Scalable Fiber-Like Micelles and Block Co-micelles by Polymerization-Induced Crystallization-Driven Self-Assembly.

Self-assembled 1D block copolymer nanoparticles (micelles) are of interest for a range of applications. However, mor-phologically pure samples are often challenging to access, and precise dimensional control is not possible. Moreover, the development of synthetic protocols that operate on a commercially viable scale has been a major challenge. Herein, we describe the preparation 1D fiber-like micelles with crystalline cores at high concentrations by a one-pot process termed polymerization-induced crystallization-driven self-assembly (PI-CDSA). We also demonstrate the formation of uniform fibers by living PI-CDSA, a process in which block copolymer synthesis, self-assembly, and seeded growth are combined. We have demonstrated that the method is successful for block copolymers that possess the same composi-tion as that of the seed (homoepitaxial growth) and also where the coronal chemistries differ to give segmented 1D fibers known as block co-micelles. We have also shown that heteroepitaxial growth allows the formation of scaled up block co-micelles where the composition of both the core and corona was varied. These proof of concept experiments indicate that PI-CDSA is a promising, scalable route to a variety of polydisperse or uniform 1D nanoparticles based on block copolymers with different crystalline core chemistries and, therefore, functions.