- Journal of the Turkish Chemical Society Section A: Chemistry
- Vol: 9 Issue: 1
- Role of Initiator Structure on Thiol-Ene Polymerization: A Comprehensive Theoretical Study
Role of Initiator Structure on Thiol-Ene Polymerization: A Comprehensive Theoretical Study
Authors : Isa Degirmenci
Pages : 149-162
Doi:10.18596/jotcsa.1003469
View : 9 | Download : 7
Publication Date : 2022-02-28
Article Type : Research
Abstract :In this study, the effects of initiator structure on thiol-ene polymerization were investigated 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 azobisisobutyronitrile (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.Keywords : Thiol-ene polymerization, density functional theory, reaction kinetics, structure-reactivity relationships