Enhanced Tensile Properties, Biostability, and Biocompatibility of Siloxane–Cross-Linked Polyurethane Containing Ordered Hard Segments for Durable Implant Application

This work developed a series of siloxane-modified polyurethane (PU-Si) containing ordered hard segments by a facile method. The polyaddition between poly(ε-caprolactone) and excess diurethane diisocyanate was carried out to synthesize a polyurethane prepolymer with terminal isocyanate groups, which was then end-capped by 3-aminopropyl triethoxysilane to produce alkoxysilane-terminated polyurethane; the target products of PU-Si were obtained with hydrolysis and the condensation of alkoxysilane groups. The chemical structures were confirmed by FT-IR and XPS, and the effect of the siloxane content or cross-linked degree on the physicochemical properties of the PU-Si films was investigated in detail. The formation of the network structure linked by Si-O-Si bonds and interchain denser hydrogen bonds endowed PU-Si films with fine phase compatibility, low crystallinity, high thermal stability, and excellent tensile properties. Due to the high cross-linked degree and low interfacial energy, the films displayed a high surface water contact angle and low equilibrium water absorption, which resulted in slow hydrolytic degradation rates. Furthermore, the evaluation of protein adsorption and platelet adhesion on the PU-Si film surface presented high resistance to biofouling, indicating superior surface biocompatibility. Consequently, the siloxane-cross-linked polyurethane, which possessed excellent tensile properties, high biostability, and superior biocompatibility, showed great potential to be explored as biomaterials for durable implants.