Some Peculiarities of Macrozwitterion Polymerization

Abstract

Abstract Using elementary analysis, NMR on 3 1P and 1H nuclei, and electroconductivity methods, the acrylonitrile, methacrylonitrile, formaldehyde, and β-propiolactone anionic polymerization in the presence of triethylphosphine is shown to follow the macrozwitterion mechanism: quartary phosphonium being on one end of a polymer chain and the growing anion on the other. The number of covalent bonds through the whole polymer chain between charges forming the active center increases with the propagation reaction. The active centers stationary concentration in the system is low when connected with both the slow initiation reaction and with the fast active centers termination reaction. Thus the ion interaction of different growing polymer chains can be ignored. The active centers parts occurring in the form of ion pairs (the ends are near and form the “cyclic”) and of free ions (the ends are separated) are determined by the monomolecular equilibrium, and its constant depends upon the macro-zwitterion polymeriza...