Controlling solvent quality by time: Self-avoiding sprints in nonequilibrium polymerization.

Abstract

A fundamental paradigm in polymer physics is that macromolecular conformations in equilibrium can be described by universal scaling laws, being key for structure, dynamics, and function of soft (biological) matter and in the materials sciences. Here we reveal that during diffusion-influenced, nonequilibrium chain-growth polymerization, scaling laws change qualitatively, in particular, the growing polymers exhibit a surprising self-avoiding walk behavior in poor and θ solvents. Our analysis, based on monomer-resolved, off-lattice reaction-diffusion computer simulations, demonstrates that this phenomenon is a result of (i) nonequilibrium monomer density depletion correlations around the active polymerization site, leading to a locally directed and self-avoiding growth, in conjunction with (ii) chain (Rouse) relaxation times larger than the competing polymerization reaction time. These intrinsic nonequilibrium mechanisms are facilitated by fast and persistent reaction-driven diffusion ("sprints") of the active site, with analogies to pseudochemotactic active Brownian particles. Our findings have implications for time-controlled structure formation in polymer processing, as in, e.g., reactive self-assembly, photocrosslinking, and three-dimensional printing.