Influence of Chain Topology (Cyclic versus Linear) on the Nucleation and Isothermal Crystallization of Poly(l‑lactide) and Poly(d‑lactide)

Ring closure click chemistry methods have been used to produce cyclic c-PLLA and c-PDLA of a number-average molecular weight close to 10 kg/mol. The effects of stereochemistry of the polymer chains and their topology on their structure, nucleation, and crystallization were studied in detail employing wide-angle X-ray scattering (WAXS), small-angle X-ray scattering (SAXS), polarized light optical microscopy (PLOM), and standard and advanced differential scanning calorimetry (DSC). The crystal structures of linear and cyclic PLAs are identical to each other, and no differences in superstructural morphology could be detected. Cyclic PLA chains are able to nucleate much faster and to produce a higher number of nuclei in comparison to linear analogues, either upon cooling from the melt or upon heating from the glassy state. In the samples prepared in this work, a small fraction of linear or higher molecular weight cycles were detected (according to SEC analyses). The presence of such “impurities” retards spherulitic growth rates of c-PLAs, making them nearly the same as those of l-PLAs. On the other hand, the overall crystallization rate determined by DSC was much larger for c-PLAs, as a consequence of the enhanced nucleation that occurs in cyclic chains. The equilibrium melting temperatures of cyclic chains were determined and found to be 5 °C higher in comparison with values for l-PLAs. This result is a consequence of the lower entropy of cyclic chains in the melt. Self-nucleation studies demonstrated that c-PLAs have a shorter crystalline memory than linear analogues, as a result of their lower entanglement density. Successive self-nucleation and annealing (SSA) experiments reveal the remarkable ability of cyclic molecules to thicken, even to the point of crystallization with extended collapsed ring conformations. In general terms, stereochemistry had less influence on the results obtained in comparison with the dominating effect of chain topology.