van der Waals Force-driven Self-healing Materials Based on Side-chain Entangled Molecular Brushes

Bin-bin Xu; Hao Zhu; Yu-qing Wang; Xin-feng Tao; Shao-liang Lin

doi:10.11777/j.issn1000-3304.2026.26072

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van der Waals Force-driven Self-healing Materials Based on Side-chain Entangled Molecular Brushes

更新时间：2026-06-12

- van der Waals Force-driven Self-healing Materials Based on Side-chain Entangled Molecular Brushes
- Acta Polymerica Sinica Pages: 1-13(2026)
- 作者机构：
  
  华东理工大学材料科学与工程学院上海市先进聚合物材料重点实验室上海 200237
- 作者简介：
  
  Xin-feng Tao, E-mail: taoxinfeng@ecust.edu.cn
  Shao-liang Lin, E-mail: slin@ecust.edu.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2026.26072
  CLC：
- CSTR：32057.14.GFZXB.2026.7596
- Received：10 March 2026，
  
  Accepted：27 March 2026，
  
  Online First：12 June 2026，
- 稿件说明：
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徐彬彬, 朱昊, 王宇晴, 陶鑫峰, 林绍梁. 范德华力驱动的侧链缠结刷状聚合物自修复材料. 高分子学报, doi: 10.11777/j.issn1000-3304.2026.26072.

Xu, B. B.; Zhu, H.; Wang, Y. Q.; Tao, X. F.; Lin, S. L. van der Waals force-driven self-healing materials based on side-chain entangled molecular brushes. Acta Polymerica Sinica (in Chinese), doi: 10.11777/j.issn1000-3304.2026.26072.
徐彬彬, 朱昊, 王宇晴, 陶鑫峰, 林绍梁. 范德华力驱动的侧链缠结刷状聚合物自修复材料. 高分子学报, doi: 10.11777/j.issn1000-3304.2026.26072. DOI： CSTR： 32057.14.GFZXB.2026.7596.

Xu, B. B.; Zhu, H.; Wang, Y. Q.; Tao, X. F.; Lin, S. L. van der Waals force-driven self-healing materials based on side-chain entangled molecular brushes. Acta Polymerica Sinica (in Chinese), doi: 10.11777/j.issn1000-3304.2026.26072. DOI： CSTR： 32057.14.GFZXB.2026.7596.

摘要

受人体内疏松结缔组织的自修复过程及其支化结构的启发，设计合成了具有典型支化结构的刷状聚合物，其薄膜可以不依靠特殊的价键作用实现室温下智能且有效的自修复过程. 首先以含2-羰基溴基团的丙烯酸酯功能性单体为基础，利用可逆加成断裂链转移聚合合成了大分子引发剂，结合原子转移自由基聚合制备了主链一侧连接甲基，另一侧接枝聚丙烯酸乙酯/丁酯侧链的2类刷状聚合物. 研究了这2类刷状聚合物薄膜在室温下以及酸性、中性、碱性条件下的自修复行为，证明了刷状聚合物薄膜具有良好的自修复功能、耐酸碱的稳定性及弹性特征. 最后结合计算机模拟探索了刷状聚合物的仿生自修复机制，主要源于侧链间的范德华相互作用和链互锁作用. 本研究无需常规自修复材料对特殊价键作用的依赖，仅依靠聚合物的拓扑结构和范德华力即可实现其室温下的高效自修复过程，为设计结构简单的自修复智能高分子材料提供了新思路.

Abstract

Inspired by the self-repairing process and the branched structure of the loose connective tissue in the human

body

we designed and synthesized molecular brush-based films with typical branched structures

which can achieve intelligent and effective self-repairing processes at room temperature without relying on dynamic covalent/noncovalent bonds. First

a macro-initiator (P(MA-Br)) was synthesized by reversible addition-fragmentation chain transfer homopolymerization based on the functional monomer containing an active bromine group (MA-Br). Subsequently

two types of molecular brushes were constructed by atom transfer radical polymerization: in each

a methyl group was installed at one side of the backbone

while poly(ethyl acrylate) or poly(butyl acrylate) side chains were densely grafted from the opposite side

labeling as PMA-

-PEA and PMA-

-PBA

respectively. The self-repairing behaviors of the molecular brush-based films at room temperature

as well as under acidic

neutral

and alkaline conditions

were studied. It was proved that the molecular brush-based films have good self-repairing functions

stability against acids and alkalis

and elastic characteristics. Compared with the PMA-

-PEA film

the PMA-

-PBA film showed a higher repair efficiency

which was attributted to better flexibility and stronger mobility of butyl chians at room temperature. It made PMA-

-PBA more likely to achieve self-repair after being damaged

driven by the stronger van der Waals force. Finally

the biomimetic self-healing mechanism of the molecular brushes was explored through computer simulation. The main reason lied in the van der Waals interactions between the side chains and the chain interlocking effect. This work overcomes the conventional reliance of self-healing materials on specific covalent or dynamic noncovalent interactions

achieving efficient room-temperature self-repair solely through the synergistic effect of polymer topology—specifically

the densely grafted brush architecture—and intrinsic

ubiquitous van der Waals interactions amo

ng side chains. Our strategy establishes a paradigm for designing structurally simple yet functionally robust self-healing polymeric materials.

