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Making and Unmaking Poly(trisulfides) with Light: Precise Regulation of Radical Concentrations via Pulsed LED
Thomas P Nicholls1, Jasmine M M Pople1, Madison R Harvey1
1College of Science and Engineering, Flinders University, Bedford Park, South Australia 5042, Australia.
Journal of the American Chemical Society
|December 3, 2025
Summary
Researchers developed new photopolymerization methods for sulfur-rich polymers, enabling controlled synthesis of poly(trisulfides) for advanced applications like Li-S batteries and recyclable materials.
Area of Science:
- Polymer Chemistry
- Materials Science
- Photochemistry
Background:
- Organic polysulfide polymers offer high-value applications in Li-S batteries, infrared optics, heavy metal remediation, and antimicrobial agents.
- Existing synthesis methods lack control over polymer structure and molecular weight.
Purpose of the Study:
- To develop photopolymerization methods for synthesizing poly(trisulfides) with controlled structure and molecular weight.
- To overcome challenges in controlling polymerization due to light-induced bond cleavage.
Main Methods:
- Ring-opening polymerization of cyclic trisulfides initiated by photochemical S-S bond cleavage.
- Utilized a photochemical flow reactor for spatial control of irradiation.
- Employed pulsed light-emitting diode (LED) irradiation for temporal control in batch reactors.
Main Results:
- Achieved synthesis of poly(trisulfides) with well-defined sulfur-rank, narrow dispersity, and controlled molecular weights.
- Demonstrated that pulsed irradiation prevents polymer degradation, unlike continuous irradiation.
- Successfully produced polymers with molecular weights exceeding 20,000 g/mol.
Conclusions:
- Photopolymerization offers a controlled route to synthesize advanced organic polysulfide polymers.
- Pulsed light irradiation is critical for preserving polymer chains and achieving high molecular weights.
- The controlled polymerization enables new applications in recyclable coatings, adhesives, and photoresists.
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