亚甲氨基硝基胍(MANG)的合成、晶体结构及热行为

杨航; 冯治存; 关晓鸽; 徐抗震; 宋纪蓉; 赵凤起; YANG Hang; FENG Zhi-cun; GUAN Xiao-ge; XU Kang-zhen; SONG Ji-rong; ZHAO Feng-qi

引 en

亚甲氨基硝基胍（MANG）的合成、晶体结构及热行为 PDF

杨航¹

机构：西北大学化工学院，陕西西安 710069

邮箱：136754374@qq.com

作者简介：杨航(1994-), 女, 硕士研究生, 从事含能材料研究。e‑mail:136754374@qq.com
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冯治存¹

机构：西北大学化工学院，陕西西安 710069

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关晓鸽¹

机构：西北大学化工学院，陕西西安 710069

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徐抗震^{1xukz@nwu.edu.cn}

机构：西北大学化工学院，陕西西安 710069

角色：通讯作者

邮箱：xukz@nwu.edu.cn

作者简介：徐抗震(1976-), 男, 教授, 从事新型含能材料的研究。e‑mail:xukz@nwu.edu.cn
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宋纪蓉¹

机构：西北大学化工学院，陕西西安 710069

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赵凤起²

机构：西安近代化学研究所，陕西西安 710065

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1. 西北大学化工学院，陕西西安 710069； 2. 西安近代化学研究所，陕西西安 710065

中图分类号: TJ55； O62

DOI:10.11943/CJEM2018184

Synthesis, Crystal Structure and Thermal Behavior of Methyleneaminonitroguanidine (MANG) PDF

YANG Hang¹

Affiliation：School of Chemical Engineering, Northwest University, Xi′an 710069, China

Email：136754374@qq.com
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FENG Zhi‑cun¹

Affiliation：School of Chemical Engineering, Northwest University, Xi′an 710069, China

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GUAN Xiao‑ge¹

Affiliation：School of Chemical Engineering, Northwest University, Xi′an 710069, China

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XU Kang‑zhen^{1xukz@nwu.edu.cn}

Affiliation：School of Chemical Engineering, Northwest University, Xi′an 710069, China

Role：Corresponding author

Email：xukz@nwu.edu.cn
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SONG Ji‑rong¹

Affiliation：School of Chemical Engineering, Northwest University, Xi′an 710069, China

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ZHAO Feng‑qi²

Affiliation：Xi′an Modern Chemistry Research Institute, Xi′an 710065, China

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1. School of Chemical Engineering, Northwest University, Xi′an 710069, China； 2. Xi′an Modern Chemistry Research Institute, Xi′an 710065, China

CLC: TJ55； O62

DOI:10.11943/CJEM2018184

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摘要

以氨基硝基胍（ANQ）和甲醛为原料，合成了新的化合物亚甲氨基硝基胍（MANG），并对其反应过程进行了分析。采用X‑射线单晶衍射仪分析了MANG的晶体结构，结果表明，其晶体属于正交晶系，空间群为P_nn2，每个晶胞中包含4个MANG分子，晶体密度为1.63 g·cm^-3。通过差示扫描量热法（DSC）和热重分析技术（TG‑DTG）研究了MANG的热行为，其只呈现一个非常剧烈的放热分解过程。在5 ℃·min^-1的升温速率下，MANG的分解峰温和放热量分别为170.9 ℃和1440 J·g^-1。计算得到MANG的标准摩尔燃烧热和生成焓分别为-1526.09 kJ·mol^-1和33.81 kJ·mol^-1。用Kamlet‑Jacobs方程预估MANG的爆速（7.1 km·s^-1）和爆压（20.9 GPa）均小于ANQ，但高于三硝基甲苯（TNT）。MANG的撞击感度（>7.9 J）低于ANQ（3 J）和黑索今（RDX）（7.4 J）。

