The equilibrium polymerization of sodium poly-α-methylstyryl in tetrahydrofuran was studied in the temperature range from -60 to 15°C. For the first time, the reversible process of formation/cleavage of the chemical bond was theoretically analyzed in terms of the electronic excitation views. On this basis a new mechanism of the “living” polymer depolymerization was proposed. The geometry, electronic structure of the model fragments of “living” polymers comprised of two units were calculated ab initioby the 6-31G* method. The energies of the triplet excited states belonging to the complex of the reactants, on the one hand, and to the reaction product, on the other, proved to be close. The theoretical activation energies for depolymerization of sodium poly-α-methylstyryl reasonably agree with the experiment.
Russian Journal of Applied Chemistry – Springer Journals
Published: Oct 13, 2004
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