Sulfonimide-containing poly(arylene ether)s and poly(arylene ether sulfone)s, methods for producing the same, and uses thereof
The present invention is directed to sulfonimide-containing polymers, specifically sulfonimide-containing poly(arylene ether)s and sulfonimide-containing poly(arylene ether sulfone)s, and processes for making the sulfonimide-containing poly(arylene ether)s and sulfonimide-containing poly(arylene ether sulfone)s, for use conductive membranes and fuel cells.
1. A process for making a polymer comprising polymerizing a compound having the formula:
wherein R f is a straight chain, branched or cyclic, poly- or per-halogenated alkylene having from 1 to 20 carbon atoms and optionally substituted with one or more ether oxygens, M is a monovalent cation, and X and X′ are each Independently OH, SH, F, CI or NO 2 .
2. The process of claim 1 wherein R f is perfluorinated.
3. The process of claim 1 wherein X and X′ are both F.
4. The process of claim 1 wherein M is potassium.
5. The process of claim 1 wherein M is sodium.
6. The process of claim 1 wherein said polymerizing comprises contacting said compound with a first comonomer under such conditions that said compound and said first comonomer copolymerize.
7. The process of claim 6 wherein said first comonomer is a biphenol.
8. The process of claim 6 , further comprising contacting said monomer and said first comonomor with a second comonomer.
9. The process of claim 6 wherein said first comonomer has the formula:
wherein T is a carbon-carbon single bond or is selected from the group consisting of C(CH 3 ) 2 —, C(CF 3 ) 2 —, C(CF 3 )(C 6 H 5 )—, —C(O)—, S(O) 2 —, and —P(O)(C 6 H 5 )—.
10. The process of claim 8 wherein said second comonomer has the formula:
wherein Y is selected from —S—, —S(O)—, —S(O) 2 —, —C(O)—, —P(O)(C 6 H 5 )—, and combinations thereof; and R′ is F, Cl, dichloro-, difluoro-, dinitroaromatic substitutions and combinations thereof.
11. A polymer comprising as polymerized units:
wherein k is an integer indicating the number of repeat units in the polymer, the quantity x/(x+y) is from greater than 0 to about 1, Q is O or S, R f is a straight chain, branched or cyclic, poly- or per-halogenated alkylene having from 1 to 20 carbon atoms and optionally substituted with one or more ether oxygens, M′ is a cation, Y is selected from —S—, —S(O)—, —S(O) 2 —, —C(O)—, —P(O)(C 6 H 5 )—, and combinations thereof and T is a carbon-carbon single bond or is selected from C(CH 3 ) 2 —, C(CF 3 ) 2 —, C(CF 3 )(C 6 H 5 )—, —C(O)—, S(O) 2 —, and —P(O)(C 6 H 5 )—.
12. The polymer of claim 11 wherein the quantity x/(x+y) is from about 0.2 to about 0.6.
13. The polymer of claim 11 wherein the quantity x/(x+y) is 1.
14. The polymer of claim 11 , wherein M′ is H.
15. The polymer of claim 11 , wherein M′ is Li.
16. A conductive membrane comprising a polymer of claim 11 .
17. The conductive membrane of claim 16 , said membrane having a conductivity of at least about 10 mS/cm at 80° C. and 95% relative humidity.
18. The conductive membrane of claim 16 , said membrane having a conductivity of at least about 50 mS/cm at 80° C. and 95% relative humidity.
19. The conductive membrane of claim 16 , said membrane having a water swellabitity of less than 100% at 25° C.
20. A fuel cell assembly comprising the conductive membrane of claim 16 .
21. A polymer comprising as polymerized units:
wherein k is an integer indicating the number of repeat units in the polymer, Q is O or S, R f is a straight chain, branched or cyclic, poly- or per-haolgenated alkylene having from 1 to 20 carbon atoms and optionally substituted with one or more ether oxygens, M′ is a cation.
22. The polymer of claim 21 , wherein M′ is a monovalent cation.
23. The polymer of claim 22 , wherein M′ is H, Li, Na or K.
24. The polymer of claim 21 , wherein more than one M′ has been replaced by a multivalent cation.
25. The polymer of claim 24 , wherein the multivalent cation is Mg, Ca or Al.