Method for synthesizing quaternary ammonium systems

• US 8,426,593 B2
• Filed: 08/28/2006
• Issued: 04/23/2013
• Est. Priority Date: 08/30/2005
• Status: Expired due to Fees

• Current Assignee: Colleen Szuch, Honeywell International Inc.
• Original Assignee: Honeywell International Inc.
• Inventors: Siggel, Alfred, Nerenz, Frank, Palanisamy, Thirumalai, Poss, Andrew, Demel, Sonja
• Primary Examiner(s): MCDOWELL, BRIAN E
• Application Number:
  US11/511,938
• Publication Number:
  US 20070049750A1
• Time in Patent Office: 2,430 Days
• Field of Search: 546/15
• US Class Current: 546/15
• CPC Class Codes: C07D 471/10 Spiro-condensed systems
• CPC Class Codes: C07D 487/10 Spiro-condensed systems
• CPC Class Codes: H01G 9/035 Liquid electrolytes, e.g. impregnating materials H01G11/54 takes precedence

Abstract

A method for preparing a spiro quaternary ammonium system and electrolytes containing spiro quaternary ammonium cations, comprising a synthesizing step wherein a spiro ammonium system having a structure of:

wherein n is independently an integer from about 0 to about 6;

• • R₁ is independently CH₂, CHF, CF₂, CH, CF;
  • R₂ is CH₂, CF, CR₃, CHF, CF₂, CHR₃, CR₃R₃, NH, O, S, 3-8 member cyclic or heterocyclic, or a polycyclic or polyheterocyclic wherein each ring has 3 to 8 members;
  • R₃ is independently
    • (a) H;
    • (b) a C₁-C₆ alkyl, C₁-C₆ alkoxy, or C₁-C₆ alkenyl group; or
    • (c) heteroalkyl groups with a chain length of about 1 to about 6;
  • R₄ is CF, CH₂, CR₃, CHF, CF₂, CHR₃, CR₃R₃, NH, O, S, or a quaternary ammonium spiro junction
  • is formed in a medium that can serve as both the reaction solvent and as an electrolyte solvent.

Claims

1. A one-solution method of making a non-aqueous electrolyte composition that comprises at least one of a spiro quaternary ammonium tetrafluoroborate compound or a spiro quaternary ammonium bis(trifluoromethylsulfonyl)imide compound and an electrolyte solvent, the method comprising:

reacting in the electrolyte solvent a cyclic amine, an alkylating agent, and at least one of a metal tetrafluoroborate and a metal bis (trifluoromethylsulfonyl)imide in the presence of a base, thereby forming the electrolyte composition,

wherein said electrolyte solvent is selected from the group consisting of acetonitrile, succinonitrile, glutaronitrile, propionitrile, phenylacetonitrile, isobutylronitrile, benzonitrile, acrylonitrile, propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, methyl 2,2,2-trifluoroethyl carbonate, gamma-butryolactone, methylpropylketone, methylisobutylketone, N-methylpyrrolidone, N,N-dimethylformamide, dimethylacetamide, sulfolane, and mixtures thereof, and

wherein said cyclic amine comprises a cyclic secondary amine moiety having the formula;

2. The method of claim 1 further comprising purifying the composition by removing at least a portion of a precipitate formed.

3. The method of claim 1 wherein said at least one of a spiro quaternary ammonium tetrafluoroborate compound or a spiro quaternary ammonium bis(trifluoromethylsulfonyl)imide compound comprises at least one of 6-azoniaspiro[5.5]undecane, or 5-azoniaspiro[4.5]undecane, 5-azoniaspiro[4.4]nonane.

4. The method of claim 1 wherein said metal tetrafluoroborate is potassium tetrafluoroborate and said metal bis(trifluoromethylsulfonyl)imide is potassium bis(trifluoromethylsulfonyl)imide.

5. The method of claim 1 wherein said alkylating agent is selected from the group consisting of 1,4-dichlorobutane, 1,5-dichloropentane, 1,4-dibromobutane, 1,5-dibromopentane, 1,5-chlorobromopentane, 1,4-dichloropentane, 1,4-dibromopentane, 1-Bromo-4-chlorobutane, bis(2-bromoethyl) ether, 2-bromoethyl 2-chloroethyl ether, bis(2-chloroethyl) ether;

1-bromomethyl 2-chloroethyl ether, 2-bromoethyl 1-chloromethyl ether, 1,4-ditosylbutane, 1,5-ditosylpentane, 1,5-tosylbromopentane, 1,4-ditosylpentane, 1bromo-4-tosylbutane, 1,4-dimesylbutane, 1,5-dimesylpentane, 1,4-bromomesylbutane, 1,5-mesylbromopentane, 1,4-dimesylpentane, 1,4-ditriflylbutane, 1,5-ditriflylpentane, 1,4-bromotriflylbutane, 1,5-triflylbromopentane, 1,4-ditriflylpentane, and 1-bromo-4-triflylbutane.

6. The method of claim 1 wherein said cyclic secondary amine is selected from the group consisting of pyrrolidine, and piperidine.

7. The method of claim 1 wherein said base is selected from the group consisting of alkali metal hydroxides and alkaline earth metal hydroxides, alkali metal and alkaline earth metal oxides, alkali metal hydrides and alkaline earth metal hydrides, alkali metal amides, alkali metal carbonates and alkaline earth metal carbonates, alkali metal hydrogen carbonates, basic metal oxidhydroxides, organometallic compounds, alkylmagnesium halides, and alkali metal alcoholates and alkaline earth metal alcoholates.

8. The method of claim 1 wherein said base has a formula selected from the group consisting of M_a(CO3)_c, M_aH_b(CO₃)_c, M_a(PO₄)_c, M_aH_b(PO₄)_c, and M(OH)_c,

wherein M is an alkali or alkaline-earth metal,

a is an integer from about 1 to about 2,

b and c are independently an integer from 0 to about 2.

9. The method of claim 1 wherein

R₃ is H;

and

R₄ is CH₂.

10. The method of claim 1 wherein said electrolyte composition comprises a spiro quaternary ammonium compound selected from the group consisting of 6-azoniaspiro[5.5]decane tetrafluoroborate, 5-azoniaspiro[4.5]undecane tetrafluoroborate, 5-azoniaspiro[4.4]nonane tetrafluoroborate, 6-azoniaspiro[5,5]undecane bis(trifluoromethylsulfonyl)imide, 5-azoniaspiro[4.5]undecane bis(trifluoromethylsulfonyl)imide, and 5-azoniaspiro[4.4]nonane bis(trifluoromethylsulfonyl)imide.

11. The method of claim 1, wherein said electrolyte solvent is selected from the group consisting of succinonitrile, glutaronitrile, propionitrile, phenylacetonitrile, isobutylronitrile, benzonitrile, acrylonitrile, propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, methyl 2,2,2-trifluoroethyl carbonate, gamma-butryolactone, methylpropylketone, methylisobutylketone, N-methylpyrrolidone, N,N-dimethylformamide, dimethylacetamide, sulfolane, and mixtures thereof.

12. The method of claim 1, wherein said electrolyte solvent is selected from the group consisting of propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, methyl 2,2,2-trifluoroethyl carbonate, and mixtures thereof.

13. The method of claim 1 further comprising purifying the composition by removing through filtration at least a portion of a precipitate formed, wherein the filtrate comprises the at least one of a spiro quaternary ammonium tetrafluoroborate compound or a spiro quaternary ammonium bis(trifluoromethylsulfonyl)imide compound in the electrolyte solvent.