Effect of electron-donating ability of terminal groups of cationic polymethine dyes on thermal polymerization of methyl methacrylate in solution

Мова статті: 
Англійська
Автор(и) статті: 
G. P. Grabchuk, N. A. Derevyanko, A. A. Ishchenko
Вихідні данні статті: 
Russian Journal of Applied Chemistry May 2013, Volume 86, Issue 5, pp 739-746
Назва журналу: 
Russian Journal of Applied Chemistry
Рік публікації: 
2013
Volume: 
86
Issue: 
5
Ключові слова: 
polymethine dyes
Ключове слово: 
dye-doped polymers
Thermal polymerizability of methyl methacrylate solution was examined in dimethylformamide in the presence of cationic symmetric and asymmetric polymethine dyes with different terminal electron-donating groups by dilatometric method. It was found that the polymethine dyes according to the electronic structure can initiate or inhibit the polymerization of methyl methacrylate both in the presence of standard initiator, azoisobutyronitrile, and in its absence by a radical mechanism. It was shown that the initiating ability was weakened with altering an electron-donating activating ability of terminal groups of dyes from the average level in both directions of its increasing or decreasing. The transition from symmetric to asymmetric dyes in the same structural type is accompanied by a loss of initiating ability. Based on the comparison of experimental kinetic data of polymerization of methyl methacrylate in the presence of dyes and quantum chemical calculations of electronic structure for dyes it was demonstrated that a HOMO energy value of an initiating dye must be higher and that of an inhibiting dye, lower than the methyl methacrylate value.
Назва підрозділу: 
Кафедра супрамолекулярної хімії та біохімії
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Дизайн: Інститут високих технологій
Ivan Ivanov