

FOLLOWUS
State Key Laboratory of Advanced Fiber Materials, Center for Advanced Low-Dimension Materials, College of Materials Science and Engineering, Donghua University, Shanghai 201620, China
guoqy@dhu.edu.cn (Q.Y.G.)
liuh@dhu.edu.cn (H.L.)
Received:30 December 2025,
Accepted:23 January 2026,
Online First:07 April 2026,
Published:2026-03
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Hong, C. Y.; Yu, K.; You, H. Z.; Tian, W.; Guo, Q. Y.; Liu, H. Core structure modulation of 2D nanosheets by selective crystallization-driven self-assembly of polyhedral oligomeric silsesquioxane-containing block copolymers. Chinese J. Polym. Sci. https://doi.org/10.1007/s10118-026-3588-7
Cheng-Yang Hong, Kun Yu, Heng-Zhi You, et al. Core Structure Modulation of 2D Nanosheets by Selective Crystallization-driven Self-assembly of Polyhedral Oligomeric Silsesquioxane-containing Block Copolymers[J/OL]. Chinese Journal of Polymer Science, 2026, 441-11.
Hong, C. Y.; Yu, K.; You, H. Z.; Tian, W.; Guo, Q. Y.; Liu, H. Core structure modulation of 2D nanosheets by selective crystallization-driven self-assembly of polyhedral oligomeric silsesquioxane-containing block copolymers. Chinese J. Polym. Sci. https://doi.org/10.1007/s10118-026-3588-7 DOI:
Cheng-Yang Hong, Kun Yu, Heng-Zhi You, et al. Core Structure Modulation of 2D Nanosheets by Selective Crystallization-driven Self-assembly of Polyhedral Oligomeric Silsesquioxane-containing Block Copolymers[J/OL]. Chinese Journal of Polymer Science, 2026, 441-11. DOI: 10.1007/s10118-026-3588-7.
Self-assembly of block copolymers (BCPs) into well-defined nanostructures has emerged as a powerful strategy for tailoring material properties across diverse applications. Crystallization-driven self-assembly (CDSA) has been particularly effective in constructing hierarchical nanostructures with precise control over size
morphology
and functionality. Polyhedral oligomeric silsesquioxane (POSS) cages
known for their unique chemical and physical properties
have recently been used to create hybrid POSS-containing polymers
which show different crystallization mechanisms from the folded-chain model of conventional polymers. In this study
we designed and synthesized two hybrid block copolymers by covalently attaching a crysta
lline POSS-containing polymer segment (exact four repeating units
BP
4
) to poly(ethylene oxide) (PEO) or poly(methyl methacrylate) (PMMA)
affording
BP
4
-PEO
and
BP
4
-PMMA
respectively. We systematically investigated the CDSA behavior of these hybrid block copolymers under various conditions using the self-seeding and direct cooling methods. Our findings demonstrate the potential for selective CDSA of either the
BP
4
segment or the PEO block in
BP
4
-PEO
leading to a similar nanosheet morphology and distinct core crystal structures. Monocrystalline
BP
4
-PMMA
exclusively forms
BP
4
-crystallized nanosheets owing to the amorphous nature of PMMA under the given conditions. The dimensions of self-assembled 2D nanostructures can be tuned by varying the cooling rate and initial concentration. This work provides insights into programmable crystallization pathways in hybrid block copolymers and highlights the potential for designing advanced functional nanomaterials with tailored morphologies and properties.
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