Radiopaque polymers for medical devices

1. A polymer composition comprising a crosslinked network, the network comprising:

a) a first repeating unit represented by one of Formula 1, 1-A, 1-B or 1-C:

wherein X is Br or I;

m is an integer from 3 to 5;

R 1 is substituted or unsubstituted C 2 -C 36 alkylene, C 2 -C 36 cycloalkylene, C 2 -C 36 alkenylene, C 2 -C 36 cycloalkenylene, C 2 -C 36 alkynylene, C 5 -C 36 arylene, or C 5 -C 36 heteroarylene;

L 1 is a single bond, —(CH 2 ) n —, —(HCCH) n —, —O—, —S—, —SO—, —SO 2 —, —SO 3 —, —OSO 2 —, —NR 2 —, —CO—, —COO—, —OCO—, —OCOO—, —CONR 3 —, —NR 4 CO—, —OCONR 5 —, —NR 6 COO—, or —NR 7 CONR 8 —;

Ar 1 is a C 5 -C 30 aryl or C 5 -C 30 heteroaryl that is substituted with three or more I, Br or Bi atoms;

each of R 2 -R 8 is independently hydrogen or C 1 -C 10 alkyl; and

n is an integer selected from the range of 1 to 16;

wherein the amount of the first repeating unit in the polymer composition is from 15 to 35 wt %; and

b) a second repeating unit represented by Formula 2:

wherein R 9 is

wherein R 11 is C 6 -C 20 alkylene and n 4 is an integer from 1 to 50; and

wherein the amount of the second repeating unit in the polymer composition is from 65 to 85 wt %.

2. The polymer composition of claim 1 , wherein the first repeating unit is represented by Formula 1-D,

wherein n is an integer from 1 to 8, each of X 1 -X 5 is iodine or hydrogen and at least three of X 1 -X 5 are iodine.

3. The polymer composition of claim 1 , wherein the second repeating unit is represented by Formula 2-B, where R 11 is C 6 -C 20 alkylene and n 4 is an integer from 1 to 25

4. The polymer composition of claim 1 , wherein the network further comprises an additional repeating unit represented by Formula 7:

where R 14 is substituted or unsubstituted C 2 -C 36 alkylene, C 2 -C 36 cycloalkylene, C 2 -C 36 alkenylene, C 2 -C 36 cycloalkenylene, C 2 -C 36 alkynylene, C 5 -C 36 arylene, C 5 -C 36 heteroarylene, an oligomeric polyester, an oligomeric polycarbonate, an oligomeric polyurethane,

wherein R 10 is C 4 -C 20 alkylene and n 3 is an integer from 1 to 50 or

wherein R 11 is C 3 -C 20 alkylene and n 4 is an integer from 1 to 50, and R 14 is other than R 9 .

5. The polymer composition of claim 4 , wherein the combined amount of the second repeating unit and the repeating unit of claim 4 is from 65 to 85 wt % of the polymer composition.

6. A polymer composition comprising a crosslinked network formed by polymerization of a monomer mixture comprising:

a) a first monomer having the general structure of one of Formula 8, 8-A, 8-B or 8-C

wherein X is Br or I;

m is an integer from 3 to 5;

wherein R 1 is substituted or unsubstituted C 2 -C 36 alkylene, C 2 -C 36 cycloalkylene, C 2 -C 36 alkenylene, C 2 -C 36 cycloalkenylene, C 2 -C 36 alkynylene, C 5 -C 36 arylene, or C 5 -C 36 heteroarylene;

L 1 is a single bond, —(CH 2 ) n —, —(HCCH) n —, —O—, —S—, —SO—, —SO 2 —, —SO 3 —, —OSO 2 —, —NR 2 —, —CO—, —COO—, —OCO—, —OCOO—, —CONR 3 —, —NR 4 CO—, —OCONR 5 —, —NR 6 COO—, or —NR 7 CONR 8 —;

Ar 1 is a C 5 -C 30 aryl or C 5 -C 30 heteroaryl that is substituted with three or more I, Br or Bi atoms; and

each of R 2 -R 8 is independently hydrogen or C 1 -C 10 alkyl;

n is an integer selected from the range of 1 to 16;

wherein the amount of the first monomer is from 15 to 35 wt % of the monomer mixture; and

b) a second monomer having the general structure of Formula 9

wherein R 9 is

wherein R 11 is C 6 -C 20 alkylene and n 4 is an integer from 1 to 50; and

wherein the amount of the second monomer is from 65 to 85 wt % of the monomer mixture.

7. The polymer composition of claim 6 , wherein the structure of the first monomer is given by Formula 13-A,

and at least three of X 1 -X 5 are iodine and n is an integer from 1 to 8.

