(708e) Hierarchical Assembly of Inhomogeneous Supramolecular Polymers from Hybrid Particle-Field Simulations

Through hierarchical assembly at multiple length scales, inhomogeneous supramolecular polymers (ISPs) serve as a promising self-assembly foundry for fabricating advanced functional materials by combining structural and functional capabilities. Understanding the mechanisms governing hierarchical assembly of ISPs plays a key role in unlocking such potential. By considering a “bare-bones” case of ISP – a two-component end-functionalized homopolymer blend, this study applies hybrid particle-field simulations to elucidate complicated interplay of association and phase equilibrium, association kinetics and polymer dynamics in the model system. Simulation results on micro-phase ordering systems are compared to the homogeneous system, as well as the reference system of non-associative block copolymers to illustrate couplings of the different factors. It is found that compositional phase ordering reduces association equilibrium constant, increases effective associative bond life, and slows down polymer diffusion compared to the homogenous phase. Reversible associations greatly enhanced mobility of polymers in the ordered micro-phase as compared to the non-associative block copolymers system. Segments carrying associative sites exhibit faster-than-Rouse diffusion behaviors, and a distinct diffusion mechanism in the ordered phase. Future studies on IPSs with more complex topological structures will be discussed, with an aim of providing predictive knowledge for guiding experimental investigations.