Cyclic Multiblock Copolymers via Combination of Iterative Cu(0)‐Mediated Radical Polymerization and Cu(I)‐Catalyzed Azide‐Alkyne Cycloaddition Reaction

Cyclic multiblock polymers with high‐order blocks are synthesized via the combination of single‐electron transfer living radical polymerization (SET‐LRP) and copper‐catalyzed azide‐alkyne cycloaddition (CuAAC). The linear α,ω‐telechelic multiblock copolymer is prepared via SET‐LRP by sequential addition of different monomers. The SET‐LRP approach allows well control of the block length and sequence as A‐B‐C‐D‐E, etc. The CuAAC is then performed to intramolecularly couple the azide and alkyne end groups of the linear copolymer and produce the corresponding cyclic copolymer. The block sequence and the cyclic topology of the resultant cyclic copolymer are confirmed by the characterization of ¹H nuclear magnetic resonance spectroscopy, gel permeation chromatography, Fourier transform infrared spectroscopy, and matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry.