Photophysical, kinetic and thermodynamic study of one-component Type II thioxanthone acetic acid photoinitiators
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Dosyalar
Tarih
2020
Dergi Başlığı
Dergi ISSN
Cilt Başlığı
Yayıncı
Pergamon-Elsevier Science Ltd
Erişim Hakkı
info:eu-repo/semantics/closedAccess
Özet
In this study, One-Component Type II thioxanthone acetic acid based photoinitiators, as well as the conventional Type II photoinitiator with phenyl acetic acid based co-initiators, have been investigated in terms of their photophysical, kinetic and thermodynamic properties by a series of Density Functional Theory (DFT) calculations. Experimental UV-Vis spectra have been compared with computationally generated UV-Vis spectra via Time-Dependent DFT (TD-DFT) and by taking into consideration the vibrational and dynamic effects (Wiggler). Natural transition orbitals have been generated for thioxanthone acetic acid derivatives to understand the physical nature of electronic transitions. Furthermore, kinetic and thermodynamic parameters of radical attack to the monomer of thioxanthone acetic acid based radicals and phenyl acetic acid based co-initiator radicals have been investigated. Comparison of the thermodynamic parameters of the initiating radicals has shown that initiation is more favorable with exocyclic radicals in both cases. Exocyclic radicals of the thioxanthone acetic acid derivatives and phenyl acetic acid derivates have been found to have comparable activation energies for their attack to methyl methacrylate. Furthermore, the spin densities and the radical Fukui functions of the attacking radicals have been nicely correlated with the activation barriers. In this way, a fast and predictive approach for the determination of radical reactivity in photopolymerization reactions has been proposed; this enables the evaluation of the initiation efficiency of the photoinitiators prior to synthesis.
Açıklama
Metin, Eyup/0000-0001-8061-5280; Arsu, Nergis/0000-0002-1362-2517; Aviyente, Viktorya/0000-0001-9430-4096
WOS:000562571200010
WOS:000562571200010
Anahtar Kelimeler
Thioxanthone, Dft, Photoinitiator, Fukui Function, Spin Density, Natural Transition Orbitals
Kaynak
European Polymer Journal
WoS Q Değeri
Q1
Scopus Q Değeri
Q1
Cilt
136
