The Hidden Isodimorphic Crystallization of Poly(ε-Caprolactone-Ran-ω-Pentadecalactone) Copolymers.

Poly(ε-caprolactone-ran-ω-pentadecalactone) (PCLx-PPDLy) copolymers were synthesized by using ring-opening polymerization with Candida antarctica lipase B as a catalyst across various compositions. The aim was to study their crystallization behavior and ascertain whether they are isomorphic or isodimorphic. Differential scanning calorimetry, polarized light optical microscopy, in situ wide- and small-angle X-ray scattering, and Fourier-transform infrared spectroscopy were employed to assess the crystallization mode. Various crystallization conditions were used to investigate their influence on the comonomer inclusion/exclusion balance. The copolymers exhibited pseudoeutectic behavior across all compositions, crystallizing in either PPDL-type or PCL-type unit cells and conformations, independent of crystallization conditions. This indicates that they are isodimorphic, contrary to previous reports. Self-nucleation tests showed that the Domain II width decreases with increasing comonomer content, supporting isodimorphism. The pseudoeutectic point was observed at CL contents above 83%, which explains the previously unrecognized isodimorphic character of these copolyesters.