Structure and properties of bottlebrush polyelectrolyte complexes

Structural variation of polyelectrolytes has been shown to play an important role in altering polyelectrolyte complex (PEC) properties in recent years. However, molecular-level details such as polyelectrolyte architecture remain underdeveloped. Here, we use a combination of ring-opening metathesis polymerization (ROMP), atom-transfer radical polymerization (ATRP), and postpolymerization reactions to create densely branched bottlebrushes of poly(dimethylamino ethyl methcacrylate) and poly(tert-butyl methacrylate) with high molecular weights (MDa), which we then convert into fully charged and densely branched bottlebrushes of poly(trimethylaminoethyl methacrylate) (PTMAEMA) and poly(methacrylic acid) (PAA). We investigate the structure and properties of bottlebrush polyelectrolyte complexes (BPECs) using optical microscopy, rheology, cryogenic transmission electron microscopy (Cryo-TEM), and small-angle X-ray scattering (SAXS). Bottlebrush polyelectrolyte complexes are white solids, which exhibit gel-like mechanical properties, which we attribute to sidechain interpenetration. Using a combination of Cryo-TEM and SAXS, we are able to outline the structural development of BPECs, detailing how the network topology, sidechain conformation, and interdigitation spacing changes as a function of salt. Our results provide a foundation for further exploration of branched architectures within polyelectrolyte complexation.