Radio-opaque polymer biomaterials

1. An implantable, radio-opaque medical device comprising a radio-opaque, iodine- or bromine-substituted polymer described by the formula VIII:

wherein X 1 and X 2 are independently I or Br; Y1 and Y2 are independently 0,1, or 2; R 9 and R 12 are independently an alkyl, aryl, or alkylaryl group containing up to 18 carbon atoms; A is:

wherein R 8 is selected from the group consisting of saturated and unsaturated, substituted and unsubstituted alkyl, aryl, and alkylaryl groups containing up to 18 carbon atoms; R 8 , R 9 , or R 12 is optionally bromine- or iodine-substituted; and g is between 0 and 0.99, inclusive.

2. The implantable, radio-opaque medical device of claim 1 wherein g is zero.

3. The implantable, radio-opaque medical device of claim 1 wherein R 9 has the structure:

wherein R 0 is selected from the group consisting of —CH═CH—, —CHJ 1 -CHJ 2 -, and (—CH 2 —) m , R 4 is selected from the group consisting of —CH═CH—, —CHJ 1 -CHJ 2 -, and (—CH 2 —) a , wherein m and a are independently between 0 and 8, inclusive; J 1 and J 2 are independently Br or I; and Z is selected from the group consisting of hydrogen, a free carboxylic acid group, and carboxylic acid esters and amides, wherein said ester and amides are selected from the group consisting of esters and amides of straight and branched alkyl and alkyaryl groups containing up to 18 carbon atoms and esters and amides of biologically and pharmaceutically active compounds.

4. The implantable, radio-opaque medical device of claim 3 wherein g is greater than zero and R 12 has the structure:

wherein R 0 is selected from the group consisting of —CH═CH—, —CHJ 1 -CHJ 2 -, and (—CH 2 —)m, R 4 is selected from the group consisting of —CH═CH—, —CHJ 1 -CHJ 2 -, and (—CH 2 —) a , wherein m and a are independently between 0 and 8, inclusive; J 1 and J 2 are independently Br or I; and Z is selected from the group consisting of hydrogen, a free carboxylic acid group, and carboxylic acid esters and amides, wherein said ester and amides are selected from the group consisting of esters and amides of straight and branched alkyl and alkyaryl groups containing up to 18 carbon atoms and esters and amides of biologically and pharmaceutically active compounds.

5. The implantable, radio-opaque medical device of claim 4 wherein R 9 has the structure:

and R 12 has the structure:

wherein a and c are two and b and d are one.

6. The implantable, radio-opaque medical device of claim 4 wherein each Z of R 9 and R 12 is an ester of a carboxylic acid; wherein each ester group is independently selected from the group consisting of ethyl, butyl, hexyl, octyl, and benzyl groups.

7. The implantable, radio-opaque medical device of claim 1 wherein A is:

8. The implantable, radio-opaque medical device of claim 1 wherein A is:

9. The implantable, radio-opaque medical device of claim 8 wherein R 8 is selected from the group consisting of saturated and unsaturated, substituted and unsubstituted alkyl groups containing up to 8 carbon atoms.

10. The implantable, radio-opaque medical device of claim 9 wherein R 8 is selected from the group consisting of —CH 2 —C(═O)—, —CH 2 CH 2 —C(═O)—, CH═CH—, and (—CH 2 —) Q , wherein Q is between 0 and 8, inclusive.

11. The implantable, radio-opaque medical device of claim 8 wherein R 8 is selected from the group consisting of saturated and unsaturated, substituted and unsubstituted aryl and alkyaryl groups containing from 13 to 20 carbon atoms.

12. The implantable, radio-opaque medical device of claim 8 wherein Y 1 +Y 2 is greater than zero.

13. The implantable, radio-opaque medical device of claim 1 wherein said polymer further comprises one or more poly(alkylene oxide) blocks.

