Theory and Applications of Thiyl Radicals in Polymer Chemistry

Michelle Coote, Isa Degirmenci

Research output: Chapter in Book/Report/Conference proceedingChapterpeer-review

6 Citations (Scopus)


Sulfur-centered radicals are important intermediates in radical-based polymerization processes, such as thiol-ene, thiol-yne, and certain free-radical polymerizations. They are also important in the repair mechanism of certain classes of self-healing materials. This chapter outlines these applications, with a special emphasis on their mechanistic aspects, as clarified by computational chemistry. Based on a review of the literature, we outline structure-reactivity considerations in reagent design for these processes, explain why sulfur-centered radical addition reactions are so reactive despite their thermodynamic unfavorability, and clarify the mechanism by which dithiuram-based self-healing polymers undergo reshuffling
Original languageEnglish
Title of host publicationComputational Quantum Chemistry
Subtitle of host publicationInsights into Polymerization Reactions
EditorsMasoud Soroush
Place of PublicationNetherlands
PublisherElsevier Ltd
Number of pages24
ISBN (Electronic)9780128159835
ISBN (Print)9780128159835
Publication statusPublished - 2019
Externally publishedYes


  • Thiol
  • chain transfer agents
  • thiol-ene polymerization
  • thiol-yne polymerization
  • self-healing polymers


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