Issue 9, 2020

Copolymerization of an aryl halide and elemental sulfur as a route to high sulfur content materials

Abstract

High sulfur-content materials (HSMs) have been investigated for a plethora of applications owing to a combination of desirable properties and the low cost of waste sulfur as a starting monomer. Whereas extended sulfur catenates are unstable with respect to orthorhombic sulfur (S8 rings) at STP, oligomeric/polymeric sulfur chains can be stabilized when they are confined in a supporting matrix. The vast majority of reported HSMs have been made by inverse vulcanization of sulfur and olefins. In the current case, a radical aryl halide–sulfur polymerization (RASP) route was employed to form an HSM (XS81) by copolymerizing elemental sulfur with the xylenol derivative 2,4-dimethyl-3,5-dichlorophenol (DDP). XS81 is a composite of which 81 wt% is sulfur, wherein the sulfur is distributed between cross-linking chains averaging four sulfur atoms in length and trapped sulfur that is not covalently attached to the network. XS81 (flexural strength = 2.0 MPa) exhibits mechanical properties on par with other HSMs prepared by inverse vulcanization. Notably, XS81 retains mechanical integrity over many heat-recast cycles, making it a candidate for facile recyclability. This is the first report of an HSM comprising stabilized polymeric sulfur that has been successfully prepared from a small molecular comonomer by RASP. Preparation of XS81 thus demonstrates a new route to access HSMs using small molecular aryl halides, a notable expansion beyond the olefins required for the well-studied inverse vulcanization route to HSMs from small molecular comonomers.

Graphical abstract: Copolymerization of an aryl halide and elemental sulfur as a route to high sulfur content materials

Supplementary files

Article information

Article type
Paper
Submitted
11 Nov 2019
Accepted
15 Jan 2020
First published
22 Jan 2020

Polym. Chem., 2020,11, 1621-1628

Author version available

Copolymerization of an aryl halide and elemental sulfur as a route to high sulfur content materials

M. S. Karunarathna, M. K. Lauer, A. G. Tennyson and R. C. Smith, Polym. Chem., 2020, 11, 1621 DOI: 10.1039/C9PY01706B

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