Polymer networks generally consist of an ensemble of single chains. However, understanding how chain conformation affects the structure and properties of polymer networks remains a challenge for optimizing their functionality. Here, we present the fabrication and comparative study of a polymer network composed of collapsed self-entangled chains (intrachain entangled network) and a standard polymer network in which random-coil chains are entangled with each other (interchain entangled network). For poly(methyl methacrylate) thin films composed of these networks, we coupled solvent vapor swelling and single-molecule tracking techniques to examine the anomalies in the dynamics of a small-molecular probe included in the system. We demonstrate that when compared to the interchain entangled network the intrachain one exhibits a more substantial structural heterogeneity, particularly under highly crowded conditions. This network also exhibits physical compactness, which keeps the heterogeneous network structure frozen over time and impedes network plasticization through solvent uptake by the film.
Keywords: Polymer network; anomalous diffusion; entanglement; plasticization; single-molecule tracking; solvent vapor swelling; structural heterogeneity.