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Effect of Intramolecular Transfer to Polymer on Stationary Free Radical Polymerization of Alkyl Acrylates, 2
Author(s) -
Nikitin Anatoly N.,
Hutchinson Robin A.
Publication year - 2006
Publication title -
macromolecular theory and simulations
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.37
H-Index - 56
eISSN - 1521-3919
pISSN - 1022-1344
DOI - 10.1002/mats.200500063
Subject(s) - radical , intramolecular force , chemistry , kinetic chain length , chain transfer , radical polymerization , chain termination , monomer , acrylate , polymer chemistry , polymer , chain (unit) , cobalt mediated radical polymerization , alkyl , radical disproportionation , polymerization , photochemistry , organic chemistry , disproportionation , physics , astronomy , catalysis
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.