Thiol-Ene Polymerization of Natural Monomers: A DFT Study

Mohaman H., Tuncer D., Değirmenci İ.

MACROMOLECULAR THEORY AND SIMULATIONS, vol.31, no.3, 2022 (SCI-Expanded) identifier identifier

  • Publication Type: Article / Article
  • Volume: 31 Issue: 3
  • Publication Date: 2022
  • Doi Number: 10.1002/mats.202100073
  • Journal Name: MACROMOLECULAR THEORY AND SIMULATIONS
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus, Academic Search Premier, Aerospace Database, Applied Science & Technology Source, Chemical Abstracts Core, Chimica, Communication Abstracts, Compendex, INSPEC, Metadex, Civil Engineering Abstracts
  • Keywords: density functional theory, M06-2X, natural monomers, thiol-ene polymerization, CIS-TRANS ISOMERIZATION, FREE-RADICAL POLYMERIZATION, CARBON-CENTERED RADICALS, FATTY-ACID RESIDUES, CLICK CHEMISTRY, CHAIN TRANSFER, D-LIMONENE, KINETICS, MECHANISM, PHOTOPOLYMERIZATION
  • Ondokuz Mayıs University Affiliated: Yes

Abstract

This study investigates the thiol-ene reaction mechanism of natural monomers using quantum chemical tools. The structure-reactivity relationship for these monomers is elaborated by the aid of radical stabilization energies (RSEs), intermolecular interactions, the curve-crossing model, Hammond Postulate, and Evans-Polanyi relationships. Geometry optimizations, frequency, and energy calculations are performed at the M06-2X/6-31++G(d,p) level of theory. A crucial parameter for thiol-ene polymerization, which is the ratio of the propagation reaction (k(p)) and the chain transfer reaction (k(ct)) rate constants (k(p)/k(ct)), is calculated in order to elucidate the thiol-ene reaction mechanism. In light of these energetic and kinetic calculations, it is suggested that linalool, d-limonene, terpinolene, and gamma-terpinene are considered natural monomer candidates for thiol-ene polymerization due to their almost equal magnitude of the rate constants (k(p)/k(ct)approximate to 1). The thiol-ene polymerization potential of some specific unsaturated fatty acids is another prominent finding in this study.