Abstract

A new compound methyleneaminonitroguanidine (MANG) was synthesized using aminoguanidine （ANQ）and formaldehyde as raw materials, and the reaction process was analyzed. The crystal structure of MANG was analyzed by an X‑ray single diffractometer. Results show that the crystal belongs to an orthorhombic crystal system. Its space group is P_nn2. Each unit cell contains four MANG molecules, and the crystal density is 1.63 g·cm^-3. Thermal behaviors of MANG were studied by differential scanning calorimetry(DSC) and thermogravimetry‑derivative thermogravimetry (TG‑DTG). MANG presents only one intense exothermic decomposition process. At a heating rate of 5 ℃·min^-1, the decomposition peak temperature and exothermic quantity of MANG are 170.9 ℃ and 1440 J·g^-1, respectively. The standard molar enthalpy of combustion and the standard molar enthalpy of formation of MANG obtained by calculation are -1526.09 kJ·mol^-1 and 33.81 kJ·mol^-1, respectively. The detonation velocity 7.1 km·s^-1 and detonation pressure 20.9 GPa of MANG predicted by Kamlet‑Jacobs(K‑J) equation are less than those of ANQ, but higher than those of TNT. The impact sensitivity(>7.9 J) of MANG is lower than that of ANQ(3 J) and RDX(7.4 J).

关键词

氨基硝基胍（ANQ）; 亚甲氨基硝基胍（MANG）; 合成; 晶体结构

Keywords

energetic materials; amino‑nitroguanidine（ANQ）; methyleneaminonitroguanidine (MANG); synthesis; crystal structure

1 引言

近年来，为满足新型含能材料发展的需要，一系列富氮高能含能材料被合成，其中胍类物质由于其独特的结构引起了研究者的广泛兴趣^[1,2,3,4,5]。胍类物质含氮丰富，其氮含量高达71%^[6]，并且分解产物是氮气，绿色环保。硝基胍结构简单易制备，由于其良好的爆炸性能，应用于推进剂、发射药、低损性炸药等^[7]。其衍生物也在医学、农业、炸药等方面得到广泛应用^[8,9]。氨基硝基胍（ANQ）是硝基胍的一种重要的含能衍生物，通过硝基胍与水合肼反应获得^[10]，其爆轰性能与RDX相当，具有广阔的应用^[11,12]。

ANQ在一个碳原子上分别连接一个硝酰基、一个氨基和一个肼基，具有很高的反应性，因此，大量的ANQ衍生物被合成报道。金兴辉等^[13]以ANQ和4‑硝胺基‑1，2，4‑三唑为原料合成了一种钝感的1‑氨基‑2‑硝基胍4‑硝胺基‑1，2，4‑三唑盐。Eugene L等^[14]在KNO₂/AcOH中合成了5‑硝氨基四唑，该四唑由于分子环张力以及具有含能N—N，C—N，N—N键，故其能量更高，稳定性更好。5‑硝氨基四唑可以进一步反应生成一系列盐和金属含能配合物，其中一些化合物具有良好的爆轰性能^{[14,15,16,17]}。O'Connor等^[18]在HCl/NaNO₂的体系中合成了叠氮硝基胍。本课题组^[19]前期将ANQ分别与二硝基氯苯、三硝基氯苯和3,5‑二硝基水杨酸反应，合成了三种新的ANQ的含能衍生物，并且发现ANQ与三硝基氯苯反应得到的含能化合物性能最好。与上述ANQ的衍生物相比，本文研究的MANG合成方法简单（一步反应）、反应时间短、产率高、放热剧烈，具有潜在的应用价值。

本研究以ANQ为原料，意外地合成了新化合物亚甲氨基硝基胍（MANG），得到了MANG的单晶，并用X‑射线仪对其晶体结构进行了测定。采用差示扫描量热分析技术(DSC)和热重分析技术(TG‑DTG)研究其热分解性能，计算得到其非等温动力学参数和热爆炸临界温度等热力学参数。利用氧弹量热技术测定其燃烧热，并计算得到其标准生成焓。测试了其撞击感度，为MANG的研究应用提供参考。

表1 MANG的晶体参数与精修数据

Table 1 Crystallographic data and structure refinement details for MANG

compound	MANG
formula	C₂H₅N₅O₂
formula mass	131.11
temperature /K	298(2)
crystal system	orthorhombic
space group	P_nn2
a /Å	9.070(4)
b /Å	16.591(6)
c /Å	3.5508(13)
V /Å³	534.3(4)
Z	4
D_c / g·cm^-3	1.63
absorption coefficient / mm^-1	0.142
θ / (°)	2.46‑20.99
F(000)	272
h, k and l	-9<h<9,-16<k<13, -3<l<3
reflections collected	1696
independent reflections (R_int)	561 (0.0447)
data/restraints/parameters	561 / 4 / 102
goodness‑of‑fit on F²	1.019
final R₁, wR₂ [I>2σ(I)]	0.0517, 0.0866
R₁,wR₂ (all data)	0.1047, 0.1057
largest difference peak and hole (e·Å^-3)	0.188, -0.211

