US3423299A - Electrochemical fluorination of polymethylene sulfones to produce perfluoroalkylsulfonyl fluorides - Google Patents

Electrochemical fluorination of polymethylene sulfones to produce perfluoroalkylsulfonyl fluorides Download PDF

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Publication number
US3423299A
US3423299A US509210A US3423299DA US3423299A US 3423299 A US3423299 A US 3423299A US 509210 A US509210 A US 509210A US 3423299D A US3423299D A US 3423299DA US 3423299 A US3423299 A US 3423299A
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United States
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produce
cell
electrochemical fluorination
perfluoroalkylsulfonyl
sulfone
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US509210A
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Lorne A Loree
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Dow Silicones Corp
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Dow Corning Corp
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/27—Halogenation
    • C25B3/28—Fluorination

Definitions

  • U.S. Patent 2,519,983, issued to Simons discloses the electrochemical fluorination of organic materials with anhydrous hydrofluoric acid.
  • US. Patent 2,732,398, issued to Brice and Trott discloses the use of the process of Simons to convert hydrocarbon sulfonyl halides into perfluoroalkylsulfonyl fluorides.
  • compositions which are made by the reaction of the appropriate alpha-omega-diolefin (e.g. butadiene) with S0
  • alpha-omega-diolefin e.g. butadiene
  • S0 alpha-omega-diolefin
  • the major advantage of the process of this invention is its relatively high yield of product, which renders it commercially desirable.
  • the process is also unique in that the electrochemical fluorination process has never before been found to cause ring cleavage at a carbonsulfur linkage to form a perfluoroalkylsulfonyl fluoride.
  • the conductivity of the alkylene sulfone-hydrogen fluoride solution is usually adequate to permit electrolysis at a sufliciently low voltage to prevent the evolution of elemental fluorine, which begins to form when about 10 to 12 volts are applied to a cell anode.
  • conductivity additives such as sodium or potassium fluoride can be added, if desired.
  • voltages of from 4 to 8 volts generally give the best results.
  • the cathodes and anodes can be made of any conductive material which is not corroded by anhydrous HF, e.g., nickel, Monel, carbon, silicon carbide, etc.
  • the cell was cooled to l0 C., and anhydrous HF vapor was added until about 3500 ml. of liquid HF were present in the cell.
  • To this was added 1242.5 g. of tetramethylene sulfone, and the cell was operated for 5 days at about 0 C. with a direct current of about amperes and 5.5 volts.
  • EXAMPLE 2 When an electrochemical cell, fitted with a graphite anode and cathode and the same condenser as in Example l is filled with 1 kg. of octamethylene sulfone and 2 kg. of liquid HF, electrolysis for several days at 10 C. at a voltage of 7 volts produces a liberal yield of nperfluorooctylsulfonyl fluoride.
  • Electrolysis was initiated at 10 C., and an average current of 85 amperes and 5.5 volts was maintained for 48 hours with an average temperature of C. At the end of the period, the current began to decrease. When it had fallen to 15 amperes, the electrolysis was discontinued, and 532.4 g. of a water-white crude cell product was drained from the bottom of the cell.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US509210A 1965-11-22 1965-11-22 Electrochemical fluorination of polymethylene sulfones to produce perfluoroalkylsulfonyl fluorides Expired - Lifetime US3423299A (en)

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US50921065A 1965-11-22 1965-11-22

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US3423299A true US3423299A (en) 1969-01-21

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US509210A Expired - Lifetime US3423299A (en) 1965-11-22 1965-11-22 Electrochemical fluorination of polymethylene sulfones to produce perfluoroalkylsulfonyl fluorides

