Inverse Vulcanization of Aziridines: Enhancing Polysulfides for Superior Mechanical Strength and Adhesive Performance

Angew Chem Int Ed Engl. 2024 Nov 19:e202418764. doi: 10.1002/anie.202418764. Online ahead of print.

Abstract

This study introduces a novel approach to inverse vulcanization by utilizing a commercially available triaziridine crosslinker as an alternative to conventional olefin-based crosslinkers. The model reactions reveal a self-catalyzed ring-opening of "unactivated" aziridine with elemental sulfur, forming oligosulfide-functionalized diamines. The triaziridine-derived polysulfides exhibit impressive mechanical properties, achieving a maximum stress of ~8.3 MPa and an elongation at break of ~107%. The incorporation of silicon dioxide (20 wt%) enhances the composite's rigidity, yielding a Young's modulus of ~0.94 GPa. Furthermore, these polysulfides display excellent adhesion strength on various substrates, such as aluminum (~7.0 MPa), walnut (~9.6 MPa), and steel (~11.0 MPa), with substantial retention of adhesion strength (~3.3 MPa on steel) at -196 °C. The straightforward synthetic process, combined with the accessibility of the triaziridine crosslinker, emphasizes the potential for further innovations in sulfur polymer chemistry.

Keywords: adhesive; aziridines; elemental sulfur; inverse vulcanization; polysulfides.