Hydrogen-Transfer Reaction in Nitroxide Mediated Polymerization of Methyl Methacrylate: 2.2-Diphenyl-3-phenylimino-2,3-dihydroindol-1-yloxyl Nitroxide (DPAIO) vs. TEMPO

Hydrogen-Transfer Reaction in Nitroxide Mediated Polymerization of Methyl Methacrylate: 2.2-Diphenyl-3-phenylimino-2,3-dihydroindol-1-yloxyl Nitroxide (DPAIO) vs. TEMPO Научная публикация

Журнал

Journal of Polymer Science, Part A: Polymer Chemistry
ISSN: 0887-624X , E-ISSN: 1099-0518

Вых. Данные

Год: 2008, Том: 46, Номер: 20, Страницы: 6828-6842 Страниц : 15 DOI: 10.1002/pola.22991

Ключевые слова

activation energy; disproportionation; H-transfer; initiators; kinetics; liquid chromatography; living radical polymerization; nitroxide; NMR

Авторы

Edeleva Maria ^1,2 , Marque Sylvain R.A. ³ , Bertin Denis ³ , Gigmes Didier ³ , Guillaneuf Yohann ³ , Morozov Sergey V. ⁴ , Bagryanskaya Elena G. ¹

Организации

1	(Данные Web of science) RAS, Int Tomog Ctr SB, Novosibirsk 630090, Russia
2	(Данные Web of science) Novosibirsk State Univ, Novosibirsk 630090, Russia
3	(Данные Web of science) Aix Marseille Univ, Lab Chim Prov, Unite Mixte Rech 6264, F-13397 Marseille 20, France
4	(Данные Web of science) SB RAS, NN Vorozhtsov Novosibirsk Inst Organ Chem, Novosibirsk 630090, Russia

In a recent article, we have showed that the nitroxide mediated polymerization of methyl methacrylate was possible up to 80% conversion for reasonable masses M-n = 60,000 g mol(-1) when 2,2-diphenyl-3-phenylimino-2,3-dihydroindol-1-yloxyl nitroxide (DPAIO) was used as control agent. We have claimed that the success of this experiment relied on the absence of H-transfer reaction both in the alkoxyamine and between alkyl and nitroxyl radical. In this article, the decomposition of 4-nitrophenyl 2-(2,2,6,6-tetramethylpiperidine-1-yloxy)-2-methylpropionate (1a) and 4-nitrophenyl 2-(2,2-diphenyl-3-phenylimino-2,3-dihydroindol-1-yloxy)-2-methylpropanoate (2a) has been studied by H-1 NMR in the presence and in the absence (persistent radical effect condition) of scavenger (thiophenol PhSH). At temperature lower than the one used for polymerization, fast and quantitative H-transfer reaction was observed for la whereas no H-transfer reaction was observed for 2a. The scavenging technique proved for the first time that the H-transfer was an intermolecular process for la. However, the slow side-reaction of N-OC bond homolysis, which did not impede the control of the polymerization but may exert a detrimental effect on the livingness, was observed and quantified for 2a. (c) 2008 Wiley Periodicals, Inc.

Edeleva M. , Marque S.R.A. , Bertin D. , Gigmes D. , Guillaneuf Y. , Morozov S.V. , Bagryanskaya E.G.
Hydrogen-Transfer Reaction in Nitroxide Mediated Polymerization of Methyl Methacrylate: 2.2-Diphenyl-3-phenylimino-2,3-dihydroindol-1-yloxyl Nitroxide (DPAIO) vs. TEMPO
Journal of Polymer Science, Part A: Polymer Chemistry. 2008. V.46. N20. P.6828-6842. DOI: 10.1002/pola.22991 WOS Scopus РИНЦ OpenAlex

Опубликована online:	15 сент. 2008 г.
Опубликована в печати:	15 окт. 2008 г.

Web of science:	WOS:000260071300016
Scopus:	2-s2.0-55349118819
РИНЦ:	13597294
OpenAlex:	W2031877251

БД	Цитирований
Web of science	46
Scopus	46
РИНЦ	45
OpenAlex	46