8. The polymer composition of claim 6 wherein the second monomer has the structure of Formula 9-A where R 11 is C 6 -C 20 alkylene and n 4 is an integer from 1 to 25

9. The polymer composition of claim 6 , wherein the mixture further comprises a monomer having the general structure of Formula 12

wherein R 14 is substituted or unsubstituted C 2 -C 36 alkylene, C 2 -C 36 cycloalkylene, C 2 -C 36 alkenylene, C 2 -C 36 cycloalkenylene, C 2 -C 36 alkynylene, C 5 -C 36 arylene, C 5 -C 36 heteroarylene, an oligomeric polyester, an oligomeric polycarbonate, an oligomeric polyurethane,

wherein R 10 is C 4 -C 20 alkylene and n 3 is an integer from 1 to 50 or

wherein R 11 is C 3 -C 20 alkylene and n 4 is an integer from 1 to 50

and R 14 is other than R 9.

10. The polymer composition of claim 9 , wherein the amount of the combined amount of the second monomer and the monomer of claim 9 is from 65 to 85 wt % of the monomer mixture.

11. A method for making a polymer composition comprising a crosslinked network, the method comprising the steps of:

a) forming a monomer mixture comprising

i) a first monomer having the general structure of one of Formula 8, 8-A, 8-B or 8-C

wherein X is Br or I;

m is an integer from 3 to 5;

wherein R 1 is substituted or unsubstituted C 2 -C 36 alkylene, C 2 -C 36 cycloalkylene, C 2 -C 36 alkenylene, C 2 -C 36 cycloalkenylene, C 2 -C 36 alkynylene, C 5 -C 36 arylene, or C 5 -C 36 heteroarylene;

L 1 is a single bond, —(CH 2 ) n —, —(HCCH) n —, —O—, —S—, —SO—, —SO 2 —, —SO 3 —, —OSO 2 —, —NR 2 —, —CO—, —COO—, —OCO—, —OCOO—, —CONR 3 , —NR 4 CO—, —OCONR 5 —, —NR 6 COO—, or —NR 7 CONR 8 —;

Ar 1 is a C 5 -C 30 aryl or C 5 -C 30 heteroaryl that is substituted with three or more I, Br or Bi atoms; and

each of R 2 -R 8 is independently hydrogen or C 1 -C 10 alkyl;

n is an integer selected from the range of 1 to 16;

wherein the amount of the first monomer is from 15 to 35 wt % of the monomer mixture; and

ii) a second monomer having the general structure of Formula 9

wherein R 9 is

wherein R 11 is C 6 -C 20 alkylene and n 4 is an integer from 1 to 50; and R 14 is other than R 9 ; and

wherein the amount of the second monomer is from 65 to 85 wt % of the total amount of monomer in the monomer mixture; and

iii) a free radical initiator; and

b) polymerizing the monomer mixture.

12. The method of claim 11 , wherein during step b) the monomer mixture is held at a temperature between 65° C. and 150° C.

13. The method of claim 11 , wherein the method further comprises a curing step following step b), wherein the curing temperature is from 50° C. and 150° C. and the curing time from 5 seconds to 60 minutes.

14. The method of claim 11 , wherein the structure of the first monomer is given by Formula 13-A,

at least three of X 1 -X 5 are iodine and n is an integer from 1 to 8.

15. The method of claim 11 , wherein the second monomer has the structure of Formula 9-A where R 11 is C 6 -C 20 alkylene and n 4 is an integer from 1 to 25

16. The method of claim 11 , wherein the mixture further comprises a monomer having the general structure of Formula 12

wherein R 14 is substituted or unsubstituted C 2 -C 36 alkylene, C 2 -C 36 cycloalkylene, C 2 -C 36 alkenylene, C 2 -C 36 cycloalkenylene, C 2 -C 36 alkynylene, C 5 -C 36 arylene, C 5 -C 36 heteroarylene, an oligomeric polyester, an oligomeric polycarbonate, an oligomeric polyurethane,

wherein R 10 is C 4 -C 20 alkylene and n 3 is an integer from 1 to 50 or

wherein R 11 is C 3 -C 20 alkylene and n 4 is an integer from 1 to 50, and R 14 is other than R 9 .

17. The method of claim 16 , wherein the combined amount of the second monomer and the monomer of claim 16 is from 65 to 85 wt % of the monomer mixture.

18. The polymer composition of claim 2 , wherein n is an integer from 3 to 8.

19. The polymer composition of claim 7 , wherein n is an integer from 3 to 8.

20. The polymer composition of claim 4 , wherein n is an integer from 3 to 8.