Despite significant efforts, the design of alkoxyamines for polymerization of methacrylic monomers in a well-controlled fashion with good retention of the active chain ends remains a challenge. Herein, the facile synthesis of several alkoxyamines, which are capable of achieving this long sought-after goal, is reported. Controlled homopolymerization of methyl methacrylate is achieved as determined by a linear increase in molecular weight with conversion and first-order rate plots for various alkoxyamine concentrations. The versatility of the alkoxyamines is further exemplified by the ability to control the homopolymerization of styrene and by synthesis of a block copolymer of a second methacrylate in an efficient chain extension process.

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The synthesis of poly(n-butyl methacrylate) by nitroxide mediated miniemulsion polymerization is described using the alkoxyamine 3-(((2-cyanopropan-2-yl)oxy)(cyclohexyl)amino)-2,2-dimethyl-3-phenylpropanenitrile.

The effect of reversible-deactivation radical polymerization on the structure of the network formed by copolymerization of mono- and divinyl monomers is studied. The nitroxide-mediated radical copolymerization (NMP) of butyl methacrylate and ethylene glycol dimethacrylate, initiated with the alkoxyamine 3-(((2-cyanopropan-2-yl)­oxy)­cyclohexylamino)-2,2-dimethyl-3-phenylpropanenitrile (Dispolreg 007) in an aqueous miniemulsion was used as a case study. Combination of asymmetric-flow field-flow fractionation and small-angle X-ray scattering clearly showed that NMP led to a more homogeneous network structure formed by regions of relatively open networks connected with short polymer chain segments, whereas that of the polymer formed by free radical polymerization consists of densely cross-linked regions linked by long polymer chain portions.