Monomers and polymers carrying imidazole and benzimidazole groupings, and proton exchange membrane containing the same for the production of a fuel cell

Patent metadata

Field	Value
Publication number	US-9252446-B2
Application number	US-201414477381-A
Country	US
Kind code	B2
Filing date	Sep 4, 2014
Priority date	Jun 7, 2006
Publication date	Feb 2, 2016
Grant date	Feb 2, 2016

Abstract

The invention relates to a monomer (6, 14) carrying an imidazole-type heterocycle (3). According to the invention, the chemical structure of said monomer (6, 14) comprises at least one unit of formula (I) wherein R1 comprises an alkenyl grouping and R2 comprises a grouping for protecting one of the nitrogen atoms of the heterocycle. The invention also relates to a monomer carrying a benzimidazole-type heterocycle, and to protected polymers obtained from said monomers, deprotected polymers produced by the protected polymers, a proton exchange membrane based on deprotected polymers, and a fuel cell provided with said membrane. Furthermore, the invention relates to methods for producing the above-mentioned monomers and polymers.

First claim

The invention claimed is:

1. Monomer, capable of being used for the production of an ionic conductive membrane, said monomer having the formula:

wherein R is a nitrogen atom protection group.

2. Monomer according to claim 1 , wherein the protection group is a benzyl, trialkylsilyl or carbamate group.

3. Method of producing the monomer of claim 1 , wherein said method comprises:
at least one step (a) of reacting a compound comprising an ortho-phenylene diamine, with a hexafluoropropene, in the presence of an organic solvent, by which a fluorinated intermediate molecule carrying a heterocycle of the benzimidazole type is obtained,
at least one step (b) of protecting a nitrogen atom (N1) of the benzimidazole group of the intermediate molecule by a group R,
at least one step (c) of dehydrofluorinating the compound obtained at step (b) by reacting this compound with a base, by which a protected monomer is formed.

4. Method according to claim 3 , wherein the synthesis step (a) is performed at a temperature of about 75° C.

5. Method according to claim 3 , wherein the synthesis step (a) is performed in the autoclave under high pressure in a range of 5-50 bar.

6. Method according to claim 3 , wherein the protection step (b) is a reaction between the intermediate molecule and a reagent of the formula R—Cl, performed in the presence of a base.

7. Method according to claim 6 , wherein the bases used in steps (b) and (c) are selected from butyl lithium, ter-butyl lithium, lithium diisopropylamine and sodium hydride.

8. Method according to claim 3 , wherein the steps (b) and (c) are performed in the presence of an anhydrous organic solvent.

9. Method according to claim 3 , wherein the dehydrofluorination step (c) is performed at least in part at low temperature of about −78° C.

10. Protected polymer comprising the monomer of claim 1 .

11. Protected polymer according to claim 10 , wherein the polymer is an acid.

12. Method of producing a protected polymer from the monomer of claim 1 , comprising at least one step (d) of polymerizing the monomer.

13. Method according to claim 12 , wherein the polymerization step consists of a homopolymerization of the monomer by radical initiation.

14. Method according to claim 12 , wherein the polymerization step consists of a copolymerization of this monomer with fluorinated monomers.

15. Method according to claim 13 , wherein the fluorinated monomers are fluorinated olefins.

16. Deprotected polymer, comprising a monomer, capable of being used for the production of an ionic conductive membrane, said monomer having the formula:

wherein R is hydrogen.

17. Method of producing a deprotected polymer using the protected polymer of claim 10 , comprising at least one step (e) of deprotecting nitrogen atoms by which protection groups of the protected polymer are replaced by hydrogen atoms, forming the deprotected polymer which is a proton conductor.

18. Ionic conductive membrane, comprising the polymer of claim 16 .

19. Electrochemical device comprising the ionic conductive membrane of claim 18 as electrolyte.

20. Fuel cell comprising the ionic conductive membrane of claim 18 as electrolyte.

21. Method of powering the motion of a motor vehicle, comprising using the fuel cell of claim 20 to power the motion of the motor vehicle.

22. Electrolyzer comprising the ionic conductive membrane of claim 18 as electrolyte.

Assignees

• Peugeot Citroen Automobiles Sa
• Centre Nat Rech Scient

Inventors

• Glipa Xavier
• Ameduri Bruno
• Delon Louis
• Jones Deborah
• Roziere Jacques
• Frutsaert Guillaume

Classifications

• Y02E60/50

  Fuel cells · CPC title

• B01D71/62

  Polycondensates having nitrogen-containing heterocyclic rings in the main chain · CPC title

• C08J2327/12

  containing fluorine atoms · CPC title

• H01M8/1027

  having carbon, oxygen and other atoms, e.g. sulfonated polyethersulfones [S-PES] · CPC title

• H01M2250/20

  Fuel cells in motive systems, e.g. vehicle, ship, plane · CPC title