RESUMO
Dynamic covalent liquid crystal networks (DCv-LCNs) with straightforward (re)programmability, reprocessability, and recyclability facilitates the manufacture of sophisticated LCN actuators and intelligent robots. However, the DCv-LCNs are still limited to heat-assisted programming and polymer-to-polymer reprocessing/recycling, which inevitably lead to deterioration of the LCN structures and the actuation performances after repeated programming/processing treatments, owing to the thermal degradation of the polymer network and/or external agent interference. Here, a totally renewable azobenzene-based DCv-LCN with room-temperature programmability and polymer-to-monomers chemical recyclability is reported, which was synthesized by crosslinking the azobenzene-containing dibenzaldehyde monomer and the triamine monomer via the dynamic and dissociable imine bonds. Thanks to the water-activated dynamics of the imine bonds, the resultant DCv-LCN can be simply programmed, upon water-soaking at room temperature, to yield a UV-Vis light-driven actuator. Importantly, the reported DCv-LCN undergoes depolymerization in an acid-solvent medium at room temperature because of the acid-catalyzed hydrolysis of the imine bonds, giving rise to easy separation and recovery of both monomers in high purity, even with tolerance to additives. The recovered pure monomers can be used to regenerate totally new DCv-LCNs and actuators, and their functionalities can be reconfigured by removing old and introducing new additives, by implementing the closed-loop polymer-monomers-polymer recycling.
RESUMO
Development of closed-loop chemically recyclable plastics (CCRPs) that can be widely used in daily life can be a fundamental solution to the global plastic waste crisis. Hence, it is of great significance to develop easy-to-recycle CCRPs that possess superior or comparable material properties to the commodity plastics. Here, a novel dual crosslinked CCRP, namely, supramolecular covalent adaptable networks (supra-CANs), is reported, which not only displays mechanical properties higher than the strong and tough commodity polycarbonate, but also exhibits excellent solvent resistance as thermosets. The supra-CANs are constructed by introducing reversible noncovalent crosslinks into the dynamic covalent polymer networks, resulting in highly stiff and strong thermosets that also exhibit thermoplastic-like ductile and tough behaviors as well as reprocessability and rehealability. In great contrast, the analogs that do not have noncovalent crosslinks (CANs) show elastomeric properties with significantly decreased mechanical strength. Importantly, the developed supra-CANs and CANs can be converted back into the initial monomers in high yields and purity at room temperature, even with additives, which enables the sustainable polymer-monomer-polymer circulation. This work provides new design principles for high-performance chemically recyclable polymers as sustainable substitutes for the conventional plastics.
