Ring-Opening Polymerization as a Platform for Tailored Polymers from Isosorbide and Other Renewable Feedstocks

Abstract

To withstand the critical need for plastics, we must innovate how polymers are constructed and deconstructed. Isosorbide and other renewable feedstocks have shown exceptional promise as replacements for commodity plastics. The work in thesis describes ring-opening polymerization as a previously unexplored strategy to synthesize polymers primarily from isosorbide, as well as several other renewable feedstocks. We describe traditional and contemporary approaches to synthesizing polymers from isosorbide along with the current challenges faced (Chapter 1). Initial efforts were aimed at developing polyethers with isosorbide in the backbone through ring-opening polymerization of an annulated isosorbide derivative, ultimately providing control over both the polymer microstructure and macromolecular architecture, enabling cyclic or linear polymers to be targeted (Chapter 2). This work is a stepping-stone for polymerization of complex heterocycles from renewable feedstocks. We then turned our focus to polycarbonate analogs to the poly(meth)acrylates previously developed in our lab (Chapter 3). Specifically, we established a method for the rapid synthesis of chemically recyclable, functional (co)polycarbonates with tailored thermal properties from isosorbide and other renewably derived alcohols. The polycarbonates were then redesigned to exploit industrial waste streams—specifically glycerol and carbon dioxide—to construct the value-added polymer backbone (Chapter 4). Tandem functionalization and ring-opening polymerization is being pursued to afford polycarbonates with 100% renewable content. These efforts may facilitate the development of commercially relevant sustainable polycarbonates with tailored properties that work toward eliminating plastic waste streams.