Alternating Copolymerization by Nitroxide-Mediated Polymerization and Subsequent Orthogonal Functionalization

A novel method for the preparation of functionalized alternating copolymers is presented. Nitroxide‐mediated polymerization of hexafluoroisopropyl acrylate with 7‐octenyl vinyl ether provides the corresponding alternating polymer, which can be chemically modified using two orthogonal polymer‐analogous reactions. A thiol–ene click reaction followed by amidation provides dual‐functionalized alternating copolymers. The potential of this method is illustrated by the preparation of a small library (15 examples) of functionalized alternating copolymers. Alternating through double click: The title reaction of A with hexafluoroisopropyl acrylate (HFIPA) provides alternating polymer B, which can be chemically modified using two orthogonal polymer‐analogous reactions. With this method, a small library of fifteen functionalized alternating copolymers was prepared.