Premium
The Effect of Intramolecular Transfer to Polymer on Stationary Free‐Radical Polymerization of Alkyl Acrylates, 3 – Consideration of Solution Polymerization up to High Conversions
Author(s) -
Nikitin Anatoly N.,
Hutchinson Robin A.,
Kalfas George A.,
Richards John R.,
Bruni Christopher
Publication year - 2009
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.200900009
Subject(s) - branching (polymer chemistry) , polymerization , chain transfer , polymer chemistry , chemistry , radical polymerization , arrhenius equation , kinetics , reaction rate constant , intramolecular force , acrylate , polymer , kinetic chain length , organic chemistry , copolymer , activation energy , physics , quantum mechanics
The kinetics of butyl acrylate solution polymerization up to high conversion are studied both experimentally and theoretically. New expressions taking into account both inter‐ and intra‐molecular transfer to polymer are derived for polymerization rate, average chain‐length and branching level. These expressions are used for comparative analysis of these two chain transfer events and for evaluation of the backbiting rate coefficient, k bb , and the constant of chain transfer to solvent (xylene), C trS . Using batch experiments performed at 50, 60 and 70 °C, the Arrhenius parameters for k bb and C trS are estimated to be, respectively, A ( k bb ) = (7.4 ± 1.5) × 10 7 s −1 , E a ( k bb ) = (32.7 ± 0.5) kJ · mol −1 and A ( C trS ) = 10.5 ± 3.5, E a ( C trS ) = (26.9 ± 1.9) kJ · mol −1 .