Thermadapt Shape Memory PCL-co-PBA Network Exhibiting Tunable Properties and Dynamics of Ester–Ester Exchange Reactions

Beyond self-repairability and reprocessability, permanent shape reconfigurability in thermadapt shape memory polymers (TSMPs) is a prominent functionality in dynamic covalent polymer networks. The design and synthesis of TSMPs with a wide range of tunable macroscopic properties that do not require sophisticated chemistry or modification are highly desirable for real-world device applications but are a significant challenge. Herein, we present a straightforward yet efficient strategy to prepare TSMPs with adjustable properties, good reconfigurability, and self-repairability via ester–ester exchange. The class of TSMPs is engineered as the architecture of AB copolymer networks (AB-CPNs), which are composed of the semicrystalline polycaprolactone (PCL) as the A-segment and the poly(butyl acrylate) (PBA) as the B-segment. Regulating the weight content of the PCL segment in the thermadapt shape memory PCL-co-PBA networks can govern the network rearrangement kinetics, thermal properties, thermomechanical properties, switching temperature, and shape memory properties. The thermadapt shape memory AB-CPNs with ester–ester exchange do not require the introduction of extra hydroxyl groups, and their network structure is readily adjusted, allowing for considerable flexibility in the structure design and property adjustment. It is anticipated that a large family of thermadapt shape memory AB-CPNs with widely tunable macroscopic properties and the commercial availability of precursors will contribute significantly to real-world applications of SMP devices.