Abstract
Experimental data and models are presented for initiator efficiency in emulsion polymerization systems in the absence of particle formation. The data show that a number of models are inapplicable, viz., those assuming that the rate-determining step for free radical entry into a particle is either diffusional capture, surfactant displacement, or colloidal entry. The data however support the model (first suggested by Priest) of aqueous phase propagation to a critical degree of polymerization, whereupon capture of the resulting oligomeric free radical by a particle is instantaneous. Mutual aqueous phase termination of smaller species also occurs; one must take account of the fact that the rate coefficient for this is some two orders of magnitude greater than that for low molecular weight species in polymeric systems. This model is in quantitative and qualitative accord with the experimental dependences of the entry rate coefficient on the concentrations of initiator, of surfactant, of aqueous phase monomer, and of latex particles, as well as on particle size, on ionic strength and on temperature.
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© 1990 Elsevier Science Publishers Ltd
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Maxwell, I.A., Morrison, B.R., Gilbert, R.G., Napper, D.H. (1990). Radical Capture Efficiencies in Emulsion Polymerization Kinetics. In: Lemstra, P.J., Kleintjens, L.A. (eds) Integration of Fundamental Polymer Science and Technology—4. Springer, Dordrecht. https://doi.org/10.1007/978-94-009-0767-6_15
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DOI: https://doi.org/10.1007/978-94-009-0767-6_15
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