2-cyanoprop-2-yl dithiobenzoate (CPDB) mediated RAFT polymerization of dimethylaminoethyl methacrylate (DMAEMA) was carried out in dioxane at 90 8C. The influence of several parameters, such as the monomer to CPDB molar ratio (100 to 500), the monomer concentration (2 mol Á L À1 to 5.9 mol Á L À1 ), and CPDB to initiator molar ratio (1 to 10), was evaluated with regards to conversion and polymerization duration, as well as control of molar mass and molar mass distributions. Number average molar masses from 10,000 to 70,000 g Á mol À1 can be targeted. The determination of the molar masses has been carried out by size exclusion chromatography (SEC) with a refractometer detector with poly(methyl methacrylate) (PMMA) standards. The experimental values were lower than the expected ones. Then, SEC in aqueous medium with an online laser light scattering detector was used both to get absolute molar masses and to recalibrate the SEC column in THF. Characterization of well-controlled PDMAEMA samples has been performed by proton NMR spectroscopy and matrix assisted laser desorption ionization time of flight mass spectrometry. Finally, a chain extension experiment was evaluated with regard to living features. V V C 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: [3551][3552][3553][3554][3555][3556][3557][3558][3559][3560][3561][3562][3563][3564][3565] 2005