SYNTHESIS OF HETERO COMPOUNDS USING DIALKYLCARBONATE QUATERNATION

• US 20120321969A1
• Filed: 06/18/2012
• Published: 12/20/2012
• Est. Priority Date: 06/17/2011
• Status: Active Grant

• Current Assignee: Fluidic, Inc.
• Original Assignee: Fluidic, Inc.
• Inventors: Friesen, Cody A., Wolfe, Derek, Johnson, Paul Bryan
• Granted Patent: US 9,793,586 B2
• Time in Patent Office: Days
• US Class Current: 429/403
• CPC Class Codes: C07D 471/04 Ortho-condensed systems
• CPC Class Codes: C07D 471/08 Bridged systems
• CPC Class Codes: C07D 487/08 Bridged systems
• CPC Class Codes: C25B 9/17 Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
• CPC Class Codes: H01M 10/26 Selection of materials as electrolytes
• CPC Class Codes: H01M 12/06 with one metallic and one gaseous electrode
• CPC Class Codes: H01M 2004/021 Physical characteristics, e.g. porosity, surface area
• CPC Class Codes: H01M 2004/023 Gel electrode
• CPC Class Codes: H01M 2300/0014 Alkaline electrolytes
• CPC Class Codes: H01M 2300/0045 Room temperature molten salts comprising at least one organic ion
• CPC Class Codes: H01M 4/244 Zinc electrodes
• CPC Class Codes: H01M 4/38 of elements or alloys
• CPC Class Codes: H01M 50/44 Fibrous material
• CPC Class Codes: H01M 6/045 characterised by aqueous electrolyte
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

Methods of preparing hetero ionic complexes, and ionic liquids from bisulfate salts of heteroatomic compounds using dialkylcarbonates as a primary quaternizing reactant are disclosed. Also disclosed are methods of making electrochemical cells comprising the ionic liquids, and an electrochemical cell comprising an alkaline electrolyte and a hetero ionic complex additive.

Claims

1. A method for preparing an ionic liquid comprising:

(1) reacting a heteroatomic compound with dialkylcarbonate to produce an alkylcarbonate salt of the heteroatomic compound;

(2) acidifying the alkylcarbonate salt with a sulfate-containing acid to produce a bisulfate salt of the heteroatomic compound; and

(3) converting the bisulfate salt of the heteroatomic compound to an ionic liquid comprising an alkyl-heteroatomic cation and an anion.

2. The method as claimed in claim 1, wherein converting the bisulfate salt of the heteroatomic compound is carried out by either:

(a) reacting the bisulfate salt of the heteroatomic compound with a sodium salt to produce an ionic liquid comprising the cation of the alkyl-heteroatomic compound and the anion of the sodium salt;

or

(b) contacting the bisulfate salt of the heteroatomic compound with a strong anion exchange resin containing the anion to produce an ionic liquid comprising the cation of the alkyl-heteroatomic compound and the anion.

3. The method of claim 1, wherein the heteroatomic compound has the formula hetero-R—

X, wherein R is selected from the group consisting of hydrogen, substituted and unsubstituted C1-C20 alkyl, substituted and unsubstituted aralkyl, X is a heteroatom selected from the group consisting of N, O, P, S, and mixtures thereof, which can be linear or can form a hetero or heteroaromatic ring, or bicyclic ring, with the proviso that hetero-R—

X cannot form a linear amine or an imidazole group.

4. The method of claim 1, wherein R is hydrogen.

5. The method of claim 1, wherein the dialkylcarbonate contains two alkyl groups, each alkyl group being the same or different and being selected from the group consisting of substituted and unsubstituted C1-C20 alkyl, substituted and unsubstituted aralkyl, and mixtures thereof.

6. The method of claim 4, wherein the alkyl groups are methyl.

7. The method of claim 1, wherein acidifying comprises reacting the alkylcarbonate salt with sulfuric acid.

8. The method of claim 2, wherein reacting the bisulfate salt of the heteroatomic compound with a sodium salt is performed in a mixture of alcohol and water.

9. The method of claim 8, wherein the alcohol is selected from the group consisting of ethanol, a mixture of about 90% ethanol, 5% isopropanol, and 5% methanol, methanol, tetrahydrofuran, and mixtures thereof.

10. The method of claim 2, wherein the anion exchange resin is a crosslinked polystyrene polymer comprising divinylbenzene (DVB) units in an amount of from about 2.5 to about 30% by weight, based on the weight of the resin, wherein the resin comprises an anion.

