropropane composition
US5034149A (en) * 1990-03-21 1991-07-23 E. I. Du Pont De Nemours And Company Binary azeotropic compositions of 3-chloro-1,1,1-trifluoropropane with methanol or ethanol, or trans-1,2-dichloroethylene

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Chemical Abstracts, vol. 114, no. 10, 11 March 1991, (Columbus, Ohio, US) see page 140, abstract 84384m, & JP, A, 02221386 (ASAHI GLASS CO., LTD) 4 September 1990 *
Chemical Abstracts, vol. 114, no. 4, 28 January 1991, (Columbus, Ohio, US) see page 120, abstract 26249k, & JP, A, 2207031 (ASAHI GLASS CO., LTD) 16 August 1990 *
Database WPIL, no. 91-198060, Derwent Publications Ltd. (London, GB) & JP, A, 3123743 (ASAHI GLASS K.K.) 27 May 1991, see abstract *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013062733A1 (en) * 2011-10-24 2013-05-02 E. I. Du Pont De Nemours And Company Catalytic processes for making hydromonochlorofluorobutane and hydromonochlorofluoropentane compounds
CN103917507A (en) * 2011-10-24 2014-07-09 纳幕尔杜邦公司 Catalytic processes for making hydromonochlorofluorobutane and hydromonochlorofluoropentane compounds
US9212109B2 (en) 2011-10-24 2015-12-15 The Chemours Company Fc, Llc Catalytic processes for making hydromonochlorofluorobutane and hydromonochlorofluoropentane compounds

Also Published As

Publication number Publication date
WO1992016674A3 (en) 1993-03-18
AU1786892A (en) 1992-10-21

Similar Documents

Publication Publication Date Title
US5705716A (en) Hydrochlorofluorocarbons having OH rate constants which do not contribute substantially to ozone depletion and global warming
US5059728A (en) Partially fluorinated alkanes having a tertiary structure
US4947881A (en) Method of cleaning using hydrochlorofluorocarbons
US5273592A (en) Method of cleaning using partially fluorinated ethers having a tertiary structure
US5091104A (en) Azeotrope-like compositions of tertiary butyl 2,2,2-trifluoroethyl ether and perfluoromethylcyclohexane
CN108026490B (en) Solvent composition, cleaning method, and method for forming coating film
US5288422A (en) Azeotrope-like compositions of 1,1,1,3,3,5,5,5-octafluoropentane, chlorinated ethylenes, and optionally nitromethane
US5158617A (en) Method of cleaning using hydrochlorofluorocarbons having 3 to 5 carbon atoms
EP0638131B1 (en) Azeotrope-like compositions of 1,1,2,3,3-pentafluoropropane
US5152845A (en) Method of cleaning using 1-chloro-3,3,3-trifluoropropane
US5254755A (en) Partially fluorinated alkanols having a tertiary structure
US5146015A (en) Hydrochlorofluorocarbons having a tertiary structure and OH rate constants which do not contribute substantially to ozone depletion and global warming
US5219488A (en) Azeotrope-like compositions of 2-trifluoromethyl-1,1,1,2-tetrafluorobutane and ethanol or isopropanol
US5264044A (en) Method of cleaning using hydrochlorofluorocarbons having a tertiary structure
US5087777A (en) Partially fluorinated alkenes having a tertiary structure
WO1992016674A2 (en) A method of cleaning using hydrochlorofluorocarbons having 3 to 5 carbon atoms
EP0994929B1 (en) Azeotrope and azeotrope-like compositions of 1-bromopropane and highly fluorinated hydrocarbons
US5259983A (en) Azeotrope-like compositions of 1-H-perfluorohexane and trifluoroethanol or n-propanol
US5118360A (en) Method of cleaning using partially fluorinated alkenes having a tertiary structure as solvent
US5219489A (en) Azeotrope-like compositions of 2-trifluoromethyl-1,1,1,2-tetrafluorobutane and methanol
US5124503A (en) Dichlorotrifluoroethane stabilized to minimize hydrolysis thereof
WO1992010454A1 (en) Partially fluorinated alkanols having a tertiary structure
US5352375A (en) Azeotrope-like compositions of 1,1,1,2,2,3,3,-heptafluoropentane, C1 -C3 alkanol and optionally nitromethane
EP0599984A1 (en) Azeotrope-like compositions of 2-trifluoromethyl-1,1,1,2-tetrafluorobutane and methanol, ethanol or isopropanol
IE902513A1 (en) Azeotrope-like compositions of 1,1-dichloro-1-fluoroethane,¹dichlorotrifluoroethane, and nitromethane

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A2

Designated state(s): AU BB BG BR CA CS FI HU JP KP KR LK MG MN MW NO PL RO RU SD

AL Designated countries for regional patents

Kind code of ref document: A2

Designated state(s): AT BE BF BJ CF CG CH CI CM DE DK ES FR GA GB GN GR IT LU MC ML MR NL SE SN TD TG

AK Designated states

Kind code of ref document: A3

Designated state(s): AU BB BG BR CA CS FI HU JP KP KR LK MG MN MW NO PL RO RU SD

AL Designated countries for regional patents

Kind code of ref document: A3

Designated state(s): AT BE BF BJ CF CG CH CI CM DE DK ES FR GA GB GN GR IT LU MC ML MR NL SE SN TD TG

NENP Non-entry into the national phase in:

Ref country code: CA

122 Ep: pct application non-entry in european phase