Functional Polyethylenes with Precisely Placed Thioethers and Sulfoniums through Thiol–Ene Polymerization

Abstract

The precise functionalization of polyethylenes, often accomplished through acyclic diene metathesis polymerization (ADMET), is a significant area of research that has improved polyethylene properties and performance. Here, the synthesis of precisely functionalized polyethylenes was accomplished using the thiol–ene step-growth (TES) polymerization. The simplicity and versatility of this technique allowed for the synthesis of a variety of polymers and enabled the study of carbon spacer length between and repeat unit symmetry about the resulting backbone thioether moiety. In addition, the backbone thioethers of some samples were functionalized postpolymerization with methyl triflate to produce polyethylenes containing sulfonium cations. All polymers were then characterized for their thermal stability, crystallinity, and morphology using differential scanning calorimetry (DSC) and X-ray scattering. While the carbon spacer length and repeat unit symmetry had no effect on polymer thermal stability, the incorpor...