Eugenol-DOPO: A Bio-Based Phosphorous-Containing Monomer for Thiol-ene Photocurable Thermosets

Özükanar Ö., ÇAKMAKÇI E., Sagdic G., Günay U. S., Durmaz H., Kumbaracı İ. V.

Journal of Polymers and the Environment, 2023 (SCI-Expanded) identifier identifier

  • Publication Type: Article / Article
  • Publication Date: 2023
  • Doi Number: 10.1007/s10924-023-02813-1
  • Journal Name: Journal of Polymers and the Environment
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus, PASCAL, Aerospace Database, BIOSIS, Chemical Abstracts Core, Chimica, Communication Abstracts, Compendex, Environment Index, Geobase, Greenfile, Metadex, Pollution Abstracts, Civil Engineering Abstracts
  • Keywords: Eugenol, Piperazine, DOPO, Thiol-ene, Thermoset
  • Istanbul Technical University Affiliated: Yes


The adverse health and environmental effects of petroleum-based materials have become a driving force for the fabrication of bio-based monomers. In this study, we synthesized a novel bio-based reactive phosphorus-containing; eugenol-DOPO, which was prepared in one step by the reaction of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and eugenol via Atherton–Todd reaction. Moreover, a diallyl compound was also prepared by using eugenol and piperazine. All monomers were characterized by nuclear magnetic resonance (NMR), mass, and Fourier-transform infrared (FTIR) spectroscopies. Thiol-ene photocured polysulfide thermoset networks were prepared by using these newly synthesized bio-based monomers. Thermal and thermomechanical properties of the thermosets were measured. Photo-crosslinked networks displayed over 88% gel content values. The thermal stability of the networks as well as the resulting char yields were improved as the percentage of eugenol-DOPO was increased in the formulations. The presence of N and P played a synergistic effect and the limiting oxygen index (LOI) values for the thermoset materials were enhanced. We believe eugenol-DOPO is not only a good alternative monomer for the preparation of thermally stable photocurable thermosets, but it is also a suitable bio-based additive for other polymers as well. Graphical Abstract: [Figure not available: see fulltext.].