Abstract: | Numerous nontoxic (resorbable) salts were prepared from cations and anions belonging to the human metabolism, such as Na, K, Mg, Ca, Zn and Fe in combination with chloride, iodide, hydroxide, carbonate, acetate, stearate, glycolate, L‐lactate, D‐mandelate and various N‐substituted α‐amino acids. All these salts were used as initiators for polymerizations of L‐lactide in bulk at 100–180°C. Furthermore, Grignard reagents, hemin and hematin were included in this study. Zn L‐lactate was found to be the most useful initiator in terms of reactivity, maximum molecular weight of the isolated poly(L‐lactide) and its optical purity. Zn L‐lactate initiated copolymerizations of L‐lactide and glycolid or L‐lactide and ϵ‐caprolactone were also studied. Finally, first studies of the polymerization mechanism of zinc stearate and zin 2‐ethylhexanoate were performed. They suggest that zinc carboxylates combined with an alcohol as coinitiator form reactive zinc alkoxides which are the true initiators at temperatures < 150°C. |