Effect of Deuteration on the Structure and Thermal Behavior of TATP

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（νC—H/νC—D）is about 1.36. The apparent activation energy of TATP-d18（EK=80.54 kJ·mol-1，EO=83.56 kJ·mol-1，EF=72.27 kJ mol-1）is higher than that of TATP（EK=67.91 kJ·mol-1，EO=71.01 kJ·mol-1，EF=63.79 kJ·mol-1），indicating that TATP-d18 has higher thermal stability. The calculated thermal explosion critical temperatures for TATP（Tb=402.37 K）and TATP-d18（Tb=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. © 2022 Institute of Chemical Materials, China Academy of Engineering Physics. All rights reserved.