The ring-opening polymerization of F.-caprolactone initiated by Ti[O(CH2)(4)OCH=CH2](4) was investigated by differential scanning calorimetry (DSC). Both isothermal and dynamic experiments have been applied to obtain the kinetic parameters. The apparent polymerization rate constant for different experiments was determined; the activation energy determined is 76-88 KJ/mol by the isothermal method and 75-86 KJ/mol by the dynamic method. Using the obtained kinetic parameters, a model to predict the polymerization process was developed and can well describe the polymerization process, which demonstrates that DSC is a convenient and reliable method to study the kinetics of ring-opening polymerization. The kinetic results also demonstrate that Ti[O(CH2)(4)OCH=CH2](4) is an efficient initiator in the ring-opening polymerization of E-caprolactone. (C) 2008 Wiley Periodicals, Inc. J Appl Polym Sci 110: 3990-3998, 2008