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Issue 20, 2001
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Joint experimental and theoretical study of the poly(styryl sodium) and poly(α-methylstyryl sodium) polymerization/depolymerization

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Abstract

Ab initio 6-31G* optimization of a fragment of poly(styryl sodium) and poly(α-methylstyryl sodium) composed of two monomer units in cis-configuration gives rise to low energies of the triplet state. The novel mechanism of living polymer depolymerization is proposed, involving thermal excitation into the low-lying triplet state of charge transfer character followed by bond breaking. In the elementary stage of depolymerization the electronic excitation of the reaction structure in the cis-configuration is accompanied by a minor (∽0.5 Å) displacement of the Na+ cation between the terminal and the penultimate monomer units. The direct reaction of adding the styrene molecule to the terminal unit of a living polymer was also considered. The reversible reaction of polymerization/depolymerization of poly(α-methylstyryl sodium) in THF was studied experimentally. A semi-empirical AM1 method was used to estimate the geometry and the charge distribution.

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Publication details

The article was received on 19 Jun 2001, accepted on 13 Aug 2001 and first published on 20 Sep 2001


Article type: Paper
DOI: 10.1039/B105389M
Citation: Phys. Chem. Chem. Phys., 2001,3, 4542-4546

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    Joint experimental and theoretical study of the poly(styryl sodium) and poly(α-methylstyryl sodium) polymerization/depolymerization

    K. K. Kalninsh, Phys. Chem. Chem. Phys., 2001, 3, 4542
    DOI: 10.1039/B105389M

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