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Reversible Thiyl Radical Addition-Fragmentation Chain Transfer Polymerization.

Yongjin Wang1, Jiaman Du1, Hanchu Huang1

  • 1School of Materials Science and Engineering, Key Laboratory for Polymeric Composite and Functional Materials of Ministry of Education, Sun Yat-Sen University, Guangzhou, 510006, China.

Angewandte Chemie (International Ed. in English)
|January 29, 2024
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Summary

This study introduces a novel reversible thiyl radical addition-fragmentation chain transfer (SRAFT) polymerization. This method enables direct control over thiyl radical polymerization, yielding polymers with precise architectures.

Keywords:
allyl sulfideclick reactioncontrolled polymerizationradical polymerizationthiyl radical

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Area of Science:

  • Polymer Chemistry
  • Organic Chemistry
  • Materials Science

Background:

  • Developing controlled radical polymerization methods is crucial for synthesizing polymers with specific properties.
  • Directly controlling thiyl radical propagation in polymerization remains a significant challenge in polymer chemistry.

Purpose of the Study:

  • To develop a novel reversible-deactivation radical polymerization (RDRP) strategy for direct thiyl radical control.
  • To utilize allyl sulfides as chain transfer agents in a new SRAFT polymerization.

Main Methods:

  • Implementation of the reversible thiyl radical addition-fragmentation chain transfer (SRAFT) polymerization.
  • Utilizing allyl sulfides as chain transfer agents to deactivate propagating thiyl radicals.
  • Characterization of polymer molecular weight, chain-end fidelity, and chain extension efficiency.
  • Density functional theory (DFT) calculations to investigate the deactivation mechanism.

Main Results:

  • Successful demonstration of the first SRAFT polymerization strategy.
  • Achieved direct control over thiyl radical chain polymerization, producing polymers with well-defined architectures.
  • Observed linear molecular weight dependence on conversion, high chain-end fidelity, and efficient chain extension, indicating good polymerization control.
  • DFT calculations provided insights into the reversible deactivation mechanism of allyl sulfides.

Conclusions:

  • The developed SRAFT strategy offers a robust method for controlled thiyl radical polymerization.
  • This approach allows for the synthesis of polymers with precise control over their architecture.
  • The SRAFT strategy opens new avenues for discovering controlled polymerization techniques based on thiyl radical chemistry.