Synthesis and Characterization of Double Crystalline Cyclic Diblock Copolymers of Poly(ε‐caprolactone) and Poly(<scp>l</scp>(<scp>d</scp>)‐lactide) (<i>c</i>(PCL‐<i>b</i>‐ PL(D)LA))

Abstract

The synthesis of symmetric cyclo poly(ε-caprolactone)-block-poly(l(d)-lactide) (c(PCL-b-PL(D)LA)) by combining ring-opening polymerization of ε-caprolactone and lactides and subsequent click chemistry reaction of the linear precursors containing antagonist functionalities is presented. The two blocks can sequentially crystallize and self-assemble into double crystalline spherulitic superstructures. The cyclic chain topology significantly affects both the nucleation and the crystallization of each constituent, as gathered from a comparison of the behavior of linear precursors and cyclic block copolymers. The stereochemistry of the PLA block does not have a significant effect on the nonisothermal crystallization of both linear and cyclo PCL-b-PDLA and PCL-b-PLLA copolymers.