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Determination of the Mode of Radical Termination from Pulsed Laser Polymerization Experiments in the Presence of Retardation and Chain Transfer to Agent
Author(s) -
Nikitin Anatoly N.,
Hutchinson Robin A.,
Hesse Pascal
Publication year - 2013
Publication title -
macromolecular chemistry and physics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.57
H-Index - 112
eISSN - 1521-3935
pISSN - 1022-1352
DOI - 10.1002/macp.201300411
Subject(s) - chain transfer , polymerization , radical polymerization , polymer chemistry , laser , chemistry , chain termination , transfer agent , photochemistry , materials science , polymer , organic chemistry , optics , physics
The pulsed laser polymerization–high termination rate limit–size‐exclusion chromatography (PLP–HTRL–SEC) technique is used to estimate the mode of termination ( δ ) for n ‐butyl methacrylate ( n ‐BMA) polymerization at 30 °C. It is found that molecular mass distributions measured in these experiments are influenced by an unknown side reaction such as retardation or chain transfer that results in a marked decrease of intensity of the PLP peak. A new approach is developed to evaluate δ , with numerical experiments used to demonstrate the robustness of the methodology in the presence of retardation or chain transfer to agent. Application to the experimental n‐ BMA polymerization at 30 °C leads to an estimate for δ of 0.60 ± 0.03.