There is an increasing demand for new materials in biomedical applications with material properties that are highly specific for each application area. The search for new materials requires the creation of materials with suitable mechanical properties, functionalities, three-dimensional structures and a controlled degradation profile. The focus of the work described in this thesis has been on the synthesis of functional degradable aliphatic polyesters, on the design of porous scaffolds and on their synthesis with bio-safe catalyst/initiator systems.  

An unsaturated aliphatic polyester has been synthesized by condensation polymerization to produce poly(but-2-ene-1,4-diyl malonate) (PBM), which was applicable as a cross-linked network and as a macro-co-initiator for the ring-opening polymerization (ROP) of cyclic ester monomers. The method of preparation of PBM was simple and straightforward and there was no need to purify the monomers or add a catalyst. PBM was successfully cross-linked with UV-radiation to form a transparent, colorless, flexible and strong film. When PBM was used as a macro-co-initiator, a triblock copolymer was formed with PBM middle blocks and poly(L-lactide) (PLLA) or poly(ε-caprolactone) side blocks. The ductility of the triblock copolymer of PLLA was greatly enhanced and the strength was maintained compared to the polymer obtained when PLLA was polymerized with ethylene glycol as co-initiator. The triblock copolymers were easily cross-linked to give materials with greater strength and higher modulus as a result. When these polymers were subjected to hydrolysis, a rapid initial hydrolysis of the amorphous PBM middle block changed the microstructure from triblock to diblock, with a significant reduction in ductility and number average molecular weight. Highly porous scaffolds were created from these functional materials and the mechanical properties were evaluated by a cyclic compression test under mimicked physiological conditions.

Copolymers of L-lactide (LLA) and ε-caprolactone (CL), trimethylene carbonate (TMC) or 1,5-dioxepane-2-one (DXO) have been synthesized with a low stannous-2-ethyl hexanoate  (Sn(Oct)₂) ratio and used to fabricate porous tubular scaffolds. The tubes were designed to have a range of mechanical properties suitable for nerve regeneration, with different porosities and different numbers of layers in the tube wall. The adaptability of an immersion-coating and porogen-leaching technique was demonstrated by creating tubes with different dimensions.

Although a low amount of residual tin (monomer-to-initiator ratio of 10000:1) is accepted in biomedical applications, an efficient bio-safe catalyst/initiator system would be favored. The catalytic activities of bio-safe Bi (III) acetate and creatinine towards the ROP of LLA have been compared with those of Sn(Oct)₂-based systems and with those of a system catalyzed by enzymes. All these systems were shown to be suitable catalysts for the synthesis of high and moderate molecular weight PLLAs.