Document Detail


Copper-Mediated Controlled/"Living" Radical Polymerization in Polar Solvents: Insights into Some Relevant Mechanistic Aspects.
MedLine Citation:
PMID:  22378618     Owner:  NLM     Status:  Publisher    
Abstract/OtherAbstract:
The field of transition-metal-mediated controlled/"living" radical polymerization (CLRP) has become the subject of intense discussion regarding the mechanism of this widely-used and versatile process. Most mechanistic analyses (atom transfer radical polymerization (ATRP) vs. single-electron transfer living radical polymerization (SET-LRP)) have been based on model experiments, which cannot correctly mimic the true reaction conditions. We present, for the first time, a determination of the [Cu(I) Br]/[L] (L=nitrogen-based chelating ligand) ratio and the extent of Cu(I) Br/L disproportionation during CLRP of methyl acrylate (MA) in dimethylsulfoxide (DMSO) with Cu(0) wire as a transition-metal catalyst source. The results suggest that Cu(0) acts as a supplemental activator and reducing agent of Cu(II) Br(2) /L to Cu(I) Br/L. More importantly, the Cu(I) Br/L species seem to be responsible for the activation of SET-LRP.
Authors:
Tamaz Guliashvili; Patrícia V Mendonça; Arménio C Serra; Anatoliy V Popov; Jorge F J Coelho
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Publication Detail:
Type:  JOURNAL ARTICLE     Date:  2012-2-29
Journal Detail:
Title:  Chemistry (Weinheim an der Bergstrasse, Germany)     Volume:  -     ISSN:  1521-3765     ISO Abbreviation:  -     Publication Date:  2012 Feb 
Date Detail:
Created Date:  2012-3-1     Completed Date:  -     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  9513783     Medline TA:  Chemistry     Country:  -    
Other Details:
Languages:  ENG     Pagination:  -     Citation Subset:  -    
Copyright Information:
Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Affiliation:
GE Power and Water; Water & Process Technologies, 4636 Somerton Road, Trevose, PA 19053 (USA), Fax: (+1) 215-953-2361. tamaz.guliashvili@ge.com.
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