Post-Crosslinked Polyurethanes with Excellent Shape Memory Property

Shape-memory polymers are highly desirable in implant biomaterials for minimally invasive surgical procedures. However, most of them lack suitable transition temperature, mechanical properties, and biodegradability. Here, a series of shape-memory polyurethanes are synthesized by postcrosslinking in hard-segment domains using a flexible crosslinker. The materials used are all nontoxic and biodegradable. Through postcrosslinking of unsaturated linear polyurethanes with flexible and biodegradable crosslinker, the crosslinked polyurethanes (CPUs) show good mechanical properties, excellent shape-memory property, and repeatability. The post-crosslinking structure and shape-memory mechanism of CPUs are investigated by Fourier transform infrared spectroscopy, differential scanning calorimetry, and dynamic mechanical analysis tests. The crosslinker endows the fixed phase enough crosslinking and inserts in the hard segments to give the fixed phase certain elasticity. The elastic hard segments make them form more hydrogen bonds with soft segments during shape deformation. The low-molecular-weight poly (ε-caprolactone) offers the samples a shape-memory transition temperature at around 37 °C, which is suitable for implant devices in vivo. This work expands CPUs with an elastic crosslinking structure as potential candidates for implant biomaterials. Since the post-crosslinking polymerization is facile, it can be convenient for industrial production.