L-Lactide was polymerized in toluene with various alkoxide initiators. These initiators were prepared in situ from potassium t.-butoxide and primary or secondary alcohols such as tetradecanol, diethylene glycol butyl ether, menthol or testosteron. All these alcohols were incorporated as ester endgroups into the polylactide chain. However H-1-NMR spectroscopy proves the existence of more OH-endgroup than ester endgroups. This finding and 10-20% racemization observed for all anionic polymerizations suggest that chain-transfer reactions with the monomer via deprotonation take place. When poly(ethylene glycol) monomethyl ether in combination with KOtBu was used as initiator, twoblock copolymers were obtained. With poly(ethylene glycol) A-B-A-triblock copolymers could be synthesized. The quantitative reaction of the poly(ethylene glycol)s with L-lactide could be proven by both H-1 NMR spectroscopy and gelpermeation chromatography. DSC-measurements show that depending on their lengths either the polylactide or the poly(ethylene oxide)blocks can crystallize. Due to partial racemization the melting temperatures (T(m)) of the poly(L-lactide) blocks did not exceed 155-degrees-C.
