Abstract
Over the course of this work, the elaboration and the organocatalysed polymerisation and copolymerisation of morpholine-2,5-diones, monomers derived from α-amino acids, was studied. Firstly, an experimental protocol was developed, allowing for the synthesis of morpholine-2,5-diones from different amino-acids. The latter was then used for the production of a mix of morpholine-2,5-diones from a blend of amino-acids. This mixture of morpholine-2,5-diones was subsequently copolymerised using different catalysts. Next, the ring-opening polymerisation of 3S-(isobutyl)morpholine-2,5-dione as well as its copolymerisation with lactide was investigated via organocatalysis using 1,8-diazabicyclo[5.4.0]undec-7-ene and a thiourea co-catalyst. This catalytic system granted great control over the synthesis of polydepsipeptides and poly(depsipeptide-r-lactide) copolymers. Finally, with the aim of reducing the environmental impact of the different reactions developed herein, mechanochemical and microwave-based procedures were investigated. Using these techniques, a range of morpholine-2,5-diones were successfully produced in a much simpler and faster manner whilst using considerably less solvent and energy. Mechanochemistry also proved successful for the organocatalysed ring-opening polymerisation of 3S-(isobutyl)morpholine-2,5-dione and its copolymerisation with lactide. This study grants access to the direct comparison between solution and mechanochemical based ROPs which is, to date, a mostly unexplored field.