Sequence-regulated vinyl copolymers by metal-catalysed step-growth radical polymerization

Proteins and nucleic acids are sequence-regulated macromolecules with various properties originating from their perfectly sequenced primary structures. However, the sequence regulation of synthetic polymers, particularly vinyl polymers, has not been achieved and is one of the ultimate goals in polymer chemistry. In this study, we report a strategy to obtain sequence-regulated vinyl copolymers consisting of styrene, acrylate and vinyl chloride units using metal-catalysed step-growth radical polyaddition of designed monomers prepared from common vinyl monomer building blocks. Unprecedented ABCC-sequence-regulated copolymers with perfect vinyl chloride–styrene–acrylate–acrylate sequences were obtained by copper-catalysed step-growth radical polymerization of designed monomers possessing unconjugated C=C and reactive C–Cl bonds. This strategy may open a new route in the study of sequence-regulated synthetic polymers. The synthesis of sequence-regulated copolymers continues to challenge polymer chemists. Here step-growth radical polymerisation of designed abc and abcc monomers leads to vinyl copolymers with repeating ABC and ABCC sequences.