Controlled Synthesis and Crystallization-Driven Self-Assembly of Poly(-caprolactone)--polysarcosine Block Copolymers.

Poly(ε-caprolactone)--polysarcosine (PCL--PSar) block copolymers (BCPs) emerge as a promising alternative to conventional poly(-caprolactone)--poly(ethylene oxide) BCPs for biomedical applications, leveraging superior biocompatibility and biodegradability. In this study, we synthesized two series of PCL--PSar BCPs with controlled polymerization degrees ( of PCL: 45/67; of PSar: 28-99) and low polydispersity indexes ( ≤ 1.1) and systematically investigated their crystallization-driven self-assembly (CDSA) in alcohol solvents (ethanol, -butanol, and -hexanol). It was found that the limited solubility of PSar in alcohols resulted in competition between micellization and crystallization during self-assembly of PCL--PSar, and thus coexistence of lamellae and spherical micelles. To overcome this morphological heterogeneity, we developed a modified self-seeding method by employing a two-step crystallization strategy (i.e., = 33 °C and = 8 °C), achieving conversion of micelles into crystals and yielding uniform self-assembled structures. PCL--PSar BCPs with short PSar blocks tended to form well-defined two-dimensional lamellar crystals, while those with long PSar blocks induced formation of hierarchical structures in the PCL series and polymer aggregation on crystal surfaces in the PCL series. Solvent quality notably influenced the self-assembly pathways of PCL--PSar. Lamellar crystals were formed in ethanol and -butanol, but micrometer-scale dendritic aggregates were generated in -hexanol, primarily due to a significant Hansen solubility parameter mismatch. This study elucidated the CDSA mechanism of PCL--PSar in alcohols, enabling precise structural control for biomedical applications.