Beuermann, S.; Buback, M.; Hesse, P.; Hutchinson, R. A.; Kukuckova, S.; Lacik, I.
Termination Kinetics of the Free-Radical Polymerization of Nonionized Methacrylic Acid in Aqueous Solution
Macromolecules 2008, 41, 3513-3520.
 

The termination kinetics of free-radical polymerization of nonionized methacrylic acid (MAA) in aqueous solution has been investigated at two MAA concentrations, 30 and 60 wt %, by single-pulse pulsed-laser initiated polymerization carried out in conjunction with µs time-resolved in-line monitoring of monomer conversion via near-infrared spectroscopy (SP−PLP−NIR). From measured values of kt/kp for 2000 bar, with the conversion-dependent propagation rate coefficient, kp, being inferred from literature data, the chain-length-averaged termination rate coefficient, kt, is deduced as a function of monomer conversion, x. As with methyl methacrylate polymerization, the kt vs x dependence may be modeled under the assumption that, toward higher degrees of monomer conversion, kt is successively controlled by segmental diffusion, translational diffusion, and reaction diffusion. For 50 °C, 2000 bar, and initial monomer concentrations in water of 30 and 60 wt %, chemically initiated polymerizations have also been carried out. The resulting kt values are in good agreement with the data from SP−PLP−NIR.