Bis(perfluorosulfonyl)methane salts, and a process for preparing same

• US 5,446,134 A
• Filed: 07/08/1993
• Issued: 08/29/1995
• Est. Priority Date: 11/08/1991
• Status: Expired due to Fees

• Current Assignee: Centre National De La Recherche Scientifique, Hydro-Quebec (Province of Québec)
• Original Assignee: Centre National De La Recherche Scientifique, Hydro-Quebec (Province of Québec)
• Inventors: Armand, Michel, Sanchez, Jean-Yves, Benrabah, Djamila
• Primary Examiner(s): Higel, Floyd D.
• Application Number:
  US08/084,217
• Time in Patent Office: 782 Days
• Field of Search: 534/558, 534/565, 534/728, 534/886, 568/28, 568/31, 568/35, 568/36, 558/438, 558/397, 546/340, 546/346, 549/394, 549/406, 564/440, 548/262.4
• US Class Current: 534/558
• CPC Class Codes: C07C 317/04 of an acyclic saturated carbon skeleton
• CPC Class Codes: C07C 317/18 with sulfone or sulfoxide groups bound to acyclic carbon atoms of the carbon skeleton
• CPC Class Codes: C07C 317/24 having sulfone or sulfoxide groups and doubly-bound oxygen atoms bound to the same carbon skeleton
• CPC Class Codes: C07C 317/28 with sulfone or sulfoxide groups bound to acyclic carbon atoms of the carbon skeleton
• CPC Class Codes: C07C 317/44 having sulfone or sulfoxide groups and carboxyl groups bound to the same carbon skeleton
• CPC Class Codes: C07C 317/48 the carbon skeleton being further substituted by singly-bound nitrogen atoms, not being part of nitro or nitroso groups
• CPC Class Codes: C07C 323/65 containing sulfur atoms of sulfone or sulfoxide groups bound to the carbon skeleton
• CPC Class Codes: C07D 207/335 Radicals substituted by nitrogen atoms not forming part of a nitro radical
• CPC Class Codes: C07D 311/72 3,4-Dihydro derivatives having in position 2 at least one methyl radical and in position 6 one oxygen atom, e.g. tocopherols
• CPC Class Codes: C07D 311/82 Xanthenes
• CPC Class Codes: C07F 17/02 of metals of Groups 8, 9 or 10 of the Periodic Table
• CPC Class Codes: C07F 9/4407 Amides of acyclic saturated acids which can have further substituents on alkyl
• CPC Class Codes: C09B 11/24 Phthaleins containing amino groups ; Phthalanes; Fluoranes; Phthalides; Rhodamine dyes; Phthaleins having heterocyclic aryl rings; Lactone or lactame forms of triarylmethane dyes
• CPC Class Codes: C09B 69/045 of anionic azo dyes
• CPC Class Codes: C09K 9/02 Organic tenebrescent materials
• CPC Class Codes: G02F 1/1525 characterised by a particular ion transporting layer, e.g. electrolyte
• CPC Class Codes: H01B 1/122 Ionic conductors
• CPC Class Codes: H01M 10/052 Li-accumulators
• CPC Class Codes: H01M 10/0565 Polymeric materials, e.g. gel-type or solid-type
• CPC Class Codes: H01M 4/60 of organic compounds
• CPC Class Codes: H01M 6/166 : by the solute
• CPC Class Codes: H01M 6/181 : with polymeric electrolytes
• CPC Class Codes: H01M 8/0289 : Means for holding the electrolyte solid polymer electrolytes H01M8/1018
• CPC Class Codes: H01M 8/10 : Fuel cells with solid electrolytes
• CPC Class Codes: Y02E 60/10 : Energy storage using batteries
• CPC Class Codes: Y02E 60/50 : Fuel cells
• CPC Class Codes: Y02P 70/50 : Manufacturing or production processes characterised by the final manufactured product

Abstract

Bis(perfluorosulphonyl)methanes, process for preparing same and uses thereof. The compounds of the invention are based on the formula (1/nM) [(R_F SO₂)₂ CY]^- in which Y denotes an electron-attracting group chosen from --C═N and RZ groupings in which Z denotes a carbonyl grouping, sulphonyl grouping or a phosphonyl grouping and R denotes an organic monovalent grouping, M denotes a metal having valency n or an organic group capable of existing in the cationic form, R_F denotes a perfluoroalkyl or perfluoroaryl grouping. Said compounds are especially useful in the production of electrochemical devices.

Claims

1. A process for the preparation of a compound of the formula

2. The process of claim 1, wherein said pseudohalide is selected from the group consisting of RSO₃^-, RCO2^-, succinimidyloxy, phthalimidoxy, 1-benzotriazoloxy, oxynorbornene-2,3-dicarboximide, trifuloroethoxy, trichloroethoxy, imidazolyl, triazolyl, nitrophenoxy, dinitrophenoxy, perhalophenoxy and O-acylurea.

3. The process of claim 1, wherein said aprotic nucleophilic base is selected from the group consisting of trialkylamines, pyridines, imidazoles, amidines, guanidines and mixtures thereof.

