Renewable Monomers and Polymers from Biomass-derived Acids and Furans

Abstract

Biomass-derived acids and furans are great building blocks of renewable plastics. This thesis focuses on the synthesis of novel biomass-based reactive monomers and polymers as well as the study of degradation of polymeric materials. Chapter 2 covers the synthesis of a reactive lactone monomer from levulinic acid. Polymerization of this lactone produced a semicrystalline polyketoester with high melting temperatures. The hydrolytic degradation of this polyketoester was also studied. Under aqueous basic conditions or Brønsted acidic conditions, different degradation products were observed. Chapter 3 details the Diels-Alder reaction between furans and itaconic anhydride. The highly efficient Diels-Alder reaction between furfuryl alcohol and itaconic anhydride into a single diastereomeric adduct. This adduct was demonstrated to be a good building block for production of several aromatic compounds that are potentially reactive monomers and a metathesis polymer. Chapter 4 describes the production of alpha-methyleneglutarimides as reactive monomers for radical polymerizations. The synthesis of this monomer started from an itaconic acid derivative. We reported the thermal properties of these polymers as well as the attempt to depolymerization through mere heat. Chapter 5 is about an ongoing project targeting dimethylnaphthalenes from biomass. Poly(ethylene naphthalate) (PEN) is a poly(ethylene terephthalate) (PET) substitute with better mechanical properties, and dimethylnaphthalene is a precursor for producing PEN. Our attempt towards the synthesis of dimethylnaphthalene from biomass-derived feedstock is discussed in this chapter.