ORS11-0457
Molecular Design of Bottlebrush Copolymers for Hierarchical Macromolecular Assemblies
Topic
S11. PMSE–PSK50 Anniversary Symposium: Advancing Polymer Science for a Sustainable and Intelligent Future
When and Where
Sep 29, 2026
12:05 - 12:20
Room 110
Session Chairs
Jeong Jae WIE
Presenter(s)
Jaeman Shin (Soongsil University)
Co-Author(s)
Abstract
Hierarchically structured polymer colloids offer exceptional promise for advanced applications in smart soft materials, optical sensing, and adaptive nanotechnology. Here, we introduce a comprehensive set of strategies for engineering macromolecular assemblies by systematically tuning the molecular structure of bottlebrush copolymer as a self-assembly building block, including a i) precision grafting-density-controlled polymers to ii) bottlebrushes with a dynamic, stimulus-responsive backbone, and to iii) a mixed-graft bottlebrush architecture.
First, we examine the confined self-assembly of poly(norbornene)-graft-(polystyrene-random-polydimethylsiloxane) heterografted bottlebrush copolymers. Densely grafted side chains suppress chain entanglement, facilitating rapid microphase separation into well-ordered nanostructures within minutes. Further synthetic control of the side-chain grafting density allowed observation of a wide range of grafting density for retaining the nanostructures with relatively constant domain spacing, uniquely dictated by the side-chain length. Second, we incorporate a dynamic polydisulfide backbone to enable stimuli-responsive morphological shifts. The reversible polymerization-depolymerization of the backbone triggers transitions between compartmentalized and nanostructured particles. Integrating sequestered AIEgens allows for phase-dependent photoluminescence, highlighting potential for responsive optical switching. Finally, we utilize mixed-graft bottlebrushes (PS, PDMS, PLA) to achieve higher hierarchical complexity. This architecture allows simultaneous phase separation across two length scales, forming ternary morphologies such as lamellae-in-lamellae. Precise control over block sequences and volume fractions enables the tuning of both substructures and superstructures, inducing transitions in the shape and morphology of the resulting nanostructured particles.
First, we examine the confined self-assembly of poly(norbornene)-graft-(polystyrene-random-polydimethylsiloxane) heterografted bottlebrush copolymers. Densely grafted side chains suppress chain entanglement, facilitating rapid microphase separation into well-ordered nanostructures within minutes. Further synthetic control of the side-chain grafting density allowed observation of a wide range of grafting density for retaining the nanostructures with relatively constant domain spacing, uniquely dictated by the side-chain length. Second, we incorporate a dynamic polydisulfide backbone to enable stimuli-responsive morphological shifts. The reversible polymerization-depolymerization of the backbone triggers transitions between compartmentalized and nanostructured particles. Integrating sequestered AIEgens allows for phase-dependent photoluminescence, highlighting potential for responsive optical switching. Finally, we utilize mixed-graft bottlebrushes (PS, PDMS, PLA) to achieve higher hierarchical complexity. This architecture allows simultaneous phase separation across two length scales, forming ternary morphologies such as lamellae-in-lamellae. Precise control over block sequences and volume fractions enables the tuning of both substructures and superstructures, inducing transitions in the shape and morphology of the resulting nanostructured particles.
