Selective Monomer Synthesis and Metathesis Polymerizations toward Functional Polymers

Selective reactions not only enable the precise synthesis of molecular architectures but also provide efficient access to structurally diverse compounds. Our research focuses on the synthesis of functional monomers through chemo-, regio-, and stereoselective reactions and their application in metathesis polymerization for the preparation of well-defined functional polymers and chemically recyclable polymers.
Recently, we developed a selective synthetic strategy for amide-containing bridged and fused bicyclic monomers via the Schmidt reaction of azido-cycloheptenones.  Due to their different ring-strain energies, the resulting monomers exhibited divergent behaviors in ring-opening metathesis polymerization (ROMP). Highly strained bridged monomers enabled molecular-weight-controlled polymerization, whereas low-strained fused monomers afforded chemically recyclable polymers that underwent ring-closing metathesis depolymerization (RCMD) to regenerate the corresponding monomers. Furthermore, copolymerization of the amide-containing monomers with cyclooctene demonstrated that the incorporation of amide functionalities significantly enhanced the mechanical properties of the resulting polyolefins while imparting degradability and recyclability.