This article presents the results of TMC and DMC polymerization with the use of acetylacetonates of low‐toxic metals: iron, zinc, and zirconium. Zinc (II) acetylacetonate proves to be a very good initiator of homopolymerization. The reaction carried out with the use of this initiator at 110 °C is very rapid and of high yield. Using both zinc and iron (III) acetylacetonates, as well as the zirconium (IV) one, in high temperatures it is possible to obtain PTMC possessing high molecular mass, thus ensuring optimization of the relation between the duration of the polymerization and its yield. A strong influence of thermal degradation on the course of the reaction has been observed, particularly at 160 °C, with the use of Fe(acac)3 as the initiator. DMC polymerization proceeds much more slowly when initiated by iron and zinc acetylacetonates. A high conversion of the monomer is obtained in this case as well. The relation between the molecular mass of the obtained PDMC and the conversion of the monomer is directly proportional; however, those masses, determined on the basis of polystyrene standards, are much lower than those estimated theoretically. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1913–1922, 2005

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Biodegradable polyacid is obtained in one-step ring-opening polymerization (ROP) of carboxylic-acid-functionalized six-membered cyclic carbonate mediated with zirconium (IV) acetylacetonate. Exemplary copolymers with L,L-lactide are described as well. Moreover, zirconium (IV) acetylacetonate is found to be active catalyst of trimethylene carbonate (TMC) ROP in presence of carboxylic acid yielding PTMC end-capped with the acid derivative. Polymerization mechanism is hypothesized demonstrating possibilities of the method in work-saving polycation synthesis and one-step method of conjugate synthesis of well-known biocompatible polyesters and polycarbonates.