Radiopaque shape memory polymers for medical devices
Radiopaque polymer compositions and methods for making the compositions are provided. These radiopaque polymer compositions include shape memory polymer compositions comprising a crosslinked polymer network, the network comprising a first repeating unit derived from a monofunctional iodinated monomer and a second repeating unit derived from a multifunctional non-iodinated monomer wherein neither of the two monomers is fluorinated. Devices formed from radiopaque polymer compositions are also provided.
1. A polymer composition comprising a crosslinked network, the network comprising:
a) a first repeating unit having the formula:
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 —(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 an iodinated C 5 -C 30 aryl having at least 3 iodine adoms or a C 5 -C 30 heteroaryl; having at least 3 iodine adoms;
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 10
b) a second repeating unit having the formula:
wherein R 9 is an oligomeric polycarbonate.
2. The polymer composition of claim 1 , wherein R 1 is C 2 -C 6 alkylene or —CH 2 CH 2 SCH 2 CH 2 —.
3. The polymer composition of claim 1 , wherein Ar 1 is an iodinated C 6 aryl, wherein the iodine atoms are attached directly to the aryl ring and the number of iodine atoms is from 3 to 5.
4. The polymer composition of claim 1 , wherein L 1 is —COO—or —CONR 3 —.
5. The polymer composition of claim 1 , wherein the network further comprises a repeating unit having the formula:
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 n3 is an integer from 1 to 50 or
wherein R 11 is C 3 -C 20 alkylene and n4 is an integer from 1 to 50, and R 14 is other than R 9 .
6. The polymer composition of claim 1 , wherein the polymer is substantially amorphous.
7. A polymer composition comprising a crosslinked network formed by polymerization of a monomer mixture comprising
a) a first monomer having the general structure
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 —(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 an iodinated C 5 -C 30 aryl having at least 3 iodine atoms or C 5 -C 30 heteroaryl having at least 3 iodine 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 10
b) a second monomer having the general structure
R 9 is an oligomeric polycarbonate.
8. The polymer composition of claim 7 , wherein R 1 is R 1 is C 2 -C 6 alkylene or —CH 2 CH 2 SCH 2 CH 2 —.
9. The polymer composition of claim 7 , wherein Ar 1 is an iodinated C 6 aryl, wherein the iodine atoms are attached directly to the aryl ring and the number of iodine atoms is from 3 to 5.
10. The polymer composition of claim 7 wherein L 1 is —COO—or —CONR 3 —.
11. The polymer composition of claim 7 , wherein the monomer mixture further comprises a third monomer having the general structure
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 n3 is an integer from 1 to 50 or
wherein R 11 is C 3 -C 20 alkylene and n4 is an integer from 1 to 50 and R 14 is other than R 9 .
12. A method for making a polymer composition comprising a crosslinked network, the method comprising the steps of:
a) forming a monomer mixture comprising
a first monomer having the general structure
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 —(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 an iodinated C 5 -C 30 aryl having at least 3 iodine atoms or C 5 -C 30 heteroaryl having at least 3 iodine 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 10
a second monomer having the general structure
R 9 is an oligomeric polycarbonate and a free radical initiator; and
b) polymerizing the monomer mixture.
13. The method of claim 12 , wherein the monomer mixture is substantially homogeneous.
14. The method of claim 12 , wherein during step b) the monomer mixture is held at a temperature between 65° C. and 150° C.
15. The method of claim 12 , 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.
16. The method of claim 12 , wherein R 1 is C 2 -C 6 alkylene or —CH 2 CH 2 SCH 2 CH 2 —.
17. The method of claim 12 , wherein Ar 1 is an iodinated C 6 aryl, wherein the iodine atoms are attached directly to the aryl ring and the number of iodine atoms is from 3 to 5.
18. The method of claim 12 , wherein L 1 is —COO—or —CONR 3 —.
19. The method of claim 12 , wherein the mixture further comprises a third monomer having the general structure
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 n3 is an integer from 1 to 50 or
wherein R 11 is C 3 -C 20 alkylene and n4 is an integer from 1 to 50 and R 14 is other than R 9 .
20. A radiopaque polymer device for medical applications, the device or device feature comprising a polymer composition according to claim 1 .
21. The polymer composition of claim 1 , wherein the network further comprises repeating units derived from a monofunctional iodinated monomer comprising a styrene, acrylamide or methacrylamide polymerizable group.
22. The polymer composition of claim 1 wherein the polymer composition is a shape memory polymer composition.
23. The polymer composition of claim 11 , wherein the second monomer has a higher molecular weight than the third monomer, the weight percentage of the second monomer is from 10 to 55 wt % and the weight percentage of the third monomer is from 1 to 35 wt %.
24. The polymer composition of claim 7 , wherein the mixture further comprises a monofunctional iodinated monomer comprising a styrene, acrylamide or methacrylamide polymerizable group.
25. The polymer composition of claim 7 wherein the polymer composition is a shape memory polymer composition.
26. The method of claim 19 , wherein the second monomer has a higher molecular weight than the third monomer, the weight percentage of the second monomer is from 10 to 55 wt % and the weight percentage of the third monomer is from 1 to 35 wt %.
27. The method of claim 12 , wherein the mixture further comprises a monofunctional iodinated monomer comprising a styrene, acrylamide or methacrylamide polymerizable group.
28. The method of claim 12 , wherein the polymer composition is a shape memory polymer composition.
29. The polymer composition of claim 1 , wherein the oligomeric polycarbonate is poly(C2-C36 carbonate).
30. The polymer composition of claim 7 , wherein the second monomer is a poly(C2-C36 carbonate) diacrylate.
31. The polymer composition of claim 7 , wherein the molecular weight of the second monomer is from 200 to 2000.
32. The polymer composition of claim 19 , wherein the monomer of Formula 9 and the monomer of Formula 12 are of different molecular weights.
33. The polymer composition of claim 7 wherein the polymer composition is substantially amorphous.