The synthesis of biodegradable polymers with functional side chains

Abstract

AbstractTrifunctional hydroxy‐terminated oligomeric polyesters, Mn 500, 1000, and 2000, were prepared by initiating ring‐opening copolymerization of δ‐valerolactone and ε‐caprolactone with glycerol. The prepolymers were converted to crosslinked polyester‐urethanes by their reaction with hexane‐1,6‐diisocyanate in proportions corresponding to 70, 80, 90, and 100% of the hydroxyl content. The moduli of the resulting elastomers varied between 0.12 MPa and 3.83 MPa, and the elongation at break between 60 and 2000%. The residual hydroxyl groups were derivatized by heterogeneous reaction with chloroacetic anhydride or excess hexane‐1,6‐diisocyanate, and these and further transformations of the functional groups were verified by infrared spectroscopy and electron probe x‐ray microanalysis. A second series of hydroxy‐substituted elastomers was synthesized by copolymerization of δ‐valerolactone, ε‐caprolactone, and 4‐(t‐butyldimethylsilyloxy)‐ε‐caprolactone, using different amounts of 2,2‐bis(caprolacton‐4‐yl)propane as the crosslinking agent; removal of the t‐butyldimethylsilyl group to liberate pendant hydroxyl groups was achieved with acetic acid but not fluoride ion. The hydroxylated polyester (but not the polyesterurethanes) was shown to undergo enzymatic surface erosion in rabbit. The biodegradation data were compared with results previously obtained with low‐modulus elastomeric polyesters.