Synthesis of three biodegradable aliphatic polyesters, namely poly(ethylene succinate), poly(propylene succinate) and poly(butylene succinate) is presented using the appropriate diols and succinic acid in the presence of tetrabutoxytitanium as catalyst. A theoretical mathematical model for the esterification reaction, based on the functional group approach, is developed and applied successfully in the simulation of all experimental data. Values for the kinetic rate constants are proposed for different catalyst molar ratios and comonomer chemical structure. It was found that the presence of the metal catalyst used leads to a poor activity of self-catalyzed acid and the main kinetic rate constant of the esterification reaction correlates well with the square root of the catalyst concentration. Different glycols do not influence much the number average degree of polymerization (NADP) values of the oligomers produced, even thought they slightly affect esterification rates in the order BG > PG > EG. In contrast, these values are affected by the amount of catalyst, with larger catalyst molar ratio giving polymer with bigger average molecular weight. These results were verified from measurements of the final polyester average molecular weight obtained at different polycondensation temperatures. Finally, from theoretical simulation results it was found that although higher initial ratios of glycol to succinic acid are useful to increase the esterification rate, they lower the NADP of the oligomers formed at a fixed conversion of acid end groups. (c) 2006 Elsevier Ltd. All rights reserved.