Other Oxygen-Centered Radical Mediated Polymerization

7 Other Oxygen-Centered Radical-Mediated Polymerizations 

A number of other chemistries which involve C-O bond cleavage have been reported. Druliner has reported on systems where NCO, 112, 113 or related species is the persistent radical. Homolysis rates for these systems were stated to be suitable for MMA polymerization at ambient temperature. The use of NCO has also been studied by Grande el most recently for AA 

Chung and coworkers have reported on the use of stable borinate or boroxyl radicals e.g. 114) to mediate radical polymerization. Methacrylates (MMA) and acrylates (trifluoroethyl acrylate) have been polymerized at ambient temperature to yield polymers with relatively narrow molecular weight distributions.The method has been used to prepare block copolymers and polyolefin graft copolymers, 

A living radical polymerization mechanism was proposed for the polymerization of MMA and VAc initiated by certain aluminum complexes in the presence of nitroxides. It was originally thought that a carbon-aluminum bond was formed in a reversible termination step. However, a more recent study found the results difficult to reproduce and the mechanism to be complex. 

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