Mixed-sulfonation block copolymers
View Patent ↗Sulfonated block copolymers that may be used as membranes for fuel cells include sulfonated polyaryletherketone blocks and lightly sulfonated polyethersulfone blocks. The sulfonated polyaryletherketone blocks include structural units of formula and the lightly sulfonated polyethersulfone blocks include structural units of formula wherein R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are independently C 1 -C 10 alkyl, C 3 -C 12 cycloalkyl, C 6 -C 14 aryl, allyl, alkenyl, alkoxy, halo, or cyano; Z, Z 1 and Z 2 are independently a direct bond or O, S, (CH 2 ) r , (CF 2 ) r , C(CH 3 ) 2 , C(CF 3 ) 2 , or a combination thereof; M is H, a metal cation, a non-metallic inorganic cation, an organic cation or a mixture thereof; a and e are independently 0 or an integer from 1 to 3; b, c, d, and f are independently 0 or an integer from 1 to 4; m, n and p are independently 0 or 1; and r is an integer from 1 to 5.
1. A sulfonated block copolymer comprising
sulfonated polyaryletherketone blocks comprising structural units of formula
and polyethersulfone blocks comprising structural units of formula
wherein
R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are independently C 1 -C 10 alkyl, C 3 -C 12 cycloalkyl, C 6 -C 14 aryl, allyl, alkenyl, alkoxy, halo, or cyano;
Z, Z 1 and Z 2 are independently a direct bond or O, S, (CH 2 ) r , (CF 2 ) r , C(CH 3 ) 2 , C(CF 3 ) 2 , or a combination thereof;
M is H, a metal cation, a non-metallic inorganic cation, an organic cation or a mixture thereof;
a and e are independently 0 or an integer from 1 to 3;
b, c, d, and f are independently 0 or an integer from 1 to 4;
m, n and p are independently 0 or 1; and
r is an integer from 1 to 5.
2. A sulfonated block copolymer according to claim 1 , wherein a is 0.
3. A sulfonated block copolymer according to claim 1 , wherein b is 0.
4. A sulfonated block copolymer according to claim 1 , wherein c is 0.
5. A sulfonated block copolymer according to claim 1 , wherein d is 0.
6. A sulfonated block copolymer according to claim 1 , wherein e is 0.
7. A sulfonated block copolymer according to claim 1 , wherein f is 0.
8. A sulfonated block copolymer according to claim 1 , wherein m is 0.
9. A sulfonated block copolymer according to claim 1 , wherein n is 0.
10. A sulfonated block copolymer according to claim 1 , wherein Z is a direct bond.
11. A sulfonated block copolymer according to claim 1 , wherein Z 1 is a direct bond.
12. A sulfonated block copolymer according to claim 1 , wherein Z 2 is a direct bond.
13. A sulfonated block copolymer according to claim 1 , wherein at least one of Z, Z 1 and Z 2 is C(CF 3 ) 2 .
14. A sulfonated block copolymer comprising structural units of formula VI, VII and VIII
wherein
R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are independently C 1 -C 10 alkyl, C 3 -C 12 cycloalkyl, C 6 -C 14 aryl, allyl, alkenyl, alkoxy, halo, or cyano;
Z, Z 1 and Z 2 are independently a direct bond or O, S, (CH 2 ) r , (CF 2 ) r , C(CH 3 ) 2 , C(CF 3 ) 2 , or a combination thereof;
M is H, a metal cation, a non-metallic inorganic cation, an organic cation or a mixture thereof;
a and e are independently 0 or an integer from 1 to 3;
b, c, d, and f are independently 0 or an integer from 1 to 4; and
m, n and p are independently 0 or 1;
r is an integer from 1 to 5;
x ranges from about 1 to about 50;
(y+z) ranges from about 1 to about 100;
x/(x+y+z) ranges from about 0.2 to about 0.8; and
z/(y+z) ranges from about 0.1 to about 0.9.
15. A sulfonated block copolymer according to claim 14 , wherein a is 0.
16. A sulfonated block copolymer according to claim 14 , wherein b is 0.
17. A sulfonated block copolymer according to claim 14 , wherein c is 0.
18. A sulfonated block copolymer according to claim 14 , wherein d is 0.
19. A sulfonated block copolymer according to claim 14 , wherein e is 0.
20. A sulfonated block copolymer according to claim 14 , wherein f is 0.
21. A sulfonated block copolymer according to claim 14 , wherein m is 0.
22. A sulfonated block copolymer according to claim 14 , wherein n is 0.
23. A sulfonated block copolymer according to claim 14 , wherein Z is a direct bond.
24. A sulfonated block copolymer according to claim 14 , wherein Z 1 is a direct bond.
25. A sulfonated block copolymer according to claim 1 , wherein Z 2 is a direct bond.
26. A sulfonated block copolymer according to claim 14 , wherein at least one of Z, Z 1 , and Z 2 is C(CF 3 ) 2 .
27. A sulfonated block copolymer according to claim 14 , wherein x ranges from about 5 to about 50.
28. A sulfonated block copolymer according to claim 14 , wherein x ranges from about 25 to about 45.
29. A sulfonated block copolymer according to claim 14 , wherein (y+z) ranges from about 40 to about 70.
30. A sulfonated block copolymer according to claim 14 , wherein (x+z)/(x+y+z) ranges from about 0.4 to about 0.6.
31. A sulfonated block copolymer according to claim 14 , wherein (x+z)/(x+y+z) ranges from about 0.35 to about 0.45.
32. A sulfonated block copolymer according to claim 14 , wherein z/(y+z) ranges from about 0.1 to 0.5.
33. A sulfonated block copolymer according to claim 14 , wherein z/(y+z) ranges from about 0.15 to 0.35.
34. A membrane comprising a sulfonated block copolymer according to claim 1 .
35. A fuel cell comprising a membrane according to claim 34 .