Polyester compositions, methods of manufacturing said compositions, and articles made therefrom
View Patent ↗Crosslinked polymer compositions have backbones with first and second divalent saturated aliphatic moieties, a divalent saturated aliphatic secondary alcohol moiety, and a trivalent saturated aliphatic moiety. Hydrolytically labile ester bonds joined together these moieties. These polyesters may be polycondensation reaction products of a diol, a triol and a diacid. A molar ratio of the first divalent saturated aliphatic moiety, the divalent saturated aliphatic secondary alcohol moiety, and the trivalent saturated aliphatic moiety to the second divalent saturated aliphatic moiety is in the range of about 0.85 to about 1.5. Preferably, these polyesters are non-cytotoxic, biocompatible, bioabsorbable, or exhibit shape memory behavior with at least one transition temperature of greater than about 30° C. and less than about 100° C. and most preferably exhibit each of these qualities. The compositions may be adapted for a wide variety of uses, including medical applications.
1. A crosslinked polycondensation product of:
a. polyol comprising saturated aliphatic triol, and saturated aliphatic diol, in which the moles of saturated aliphatic triol divided by the total moles of polyol is in the range of about 0.2 to about 0.8, and
b. at least one saturated linear aliphatic diacid or derivative thereof, in which the total moles of polyol divided by the moles of diacid is in the range of about 0.9 to about 1.2.
2. The crosslinked polycondensation product of claim 1 , in which said polyol comprises glycerol and ethylene glycol.
3. The crosslinked polycondensation product of claim 1 , in which said at least one saturated linear aliphatic diacid comprises sebacic acid.
4. The crosslinked polycondensation product of claim 1 , in which said diacid or derivative thereof comprises at least one diester of a saturated linear aliphatic diacid in which the total moles of polyol divided by the moles of diester of saturated linear aliphatic diacid is in the range of about 0.9 to about 1.2.
5. The crosslinked polycondensation product of claim 1 , in which said diacid or derivative thereof comprises at least one diacyl halide of a saturated linear alphatic diacid in which the total moles of polyol divided by the moles of diacyl halide of saturated linear aliphatic diacid is in the range of about 0.9 to about 1.2.
6. The crosslinked polycondensation product of claim 1 comprising randomly linked moieties.
7. The crosslinked polycondensation product of claim 6 , in which the moles of saturated aliphatic triol divided by the total moles of polyol is in the range of about 0.20 to about 0.65.
8. The crosslinked polycondensation product of claim 1 comprising block or multi-block linked moieties.
9. A crosslinked polycondensation product of:
polyol comprising glycerol and ethylene glycol, in which the moles of glycerol divided by the total moles of polyol is in the range of about 0.2 to about 0.8, and
sebacic acid, in which the total moles of polyol divided by the moles of sebacic acid is in the range of about 0.9 to about 1.2.
10. A crosslinked polycondensation product of:
polyol comprising glycerol and 1,3 propanediol, in which the moles of glycerol divided by the total moles of polyol is in the range of about 0.2 to about 0.8, and
sebacic acid, in which the total moles of polyol divided by the moles of sebacic acid is in the range of about 0.9 to about 1.2.
11. A crosslinked polycondensation product of:
polyol comprising glycerol and 1,4 butanediol, in which the moles of glycerol divided by the total moles of polyol is in the range of about 0.2 to about 0.8, and
sebacic acid, in which the total moles of polyol divided by the moles of sebacic acid is in the range of about 0.9 to about 1.2.
12. The crosslinked polycondensation product as in one of claims 1 - 11 having a residual acidity range of less than about 1.0 milliequivalents of acid per gram of product.
13. The crosslinked polycondensation product as in one of claims 1 - 11 that is non-cytotoxic.
14. The crosslinked polycondensation product as in one of claims 1 - 11 that exhibits shape memory behavior.
15. A porous polymer comprising the crosslinked polycondensation product of claims 1 - 11 .
16. A polymer composition having a backbone consisting essentially of linked ester units, A, B, and C, wherein said linked ester units are of the formulae:
where R 1 has the formula:
—[CH 2 ] B —
where R 2 has the formula:
R 3 has the formula:
R 4 has the formula:
—[CH 2 ] f —
where a and f are, independently integers between 2 and 35, and b, c, d and e are, independently, integers between 1 and 35, and
wherein
βand φare given by the formulae:
β
=
[
moles
R
1
+
moles
R
2
+
moles
R
3
]
[
moles
R
4
]
φ
=
[
moles
R
2
+
moles
R
3
]
[
moles
R
1
+
moles
R
2
+
moles
R
3
]
.
and satisfy the following expressions:
0.9≦β≦1.2,
0.20≦φ≦0.80.
17. The polymer composition of claim 16 , in which the moieties are randomly linked, and wherein φ is in the range of 0.20 to 0.65.
18. The polymer composition of claim 17 , in which φ is in the range of 0.20 to 0.50.
19. The polymer composition of claim 16 , in which the moieties are block or multi-block linked moieties.
20. The polymer composition of claim 19 , which is at least partially phase separated.
21. The polymer composition of claim 19 , in which the following expression is satisfied:
0.50≦φ≦0.80.
22. The polymer composition of claim 16 , in which the R 1 moiety comprises about 4 to about 30 mol % of the polymer composition.
23. The polymer composition of claim 16 , in which the R 2 moiety and the R 3 moiety comprise about 4 to about 30 mol % of the polymer composition.
24. The polymer composition of claim 16 , in which the R 4 moiety comprises about 20 to about 30 mol % of the polymer composition.
25. The polymer composition of claim 16 , in which the ester linkages comprise about 35 to about 55 mol % of the polymer composition.
26. The polymer composition of claim 16 , in which the polymer composition is crosslinked.
27. The polymer composition of claim 16 having less than 1.0 milliequivalents of a residual acid per gram of the polymer composition.
28. The polymer composition of claim 16 that is non-cytotoxic.
29. The polymer composition of claim 16 that exhibits shape memory behavior.
30. The polymer composition of claim 16 , which exhibits crystallization upon cooling at a rate of 2° C./min. from a temperature of about 100° C. to a temperature of about 20° C.
31. The polymer composition of claim 16 , having at least a semicrystalline structure at temperatures between 20° C. and 25° C., and having an amorphous structure at temperatures between about 30° C. and about 100° C.
32. The polymer composition of claim 16 , in which R 1 has at most 10 carbon atoms, R 2 has at most 4 carbon atoms, R 3 has at most 4 carbon atoms and R 4 has at most 10 carbon atoms.
33. The polymer composition of claim 16 , in which R 1 comprises 2 carbon atoms.
34. The polymer composition of claim 16 , in which R 1 comprises 3 carbon atoms.
35. The polymer composition of claim 16 , in which R 1 comprises 4 carbon atoms.
36. The polymer composition of claim 16 , in which R 2 comprises 3 carbon atoms.
37. The polymer composition of claim 16 , in which R 3 comprises 3 carbon atoms.
38. The polymer composition of claim 16 , in which R 4 comprises 8 carbon atoms.
39. The polymer composition of claim 16 , further comprising urethane and urea linkages which comprise about 15 mole % or less of the polymer composition, and in which non-polymeric void spaces are defined within the polymer composition.
40. The polymer composition of claim 39 , in which the urethane linkages consist essentially of:
in which the urea linkages consist essentially of:
where R 5 , R 6 , and R 7 , are each independently a divalent aromatic or aliphatic moiety.