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The thermal behaviour and decomposition reaction kinetics of 3,3-bis(azidomethyl)-oxetan(BAMO)and 3-azido-methyl-3-methyl oxetane(AMMO)copolymer(BAMO/AMMO)were determined by TG,DSC.The E values calculated using the Kissinger and Flynn-Wall-Ozawa equations and integral isoconversional non-linear equations were used to check the validity of activation energy.The results show that the kinetic model function in integral form and the values of Ea and A of the decomposition reaction of BAMO/AMMO copolymer are(1-α)1/2,160.75 kJ·mol-1 and 1013.61 s-1,respectively.The entropy of activation(ΔS≠),enthalpy of activation(ΔH≠),and free energy of activation(ΔG≠)of the reaction are: 13.05 J·mol-1·K-1,159.93 kJ·mol-1 and 153.31 kJ·mol-1 for 1 k 164150 J·mol-1,A=AK=101414s-1.The specific heat capacity of BAMO/AMMO was determined with the continuous Cp mode of mircocalorimeter(Micro-DSCIII).The equation of Cp to temperature was obtained.The standard molar heat capacity of BAMO/AMMO was 43265J·mol-1·K-1 at 298.15K.The self-accelerating decomposition temperature(TSADT),critical temperature of thermal explosion(Tb),adiabatic time-to-explosion(tTIad),critical temperature of hot-spot initiation(Tcr,hot-spot),safety degree(SD)and thermal explosion probability(PTE)are calculated.