Crystallization-driven sphere-to-rod transition of poly(lactide)-b-poly(acrylic acid) diblock copolymers: mechanism and kinetics

The aqueous crystallization-driven sphere-to-rod transition of poly(lactide)-b-poly(acrylic acid), PLA-b-PAA block copolymers, with a short homochiral PLA core forming block and a 10 times longer (in terms of degree of polymerization) PAA corona forming block is presented. Transmission electron microscopy (TEM) and dynamic light scattering (DLS) is utilized to follow the kinetics of the transition and wide angle X-ray diffraction (WAXD) to confirm the correlation between degree of crystallinity and morphology. Studies at different concentrations and solvent mixtures provide valuable information regarding the nucleation and growth mechanism of the system, showing that the micelle dynamics are a key aspect of the assembly process. Furthermore, the in situ crystallization-driven cylinder formation during the acrylate ester hydrolysis reaction is demonstrated. Finally, we report that the micelle morphology can be switched between cylinders and spheres by facilitating or blocking the crystallization of the core block, demonstrating a simple method to control the morphology of the resultant assembly.