Synthesis and Morphology of High‐Molecular‐Weight Polyisobutylene–Polystyrene Block Copolymers Containing Dynamic Covalent Bonds

Incorporating dynamic covalent bonds into block copolymers provides useful molecular level information during mechanical testing, but it is currently unknown how the incorporation of these units affects the resultant polymer morphology. High‐molecular‐weight polyisobutylene‐b‐polystyrene block copolymers containing an anthracene/maleimide dynamic covalent bond are synthesized through a combination of postpolymerization modification, reversible addition–fragmentation chain‐transfer polymerization, and Diels–Alder coupling. The bulk morphologies with and without dynamic covalent bond are characterized by atomic force microscopy and small‐angle X‐ray scattering, which reveal a strong dependence on annealing time and casting solvent. Morphology is largely unaffected by the inclusion of the mechanophore. The high‐molecular‐weight polymers synthesized allow interrogation of a large range of polymer domain sizes. High‐molecular‐weight (>100 kg mol−1) polyisobutylene‐b‐polystyrene block copolymers containing an anthracene/maleimide (Anth‐MI) dynamic covalent bond are synthesized through a combination of postpolymerization modification, reversible addition–fragmentation chain‐transfer polymerization, and Diels–Alder coupling. The bulk morphologies with and without dynamic covalent bond reveal a strong dependence on annealing time and casting solvent, but no influence of the Anth‐MI junction.