Developing Hydroesterification as a Tool for Sustainable Polymer Synthesis

Abstract

The development of new inexpensive routes to sustainable polymers is of paramount importance. The focus of this this thesis is on the development of sustainable polyesters from bioderived monomers via a carbonylative reaction, hydroesterification. Chapter 1 gives a literature background on carbonylation chemistry, the mechanism of hydroesterification, and previous work developing this reaction for polymerization. Chapter 2 discusses the development and polymerization of α,ω-enol ether monomers containing rigid and bioderived diol moieties. Chapter 3 describes catalyst controlled polyester branching in the polymerization of 10-undecenol allowing for tuning ranging from 72% linear to 78% branched. Lastly, Chapter 4 details further developments of this reaction including the use of oleyl alcohol as a monomer, depolymerization efforts, and the use of (py)2Co(CH2SiMe3)2 as a catalyst for methoxycarbonylation.