Granted Patent B2

US 8,048,963 · App. 12/551,272 · Granted Nov 1, 2011

Abstract

Claims (143)

1. A method of making an ion exchange membrane comprising:

a) providing a block copolymer comprising a hydrophobic polymer segment and a polar polymer segment wherein said block copolymer comprises a cyclobutyl moeity;

b) forming a membrane comprising said block copolymer and a solvent; and

c) placing said membrane in steam, water or an electric field at a temperature greater than about 40° C. for a sufficient amount of time to develop a bicontinuous morphology.

2. The method of claim 1 wherein said polar polymer segment is an ionic polymer segment comprising a sulfonic acid group.

3. The method of claim 1 wherein the block copolymer comprises polymer segments 1 and 2:

[E 1 (Z 1 ) d ]—P 1 -Q 1 -P 2   1

E 2 -P 3 -Q 2 -P 4   2

wherein:

Z 1 is a protogenic group;

E 1 is an aromatic-containing moiety;

E 1 is an aromatic-containing moiety;

E 2 is an unsulfonated aromatic-containing and/or aliphatic-containing moiety;

X is an —OH, a halogen, an ester, or

d is 0, 1, 2, 3, or 4;

P 1 , P 2 , P 3 , P 4 are each independently absent, —O—, —S—, —SO—, —CO—, —SO 2 —, —NR 1 H—, NR 2 —, or —R 3 —, and

R 2 is C 1-25 alkyl, C 1-25 aryl or C 1-25 arylene;

R 3 is C 1-25 alkylene, C 1-25 perfluoroalkylene, perfluoroalkyl ether, alkylether, or C 1-25 arylene;

R 4 is trifluoromethyl, C 1-25 alkyl, C 1-25 perfluoroalkylene, C 1-25 aryl, or another E 1 group; and

Q 1 , Q 2 are each independently a fluorinated cyclobutyl moiety.

4. The method of claim 1 wherein the block copolymer includes polymer segments 3 and 4:

wherein:

Z 1 is a protogenic group;

E 1 , E 2 are each independently an aromatic-containing and/or aliphatic-containing moiety;

X is an —OH, a halogen, an ester, or

d is 0, 1, 2, 3, or 4;

P 1 , P 2 , P 3 , P 4 are each independently: absent, —O—, —S—, —SO—, —CO—, —SO 2 —, —NH—, NR 2 —, or —R 3 —, and

R 2 is C 1-25 alkyl, C 1-25 aryl or C 1-25 arylene;

R 3 is C 1-25 alkylene, C 1-25 perfluoroalkylene, perfluoroalkyl ether, alkylether, or C 1-25 arylene;

R 4 is trifluoromethyl, C 1-25 alkyl, C 1-25 perfluoroalkylene, C 1-25 aryl, or another E 1 group;

R 8 (Z 1 ) d is a moiety having d number of protogenic groups; and

Q 1 , Q 2 are each independently a fluorinated cyclobutyl moiety.

5. The method of claim 1 wherein the block copolymer comprises polymer segments 5 and 6:

E 1 (SO 2 X) d —P 1 -Q 1 -P 2   5

E 2 -P 3 -Q 2 -P 4   6

connected by a linking group L 1 to form polymer units 7 and 8:

wherein:

Z 1 is a protogenic group;

E 1 is an aromatic-containing moiety;

E 2 is an unsulfonated aromatic-containing and/or aliphatic-containing moiety;

L 1 is a linking group;

X is an —OH, a halogen, an ester, or

d is 0, 1, 2, 3, or 4;

P 1 , P 2 , P 3 , P 4 are each independently absent, —O—, —S—, —SO—, —SO 2 —, —CO—, —NH—, NR 2 —, —R 3 —, and

R 2 is C 1-25 alkyl, C 1-25 aryl or C 1-25 arylene;

R 3 is C 1-25 alkylene, C 1-25 perfluoroalkylene, or C 1-25 arylene;

R 4 is trifluoromethyl, C 1-25 alkyl, C 1-25 perfluoroalkylene, C 1-25 aryl, or another E 1 group;

Q 1 , Q 2 are each independently a fluorinated cyclobutyl moiety;

i is a number representing repetition of polymer segment 5; and

j is a number representing repetition of polymer segment 6.

