Synthesis and characterization of double crystalline cyclic diblock copolymers of poly(e-caprolactone) and poly(L(D)-lactide) (c(PCL-b- PL(D)LA)).


The synthesis of symmetric cyclo poly(ε-caprolactone)–block–poly(L(D)-lactide) (c(PCL–b–PL(D)LA)) by combining ROP 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 non-isothermal crystallization of both linear and cyclo PCL-b-PDLA and PCL-b-PLLA copolymers. 

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