Macromolecular Rapid Communications, Vol.19, No.10, 533-538, 1998
Chain-length dependent termination in pulsed-laser polymerization, 6 -The evaluation of the rate coefficient of bimolecular termination k(t) for the reference system methyl methacrylate in bulk at 25 degrees C
The values for the rate coefficient of chain termination k(t) in the bulk polymerization of methyl methacrylate at 25 degrees C were formally calculated (i) from the second moment of the chain-length distribution and (ii) from the rate equation for laser-initiated pseudostationary polymerization (both expressions were originally derived for chain-length independent termination) by inserting the appropriate experimental data including the rate constant of chain propagation k(p). These values were treated as average values, <(k(t)(m))over bar> and <(k(t)*)over bar>, respectively. They exhibited good mutual agreement, even the predicted gradation (<(k(t)(m))over bar> < <(k(t)*)over bar> by about 20%) was recovered. The log-log plot of <(k(t))over bar> vs. the average degree of polymerization of the chains at the moment of their termination nu' yielded exponents b of 0.16-0.17 in the power-law <(k(t))over bar> = A . nu'(-b), A ranging from 1.1 x 10(8) to 1.3 x 10(8) (L.mol(-1) s(-1)). A 70% contribution of disproportionation to overall termination has been assumed in the calculations.