Polymerization of Acrylonitrile Initiated by the System of Tetraalkyl-2-tetrazene and Benzyl Chloride

Abstract

In order to exa. mine the reactivities of 2-tetrazenes, the polymerization of acrylonitrile (AN)initiated. by tetrqalkyl-2-tetrazenes in the presence of benzyl chloride (BC) was carried out in dimethylformamide (DMF).2-Terazenes used were tetramethyl-2-te'tre2ene (1), tetraethyl2-tetrazene (2), tetrapropyl-2-tetrazene (3), and tetrabutyF2-tetrazene (4). The order T of the catalytic activity. for th. e yolymerization of AN is (1) (2) (3) (4).
In order to elucidate the, effect of substitute at at 1, 4-position of 2-tetrazenes on the rate of Polymerization r of AN, the kinetibs of the reaction of 2-tetrazenes with BC in the absence of AN were also studied in DMF. dG is scarcely influenced by any kind of substkuentS. The values of aHi 13.2 to 18i g kcal/inob ahd dSelF (-29.0 to -36.3cal/ K) are characteristic of Shose reactions with SN2 mechanism. Furthermore 2-tetrazenes react-with BC to produce benzyldialkylamines.
On the basis of the results, it was found that the reaction of 2-tetrazenes'with BC proceeds via Menschutkin-like reaction.