Postpolymerization Modification and Topological Structure Design of Poly(vinyl ether)s Based on the Selective Addition Reaction of Electrophilic Selenium Reagent and Divinyl Monomers

Poly(vinyl ether)s (PVEs) are typical products from living cationic polymerization. However, postpolymerization modification (PPM) and topological structure design of poly(vinyl ether)s under relatively mild conditions are rare, which limits their practical applications. Herein, we report a facile method to overcome this limitation by exploiting the selective addition reaction of electrophilic selenium reagent and divinyl monomers, which can produce PVEs with pendent vinyl groups in each repeat unit or end-functionalized PVEs. PPM of PVEs was realized by a thiol–ene click reaction. Furthermore, brush polymers and core cross-linked star polymers were successfully prepared by using end-functionalized PVEs as macromonomers, providing a general method for the preparation of topological polymers and laying a foundation for the development and application of PVEs.