Impact-Resistant Poly(3-Hydroxybutyrate)/Poly(ε-Caprolactone)-Based Materials, through Reactive Melt Processing, for Compression-Molding and 3D-Printing Applications

Biobased and biocompatible polymers, such as polyhydroxyalkanoates (PHAs), are of great interest for a large range of applications in the spirit of green chemistry and upcoming reuse and recycling strategies. Polyhydroxybutyrate (PHB), as a promising biocompatible polymer belonging to PHAs, is subject to increased research concern regarding the high degree of crystallinity and brittle behavior of the resulting materials. Therefore, the improvement of PHB’s physico-mechanical properties aims to decrease the Young’s modulus values and to increase the ductility of samples. Here, we proposed an ambitious approach to develop melt-processed materials, while combining PHB characteristics with the ductile properties of poly(ε-caprolactone) (PCL). In order to compatibilize the poorly miscible PHB/PCL blends, dicumyl peroxide (DCP) was used as a free-radical promotor of polyester interchain reactions via the reaction extrusion process. The resulting PHB/PCL-DCP materials revealed a slight increase in the elongation at break, and significant improvement in the impact resistance (7.2 kJ.m(−2)) as compared to PHB. Additional decrease in the Young’s modulus values was achieved by incorporating low molecular polyethylene glycol (PEG) as a plasticizer, leading to an important improvement in the impact resistance (15 kJ.m(−2)). Successful 3D printing using fused deposition melting (FDM) of the resulting PHB/PCL-based blends for the design of a prosthetic finger demonstrated the great potential of the proposed approach for the development of next-generation biomaterials.