Establishing Structure‐Property Relationships in Model Amphiphilic Polymer Co‐Networks

Abstract

Amphiphilic polymer co‐networks (APCNs) offer a versatile platform as materials for numerous applications, yet their rational design requires a fundamental understanding of the complex interplay between molecular architecture and macroscopic properties. Here, we present a well‐defined model platform based on the heterocomplementary coupling of tetra‐PEG and tetra‐PCL star polymers. This system enables the systematic exploration of how synthesis conditions govern network formation, mechanical response, and transport behavior. Network properties were characterized through swelling studies and rheology, while the diffusion of star polymers was probed using combined Fluorescence Recovery After Photobleaching (FRAP) and Forced Rayleigh Scattering (FRS). Complementary Dynamic Light Scattering (DLS) experiments with diffusive probes enabled the extraction of diffusion‐governing length scales, such as the network correlation length and the hydrodynamic screening length. This multi‐methodological approach establishes quantitative structure–property–transport relationships and highlights the interplay between synthesis, network architecture, and functional properties. The PEG–PCL model APCN platform thus provides a predictive framework for the rational design of tailor‐made amphiphilic materials with tunable mechanics and transport characteristics.