Synthesis and polymerizability of CN monomers

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. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012