14. The implantable, radio-opaque medical device of claim 1 wherein said medical device is formed from said polymer.

15. The implantable, radio-opaque medical device of claim 1 wherein said medical device is coated with said polymer.

16. The implantable, radio-opaque medical device of claim 1 wherein said device comprises a radio-opaque, biocompatible stent comprising said polymer.

17. The implantable, radio-opaque medical device of claim 14 wherein said device is a radio-opaque, biocompatible stent.

18. An implantable, radio-opaque medical device comprising a radio-opaque, iodine- or bromine-substituted polymer described by the formula VIIIa:

wherein:

(a) R 5 , R 6 , R 16 , and R 17 are each independently selected from the group consisting of H, Br, I and straight and branched alkyl groups having up to 18 carbon atoms; provided that when g is zero, R 5 and R 6 are independently Br or I unless R 15 is —CJ 1 -CJ 2 -;

(b) R 15 is selected from the group consisting of (—CH 2 —) c , —CH═CH—, and —CJ 1 -CJ 2 -, wherein -J 1 and J 2 are independently Br or I and c is between 0 and 8, inclusive;

(c) X2 is Br or I, and Y2 is 0, 1 or 2;

(d) Z is selected from the group consisting of hydrogen, a free carboxylic acid group or an ester or amide thereof;

(e) A is:

wherein R 8 is selected from the group consisting of saturated and unsaturated, substituted and unsubstituted alkyl, aryl, and alkylaryl groups containing up to 18 carbon atoms;

(f) each R 0 is independently —CH═CH— or (—CH 2 —) d , wherein d is between 0 and 8 inclusive; and

(g) g is greater than zero but less than one.

19. The implantable, radio-opaque medical device of claim 18 wherein R 0 or R 15 are (—CH 2 —) d or (—CH 2 —) c , respectively, wherein c or d are 0, and R 5 , R 6 , R 16 , and R 17 are independently hydrogen or a methyl group.

20. The implantable, radio-opaque medical device of claim 19 wherein R 5 , R 6 , R 16 , and R 17 are all hydrogen.

21. The implantable, radio-opaque medical device of claim 19 wherein one of R 5 and R 6 or R 16 and R 17 is hydrogen and the others are methyl.

22. The implantable, radio-opaque medical device of claim 18 wherein each Z is an ester of a carboxylic acid, wherein each ester group is independently selected from the group consisting of ethyl, butyl, hexyl, octyl, and benzyl groups.

23. The implantable, radio-opaque medical device of claim 22 wherein both R 0 and R 15 are (—CH 2 —) and each Z is an ethyl ester of a carboxylic acid.

24. The implantable, radio-opaque medical device of claim 16 wherein A is:

25. The implantable, radio-opaque medical device of claim 18 wherein A is:

26. The implantable, radio-opaque medical device of claim 25 wherein R 8 is selected from the group consisting of saturated and unsaturated, substituted and unsubstituted alkyl groups containing up to 8 carbon atoms.

27. The implantable, radio-opaque medical device of claim 26 wherein R 8 is selected from the group consisting of —CH 2 —C(═O)—, —CH 2 CH 2 —C(═O)—, CH═CH—, and (—CH 2 —) Q , wherein Q is between 0 and 8, inclusive.

28. The implantable, radio-opaque medical device of claim 25 wherein R 8 is selected from the group consisting of saturated and unsaturated, substituted and unsubstituted aryl and alkyaryl groups containing from 13 to 20 carbon atoms.

29. The implantable, radio-opaque medical device of claim 18 wherein said polymer further comprises one or more poly(alkylene oxide) blocks.

30. The implantable, radio-opaque medical device of claim 18 wherein Y 2 is 1 or 2.

31. The implantable, radio-opaque medical device of claim 18 wherein said medical device is formed from said polymer.

32. The implantable, radio-opaque medical device of claim 18 wherein said medical device is coated with said polymer.

33. The implantable, radio-opaque medical device of claim 18 wherein said device comprises a stent comprising said polymer.

34. The implantable, radio-opaque medical device of claim 31 wherein said device is a stent.