Oxygen permeable polymers, ionomers and methods of making the same

1. An oxygen permeable polymer having the following formula:

wherein R s is a non-sulfonyl halide portion of a sulfonyl halide monomer or polymer; X P is —NH or —NHCO; A is an optionally substituted alkyl; L is 0, 1 or 2; m is 2 or 3; Z is H or CH 3 ; and n is 5-m.

2. The oxygen permeable polymer of claim 1 , produced from reacting the sulfonyl halide monomer or polymer with an oxygen absorbing compound having the following formula:

wherein X is —NH 2 , —COOH, —COOR or —COH; and R is ether or ester.

3. The oxygen permeable polymer of claim 2 , wherein the oxygen absorbing compound is a benzoic acid-based compound and the sulfonyl halide monomer or polymer is treated with ammonia to convert a sulfonyl halide portion to a sulfonamide prior to reacting with the oxygen absorbing compound.

4. The oxygen permeable polymer of claim 3 , wherein the oxygen absorbing compound is gallic acid, an ester of gallic acid, an ether of gallic acid, 2,4,5-trihydroxybenzoic acid, 2,3,4-trihydroxybenzoic acid, or 3,4,5-trihydroxybenzoic acid.

5. The oxygen permeable polymer of claim 2 , wherein the oxygen absorbing compound comprises 5-(2-aminoethyl)-pyrogallol, 5-(aminomethyl)benzene-1,2,4-triol, 5-(aminomethyl)benzene-1,2,3-triol, 5-(2-aminoethyl)-6-methylbenzene-1,2,4-triol, 5-(2-aminoethyl)-3-methylbenzene-1,2,4-triol, 5-(2-aminoethyl)-3,6-dimethylbenzene-1,2,4-triol, 5-(2-amino-1-hydroxyethyl)-1,2,4-benzenetriol, 4-aminobenzene-1,2,3-triol, 2,3,5-trihydroxyphenethylamine, 3,4-dihydroxyphenethylamine, 3,4,5-trihydroxyphenethylamine, 2-hydroxydopamine or 5-hydroxydopamine.

6. The oxygen permeable polymer of claim 2 , wherein the oxygen absorbing compound is an aldehyde-based compound and the sulfonyl halide monomer or polymer is treated with ammonia to convert a sulfonyl halide portion to a sulfonamide prior to reacting with the oxygen absorbing compound.

7. The oxygen permeable polymer of claim 6 , wherein the oxygen absorbing compound is 3,4,5-trihydroxybenzaldehyde, 2,4,5-trihydroxybenzaldehyde, 2,3,4-trihydroxybenzaldehyde, 2,4,6-trihydroxybenzaldehyde, 2,3,6-trihydroxybenzaldehyde, 2,3,5-trihydroxybenzaldehyde or 2,3,4-trihydroxyacetophenone.

8. An air separation device comprising the oxygen permeable polymer of claim 1 .

9. An electrode of an electrochemical device comprising an ionomer and the oxygen permeable polymer of claim 1 .

10. A battery comprising the electrode of claim 9 .

11. A fuel cell comprising the electrode of claim 9 .

12. The oxygen permeable polymer of claim 1 , further comprising a proton conductor SO 3 H as shown in the following formula:

13. A method of making the oxygen permeable polymer of claim 1 , comprising:

reacting under a mild base condition a sulfonyl halide monomer or polymer (1) with an oxygen absorbing compound (2) to produce the oxygen permeable polymer (3):

wherein:

R s is a non-sulfonyl halide portion of the sulfonyl halide monomer or polymer and Y is F or Cl;

X is —NH 2 , —COOH, —COOR, or —COH and R is an ester or an ether;

A is an optionally substituted alkyl;

L is 0, 1 or 2;

m is 2 or 3;

Z is H or CH 3 ;

n is 5-m; and

X P is —NH or —NHCO; and

when X is —COOH, —COOR or —COH, the reacting comprises first treating the sulfonyl halide monomer or polymer with ammonia to convert a sulfonyl halide portion to a sulfonamide.

14. The method of claim 13 , wherein the reacting under a mild base condition comprises:

soaking the sulfonyl halide monomer or polymer or the sulfonamide in a solvent;

adding a base to form the mild base condition;

adding the oxygen absorbing compound; and

reacting at a temperature of 100° C. or less for a period of time.

15. The method of claim 14 , wherein the period of time is greater than twelve hours.

16. The method of claim 13 , wherein X is —COOH or —COOR and the oxygen absorbing compound is gallic acid, an ester of gallic acid, an ether of gallic acid, 2,4,5-trihydroxybenzoic acid, 2,3,4-trihydroxybenzoic acid, or 3,4,5-trihydroxybenzoic acid.

17. The method of claim 13 , wherein X is —COH and the oxygen absorbing compound is 3,4,5-trihydroxybenzaldehyde, 2,4,5-trihydroxybenzaldehyde, 2,3,4-trihydroxybenzaldehyde, 2,4,6-trihydroxybenzaldehyde, 2,3,6-trihydroxybenzaldehyde, 2,3,5-trihydroxybenzaldehyde or 2,3,4-trihydroxyacetophenone.

18. The method of claim 13 , wherein X is —NH 2 and the oxygen absorbing compound comprises 5-(2-aminoethyl)-pyrogallol, 5-(aminomethyl)benzene-1,2,4-triol, 5-(aminomethyl)benzene-1,2,3-triol, 5-(2-aminoethyl)-6-methylbenzene-1,2,4-triol, 5-(2-aminoethyl)-3-methylbenzene-1,2,4-triol, 5-(2-aminoethyl)-3,6-dimethylbenzene-1,2,4-triol, 5-(2-amino-1-hydroxyethyl)-1,2,4-benzenetriol, 4-aminobenzene-1,2,3-triol, 2,3,5-trihydroxyphenethylamine, 3,4-dihydroxyphenethylamine, 3,4,5-trihydroxyphenethylamine, 2-hydroxydopamine or 5-hydroxydopamine.

19. A method of making an oxygen-conducting and proton-conducting ionomer, comprising the method of claim 13 , and further comprising:

adding a proton conducting functional group to an unreacted portion of the sulfonyl halide monomer or polymer, wherein the oxygen-conducting and proton-conducting ionomer has the following formula:

20. The method of claim 19 , wherein adding the proton conducting functional group comprises:

hydrolyzing the unreacted portion of the sulfonyl halide monomer or polymer with a base and an alcohol;

ion exchanging the hydrolyzed unreacted portion of the sulfonyl halide monomer or polymer with an acid to form an oxygen permeable polymer and proton conducting material.