期刊
MACROMOLECULAR CHEMISTRY AND PHYSICS
卷 209, 期 13, 页码 1345-1357出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/macp.200800099
关键词
kinetics (polym.); living polymerization; nitroxides; nitroxide-mediated polymerization (NMP); styrene
Values of k(d) for the C-ON bond homolysis were measured for alkoxyamines based on imidazoline and imidazole nitroxides. They were analyzed in terms of polar/stabilization, steric, and entropic effects. k(d) decreased with increasing electron-withdrawing capacities of the groups attached to the nitroxide, but increasing with both the bulkiness of the group attached to the nitroxide and the presence of substituents on the ring. With three alkoxyamines, it was shown that the fate of the NMP of styrene depended on the type of initiating alkyl radical: successful for initiating 1-phenylethyl radicals and unsuccessful for initiating p-nitropheriyloxycarbonyl-2-prop-2-yl radicals.
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