High-Efficient Access to Inverse Morphologies via Living Anionic Polymerization-Mediated Polymerization-Induced Cooperative Assembly

Polymerization-induced cooperative assembly (PICA), originating from polymerization-induced self-assembly, is believed to be a high-efficient method to access higher-order morphologies. Living anionic polymerization (LAP) possesses numerous advantages, such as high monomer conversion, rapid polymerization rate, and excellent controllability. We herein reported a facile strategy to prepare higher-order morphologies using a living anionic polymerization-mediated polymerization-induced cooperative assembly (LAP PICA) process based on polyisoprene-b-polystyrene/polystyrene (PS) blends. The morphological transition ranging from spherical micelles to worms, jellyfish, vesicles, sponges, and ordered mesophases of Im3m cubosomes and p6mm hexosomes was observed and demonstrated by transmission electron microscopy, field-emission scanning electron microscopy, and small-angle X-ray scattering. Moreover, morphological distribution diagrams including factors, such as the degree of polymerization and content of the PS homopolymer, and solid contents were depicted to unveil the effect of LAP PICA on morphologies and provide guiding principles for preparing a variety of morphologies. Furthermore, a relevant morphological transition mechanism via LAP PICA was put forward.