1，4，5，8-四硝基-1，4，5，8-四氮杂双环[4.4.0]癸烷合成工艺的改进?

为了改进1,4,5,8-四硝基-1,4,5,8-四氮杂双环[4.4.0]癸烷(TNAD)的合成方法,以1,4,5,8-四氮杂双环[4.4.0]癸烷(THAD)为原料,经成盐、硝化两步反应合成出了TNAD,反应总收率为90%,纯度为98.7%。采用红外光谱、核磁共振氢谱及元素分析对产品结构进行了表征。考察了硝化体系、物料比、反应温度、反应时间对硝化反应的影响,确定了最佳的反应条件:n(THAD.4HNO_3):n(98%HNO_3):n(AC_2O)=1:24:15,反应温度为25℃,反应时间为2 h。     

四硝基并哌嗪的催化热分解及机理研究

采用高压差示扫描量热法(PDSC)、热重分析法(TGA)和快速扫描傅里叶变换红外光谱法(FT-IR),研究了四硝基并哌嗪(TNAD)的热分解机理,并采用FT-IR技术和TG/MS(质谱)联用分析了TNAD热分解过程的凝聚相变化,确认其热分解机理与化学反应过程。研究表明,在1MPa压力下TNAD的分解过程较简单,无熔融吸热峰出现,属固相分解,主要放热峰出现在212.5～251.7℃。NTO-Pb、TNAD/φ-Pb、β-Cu和AD-Cu等铅铜盐对TNAD的催化作用明显,都能使其热分解反应提前,相比之下,β-Cu和NTO-Pb催化效果更好。炭黑、Al_2O_3、Al等添加剂对TNAD起到稀释作用,缓和了分解放热过程,可起到稳定燃烧的作用。TNAD热分解主要有2个历程,分解过程中产生的主要气体产物为HCHO、NO、HCN和-C2_H_2、-CHO等碎片离子。     

Thermal Behavior and Thermolysis Kinetics of the Explosive Trans‐1,4,5,8‐Tetranitro‐1,4,5,8‐Tetraazadecalin (TNAD)

Trans‐1,4,5,8‐Tetranitro‐1,4,5,8‐Tetraazadecalin (TNAD), a cyclic nitroamine, has been studied with regard to the kinetics and mechanism of thermal decomposition, using thermogravimetry (TG), IR spectroscopy, and pressure differential scanning calorimetry (PDSC). The IR spectra of TNAD have also been recorded, and the kinetics of thermolysis has been followed by non‐isothermal TG. The activation energy of the solid‐state process was determined by using the Flynn‐Wall‐Ozawa method. Compared with the activation energy obtained from the Ozawa method, the reaction mechanism of the exothermic process of TNAD was classified by the Coats‐Redfern method as a nucleation and nuclear growth (Avrami equation 1) chemical reaction (α=0.30–0.60) and a 2D diffusion (Valensi equation) chemical reaction (α=0.60–0.90). E_a and ln A were established to be 330.14 kJ mol⁻¹ and 29.93 (α=0.30–0.60) or 250.30 kJ mol⁻¹ and 21.62 (α=0.60–0.90).     

Compatibility study of trans-1,4,5,8-tetranitro-1,4,5,8-tetraazadecalin (TNAD) with some energetic components and inert materials

The compatibility of trans-1,4,5,8-tetranitro-1,4,5,8-tetraazadecalin (TNAD) with some energetic components and inert materials of solid propellants was studied by using the pressure DSC method where, cyclotetramethylenetetranitroamine (HMX), cyclotrimethylenetrinitramine (RDX), 1,4-dinitropiperazine (DNP), 1.25/1-NC/NG mixture, lead 3-nitro-1,2,4-triazol-5-onate (NTO–Pb), aluminum powder (Al, particle size = 13.6 μm) and N-nitrodihydroxyethylaminedinitrate (DINA) were used as energetic components and polyethylene glycol (PEG), polyoxytetramethylene-co-oxyethylene (PET), addition product of hexamethylene diisocyanate and water (N-100), 2-nitrodianiline (2-NDPA), 1,3-dimethyl-1,3-diphenyl urea (C₂), carbon black (C.B.), aluminum oxide (Al₂O₃), cupric 2,4-dihydroxy-benzoate (β-Cu), cupric adipate (AD-Cu) and lead phthalate (φ-Pb) were used as inert materials. It was concluded that the binary systems of TNAD with NTO–Pb, RDX, PET and Al powder are compatible, and systems of TNAD with DINA and HMX are slightly sensitive, and with 2-NDPA, φ-Pb, β-Cu, AD-Cu and Al₂O₃ are sensitive, and with PEG, N-100, C₂ and C.B. are incompatible. The impact and friction sensitivity data of the TNAD and TNAD in combination with the other energetic materials under present study was also obtained, and there was no consequential affiliation between sensitivity and compatibility.     

四硝基并哌嗪在二甲基亚砜中的溶解结晶过程及晶体结构研究

采用扫描电子显微镜(SEM)、核磁共振氢谱(1H-NMR)、X射线衍射(XRD)和密度泛函理论(DFT)等测试手段和方法研究一种硝胺化合物四硝基并哌嗪(TNAD)的溶解及结晶过程,表征了其晶体结构;并通过理论分析进一步研究了其晶胞参数和可能存在的分子构型。研究表明,TNAD在二甲基亚砜(DMSO)中溶解性良好,且溶解度曲线采用波尔兹曼函数拟合最合适;从过饱和的DMSO中能得到稳定的TNAD晶体,晶体属于四方晶系。扫描电镜观察晶体形状为规整的长方体。DFT分析表明TNAD可能存在5种不同构型,其中"椅-椅结合式异向构象"和"船-船结合式异向构象"最稳定。