6. The method of claim 1 wherein the block copolymer includes polymer segments 9 and 10:

E 1 (Z 1 ) d —P 1 -Q 1 -P 2   9

E 2 (Z 1 ) f -P 3   10

wherein:

Z 1 is a protogenic group;

E 1 , E 2 is an aromatic or aliphatic-containing moiety wherein at least one of E 1 and E 2 includes an aromatic substituted with Z 1 ;

X is an —OH, a halogen, an ester, or

d is 0, 1, 2, 3, or 4;

f is 0, 1, 2, 3, or 4;

P 1 , P 2 , P 3 are each independently absent, —O—, —S—, —O—, —SO 2 —,—CO—, —NH—, —NR 2 —, —R 3 —, and

R 2 is C 1-25 alkyl, C 1-25 aryl or C 1-25 arylene;

R 3 is C 1-25 alkylene, C 1-25 perfluoroalkylene, perfluoroalkyl ether, alkyl ether, or C 1-25 arylene;

R 4 is trifluoromethyl, C 1-25 alkyl, C 1-25 perfluoroalkylene, C 1-25 aryl, or another E 1 group; and

Q 1 is a fluorinated cyclobutyl moiety,

with the proviso that when d is greater than zero, f is zero and when f is greater than zero, d is zero.

7. The method of claim 1 wherein said temperature is below 200° C. or a glass transition temperature of said block copolymer.

8. The method of claim 1 , wherein at step c, said membrane is placed in boiling water at a temperature of about 100° C.

9. The method of claim 1 , wherein said electric field is at least 100 V/mm.

10. The method of claim 1 wherein a second polymer is provided along with the block copolymer is provided.

11. The method of claim 10 wherein the second polymer is a non-ionic polymer.

12. A method of making an ion exchange membrane comprising:

a) providing a block copolymer comprising a hydrophobic polymer segment and a polar polymer segment wherein said block copolymer comprises a hydrophobic perfluorocyclobutane ether polymer segment and a sulfonated hydrophilic perfluorocyclobutane ether polymer segment;

b) dissolving or dispersing said block copolymer in a solvent to form a resin mixture;

c) forming a film layer from said resin mixture;

d) placing said film layer between 2 planar electrodes;

e) heating said film layer to a temperature above about 40° C.;

f) applying a voltage across said planar electrodes; and

g) removing at least part of the solvent in the film layer.

13. The method of claim 12 wherein said polar polymer segment comprises a sulfonic acid group.

14. The method of claim 12 wherein the block copolymer comprises polymer segments 1 and 2:

[E 1 (Z 1 ) d ]—P 1 -Q 1 -P 2   1

E 2 -P 3 -Q 2 -P 4   2

wherein:

Z 1 is a protogenic group;

E 1 is an aromatic-containing moiety;

E 1 is an aromatic-containing moiety;

E 2 is an unsulfonated aromatic-containing and/or aliphatic-containing moiety;

X is an —OH, a halogen, an ester, or

d is the number of Z 1 attached to E 1 ;

P 1 , P 2 , P 3 , P 4 are each independently: absent, —O—, —S—, —SO—, —CO—, —SO 2 —, —NR 1 H—, NR 2 —, or —R 3 —, and

R 2 is C 1-25 alkyl, C 1-25 aryl or C 1-25 arylene;

R 3 is C 1-25 alkylene, C 1-25 perfluoroalkylene, perfluoroalkyl ether, alkylether, or C 1-25 arylene;

R 4 is trifluoromethyl, C 1-25 alkyl, C 1-25 perfluoroalkylene, C 1-25 aryl, or another E 1 group; and

Q 1 , Q 2 are each independently a fluorinated cyclobutyl moiety.