2 实验

2
2.1 试剂与仪器

2.1

硝基胍，上海阿拉丁试剂有限公司，分析纯；水合肼（80%）、甲醛溶液（38%），天津市科密欧化学试剂有限公司，分析纯；ANQ为实验室根据文献[9]制备。

EQ UINOX‑550 型傅里叶变换红外光谱仪，德国BRUKER 公司；INOVA‑400 MHz型核磁共振仪，美国Varian公司；SGW X‑4B型显微熔点测定仪，上海仪电物理光学仪器有限公司；Bruker Smart APEX Ⅱ CCD X‑射线面探衍射仪，德国BRUKER公司；DSC200F3差示扫描量热仪，德国NETZSCH公司；SDT‑Q600同步热分析仪，美国TA公司；IKA C5000氧弹量热仪，德国IKA公司；ZBL‑B型撞击感度仪，北京纳辰科技发展有限公司。
2.2 MANG的合成

2.2

将0.15 g（0.0013 mol）ANQ加入10 mL蒸馏水中，常温搅拌均匀后，加入1 mL 38%的甲醛溶液，搅拌并加热至35 ℃，反应物先溶解，几分钟后开始出现絮状白色物质，2 h结束反应。将反应液冷却至室温，过滤洗涤，烘干后得到MANG白色粉末产物0.142 g，产率约为86%。¹³C NMR(DMSO‑d₆, 500 MHz): 158.584, 139.331；¹H NMR(DMSO‑d₆,500 MHz)：6.686, 7.132, 8.377, 8.736, 11.654；IR(KBr，ν/cm^-1): 3388, 3283, 3209, 3082, 2930, 1648, 1606, 1411, 1271, 1132, 1060, 988, 938, 637；Anal.calcd for C₂H₅N₅O₂(%): C 18.32, H 3.82, N 53.44; found C 18.18, H 3.74, N 53.83。
2.3 晶体培养与结构测定

2.3

将MANG粉末溶于乙腈和水的混合液中(体积比1∶2)，室温下缓慢挥发，15 d后得到无色棒状晶体。选取尺寸为0.30 mm×0.15 mm×0.15 mm的单晶置于Bruker SMART APEX Ⅱ CCD的X‑射线单晶衍射仪上：用石墨单色器单色化的Mo K_α射线（λ=0.071073 nm）光源，测试温度298(2) K，晶体结构通过直接法由SHELXS‑97解析得到^[20]，并由全矩阵最小二乘法精修用SHELXL‑97程序完成^[21]。晶体参数和精修结果列于表1。（CCDC：1852040）
2.4 测试方法

2.4

DSC测试采用DSC200F3差示扫描量热仪，动态氮气气氛，流速80 mL·min^-1，升温速率为5，10，15，20 ℃·min^-1，温度范围为30~350 ℃，样品量约0.5 mg。TG/DTG测试采用SDT‑Q600同步热分析仪，动态氮气气氛，流速100 mL·min^-1，升温速率为10 ℃·min^-1，样品量0.3~0.5 mg。测定燃烧热时仪器经苯甲酸标准样校准，样品量200 mg左右，平行测定六次。撞击感度测试时落锤质量为0.8 kg，样品量为30 mg，测定六次。
3 结果与讨论

3
3.1 合成过程

3.1

ANQ的特殊结构使其易发生加成反应、成环反应、成盐反应、酰基化反应、还原反应等^[19]。在前期研究^[22,23]中，本课题组将硝基胍和甲醛反应生成了亚甲基二硝基胍，基于此本研究设计用亚甲基将两分子ANQ连接的路线，以合成具有对称结构的新型含能化合物A或B，但尝试了多种方法都没有得到目标产物。然而，却意外以较高收率（86%）合成了亚甲氨基硝基胍（MANG）（Scheme 1）。分析原因应该是肼基上的氨基亲核性更强，首先进攻羰基基团上带正电荷的碳原子，发生亲核加成反应，生成的中间物进一步脱水生成了MANG，此过程即经典的醛氨缩合反应。此外，希望通过成环反应得到更加稳定的五元氮杂环化合物C的努力也失败了。在此体系中，醛氨缩合更具有优势，链反应与成环反应难以发生。