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US (1) US3423299A (enrdf_load_stackoverflow)
AT (1) AT264483B (enrdf_load_stackoverflow)
DE (1) DE1264440B (enrdf_load_stackoverflow)
FR (1) FR1501396A (enrdf_load_stackoverflow)
GB (1) GB1099240A (enrdf_load_stackoverflow)
NL (2) NL6616346A (enrdf_load_stackoverflow)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3623963A (en) * 1969-03-13 1971-11-30 Bayer Ag Process for the manufacture of perfluoralkylsulphonyl fluorides
US3951762A (en) * 1972-01-14 1976-04-20 Bayer Aktiengesellschaft Preparation of perfluorinated organic sulfonyl fluorides
US4425199A (en) 1981-04-02 1984-01-10 Asahi Kasei Kogyo Kabushiki Kaisha Process for the preparation of (ω-fluorosulfonyl)-haloaliphatic carboxylic acid fluorides
US5286352A (en) * 1990-02-28 1994-02-15 Minnesota Mining And Manufacturing Company Electrochemical production of higher pentafluorosulfonyl acid fluorides
US5541235A (en) * 1995-03-06 1996-07-30 Minnesota Mining And Manufacturing Company Organic soluble cationic dyes with fluorinated alkylsulfonyl counterions
US5554664A (en) * 1995-03-06 1996-09-10 Minnesota Mining And Manufacturing Company Energy-activatable salts with fluorocarbon anions
US5874616A (en) * 1995-03-06 1999-02-23 Minnesota Mining And Manufacturing Company Preparation of bis (fluoroalkylenesulfonyl) imides and (fluoroalkysulfony) (fluorosulfonyl) imides

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3043427A1 (de) 1980-11-18 1982-07-08 Bayer Ag, 5090 Leverkusen Perfluorierte sulfonsaeurefluoride sowie verfahren zu deren herstellung
US5011983A (en) * 1987-01-23 1991-04-30 Minnesota Mining And Manufacturing Company Preparation and reactions of omega-halosulfonyl perfluoroalkanesulfonates

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2519983A (en) * 1948-11-29 1950-08-22 Minnesota Mining & Mfg Electrochemical process of making fluorine-containing carbon compounds
US2732398A (en) * 1953-01-29 1956-01-24 cafiicfzsojk

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2519983A (en) * 1948-11-29 1950-08-22 Minnesota Mining & Mfg Electrochemical process of making fluorine-containing carbon compounds
US2732398A (en) * 1953-01-29 1956-01-24 cafiicfzsojk

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3623963A (en) * 1969-03-13 1971-11-30 Bayer Ag Process for the manufacture of perfluoralkylsulphonyl fluorides
US3951762A (en) * 1972-01-14 1976-04-20 Bayer Aktiengesellschaft Preparation of perfluorinated organic sulfonyl fluorides
US4425199A (en) 1981-04-02 1984-01-10 Asahi Kasei Kogyo Kabushiki Kaisha Process for the preparation of (ω-fluorosulfonyl)-haloaliphatic carboxylic acid fluorides
US5286352A (en) * 1990-02-28 1994-02-15 Minnesota Mining And Manufacturing Company Electrochemical production of higher pentafluorosulfonyl acid fluorides
US5541235A (en) * 1995-03-06 1996-07-30 Minnesota Mining And Manufacturing Company Organic soluble cationic dyes with fluorinated alkylsulfonyl counterions
US5554664A (en) * 1995-03-06 1996-09-10 Minnesota Mining And Manufacturing Company Energy-activatable salts with fluorocarbon anions
US5874616A (en) * 1995-03-06 1999-02-23 Minnesota Mining And Manufacturing Company Preparation of bis (fluoroalkylenesulfonyl) imides and (fluoroalkysulfony) (fluorosulfonyl) imides

Also Published As

Publication number Publication date
NL6616346A (enrdf_load_stackoverflow) 1967-05-23
GB1099240A (en) 1968-01-17
FR1501396A (fr) 1967-11-10
DE1264440B (de) 1968-03-28
AT264483B (de) 1968-09-10
NL127400C (enrdf_load_stackoverflow)

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