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Draft:Thiyl Radical Addition-Fragmentation Chain Transfer (SRAFT) Polymerization

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polymer chemistry

Thiyl Radical Addition-Fragmentation Chain Transfer (SRAFT) Polymerization is a method within the broader category of reversible-deactivation radical polymerization (RDRP). This technique specifically targets the control of thiyl radical propagation, which has historically been challenging due to the unique properties of thiyl radicals.

Key Aspects of SRAFT Polymerization:

1. Thiyl Radical Control: SRAFT polymerization is designed to control the propagation of thiyl radicals using allyl sulfides as chain transfer agents. These agents enable the reversible deactivation of the thiyl radicals, allowing for precise control over the polymerization process, which is crucial for synthesizing polymers with well-defined architectures.

2. Allyl Sulfides as Chain Transfer Agents: In this method, allyl sulfides serve as the key component in reversibly deactivating the thiyl radicals. This reversible deactivation allows for the controlled growth of the polymer chains, akin to other RDRP techniques but tailored to the unique challenges posed by thiyl radicals.

3. Polymerization Outcomes: The SRAFT method demonstrates a linear relationship between molecular weight and monomer conversion, high chain-end fidelity, and effective chain extension, indicating good control over the polymerization process.

4. Density Functional Theory (DFT) Insights: DFT calculations in this research provide a deeper understanding of the reversible deactivation capabilities of allyl sulfides, further supporting the effectiveness of the SRAFT process.

Significance:

This innovative approach opens up new avenues in controlled polymerization, particularly in the realm of thiyl radical chemistry. The development of SRAFT polymerization represents a significant advancement in the ability to create well-defined polymer architectures using challenging radical species.

This method holds promise for the discovery and development of new controlled polymerization techniques that leverage the unique properties of thiyl radicals, potentially leading to novel materials with specialized functions.

References

  1. Wang, Yongjin; Du, Jiaman; Huang, Hanchu (March 18, 2024). "Reversible Thiyl Radical Addition−Fragmentation Chain Transfer Polymerization". Angewandte Chemie International Edition. 63 (12): e202318898. doi:10.1002/anie.202318898.
  2. Huang, Hanchu; Sun, Bohan; Huang, Yingzi; Niu, Jia (June 19, 2018). "Radical Cascade-Triggered Controlled Ring-Opening Polymerization of Macrocyclic Monomers". Journal of the American Chemical Society. 140 (33): 10402–10406. doi:10.1021/jacs.8b05365.
  3. Zhang, Shuai; Wang, Yongjin; Huang, Hanchu; Cao, Derong (July 21, 2023). "A Strategy for Controlling the Polymerizations of Thiyl Radical Propagation by RAFT Agents". Angewandte Chemie International Edition. 62 (37): e202308524. doi:10.1002/anie.202308524.
  4. Zhang, Shuai; Cao, Chi; Jiang, Suqiu; Huang, Hanchu (October 19, 2022). "A General Strategy for Radical Ring-Opening Polymerization of Macrocyclic Allylic Sulfides". Macromolecules. 55 (21): 9411–9419. doi:10.1021/acs.macromol.2c01636.
  5. Sbordone, Federica; Frisch, Hendrik (May 31, 2024). "Plenty of Space in the Backbone: Radical Ring-Opening Polymerization". Chemistry-A European Journal. 30 (44): e202401547. doi:10.1002/chem.202401547.
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