Cyclic alkoxyamines for nitroxide-mediated radical polymerization

A 5-membered cyclic alkoxyamine and a 17-membered cyclic alkoxyamine were synthesized and used in the polymerization of styrene. Polymerizations using the 5-membered cyclic alkoxyamine resulted in polymers with uncontrolled molecular weights and high polydispersities. Polymerizations using the 17-me...

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Bibliographic Details
Published in:Journal of polymer science. Part A, Polymer chemistry Polymer chemistry, 2008-12, Vol.46 (24), p.8049-8069
Main Authors: Ruehl, Jean, Ningnuek, Niwat, Thongpaisanwong, Thanchanok, Braslau, Rebecca
Format: Article
Language:English
Subjects:
alkoxyamine
Applied sciences
cyclopolymerization
Exact sciences and technology
living polymerization
macrocycles
nitroxide
Organic polymers
Physicochemistry of polymers
Polymerization
Preparation, kinetics, thermodynamics, mechanism and catalysts
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Summary:A 5-membered cyclic alkoxyamine and a 17-membered cyclic alkoxyamine were synthesized and used in the polymerization of styrene. Polymerizations using the 5-membered cyclic alkoxyamine resulted in polymers with uncontrolled molecular weights and high polydispersities. Polymerizations using the 17-membered cyclic alkoxyamine produced oligomeric polymers in which multiple polymer chains are linked through NO-C bonds. EPR homolysis experiments revealed that the 5-membered cyclic alkoxyamine does not dissociate to form a nitroxide species, even at temperatures as high as 403 K. In contrast, the 17-membered cyclic alkoxyamine does dissociate to form nitroxide, but the rate of dissociation is slower than that of parent acyclic alkoxyamine 2,2,5-trimethyl-3-(1-phenylethoxy)-4-phenyl-3-azahexane.
ISSN:0887-624X
1099-0518
DOI:10.1002/pola.23103