Impact of the architecture on the crystallization kinetics of poly(ε-caprolactone)/poly(trimethylene carbonate) block copolymers. (October 2017) - Castillo, R. Veronica
Graphical abstract: Highlights: MSA organocatalyzed preparation of well-defined block copolymers of ε-CL and TMC. The PCL and PTMC blocks of the diblock copolymers of high enough Mn segregate in bulk. The segregation has no marked impact on the crystallization kinetics of the PCL block. The architecture polymers has a strong impact on the overall crystallization kinetics. Abstract: Well defined block copolymer architectures based on poly(ε-caprolactone) and poly(trimethylene carbonate) were prepared thanks to the methane sulfonic acid (MSA) organocatalyzed ROP of the corresponding monomers. The interplay between the crystallization kinetics, self-assembling behavior and superstructural morphology was investigated. In order to probe the influence of the block copolymer architecture (molecular weight, number of blocks and sequence), kinetics theories of polymer crystallization were applied to the isothermal crystallization kinetics data obtained by differential scanning calorimetry and polarized optical microscopy. The results suggest that the PCL crystallization kinetic is only slightly disturbed by the segregation strength for weakly segregated systems while the block copolymer sequence shows a strong impact on the overall crystallization kinetics, and particularly on the nucleation step due to topological constraints.