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Structural evolution during inverse vulcanization

Author

Listed:
  • Botuo Zheng

    (Fujian Normal University)

  • Liling Zhong

    (Fujian Normal University)

  • Xiaoxiao Wang

    (Fujian Normal University)

  • Peiyao Lin

    (Fujian Normal University)

  • Zezhou Yang

    (Fujian Normal University)

  • Tianwen Bai

    (Jiaxing University)

  • Hang Shen

    (Minjiang University)

  • Huagui Zhang

    (Fujian Normal University)

Abstract

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.

Suggested Citation

  • Botuo Zheng & Liling Zhong & Xiaoxiao Wang & Peiyao Lin & Zezhou Yang & Tianwen Bai & Hang Shen & Huagui Zhang, 2024. "Structural evolution during inverse vulcanization," Nature Communications, Nature, vol. 15(1), pages 1-17, December.
  • Handle: RePEc:nat:natcom:v:15:y:2024:i:1:d:10.1038_s41467-024-49374-y
    DOI: 10.1038/s41467-024-49374-y
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    References listed on IDEAS

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    1. Derek J. Bischoff & Taeheon Lee & Kyung-Seok Kang & Jake Molineux & Wallace O’Neil Parker & Jeffrey Pyun & Michael E. Mackay, 2023. "Unraveling the rheology of inverse vulcanized polymers," Nature Communications, Nature, vol. 14(1), pages 1-11, December.
    2. Xiaofeng Wu & Jessica A. Smith & Samuel Petcher & Bowen Zhang & Douglas J. Parker & John M. Griffin & Tom Hasell, 2019. "Catalytic inverse vulcanization," Nature Communications, Nature, vol. 10(1), pages 1-9, December.
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