15. The method of claim 12 wherein the block copolymer includes polymer segments 3 and 4:

wherein:

Z 1 is a protogenic group;

E 1 , E 2 are each independently an aromatic-containing and/or aliphatic-containing moiety;

X is an —OH, a halogen, an ester, or

d is the number of Z 1 attached to E 1 ;

P 1 , P 2 , P 3 , P 4 are each independently: absent, —O—, —S—, —SO—, —CO—, —SO 2 —, —NH—, NR 2 —,or —R 3 —, and

R 2 is C 1-25 alkyl, C 1-25 aryl or C 1-25 arylene;

R 3 is C 1-25 alkylene, C 1-25 perfluoroalkylene, perfluoroalkyl ether, alkylether, or C 1-25 arylene;

R 4 is trifluoromethyl, C 1-25 alkyl, C 1-25 perfluoroalkylene, C 1-25 aryl, or another E 1 group; and

R 8 (Z 1 ) d is a moiety having d number of protogenic groups; and

Q 1 , Q 2 are each independently a fluorinated cyclobutyl moiety.

16. The method of claim 12 wherein the block copolymer comprises polymer segments 5 and 6:

E 1 (SO 2 X) d —P 1 -Q 1 -P 2   5

E 2 -P 3 -Q 2 -P 4   6

connected by a linking group L 1 to form polymer units 7 and 8:

wherein:

Z 1 is a protogenic group;

E 1 is an aromatic-containing moiety;

E 2 is an unsulfonated aromatic-containing and/or aliphatic-containing moiety;

L 1 is a linking group;

X is an —OH, a halogen, an ester, or

d is a number of Z 1 functional groups attached to E 1 ;

P 1 , P 2 , P 3 , P 4 are each independently absent, —O—, —S—, —SO—, —SO 2 —, —CO—, —NH—, NR 2 —, —R 3 —, and

R 2 is C 1-25 alkyl, C 1-25 aryl or C 1-25 arylene;

R 3 is C 1-25 alkylene, C 1-25 perfluoroalkylene, or C 1-25 arylene;

R 4 is trifluoromethyl, C 1-25 alkyl, C 1-25 perfluoroalkylene, C 1-25 aryl, or another E 1 group;

Q 1 , Q 2 are each independently a fluorinated cyclobutyl moiety;

i is a number representing repetition of segment 5; and

j is a number representing repetition of polymer segment 6.

17. The method of claim 12 wherein the block copolymer includes polymer segments 9 and 10:

E 1 (Z 1 ) d —P 1 -Q 1 -P 2   9

E 2 (Z 1 ) f —P 3   10

wherein:

Z 1 is a protogenic group;

E 1 , E 2 is an aromatic or aliphatic-containing moiety wherein at least one of E 1 and E 2 includes an aromatic substituted with Z 1 ;

X is an —OH, a halogen, an ester, or

d is the number of (SO 2 X) functional groups attached to E 1 ,

f is the number of (SO 2 X) functional groups attached to E 2 ;

P 1 , P 2 , P 3 are each independently absent, —O—, —S—, —O—, —SO 2 —,—CO—, —NH—, NR 2 —, —R 3 —, and

R 2 is C 1-25 alkyl, C 1-25 aryl or C 1-25 arylene;

R 3 is C 1-25 alkylene, C 1-25 perfluoroalkylene, perfluoroalkyl ether, alkyl ether, or C 1-25 arylene;

R 4 is trifluoromethyl, C 1-25 alkyl, C 1-25 perfluoroalkylene, C 1-25 aryl, or another E 1 group; and

Q 1 is a fluorinated cyclobutyl moiety,

with the proviso that when d is greater than zero, f is zero and when f is greater than zero, d is zero.

18. The method of claim 12 , wherein said solvent is selected from the group consisting of water, N,N-dimethyl formamide, N,N-dimethyl acetamide, N-methylpyrolidinone, dimethylsulfoxide, fluorinated hydrocarbon, chlorinated hydrocarbon, ketones, tetrahydrofuran, chlorinated aromatics, chlorofluorinated hydrocarbon and mixtures thereof.

19. The method of claim 12 , wherein said temperature is at least 80° C. and said voltage is at least 100 V per millimeter of electrode separation.

20. The method of claim 12 , wherein after steps a) through g), said film layer is removed from between said electrodes and contacted with boiling water, steam or solvent vapors.

21. The method of claim 12 wherein the distance between said electrodes is about 1 to about 1.5 mm, and said voltage is about 1000 volt.

Assignments (8)