Polyester microspheres were synthesized by the ring-opening polymeriza
tion of lactides (racemate or optically active L,L-isomer) and epsilon
-caprolactone. Polymerizations were carried out in the 1,4-dioxane-hep
tane mixed solvents in the presence of poly(dodecyl acrylate)-g-poly(e
psilon-caprolactone) (poly(DA-CL)) used as surface-active agent. Polym
erizations were initiated with tin(II) 2-ethylhexanoate (lactides), di
ethylaluminum ethoxide or sodium trimethylsilanolate (epsilon-caprolac
tone). In the studies of the polymerization of lactides, relations wer
e determined between diameters, the distribution of diameters of synth
esized microspheres, and the structure of poly(DA-CL). It was found th
at it is possible, depending on thermal treatment of microspheres afte
r synthesis, to obtain polylactide microspheres differing in the degre
e of crystallinity. Kinetics of the dispersion pseudoanionic and anion
ic polymerizations of epsilon-caprolactone were also investigated and
the results of these studies were compared with the data for the corre
sponding polymerizations of epsilon-caprolactone in solution.