Imidazolidinone Nitroxide-Mediated Polymerization

• Published in: Macromolecules Vol. 32; no. 21; pp. 6895 - 6903
• Main Authors: Chong, ) Y. K, Ercole, Frances, Moad, Graeme, Rizzardo, Ezio, Thang, San H, Anderson, Albert G
• Format: Journal Article
• Language: English
• Published: Washington, DC American Chemical Society 19.10.1999
• Subjects: Applied sciences; Exact sciences and technology; Organic polymers; Physicochemistry of polymers; Polymerization; Preparation, kinetics, thermodynamics, mechanism and catalysts; Substituent effect; Imidazole derivatives; Nitroxyl; Butyl acrylate polymer; Living polymer; Reaction regulator; Methyl methacrylate polymer; Experimental study; Radical scavenger; Monodispersed polymer; Free radical polymerization; Preparation; Diblock copolymer; Styrene polymer; Styrene(methyl) copolymer; Radical copolymerization; Chemical reactivity; Chemical synthesis; Styrene copolymer
• ISSN: 0024-9297; 1520-5835
• DOI: 10.1021/ma9904868

Derivatives of 2,2,5,5-tetraalkylimidazolidin-4-one-1-oxyl have been found to offer significant advantages over many of the nitroxides previously employed in nitroxide-mediated polymerization:  homopolymers [e.g., polystyrene and poly(alkyl acrylate)], statistical copolymers [e.g., poly(styrene-co-acrylonitrile)], and block copolymers [e.g., poly(4-methylstyrene)-block-polystyrene and poly(n-butyl acrylate)-block-polystyrene] can be synthesized with controlled molecular weight, narrow molecular weight distribution, and defined end group functionality. The effect of substituents α to the nitroxide nitrogen and at the transannular nitrogen on the outcome of polymerization is explored. Appropriate selection of these substituents provides polymers of lower polydispersities than, for example, 2,2,6,6-tetramethylpiperidin-2-oxyl and derivatives. The nitroxides are synthesized from readily available precursors by a simple experimental route. Moreover, they are subject to fewer side reactions. In particular, disproportionation between the propagating radical with nitroxide appears to be of lesser significance.