Electrochemical Synthesis of Poly(trisulfides)

Area of Science:

• Polymer Chemistry
• Materials Science
• Electrochemistry

Background:

• Growing demand for high sulfur content polymers necessitates safer and more controlled synthesis methods.
• Current methods like inverse vulcanization often require high temperatures and hazardous initiators.

Purpose of the Study:

• To develop a novel, safe, and controlled synthesis route for well-defined, high sulfur content polymers.
• To investigate the structural properties and potential applications of the synthesized polymers.

Main Methods:

• Electrocatalyzed ring-opening polymerization of norbornene-based cyclic trisulfide monomers.
• Density functional theory (DFT) calculations to elucidate reaction mechanisms.
• Thermogravimetric analysis (TGA) coupled with mass spectrometry (MS) for depolymerization studies.

Main Results:

• Successfully synthesized well-defined, linear poly(trisulfides) via electrochemically initiated polymerization.
• DFT revealed a reversible 'self-correcting' mechanism ensuring controlled sulfur rank.
• Demonstrated polymer recyclability to monomer via thermal depolymerization.
• Poly(trisulfide) showed effectiveness as a gold sorbent and copper binder.

Conclusions:

• Electrochemical initiation offers a safer and more controlled alternative to traditional polymer synthesis methods.
• The synthesized poly(trisulfides) exhibit tunable structures and properties, with promising applications in metal recovery and recycling.
• This work establishes a new benchmark for controlling sulfur rank in high sulfur content polymers.