We herein report a facile strategy to prepare triggered degradable block copolymer nano/macro-objects, ranging from typical micelles, worms, jellyfish, and vesicles to rarely achieved spongosomes, cubosomes, and hexosomes via RAFT-mediated polymerization-induced self-assembly (PISA). The morphological transitions from a simple spherical micelle to a spongosome, ordered Imm cubosome, and p6mm hexosome were captured and demonstrated by TEM, SEM, and synchrotron SAXS. In addition, morphological phase diagrams including important factors, such as solid contents, degree of polymerization (DP), and stabilizer block chain length, were constructed to unveil the formation mechanism and guide the scalable preparation of complex morphologies with packing parameter (P) > 1. This study not only represents an example that achieved inverse mesophases via acrylate-based monomers with high conversion but also reports a triggered degradable system in the most extended morphological range via PISA. The facile synthesis and stimuli-responsiveness of our system should greatly expand the utility of polymer inverse mesophases for triggered releasing, templating, and many other applications.
Keywords: PISA; cubosome; hexosome; inverse mesophases; self-assembly; stimuli-responsive.