Organo-copper reagents for attaching perfluorosulfonic acid groups to polyolefins

1. A method of forming an ion conducting polymeric membrane for fuel cells, the method comprising:

a) reacting a polymer having formula 1 with a compound having formula 2

in the presence of an organocuprate compound to form a polymer having formula (3):

wherein:

X 1 , X 2 are each independently a halogen;

R 1 , R 2 , and R 3 are each independently hydrogen or C 1 -C 6 alkyl;

R 4 , R 5 are each independently phenyl, C 1 -C 12 alkyl, C 1 -C 12 alkyl ether, C 1 -C 12 fluoroalkyl, C 1 -C 12 fluoroalkyl ether, C 7 -C 30 arylalkyl, C 7 -C 30 phenylalkyl, C 7 -C 12 aryl, —(CH 2 ) r — or —(CF 2 ) p —O—(CF 2 ) q —;

Z is hydrogen or a metal;

n is a number from 10 to 500; and

p, q, r are each independently an integer from 2 to 10; and

b) forming a membrane from the polymer having formula (3).

2. The method of claim 1 wherein the organocuprate compound is formed via the reaction of alkyl lithium with copper (I) iodide via the following synthetic scheme:

2R—Li+CuI→R 2 Cu ⊖ Li ⊕ +LiI

wherein R is C 1 -C 12 alkyl.

3. The method of claim 1 wherein R 4 is —(CH 2 ) t — and t is an integer from 1 to 12.

4. The method of claim 1 wherein R 4 is

v is an integer from 0 to 12, and w is an integer from 0 to 12.

5. The method of claim 1 wherein R 5 is —(CF 2 ) p —O—(CF 2 ) q — or —(CH 2 ).

6. The method of claim 1 wherein R 5 is —CF 2 CF 2 —O—CF 2 CF 2 —.

7. The method of claim 1 wherein the membrane is formed by melt casting, spin coating, solution casting, extrusion casting, calendaring, spray coating, blow molding, fixed gap coating, or hot pressing and the like.

8. The method of claim 1 wherein the thickness of the membrane is from 2 micrometers to about 200 micrometers.

9. The method of claim 1 further comprising positioning the membrane between an anode layer and a cathode layer.