One‐Pot Synthesis of Alternating (Ultra‐High Molecular Weight) Multiblock Copolymers via a Combination of Anionic Polymerization and Polycondensation

Abstract This article presents a fast, straightforward synthesis approach to polymerize alternating multiblock copolymers, ultra‐high molecular weight (UHMW) (homo)polymers as well as precursors for complex macromolecular topologies such as comb or barbwire architectures. The one‐pot synthesis strategy proposed in this work is based on anionic polymerization via a bifunctional initiator and the subsequent linking of macro dianions with a bifunctional linker, additionally overcoming the limitations associated with the monomer reactivity. Thus, the synthetic route guarantees the repeating size of polymer blocks and an equal distribution of functional groups in precursors for complex topologies. Dianions of polystyrene (PS), polyisoprene‐ b ‐polystyrene‐ b ‐polyisoprene, and poly‐2‐vinylpyridine‐ b ‐polystyrene‐ b ‐poly‐2‐vinylpyridine are linked with ‐dibromo‐para‐xylene to UHMW and multiblock copolymers. Multiblock copolymers with on average up to 50 well‐defined alternating A and B blocks are accessible within 15 min.