Polyethersulfone compositions
View Patent ↗Novel polyethersulfone compositions have been discovered which incorporate structural subunits derived from sulfonated bis(halophenyl)sulfones, dihydroxy terphenyls, and/or bis(hydroxyphenyl)pyridines. The sulfonated polyethersulfones show promise as materials for use in polymer electrolyte membranes (PEMs) in fuel cells owing to their high proton conductivities (0.02-0.07 S/cm at 20° C. and 100 percent humidity). In addition, a novel unsulfonated thermoplastic polyethersulfone comprising structural subunits derived from a non-sulfonated bis(halophenyl)sulfone bis4-fluorophenyl)sulfone and 4,4′-dihydroxyphenyl-2,6-pyridine (CAS No. 171820-16-9) is disclosed.
1. A polymer composition comprising structural units I
wherein R 1 , R 2 , and R 3 are independently at each occurrence halogen, a C 1 -C 10 aliphatic radical, a C 3 -C 12 cycloaliphatic radical, or a C 3 -C 15 aromatic radical; X is N, or + NH; Q is independently at each occurrence hydrogen, a metal cation, a non-metallic inorganic cation, or an organic cation; “a” is independently at each occurrence an integer from 0 to 4; and “b” and “c” are independently at each occurrence integers from 0 to 3.
2. The polymer composition according to claim 1 , further comprising subunits derived from 1,3-(bis(4-hydroxyphenyl))benzene.
3. The polymer composition according to claim 1 , further comprising subunits derived from 1,4-(bis(4-hydroxyphenyl))benzene.
4. The polymer composition according to claim 1 , comprising subunits derived from 2,6-(bis(4-hydroxyphenyl))pyridine.
5. The polymer composition according to claim 1 , comprising subunits derived from the disulfonated bis(4-halophenyl)sulfone II
wherein Z is independently at each occurrence fluoro, chloro, or bromo; R 3 is independently at each occurrence halogen, a C 1 -C 10 aliphatic radical, a C 3 -C 12 cycloaliphatic radical, or a C 3 -C 15 aromatic radical; Q is independently at each occurrence hydrogen, a metal cation, a non-metallic inorganic cation, or an organic cation; and “c” is independently at each occurrence an integer from 0 to 3.
6. A polymer composition comprising structural units III
wherein R 1 , R 2 , and R 3 are independently at each occurrence halogen, a C 1 -C 10 aliphatic radical, a C 3 -C 12 cycloaliphatic radical, or a C 3 -C 15 aromatic radical; “a” is independently at each occurrence an integer from 0 to 4; and “b” and “c” are independently at each occurrence integers from 0 to 3.
7. The polymer composition according to claim 6 further comprising subunits IV
wherein R 3 is independently at each occurrence halogen, a C 1 -C 10 aliphatic radical, a C 3 -C 12 cycloaliphatic radical, or a C 3 -C 15 aromatic radical; Q is independently at each occurrence hydrogen, a metal cation, a non-metallic inorganic cation, or an organic cation; and “c” is independently at each occurrence an integer from 0 to 3.
8. The polymer composition according to claim 7 comprising subunits derived from 2,6-(bis(4-hydroxyphenyl))pyridine.
9. The polymer composition according to claim 7 comprising subunits derived from at least one bis(halophenyl)sulfone selected from the group consisting of bis(4-chlorophenyl)sulfone and bis(4-fluorophenyl)sulfone.
10. An article comprising a polyethersulfone composition, said composition comprising structural units I
wherein R 1 , R 2 and R 3 are independently at each occurrence halogen, a C 1 -C 10 aliphatic radical, a C 3 -C 12 cycloaliphatic radical, or a C 3 -C 15 aromatic radical; X is N, or + NH; Q is independently at each occurrence hydrogen, a metal cation, a non-metallic inorganic cation, or an organic cation; “a” is independently at each occurrence an integer from 0 to 4; “b” and “c” are independently at each occurrence integers from 0 to 3.
11. The article according to claim 10 comprising at least one film layer comprising said polyethersulfone composition.
12. The article according to claim 11 which is a membrane.
13. The article according to claim 12 which is a fuel cell membrane.
14. A method for making a polymer composition comprising structural units I
wherein R 1 , R 2 , and R 3 are independently at each occurrence halogen, a C 1 -C 10 aliphatic radical, a C 3 -C 12 cycloaliphatic radical, or a C 3 -C 15 aromatic radical; X is N, + NH, CH, or C; Q is independently at each occurrence hydrogen, a metal cation, a non-metallic inorganic cation, or an organic cation; “a” is independently at each occurrence an integer from 0 to 4 “b” and “c” are independently at each occurrence integers from 0 to 3;
said method comprising:
contacting in a solvent in the presence of a base under reactive conditions
(a) at least one dihydroxy aromatic compound having structure V
wherein R 1 , and R 2 are independently at each occurrence halogen, a C 1 -C 10 aliphatic radical, a C 3 -C 12 cycloaliphatic radical, or a C 3 -C 15 aromatic radical; X is N, or + NH; and “a” is independently at each occurrence an integer from 0 to 4; “b” is independently at each occurrence integer from 0 to 3;
with
(b) at least one disulfonated bis(4-halophenyl)sulfone having structure II
wherein, in structure II, Z is independently at each occurrence fluoro, chloro, or bromo; R 3 is independently at each occurrence halogen, a C 1 -C 10 aliphatic radical, a C 3 -C 12 cycloaliphatic radical, or a C 3 -C 15 aromatic radical; Q is independently at each occurrence hydrogen, a metal cation, a non-metallic inorganic cation, or an organic cation; and “c” is independently at each occurrence an integer from 0 to 3;
and, optionally,
(c) one or more dihalodiphenyl sulfones having structure VI
wherein, in structure VI, Z is independently at each occurrence fluoro, chloro, or bromo; R 3 is independently at each occurrence halogen, a C 1 -C 10 aliphatic radical, a C 3 -C 12 cycloaliphatic radical, or a C 3 -C 15 aromatic radical; and “c” is independently at each occurrence an integer from 0 to 4.
15. The method according to claim 14 wherein said at least one dihydroxy aromatic compound comprises at least one bisphenol chosen from 1,3-(bis(4-hydroxyphenyl))benzene, 1,4-(bis(4-hydroxyphenyl))benzene, and 2,6-(bis(4-hydroxyphenyl))pyridine.
16. The method according to claim 14 wherein said at least one dihydroxy aromatic compound comprises 2,6-(bis(4-hydroxyphenyl))pyridine.
17. A polymer composition comprising structural units VII
wherein X is N, or + NH; and Q is independently at each occurrence hydrogen, a metal cation, a non-metallic inorganic cation, or an organic cation.
18. The polymer composition according to claim 17 , comprising subunits derived from 2,6-(bis(4-hydroxyphenyl))pyridine.
19. An article comprising a polyethersulfone composition, said composition comprising structural units VII
wherein X is N, or + NH; and Q is independently at each occurrence hydrogen, a metal cation, a non-metallic inorganic cation, or an organic cation.
20. The article according to claim 19 comprising at least one film layer comprising said polyethersulfone composition.
21. The article according to claim 19 which is a membrane.
22. An article comprising a polyethersulfone composition, said composition comprising structural units VIII
23. The article according to claim 22 comprising at least one film layer comprising said polyethersulfone composition.
24. The article according to claim 22 which is a membrane.
25. The article according to claim 22 which is a molded article.