Dynamic Covalent Chemistry of Enamine-Ones: Exploring Tunable Reactivity in Vitrimeric Polymers and Covalent Organic Frameworks

Dynamic covalent chemistry (DCC) has revolutionized the field of polymer science by offering new opportunities for the synthesis, processability, and recyclability of polymers as well as in the development of new materials with interesting properties such as vitrimers and covalent organic frameworks (COFs). Many DCC linkages have been explored for this purpose, but recently, enamine-ones have proven to be promising dynamic linkages because of their facile reversible transamination reactions under thermodynamic control. Their high stability, stimuli-responsive properties, and tunable kinetics make them promising dynamic cross-linkers in network polymers. Given the rapid developments in the field in recent years, this review provides a critical and up-to-date overview of recent developments in enamine-one chemistry, including factors that control their dynamics. The focus of the review will be on the utility of enamine-ones in designing a variety of processable and self-healable polymers with important applications in vitrimers and recyclable closed-loop polymers. The use of enamine-one linkages in crystalline polymers, known as COFs and their applications are also summarized. Finally, we provide an outlook for future developments in this field. This review summarizes the dynamic covalent chemistry of enamine-ones, focusing on factors affecting the tunable exchange kinetics and its exploitation in the development of recyclable, reprocessable and self-healable vitrimers. Enamine-one integrated commodity polymers such as siloxanes, epoxies, acrylates, polyethylene glycols (PEGs), fluoropolymers and bio-based materials are described. Enamine-one linkages based covalent organic frameworks (COFs) and their applications are also summarized. image