Synthesis and characterization of divinyl-fumarate poly-ε-caprolactone for scaffolds with controlled architectures

Abstract

A vinyl-terminated polycaprolactone has been developed for tissue engineering applications using a one-step synthesis and functionalization method based on ring opening polymerization (ROP) of ε-Caprolactone, with hydroxyl ethyl vinyl ether (HEVE) acting both as the initiator of ROP and as photo-curable functional group. The proposed method employs a catalyst based on aluminium, instead of the most popular Tin(II) 2-ethylhexanoate, to reduce the cytotoxicity. Following the synthesis of the vinylterminated polycaprolactone, its reaction with fumaryl chloride (FuCl) results in a divinyl-fumarate polycaprolactone (VPCLF). The polymers obtained were thoroughly characterized using Fourier transform infrared spectroscopy (FTIR) and gel permeation chromatography (GPC) techniques. The polymer has been successfully employed, in combination with N-vinyl pyrrolidone (NVP), to fabricate films and computer-designed porous scaffolds by micro-stereolithography (μ-SL) with gyroid and diamond architectures. Characterization of the networks indicated the influence of NVP content on the network properties. Human mesenchymal stem cells adhered and spread onto VPCLF/NVP networks showing good biological properties and no cytotoxic effect.

Photo-crosslinked synthetic biodegradable polymer networks for biomedical applications

“…As additive manufacturing is such an important method to prepare photo-crosslinked biodegradable polymer networks, it is important to discuss the photo-crosslinkable systems that have been developed for use in additive manufacturing. Photo-crosslinkable systems based on fumarate-functionalized oligomers were developed [10,129,[172][173][174][175]. These systems were based on PDLLA, PCL or poly(propylene fumarate) (PPF).…”

“…These systems were based on PDLLA, PCL or poly(propylene fumarate) (PPF). The disadvantage of these materials is that they need a reactive diluent such as N-vinyl-2pyrrolidone (NVP) [173,175] and diethyl fumarate [129,172,174]. As described earlier, this increases the non-degradable content of the resulting polymer networks.…”

“…A photo-crosslinkable system for SLA based on divinyl-fumarate poly(e-caprolactone) was used to prepare tissue engineering scaffolds [175]. Initially, resin were prepared with either a non-reactive solvent (N-methyl-2-pyrrolidone, NMP) or with NVP as a reactive diluent.…”

Synthesis and Electrospinning of Polycaprolactone from an Aluminium-Based Catalyst: Influence of the Ancillary Ligand and Initiators on Catalytic Efficiency and Fibre Structure

“…For these reasons, and due to the inherent low toxicity of aluminium oxide compounds [11], we decided to focus our attention on this class of catalysts. We have reported previously [12] on the possibility to synthesise PCL with photo-curable vinyl groups using an aluminium catalyst with 2,6-di- tert -butyl-4-methylphenol (BHT), similar to that reported by Akatsuka et al in 1995 [13].…”

“…We have previously reported on the catalytic performance of an Al-(BHT) 2 catalyst in the presence of suitable alcohol initiators [12].…”