C. Bamford, E. Schofield, J. M. Eilers
Mar 1, 1989
Citations
0
Influential Citations
15
Citations
Journal
Polymer
Abstract
The structure of acenaphthylene suggests that degradative addition to monomer may occur during free-radical polymerization. We present an analysis, based on the kinetic treatment in an earlier paper, of the kinetic data of Romani and Weale1 on the polymerization of acenaphthylene in toluene at 1 atm pressure. Two cases are considered: (i) where the termination coefficient is constant, and (ii) where kt is size-dependent. The latter case is appropriate because small radicals are involved; analysis is facilitated by introduction of the concept of a ‘group-termination-coefficient’. Both treatments lead to results in good agreement with the experimental data, which are, therefore, consistent with the occurrence of degradative addition in this polymerization. The estimated kinetic parameters have different values in (i) and (ii), notably in that reinitiation is important in the latter, but insignificant in the former. Possible techniques for more detailed examination of re-initiation are outlined. Molecular weight distributions for the polymerization with degradative addition to monomer with constant kt have been calculated.