Unraveling the rheology of inverse vulcanized polymers

Derek J. Bischoff, Taeheon Lee, Kyung-Seok Kang, Jake Molineux, Wallace O’Neil Parker, Jeffrey Pyun () and Michael E. Mackay ()
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Derek J. Bischoff: University of Delaware
Taeheon Lee: University of Arizona
Kyung-Seok Kang: University of Arizona
Jake Molineux: University of Arizona
Wallace O’Neil Parker: Eni S.p.A.
Jeffrey Pyun: University of Arizona
Michael E. Mackay: University of Delaware

Nature Communications, 2023, vol. 14, issue 1, 1-11

Abstract: Abstract Multiple relaxation times are used to capture the numerous stress relaxation modes found in bulk polymer melts. Herein, inverse vulcanization is used to synthesize high sulfur content (≥50 wt%) polymers that only need a single relaxation time to describe their stress relaxation. The S-S bonds in these organopolysulfides undergo dissociative bond exchange when exposed to elevated temperatures, making the bond exchange dominate the stress relaxation. Through the introduction of a dimeric norbornadiene crosslinker that improves thermomechanical properties, we show that it is possible for the Maxwell model of viscoelasticity to describe both dissociative covalent adaptable networks and living polymers, which is one of the few experimental realizations of a Maxwellian material. Rheological master curves utilizing time-temperature superposition were constructed using relaxation times as nonarbitrary horizontal shift factors. Despite advances in inverse vulcanization, this is the first complete characterization of the rheological properties of this class of unique polymeric material.

Date: 2023
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DOI: 10.1038/s41467-023-43117-1

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