Scheme 1 Synthesis route of MANG

3.2 晶体结构

MANG的分子结构如图1所示，由图1可以看出，MANG分子比较简单，包括一个氨基、一个硝酰基和一个亚甲氨基，比ANQ只多了一个亚甲基。晶体结构的主要键长、键角和二面角见表2，由表2可知，N(5)—C(2)双键键长为1.250 Å，比常见的碳氮双键键长 (1.34~1.38 Å)还略为短些，但显著长于碳氮叁键键长（1.14~1.16 Å）。N(2)—C(1)、N(3)—C(1)和N(4)—C(1)键长分别为1.359、1.303 Å和1.340 Å，因共轭效应均表现为典型的共轭双键。原来肼基上的N(4)—N(5)键（1.376 Å）也因两边的共轭效应，使其更接近氮氮共轭双键（1.22~1.30 Å）。整个分子中原子分布比较规律，键角都接近于120°，结构规整。分子中最大的二面角O(1)—N(1)—N(2)—C(1)为6.8(7)°，其他二面角均约为1°，即整个化合物分子中所有非氢原子几乎都处在同一个平面上。

MANG的氢键图和堆积图见图2和图3。由图2可知，MANG晶体中存在三种氢键，一种分子内氢键N(3)—H(3B)…O(1)[d(D…A)=2.568 Å,∠DHA=124.2°]和两种分子间氢键[N(3)—H(3A)…O(1)#1(d(D…A)=2.993 Å,∠DHA=166°)和N(4)—H(4)…N(2)#2(d(D…A)=3.041 Å,∠DHA=169°); symmetry transformations: #1:x‑1/2,‑y+1/2,z‑1/2;#2:‑x+1,‑y+1,z]。每个MANG分子与周围其他三个分子通过四个分子间氢键连接（两两对称），向外无限扩展，加以范德华力形成了有序的3D空间结构（图3）。

图1 MANG的分子结构图

Fig.1 Molecular structure of MANG

表2 MANG的部分键长、键角和二面角

Table 2 Selected bond lengths, bond angles and torsion angles of MANG

bond	length / Å
O(2)—N(1)	1.238(4)
O(1)—N(1)	1.239(5)
N(1)—N(2)	1.354(5)
N(3)—C(1)	1.303(5)
N(4)‑—C(1)	1.340(5)
N(2)—C(1)	1.359(5)
N(5)—C(2)	1.250(5)
N(4)—N(5)	1.376(5)
bond	angle / (°)
O(1)—N(1)—O(2)	122.2(4)
O(2)—N(1)—N(2)	114.6(4)
O(1)—N(1)—N(2)	123.2(4)
N(1)—N(2)—C(1)	117.9(4)
C(1)—N(4)—N(5)	118.8(4)
C(2)—N(5)—N(4)	116.6(4)
N(3)—C(1)—N(2)	129.4(4)
N(4)—C(1)—N(2)	111.1(4)
N(3)—C(1)—N(4)	119.5(4)
O(2)—N(1)—N(2)—C(1)	-174.2(4)
O(1)—N(1)—N(2)—C(1)	6.8(7)
N(3)—C(1)—N(2)—N(1)	-0.8(7)
N(4)—C(1)—N(2)—N(1)	178.9(4)
N(2)—C(1)—N(4)—N(5)	-179.0(4)
N(3)—C(1)—N(4)—N(5)	0.8(7)
C(1)—N(4)—N(5)—C(2)	-180.0(5)

3.3 热性能

MANG的热分解DSC及TG‑DTG曲线见图4和图5。由图4和图5可知，MANG的热行为呈现出一个剧烈的放热分解过程，相对应的失重约为43%。5 ℃·min^-1的升温速率下，起始分解温度、峰温和放热量分别为：170.2，170.9 ℃和1440 J·g^-1。对比ANQ的DSC结果^[6]可知，亚甲基的引入反而使热稳定性降低，但分解过程更加剧烈，热流率可达240 mW·mg^-1。

图4 MANG和ANQ的DSC曲线(5 ℃·min^-1)

Fig.4 DSC curves of MANG and ANQ at a heating rate of 5 ℃·min^-1

图5 MANG的TG‑DTG曲线(10 ℃·min^-1)

