Photo-Crosslinked Poly(ε-caprolactone fumarate) Networks: Roles of Crystallinity and Crosslinking Density in Determining Mechanical Properties.

We present a material design strategy of combining crystallinity and crosslinking to control the mechanical properties of polymeric biomaterials. Three polycaprolactone fumarates (PCLF530, PCLF1250, and PCLF2000) synthesized from the precursor polycaprolactone (PCL) diols with nominal molecular weights of 530, 1250, and 2000 g.mol(-1), respectively, were employed to fabricate polymer networks via photo-crosslinking process. Five different amounts of photo-crosslinking initiator were applied during fabrication in order to understand the role of photoinitiator in modulating the crosslinking characteristics and physical properties of PCLF networks. Thermal properties such as glass transition temperature (T(g)), melting temperature (T(m)), and degradation temperature (T(d)) of photo-crosslinked PCLFs were examined and correlated with their rheological and mechanical properties.