Iodine-mediated Atom Transfer Radical Polymerization Enabled by the Cooperative Reverse Iodine Transfer Polymerization and Reversible Complexation Mediated Polymerization

Meng-Qi Ge; Xin-Wei Chen; Liang Wu; Xiang-Yi Wang; Ning Ren; Xin-Yuan Zhu

doi:10.1007/s10118-026-3669-7

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Iodine-mediated Atom Transfer Radical Polymerization Enabled by the Cooperative Reverse Iodine Transfer Polymerization and Reversible Complexation Mediated Polymerization

RESEARCH ARTICLE | Updated：2026-07-27

- Iodine-mediated Atom Transfer Radical Polymerization Enabled by the Cooperative Reverse Iodine Transfer Polymerization and Reversible Complexation Mediated Polymerization
- Iodine-mediated Atom Transfer Radical Polymerization Enabled by the Cooperative Reverse Iodine Transfer Polymerization and Reversible Complexation Mediated Polymerization
- Chinese Journal of Polymer Science 2026年44卷第8期页码：2570-2584
- Affiliations：
  
  a.School of Chemistry and Chemical Engineering, State Key Laboratory of Polyolefins and Catalysis, Research Institute of Polymer Materials, Shanghai Jiao Tong University, Shanghai 200240, China
  b.Frontiers Science Center for Transformative Molecules, Shanghai Jiao Tong University, Shanghai 200240, China
- Author bio：
  
  ningren@sjtu.edu.cn (N.R.)
  xyzhu@sjtu.edu.cn (X.Y.Z.)
- Funds：
  
  X.Z. acknowledges the National Key Research and Development Program of China (No. 2023YFF0724100) and the National Natural Science Foundation of China (No. 52421006). N.R. acknowledges the State Key Laboratory of Polyolefins and Catalysis (No. SKLZX-2025-01).;Xin-Yuan Zhu is an editorial board member for Chinese Journal of Polymer Science and was not involved in the editorial review or the decision to publish this article. 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/s10118-026-3669-7.The related data (DOI: 10.57760/sciencedb.j00189.00056) for this paper is available in the Science Data Bank (ScienceDB) database (https://www.scidb.cn/s/QZ7Bbe).
- DOI：10.1007/s10118-026-3669-7
  中图分类号：
- 收稿：2026-02-26，
  
  录用：2026-03-16，
  
  网络首发：2026-06-26，
  
  纸质出版：2026-08-15
- Accepted：
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Ge, M. Q.; Chen, X. W.; Wu, L.; Wang, X. Y.; Ren, N.; Zhu, X. Y. Iodine-mediated atom transfer radical polymerization enabled by the cooperative reverse iodine transfer polymerization and reversible complexation mediated polymerization. Chinese J. Polym. Sci. 2026, 44, 2570–2584

Meng-Qi Ge, Xin-Wei Chen, Liang Wu, et al. Iodine-mediated Atom Transfer Radical Polymerization Enabled by the Cooperative Reverse Iodine Transfer Polymerization and Reversible Complexation Mediated Polymerization[J]. Chinese Journal of Polymer Science, 2026, 44(8): 2570-2584.
Ge, M. Q.; Chen, X. W.; Wu, L.; Wang, X. Y.; Ren, N.; Zhu, X. Y. Iodine-mediated atom transfer radical polymerization enabled by the cooperative reverse iodine transfer polymerization and reversible complexation mediated polymerization. Chinese J. Polym. Sci. 2026, 44, 2570–2584 DOI： 10.1007/s10118-026-3669-7.

Meng-Qi Ge, Xin-Wei Chen, Liang Wu, et al. Iodine-mediated Atom Transfer Radical Polymerization Enabled by the Cooperative Reverse Iodine Transfer Polymerization and Reversible Complexation Mediated Polymerization[J]. Chinese Journal of Polymer Science, 2026, 44(8): 2570-2584. DOI： 10.1007/s10118-026-3669-7.

摘要

An iodine-mediated reversible deactivation radical polymerization (RDRP) integrating reverse iodine transfer polymerization (RITP)

reversible complexation mediated polymerization (RCMP)

and atom transfer radical polymerization (ATRP) enabled

in situ

generation of alkyl iodide initiators. Their cooperative interplay enables controlled polymerization of methacrylates and provides insight into multi-mechanism radical polymerization.

Abstract

Iodine is an attractive candidate for living radical polymerization owing to its strong halogen bonding ability and the vigorous C―I bond

enabling diverse mechanisms including iodine transfer polymerization (ITP)

reverse iodine transfer polymerization (RITP)

reversible complexation medi

ated polymerization (RCMP)

and atom transfer radical polymerization (ATRP). Among them

iodine-mediated ATRP stands out for its high activation rate constants

low equilibrium constants

and convenient post-polymerization modification. However

the use of alkyl iodides as initiators remains challenging because they are thermally and photochemically unstable. To solve this question

RITP mechanism was incorporated into the ATRP for the

in situ

generation of the alkyl iodide from I

. Further studies revealed that the ATRP ligands could also trigger the RCMP mechanism. Kinetic studies

radical trap experiments

and density functional theory (DFT) calculations clarified the contributions of each mechanism. This RITP/RCMP/ATRP ternary polymerization avoids the use of unstable initiators and achieves controlled polymerization of various monomers.

关键词

Keywords

references

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