DNDZ-有机胺Cd、Zn含能配合物的合成及性能研究
发布时间：2018-08-11 08:54
【摘要】：2-(二硝基亚甲基)-1,3-二氮杂环戊烷(DNDZ)是以FOX-7为原料合成出的,它是FOX-7亲核反应的一种重要的衍生物,是一类新型的含能材料,表现出优越的高能钝感性能。本课题组以DNDZ为主配体,以有机胺类溶液为辅助配体,与金属(Cd、Zn)发生配位反应,在与甲胺溶液的反应过程中DNDZ首次开环形成N-(2-氨基乙基)-2,2-二硝基乙酰胺(ADNA)。本论文合成出五种配合物,其中两种DNDZ的配合物,三种ADNA的配合物,培养出四种配合物的单晶。同时,利用X-射线衍射仪测定了这些配合物的晶体结构。并对数据进行分析处理,进而了解这些配合物的分子结构、分子间的作用力和晶体的堆积情况。Cd(NH_3)_4(DNDZ)_2:单斜晶系；P_(21/c)空间群；[Cd(CH_3NH_2)_2(ADNA)_2]_n:三斜晶系；P_(-1)空间群；[Cd(C_2H_5NH_2)_2(ADNA)_2]_n:三斜晶系；P_(-1)空间群；Zn(NH_3)_2(DNDZ)_2:四方晶系；P_(4_12_12)空间群；在非等温条件下,测定五种配合物的DSC和TG/DTG曲线,并研究了其热分解行为,使用Kissinger法和Ozawa法计算得到了它们的热分解动力学参数。测定Cd(NH_3)_4(DNDZ)_2、[Cd(CH_3NH_2)_2(ADNA)_2]_n和Zn(NH_3)_2(DNDZ)_2的连续比热容。在比热容方程的基础上,计算出配合物在298.15 K时的摩尔热容分别为：642.0,608.6,636.6和521.3 J·mor1·K-1。并据此估算它们的绝热至爆时间,计算结果分别为：59.4,22.7,48.6,64.3 s。测定配合物Cd(NH_3)_4(DNDZ)_2, [Cd(NH_3)_2(ADNA)_2]n, [Cd(CH_3NH_2)_2(ADNA)_2]_n, [Cd(C_2H_5NH_2)_2(ADNA)_2]_n和Zn(NH_3)_2(DNDZ)_2的撞击感度来评价其热安定性,其值分别为：20,18,17,11,15 J。
[Abstract]:2- (dinitromethylene) -1n 3-diazacyclopentane (DNDZ) is synthesized from FOX-7. It is an important derivative of FOX-7 nucleophilic reaction. It is a new type of energetic materials and has excellent high energy passivity. DNDZ was the main ligand and organic amine solution was used as auxiliary ligand to coordinate with metal (CD ~ (2 +) Zn). During the reaction with methylamine solution, DNDZ formed N- (2-aminoethyl) -2o _ 2-dinitroacetamide (ADNA). For the first time in the process of reaction with methylamine solution. In this paper, five complexes were synthesized, including two complexes of DNDZ and three complexes of ADNA, and the single crystals of four complexes were grown. At the same time, the crystal structure of these complexes was determined by X-ray diffractometer. The data are analyzed and processed to understand the molecular structure of these complexes, the intermolecular force and the stacking of crystals. CD (NH_3) 4 (DNDZ) 2: monoclinic S / S P _ (21 / c) space group; [CD (CH_3NH_2) _ 2 (ADNA) _ 2] n: triclinic system P _ (-1) space group; [CD (C_2H_5NH_2) _ 2 (ADNA) _ 2] n: triclinic crystal system P-1 space group; [CD (CH_3NH_2) _ 2 (ADNA) _ 2 (ADNA) _ 2]; [CD (C_2H_5NH_2) _ 2 (ADNA) _ 2] n: triclinic crystal system P _ (-1) space group; [CD (CH_3NH_2) 2 (ADNA) 2] n: P _ (-1) space group; The DSC and TG/DTG curves of the five complexes were measured under non-isothermal conditions, and their thermal decomposition behaviors were studied. The kinetic parameters of their thermal decomposition were calculated by Kissinger and Ozawa methods. The continuous specific heat capacity of CD (NH_3), [CD (CH_3NH_2) _ 2 (ADNA) _ 2] and Zn (NH_3) _ 2 (DNDZ) _ 2 was measured. On the basis of the specific heat capacity equation, the molar heat capacities of the complexes at 298.15 K were calculated to be: 642.0608.6636.6 and 521.3 J mor1 K-1, respectively. Their adiabatic time to explosion time is estimated, and the calculated results are respectively: 59.422.7 / 48.6 / 64.3s. The thermal stability of CD (NH_3), [CD (NH_3) _ 2 (ADNA) _ 2] n, [CD (CH_3NH_2) _ 2 (ADNA) _ 2] _ n, [CD (C_2H_5NH_2) _ 2 (ADNA) _ 2] _ S _ n and Zn (NH_3) _ 2 (DNDZ) _ 2 are measured to evaluate their thermal stability.
