Granted Patent B2

US 7,993,792 · App. 11/459,970 · Granted Aug 9, 2011

Abstract

Claims (42)

1. A block copolymer having formula 1a or formula 1b:

(A m B n ) p   1a

A m B n C s   1b

wherein

A is a first polymer segment that is repeated m times to form first polymer block A m that is either hydrophobic or hydrophilic;

B is a second polymer segment that is repeated n times to form second polymer block B n that is either hydrophobic or hydrophilic;

C is a third polymer segment that is repeated s times to form third polymer block C s that is either hydrophobic or hydrophilic;

at least one of A, B, and C is described by formula 2

Y 1 is —O—, —S—, —CO—, —SO 2 —, —C(CH 3 ) 2 —, —C(CF 3 ) 2 —, —P(O)(T 1 )-, —C(CH 3 )(T 1 )-, —P(O)(R 4 )—, diphenyl methylene, diphenyl silicon, fluorenyl, an alkylene, a bond single chemical bond, or

R 1 , R 2 , and R 3 are each independently H, C 1-10 alkyl, C 6-18 aryl, C 6-18 aralkyl, SO 3 H, —SO 3 − M + , —COOH, —COO − M + , —PO 3 H 2 , —PO 3 H − M + , or —PO 3 2− M 2 + , —PO 3 2− M 2+ ;

R 4 is H, C 1-10 alkyl, C 6-18 aryl, or C 6-18 aralkyl;

m, n, and s are each independently an integer from 1 to 200;

p is an integer from 1 to 20;

i is an integer from 1 to 6;

T 1 is H or a moiety having formula 3:

Y 2 and Y 4 are each independently —O—, —S—, —CO—, —SO 2 —, —C(CH 3 ) 2 —, —C(CF 3 ) 2 —, —P(O)(R 4 )—, diphenyl methylene, diphenyl silicon, fluorenyl, an alkylene, or a bond;

R 4 is H, C 1-10 alkyl, C 6-18 aryl, or C 6-18 aralkyl;

R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , and R 13 are each independently H, C 1-10 alkyl, C 6-18 aryl, C 6-18 aralkyl, SO 3 H, —SO 3 − M + , —COOH, —COO − M + , —PO 3 H 2 , —PO 3 H − M + , —PO 3 2− M 2 + , or —PO 3 2− M 2+ ;

M is a metal, ammonium, or alkylammonium; and

j is an integer from 0 to 30;

with the proviso that when j>1, the Y 2 between sequential aromatic rings are the same or different; the R 5 , R 6 , R 7 , R 8 , and R 9 on sequential aromatic rings are the same or different; and

at least one of R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , and R 13 is —SO 3 H, —SO 3 − M + , —COOH, —COO − M + , —PO 3 H 2 , —PO 3 H − M + , —PO 3 2− M 2 + , or —PO 3 2− M 2+ , wherein at least one of A, B, or C comprises a component selected from the group consisting of polymer segments having formulae 8, 9, 10, and 11, and salts thereof:

2. The block copolymer of claim 1 wherein polymer blocks A m and C s is hydrophobic and the polymer block B n is hydrophilic.

3. The block copolymer of claim 2 wherein the block copolymer has a micro-phase separated morphology.

4. The block copolymer of claim 1 having a micro-phase separated morphology comprising spheres, cylinders, lamellae, ordered bicontinuous double diamond structures, disordered bicontinuous morphologies, and combinations thereof.

5. The block copolymer of claim 1 wherein polymer blocks A m , B n , and C s each individually have a molecular weight from about 5×10 2 to about 5×10 5 (g/mol).

6. An ion conductive membrane comprising the block copolymer of claim 1 .

7. A polymer block B n comprising a polymer segment B that is repeated n times, wherein n is an integer from 1 to 200 and B comprises a component selected from the group consisting of polymer segments having formulae 4, 5, 6a, 6b, 6c, 6d, and 6e, and salts thereof:

8. The polymer block of claim 7 having a molecular weight from about 5×10 2 to about 5×10 5 (g/mol).

9. An ion conductive membrane comprising the polymer block of claim 7 .

10. A block copolymer having formula 1a or formula 1b:

(A m B n ) p   1a

A m B n C s   1b

wherein

A is a first polymer segment that is repeated m times to form first polymer block A m that is either hydrophobic or hydrophilic;

B is a second polymer segment that is repeated n times to form second polymer block B n that is either hydrophobic or hydrophilic;

C is a third polymer segment that is repeated s times to form third polymer block C s that is either hydrophobic or hydrophilic;

m, n, and s are each independently an integer from 1 to 200; and

p is an integer from 1 to 20;

wherein at least one of A, B, or C comprises a component selected from the group consisting of polymer segments having formulae 4, 5, 6a, 6b, 6c, 6d, and 6e:

11. The block copolymer of claim 10 wherein polymer blocks A m , B n , and C s each independently have a molecular weight from about 5×10 2 to about 5×10 5 (g/mol).

12. An ion conductive membrane comprising the block copolymer of claim 10 .

Assignments (12)