Atomistic Molecular Dynamics Study of Linear and Branched Imidazole-Functionalized Polymers

We present atomistic molecular dynamics simulations of linear and branched fluorinated polymer chains, with and without imidazole functionalization, designed as a model for solvent-free proton-conducting membranes for high-temperature fuel cell applications. Simulations conducted over a temperature range of 300 to 550 K, and diffusion-based relaxation times reveal that glass transition temperatures depend on polymer architecture: the branched and functionalized systems exhibit transitions near 400 K compared to 500 K for the linear chain. Fluorine-fluorine radial distribution functions demonstrate that branching disrupts local packing order, while imidazole substitution creates specific intra-chain interactions. Radius-of-gyration distributions reveal that branching significantly increases chain extension and creates multiple conformational families, whereas imidazole groups stabilize compact conformations at low temperatures that transition to more diverse states upon heating. These findings provide molecular-scale insight into how polymer architecture controls thermal transitions and structural organization in model high-temperature polymer electrolyte membranes.