Role of Initiator Structure on Thiol-Ene Polymerization: A Comprehensive Theoretical Study

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Değirmenci İ.

Journal of the Turkish Chemical Society, Section A: Chemistry, vol.9, no.1, pp.149-162, 2022 (Scopus) identifier identifier

  • Publication Type: Article / Article
  • Volume: 9 Issue: 1
  • Publication Date: 2022
  • Doi Number: 10.18596/jotcsa.1003469
  • Journal Name: Journal of the Turkish Chemical Society, Section A: Chemistry
  • Journal Indexes: Scopus, TR DİZİN (ULAKBİM)
  • Page Numbers: pp.149-162
  • Keywords: density functional theory, reaction kinetics, structure-reactivity relationships, Thiol-ene polymerization
  • Ondokuz Mayıs University Affiliated: Yes

Abstract

The effect of initiator nature on thiol-ene polymerization was elaborated in this work with two initiators, four thiols, and eight monomers by utilizing the M06-2X/6-31++G(d,p) level of theory. For this purpose, a comparative investigation was carried out by modeling hydrogen abstraction from thiols (kHA) and addition reaction to monomers (ki), which is considered a side reaction. It was confirmed that the 2,2-dimethoxy-2-phenylacetophenone (DMPA) initiator is a suitable thiol-ene initiator except for the polymerization of electron-deficient or conjugated monomers. It was determined that the azobis(isobutyronitrile) (AIBN) initiator could not give a homogeneous thiol-ene product regardless of the monomer structure. However, it has been found that aromatic thiols should be used to obtain relatively better results with this initiator.