The nitrone mediated polymerization of methyl methacrylate (MMA) via the enhanced (termination) spin capturing polymerization (ESCP) process is made possible via the addition of small amounts of styrene (between 5 and 10 vol.%) to the reaction mixture. Efficient control over the molecular weight between 7000 and 57,000 g mol(-1) (at 60 degrees C) yields macromolecules that feature a mid-chain alkoxyamine functionality and are rich in methyl methacrylate. The collated kinetic and molecular weight data allow for a deduction of the spin capturing constant, C-SC, in the range between 0.15 and 0.30. During the ESCP process, the number average molecular weight, M-n of the formed mid-chain functional polymer is constant up to high monomer to polymer conversions (i.e. 80%). The high degree of alkoxyamine mid-chain functionality present in the generated polymeric material is evidenced via a subsequent nitroxide-mediated polymerization process employing the formed ESCP polymer, indicating a chain extension from 37,700 to 118,000 g mol(-1) with a concomitant reduction in polydispersity (from 2.3 to 1.5). (C) 2010 Elsevier Ltd. All rights reserved.