Computational Study Linking Polysulfamide Chain Design to the Hydrogen Bonding Induced Chain Aggregation

Recent advances in sulfur(VI) fluoride exchange (SuFEx) click chemistry have led to a new family of polymers - poly-N, N’-disubstituted sulfamides [Chem. Sci., 2020, 11, 7807-7812] that are analogous to polyureas. Before these polymers can replace polyureas in many commercial applications, we need better fundamental understanding of poly-N, N’-disubstituted sulfamides. We present a computational study of polysulfamide chains and their assembly driven by hydrogen bonding interactions between the sulfamide groups. These computations support experiments that show different extents of chain crystallinity for varying aliphatic and aromatic chemical substitutions on either side of the sulfamide groups. Using a coarse-grained model that captures directional interactions in polymers and molecular dynamics simulations we link the contour length, bulkiness, and flexibility of the substituted chemistries on either side of the sulfamide group to the morphology (e.g., positional and orientational order among the chains) in the polysulfamide aggregates. We will conclude this talk with a sensitivity analysis based on the variations in the chain design parameters and the resulting change in positional and orientational order of the polysulfamide chains in the chain aggregates.