Fig.5 TG‑DTG curve of MANG at a heating rate of 10 ℃·min^-1

图2 MANG的氢键图

Fig.2 H‑bond diagram of MANG

不同升温速率下的DSC外推起始温度、峰温及采用Kissinger法^[24]和Ozawa法^[25]计算的动力学参数列于表3。由表3可知，两种方法计算得到的表观活化能接近，且线性相关系数都接近于1，因此该测试结果可信。表观活化能较低表明容易发生分解。

图3 MANG晶体的堆积图

Fig.3 Packing diagram of MANG in the crystal lattice

自加速分解温度（T_SADT）和热爆炸临界温度（T_b）是评估含能材料的热稳定性的两个重要参数。T_SADT和T_b可以由方程（1）和（2）得到^[26,27]。计算得到的MANG的T_SADT和T_b分别为163.73 ℃和165.04 ℃，显著低于ANQ（184.5 ℃和192.68 ℃）^[6]。

$T S A D T = T e 0 = T e i - n β i - m β i 2$

$i = 1 - 4$

（1）

$T b = E o - E o 2 - 4 E o R T e 0 2 R$

（2）

3.4 爆轰性能

MANG的燃烧热平行测定六次，均值为-11629 J·g^-1，标准不确定度为45.5，因此MANG的恒容燃烧热为（-11629±45.5） J·g^-1。通过燃烧反应方程式（a）和（b）以及计算式（3）^[23]得到其标准摩尔燃烧热（Δ_cH_m）为-1526.09 kJ·mol^-1。

$C 2 H 5 N 5 O 2 ( s ) + 13 4 O 2 ( g ) = 2 C O 2 ( g ) + 5 2 H 2 O ( l ) + 2 N 2 ( g ) + N O 2 ( g )$ （a）

表3 不同升温速率下MANG的动力学参数

Table 3 Values of the kinetic parameters for MANG at various β

β / ℃·min^-1	T_e/ ℃	T_p / ℃	E_K / kJ·mol^-1	log(A / s^-1)	r_k	E_O / kJ·mol^-1	r_O
5	170.18	170.90	174.84	18.52	0.9992	173.39	0.9993
10	176.77	176.95
15	180.41	180.61
20	183.42	183.80

NOTE: β is the heating rate. T_e and T_p are the extrapolated onset temperature and the peak temperature, respectively. E is the apparent activation energy. A is the pre‑exponential factor. r is the linear correlation coefficient. Subscript K and subscript O are data obtained by Kissinger method and Ozawa method.

$N O 2 ( g ) + 1 3 H 2 O ( l ) = 2 3 H N O 3 ( l ) + 1 3 N O ( g )$ （b）

$Δ c H m θ = Δ c U m θ + Δ n 1 R T + Δ n 2 R T$

（3）

其中， $Δ n = ∑ n i ( p r o d u c t s , g ) - ∑ n i ( r e a c t a n t s , g )$

标准摩尔生成焓（ $Δ f H m θ$ ）可以用盖斯定律计算，通过方程（4）得出MANG的标准摩尔生成焓为33.81 kJ·mol^-1。

$Δ f H m θ M A N G , s = 2 Δ f H m θ C O 2 , g + 13 6 Δ f H m θ H 2 O , l + 1 3 Δ f H m θ N O , g + 2 3 Δ f H m θ H N O 3 , l - Δ c H m θ M A N G , s$

（4）

已知 $Δ f H m θ$ (CO₂,g)=-(393.51±0.13) kJ·mol^-1， $Δ f H m θ$ (H₂O,l)=-(285.83±0.04) kJ·mol^-1, $Δ f H m θ$ (HNO₃,l)=-(174.10±0.8) kJ·mol^-1和 $Δ f H m θ$ (NO,g)=(90.25±0.75) kJ·mol^-1[28,29]

采用Kamlet‑Jacobs(K‑J)方程^[30]计算了MANG的爆速、爆压，并测试了其撞击感度（IS），结果列于表4，并与ANQ、TNT和RDX进行了对比。从表4可以看出MANG的爆速（7.1 km·s^-1）和爆压（20.9 GPa）均优于TNT（6.9 km·s^-1和19.1 GPa），但显著低于ANQ和RDX。MANG的感度（>7.9 J）低于ANQ (3.0 J)，接近于RDX的撞击感度（7.4 J），故MANG相对不敏感。

表4 MANG与ANQ、TNT和RDX的性能对比

Table 4 Properties of MANG compared with ANQ, TNT and RDX

compound	M / g·mol^-1	ρ(crystal) / g·cm^-3	D / km·s^-1	p / GPa	IS / J
MANG	131.11	1.63	7.1	20.9	>7.9
ANQ^[31]	119.08	1.72	8.7	30.7	3.0
TNT^[19]	227.13	1.63	6.9	19.1	15.0
RDX^[19]	222.12	1.82	8.7	33.7	7.4

NOTE: M is the molecular mass. ρ is the crystal density. D is the detonation velocity. p is the detonation pressure. IS is the impact sensitivity.

