A kinetic study of the synthesis of poly(4-oxybenzoate) by melt-step growth
polymerization using para-propionoxybenzoic acid is reported. The polycond
ensations obey second-order kinetics, irrespective of whether the reaction
was catalyzed or uncatalyzed. Breaks are observed in the kinetic plots, sug
gesting the presence of different kinetic regimes during the course of the
reaction. An elaborate kinetic model that presupposes precipitation of olig
omers predicts two-stage kinetics as well as breaks in the rate plots and f
its experimental data well throughout the course of the reaction and the pe
rformance of two transesterification catalysts are estimated. No isokinetic
temperature is displayed for the transesterification reaction. Activation
energy values for catalyzed reactions are found to be higher than the uncat
alyzed reaction, indicating that entropy factors drive the reaction to comp
letion. (C) 1999 John Wiley & Sons, Inc.