Abstract
The discovery of inverse vulcanization has allowed stable polymers to be made from elemental sulfur, an unwanted by-product of the petrochemicals industry. However, further development of both the chemistry and applications is handicapped by the restricted choice of cross-linkers and the elevated temperatures required for polymerisation. Here we report the catalysis of inverse vulcanization reactions. This catalytic method is effective for a wide range of crosslinkers reduces the required reaction temperature and reaction time, prevents harmful H2S production, increases yield, improves properties, and allows crosslinkers that would be otherwise unreactive to be used. Thus, inverse vulcanization becomes more widely applicable, efficient, eco-friendly and productive than the previous routes, not only broadening the fundamental chemistry itself, but also opening the door for the industrialization and broad application of these fascinating materials.
Highlights
The discovery of inverse vulcanization has allowed stable polymers to be made from elemental sulfur, an unwanted by-product of the petrochemicals industry
Inspired by accelerators used in conventional vulcanization[42], the introduction of catalysts into this inverse vulcanization was trialed (Fig. 1e; Table 1)
The reaction of cross-linker ethylene glycol dimethacrylate (EGDMA) with sulfur was used as a model reaction, as it was found to be un-reactive without catalysis
Summary
Of the crosslinkers able to react in the absence of catalyst (Fig. 1b, c), as well as reduced reaction times, many showed an increase in glass transition temperature (Tg) when catalyzed (Fig. 2g, S27–S33, supplementary table 5). It is likely the catalysis produces more crosslinking, and a more even distribution of sulfur leading to shorter sulfur chains between crosslinkers. Exposure of this powder to aqueous solutions of mercury chloride gives a significant increase in mercury uptake
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