4 结论

4

（1）以ANQ和甲醛为原料意外合成了MANG，产率86%。MANG属于正交晶系，空间群为P_nn2，密度为1.63 g·cm^-3。MANG分子间通过4个两两对称的氢键与周围3个分子连接，形成了高度有序的3Ｄ空间结构。

（2）MANG的热行为只有一个剧烈的放热分解过程。MANG的T_SADT和T_b分别为163.73 ℃和165.04 ℃，亚甲基的引入使其热稳定性相较于ANQ有所下降。MANG的标准摩尔燃烧热和生成焓分别为-1526.09 kJ·mol^-1和33.81 kJ·mol^-1，爆速和爆压分别为7.1 km·s^-1和20.9 GPa，撞击感度>7.9 J，具有作为含能材料的潜力。
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基本信息

DOI:10.11943/CJEM2018184

中图分类号: TJ55； O62

文献标识码: A

引用信息

杨航,冯治存,关晓鸽，等. 亚甲氨基硝基胍（MANG）的合成、晶体结构及热行为[J]. 含能材料,2019,27(2): 125-130.

YANG Hang,FENG Zhi‑cun,GUAN Xiao‑ge,et al. Synthesis, Crystal Structure and Thermal Behavior of Methyleneaminonitroguanidine (MANG)[J]. Chinese Journal of Energetic Materials（Hanneng Cailiao）,2019,27(2): 125-130.

基金信息

国家自然科学基金(21673178)

稿件历史

网刊发布 : 2018-10-30
纸刊出版 : 2019-02-25
收稿日期 : 2018-07-07
修回日期 : 2018-07-31

杨航

机构：西北大学化工学院，陕西西安 710069

Affiliation：School of Chemical Engineering, Northwest University, Xi′an 710069, China

邮箱：136754374@qq.com

作者简介：杨航(1994-), 女, 硕士研究生, 从事含能材料研究。e‑mail:136754374@qq.com

冯治存

机构：西北大学化工学院，陕西西安 710069

Affiliation：School of Chemical Engineering, Northwest University, Xi′an 710069, China

关晓鸽

机构：西北大学化工学院，陕西西安 710069

Affiliation：School of Chemical Engineering, Northwest University, Xi′an 710069, China

徐抗震

机构：西北大学化工学院，陕西西安 710069

Affiliation：School of Chemical Engineering, Northwest University, Xi′an 710069, China

角色：通讯作者

Role：Corresponding author

邮箱：xukz@nwu.edu.cn

作者简介：徐抗震(1976-), 男, 教授, 从事新型含能材料的研究。e‑mail:xukz@nwu.edu.cn

宋纪蓉

机构：西北大学化工学院，陕西西安 710069

Affiliation：School of Chemical Engineering, Northwest University, Xi′an 710069, China

赵凤起

机构：西安近代化学研究所，陕西西安 710065

Affiliation：Xi′an Modern Chemistry Research Institute, Xi′an 710065, China

compound	MANG
formula	C₂H₅N₅O₂
formula mass	131.11
temperature /K	298(2)
crystal system	orthorhombic
space group	P_nn2
a /Å	9.070(4)
b /Å	16.591(6)
c /Å	3.5508(13)
V /Å³	534.3(4)
Z	4
D_c / g·cm^-3	1.63
absorption coefficient / mm^-1	0.142
θ / (°)	2.46‑20.99
F(000)	272
h, k and l	-9<h<9,-16<k<13, -3<l<3
reflections collected	1696
independent reflections (R_int)	561 (0.0447)
data/restraints/parameters	561 / 4 / 102
goodness‑of‑fit on F²	1.019
final R₁, wR₂ [I>2σ(I)]	0.0517, 0.0866
R₁,wR₂ (all data)	0.1047, 0.1057
largest difference peak and hole (e·Å^-3)	0.188, -0.211

