Mechanism of Nitrogen-Containing Cyclic Polymerization

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Abstract
The comprehensive polymerization mechanism of the nitrogen-containing cycles 1-azobicyclo (3,1,0)-hexane (ABH), conidine, quinuclidine, and triethylenediamine under the action of quaternary ammonium salts, ammonium salts, and BF3 complex with conidine is studied. Polymerization is of the living polymers type, and the active centers of monomer polymerization are ions and ion pairs: the activity of the latter is comparable to and exceeds that of the free ions. The effects of the nature of the counterion, cation, and medium polarity on the reaction rate are investigated. The polymerization rate is found to depend on the nature of the counterion in the polymerization of ion pairs, but not to depend on the counterion in the polymerization of free ions. The reaction rate is proportional to the counterion size in the polymerization of ion pairs. In the case of conidine K+ = 0.2, K±(Cl−) = 0.28, K±(Br−) = 0.36, K±(I−) = 0.51, and K±(ClO4 −) = 0.62 (liter)/(mole)(min). The heats of nitrogen-cyclic polymerization are measured and correlated with the activation energy.

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