Preparation of bis (fluoroalkylenesulfonyl) imides and (fluoroalkysulfony) (fluorosulfonyl) imides

• US 5,874,616 A
• Filed: 12/22/1995
• Issued: 02/23/1999
• Est. Priority Date: 03/06/1995
• Status: Expired due to Term

• Current Assignee: Minnesota Mining and Manufacturing Co (3M Company)
• Original Assignee: Minnesota Mining and Manufacturing Co (3M Company)
• Inventors: Waddell, Jennifer, Howells, Richard D., Lamanna, William M., Fanta, Alan D.
• Primary Examiner(s): O SULLIVAN, PETER G
• Application Number:
  US08/577,425
• Time in Patent Office: 1,159 Days
• Field of Search: 562/822, 564/82, 564/83
• US Class Current: 564/82
• CPC Class Codes: C07C 303/38 by reaction of ammonia or amines with sulfonic acids, or with esters, anhydrides, or halides thereof
• CPC Class Codes: C07C 311/48 having nitrogen atoms of sulfonamide groups further bound to another hetero atom
• CPC Class Codes: H01M 6/04 Cells with aqueous electrolyte
• CPC Class Codes: H01M 6/166 by the solute

Abstract

A method for preparing fluoroalkylsulfonyl imides by reacting a fluoroalkylsulfonamide with a fluoroalkylsulfonyl halide or a fluorosulfonyl halide in the presence of a non-nucleophilic base. One reaction is:

Z--R.sub.f --SO.sub.2 NH.sub.2 +Z--R'"'"'.sub.f --SO.sub.2 --X+2B(Z--R.sub.f

--SO₂)(Z--R'"'"'_f --SO₂)N^-.BH⁺ +BHX,

where each Z is a fluorine atom or a polymerizable organic functional group, R_f and R'"'"'_f are fluoroalkylene groups optionally containing catenary oxygen or nitrogen, X is a halogen atom, and B is a non-nucleophilic base.

Unsymmetrical imides and polymeric imides can be prepared.

Claims

1. A process for the preparation of a bis(fluoroalkylsulfonyl)imide salt comprising the step of reacting at least two equivalents of a fluoroalkylsulfonyl halide (wherein the fluoroalkyl is substantially fluorinated) with one equivalent of ammonia and at least three equivalents of a non-nucleophilic base at a temperature and for a time sufficient to yield the imide salt, provided that if the fluoroalkylsulfonyl halide is a perfluoroalkylsulfonyl halide, the alkyl group has at least 2 carbon atoms.

2. The process of claim 1 where the ammonia is generated in situ by the reaction of an ammonium salt with a non-nucleophilic base.

3. The process of claim 1 characterized by the reaction scheme

4. The process of claim 3 further comprising contacting the bis(fluoroalkylsulfonyl)imide salt with an inorganic base having an alkali metal cation M⁺, volatilizing the non-nucleophilic base B, and isolating the resulting bis(fluoroalkylsulfonyl)imide salt of the formula (Z--R_f SO₂)₂ N^-.M⁺ by filtration, evaporating volatile components from the residue, followed by solvent extraction of the filtrate and removal of the solvent.

5. A process for preparing a bis(fluoroalkylsulfonyl)imide which comprises contacting a sulfonamidofluoroalkylenesulfonyl halide of the formula X--SO₂ --R_f --SO₂ NH₂ with a non-nucleophilic base at a temperature and for a time sufficient to produce a polymeric fluoroalkylsulfonimide having the repeat unit .paren open-st.SO₂ --R_f --SO₂ N^- .paren close-st._n, wherein n is an integer greater than 1 and X is a halogen atom.

6. A process for preparing a polymeric fluoroalkylsulfonimide comprising a reaction step characterized by the reaction scheme:

space="preserve" listing-type="equation">H.sub.2 NSO.sub.2 --R.sub.f --SO.sub.2 NH.sub.2 +X--SO.sub.2 --R'"'"'.sub.f --SO.sub.2 --X+4B.paren open-st.SO.sub.2 --R.sub.f --SO.sub.2 N.sup.- --SO.sub.2 --R'"'"'.sub.f N.sup.-).sub.n 2BH.sup.+ +2B.HX,

wherein n is an integer greater than 1 and X is a halogen atom.

7. A process for preparing a polymeric fluoroalkylsulfonimide comprising a reaction step characterized by the reaction scheme:

space="preserve" listing-type="equation">X--SO.sub.2 --R.sub.f --SO.sub.2 --X+NH.sub.3 +3B.paren open-st.SO.sub.2 --R.sub.f --SO.sub.2 --N.sup.- .paren close-st..sub.n +2B.HX,

wherein n is an integer greater than 1, R_f is a fluoroalkylene group, B is a non-nucleophilic base and X is a halogen atom.

8. The process of claim 7 wherein the ammonia is generated in-situ by the reaction of an ammonium salt with a non-nucleophilic base.