Diffusion‐controlled vinyl polymerization. III. Free volume parameters and diffusion‐controlled propagation
- 1 May 1982
- journal article
- research article
- Published by Wiley in Journal of Polymer Science: Polymer Chemistry Edition
- Vol. 20 (5) , 1331-1344
- https://doi.org/10.1002/pol.1982.170200515
Abstract
The values of the parameters that are necessary to compute the free volume changes accompanying polymerization were determined from viscosity data of concentrated polymer solutions. Relationships applicable above and below the glass transition temperature of the polymer were quantified. A general treatment of the variation of the propagation rate constant with free volume was postulated, based on the variation of the monomeric diffusivity with free volume. This, in turn, was related to the friction coefficient of a polymer chain segment, the values of which are readily available. A discussion of the reaction behavior in the last stage of polymerization and the occurrence of limiting conversion is also presented.Keywords
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