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The kinetics of acrylamide (AAm) free radical polymerization at low conversion of monomer to polymer in the aqueous phase was investigated at 50 degrees C using gamma-radiolysis relaxation, which is sensitive to radical-loss processes. The values of the termination rate coefficients for AAm ranged from 8 X 10(6) to 3 X 10(7) M-1 s(-1) as the weight fraction of polymer ranged from 0.002 to 0.0035, which is significantly lower than the low-conversion values for monomers such as styrene (2 X 10(8) M-1 s(-1)) and methyl methacrylate (4 X 10(7) M-1 s(-1)) in organic media. These can be quantitatively explained by applying a chain-length-dependent model of free-radical polymerization kinetics [Russell GT, Gilbert RG, Napper DH. Macromolecules 1992;25:2459. [19]] in which termination kinetics are expressed in terms of a diffusion-controlled encounter of radicals which ultimately yields an expression for the chain-length-averaged termination rate coefficient, .The lower for AAm arises due to a combination of the high k(p) value, promoting rapid formation of slower terminating long chains, and the slow diffusion of short propagating chains, relative to other common monomers. The chain transfer to monomer constant for AAm in water at 50 degrees C, Cm, was estimated using the chain-length-distribution method with correction for band-broadening [Castro JV, van Berkel KY, Russell GT, Gilbert RG. Aust J Chem 2005;58:178. [21]] and found to be 1.2 X 10(-4) (+/- 10%). The diffusion characteristics for AAm were adapted from those obtained for a similar aqueous system (hydroxyethyl methacrylate) together with a 0.5 exponent for the power law dependence on penetrant degree of polymerization at zero weight fraction polymer. This provides an adequate fit to the data. This is the first application of the chain-length-dependent model to describe experimental termination rate coefficients for an aqueous system at low conversion to polymer. The result that the experimental termination rate coefficients can be reproduced with an a priori model with physically reasonable parameters supports the physical assumptions underlying that model. (c) 2005 Elsevier Ltd. All rights reserved. |
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