UNSPECIFIED (2003) Copper mediated living radical polymerisation: interactions between monomer and catalyst. In: Dalton Discussion on Organometallic Chemistry and Catalysis, UNIV YORK, YORK, ENGLAND, SEP 09-11, 2003. Published in: DALTON TRANSACTIONS (21). pp. 4175-4180.

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Abstract

The mechanism of copper(I) mediated living radical polymerisation (ATRP) of vinyl monomers has been widely assumed to be relatively simple. However, monomer reactivity ratios in ATRP can be significantly different from those in conventional radical polymerisation, and the exact nature of the catalyst is not well understood due to rapid exchange of ligand and monomer at the copper centre under the polymerisation conditions. This paper illustrates aspects of this catalyst system, which complicate the accepted mechanism of this new and important reaction. Coordination of aminoethyl methacrylates and methoxy[poly(ethylene glycol)] methacrylate monomers is demonstrated by NMR with r(MMA)=0.96(2), 0.98(1) and 0.97(1) for dimethylaminoethyl methacrylate (DMAEMA), (diethylamino) ethyl methacrylate (DEAEMA) and (tert-butylamino) ethyl methacrylate (TBAEMA) under free radical polymerisation and 0.74(3), 0.79(3) and 0.69(3) for transition-metal mediated polymerisation.

Item Type:	Conference Item (UNSPECIFIED)
Subjects:	Q Science > QD Chemistry
Journal or Publication Title:	DALTON TRANSACTIONS
Publisher:	ROYAL SOC CHEMISTRY
ISSN:	1477-9226
Date:	2003
Number:	21
Number of Pages:	6
Page Range:	pp. 4175-4180
Identification Number:	10.1039/b303888b
Publication Status:	Published
Title of Event:	Dalton Discussion on Organometallic Chemistry and Catalysis
Location of Event:	UNIV YORK, YORK, ENGLAND
Date(s) of Event:	SEP 09-11, 2003
URI:	http://wrap.warwick.ac.uk/id/eprint/9129

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