Photocurable biodegradable polyesters from poly(L‐lactide) diols

Abstract

Abstractα,ω‐Dihydoxy‐terminated poly(L‐lactide)s (PLLA diols) with various molecular weights (1000, 2000 and 3000 g mol−1) were prepared by the ring‐opening polymerization of L‐lactide using 1,6‐hexanediol as an initiator. These were subsequently chain‐extended with the diacyl chloride of 4,4′‐(adipoyldioxy)dicinnamic acid (CAC) to obtain high‐molecular‐weight photocurable polyesters (CAC/PLLAs). The resulting polyesters were characterized by gel permeation chromatography, Fourier‐transform infrared, ultraviolet–visible and proton nuclear magnetic resonance spectroscopies, differential scanning calorimetry and thermogravimetry. These photoreactive polyesters were irradiated with a high‐pressure mercury lamp (λ > 280 nm) for 30–180 min to produce the crosslinked polyesters. The gel fraction yield increased with photocuring time, and exceeded 80 % after 180 min. The photocuring process disturbed the crystallization of the CAC/PLLA films, while it enhanced their thermal stabilities. With increasing photocuring time, both the tensile strength and modulus increased markedly. The best mechanical properties (tensile strength = 41 MPa; tensile modulus = 1550 MPa) were obtained for a CAC/PLLA‐3000 film photocured for 180 min. The tensile modulus of this photocured film was larger than that of pure PLLA. The hydrolytic degradation rates of the CAC/PLLA films in a phosphate buffer solution (pH, 7.2) of proteinaze‐k at 37 °C were much slower than those of pure PLLA films. Copyright © 2004 Society of Chemical Industry