Probing the Growth Kinetics for the Formation of Uniform 1D Block Copolymer Nanoparticles by Living Crystallization-Driven Self-Assembly

Living crystallization-driven self-assembly (CDSA) is a seeded growth method for crystallizable block copolymers (BCPs) and related amphiphiles in solution and has recently emerged as a highly promising and versatile route to uniform core-shell nanoparticles (micelles) with control of dimensions and architecture. However, the factors that influence the rate of nanoparticle growth have not been systematically studied. Using transmission electron microscopy, small and wide-angle X-ray scattering, and super-resolution fluorescence microscopy techniques, we have investigated the kinetics of the seeded growth of poly(ferrocenyldimethylsilane)-b-(polydimethylsiloxane) (PFS-b-PDMS), as a model living CDSA system for those employing, for example, crystallizable emissive and biocompatible polymers. By altering various self-assembly parameters including concentration, temperature, solvent, and BCP composition our results have established that the time taken to prepare fiber-like micelles via the living CDSA method can be reduced by decreasing temperature, by employing solvents that are poorer for the crystallizable PFS core-forming block, and by increasing the length of the PFS core-forming block. These results are of general importance for the future optimization of a wide variety of living CDSA systems. Our studies also demonstrate that the growth kinetics for living CDSA do not exhibit the first-order dependence of growth rate on unimer concentration anticipated by analogy with living covalent polymerizations of molecular monomers. This difference may be caused by the combined influence of chain conformational effects of the BCP on addition to the seed termini and chain length dispersity.