This thesis deals with the synthesis and characterization of well-defined functional polyesters, as well as their processing resulting in novel materials with enhanced degradability. The synthesized materials can be used in several biomedical applications, since they are biocompatible and biodegradable, can be processed into various shapes such as 3D highly porous scaffolds, provide functional groups for pre- or post-processing functionalization, and exhibit, after processing, mechanical properties which resemble those of natural devices.
All polymer structures and networks within this thesis are based on poly(-caprolactone), a biodegradable polymer well-known in biomedical applications. Star-shaped poly(-caprolactone)s were synthesized via anionic ring-opening polymerization of -caprolactone with metal catalysts or enzymes in the presence of 4 and 6-arm star-shaped multifunctional initiators. Hydroxy end groups were functionalized, resulting in acrylate or methacrylate functionalized prepolymers. A broad library of precisely defined prepolymers with different architecture and molar masses is presented…