Hybrid copolymerization via mechanism interconversion between radical vinyl-addition and anion ring-opening polymerization

Abstract

Hybrid copolymerization of two or more structurally distinct monomers (e.g., cyclic monomers and vinyl-type monomers) is very interesting because it can produce new types of copolymers and open up new research directions in the field of polymer chemistry. However, it has long been a challenge because the reactivity and polymerization mechanism of different monomers are extremely different. Here, we report a new hybrid copolymerization via an interconvertible living free radical and anion ring-opening polymerization mechanism, in which the copolymerization of cyclic monomers and vinyl-type monomers can be achieved. Via this novel hybrid copolymerization, the cyclic monomers and vinyl monomers, which generally cannot be copolymerized, now can be copolymerized into one polymer chain. Furthermore, the monomer arrangement in the chains could be easily regulated by the interconverting behavior. This new hybrid copolymerization will provide a powerful means for producing materials that have not been accessible by any other means.