Polybenzimidazoles and methods of making and using thereof
Disclosed are polybenzimidazoles containing sulfonyl groups. The polymers can be synthesized in Eaton's reagent from 3,3′,4,4′-tetraaminodiphenylsulfone, which itself can be synthesized from 4,4′-dichlorodiphenylsulfone. Methods of synthesizing the polymers are disclosed. The disclosed polymers can be used for high temperature H 2 /CO 2 separation membranes and other uses.
1. A polymer comprising Formula I:
wherein
A is an aryl or heteroaryl containing moiety where the aryl containing moiety is chosen from one or more of
and the heteroaryl containing moiety is chosen from one or more of
R 1 is H or substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted COC 1-20 alkyl, substituted or unsubstituted CO 2 C 1-20 alkyl, substituted or unsubstituted CO 2 aryl, substituted or unsubstituted CO 2 C 1-6 alkylaryl, substituted or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 2-20 alkynyl, substituted or unsubstituted C 1-20 heteroalkyl, substituted or unsubstituted C 2-20 heteroalkenyl, substituted or unsubstituted C 2-20 heteroalkynyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, or mixtures thereof, wherein the substituted groups are substituted with one or more of alkyl, halogenated alkyl, alkoxy, alkenyl, alkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone, nitro, silyl, sulfo-oxo, sulfonyl, sulfone, sulfoxide, or thiol groups;
each R 2 is, independent of any other, substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 2-20 alkynyl, substituted or unsubstituted C 1-20 alkoxyl, substituted or unsubstituted C 1-20 heteroalkyl, substituted or unsubstituted C 2-20 heteroalkenyl, substituted or unsubstituted C 2-20 heteroalkynyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, amino, hydroxyl, halide, or mixtures thereof, wherein the substituted groups are substituted with one or more of alkyl, halogenated alkyl, alkoxy, alkenyl, alkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone, nitro, silyl, sulfo-oxo, sulfonyl, sulfone, sulfoxide, or thiol groups;
R 3 is H, substituted or unsubstituted C 1-20 alkyl, or substituted or unsubstituted COC 1-20 alkyl, wherein the substituted groups are substituted with one or more of alkyl, halogenated alkyl, alkoxy, alkenyl, alkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone, nitro, silyl, sulfo-oxo, sulfonyl, sulfone, sulfoxide, or thiol groups;
each R 4 is, independent of any other, substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 2-20 alkynyl, substituted or unsubstituted C 1-20 alkoxyl, substituted or unsubstituted C 1-20 heteroalkyl, substituted or unsubstituted C 2-20 heteroalkenyl, substituted or unsubstituted C 2-20 heteroalkynyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, amino, hydroxyl, halide, or mixtures thereof, wherein the substituted groups are be substituted with one or more of alkyl, halogenated alkyl, alkoxy, alkenyl, alkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone, nitro, silyl, sulfo-oxo, sulfonyl, sulfone, sulfoxide, or thiol groups;
each m is from 0 to 4;
each p is from 0 to 4; and
n is from 2 to 200,000.
2. The polymer of claim 1 , wherein the polymer is a homopolymer.
3. The polymer of claim 1 , wherein the polymer is a graft or block copolymer.
4. The polymer of claim 1 , wherein A is the aryl containing moiety.
5. The polymer of claim 1 , wherein A is the aryl containing moiety and is chosen from one or more of the following:
6. The polymer of claim 1 , wherein m is 0.
7. The polymer of claim 1 , wherein A is the heteroaryl containing moiety.
8. The polymer of claim 1 , wherein R 1 is hydrogen.
9. The polymer of claim 1 , wherein R 1 is C 1-6 alkyl, COC 1-6 alkyl, CO 2 C 1-6 alkyl, C 1-6 haloalkyl, COC 1-6 haloalkyl, CO 2 C 1-6 haloalkyl, CO 2 C 1-6 aryl, or CO 2 C 1-6 alkylaryl.
