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Structural evolution during inverse vulcanization
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DOI：10.1038/s41467-024-49374-y.png)
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Abstract
En 中文
Inverse vulcanization exploits S8 to synthesize polysulfides. However, evolution of products and its mechanism during inverse vulcanization remains elusive. Herein, inverse vulcanization curves are obtained to describe the inverse vulcanization process in terms of three stages: induction, curing and over-cure. The typical curves exhibit a moduli increment before declining or plateauing, reflecting the process of polysulfide network formation and loosing depending on monomers. For aromatic alkenes, in the over-cure, the crosslinked polysulfide evolves significantly into a sparse network with accelerated relaxation, due to the degradation of alkenyl moieties into thiocarbonyls. The inverse vulcanization product of olefins degrades slowly with fluctuated relaxation time and modulus because of the generation of thiophene moieties, while the inverse vulcanization curve of dicyclopentadiene has a plateau following curing stage. Confirmed by calculations, the mechanisms reveal the alkenyl groups react spontaneously into thiocarbonyls or thiophenes via similar sulfur-substituted alkenyl intermediates but with different energy barriers. Inverse vulcanization exploits elemental sulfur to synthesize versatile polysulfides but the mechanism of inverse vulcanization remains elusive. Herein, the authors use inverse vulcanization curves to describe the three-stage structural evolution during the inverse vulcanization process.
Keywords:
DYNAMIC COVALENT POLYMERS
ELEMENTAL SULFUR
COPOLYMERIZATION
RHEOLOGY
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