Exploring the first steps of an electrochemically-triggered controlled polymerization sequence: Activation of alkyl- and benzyl halide initiators by an electrogenerated Fe(II)Salen complex

Printer-friendly version
TitleExploring the first steps of an electrochemically-triggered controlled polymerization sequence: Activation of alkyl- and benzyl halide initiators by an electrogenerated Fe(II)Salen complex
Publication TypeJournal Article
Year of Publication2009
AuthorsBonometti, V, Labbe E, Buriez O, Mussini P, Amatore C
JournalJournal of Electroanalytical Chemistry
Volume633
Issue1
Pagination99-105
Date PublishedAug
ISBN Number1572-6657
Accession NumberISI:000268938900013
Abstract

This works investigates the mechanistic features related to the reactions between Fe(II)Salen and several organic halides used as initiators in Atom Transfer Radical Polymerization, Within the time scale of cyclic voltammetry, a fast reaction is observed between electrogenerated Fe(II)Salen and either ethyl 2-bromoisobutyrate, carbon tetrachloride or 1-chloro-1-phenylethane. Since no catalytic current is observed in cyclic voltammetry in the presence of RX, no fast mediated reductive cleavage of RX into R- + X- occured. An intermediate [R..X..FeSalen] complex was formed which was either relatively stable (ethyl 2-bromoisobutyrate and 1-chloro-1-phenylethane) or underwent further reduction (CCl4). In the presence of styrene and at 110 degrees C, polymerization is observed and the polydispersity of the resulting polystyrene appears to depend on the Fe(III)Salen/Fe(II)Salen initial ratio, The role of both Fe Salen and Fe(II)Salen in the regulation of radical concentration provided a controlled character to the polymerization. (C) 2009 Elsevier B.V. All rights reserved.

URL<Go to ISI>://000268938900013
DOI10.1016/j.jelechem.2009.04.030
Short TitleExploring the first steps of an electrochemically-triggered controlled polymerization sequence: Activation of alkyl- and benzyl halide initiators by an electrogenerated Fe(II)Salen complex
Unit: 
UMR 8640