Electrochemical Synthesis of Poly(trisulfides)

Date

2023

Authors

Pople, J.M.M.
Nicholls, T.P.
Pham, L.N.
Bloch, W.M.
Lisboa, L.S.
Perkins, M.V.
Gibson, C.T.
Coote, M.L.
Jia, Z.
Chalker, J.M.

Editors

Advisors

Journal Title

Journal ISSN

Volume Title

Type:

Journal article

Citation

Journal of the American Chemical Society, 2023; 145(21):11798-11810

Statement of Responsibility

Jasmine M. M. Pople, Thomas P. Nicholls, Le Nhan Pham, Witold M. Bloch, Lynn S. Lisboa, Michael V. Perkins, Christopher T. Gibson, Michelle L. Coote, Zhongfan Jia, and Justin M. Chalker

Conference Name

DOI

10.1021/jacs.3c03239

Abstract

With increasing interest in high sulfur content polymers, there is a need to develop new methods for their synthesis that feature improved safety and control of structure. In this report, electrochemically initiated ring-opening polymerization of norbornene-based cyclic trisulfide monomers delivered well-defined, linear poly(trisulfides), which were solution processable. Electrochemistry provided a controlled initiation step that obviates the need for hazardous chemical initiators. The high temperatures required for inverse vulcanization are also avoided resulting in an improved safety profile. Density functional theory calculations revealed a reversible "self-correcting" mechanism that ensures trisulfide linkages between monomer units. This control over sulfur rank is a new benchmark for high sulfur content polymers and creates opportunities to better understand the effects of sulfur rank on polymer properties. Thermogravimetric analysis coupled with mass spectrometry revealed the ability to recycle the polymer to the cyclic trisulfide monomer by thermal depolymerization. The featured poly(trisulfide) is an effective gold sorbent, with potential applications in mining and electronic waste recycling. A water-soluble poly(trisulfide) containing a carboxylic acid group was also produced and found to be effective in the binding and recovery of copper from aqueous media.

School/Discipline

Dissertation Note

Provenance

Description

Access Status

Rights

© 2023 American Chemical Society

License

Grant ID

http://purl.org/au-research/grants/arc/DP200100090
 http://purl.org/au-research/grants/arc/DP210100025
 http://purl.org/au-research/grants/arc/LP200301660
 http://purl.org/au-research/grants/arc/LP200301661
 http://purl.org/au-research/grants/arc/DP230100587
 http://purl.org/au-research/grants/arc/FT220100054

Published Version

https://doi.org/10.1021/jacs.3c03239

Call number

Persistent link to this record

https://hdl.handle.net/2440/138806