Kinetics of free-radical polymerizations

North, A. M., The Kinetics of Free Radical Polymerization, PeTgamon, Ne < York, 1966. 

Eastmond, G. C., The Kinetics of Free Radical Polymerization of Vinyl Monomers in Homogeneous Solutions, Chap. 1 in Comprehensive Chemical Kinetics, Vol. 14A, C. H. Bamford and C. F. H. Tipper, eds., American Elsevier, New York, 1976a. 

The kinetics of free-radical polymerization of methyl methacrylate and other monomers with small amounts of S02 and tert-butyl hydroperoxide in bulk and solution have been investigated by P. Ghosh and... 

Polymerization rate expression. The equations describing kinetics of free-radical polymerization steps contain a term for the concentration of radicals [M ], which exists at very low concentration ( 10 M) and thus... 

Woecht I, Schmidt-Naake G, Beuermann S, et al. Propagation kinetics of free-radical polymerizations in ionic liquids. J. Polym. ScL, Part A Polym. Chem. 2008. 46, 1460-1469. 

Though ionic polymerization resembles free-radical polymerization in terms of initiation, propagation, transfer, and termination reactions, the kinetics of ionic polymerizations are significantly diflFerent from free-radical polymerizations. In sharp contrast to free-radical polymerizations, the initiation reactions in ionic polymerizations have very low activation energies, chain termination by mutual destruction of growing species is nonexistent, and solvent effects are much more pronounced, as the nature of solvent determines whether the chain centers are ion pairs, free ions, or both. No such solvent role is encountered in free-radical polymerization. The overall result of these features is to make the kinetics of ionic polymerization much more complex than the kinetics of free-radical polymerization. 

North,A.M. The kinetics of free radical polymerization, p. 79. Oxford Pergamon Press 1966. 

IV. Steady-State Kinetics of Free-Radical Polymerization... 

IV. STEADY-STATE KINETICS OF FREE-RADICAL POLYMERIZATION... 

Viciosa, M.T., Dionlsio, M., and G6mez Ribelles, J.L. 2011. Kinetics of free radical polymerization probed by dielectric relaxation spectroscopy under high conductivity conditions. Polymer 52 1944-1953. 

Thus, in summary, the kinetics of free radical polymerization are characterized by the following features ... 

Quantum chemistry thus provides an invaluable tool for studying the mechanism and kinetics of free-radical polymerization, and should be seen as an important complement to experimental procedures. Already quantum chemical studies have made major contributions to our understanding of free-radical copolymerization kinetics, where they have provided direct evidence for the importance of penultimate imit effects (1,2). They have also helped in our understanding of substituent and chain-length effects on the frequency factors of propagation and transfer reactions (2-5). More recently, quantum chemical calculations have been used to provide an insight into the kinetics of the reversible addition fragmentation chain transfer (RAFT) polymerization process (6,7). For a more detailed introduction to quantum chemistry, the interested reader is referred to several excellent textbooks (8-16). 

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