CHEMICALLY RECYCLABLE POLYMERS VIA ACCEPTORLESS DEHYDROGENATIVE POLYMERIZATION: SYNTHESIS AND CHARACTERIZATION OF FUNCTIONAL POLYESTERS AND POLYAMIDES

Abstract

This dissertation presents advancements in the development of acceptorless dehydrogenative polymerization (ADP) and its application to the synthesis of polyesters, polyamides, and their copolymers. ADP is an emerging catalytic strategy that overcomes many limitations of traditional polymerization methods, offering key advantages such as improved atom economy, enhanced sustainability, and a broader monomer scope. These features position ADP as a powerful platform for the synthesis of functional, structurally diverse polymers. The motivation for this work stems from the escalating plastic waste crisis. While plastics have undeniably advanced modern society through their performance and versatility, the linear nature of their life cycle continues to drive global pollution. Polyolefins, in particular, combine excellent material properties with extreme resistance to degradation, allowing them to persist in the environment for decades. The central challenge is to create materials that not only rival polyolefins in performance but also offer improved pathways for depolymerization and recycling. In this context, both ruthenium- and manganese-catalyzed ADP are explored as strategies to synthesize a range of polymers with tunable properties and built-in degradability via ester linkages. These polymers can be selectively deconstructed, offering a pathway to closed-loop recycling. The dissertation highlights recent progress in ADP, its mechanistic underpinnings, and its potential to support a circular polymer economy.