10. The polymer of claim 1 , wherein the polymer comprises the formula:
11. The polymer of claim 1 , wherein the polymer is crosslinked.
12. A method of synthesizing a polymer, comprising: contacting 3,3′,4,4′-tetraaminodiphenylsulfone with a polycarboxylic acid, salt thereof, or activated ester thereof, in the presence of phosphorus pentoxide and methanesulfonic acid, wherein the 3,3′,4,4′-tetraaminodiphenylsulfone is synthesized by contacting dichlorodiphenylsulfone with a nitration reagent, to thereby provide a dinitrodichlorodiphenylsulfone, contacting the dinitrodichlorodiphenylsulfone with an amination reagent, to thereby provide dinitrodiaminodiphenylsulfone, and contacting the dinitrodiaminodiphenylsulfone with a reducing reagent, to thereby provide the 3,3′,4,4′-tetraaminodiphenylsulfone.
13. The method of claim 12 , wherein 3,3′,4,4′-tetraaminodiphenylsulfone is contacted with an aryl or heteroaryl dicarboxylic acid, salt thereof, or activated ester thereof.
14. The method of claim 13 , wherein 3,3′,4,4′-tetraaminodiphenylsulfone is contacted with the aryl dicarboxylic acid, salt thereof, or activated ester thereof and the aryl dicarboxylic acid, salt thereof, or activated ester thereof is chosen from one or more of the following compounds:
wherein
each R 2 is, independent of any other, substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 2-20 alkynyl, substituted or unsubstituted C 1-20 alkoxyl, substituted or unsubstituted C 1-20 heteroalkyl, substituted or unsubstituted C 2-20 heteroalkenyl, substituted or unsubstituted C 2-20 heteroalkynyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, amino, hydroxyl, halide, or mixtures thereof, wherein the substituted groups are substituted with one or more of alkyl, halogenated alkyl, alkoxy, alkenyl, alkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone, nitro, silyl, sulfo-oxo, sulfonyl, sulfone, sulfoxide, or thiol groups;
R 3 is H, substituted or unsubstituted C 1-20 alkyl, or substituted or unsubstituted COC 1-20 alkyl, wherein the substituted groups are substituted with one or more of alkyl, halogenated alkyl, alkoxy, alkenyl, alkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone, nitro, silyl, sulfo-oxo, sulfonyl, sulfone, sulfoxide, or thiol groups;
each m is from 0 to 4; and
each Y is, independent of any other, H, Na, K, NH 4 , succinimide, or carbodiimide.
15. The method of claim 14 , wherein the aryl dicarboxylic acid is chosen from one or more of the following:
16. The method of claim 14 , wherein m is 0 and Y is H.
17. The method of claim 13 , wherein 3,3′,4,4′-tetraaminodiphenylsulfone is contacted with the heteroaryl dicarboxylic acid, salt thereof, or activated ester thereof and the heteroaryl dicarboxylic acid, salt thereof, or activated ester thereof is chosen from one or more of the following compounds:
wherein
each R 4 is, independent of any other, substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 2-20 alkynyl, substituted or unsubstituted C 1-20 alkoxyl, substituted or unsubstituted C 1-20 heteroalkyl, substituted or unsubstituted C 2-20 heteroalkenyl, substituted or unsubstituted C 2-20 heteroalkynyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, amino, hydroxyl, halide, or mixtures thereof, wherein the substituted groups are substituted with one or more of alkyl, halogenated alkyl, alkoxy, alkenyl, alkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone, nitro, silyl, sulfo-oxo, sulfonyl, sulfone, sulfoxide, or thiol groups;
each p is from 0 to 4; and
each Y is, independent of any other, H, Na, K, NH 4 , succinimide, or carbodiimide.
18. The method of claim 12 , further comprising crosslinking the polymer.
19. A method of synthesizing 3,3′,4,4′-tetraaminodiphenylsulfone, comprising:
contacting dichlorodiphenylsulfone with a nitration reagent, to thereby provide a dinitrodichlorodiphenylsulfone;
contacting the dinitrodichlorodiphenylsulfone with an amination reagent, to thereby provide dinitrodiaminodiphenylsulfone;
contacting the dinitrodiaminodiphenylsulfone with a reducing reagent, to thereby provide 3,3′,4,4′-tetraaminodiphenylsulfone.
20. The method of claim 19 , wherein the nitration reagent comprises nitric acid, the amination reagent comprises ammonium, and the reducing reagent comprises hydrogen with a palladium catalyst.
21. A method of separating H 2 and CO 2 from a stream, comprising: contacting the stream with a polymer of claim 1 .