The synthesis and polymerizability of imine C=N monomers is surveyed. The investigated imines were either far more reactive than similarly substituted C=C or C=O monomers, or too stable to polymerize. Imines with electron-attracting substituents on N favor polymerization by anionic mechanism, but led only to low molecular weight polymers. Imines with a donor substituent on N, such as N-arylmethyleneimines, polymerized by cationic or anionic mechanism. 1- and 2-Aza-1,3-butadienes were also rather unstable and polymerized to oligomers. The symmetrically substituted 2,3-diaza-1,3-butadienes could be purified and polymerized successfully using anionic initiators, resulting in both 1,4- and 1,2-structures in the polymer backbone, depending on the substituents. (c) 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012