From controlled ring-opening polymerization to biodegradable aliphatic polyester: Especially poly(β-malic acid) derivatives

Abstract

Biodegradable polymers represent a class of extremely useful materials for many biomedical and pharmaceutical applications, as exemplified by drug delivery systems, which in recent years have taken advantage of (bio)degradable polymeric matrices. However, before being selected for any biomedical application, a biodegradable polymer requires careful investigation of its interactions and compatibility within the human body. To date, polyesters, both natural and synthetic, constitute the most fully developed class of degradable biomaterials. Poly(ε-caprolactone) (PCL) and polylactides (PLAs), recognized as biocompatible and biodegradable polyesters, are very promising for controlled drug delivery devices. Bacterial polyesters and malic acid-based polymers (poly(malic acid), PMLA and derivatives) are poly(β-hydroxyacid)-type polyesters that represent excellent alternatives for temporary therapeutic applications. Although these polyesters can be produced by polycondensation, high molecular weight structures have, until now, been produced almost exclusively by ring-opening polymerization (ROP) of the corresponding cyclic monomers. The ability of aluminum alkoxides (AlRx(OR′)3-x) and tin(II) bis(2-ethylhexanoate) (Sn(Oct)2) to control the ROP of (di)lactones in terms of molecular parameters has opened the way to a wide range of molecular structures and topologies. Beyond the mechanistic and thermodynamic aspects of ROP of (di)lactones using organometallic compounds, this review is focused on new non-organometallic N-heterocyclic carbenes recently reported as catalysts for the controlled ROP of cyclic esters. Interestingly, the use of these simple organic molecules as catalysts or promoters in asymmetric polymer synthesis has provided organocatalytic alternatives to traditional organometallic reagents. © 2006 Elsevier Ltd. All rights reserved.