高等学校化学学报

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柔性二维高分子:高分子的新维度

徐嘉琦,施睿,朱有亮,吕中元   

  1. 吉林大学化学学院,超分子结构与材料全国重点实验室
  • 收稿日期:2025-11-07 修回日期:2025-12-01 出版日期:2025-12-01 发布日期:2025-12-01
  • 通讯作者: 朱有亮 E-mail:luzhy@jlu.edu.cn
  • 基金资助:
    国家自然科学基金(批准号:22133002,22273031)和吉林大学计算交叉创新平台项目资助

Flexible Two-dimensional Polymers: A New Dimension in Polymer

XU Jiaqi, SHI Rui, ZHU Youliang, LU Zhongyuan   

  1. State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University
  • Received:2025-11-07 Revised:2025-12-01 Online:2025-12-01 Published:2025-12-01
  • Supported by:
    Supported by the National Natural Science Foundation of China(Nos. 22133002, 22273031) and the Jilin University Computing Cross-Innovation Platform Project, China

摘要: 相较于一维和三维高分子,二维高分子的理论框架尚不完备,特别是柔性二维高分子,其独特的构象特征及由此产生的物理性质尚缺乏系统的理论解释,是当前高分子科学中亟待深入研究的核心科学问题之一。本文综合评述了柔性二维高分子在理论与计算机模拟方面的研究进展,旨在系统梳理该领域从早期的理论雏形到近期的构象研究的发展脉络。本文首先回顾了20世纪80年代关于 tethered membranes 的早期理论研究。这些研究通过分子动力学模拟揭示,自回避相互作用将导致二维网络在热力学极限下展现为平坦(flat)构象,而不会发生预期的皱缩(crumpled)转变。在此基础上,本文进一步阐述了21世纪以来该领域在理论与模拟方面取得的重要进展,主要包括:(1)通过计算机模拟系统地研究了二维片状高分子的平衡构象与其溶液中输运性质之间的关联,并对特性黏度 [η] 与标度指数 v 之间的理论关系进行了验证;(2)引入了具有可调网格尺寸的二维网络模型,从理论上建立了一个能够同时描述 flat 与 crumpled 构象的统一框架。研究发现二者可在同一体系中共存,其最终构象取决于网络尺寸与网格大小的相对关系;(3)系统地研究了柔性二维高分子在不同溶剂中的折叠(folded)行为,揭示了体系从 flat 结构经历多级folded直至最终塌缩(collapsed)的转变路径与规律,并建立了相应的理论模型。

关键词: 二维聚合物, 柔性, 构象, 标度关系

Abstract: Compared with one-dimensional (1D) and three-dimensional (3D) polymers, the theory framework of two-dimensional (2D) polymers is still incomplete, especially for flexible 2D polymers. Their unique conformation and properties are one of the mysterious questions in the polymer science. This article comprehensively reviews the theoretical and simulation research progress of flexible 2D polymers, aiming to systematically sort out the development of the field of flexible 2D polymers from early theoretical prototypes to recent conformational physics research. First, this article reviews theoretical research on tethered membranes from the 1980s. Early molecular dynamics simulations revealed that self-avoidance causes 2D networks to approach a flat state at the thermodynamic limit, rather than undergoing a crumpled transition. Second, the article elaborates on the breakthroughs achieved in theory and simulation since the 21st century: (1) systematically studied, through simulation, the correlation between the equilibrium morphology of 2D polymer sheets and their transport properties, and validated the theoretical relationship between intrinsic viscosity [η] and the scaling exponent v; (2) By introducing a 2D network model with adjustable grid size, the long-standing controversial flat and crumpled conformations were theoretically unified, finding that the two can coexist in the same system, and their conformations depend on the network size and grid size; (3) The folding behavior of flexible 2D polymers in different solvents was systematically studied, and the transition rules from flat to multi-level folding to collapsed were discovered, and the corresponding theoretical model was established.

Key words: Two-dimensional polymer, Flexible, Conformation, Scaling relations

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