关键词

Keywords

references

Li B. Z. ; Zhou Z. H. ; Wei Y. S. ; Yu Y. Z. ; Huang G. S. ; Qiu R. ; Ouyang Y. B. Cultivating resilience: a skin-inspired sandwiched self-healing coating for shielding MgLi alloy from corrosion . Surf. Coat. Technol. , 2024 , 491 , 131146 . doi: 10.1016/j.surfcoat.2024.131146 http://dx.doi.org/10.1016/j.surfcoat.2024.131146

Li W. H. ; Liu H. ; Wang H. ; Chen Y. W. ; Peng Y. ; Wu H. T. ; Hou Y. J. ; Huang Y. ; Yuan Z. Y. ; Ye B. J. ; Zhang H. J. ; Wu J. R. Biomimetic hybrid networks with excellent toughness and self-healing ability in the glassy state . Chem. Mater. , 2023 , 35 ( 2 ), 682 - 691 . doi: 10.1021/acs.chemmater.2c03266 http://dx.doi.org/10.1021/acs.chemmater.2c03266

Stenman S. ; Vaheri A. Distribution of a maj or connective tissue protein, fibronectin, in normal human tissues. J. Exp. Med ., 1978 , 147 ( 4 ), 1054 - 1064 . doi: 10.1084/jem.147.4.1054 http://dx.doi.org/10.1084/jem.147.4.1054

Grodzinsky A. J. Electromechanical and physicochemical properties of connective tissue . Crit. Rev. Biomed. Eng. , 1983 , 9 ( 2 ), 133 - 199

Hukins D. W. L. ; Aspden R. M. Composition and properties of connective tissues . Trends Biochem. Sci. , 1985 , 10 ( 7 ), 260 - 264 . doi: 10.1016/0968-0004(85)90077-5 http://dx.doi.org/10.1016/0968-0004(85)90077-5

Ayeleru O. O. ; Olubambi P. A. Concept of self-healing in polymeric materials . Mater. Today Proc. , 2022 , 62 , S158 - S162 . doi: 10.1016/j.matpr.2022.04.811 http://dx.doi.org/10.1016/j.matpr.2022.04.811

Liu Q. H. ; Wang S. Y. ; Zhao Z. Y. ; Tong J. H. ; Urban M. W. Electrically accelerated self-healable polyionic liquid copolymers . Small , 2022 , 18 ( 24 ), 2201952 . doi: 10.1002/smll.202201952 http://dx.doi.org/10.1002/smll.202201952

Hao B. R. ; Luo Y. M. ; Chan W. J. ; Cai L. Y. ; Lyu S. S. ; Luo Z. Z. Fabrication of a multiple-self-healing and self-cleaning polymer coating for mechanical-damaged optical glass surface . Chem. Eng. J. , 2024 , 496 , 153750 . doi: 10.2139/ssrn.4813128 http://dx.doi.org/10.2139/ssrn.4813128

王晴 , 李战胜 , 丁子淳 , 焦健健 , 宗立率 , 王锦艳 , 蹇锡高 . 可自修复生物基聚芳醚酮的制备与性能研究 . 高分子学报 , 2025 , 56 ( 10 ), 1801 - 1814 .

Riess G. Micellization of block copolymers . Prog. Polym. Sci. , 2003 , 28 ( 7 ), 1107 - 1170 . doi: 10.1016/s0079-6700(03)00015-7 http://dx.doi.org/10.1016/s0079-6700(03)00015-7

Wan Y. ; Li X. C. ; Yuan H. T. ; Liu D. X. ; Lai W. Y. Self-healing elastic electronics: materials design, mechanisms, and applications. Adv. Funct. Mater ., 2024 , 34 ( 27 ), 2316550 . doi: 10.1002/adfm.202316550 http://dx.doi.org/10.1002/adfm.202316550