【学位授予单位】：西北大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：TQ560.1;O641.4
本文编号：2176508
[Abstract]:2- (dinitromethylene) -1n 3-diazacyclopentane (DNDZ) is synthesized from FOX-7. It is an important derivative of FOX-7 nucleophilic reaction. It is a new type of energetic materials and has excellent high energy passivity. DNDZ was the main ligand and organic amine solution was used as auxiliary ligand to coordinate with metal (CD ~ (2 +) Zn). During the reaction with methylamine solution, DNDZ formed N- (2-aminoethyl) -2o _ 2-dinitroacetamide (ADNA). For the first time in the process of reaction with methylamine solution. In this paper, five complexes were synthesized, including two complexes of DNDZ and three complexes of ADNA, and the single crystals of four complexes were grown. At the same time, the crystal structure of these complexes was determined by X-ray diffractometer. The data are analyzed and processed to understand the molecular structure of these complexes, the intermolecular force and the stacking of crystals. CD (NH_3) 4 (DNDZ) 2: monoclinic S / S P _ (21 / c) space group; [CD (CH_3NH_2) _ 2 (ADNA) _ 2] n: triclinic system P _ (-1) space group; [CD (C_2H_5NH_2) _ 2 (ADNA) _ 2] n: triclinic crystal system P-1 space group; [CD (CH_3NH_2) _ 2 (ADNA) _ 2 (ADNA) _ 2]; [CD (C_2H_5NH_2) _ 2 (ADNA) _ 2] n: triclinic crystal system P _ (-1) space group; [CD (CH_3NH_2) 2 (ADNA) 2] n: P _ (-1) space group; The DSC and TG/DTG curves of the five complexes were measured under non-isothermal conditions, and their thermal decomposition behaviors were studied. The kinetic parameters of their thermal decomposition were calculated by Kissinger and Ozawa methods. The continuous specific heat capacity of CD (NH_3), [CD (CH_3NH_2) _ 2 (ADNA) _ 2] and Zn (NH_3) _ 2 (DNDZ) _ 2 was measured. On the basis of the specific heat capacity equation, the molar heat capacities of the complexes at 298.15 K were calculated to be: 642.0608.6636.6 and 521.3 J mor1 K-1, respectively. Their adiabatic time to explosion time is estimated, and the calculated results are respectively: 59.422.7 / 48.6 / 64.3s. The thermal stability of CD (NH_3), [CD (NH_3) _ 2 (ADNA) _ 2] n, [CD (CH_3NH_2) _ 2 (ADNA) _ 2] _ n, [CD (C_2H_5NH_2) _ 2 (ADNA) _ 2] _ S _ n and Zn (NH_3) _ 2 (DNDZ) _ 2 are measured to evaluate their thermal stability.
【学位授予单位】：西北大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：TQ560.1;O641.4
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