氘化对TATP结构和热行为的影响  

Effect of Deuteration on the Structure and Thermal Behavior of TATP

作　　者：方祝青 李树奎 刘吉平[1,2] 郁闯 郑东森[1] 乔美壮 FANG Zhu-qing;LI Shu-kui;LIU Ji-ping;YU Chuang;ZHENG Dong-sen;QIAO Mei-zhuang(School of Mechatronical Engineering,Beijing Institute of Technology,Beijing 100081,China;School of Materials Science and Engineering,Beijing Institute of Technology,Beijing 100081,China)

机构地区：[1]北京理工大学机电学院,北京100081 [2]北京理工大学材料学院,北京100081

出　　处：《含能材料》2022年第7期687-693,共7页Chinese Journal of Energetic Materials

摘　　要：为了研究氘化对三过氧化三丙酮(TATP)化学键振动性质以及热分解行为的影响,分别以丙酮和丙酮-d_(6)为原料,过氧化氢为氧化剂,硫酸为催化剂,制备了TATP和氘代三过氧化三丙酮(TATP-d_(18))。采用核磁共振波谱、傅里叶变换红外光谱和差示扫描量热法对TATP和TATP-d_(18)进行表征,使用Kissinger法、Ozawa法和Friedman法计算得到了TATP和TATP-d_(18)的非等温反应动力学参数。结果表明,TATP-d_(18)分子中各化学键的振动频率相比于TATP表现出不同程度的红移现象,C—H(D)键伸缩振动频率之比(ν_(C—H)/ν_(C—D))约为1.36;由Kissinger法、Ozawa法和Friedman法所得TATP-d_(18)的表观活化能(E_(K)=80.54 k J·mol^(-1),E_(O)=83.56 k J·mol^(-1),E_(F)=72.27 k J·mol^(-1))均高于这3种方法计算得到的TATP的表观活化能(E_(K)=67.91 k J·mol^(-1),E_(O)=71.01 k J·mol^(-1),E_(F)=63.79 k J·mol^(-1)),这表明TATP-d_(18)具有更高的热稳定性;计算所得的TATP与TATP-d_(18)的热爆炸临界温度分别为402.37 K和423.46 K,这也证实了TATP-d_(18)具有更高的热稳定性;计算得到了TATP和TATP-d_(18)的非等温分解过程热力学参数,证明了TATP和TATP-d_(18)不会自发发生热爆炸。To investigate the E_(F)fect of deuteration on the vibrational properties of chemical bonds of triacetone triperoxide(TATP)and its thermal decomposition behavior,TATP and deuterated triacetone triperoxide(TATP-d_(18))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-d_(18)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-d_(18)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-d_(18)(E_(K)=80.54 k J·mol^(-1),E_(O)=83.56 k J·mol^(-1),E_(F)=72.27 k J mol^(-1))is higher than that of TATP(E_(K)=67.91 k J·mol^(-1),E_(O)=71.01 k J·mol^(-1),E_(F)=63.79 k J·mol^(-1)),indicating that TATP-d_(18)has higher thermal stability.The calculated thermal explosion critical temperatures for TATP(Tb=402.37 K)and TATP-d_(18)(Tb=423.46 K)also confirm that deuteration improves the thermal stability of TATP-d_(18).Finally,the calculated thermodynamic parameters for the non-isothermal decomposition processes of TATP and TATP-d_(18)indicate that TATP and TATP-d_(18)would not spontanE_(O)usly undergo thermal explosions.

关 键 词：TATP-d18 氘化 热分解 热稳定性 热力学参数 

分 类 号：TJ55[兵器科学与技术—军事化学与烟火技术] O64[理学—物理化学]