Samples of poly(l,l-lactide)-block-poly(ethylene glycol)-block-poly(l,l-lactide) (PLLA-PEG-PLLA) were synthesized from l,l-lactide polymerization using stannous 2-ethylhexanoate, Sn(Oct)2 as initiator and di-hydroxy-terminated poly(ethylene glycol) (PEG) (Mn = 4000 g mol−1) as co-initiator. The chemical linkage between the PEG segment and the PLA segments was characterized by Fourier transform
infrared spectroscopy (FTIR). Thermogravimetry analysis (TG) revealed the copolymers composition and was capable to show the
deleterious effect of an excess of Sn(Oct)2 in the polymer thermal stability, while Differential Scanning Calorimetry (DSC) allowed the observation of the miscibility
between the PLLA and PEG segments in the different copolymers.