Article (Scientific journals)
Controlled radical polymerization of methacrylic monomers in the presence of a bis(ortho-chelated) arylnickel(II) complex and different activated alkyl halides
Granel, Claude; Dubois, Philippe; Jérôme, Robert et al.
1996In Macromolecules, 29 (27), p. 8576-8582
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A novel class of homogeneous nickel(II) catalysts, i.e [Ni{o,o‘(CH2NMe2)2C6H3}Br], denoted as Ni(NCN‘)Br, is reported to mediate in the presence of activated alkyl halides, e.g., CCl4 or α-halocarbonyl compounds, a well-controlled radical polymerization of methacrylic monomers [methyl and n-butyl methacrylate), (MMA, n-BuMA)] at rather low temperatures (<100 °C). The number-average molecular weight of the polymer gradually increased with the monomer conversion and was inversely proportional to the initiator concentration of alkyl halides. The molecular weight distribution (MWD) remained very narrow during the whole course of the polymerization (MWD < 1.3). All the experimental data including a successful block copolymerization (n-BuMA-b-MMA) experiment were in agreement with a living polymerization process, and remarkably enough, poly(methyl methacrylate) (PMMA) with molecular weight up to at least 105 g/mol was synthesized in a controlled fashion. Increased thermal stability of the PMMA is a further indication of the high regioselectivity and the virtually absence of termination reactions. Owing to the compatibility of the Ni(II) complexes toward water, extension to aqueous suspension polymerization was attempted successfully as attested by the promising preliminary results. Indications on the mechanism let us suggest that the reactive alkyl halide or the corresponding growing chain end is reversibly activated/deactivated by single electron transfer together with the halogen transfer.


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Keywords :
radical polymerization; atom transfer radical polymerization (ATRP)
Research center :
Center for Education and Research on Macromolecules (CERM)
Disciplines :
Chemistry
Materials science & engineering
Author, co-author :
Granel, Claude;  Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Dubois, Philippe ;  Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Jérôme, Robert ;  Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Teyssié, Philippe ;  University of Liège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Language :
English
Title :
Controlled radical polymerization of methacrylic monomers in the presence of a bis(ortho-chelated) arylnickel(II) complex and different activated alkyl halides
Publication date :
30 December 1996
Journal title :
Macromolecules
ISSN :
0024-9297
eISSN :
1520-5835
Publisher :
Amer Chemical Soc, Washington, United States - Washington
Volume :
29
Issue :
27
Pages :
8576-8582
Peer reviewed :
Peer Reviewed verified by ORBi
Funders :
Elf Atochem [FR]
BELSPO - SPP Politique scientifique - Service Public Fédéral de Programmation Politique scientifique
F.R.S.-FNRS - Fonds de la Recherche Scientifique [BE]
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