Kawamoto K. ; Zhong M. J. ; Gadelrab K. R. ; Cheng L. C. ; Ross C. A. ; Alexander-Katz A. ; Johnson J. A. Graft-through synthesis and assembly of Janus bottlebrush polymers from A-branch-B diblock macromonomers . J. Am. Chem. Soc. , 2016 , 138 ( 36 ), 11501 - 11504 . doi: 10.1021/jacs.6b07670 http://dx.doi.org/10.1021/jacs.6b07670

Cao S. Y. ; Liu W. Y. ; Yang B. C. ; Zheng Y. ; Lin S. L. ; Xu B. B. Facile synthesis of asymmetric molecular brushes with triple side chains using a multivalent monomer strategy . Polym. Chem. , 2024 , 15 ( 35 ), 3552 - 3562 . doi: 10.1039/d4py00656a http://dx.doi.org/10.1039/d4py00656a

孙子扬 , 李华安 , 黄华华 , 石毅 , 陈永明 . 聚合物分子刷在纳米载体领域的应用 . 高分子学报 , 2020 , 51 ( 6 ), 609 - 619 . doi: 10.11777/j.issn1000-3304.2020.20021 http://dx.doi.org/10.11777/j.issn1000-3304.2020.20021

Li X. ; Li B. ; Huang J. ; Zhu H. Y. ; Li Y. ; Shi G. A molecular imprinting photoelectrochemical sensor modified by polymer brushes and its detection for BSA . Chem. Eng. J. , 2024 , 483 , 149297 . doi: 10.1016/j.cej.2024.149297 http://dx.doi.org/10.1016/j.cej.2024.149297

姚远 , 何品 , 陶鑫峰 , 徐彬彬 , 林绍梁 . 含偶氮苯侧链不对称分子刷聚合物的合成及其自组装研究 . 高分子学报 , 2024 , 55 ( 4 ), 407 - 418 .

Nguyen H. V. T. ; Jiang Y. ; Mohapatra S. ; Wang W. C. ; Barnes J. C. ; Oldenhuis N. J. ; Chen K. K. ; Axelrod S. ; Huang Z. H. ; Chen Q. X. ; Golder M. R. ; Young K. ; Suvlu D. ; Shen Y. Z. ; Willard A. P. ; Hore M. J. A. ; Gómez-Bombarelli R. ; Johnson J. A. Bottlebrush polymers with flexible enantiomeric side chains display differential biological properties . Nat. Chem. , 2022 , 14 ( 1 ), 85 - 93 . doi: 10.1038/s41557-021-00826-8 http://dx.doi.org/10.1038/s41557-021-00826-8

Shi X. X. ; Zhang Y. ; Tian Y. ; Xu S. Y. ; Ren E. ; Bai S. ; Chen X. Y. ; Chu C. C. ; Xu Z. G. ; Liu G. Multi-responsive bottlebrush-like unimolecules self-assembled nano-riceball for synergistic sono-chemotherapy . Small Meth. , 2021 , 5 ( 3 ), 2000416 . doi: 10.1002/smtd.202000416 http://dx.doi.org/10.1002/smtd.202000416

Feng C. ; Huang X. Y. Polymer brushes: efficient synthesis and applications . Acc. Chem. Res. , 2018 , 51 ( 9 ), 2314 - 2323 . doi: 10.1021/acs.accounts.8b00307 http://dx.doi.org/10.1021/acs.accounts.8b00307

Zhou S. M. ; Qi N. ; Zhang Z. H. ; Jiang P. ; Li A. H. ; Lu Y. X. ; Su X. H. Recent progress in intrinsic self-healing polymer materials: mechanisms, challenges and potential applications in oil and gas development . Chem. Eng. J. , 2025 , 511 , 161906 . doi: 10.1016/j.cej.2025.161906 http://dx.doi.org/10.1016/j.cej.2025.161906

Choi C. ; Self J. L. ; Okayama Y. ; Levi A. E. ; Gerst M. ; Speros J. C. ; Hawker C. J. ; Read de Alaniz J. ; Bates C. M. Light-mediated synthesis and reprocessing of dynamic bottlebrush elastomers under ambient conditions . J. Am. Chem. Soc. , 2021 , 143 ( 26 ), 9866 - 9871 . doi: 10.1021/jacs.1c03686 http://dx.doi.org/10.1021/jacs.1c03686

Chen Y. L. ; Kushner A. M. ; Williams G. A. ; Guan Z. B. Multiphase design of autonomic self-healing thermoplastic elastomers . Nat. Chem. , 2012 , 4 ( 6 ), 467 - 472 . doi: 10.1038/nchem.1314 http://dx.doi.org/10.1038/nchem.1314

