关键词: 过氧乙酸叔丁酯(TBPA), 热解特性, 动力学参数, 相容性, 热解路径, 最大反应速率达到时间(TMR_ad)

Abstract: In order to analyze the thermal hazard of TBPA, experiments were carried out by using a differential scanning calorimetry (DSC), a Phi-TEC II adiabatic calorimeter and a gas chromatography/mass spectrometry (GC/MS) to study thermal decomposition characteristics of TBPA and the compatibility of TBPA with H₂SO₄/NaOH. Thermal decomposition products of TBPA were analyzed. A probable thermal decomposition scheme was inferred for TBPA. Kinetic parameters, such as the corresponding apparent activation energy, the pre-exponential factor and reaction order were calculated by using the Starink method and the rate constant method, which can be used to calculate θ_d24 (the onset temperature when the TMRad is 24.0 h). The results indicate that under the adiabatic condition, the initial decomposition temperature is 83.0 ℃, adiabatic temperature rise is 214.5 ℃, and θ_d24 is 63.46 ℃, that thermal behavior of TBPA mixed with H₂SO₄ is dangerous considering the lower initial decomposition temperature, and the higher heat release rate of decomposition, that the sodium hydroxide solution has a little effect on TBPA decomposition, and that the process temperature must be strictly controlled during production, storage, and transportation, that NaOH is preferable to H₂SO₄ as the reactant in TBPA synthesis, and that the effect of acidic substances on TBPA decomposition especially need to be noticed.

Key words: tert-butyl peracetate(TBPA), thermal decomposition characteristics, kinetic parameters, compatibility, thermal decomposition scheme, time to maximum rate under adiabatic conditions(TMR_ad)