The ability to prepare block, multiblock and segmented polymers is an essential and established tool in polymer chemistry to tailor the properties of materials and steer the formation of complex...
We report a facile post‐polymerization modification route to functionalized aromatic polyimides via Diels‐Alder cycloaddition. Aromatic polyimides are important, versatile high‐performance polymers; however, their structural diversity is restricted by the requirements of the step‐growth polymerization. We prepared polyimides with alkynes in their main‐chain as macromolecular dienophiles and quantitatively grafted tetraphenylcyclopentadienone based dienes. The resulting solution‐processable, wholly aromatic polyimides show a considerable increase in surface area due to the induced conformational changes and bulky, rigid, and contorted molecular structures. The orthogonality of the reaction is exploited to insert functional groups, namely bromine and sulfonates, along the polymer backbone. In a further extension, the phenylene segments undergo cyclodehydrogenation to form nanographene segments within the polymer chains. The Diels‐Alder cycloaddition onto polyimides is therefore demonstrated to be an effective, widely applicable route to tunable high‐performance polymers with value‐added functionality and thus considerable potential in a wide range of advanced materials.
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