Ethyl-(ECA) and butyl-2-cyanoacrylate (BCA) monomers of high purity and acidic stabilization were synthesized and anionically polymerized to homo- and copolymers in two different ways: by piperidine-catalyzed bulk polymerization leading to transparent, brittle films (method A) and by polymerization in aqueous medium in the presence of sodium bicarbonate to obtain white powders (Method B). The molecular structure of the synthesized monomers, hornopolymers and copolymers were corroborated by spectral methods. The polymers were studied further by thermal gravimetric analysis (TGA), differential scanning calorimetry (DSC), size exclusion chromatography (SEC) and proton nuclear magnetic resonance (H-1 NMR). Controlling the composition of the monomer feed and the way the polymerization was performed, it was possible to obtain phase separated or homogeneous cyanoacrylate copolymers with glass transitions varying between the T-g of polyECA and that of polyBCA. (C) 2008 Wiley Periodicals, Inc.