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Irregular structures in poly(vinyl chloride). I. Saturated structures

L. Valko, I. Tvaroška, and V. Kellö

Institute of Physical Chemistry, Slovak Technical University, Bratislava

 

Abstract: In the present communication, consideration of the mechanism of dehydrochlorination of PVC is mainly described on the basis of information summarized from model-compounds studies. The semiempirical method proposed by Vedeneyev was used to study the C —CI, C—H, and С —С bonds in poly(vinyl chloride). Activation energies for elimination of hydrogen chloride were calculated on the principle of the additivity of bond energies of the four-centre activated complex, for various saturated abnormal structures in the polymer molecule, such as branching, and head- -to-head or tail-to-tail addition. Branched structures having a tertiary chlorine appear to have a significant effect upon initiation of thermal dehydrochlorination. The results of activation energies calculated empirically for particular saturated structures show that the tendency of С — CI cleavage depends on the electronegativity of carbon bonded chlorine.

Full paper in Portable Document Format: 261a3.pdf

 

Chemical Papers 26 (1) 3–17 (1972)

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