Functionalized Rigid Ladder Polymers from Catalytic Arene-Norbornene Annulation Polymerization.

Rigid ladder polymers represent a unique polymer architecture but have limited synthetic accessibility and structural diversity. Using catalytic arene-norbornene annulation (CANAL) polymerization, we synthesized ladder polymers consisting of rigid and kinked norbornyl benzocyclobutene backbones and bearing various functional groups, such as alcohol, amine, ester, carbamate, amide, benzyl bromide, azide, and heterocycles. The incorporation of functional groups was achieved by either copolymerization of functionalized ladder-type dinorbornenes or postpolymerization functionalization. Functionalization of ladder polymers allows modification of their solubility, compatibility, and other properties, expanding their utilities. These ladder polymers remain microporous and highly glassy, which are desirable for separation and high-temperature applications.