4. The process of claim 1, wherein said aprotic nucleophilic base is selected from the group consisting of triethylamine, diisopropylethylamine, quinuclidine, 1,4-diazabicyclo[2.2.2[octane, pyridine, alkylpyridine, dialkylaminopyridine, N-alkylimidazole, imidazo[1,2-a]pyridine;

1,5-diazabicyclo[4.3.0]non-5-ene, 1,8-diazabicyclo[5.4.0]undec-7-ene, tetramethylquanidine, 1,3,4,7,8-hexahydro-1-methyl-2H-pyrimido[1,2-a]pyrimidine and mixtures thereof.

5. The process of claim 1, wherein said nucleophilic base is immobilized.

6. The process of claim 1, wherein said compound XY is a halide prepared in situ from an acid compound RZOH or a compound RZOM where M is a metal or an organic radical by reacting with a halogenating agent selected from the group consisting of SOCl₂, SOBr₂, SF₄, (C₂ H₅)₂ NSF₃, COCl₂ (COCl)₂, (COBr)₂, (CCl₃ O)₂ CO, [(CH₃)₂ N═

CHCl] Cl, triphenylphosphine/CCl₄ mixture, dichloromethyl methyl ether and mixtures thereof.

7. The process of claim 1 or 2, wherein when Y is RZ and Z is a carbonyl, then RZX is an anhydride RCO--O--COR.

8. The process of claim 7, wherein said anhydride RCO--O--COR is obtained in situ by reacting an acid RCOOH with a molecular dehydrating agent selected from the group consisting of carbodiimides, alkyl ethynyl ethers, succinimidyl carbonates, succinimidyl oxalates, (SCO)₂ C₂ O₂), phthalimidyl carbonates, phthalimidyl oxalates, 1-benzotriazoyl carbonates, 1-benzotriazolyl oxalates, phthalimidyl carbonates, phthalimidyl oxalates, 1-benzotriazolyl carbonates, 1-benzotriazolyl oxalates, nitrophenyl oxylate, dinitrophenyl oxylate, perhalophenyl oxalate, nitrophenyl carbonate, dinitrophenyl carbonate, perhalophenyl oxylate, trifluoroethyl carbonate, trifluoroethyl oxalate, trichloroethyl carbonate, trichloroethyl oxalate, Pφ

₃ /diethylazodicarboxylate, Pφ

₃ /dithiodipyridine, carbonyldiimidazole, phenylphosphorodiimidazole, amide acetals, 2-alkoxy-1-alkoxycarbonyl-1,2-dihydroquinoline, O-benzotriazol-1-yl-N,N,N'"'"',N'"'"'-tetramethyluronium or O-benzotriazol-1-yl-N,N,N'"'"',N'"'"'-tetramethyluronium or O-benzotriazol-1-yloxytrisdimethylaminophosphonium salts, aromatic sultones, isobutyl chloroformate, diphenylphosphorchloroiridate, ethylene chlorophosphite, diethylethlene pyrophosphite, bis(2-oxo-3-oxazolidinyl)phosphinyl chloride and mixtures thereof.

9. The process of claim 1, wherein said salt of the cation M is selected from the group consisting of carbonate, phosphate, chloride and hydroxide of the cation M.

10. A compound of the formula

11. A compound of the formula

12. A compound of the formula

13. The compound of any one of claims 10 to 12, wherein R_F is C_1-20 perfluoroalkyl or C_6-20 perfluoroaryl.

14. The compound of any one of claims 10 to 12, wherein R is selected from the group consisting of C_1-30 alkyl, C_1-8 perhaloalkyl, C_6-12 aryl, C_6-12 perhaloaryl, arylalkyl, oxaalkyl, azaalkyl and thioalkyl.

15. The compound of any one of claims 10 to 12, wherein R contains contains an element selected from the group consisting of --C═

C--, --C═

C--C═

O, --C═

SO₂, --C═

Cφ

, --OH, --NH₂, --COOH, --N═

C═

O, --O--O--, --N═

N, N₂ ═

CH--, --SO₂ N₃ and --S--S--.

16. The compound of any one of claims 10 to 12, wherein R is mesomorphic or chromophoric.

17. The compound of any one of claims 10 to 12, wherein R contains an element selected from the group consisting of a hindered phenol, a quinone an amide, a nitrile, a disulfide, a thioamide, a ferrocene, a phenothiazine, a bis(dialkylaminoaryl) group, a nitroxide or an aromatic imide.

18. The compound of any one of claims 10 to 12, wherein RZ is a polypeptide or amino acid.

19. An ion conductive material comprising at least one salt, wherein said salt is a compound according to any one of claims 10 to 12.

20. The process of claim 1, wherein the solubility of a compound M'"'"'_1/n X formed in the reaction medium is lower than that of a compound (NuH) [(R_F SO₂)₂ CY]^-, wherein said process comprises

i) reacting a compound

21. An ion conductive material comprising at least one salt, wherein said salt is a compound according to any one of claims 10 to 12;

and

a solvent for said salt.

22. The ion conductive material of claim 21 wherein said solvent is selected from the group consisting of ethylene oxide copolymer, dialkyl ether of poly(ethylene glycol), acrylonitrile-butadiene, poly(ethylene oxide), polyethylene glycol-co oxymethylene, ethylene oxide-methylglycidyl ether copolymer and mixtures thereof.