Trifluorovinyloxy monomers and polymers
View Patent ↗Reactive monomers containing the trifluorovinyloxy group may be copolymerized to form polymers useful as membranes, especially polymer electrolyte membranes for fuel cells. The monomers have the formula ((CF 2 CFO(R 1 ) p ) n ArX 2 wherein Ar is a trivalent, tetravalent or pentavalent, substituted or unsubstituted, aromatic or heteroaromatic, monocyclic or polycyclic group having from 5 to 50 carbon atoms; X is OH, SH, NR 2a R 2b , F or Br; p is 0 or 1; n is 1, 2 or 3; R 1 is substituted or unsubstituted phenyl and R 2a and R 2b are independently H, C 1 -C 8 alkyl or C 1 -C 8 perfluoroalkyl.
1. A compound containing a trifluorovinyloxy group and having the formula (CF 2 CFO(R 1 ) p ) n ArX 2
wherein
Ar is selected from
X is OH, SH, NR 2 R 3 , F or Br;
p is 0 or 1;
n is 1 or 2;
R 1 is substituted or unsubstituted phenyl and
R 2 is independently H, C 1 -C 8 alkyl or C 1 -C 8 perfluoroalkyl;
R 3 is H, aryl, substituted aryl, aryloxy, alkylaryl or arylalkyl, perfluoroalkyl, or halo;
R 4 is H, C 1 -C 3 alkyl, C 1 -C 8 perfluoroalkyl or aryl;
m is 0, 1, 2 or 3; and
L is a direct bond, O, S, CO, SO 2 , CR 1 R 2 , C y H 2y , C y F 2y , or O-Z-O and the bonds of the O or the O-Z-O group are in the 3,3′-, 3,4′-, 4,3′-, or the 4,4′-positions; and
Z is selected from
2. A compound according to claim 1 wherein n is 1.
3. A compound according to claim 1 , wherein n is 2.
4. A compound according to claim 1 , wherein p is 1.
5. A compound according to claim 1 , wherein X is OH.
6. A compound according to claim 1 , wherein Ar is
7. A compound according to claim 1 , wherein L is CR 1 R 2 .
8. A compound according to claim 1 , wherein L is a direct bond.
9. A compound according to claim 1 , wherein R 3 and R 4 are H.
10. A compound according to claim 1 , wherein m is 1, and Ar is biphenyl.
11. A compound according to claim 1 , having a formula
12. A compound according to claim 1 , having a formula
13. A compound according to claim 1
a. wherein
b. p is 1;
c. n is 1 or 2;
d. R 1 is unsubstituted phenyl and
e. R 2 and R 3 are independently H, or C 1 -C 8 alkyl.
14. A polymer comprising structural units derived from a compound according to claim 1 .
15. A polymer according to claim 14 , additionally comprising structural units derived from at least one aryl ether monomer and at least one aryl ketone monomer.
16. A polymer according to claim 15 , additionally comprising structural units derived from at least one aryl sulfone monomer.
17. A polymer according to claim 14 , additionally comprising structural units derived from at least one aryl ether monomer and at least one aryl sulfone monomer.
18. A polymer according to claim 17 , additionally comprising structural units derived from at least one aryl ketone monomer.
19. A polymer according to claim 14 , additionally comprising structural units derived from at least one aromatic anhydride monomer and at least one hydroxy aryl monomer.
20. A polymer according to claim 14 , additionally comprising structural units derived from at least one phosphine oxide monomer.
21. A polymer according to claim 14 , additionally comprising structural units derived from at least one benzonitrile monomer.
22. A membrane comprising a copolymer derived from condensation copolymerization of a compound according to claim 1 .
23. A fuel cell comprising a membrane according to claim 22 .
24. A polymer comprising structural units derived from a trifluorovinyloxy compound of formula I and at least one of an aryl ketone monomer and an aryl sulfone monomer;
(CF 2 CFO(R 1 ) p ) n ArX 2 I
wherein
Ar is a trivalent, tetravalent or pentavalent, substituted or unsubstituted, aromatic or heteroaromatic, monocyclic or polycyclic group having from 5 to 50 carbon atoms;
X is OH, SH, NR 2 R 3 , F or Br;
p is 0 or 1;
n is 1, 2 or 3;
R 1 is substituted or unsubstituted phenyl and
R 2 and R 3 are independently H, C 1 -C 8 alkyl or C 1 -C 8 perfluoroalkyl.
25. A polymer according to claim 24 , wherein Ar is selected from
R 3 is H, aryl, substituted aryl, aryloxy, alkylaryl or arylalkyl, perfluoroalkyl, or halo;
R 4 is H, C 1 -C 8 alkyl, C 1 -C 8 perfluoroalkyl or aryl;
m is 0, 1, 2 or 3; and
L is a direct bond, O, S, CO, SO 2 , CR 1 R 2 , C y H 2y , C y F 2y , or O-Z-O and the bonds of
the O or the O-Z-O group are in the 3,3′-, 3,4′-, 4,3′-, or the 4,4′-positions; and
Z is selected from
26. A polymer according to claim 24 wherein n is 1 or 2.
27. A polymer according to claim 24 , wherein n is 1.
28. A polymer according to claim 24 , wherein p is 1.
29. A polymer according to claim 24 , wherein X is OH.
30. A polymer according to claim 24 , wherein Ar is
31. A polymer according to claim 24 , wherein L is CR 1 R 2 .
32. A polymer according to claim 24 , wherein L is a direct bond.
33. A polymer according to claim 24 , wherein R 3 and R 4 are H.
34. A polymer according to claim 24 , wherein m is 1, and Ar is biphenyl.
35. A polymer according to claim 24 , having a formula
36. A polymer according to claim 24 , having a formula
37. A polymer according to claim 24
a. wherein
b. p is 1;
c. n is 1 or 2;
d. R 1 is unsubstituted phenyl and
e. R 2 and R 3 are independently H, or C 1 -C 8 alkyl.