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Anionic Ring-Opening Polymerization of Thionolactones: Status and Perspectives
Shao-Qiu Zheng1, Si-Qi Li1, Dian-Feng Chen1
1Hefei National Research Center for Physical Sciences at the Microscale and Department of Polymer Science and Engineering, University of Science and Technology of China, Hefei, China.
Macromolecular Rapid Communications
|December 21, 2025
Summary
Anionic ring-opening polymerization (aROP) of thionolactones is now understood, enabling precise synthesis of sulfur-containing polymers. This breakthrough overcomes historical challenges, offering control over molecular weight and selectivity.
Area of Science:
- Polymer Chemistry
- Organic Synthesis
- Materials Science
Background:
- Ring-opening polymerization (ROP) of thionolactones under anionic conditions (aROP) was historically unclear.
- Sulfur-containing polymers are important but challenging to synthesize.
- Recent breakthroughs have illuminated the behavior of thionolactones in aROP.
Purpose of the Study:
- Highlight the significance of sulfur-containing polymers.
- Summarize advanced initiating systems for thionolactone aROP.
- Provide perspectives on future research directions in thionolactone aROP.
Main Methods:
- Review of recent literature on thionolactone aROP.
- Analysis of state-of-the-art initiating systems.
- Discussion of mechanistic aspects, monomer design, and copolymerization.
Main Results:
- Precise control over molecular weight and dispersity is achievable.
- Complete selectivity between thiocarbonyl retention and S/O isomerization is possible.
- Established initiating systems enable controlled anionic polymerization of thionolactones.
Conclusions:
- Anionic ring-opening polymerization of thionolactones is a viable and controllable method.
- Further research into mechanistic understanding and monomer design will advance the field.
- This work provides a foundation for developing novel sulfur-containing polymers through thionolactone aROP.
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