Biomass derived furanics and their macrocycles: exploring alternative approaches to bio-based polyesters

Polymers, with their versatile properties, are indispensable in everyday life. However, increasing concerns about the environmental impact of fossil-based polymers have driven extensive research into more sustainable alternatives derived from renewable resources. Building on these premises this thesis research explores the synthesis, chemical functionalization and polymerization of novel bio-based monomers and their macrocyclic derivatives. The first part focuses on introducing nitrile functionalities to the furanic compounds to broaden their chemical reactivity and utility. A significant aspect of the research involves the synthesis of macrocyclic oligomers from FDME, BHMF, and OBMF-H, followed by their entropically-driven ring-opening polymerization (ED-ROP). Macrocycles derived from FDME are synthesized through pseudo-high dilution condensation reactions with diols such as tetraethylene glycol and hexaethylene glycol. Their subsequent ED-ROP is then explored as a synthetic route to produce furan-based polyesters under mild and controlled reaction conditions. Similarly, macrocycles derived from BHMF and OBMF-H are synthesized using aliphatic linear dimethyl esters such as succinate, adipate, and sebacate, investigating both metal-based and enzymatic catalytic approaches. Their subsequent ED-ROP is investigated using enzymatic catalysis, which provides high selectivity and operational simplicity under environmentally green conditions.