Abstract
The application of specialized pulsed‐laser techniques has led to a vastly improved understanding of the kinetics of aqueous phase solution radical polymerization of water‐soluble monomers. Propagation rate coefficients vary significantly with monomer concentration, an effect unique to the aqueous environment. In addition, the formation and reaction of mid‐chain radicals affects polymerization rates, and thus polymer molar masses, in acrylamide and acrylic acid systems. This perspective provides an overview of these mechanistic peculiarities, which have been captured in kinetic models developed to represent the homopolymerizations of N‐vinyl pyrrolidone, N‐vinyl formamide, methacrylic acid, acrylic acid, and acrylamide over a wide range of conditions. The batch studies demonstrate the importance of these effects in aqueous polymerization and the validity of the rate coefficients taken from the independent kinetic studies.
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