Investigation of Methacrylate Free-Radical Depropagation Kinetics by Pulsed-Laser Polymerization

An extensive study of free-radical depropagation kinetics has been performed for several methacrylates at high temperatures in bulk and solution using a pulsed-laser technique. As expected from theory, the relative importance of depropagation on rate increases with increasing temperature and with de...

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Bibliographic Details
Published in:Industrial & engineering chemistry research 1998-09, Vol.37 (9), p.3567-3574
Main Authors: Hutchinson, Robin A, Paquet, Donald A, Beuermann, Sabine, McMinn, John H
Format: Article
Language:English
Subjects:
Applied sciences
Exact sciences and technology
Physicochemistry of polymers
Polymerization
Polymers and radiations
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Summary:An extensive study of free-radical depropagation kinetics has been performed for several methacrylates at high temperatures in bulk and solution using a pulsed-laser technique. As expected from theory, the relative importance of depropagation on rate increases with increasing temperature and with decreasing monomer concentration. The temperature dependence of n-dodecyl methacrylate depropagation has been quantified. The resulting estimates for enthalpy (−50 to −60 kJ/mol) and entropy (−105 to −127 J/(mol·K)) of polymerization, although highly correlated, are in good agreement with available literature data. Moreover, the best-fit values (−53.8 kJ/mol and −113 J/(mol·K)) provide a good representation of high-temperature propagation/depropagation kinetics measured for n-butyl, cyclohexyl, isobornyl, and 2-hydroxypropyl methacrylates, suggesting that a single set of universal values may be employed when modeling high-temperature polymerizations of all methacrylates.
ISSN:0888-5885
1520-5045
DOI:10.1021/ie980167p