Liquid-liquid phase separation of immiscible polymers at double emulsion interfaces for configurable microcapsules

Abstract

Liquid-liquid phase separation at complex interfaces is a common phenomenon in biological systems and is also a fundamental basis to create synthetic materials in multicomponent mixtures. Understanding the liquid-liquid phase separation in well-defined macromolecular systems is anticipated to shed light on similar behaviors in cross-disciplinary areas. Here we study a series of immiscible polymers and reveal a generic phase diagram of liquid–liquid phase separation at double emulsion interfaces, which depicts the equilibrium structures by interfacial tension and polymer fraction. We further reveal that the interfacial tensions in various systems fall on a linear relationship with spreading coefficients. Based on this theoretical guideline, the liquid–liquid phase separation can be modulated by a low fraction of amphiphilic block copolymers, leading the double emulsion droplets configurable between compartments and anisotropic shapes. The solidified anisotropic microcapsules could provide unique orientation-sensitive optical properties and thermomechanical responses. The theoretical analysis and experimental protocol in this study yield a generalizable strategy to prepare multiphase double emulsions with controlled structures and desired properties.