11. The method of claim 10, wherein the anion is selected from the group consisting of halophosphates, hexafluorophosphate, alkylphosphates, arylphosphates, nitrate, sulfate, bisulfate, carbonates, alkyl carbonates, alkylsulfates, arylsulfates, perfluorinated alkyl- and arylsulfates, sulfonate, alkylsulfonates, arylsulfonates, perfluorinated alkyl- and arylsulfonates, trifluoromethylsulfonate, tosylate, perchlorate, tetrachloroaluminate, heptachlorodialuminate, tetrafluoroborate, alkylborates, arylborates, amides, perfluorinated amides, dicyanamide, saccharinate, thiocyanate, carboxylates, acetates, trifluoroacetate, bis(perfluoroalkylsulfonyl)amide, chloride (Cl—

), hydroxide (OH—

), hexafluorophosphate (PF6-), iodide, other halides, tetrafluoroborate, bis(trifluoromethylsulfonyl)imide (C2F6NO4S2-), trifluoromethanesulfonate (CF3SO3-;

TfO-), dicyanamide (N(CN)2-;

dca), benzoate, acesulfame, saccharinate, methanesulfonate, and mixtures thereof.

12. The method of claim 11, wherein the anion is hydroxide.

13. The method of claim 11, wherein the anion is methyl carbonate.

14. The method of claim 1, wherein the heteroatomic compound is 1,4, diazabicyclo[2,2,2]octane.

15. The method of claim 1, wherein reacting the heteroatomic compound with dialkylcarbonate to produce an alkylcarbonate salt of the heteroatomic compound proceeds according to the following reaction:

wherein Hetero-R—

X is the heteroatomic compound;

R, R′

, and R″

are the same or different and are selected from the group consisting of hydrogen, substituted and unsubstituted C1-C20 alkyl, substituted and unsubstituted aralkyl, and mixtures thereof;

X is a heteroatom selected from the group consisting of N, O, P, S, and mixtures thereof,

wherein Hetero-R—

X can be linear or can form a hetero or heteroaromatic ring, or bicyclic ring, with the proviso that Hetero-R—

X cannot form a linear tertiary amine or an imidazole group.

16. The method of claim 1, wherein acidifying alkylcarbonate salt with a sulfate-containing acid to produce a bisulfate salt of the heteroatomic compound proceeds according to the following reaction:

wherein Hetero-R—

X is the heteroatomic compound;

R, R′

, and R″

are the same or different and are selected from the group consisting of hydrogen, substituted and unsubstituted C1-C20 alkyl, substituted and unsubstituted aralkyl, and mixtures thereof;

X is a heteroatom selected from the group consisting of N, O, P, S, and mixtures thereof,

wherein Hetero-R—

X can be linear or can form a hetero or heteroaromatic ring, or bicyclic ring, with the proviso that Hetero-R—

X cannot form a linear tertiary amine or an imidazole group.

17. The method of claim 2, wherein converting the bisulfate salt of the heteroatomic compound to an ionic liquid comprising an alkyl-heteroatomic cation and an anion proceeds according to the following reaction:

wherein Hetero-R—

X is the heteroatomic compound;

R and R′

are the same or different and are selected from the group consisting of hydrogen, substituted and unsubstituted C1-C20 alkyl, substituted and unsubstituted aralkyl, and mixtures thereof;

X is a heteroatom selected from the group consisting of N, O, P, S, and mixtures thereof;

M selected from the group consisting of an alkali metal, an alkaline earth metal, ammonium (NH4+), and mixtures thereof, and A is an anion,

wherein Hetero-R—

X can be linear or can form a hetero or heteroaromatic ring, or bicyclic ring, with the proviso that Hetero-R—

X cannot form a linear tertiary amine or an imidazole group.

18. An electrochemical cell comprising:

a first electrode;

a second electrode, wherein the second electrode is positioned apart from the first electrode thereby defining a gap therebetween; and

an ionic conductive medium in the gap whereby the ionically conductive medium contacts both the first and second electrodes, and wherein the ionically conductive medium comprises a cation of a heteroatomic compound and an anion prepared in accordance with the method of claim 1.

19. The electrochemical cell of claim 18, wherein the first electrode is an air cathode, and the second electrode is a metal anode.

20. An electrochemical cell comprising a cell housing, an anode, a cathode, and an ionically conductive medium comprising an aqueous alkaline electrolyte and a hetero ionic complex additive comprising a heteroatomic compound cation and an anion.

