G. Montaudo et al., EVIDENCE FOR ESTER-EXCHANGE REACTIONS AND CYCLIC OLIGOMER FORMATION IN THE RING-OPENING POLYMERIZATION OF LACTIDE WITH ALUMINUM COMPLEX INITIATORS, Macromolecules, 29(20), 1996, pp. 6461-6465
Four polylactide samples, obtained by ring-opening polymerization with
an aluminum alkoxide initiator derived from a Schiffs base, were char
acterized by MALDI-TOF mass spectrometry. The MALDI mass spectra of th
ese polylactides show well-resolved signals that can be reliably assig
ned to polylactide oligomers. Remarkably, both even-membered and odd-m
embered oligomers are present in these MALDI spectra. The presence of
odd-membered oligomers cannot be explained on the basis of the lactide
ring-opening polymerization, and one must admit that ester-exchange r
eactions do occur parallel to the polymerization process, causing a ra
ndom cleavage of the polylactide chain. Furthermore, evidence for the
presence of cyclic lactides was found in the MALDI-TOF spectrum of a l
ow molecular weight polylactide fraction, indicating that ester exchan
ge occurs also in polylactides by intramolecular end-biting reactions
(ring-chain equilibration), with formation of cyclic oligomers.