氘化对 TATP 结构和热行为的影响

To investigate the effect of deuteration on the vibrational properties of chemical bonds of triacetone triperoxide（TATP）and its thermal decomposition behavior，TATP and deuterated triacetone triperoxide（TATP-d₁₈）were prepared by using acetone and acetone-d₆ as raw materials，respectively，with hydrogen peroxide acting as the oxidant source and sulfuric acid as the catalyst. TATP and TATP-d₁₈ were characterized by nuclear magnetic resonance spectroscopy（NMR），Fourier transform infrared spectroscopy（FTIR）and differential scanning calorimetry（DSC）. The non-isothermal reaction kinetic parameters of TATP and TATP-d₁₈ were calculated with Kissinger，Ozawa，and Friedman methods. The results show that the deuteration of TATP results in an evident red-shift phenomenon，and the ratio of the stretching frequencies of C—H（D）bonds（ν_C—H/ν_C—D）is about 1.36. The apparent activation energy of TATP-d₁₈（E_K=80.54 kJ·mol^-1，E_O=83.56 kJ·mol^-1，E_F=72.27 kJ mol^-1）is higher than that of TATP（E_K=67.91 kJ·mol^-1，E_O=71.01 kJ·mol^-1，E_F=63.79 kJ·mol^-1），indicating that TATP-d₁₈ has higher thermal stability. The calculated thermal explosion critical temperatures for TATP（T_b=402.37 K）and TATP-d₁₈（T_b=423.46 K）also confirm that deuteration improves the thermal stability of TATP-d₁₈. Finally，the calculated thermodynamic parameters for the non-isothermal decomposition processes of TATP and TATP-d₁₈ indicate that TATP and TATP-d₁₈ would not spontaneously undergo thermal explosions.