Method for synthesizing ionic liquids having a carbonate functional group and ionic liquids thus obtained

Patent metadata

Field	Value
Publication number	US-10026993-B2
Application number	US-201414767407-A
Country	US
Kind code	B2
Filing date	Feb 10, 2014
Priority date	Feb 13, 2013
Publication date	Jul 17, 2018
Grant date	Jul 17, 2018

Abstract

The present invention relates to a method for synthesizing ionic liquids comprising a carbonate functional group characterized in that it comprises a step of reaction A without addition of lithium between a first reactant selected among an imidazolium, a pyrrolidinium or an ammonium and a second reactant being a methyl formate imidazolium. The first reactant is an imidazolium alcohol, a pyrrolidinium alcohol or an ammonium alcohol salt, the anion of which is NTf2. The second reactant is a chloromethyl formate imidazolium.
The application of this method will be found in the field of green chemistry and more specifically in the production of ionic liquids which can be used in lithium batteries with a graphite electrode.

First claim

The invention claimed is:

1. A method for synthesizing an ionic liquid comprising a carbonate functional group that is not coordinated with lithium, the method comprising reacting without adding lithium a first reactant selected from the group consisting of an imidazolium, a pyrrolidinium and an ammonium and a second reactant being a methyl formate imidazolium, wherein no reactant contains lithium.

2. The method according to claim 1 , wherein the first reactant is an imidazolium, a pyrrolidinium or an ammonium alcohol.

3. The method according to claim 1 , wherein the first reactant is an imidazolium alcohol, a pyrrolidinium alcohol or an ammonium alcohol salt, the anion of which is bis(trifluoromethanesulfonyl)imide (NTf2).

4. The method according to claim 1 , wherein the reacting results in two products, with a main product being an ionic liquid comprising a carbonate functional group and a secondary product being a methyl imidazolium.

5. The method according to claim 4 , further comprising recycling, by Hoffmann reaction, the secondary product methyl imidazolium into an imidazolium alcohol, forming the first reactant of the reacting.

6. The method according to claim 5 , wherein methyl imidazolium reacts with 2-chloro-1-ethanol to form 1-ethanol-3-methyl imidazolium chloride.

7. The method according to claim 1 , wherein the ionic liquid obtained is selected from the group consisting of
1-[2-(methoxycarbonyloxy)ethyl]-3-methylimidazolium,
1-[2-(ethoxycarbonyloxy)ethyl]-3-methylimidazolium,
1-[2-(propoxycarbonyloxy)ethyl]-3-methylimidazolium,
1-[2-(isopropoxycarbonyloxy)ethyl]-3-methylimidazolium,
N-[2-(methoxycarbonyloxy)ethyl]-N′-methylpyrrolidinium,
N-[2-(ethoxycarbonyloxy)ethyl]-N′-methylpyrrolidinium,
N-[2-(propoxycarbonyloxy)ethyl]-N′-methylpyrrolidinium,
N-[2-(isopropoxycarbonyloxy)ethyl]-N′-methylpyrrolidinium,
N-trimethyl-N-2-[(methoxycarbonyloxy)ethyl]ammonium,
N-trimethyl-N-2-[(ethoxycarbonyloxy)ethyl]ammonium,
N-trimethyl-N-2-[(propoxycarbonyloxy)ethyl]ammonium, and
N-trimethyl-N-2-[(isopropoxycarbonyloxy)ethyl]ammonium,
wherein each ionic liquid is associated with a bis(trifluoromethanesulfonyl)imide anion.

8. The method according to claim 1 , wherein reacting is executed at ambient temperature in an acetonitrile-based solution in argon atmosphere.

9. The method of claim 1 , wherein the second reactant is a chloromethyl formate imidazolium.

10. The method according to claim 9 , wherein the second reactant is obtained by a reaction between 1-methylimidazole and methylchloroformate.

11. The method according to claim 10 , wherein the reaction is executed at 0° C. in an acetonitrile-based solution for 2 hours.

12. The method according to claim 10 , wherein the second reactant obtained by a reaction between 1-methylimidazole and methylchloroformate is directly mixed with the first reactant.

13. The method according to claim 6 , wherein the chlorine of 1-ethanol-3-methyl imidazolium chloride is substituted by NTf2 by reaction with lithium bis(trifluoromethanesulfonyl)imide (LiNTf2).

Assignees

• Commissariat Energie Atomique
• Centre Nat Rech Scient
• Univ Claude Bernard Lyon
• Cpe Lyon

Inventors

• Srour Hassan
• Rouault Helene
• Santini Catherine

Classifications

• H01M10/052

  Li-accumulators · CPC title

• H01M10/0525

  Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries · CPC title

• C07C213/06

  from hydroxy amines by reactions involving the etherification or esterification of hydroxy groups · CPC title

• H01M10/0569 Primary

  characterised by the solvents · CPC title

• Y02P20/582

  Recycling of unreacted starting or intermediate materials · CPC title