Functional polyarylethers

1. A functional polyarylether comprising structural units of formula I

wherein

X is selected OOCR 6 , R 7 , NR 4 COR 5 , NR 4 CONR 5 R 6 , NR 4 COOR 5 R 6 ,

 and combinations thereof;

R 1 , R 2 and R 3 are independently at each occurrence CH 2 X, H, halo, cyano, nitro, a C 1 -C 12 aliphatic radical, a C 3 -C 12 cycloaliphatic radical, a C 3 -C 12 aromatic radical or a combination thereof;

R 4 and R 5 are independently H, a C 1-10 aliphatic radical, a C 3 -C 12 cycloaliphatic radical, a C 3 C 12 aromatic radical, or a combination thereof;

R 6 is H, a C 2-10 aliphatic radical, a C 3 -C 12 cycloaliphatic radical, a C 3 -C 12 aromatic radical or a combination thereof;

R 7 is OCH 2 CH 2 (OCH 2 CH 2 ) q OCH 3 or OOCCH 2 (OCH 2 CH 2 ) q OCH3;

Q is a direct bond, O, S, alkenyl, alkynyl, a C 1 -C 12 aliphatic radical, a C 3 C 12 cycloaliphatic radical, a C 3 -C 12 aromatic radical or a combination thereof;

Z is a direct bond, O, S, SO, SO 2 , CO, phenylphospinyl oxide, alkenyl, alkynyl, a C 1 -C 12 aliphatic radical, a C 3 -C 12 cycloaliphatic radical, a C 3 -C 12 aromatic radical or a combination thereof;

a, b, and c are independently 1 or 2;

m, n and p are independently 0 or 1; and

q is 1-8;

with the proviso that when Z is C(CH 3 ) 2 , X is not Br or OAc.

2. A functional polyarylether according to claim 1 , wherein Z is SO 2 .

3. A functional polyarylether according to claim 1 , wherein X is NR 4 COR 5 .

4. A functional polyarylether according to claim 1 , wherein Q is a direct bond.

5. A functional polyarylether according to claim 1 , wherein Q is C(CH 3 ) 2 .

6. A functional polyarylether according to claim 1 , comprising structural units of formula III

wherein

X is OOCR 5 , OR 6 or NR 4 COR 5 .

7. A functional polyarylether according to claim 1 , wherein

X is selected from OCH 2 CH 2 (OCH 2 CH 2 ) q OCH 3 , OOCCH 2 (OCH 2 CH 2 ) q OCH 3 ,

and combinations thereof.

8. A functional polyarylether according to claim 1 , wherein

X is OOCCH 3 or

R 1 and R 2 are independently H or CH 3 ; and

Q is a direct bond or C(CH 3 ) 2 .

9. A functional polyarylether according to claim 1 , having structural units of formula

10. A functional polyarylether according to claim 1 , having structural units of formula

11. A functional polyarylether according to claim 1 , having structural units of formula

12. A functional polyarylether according to claim 1 , having structural units of formula

13. A functional polyarylether according to claim 1 , having structural units of formula

14. A membrane comprising functional polyarylether comprising structural units of formula I

wherein

X is selected OOCR 6 , R 7 , NR 4 COR 5 , NR 4 CONR 5 R 6 , NR 4 COOR 5 R 6 ,

 and combinations thereof;

R 1 , R 2 and R 3 are independently at each occurrence CH 2 X, H, halo, cyano, nitro, a C 1 -C 12 aliphatic radical, a C 3 -C 12 cycloaliphatic radical, a C 3 -C 12 aromatic radical or a combination thereof;

R 4 and R 5 are independently H, a C 1-10 aliphatic radical, a C 3 -C 12 cycloaliphatic radical, a C 3 -C 12 aromatic radical, or a combination thereof;

R 6 is H, C 2-10 aliphatic radical, a C 3 -C 12 cycloaliphatic radical, a C 3 -C 12 aromatic radical or a combination thereof;

R 7 is OCH 2 CH 2 (OCH 2 CH 2 ) q OCH 3 or OOCCH 2 (OCH 2 CH 2 ) q OCH 3 ;

Q is a direct bond, O, S, alkenyl, alkynyl, a C 1 -C 12 aliphatic radical, a C 3 -C 12 cycloaliphatic radical, a C 3 -C 12 aromatic radical or a combination thereof;

Z is a direct bond, O, S, SO, SO 2 , CO, phenylphospinyl oxide, alkenyl, alkynyl, a C 1 -C 12 aliphatic radical, a C 3 -C 12 cycloaliphatic radical, a C 3 -C 12 aromatic radical or a combination thereof;

a, b, and c are independently 1 or 2;

m, n and p are independently 0 or 1; and

q is 1-8.

15. A separation unit comprising a plurality of hollow fiber membranes, wherein at least one of the plurality of membranes comprises a functional polyarylether according to claim 1 .

16. A hemodialysis apparatus comprising a membrane according to claim 14 .

17. A bioseparation apparatus comprising a membrane according to claim 14 .

18. A process comprising mixing a brominating agent with a methyl polyarylether of formula

to form a bromomethyl polyarylether;

wherein

R 1 , R 2 and R 3 are independently at each occurrence CH 2 X, H, halo, cyano, nitro, a C 1 -C 12 aliphatic radical, a C 3 -C 12 cycloaliphatic radical, a C 3 -C 12 aromatic radical or a combination thereof;

Q is a direct bond O, S, alkenyl, alkynyl, a C 1 -C 12 aliphatic radical, a C 3 -C 12 cycloaliphatic radical, a C 3 -C 12 aromatic radical or a combination thereof;

Z is a direct bond O, S, SO, SO 2 , phenylphospinyl oxide, alkenyl, alkynyl, a C 1 -C 12 aliphatic radical, a C 3 -C 12 cycloaliphatic radical, a C 3 -C 12 aromatic radical or a combination thereof;

a, b, and c are independently 1 or 2; and

m, n and p are independently 0 or 1; and

combining the bromomethyl polyarylether with a nucleophile under basic conditions to form a functional polvarylether;

wherein the nucleophile is selected from the group consisting of HOOCR 6 ; HR 7 , NR 4 COR 5 , HNR 4 CONR 5 R 6 , HNR 4 COOR 5 R 6 ,

 and combinations thereof;

R 4 and R 5 are independently H, C 1-10 aliphatic radical, C 3 -C 12 cycloaliphatic radical, a C 3 -C 12 aromatic radical, or a combination thereof;

R 6 is H, C 2-10 aliphatic radical, a C 3 -C 12 cycloaliphatic radical, a C 3 -C 12 aromatic radical or a combination thereof;

R 7 is OCH 2 CH 2 (OCH 2 CH 2 ) q OCH 3 or OOCCH 2 (OCH 2 CH 2 ) q OCH 3 ; and q is 1-8.

19. A process according to claim 18 , wherein the mixture is irradiated to form the bromomethyl polyarylether.

20. A process according to claim 18 , wherein the bromomethyl polyarylether is formed at a temperature ranging from about 150° C.