Green polymer chemistry: living dithiol polymerization via cyclic intermediates
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Updated: May 27, 2026

Synthesis of Cyclic Polymers and Characterization of Their Diffusive Motion in the Melt State at the Single Molecule Level
Published on: September 26, 2016
Emily Q Rosenthal1, Judit E Puskas, Chrys Wesdemiotis
1Department of Polymer Science, The University of Akron, Akron, Ohio 44325, United States.
Abstract:
This paper reports the synthesis and characterization of disulfide polymers obtained by oxidation of 2-[2-(2-sulfanylethoxy)ethoxy]ethanethiol (DODT) using a benign, synergistic system comprised of air, dilute hydrogen peroxide and triethylamine as a catalyst that can be recycled. The dn/dc value of the polymer in THF was determined to obtain absolute molecular weight measurements. High molecular weight disulfide polymers (up to M(n) = 250000 g/mol) with polydispersity indices as low as M(w)/M(n) = 1.15 were obtained. Thermal analysis by DSC and TGA demonstrated that the rubbery polymers had a T(g) of -50 °C and began to degrade at 250 °C. Dithiothreitol reduced the polymers back to the original monomeric units in 33 h. MALDI-ToF showed the involvement of oligodisulfide rings (2-14 mers) in the polymerization that displayed the characteristics of a living/controlled polymerization; poly(DODT) was readily chain extended with 1,2-ethanedithiol. The chain extension indicates a class of living polymerization which is governed by radical recombination.
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