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Effect of Intramolecular Transfer to Polymer on Stationary Free Radical Polymerization of Alkyl Acrylates, 2 : Improved Consideration of Termination

✍ Scribed by Anatoly N. Nikitin; Robin A. Hutchinson

Publisher
John Wiley and Sons
Year
2006
Tongue
English
Weight
180 KB
Volume
15
Category
Article
ISSN
1022-1344

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✦ Synopsis

Abstract

Summary: Procedures are developed to estimate kinetic rate coefficients from available rate data for the free radical solution polymerization of butyl acrylate at 50 °C. The analysis is based upon a complete mechanistic set that includes the formation of mid‐chain radicals through backbiting and their subsequent reaction, and contains no assumptions on how the rate coefficient for cross‐termination of mid‐chain and end‐chain radicals is related to the two homo‐termination rate coefficients. After a thorough statistical analysis, the results of the fitting are combined with other recent literature data to provide a complete set of individual rate coefficients for the butyl acrylate system. Monomer addition to a mid‐chain radical is estimated to be slower than addition to a chain‐end radical by a factor of more than 400. The termination of two mid‐chain radicals is estimated to be two orders of magnitude slower than termination of two end‐chain radicals, with the cross‐termination rate coefficient close to the geometric mean.

Formation of a mid‐chain radical by intramolecular chain transfer to polymer by a chain‐end radical.

imageFormation of a mid‐chain radical by intramolecular chain transfer to polymer by a chain‐end radical.

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