Polymerization/Depolymerization Mechanism for “Living” Sodium Poly-α-Methylstyryl and Sodium Polystyryl

Polymerization/Depolymerization Mechanism for “Living” Sodium Poly-α-Methylstyryl and Sodium... 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. http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Russian Journal of Applied Chemistry Springer Journals

Polymerization/Depolymerization Mechanism for “Living” Sodium Poly-α-Methylstyryl and Sodium Polystyryl

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Publisher
Kluwer Academic Publishers-Plenum Publishers
Copyright
Copyright © 2001 by MAIK “Nauka/Interperiodica”
Subject
Chemistry; Chemistry/Food Science, general
ISSN
1070-4272
eISSN
1608-3296
D.O.I.
10.1023/A:1014861231809
Publisher site
See Article on Publisher Site

Abstract

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.

Journal

Russian Journal of Applied ChemistrySpringer Journals

Published: Oct 13, 2004

References

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