Core Structure Modulation of 2D Nanosheets by Selective Crystallization-driven Self-assembly of Polyhedral Oligomeric Silsesquioxane-containing Block Copolymers

Cheng-Yang Hong; Kun Yu; Heng-Zhi You; Wei Tian; Qing-Yun Guo; Hao Liu

doi:10.1007/s10118-026-3588-7

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Core Structure Modulation of 2D Nanosheets by Selective Crystallization-driven Self-assembly of Polyhedral Oligomeric Silsesquioxane-containing Block Copolymers

RESEARCH ARTICLE | Updated：2026-07-01

- Core Structure Modulation of 2D Nanosheets by Selective Crystallization-driven Self-assembly of Polyhedral Oligomeric Silsesquioxane-containing Block Copolymers
- Core Structure Modulation of 2D Nanosheets by Selective Crystallization-driven Self-assembly of Polyhedral Oligomeric Silsesquioxane-containing Block Copolymers
- Chinese Journal of Polymer Science 2026年44卷第7期页码：2294-2304
- Affiliations：
  
  State Key Laboratory of Advanced Fiber Materials, Center for Advanced Low-Dimension Materials, College of Materials Science and Engineering, Donghua University, Shanghai 201620, China
- Author bio：
  
  guoqy@dhu.edu.cn (Q.Y.G.)
  liuh@dhu.edu.cn (H.L.)
- Funds：
  
  This work was financially supported by the General Program of the Science and Technology Commission of the Shanghai Municipality (No. 24ZR1401400). We also thank the onsite staff of Beamline BL16B1 at the Shanghai Synchrotron Radiation Facility (SSRF) for their assistance with the WAXD experiments.;The authors declare no interest conflict.Electronic supplementary information (ESI) is available free of charge in the online version of this article at http://doi.org/10.1007/s10118-026-3588-7.The related data for this paper are available from the corresponding author (liuh@dhu.edu.cn) upon reasonable request.
- DOI：10.1007/s10118-026-3588-7
  中图分类号：
- 收稿：2025-12-30，
  
  录用：2026-01-23，
  
  网络首发：2026-04-07，
  
  纸质出版：2026-07-05
- Accepted：
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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. 2026, 44, 2294–2304

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]. Chinese Journal of Polymer Science, 2026, 44(7): 2294-2304.
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. 2026, 44, 2294–2304 DOI： 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]. Chinese Journal of Polymer Science, 2026, 44(7): 2294-2304. DOI： 10.1007/s10118-026-3588-7.

摘要

Selective crystallization of poly(ethylene oxide) (PEO) or

blocks in hybrid copolymers enables precise control over the core structure of 2D nanosheets

achieving either folded-chain or 2D lattice crystal morphologies.

Abstract

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 designe

d and synthesized two hybrid block copolymers by covalently attaching a crystalline POSS-containing polymer segment (exact four repeating units

) to poly(ethylene oxide) (PEO) or poly(methyl methacrylate) (PMMA)

affording

-PEO

and

-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

segment or the PEO block in

-PEO

leading to a similar nanosheet morphology and distinct core crystal structures. Monocrystalline

-PMMA

exclusively forms

-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.

关键词

Keywords

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