Reaction‐induced morphology control in block copolymers

Abstract

Controlling the self‐assembly behaviors of block copolymers (BCPs) is a focal point of many research thrusts due to their broad use in various applications. While BCP molecular weight, volume fraction, and chemical identities are key thermodynamic parameters to determine their morphology, an emergent method in this area is through reaction‐induced changes to the characteristics of a BCP in situ, which provides access to multiple morphologies and domain sizes from a single parent polymer, as well as enabling the formation of metastable morphologies which may be difficult to attain otherwise. This work provides a focused review about the current state of reaction‐induced morphology control in BCPs in both solution and solid states. Furthermore, we provide a forward‐looking perspective on the future opportunities of understanding and employing reaction engineering to manipulate and advance BCP self‐assembly. © 2023 Society of Industrial Chemistry.

Sulfonation-Induced Cross-Linking and Nanostructural Evolution of a Thermoplastic Elastomer for Ordered Mesoporous Carbon Synthesis: A Mechanistic Study

“…While the initial study suggested that varying the reaction temperature can have a major impact on the kinetics of the simultaneous sulfonation and cross-linking reactions, a fundamental understanding of the reaction conditions for developing the nanostructure and chemistry of precursors is still very lacking. Understanding the mechanisms associated with the altered nanostructures of SEBS precursors during sulfonation-induced cross-linking is critical for rational system design with direct control over final pore textures by tuning precursor self-assembly behaviors . Here, this work focuses on deconvoluting the effects of simultaneous reactions on the nanostructure development of a SEBS precursor, allowing a more complete understanding of the intricate self-assembly and nanostructural rearrangement process during sulfonation-induced cross-linking.…”

“…Understanding the mechanisms associated with the altered nanostructures of SEBS precursors during sulfonation-induced cross-linking is critical for rational system design with direct control over final pore textures by tuning precursor self-assembly behaviors. 41 Here, this work focuses on deconvoluting the effects of simultaneous reactions on the nanostructure development of a SEBS precursor, allowing a more complete understanding of the intricate self-assembly and nanostructural rearrangement process during sulfonationinduced cross-linking. Consequently, these results can provide insights into the controlled synthesis of OMCs from using TPE precursors and, more broadly, elucidate fundamental BCP selfassembly mechanisms under non-equilibrium conditions.…”

Single‐molecule fluorescence microscopy for imaging chemical reactions: Recent progress and future opportunities for advancing polymer systems

“…Morphological characterization with smFL techniques is a relevant research area, 254 and expanding these studies to encompass morphological changes within polymer reactions by coupling fluorescence techniques with other characterizations could justify processes relevant to copolymer synthesis. 256 Future studies may also examine self-assembly behaviors for topological complex polymers, such as star and bottlebrush architectures. Current work utilizes methods such as single-molecule magnetic tweezers to study in situ polymerizations of conjugated polymers, but this has not yet been expanded to singlemolecule fluorescence.…”