Impact of the architecture on the crystallization kinetics of poly(ε-caprolactone)/poly(trimethylene carbonate) block copolymers

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.