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A new kinetic model for bulk polymerization of vinyl chloride based on two-phase hypothesis

✍ Scribed by A.K. Suresh; M. Chanda


Publisher
Elsevier Science
Year
1982
Tongue
English
Weight
758 KB
Volume
18
Category
Article
ISSN
0014-3057

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✦ Synopsis


A kinetic model has been developed for the bulk polymerization of vinyl chloride using Talamini's hypothesis of two-phase polymerization and a new concept of kinetic solubility which assumes that rapidly growing polymer chains have considerably greater solubility than the thermodynamic solubility of preformed polymer molecules of the same size and so can remain in solution even under thermodynamically unfavourable conditions. It is further assumed that this kinetic solubility is a function of chain length. The model yields a rate expression consistent with the experimental data for vinyl chloride bulk polymerization and moreover is able to explain several characteristic kinetic features of this system. Application of the model rate expression to the available rate data has yielded 2.36 × 10Slmol -1 sec-1 for the termination rate constant in the polymer-rich phase; as expected, this value is smaller than that reported for homogenous polymerization by a factor of 10-30.