Dithiolane carbonate monomers and polymers thereof
1,2-Diothiolane monomers are disclosed, as are polymers and hydrogels comprising the polymers. Processes for preparing the monomers, polymers and compositions are also disclosed. The monomers have the formula: The polymers may include the following repeating units:
1. A compound of the formula (I):
wherein
Y is a linker selected from aliphatic C 1 -C 8 hydrocarbyl in which one or two carbon atoms may optionally be replaced by one or more of —O— and —C(═O)—;
R 1 is selected from hydrogen and C 1 -C 3 alkyl; and
R 2 is selected from hydrogen and C 1 -C 3 alkyl.
2. A compound according to claim 1 , wherein Y is selected from aliphatic C 1 -C 8 hydrocarbyl in which two adjacent carbon atoms are replaced by —C(═O)O—.
3. A compound according to claim 1 , wherein Y is —(CH 2 ) n —(O) m —(C═O) p —*, wherein
* represents the point of attachment to the dithiolane ring;
n is 1, 2, 3, or 4;
m is 0 or 1; and
p is 0 or 1.
4. A compound according to claim 3 , wherein Y is —(CH 2 ) n —O—C(═O)—*.
5. A compound according to claim 4 , wherein n is 2.
6. A compound according to claim 1 , wherein R 1 and R 2 are methyl.
7. A compound according to claim 1 , said compound having the formula (IA):
8. A compound according to claim 7 , said compound having the formula (IA-i):
9. A compound according to claim 1 , said compound having the formula (IB):
10. A compound according to claim 9 , wherein Y is —(CH 2 ) u —O—C(═O)—(CH 2 ) v —* wherein
* represents the point of attachment to the dithiolane ring;
u is 2, 3, or 4; and
v is 0 or an integer from 1 to 6.
11. A compound according to claim 10 , said compound having the formula (IB-i):
12. A polymer comprising a structural unit of the formula (II):
wherein
Y is a linker selected from aliphatic C 1 -C 8 hydrocarbyl in which one or two carbon atoms may optionally be replaced by one or more of —O— and —C(═O)—, and wherein Y is attached to the carbon attached to R 2a , to the carbon attached to R 2b , or to the carbon attached to R 2c ;
R 1 is selected from hydrogen and C 1 -C 3 alkyl;
R 2a , R 2b , and R 2c , are individually selected from hydrogen and C 1 -C 3 alkyl;
R 3 and R 4 are hydrogen, or R 3 and R 4 , taken together, form a direct bond between the sulfur atoms to which they are attached, thereby forming a dithiolane ring; or one of R 3 and R 4 is selected from hydrogen, pyrrolidine-2,5-dione, and propionamide, and the other is a residue of formula (IIIA):
wherein
*′ represents the point of attachment to a sulfur of (II);
X is chosen from C 1 -C 10 hydrocarbyl, C 1 -C 10 hydrocarbyl substituted with —OH, —(CH 2 ) q —O—(CH 2 ) r — and —(CH 2 ) q [—O—(CH 2 ) r ] t —;
q is 2, or 3;
r is 2, or 3; and
t is an integer from 2 to 1000.
13. A polymer according to claim 12 , wherein Y is selected from aliphatic C 1 -C 8 hydrocarbyl in which two adjacent carbon atoms are replaced by —C(═O)O—.
14. A polymer according to claim 13 , wherein Y is —(CH 2 ) n —(O) m —(C═O) p —, wherein
n is 1, 2, 3, or 4;
m is 0 or 1; and
p is 0 or 1.
15. A polymer according to claim 14 , wherein Y is —(CH 2 ) n —O—C(═O)—.
16. A polymer according to claim 15 , wherein n is 2.
17. A polymer according to claim 12 , wherein R 1 and R 2 are methyl.
18. A polymer according to claim 13 , wherein Y is —(CH 2 ) u —O—C(═O)—(CH 2 ) v —wherein
u is 2, 3, or 4; and
v is an integer from 1 to 6.
19. A polymer according to claim 12 , said polymer containing a structural unit of the formula IIa:
20. A polymer according to claim 12 said polymer containing a structural unit of the formula IIb:
21. A polymer according to claim 12 additionally comprising a structural unit of the formula (IV):
wherein
w is 1-1000.
22. A triblock polymer according to claim 21 .
23. A polymer according to claim 12 comprising a structural unit of the formula:
and a unit of formula
24. A polymer according to claim 23 additionally comprising a structural unit of the formula (IV):
wherein
w is 1-1000.
25. A triblock polymer according to claim 24 .