Sulfonated polyaryletherketone-block-polyethersulfone copolymers
Sulfonated block copolymer suitable for use as proton exchange membranes for fuel cells comprise sulfonated polyaryletherketone blocks and polyethersulfone blocks. The sulfonated polyaryletherketone blocks comprise structural units of formula I wherein R 1 is C 1 -C 10 alkyl, C 3 -C 12 cycloalkyl, C 6 -C 14 aryl, allyl, alkenyl, alkoxy, halo, or cyano; Ar 1 and Ar 2 are each independently C 6 -C 20 aromatic radicals, or Ar 1 and Ar 2 , taken together with an intervening carbon atom, form a bicyclic C 6 -C 20 aromatic radical or a tricyclic C 6 -C 20 aromatic radical; M is H, a metal cation, a non-metallic inorganic cation, an organic cation or a mixture thereof; and a is 0 or an integer from 1 to 4.
1 . A sulfonated block copolymer comprising unsulfonated polyethersulfone blocks and sulfonated polyaryletherketone blocks comprising structural units of formula I
wherein R 1 is C 1 -C 10 alkyl, C 3 -C 12 cycloalkyl, C 6 -C 14 aryl, allyl, alkenyl, alkoxy, halo, or cyano;
Ar 1 and Ar 2 are each independently C 6 -C 20 aromatic radicals, or Ar 1 and Ar 2 , taken together with an intervening carbon atom, form a bicyclic C 6 -C 20 aromatic radical or a tricyclic C 6 -C 20 aromatic radical;
M is H, a metal cation, a non-metallic inorganic cation, an organic cation or a mixture thereof; and
a is 0 or an integer from 1 to 4.
2 . A sulfonated block copolymer according to claim 1 , wherein the sulfonated polyaryletherketone blocks further comprise structural units of formula II
wherein R 2 is C 1 -C 10 alkyl, C 3 -C 12 cycloalkyl, C 6 -C 14 aryl, allyl, alkenyl, alkoxy, halo, or cyano;
b is 0 or an integer from 1 to 4; and
m is 0 or 1.
3 . A sulfonated block copolymer according to claim 1 , wherein the unsulfonated polyethersulfone blocks comprise structural units of formula III
wherein R 3 is C 1 -C 10 alkyl, C 3 -C 12 cycloalkyl, C 6 -C 14 aryl, allyl, alkenyl, alkoxy, halo, or cyano;
c is 0 or an integer from 1 to 4; and
n is 0 or 1.
4 . A sulfonated block copolymer according to claim 1 , wherein the unsulfonated polyethersulfone blocks comprise structural units of formula IV
wherein R 4 is C 1 -C 10 alkyl, C 3 -C 12 cycloalkyl, C 6 -C 14 aryl, allyl, alkenyl, alkoxy, halo, or cyano;
Z is a direct bond, O, S, (CH 2 ) r , (CF 2 ) r , C(CH 3 ) 2 , C(CF 3 ) 2 , or SO 2 ;
d is 0 or an integer from 1 to 4; and
r is an integer from 1 to 5.
5 . A sulfonated block copolymer according to claim 1 , wherein the structural units of formula I are
6 . A sulfonated block copolymer according to claim 1 , wherein the structural units of formula I are
7 . A sulfonated block copolymer according to claim 4 , wherein Z is C(CF 3 ) 2 .
8 . A sulfonated block copolymer according to claim 4 , wherein Z is SO 2 .
9 . A sulfonated block copolymer according to claim 1 , comprising from about 20 mol % to about 80 mol % of the structural units of formula I.
10 . A sulfonated block copolymer according to claim 1 , comprising from about 30 mol % to about 60 mol % of the structural units of formula I.
11 . A sulfonated block copolymer according to claim 1 , wherein the molecular weight of the sulfonated polyaryletherketone blocks ranges from about 2000 Daltons to about 15000 Daltons.
12 . A sulfonated block copolymer according to claim 1 , wherein the molecular weight of the polyethersulfone blocks ranges from about 2000 Daltons to about 20000 Daltons.
13 . A sulfonated block copolymer comprising sulfonated polyaryletherketone blocks comprising structural units of formula V
and unsulfonated polyethersulfone blocks comprising structural units of formula VI
Ar 1 and Ar 2 are each independently C 6 -C 20 aromatic radicals, or Ar 1 and Ar 2 , taken together with an intervening carbon atom, form a bicyclic C 6 -C 20 aromatic radical or a tricyclic C 6 -C 20 aromatic radical;
M is H, a metal cation, a non-metallic inorganic cation, an organic cation or a mixture thereof;
Z is a direct bond, O, S, (CH 2 ) r ; (CF 2 ) r , C(CH 3 ) 2 , C(CF 3 ) 2 , or SO 2 ;
r is an integer from 1 to 5.
14 . A sulfonated block copolymer according to claim 13 , wherein Z is C(CF 3 ) 2 .
15 . A sulfonated block copolymer according to claim 13 , wherein Z is SO 2 .
16 . A sulfonated block copolymer according to claim 13 , wherein the structural units of formula V are
17 . A sulfonated block copolymer according to claim 13 , wherein the structural units of formula V are
18 . A membrane comprising a sulfonated block copolymer according to claim 1 .
19 . A membrane-electrode assembly comprising a membrane according to claim 18 .
20 . A fuel cell comprising a membrane according to claim 18 .
21 . A membrane comprising a sulfonated block copolymer according to claim 13 .
22 . A membrane-electrode assembly comprising a membrane according to claim 21 .
23 . A fuel cell comprising a membrane according to claim 21 .