Liquid crystalline polymers (LCPs) have been synthesized from polyethylene terephthalate (PET) and 4-acetoxybenzoic acid (OB) through melt step-growth polymerization. The presence of liquid crystalline texture is first examined using optical polarizing microscopy. The thermal durability of the developed systems is studied through thermogravimetric analysis. The kinetics of the polymerization processes is analyzed. The effectiveness of three catalysts commonly used in polyesterification is investigated. The effect of reaction temperature is also examined. The progress of polycondensation reactions over time takes a nonlinear behavior of slight sigmoidal shape, irrespective of whether or not the reaction is catalyzed. Simple second and third order equations, along with a nonlinear model, are used to determine the kinetic parameters characterizing these reactions. The rate of reaction is enhanced when the reaction temperature is increased. Overall, second-order kinetics well describes the polymerization reactions when the data set is divided into two regions. Antimony trioxide induces a more visible enhancement to the rate of reaction, compared to zinc acetate and sodium acetate. The presence of a catalyst generally increases the reaction activation energy. This indicates that entropy factors outweigh the increase in activation energy and drive the catalyzed reactions to completion. (C) 2011 Wiley Periodicals, Inc. J Appl Polym Sci 123: 1359-1369, 2012