Atom Transfer Radical Polymerization of Styrene and Methyl Methacrylate Induced by RhI(cycloocta-1,5-diene) Complexes

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Title:Atom Transfer Radical Polymerization of Styrene and Methyl Methacrylate Induced by RhI(cycloocta-1,5-diene) Complexes
Creators:
Opstal, Tom
Zedník, Jiří
Sedláček, Jan
Svoboda, Jan
Vohlídal, Jiří
Verpoort, Francis
Journal or Publication Title:
Collection of Czechoslovak Chemical Communications, 67, 12, pp. 1858-1871
Uncontrolled Keywords:Controlled radical polymerizations, Rhodium diene complexes, Methyl methacrylate, Styrene, Atom transfer radical polymerizations

Abstract

Rh(I)(diene) complexes, di(μ-docosanoato)bis[(η<sup>2</sup>:η<sup>2</sup>-cycloocta-1,5-diene)rhodium(I)] (<strong>1</strong>) and bis(μ-4-methylphenolato)bis[(η<sup>2</sup>:η<sup>2</sup>-cycloocta-1,5-diene)rhodium(I)] (<strong>2</strong>) are introduced as a new class of catalysts for the atom transfer radical polymerization (ATRP) of vinyl monomers and provide new example of an involvement of rhodium compounds in radical reactions. Single complexes <strong>1</strong> and <strong>2</strong> promote a controlled radical polymerization of methyl methacrylate and styrene affording a medium to good yield of high-molecular-weight polymers with polydispersity index, <i>M</i><sub>w</sub>/<i>M</i><sub>n</sub>, values ranging from 1.45 to 1.65. However, the initiator efficiency found for these reaction systems is rather low, from 0.04 to 0.20. The addition of (Bu)<sub>2</sub>NH to these polymerization systems has a remarkable positive influence on the catalyst activity and the polymerization control, particularly, in the systems involving complex <strong>1</strong>, for which approximately tenfold increase in the initiator efficiency, up to 0.85, and decrease in the polydispersity index, to the value 1.27, has been observed. Dissociation of dinuclear Rh(I)(diene) species to the mononuclear ones is suggested as an important part of the mechanism lying behind the effect of (Bu)<sub>2</sub>NH additive. <p>

Title:Atom Transfer Radical Polymerization of Styrene and Methyl Methacrylate Induced by RhI(cycloocta-1,5-diene) Complexes
Creators:
Opstal, Tom
Zedník, Jiří
Sedláček, Jan
Svoboda, Jan
Vohlídal, Jiří
Verpoort, Francis
Uncontrolled Keywords:Controlled radical polymerizations, Rhodium diene complexes, Methyl methacrylate, Styrene, Atom transfer radical polymerizations
Divisions:Life and Chemical Sciences > Institute of Organic Chemistry and Biochemistry > Collection of Czechoslovak Chemical Communications
Journal or Publication Title:Collection of Czechoslovak Chemical Communications
Volume:67
Number:12
Page Range:pp. 1858-1871
ISSN:0010-0765
E-ISSN:1212-6950
Publisher:Institute of Organic Chemistry and Biochemistry
Related URLs:
URLURL Type
http://dx.doi.org/10.1135/cccc20021858UNSPECIFIED
ID Code:2038
Item Type:Article
Deposited On:06 Feb 2009 17:15
Last Modified:06 Feb 2009 16:15

Citation

Opstal, Tom; Zedník, Jiří; Sedláček, Jan; Svoboda, Jan; Vohlídal, Jiří; Verpoort, Francis (2002) Atom Transfer Radical Polymerization of Styrene and Methyl Methacrylate Induced by RhI(cycloocta-1,5-diene) Complexes. Collection of Czechoslovak Chemical Communications, 67 (12). pp. 1858-1871. ISSN 0010-0765

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