Sulfenyl Chlorides: An Alternative Monomer Feedstock from Elemental Sulfur for Polymer Synthesis

Kyung Seok Kang, Chisom Olikagu, Taeheon Lee, Jianhua Bao, Jake Molineux, Lindsey N. Holmen, Kaitlyn P. Martin, Kyung Jo Kim, Ki Hyun Kim, Joona Bang, Vlad K. Kumirov, Richard S. Glass, Robert A. Norwood, Jon T. Njardarson, Jeffrey Pyun

Research output: Contribution to journalArticlepeer-review

17 Scopus citations


A polymerization methodology is reported using sulfur monochloride (S2Cl2) as an alternative feedstock for polymeric materials. S2Cl2is an inexpensive petrochemical derived from elemental sulfur (S8) but has numerous advantages as a reactive monomer for polymerization vs S8. This new process, termed sulfenyl chloride inverse vulcanization, exploits the high reactivity and miscibility of S2Cl2with a broad range of allylic monomers to prepare soluble, high molar-mass linear polymers, segmented block copolymers, and crosslinked thermosets with greater synthetic precision than achieved using classical inverse vulcanization. This step-growth addition polymerization also allows for preparation of a new class of thiol-free, inexpensive, highly optically transparent thermosets (α = 0.045 cm-1at 1310 nm), which exhibit among the best optical transparency and low birefringence relative to commodity optical polymers, while possessing a higher refractive index (n > 1.6) in the visible and near-infrared spectra. The fabrication of large-sized optical components is also demonstrated.

Original languageEnglish (US)
Pages (from-to)23044-23052
Number of pages9
JournalJournal of the American Chemical Society
Issue number50
StatePublished - Dec 21 2022

ASJC Scopus subject areas

  • Catalysis
  • General Chemistry
  • Biochemistry
  • Colloid and Surface Chemistry


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