In this work, we study for the first time, the isothermal crystallization behavior of isodimorphic random poly(butylene succinate)-ran-poly(ε-caprolactone) copolyesters, PBS-ran-PCL, previously synthesized by us. We perform nucleation and spherulitic growth kinetics by polarized light optical microscopy (PLOM) and overall isothermal crystallization kinetics by differential scanning calorimetry (DSC). Selected samples were also studied by real-time wide angle X-ray diffraction (WAXS). Under isothermal conditions, only the PBS-rich phase or the PCL-rich phase could crystallize as long as the composition was away from the pseudo-eutectic point. In comparison with the parent homopolymers, as comonomer content increased, both PBS-rich and PCL-rich phases nucleated much faster, but their spherulitic growth rates were much slower. Therefore, the overall crystallization kinetics was a strong function of composition and supercooling. The only copolymer with the eutectic composition exhibited a remarkable behavior. By tuning the crystallization temperature, this copolyester could form either a single crystalline phase or both phases, with remarkably different thermal properties.

The recyclability of opaque PET, which contains TiO₂ nanoparticles, has not been as well-studied as that of transparent PET. The objective of this work is to recycle post-consumer opaque PET through reactive extrusion with Joncryl. The effect of the reactive extrusion process on the molecular structure and on the thermal/mechanical/rheological properties of recycling post-consumer opaque PET (r-PET) has been analyzed. A 1% w/w Joncryl addition caused a moderate increase in the molecular weight. A moderate increase in chain length could not explain a decrease in the overall crystallization rate. This result is probably due to the presence of branches interrupting the crystallizable sequences in reactive extruded r-PET (REX-r-PET). A rheological investigation performed by SAOS/LAOS/elongational studies detected important structural modifications in REX-r-PET with respect to linear r-PET or a reference virgin PET. REX-r-PET is characterized by a slow relaxation process with enlarged elastic behaviors that are characteristic of a long-chain branched material. The mechanical properties of REX-r-PET increased because of the addition of the chain extender without a significant loss of elongation at the break. The reactive extrusion process is a suitable way to recycle opaque PET into a material with enhanced rheological properties (thanks to the production of a chain extension and long-chain branches) with mechanical properties that are comparable to those of a typical virgin PET sample.