Process for the preparation of arylene fluorinated sulfonimide polymers and membranes
Aromatic sulfonimide ionene polymers useful as membranes in electrochemical cells are prepared.
1. A process for making a polymer comprising polymerizing a compound of Formula (I):
wherein Ar is a univalent group of Formula (II), (III), or (IV):
and is optionally substituted with one or more fluorine;
R f is a straight chain, branched or cyclic, perfluorinated alkylene group having from 1 to 20 carbon atoms and optionally substituted with one or more ether oxygens or halogens;
m is 1-6;
M is one or more of monovalent cation;
Q is S, SO 2 , CO, or CR 1 R 2 , wherein R 1 and R 2 are independently branched or cyclic perfluorinated alkyl groups having 1 to 10 carbon atoms, and wherein R 1 and R 2 can together form a ring; and
X is chlorine, bromine, iodine, methanesulfonate, or trifluoromethanesulfonate;
wherein the polymerization is performed in the presence of a zerovalent transition metal and a neutral ligand.
2. The process of claim 1 wherein the zerovalent transition metal is palladium or nickel.
3. The process of claim 1 wherein the zerovalent transition metal is bis(1,5-cyclooctadiene)nickel(0) and the neutral ligand is 2,2′-bipyridine.
4. The process of claim 1 wherein the zerovalent transition metal and neutral ligand are in the form of a complex.
5. The process of claim 1 wherein an accelerator is present.
6. The process of claim 1 wherein the polymerization is performed in a solvent.
7. The process of claim 6 wherein the solvent is one or more of N,N-dimethylformamide, toluene, tetrahydrofuran, acetone, anisole, acetonitrile, N,N-dimethylacetamide, or N-methylpyrrolidinone.
8. The process of claim 1 wherein M is K, Na, Li, or H.
9. The process of claim 1 wherein R f is a perfluorinated alkylene group having from 2 to 10 carbon atoms.
10. The process of claim 9 wherein R f is a linear, perfluorinated alkylene group having from 2 to 4 carbon atoms.
11. The process of claim 1 wherein a copolymer is formed by polymerizing a compound of Formula (I) and a compound of Formula (IX):
wherein Ar′ is a univalent group of Formula (X), (XI), or (XII):
wherein T is a boronic acid group or salt thereof, a boronic ester group or a borane group.
12. The process of claim 1 wherein Ar is a univalent group of Formula (VI), (VII), or (VIII):
13. The process of claim 12 wherein Ar is Formula (VII) or (VIII).
14. The process of claim 1 wherein m is 1.
15. The process of claim 1 wherein Q is SO 2 .
16. The process of claim 1 wherein X is Br.
17. A polymer made by the process of claim 1 .
18. The polymer of claim 17 that is a homopolymer.
19. The polymer of claim 17 that is a copolymer.
20. A membrane made from the polymer of claim 17 .
21. An electrochemical cell comprising the polymer of claim 17 .
22. A fuel cell comprising the electrochemical cell of claim 21 .