A simple route to prepare supramolecular block copolymers using telechelic polystyrene/polydimethylsiloxane pairs

While supramolecular block copolymer (BCP) self-assembly has been widely studied over the past decades as an effective means to generate functional nanomaterials, most of these systems require multiple steps of synthesis and processing. In this report, we introduce a facile approach to form linear multiblock copolymers by directly blending telechelic homopolymer pairs, using di-sulfonated polystyrene and commercially available, aminopropyl terminated polydimethylsiloxane. A series of model multiblock copolymers were prepared, in which proton transfers between polymer chain ends enable the formation of strong ionic associations. These ionic junctions not only significantly enhance thin film stability of polymer blends by forming higher molecular weight copolymers, but also improve the chemical incompatibility between different segments, resulting in ordered nanostructures upon self-assembly. These include different morphologies such as lamellae and cylinders. We also demonstrate that feature size of these BCPs can be adjusted by varying the molecular weight of the homopolymers, with a smallest domain spacing of approximately 12.9 nm being obtained. Utilizing low-cost and widely available polymers as building blocks, our simple and efficient supramolecular assembly strategy for forming multiblock copolymers may provide a promising platform for cost-efficient nanomanufacturing of polymeric materials. (c) 2021 Society of Industrial Chemistry.

Automated summary

This study introduces a facile method to form linear multiblock copolymers by blending telechelic homopolymer pairs, demonstrating that ionic associations can enhance stability and ordered nanostructures. Adjusting the molecular weight allows for control of feature size in these copolymers.