A series of flame retardant oligomers with different chemical components in molecular chains, designated as FP-1, FP-2 and FP-3, respectively, were successfully synthesized using solution polycondensation and well characterized. The thermal properties and flammability of these oligomers were investigated by thermogravimetric analysis (TGA) and microscale combustion calorimeter (MCC). The results demonstrated that FP-3 had the lowest flammability in terms of the lowest maximum mass loss rate, and FP-1 possessed the highest thermal stability and char yield, due to its higher stable hexatomic ring structure of piperazine compared with the linear alkane chain structure of neopentyl glycol. The gases evolved during decomposition were analyzed using Fourier transform infrared coupled with the thermogravimetric analyzer (TG-IR) technique. The char residues of the flame retardant oligomers were investigated by scanning electron microscopy (SEM) and Raman spectroscopy. The results demonstrated that FP-3 exhibited a synergistic interaction between the gas phase and condensation phase, increasing its flame retardancy. (c) 2013 Elsevier B.V. All rights reserved.