Architecture-Controlled Ring-Opening Polymerization for Dynamic Covalent Poly(disulfide)s

The topology of poly(disulfide)s are controlled by the nucleophilicity of initiators – aryl initiators favor ring polymers while alkyl ones favor linear chains. Both linear and cyclic polymers were dynamic and are facilely recycled back to monomers.

Scientific Achievement

We reported a strategy to access different topologies of redox-active poly(disulfide)s by ring-opening polymerization. Control over polymerization enables synthesis of high molecular-weight polymers. The polymers undergo catalytic depolymerization to recycle monomer;  a promising feature for sustainable flow batteries.

Significance and Impact

Redox-active poly(disulfide)s are promising materials for energy storage. Our methods provide control over the synthesis to enable studies of structure-property relationships. The new synthesis also expands the parameter space of polymer molecular weight and topologies for energy materials research.

Research Detail

  • Cyclic and linear topologies were supported by 1H NMR spectroscopy, mass spectrometry, viscometry, size-exclusion chromatography, and thermogravimetric analysis.
  • The kinetics and thermodynamics of polymerization were studied to enable synthesis of high polymers with 3000 repeating units.
  • Using different initiators to influence ring-chain equilibrium to obtain cyclic polymers is a new chemistry knowledge and is further supported by DFT analysis.

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DOI: 10.1021/jacs.9b08957

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