Living Supramolecular Polymerization of Rod-Coil Block Copolymers: Kinetics, Origin of Uniformity, and Its Implication.

We conduct Brownian dynamics simulations to explore the kinetics of living supramolecular polymerization using seeded growth of rod-coil block copolymers as a model system. We model the kinetics of supramolecular polymerization by developing kinetic theory for classical living covalent polymerization with length-dependent rate coefficients. The rate coefficient in the proposed kinetics theory decreases with increasing cylindrical micelle length, which is attributed to micelle rigidity and unique diffusion behavior. Like living covalent polymerization, living supramolecular polymerization can produce low-dispersity assemblies with rigidity via different mechanisms. The results nicely explain the available experimental observations.