Nitroxide-Mediated Polymerization of Methyl Methacrylate and Styrene with New Alkoxyamines from 4-Nitrophenyl 2-Methylpropionat-2-yl Radicals

摘要: The N-phenylalkoxyamine N-(1-methyl-(1-(4-nitrophenoxy)carbonyl)ethoxy)-N-(1-methyl-(1-(4-nitrophenoxy)carbonyl)ethyl)benzenamine (1) was prepared by the addition of 4-nitrophenyl 2-methylpropionat-2-yl radicals across double bond nitrosobenzene and evaluated as an initiator for nitroxide-mediated polymerization (NMP). N-Phenylalkoxyamines have not been extensively studied in NMP, though they shown promise controlling methyl methacrylate (MMA) to moderate conversions. It is thought that delocalization nitroxide radical through N-phenyl substituent may minimize cross-disproportionation with chain end has made NMP MMA difficult. Here, we show alkoxyamine 1 capable 50% conversion while maintaining narrow molecular weight distributions (Mw/Mn = 1.12−1.30). Additionally, extension from resulting PMMA macroinitiators or styrene allows formation diblock copolymers. correspo...