The morphology, crystallization and self nucleation behavior of double crystalline diblock copolymers of poly(p‐dioxanone) (PPDX) and poly(ϵ‐caprolactone) (PCL) with different compositions have been studied by different techniques, including optical microscopy (OM), atomic force microscopy (AFM) and differential scanning calorimetry (DSC). The two blocks crystallize in a single coincident exotherm when cooled from the melt. The self‐nucleation technique is able to separate into two exotherms the crystallization of each block. We have gathered evidences indicating that the PPDX block can nucleate the PCL block within the copolymers regardless of the composition. This effect is responsible for the lack of homogeneous nucleation or fractionated crystallization of the PCL block even when it constitutes a minor phase within the copolymer (25% or less). Nevertheless, we were able to show that decreasing amounts of PCL within the diblock copolymer still produces confinement effects that retard the crystallization kinetics of the PCL component and decrease the Avrami index. On the other hand evidence for confinement was also obtained for the PPDX block, since as its content is reduced within the copolymer, a depression in its self‐nucleation and annealing temperatures were observed.

ABSTRACT:The optimization of the synthesis of poly(pdioxanone), by ring-opening polymerization with tin II bis(2-ethylhexanoic acid) as the catalyst, was conducted by a new method in which programmed decreasing reaction temperatures were employed. The results were compared with those obtained for polymerization reactions performed at constant temperatures in the 80 -180°C range. In the novel method, the temperature was gradually reduced, as the reaction proceeded, to maintain a maximum polymerization rate and monomer conversion as the monomer was consumed. The experiments performed at constant temperatures confirmed previous reports that the bulk polymerization of 1,4-dioxan-2-one is an equilibrium polymerization reaction. With increasing polymerization temperature, the initial rate of polymerization increased, but the monomer conversion, reaching equilibrium, decreased. High conversions were obtained at low temperatures and long reaction times. Therefore, reducing the reaction temperature, to ensure working conditions that guaranteed the maximum polymerization rate and monomer conversion, could optimize the polymerization process. These conditions were calculated under the assumption of equilibrium polymerization reaction kinetics. With our proposed method, a 71% conversion was achieved in half the time needed when the polymerization was performed at a constant temperature of 120°C. Similarly, a 78% conversion was obtained with our proposed method in only a third of the time employed when the reaction was carried out at a constant temperature of 80°C. Our method guarantees high conversions in shorter times and a gradual reduction of the polymerization temperature.