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<p>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 mediated 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 <i>in situ</i> generation of the alkyl iodide from I<sub>2</sub>. 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.</p>

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

  • 期刊论文

  • 发表日期：

    2026年6月26日

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

摘要

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 mediated 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 I2. 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.