Thermadapt shape memory AB-copolymer networks exhibiting tunable properties and kinetics of topological rearrangement

Polycaprolactone (PCL) based thermadapt shape memory polymers (SMPs) have exhibited superiority over traditional analogues by allowing shape-editing to reconfigure permanent shapes into more complex geometrical shapes, driven by the pursuit of advanced functionalities for high-value applications. Nevertheless, although transesterification-based PCL networks exhibit impressive shape reconfigurability as prototypical thermadapt SMPs, there are still constraints in terms of the need for significant flexibility in architectural adjustment and property modulation without compromising reconfigurability, which would be relevant for practical applications. Here, we present a simple yet efficient strategy to create PCL-based thermadapt SMPs that possess a highly tunable structure and properties, as well as exceptional reconfigurability. The family of SMPs, called thermadapt shape memory AB copolymer networks (AB-CPNs), was synthesized by UV-initiated free radical polymerization between PCL diacrylate as crosslinker and 4-hydroxybutyl acrylate (HBA) as comonomer. The thermadapt AB-CPNs allow for significant structural alterations with 0 wt% to 70 wt% HBA while maintaining excellent shape memory and shape reconfigurability effects. The insertion of the polymer segment containing free hydroxyls not only promises tunable material properties but also makes network rearrangement easier since dynamic hydroxy-ester bonds are more active than dynamic ester-ester bonds. It is envisioned that the thermadapt shape memory AB-CPNs with widely tunable macroscopic properties will drive progress in the real-world applications of SMP devices with complicated geometric structures.