ORBi: Moineau Georges - Controlled radical polymerization of (meth)acrylates by ATRP with NiBr2(PPh3)2 as catalyst

Reference : Controlled radical polymerization of (meth)acrylates by ATRP with NiBr2(PPh3)2 as catalyst


	Document type :	Scientific journals : Article
	Discipline(s) :	Engineering, computing & technology : Materials science & engineering Physical, chemical, mathematical & earth Sciences : Chemistry
	To cite this reference:	http://hdl.handle.net/2268/4357

Title :	Controlled radical polymerization of (meth)acrylates by ATRP with NiBr2(PPh3)2 as catalyst
Language :	English
Author, co-author :	Moineau, Georges [University of Liège (ULg) > Department of Chemistry > Center for Education and Research on Macromolecules (CERM) > >]
	Minet, Michaël [University of Liège (ULg) > Department of Chemistry > Center for Education and Research on Macromolecules (CERM) > >]
	Dubois, Philippe [University of Liège (ULg) > Department of Chemistry > Center for Education and Research on Macromolecules (CERM) > >]
	Teyssié, Philippe [University of Liège (ULg) > Department of Chemistry > Center for Education and Research on Macromolecules (CERM) > >]
	Senninger, Thierry [Groupement de Recherches de Lacq, France > > Service Polymères de Grande Diffusion et Catalyse > >]
	Jérôme, Robert [University of Liège (ULg) > Department of Chemistry > Center for Education and Research on Macromolecules (CERM) > >]
Publication date :	12-Jan-1999
Journal title :	Macromolecules
Publisher :	Amer Chemical Soc
Volume :	32
Issue/season :	1
Pages :	27-35
Audience :	International
ISSN :	0024-9297
City :	Washington
Keywords :	[en] radical polymerization ; atom transfer radical polymerization (ATRP)
Abstract :	[en] NiBr2(PPh3)2 has been found to be an efficient catalyst for the ATRP of methyl methacrylate (MMA) and n-butyl acrylate (n-BuA) initiated by an alkyl halide in the absence of any activator (e.g., Lewis acid) at 85 °C. The molecular weight distribution of the poly(meth)acrylates is narrow (Mw/Mn = 1.1−1.4). However, some side reactions (more likely coupling reactions) are observed at high monomer conversions in the case of n-BuA. An excess of PPh3 has proved to increase the polymerization rate of MMA while preserving the control of the molecular parameters. When the catalyst/initiator molar ratio is too small (e.g., 0.05), the polymerization rate decreases, the polydispersity increases, and the initiation is less efficient. α-Acid and α-hydroxyl end groups have been successfully attached to the chains by using functional initiators, such as 2-bromo-2-methylpropionic acid and 2,2‘,2‘ ‘-tribromoethanol. Reactivity ratios for the MMA/n-BuA comonomer pair have been measured and found to be close to the values observed for a conventional free-radical polymerization. Diethyl meso-2,5-dibromoadipate has been used as a difunctional initiator for the n-BuA polymerization, leading to α,ω-bromo-poly(n-BuA) of narrow molecular weight distribution. Finally, the thermal stability of PMMA is consistent with the lack of termination reactions, while Tg is as high as 125 °C.
Research units :	Center for Education and Research on Macromolecules (CERM)
Funders :	Elf Atochem ; Politique Scientifique Fédérale (Belgique) = Belgian Federal Science Policy
Target :	Researchers
Permalink :	http://hdl.handle.net/2268/4357
DOI :	10.1021/ma980995u
Other URL :	http://pubs.acs.org/doi/pdf/10.1021/ma980995u

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