Fabrication of Polycaprolactone-Based Polyurethanes with Enhanced Thermal Stability.

The benefit of being acquainted with thermal properties, especially the thermal stability of polyurethanes (PU), and simplified methods for their improvement is manifold. Considering this, the effect of embedding different amounts of unmodified and surface-modified TiO2 nanoparticles (NPs) within PU, based on polycaprolactone (PCL) and Boltorn® aliphatic hyperbranched polyester, on PU properties was investigated. Results obtained via scanning electron microscopy, swelling measurements, mechanical tests and thermogravimetric analysis revealed that TiO2 NPs can be primarily applied to improve the thermal performance of PU. Through surface modification of TiO2 NPs with an amphiphilic gallic acid ester containing a C12 long alkyl chain (lauryl gallate), the impact on thermal stability of PU was greater due to the better dispersion of modified TiO2 NPs in the PU matrix compared to the unmodified ones. Also, the distinct shape of DTG peaks of the composite prepared using modified TiO2 NPs indicates that applied nano-filler is mostly embedded in soft segments of PU, leading to the delay in thermal degradation of PCL, simultaneously improving the overall thermal stability of PU. In order to further explore the thermal degradation process of the prepared composites and prove the dominant role of incorporated TiO2 NPs in the course of thermal stability of PU, various iso-conversional model-free methods were applied. The evaluated apparent activation energy of the thermal degradation reaction at different conversions clearly confirmed the positive impact of TiO2 NPs on the thermal stability and aging resistance of PU.

Poly(urethane-dimethylsiloxane) copolymers displaying a range of soft segment contents, noncytotoxic chemistry, and nonadherent properties toward endothelial cells.

Polyurethane copolymers based on α,ω-dihydroxypropyl poly(dimethylsiloxane) (PDMS) with a range of soft segment contents were prepared by two-stage polymerization, and their microstructures, thermal, thermomechanical, and surface properties, as well as in vitro hemo- and cytocompatibility were evaluated. All utilized characterization methods confirmed the existence of moderately microphase separated structures with the appearance of some microphase mixing between segments as the PDMS (i.e., soft segment) content increased. Copolymers showed higher crystallinity, storage moduli, surface roughness, and surface free energy, but less hydrophobicity with decreasing PDMS content. Biocompatibility of copolymers was evaluated using an endothelial EA.hy926 cell line by direct contact, an extraction method and after pretreatment of copolymers with multicomponent protein mixture, as well as by a competitive protein adsorption assay. Copolymers showed no toxic effect to endothelial cells and all copolymers, except that with the lowest PDMS content, exhibited resistance to endothelial cell adhesion, suggesting their unsuitability for long-term biomedical devices which particularly require re-endothelialization. All copolymers exhibited excellent resistance to fibrinogen adsorption and adsorbed more albumin than fibrinogen in the competitive adsorption assay, suggesting their good hemocompatibility. The noncytotoxic chemistry of these synthesized materials, combined with their nonadherent properties which are inhospitable to cell attachment and growth, underlie the need for further investigations to clarify their potential for use in short-term biomedical devices.