Polycondensation, cyclization and disproportionation of solid Poly(L-lactide) trifluoroethyl esters and the simultaneous formation of extended chain crystals and extended ring crystals

Two poly(L-lactide)s (PLAs) with a degree of polymerization (DP) of 20 or 100 were prepared by trifluoroethanol-initiated ring-opening polymerization (ROP) catalyzed by tin(II) 2-ethyl hexanoate (SnOct₂). These PLAs were annealed at 140 °C or at 160 °C in the presence of SnOct₂, and the changes in topology and molecular weight distribution (MWD) were monitored by matrix-assisted laser desorption/ionization time-of-flight (MALDI TOF) mass spectrometry and gel permeation chromatography (GPC). For the PLA with a DP 20, the main reaction was polycondensation combined with higher dispersities. In the case of the DP 100, PLA polycondensation was combined with disproportionation and the formation of a new MWD maximum around m/z 3500. In addition, extensive cyclization occurred, and the resulting cyclic PLAs crystallized separately from the linear chains in the form of extended ring crystals. These results also suggest that both extended chain and extended ring crystals posses the same crystal thickness as a result of thermodynamically controlled transesterification in the solid state.