Poly(L-lactic acid) (PLLA) and poly(ε-caprolactone) (PCL), two biodegradable and biocompatible polymers that are commonly used for biomedical applications, are, respectively, the result of the ring-opening polymerization of LA and ε-CL, cyclic esters, which can be produced according to several mechanisms (cationic, monomer-activated cationic, anionic, and coordination-insertion), except for L-lactide, which is polymerized only by anionic, cationic, or coordination-insertion polymerization. A series of well-defined PLLA-b-PCL block copolymers have been obtained starting from the same PLLA homopolymer, having a molar mass of 2500 g·mol, and being synthesized by coordination-insertion in the presence of tin octoate. PCL blocks were obtained via a cationic-activated monomer mechanism to limit transesterification reactions, and their molar masses varied from 1800 to 18,500 g·mol.
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