Using three different catalysts, water-initiated polymerizations of e-caprolactone were conducted in bulk with variation of the monomer/water ratio. The resulting CH2OH and CO2H- terminated polylactones were subjected in situ to azeotropic polycondensations. With Bi-triflate and temperatures, the polycondensations were not much successful and involved side reactions. With ZnCl2, and especially SnCl2, considerably higher molar masses were achieved. The substitution of toluene for chlorobenzene for refluxing gave better results. The polycondensations broadened the molar mass distribution of the ROP-based prepolymers, and polydispersities between 1.41.8 were obtained. The MALDITOF mass spectra revealed that the polycondensations significantly enhanced the fraction of rings due to efficient end-biting reactions. By comparison with copolymerization experiments and Sn methoxide-initiated polymerizations, it was demonstrated that equilibration reactions, such as the formation of rings by back-biting, did not occur. (c) 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012