Anomalous Liquid-Liquid Phase Separation Dynamics in Polymerization-Driven Complex Coacervation

Polymerization-driven liquid-liquid phase separation (LLPS) underpins critical biological processes and biomaterial innovations, yet its underlying kinetic pathway and domain growth law remain unclear. Here we report the first computational study of LLPS dynamics in polymerization-driven polyelectrolyte complex coacervation, where the degree of macromolecular charge asymmetry and polymer connectivity are dynamically changing during polymerization. We show that the polymerization-driven LLPS leads to two-stage kinetics in domain growth L(t): At an early stage, an exponential growth L(t) ∼ exp(t) emerges due to polymerization-driven collapse of conjugated polyions; at later stage, the coupling between polymerization and coarsening lead to a single power-law in domain growth with near-linear scaling L(t) ∼ t. Both stages show drastically faster LLPS dynamics in domain growth compared to the classical prediction of L(t) ∼ t^1/3.