Novel macromolecular architectures based on aliphatic polyesters: Relevance of the "coordination-insertion" ring-opening polymerization

Recent developments in the macromolecular engineering of aliphatic polyeste rs have been overviewed. First, aluminum alkoxides mediated living ring ope ning polymerization (ROP) of cyclic (di)esters, i.e., lactones, lactides, g lycolide, is introduced. An insight into this so-called "coordination-inser tion" mechanism and the ability of this living polymerization process to pr epare well-defined homopolymers, telechelic polymers, random and block copo lymers is then discussed. In the second part, the combination of the living ROP of (di)lactones with other well-controlled polymerization mechanisms s uch as anionic, cationic, free radical, and metathesis polyadditions of uns aturated comonomers, as well as polycondensations, is reported with special emphasis on the design of new and well-tailored macromolecular architectur es. As a result of the above synthetic breakthrough, a variety of novel mat erials have been developed with versatile applications in very different fi elds such as biomedical and microelectronics.