21. The electrochemical cell of claim 20, wherein the alkaline electrolyte is potassium hydroxide.

22. The electrochemical cell of claim 20, wherein the hetero ionic complex additive is prepared by:

(1) reacting a heteroatomic compound with dialkylcarbonate to produce an alkylcarbonate salt of the heteroatomic compound;

(2) acidifying the alkylcarbonate salt with a sulfate-containing acid to produce a bisulfate salt of the heteroatomic compound; and

(3) converting the bisulfate salt of the heteroatomic compound to a hetero ionic complex comprising an alkyl-heteroatomic cation and an anion.

23. The electrochemical cell of claim 20, wherein heteroatomic compound has the formula hetero-R—

X, wherein R is selected from the group consisting of hydrogen, substituted and unsubstituted C1-C20 alkyl, substituted and unsubstituted aralkyl, X is a heteroatom selected from the group consisting of N, O, P, S, and mixtures thereof, which can be linear or can form a hetero or heteroaromatic ring, or bicyclic ring.

24. The electrochemical cell of claim 23, wherein the heteroatomic compound is selected from the group consisting of pyrrolidines, morpholines, piperidines, piperazines, quinuclidines, bicyclic amines, amidines, guanidines, alkanolamines, monoalkylamines, dialkylamines, pyrroles, pyrazoles, triazoles, thiazoles, oxazoles, pyridines, imidazopyridines, imidazopyrimidines, monoalkylphosphines, dialkylphosphines, trialkylphosphines, monoalkylphosphites, dialkylphosphites, trialkylphosphites, phosphorus monoamines, phosphorus diamines, phosphorus triamines, mercaptans, thiophenes, dihydrothiophenes, tetrahydrothiophenes, thioethers, dialkylsulfoxides, and combinations thereof.

25. The electrochemical cell of claim 23, wherein the heteroatomic compound is 1,4, diazabicyclo[2,2,2]octane.

26. The electrochemical cell of claim 20, wherein the anion is selected from the group consisting of halophosphates, hexafluorophosphate, alkylphosphates, arylphosphates, nitrate, sulfate, bisulfate, carbonates, alkyl carbonates, alkylsulfates, arylsulfates, perfluorinated alkyl- and arylsulfates, sulfonate, alkylsulfonates, arylsulfonates, perfluorinated alkyl- and arylsulfonates, trifluoromethylsulfonate, tosylate, perchlorate, tetrachloroaluminate, heptachlorodialuminate, tetrafluoroborate, alkylborates, arylborates, amides, perfluorinated amides, dicyanamide, saccharinate, thiocyanate, carboxylates, acetates, trifluoroacetate, bis(perfluoroalkylsulfonyl)amide, chloride (Cl—

), hydroxide (OH—

), hexafluorophosphate (PF6), iodide, other halides, tetrafluoroborate, bis(trifluoromethylsulfonyl)imide (C2F6NO4S2-), trifluoromethanesulfonate (CF3SO3-;

TfO-), dicyanamide (N(CN)2-;

dca), benzoate, acesulfame, saccharinate, methanesulfonate, and mixtures thereof.

27. The electrochemical cell of claim 26, wherein the anion is an alkyl carbonate.

28. The electrochemical cell of claim 20, wherein the heteroatomic compound cation is 1-methyl-4-aza-1-azoniabicyclo[2,2,2]octane, and the anion is hydroxide or methyl carbonate.

29. The electrochemical cell of claim 20, wherein the heteroatomic compound cation is methyl-3-quinuclidinolium, and the anion is hydroxide or methyl carbonate.

30. The electrochemical cell of claim 20, wherein the hetero ionic complex additive is present in an amount sufficient to reduce the formation of dendrites on the cathode and/or anode.

31. The electrochemical cell of claim 30, wherein the hetero ionic complex additive is present in an amount of less than about 200 mM.

32. The electrochemical cell of claim 30, wherein the hetero ionic complex additive is present in an amount of from about 10 to about 40 mM.

33. The electrochemical cell of claim 20, wherein the anode comprises metal fuel and the cathode is an air cathode exposed to air.

34. The electrochemical cell of claim 32, wherein the cell is a secondary cell.

35. The electrochemical cell of claim 28, wherein the anode comprises metal fuel and the cathode is an air cathode exposed to air.

36. The electrochemical cell of claim 34, wherein the cell is a secondary cell.