Robust, Reprocessable, and Reconfigurable Cellulose-Based Multiple Shape Memory Polymer Enabled by Dynamic Metal–Ligand Bonds

Smart materials with multiple shape memory capacities have gradually attracted the interest of a lot of researchers due to their potential application in textiles, smart actuators, and aerospace engineering. However, the design and sustainable synthesis of multiple shape memory polymers (SMPs) simultaneously possessing robust mechanical strength, reprocessability, and reconfigurability still remain full of challenges. Starting from a readily available biomass material cellulose, a well-defined SMP, cellulose-graft-poly(n-butyl acrylate-co-1-vinylimidazole) copolymer (Cell-g-(BA-co-VI)) was facilely synthesized by addition–fragmentation chain transfer polymerization (RAFT) and the subsequent metallosupramolecular cross-linking. Taking advantage of the dynamic bonding, i.e., the rapid reversible fragmentation and the formation of metal ion–imidazole coordination, polymer networks with highly tunable mechanical properties, excellent solid-state plasticity, and quadruple-shape memory capacity are handily attainable. Microscopically, the metal–ligand clusters have a strong tendency to phase segregate from the soft grafted copolymers indicated by atomic force microscopy (AFM), and these serve as netpoints to construct novel SMPs. This article represents our new exploration of the next-generation SMPs based on cellulose backbone where carrying with supramolecular cross-linked soft grafted copolymers. This architecture design allows achieving robust, reprocessable, and reconfigurable thermoplastic SMPs that are difficult to realize by many other methods. Integrating these properties into one system in a synergetic manner also provides a novel approach to the high value addition application of cellulose in the fabrication of advanced functional materials.