Cucurbit[7]uril-mediated Supramolecular Fenton Catalysis for Reversible Addition-fragmentation Polymerization

Yue Zhao; Ze-sheng An

doi:10.11777/j.issn1000-3304.2026.26245

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Cucurbit[7]uril-mediated Supramolecular Fenton Catalysis for Reversible Addition-fragmentation Polymerization

Research Article | 更新时间：2026-11-02

- Cucurbit[7]uril-mediated Supramolecular Fenton Catalysis for Reversible Addition-fragmentation Polymerization
- Acta Polymerica Sinica Pages: 1-13(2026)
- 作者机构：
  
  吉林大学化学学院超分子结构与材料全国重点实验室长春 130012
- 作者简介：
  
  E-mail: anzesheng@jlu.edu.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2026.26245
  CLC：
- Received：08 August 2026，
  
  Revised：2026-09-02，
  
  Online First：02 November 2026，
- 稿件说明：
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赵越, 安泽胜. 葫芦[7]脲介导的超分子芬顿催化用于可逆加成-断裂链转移聚合. 高分子学报, doi: 10.11777/j.issn1000-3304.2026.26245.

Zhao, Y.; An, Z. S. Cucurbit[7]uril-mediated supramolecular fenton catalysis for reversible addition-fragmentation polymerization. Acta Polymerica Sinica (in Chinese), doi: 10.11777/j.issn1000-3304.2026.26245.
赵越, 安泽胜. 葫芦[7]脲介导的超分子芬顿催化用于可逆加成-断裂链转移聚合. 高分子学报, doi: 10.11777/j.issn1000-3304.2026.26245. DOI： CSTR： 32057.14.GFZXB.2026.7717.

Zhao, Y.; An, Z. S. Cucurbit[7]uril-mediated supramolecular fenton catalysis for reversible addition-fragmentation polymerization. Acta Polymerica Sinica (in Chinese), doi: 10.11777/j.issn1000-3304.2026.26245. DOI： CSTR： 32057.14.GFZXB.2026.7717.

摘要

芬顿反应是高效产生羟基自由基的重要途径，近年来已被应用于可逆加成-断裂链转移(RAFT)聚合. 然而，传统芬顿-RAFT体系仍面临诸多固有瓶颈：反应依赖酸性介质进行；羟基自由基的爆发式生成易加剧双基终止等副反应，致使高分子量聚合物的制备受限；同时，铁基催化剂循环效率偏低、氧化态物种的积累易导致自由基失活，从而制约了其实际应用前景. 受超分子主客体催化策略启发，本研究将葫芦[7]脲(CB[7])/二茂铁衍生物超分子体系引入RAFT聚合，发展出一种超分子催化的芬顿-RAFT聚合策略. 研究表明，该体系有效克服了传统芬顿反应对酸性条件的依赖，可在中性环境下高效进行聚合反应. 此外，CB[7]与不同价态二茂铁之间的差异性主客体结合能够加速羟基自由基的生成速率，从而为实现高分子量聚合物的可控合成提供了可能. 本研究系统考察了主客体相互作用对自由基生成行为与聚合动力学的调控规律，阐明了超分子识别、芬顿催化与RAFT聚合三者之间的关联机制，为发展温和高效的可控自由基聚合提供了新思路.

Abstract

Although the Fenton reaction has emerged as a promising tool for initiating reversible addition-fragmentation (RAFT) polymerization

traditional Fenton-RAFT systems are limited by their reliance on acidic media

radical-induced side reactions that restrict access to high-molecular-weight polymers

and poor catalyst cycling efficiency. To address these limitations

we employed a supramolecular Fenton catalyst based on host-guest complexation between cucurbit[7]uril (CB[7]) and a ferrocene derivative. This supramolecular Fenton catalyst accelerates hydroxyl radical generation

enabling the controlled synthesis of high-molecular-weight polymers at suitably low catalyst concentrations. Importantly

this system successfully bypassed the acidic media required in conventional Fenton reactions

successfully initiating RAFT polymerization at neutral or weakly basic pH. By establishing the correlation between host-guest chemistry

radical generation kinetics

and polymerization behavior

this work elucidates the mechanism of supramolecular Fenton-RAFT polymerization

offering a new strategy for the design of mild and efficient controlled radical polymerization systems.

关键词

Keywords

references

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