Mozhdehi D. ; Ayala S. ; Cromwell O. R. ; Guan Z. B. Self-healing multiphase polymers via dynamic metal-ligand interactions . J. Am. Chem. Soc. , 2014 , 136 ( 46 ), 16128 - 16131 . doi: 10.1021/ja5097094 http://dx.doi.org/10.1021/ja5097094

Liu J. H. ; Biswas S. ; Urban M. W. Dynamics of dipolar and ionic interactions in self-healable poly(ionic liquid) copolymers . Macromolecules , 2024 , 57 ( 12 ), 5831 - 5837 . doi: 10.1021/acs.macromol.4c00701 http://dx.doi.org/10.1021/acs.macromol.4c00701

Gaikwad S. ; Liu J. H. ; Mashkow N. ; Urban M. W. Self-healable poly(ionic liquid) copolymers driven by polar and dipolar forces . Angew. Chem. Int. Ed. , 2025 , 64 ( 34 ), e 202510066 . doi: 10.1002/anie.202510066 http://dx.doi.org/10.1002/anie.202510066

Urban M. W. ; Davydovich D. ; Yang Y. ; Demir T. ; Zhang Y. Z. ; Casabianca L. Key-and-lock commodity self-healing copolymers . Science , 2018 , 362 ( 6411 ), 220 - 225 . doi: 10.1126/science.aat2975 http://dx.doi.org/10.1126/science.aat2975

Davydovich D. ; Urban M. W. Water accelerated self-healing of hydrophobic copolymers . Nat. Commun. , 2020 , 11 , 5743 . doi: 10.1038/s41467-020-19405-5 http://dx.doi.org/10.1038/s41467-020-19405-5

Xiong H. ; Yue T. K. ; Wu Q. ; Zhang L. J. ; Xie Z. T. ; Liu J. ; Zhang L. Q. ; Wu J. R. Self-healing bottlebrush polymer networks enabled via a side-chain interlocking design . Mater. Horiz. , 2023 , 10 ( 6 ), 2128 - 2138 . doi: 10.1039/d3mh00274h http://dx.doi.org/10.1039/d3mh00274h

Zha H. ; Cheng L. ; Wang Z. W. ; Liu C. ; Hong C. Y. Efficient synthesis of bottle-brush polymers enabled by selective photoactivation strategy in NIR-induced PET-RAFT polymerization . Sci. China Chem. , 2024 , 67 ( 7 ), 2353 - 2361 . doi: 10.1007/s11426-024-2010-6 http://dx.doi.org/10.1007/s11426-024-2010-6

Bidram A. ; Rahimi M. ; Hekmatifar M. The effect of temperature on asphaltene transformation and agglomeration in oil pressure tank systems under injection of carbon dioxide in a porous structure: a molecular dynamics study . J. Mol. Liq. , 2024 , 414 , 126268 . doi: 10.1016/j.molliq.2024.126268 http://dx.doi.org/10.1016/j.molliq.2024.126268

Hafskjold B. ; Travis K. P. ; Hass A. B. ; Hammer M. ; Aasen A. ; Wilhelmsen Ø. Thermodynamic properties of the 3D Lennard-Jones/spline model . Mol. Phys. , 2019 , 117 ( 23-24 ), 3754 - 3769 . doi: 10.1080/00268976.2019.1664780 http://dx.doi.org/10.1080/00268976.2019.1664780

Ji X. F. Diffusion model of lennard-Jones fluids based on the radial distribution function . J. Phys. Chem. B , 2022 , 126 ( 44 ), 9008 - 9015 . doi: 10.1021/acs.jpcb.2c04019 http://dx.doi.org/10.1021/acs.jpcb.2c04019

Plimpton S. Fast parallel algorithms for short-range molecular dynamics . J. Comput. Phys. , 1995 , 117 ( 1 ), 1 - 19 . doi: 10.1006/jcph.1995.1039 http://dx.doi.org/10.1006/jcph.1995.1039

Humphrey W. ; Dalke A. ; Schulten K. VMD: visual molecular dynamics . J. Mol. Graph. , 1996 , 14 ( 1 ), 33 - 38 . doi: 10.1016/0263-7855(96)00018-5 http://dx.doi.org/10.1016/0263-7855(96)00018-5

Mayadunne R. T. A. ; Rizzardo E. ; Chiefari J. ; Chong Y. K. ; Moad G. ; Thang S. H. Living radical polymerization with reversible addition-fragmentation chain transfer (RAFT polymerization) using dithiocarbamates as chain transfer agents . Macromolecules , 1999 , 32 ( 21 ), 6977 - 6980 . doi: 10.1021/ma9906837 http://dx.doi.org/10.1021/ma9906837

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