Novel Macromolecular Architectures Based on Aliphatic Polyesters: Relevance of the “Coordination-Insertion” Ring-Opening Polymerization

Recent developments in the macromolecular engineering of aliphatic polyesters have been overviewed. First, aluminum alkoxides mediated living ring opening polymerization (ROP) of cyclic (di)esters, i.e., lactones, lactides, glycolide, is introduced. An insight into this so-called “coordination-insertion” mechanism and the ability of this living polymerization process to prepare well-defined homopolymers, telechelic polymers, random and block copolymers is then discussed. In the second part, the combination of the living ROP of (di)lactones with other well-controlled polymerization mechanisms such as anionic, cationic, free radical, and metathesis polyadditions of unsaturated comonomers, as well as polycondensations, is reported with special emphasis on the design of new and well-tailored macromolecular architectures. As a result of the above synthetic breakthrough, a variety of novel materials have been developed with versatile applications in very different fields such as biomedical and microelectronics.