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bond	length / Å
O(2)—N(1)	1.238(4)
O(1)—N(1)	1.239(5)
N(1)—N(2)	1.354(5)
N(3)—C(1)	1.303(5)
N(4)‑—C(1)	1.340(5)
N(2)—C(1)	1.359(5)
N(5)—C(2)	1.250(5)
N(4)—N(5)	1.376(5)
bond	angle / (°)
O(1)—N(1)—O(2)	122.2(4)
O(2)—N(1)—N(2)	114.6(4)
O(1)—N(1)—N(2)	123.2(4)
N(1)—N(2)—C(1)	117.9(4)
C(1)—N(4)—N(5)	118.8(4)
C(2)—N(5)—N(4)	116.6(4)
N(3)—C(1)—N(2)	129.4(4)
N(4)—C(1)—N(2)	111.1(4)
N(3)—C(1)—N(4)	119.5(4)
O(2)—N(1)—N(2)—C(1)	-174.2(4)
O(1)—N(1)—N(2)—C(1)	6.8(7)
N(3)—C(1)—N(2)—N(1)	-0.8(7)
N(4)—C(1)—N(2)—N(1)	178.9(4)
N(2)—C(1)—N(4)—N(5)	-179.0(4)
N(3)—C(1)—N(4)—N(5)	0.8(7)
C(1)—N(4)—N(5)—C(2)	-180.0(5)

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β / ℃·min^-1	T_e/ ℃	T_p / ℃	E_K / kJ·mol^-1	log(A / s^-1)	r_k	E_O / kJ·mol^-1	r_O
5	170.18	170.90	174.84	18.52	0.9992	173.39	0.9993
10	176.77	176.95
15	180.41	180.61
20	183.42	183.80

compound	M / g·mol^-1	ρ(crystal) / g·cm^-3	D / km·s^-1	p / GPa	IS / J
MANG	131.11	1.63	7.1	20.9	>7.9
ANQ^[31]	119.08	1.72	8.7	30.7	3.0
TNT^[19]	227.13	1.63	6.9	19.1	15.0
RDX^[19]	222.12	1.82	8.7	33.7	7.4

表1 MANG的晶体参数与精修数据

Table 1 Crystallographic data and structure refinement details for MANG

Scheme 1 Synthesis route of MANG

图1 MANG的分子结构图

Fig.1 Molecular structure of MANG

表2 MANG的部分键长、键角和二面角

Table 2 Selected bond lengths, bond angles and torsion angles of MANG

图4 MANG和ANQ的DSC曲线(5 ℃·min^-1)

Fig.4 DSC curves of MANG and ANQ at a heating rate of 5 ℃·min^-1

图5 MANG的TG‑DTG曲线(10 ℃·min^-1)

Fig.5 TG‑DTG curve of MANG at a heating rate of 10 ℃·min^-1

图2 MANG的氢键图

Fig.2 H‑bond diagram of MANG

图3 MANG晶体的堆积图

Fig.3 Packing diagram of MANG in the crystal lattice

表3 不同升温速率下MANG的动力学参数

Table 3 Values of the kinetic parameters for MANG at various β

表4 MANG与ANQ、TNT和RDX的性能对比

Table 4 Properties of MANG compared with ANQ, TNT and RDX

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image /

无注解

β is the heating rate. T_e and T_p are the extrapolated onset temperature and the peak temperature, respectively. E is the apparent activation energy. A is the pre‑exponential factor. r is the linear correlation coefficient. Subscript K and subscript O are data obtained by Kissinger method and Ozawa method.

M is the molecular mass. ρ is the crystal density. D is the detonation velocity. p is the detonation pressure. IS is the impact sensitivity.

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亚甲氨基硝基胍（MANG）的合成、晶体结构及热行为 PDF

Synthesis, Crystal Structure and Thermal Behavior of Methyleneaminonitroguanidine (MANG) PDF

摘要

Abstract

关键词

Keywords

1 引 言

1

2 实 验

2

2.1 试剂与仪器

2.1

2.2 MANG的合成

2.2

2.3 晶体培养与结构测定

2.3

2.4 测试方法

2.4

3 结果与讨论

3

3.1 合成过程

3.1

3.2 晶体结构

3.2

3.3 热性能

3.3

（1）

（2）

3.4 爆轰性能

3.4

（3）

（4）

4 结论

4

参考文献

基本信息

引用信息

基金信息

稿件历史

参考文献

1 引言

2 实验