A mechanism is proposed for the anodic polymerization of ethylenediamine (EDA). Initially, there occurs the formation of the radical cation NH 2 CH 2 CH 2 NH 2 ϩ• , followed by the breaking of the C-N bond, the expulsion of NH 2 • , and concomitant formation of the primary carbocation NH 2 CH 2 CH 2 ϩ or the aziridinium cation. This cation reacts with an NH 2 group of an EDA molecule, yielding a new amine which can be further oxidized. The product on the anode is a polyethyleneimine-like polymer. A similar product was found for diethylenetriamine, whose oxidation was studied too. Other pure -amines can also polymerize if they are primary amines and have vicinal alkyl groups which are secondary, i.e., have the formula NH 2 CH 2 RCH 2 NH 2 .

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