Open Access

Nele Schulte

• The research for plastic alternatives is one of the most important recent fields in organic and polymer chemistry, aiming to develop novel materials for a more sustainable future. As humans impact even the most remote places on earth, pollution due to the accumulation of synthetic polymers is the witness of this devastating dynamic. However, promising biomass derived polymers have been discovered,The research for plastic alternatives is one of the most important recent fields in organic and polymer chemistry, aiming to develop novel materials for a more sustainable future. As humans impact even the most remote places on earth, pollution due to the accumulation of synthetic polymers is the witness of this devastating dynamic. However, promising biomass derived polymers have been discovered, showing the potential to replace fossil-based plastics efficiently. Nevertheless, only a small number of bio-based materials having comparable properties with their petrol-based counterparts are available nowadays. Intending to enlarge the knowledge on the possible renewable, recyclable, and/or biodegradable polymer materials, developing alternative methods and synthetic routes are indispensable. The chemo-enzymatic synthesis of polymers derived from itaconic acid (IA) represents a novel route amongst the various possible alternative paths of polymer synthesis and production. IA and its diester, dimethyl itaconate (DMI), have received a lot of interest as a new chemical building block since it is biotechnologically generated from carbohydrates on a large scale. Their trifunctional structures enable the production of novel polymers such as poly(itaconates), related copolymers, and derived monomers for polycondensation such as the herein described bispyrrolidone (BP) structures, dimethyl 2-((diethylamino)methyl)succinate (DAMS) and dimethyl 2-((octylthio)methyl)succinate (DOMS). This thesis elucidates, for the first time, the use of BP and DOMS as monomers for enzymatically catalyzed polymerization reactions. Novel BP monomers were prepared from reactions between renewable DMI and various aliphatic diamines. These BP monomers were synthesized with high conversions and purity showing versatility as monomer for polycondensation and as plasticizing additives in polymer blends with poly(lactic acid) (PLA). In particular, the monomers and new polyesters obtained by their polycondensation demonstrated remarkable thermal stability. Being a rather new field of research, polyesters generated from unsaturated acids like IA have only just begun to receive attention, despite a wide range of possible uses, including UV-curing resins for coatings, inks or adhesives, and thermally curing compositions, to mention a few. Establishing ecofriendly synthesis routes, combining the various tools available and theoretical organic chemistry, is an important step to allow the development of more sustainable synthesis and work-up procedures in the polymer industry. Within this project, further investigation into the synthesis and the potential of itaconate-based polyesters is described. The BP monomers synthesis and polymerization (using an immobilized enzyme) creating novel bio-based polyesters is particularly highlighted.…