ATRP enhances structural correlations in polymerization-induced phase separation

TL;DR

This paper demonstrates that ATRP can be used in solid-state polymerization to control and stabilize nanoscale phase-separated structures with high precision, enabling new material design possibilities.

Contribution

It introduces a novel method of controlling phase separation in solids using ATRP, achieving durable, well-correlated nanostructures with tunable length scales.

Findings

ATRP controls nucleation, growth, and stabilization of phase-separated domains.

Nanostructures exhibit low size dispersity and high structural correlation.

Material length scale is tunable via synthesis parameters.

Abstract

Synthetic methods to control the structure of materials at sub-micron scales are typically based on the self-assembly of structural building blocks with precise size and morphology. On the other hand, many living systems can generate structure across a broad range of length scales in one step directly from macromolecules, using phase separation. Here, we introduce and control structure at the nano- and microscales through polymerization in the solid state, which has the unusual capability of both triggering and arresting phase separation. In particular, we show that atom transfer radical polymerization (ATRP) enables control of nucleation, growth, and stabilization of phase-separated poly-methylmethacrylate (PMMA) domains in a solid polystyrene (PS) matrix. ATRP yields durable nanostructures with low size dispersity and high degrees of structural correlations. Furthermore, we demonstrate that the length scale of these materials is controlled by the synthesis parameters.