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4-(2,4,6-三硝基苯胺基)苯甲酸(TABA)的新型铅配合物: 制备、晶体结构及热分解性质
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(西安近代化学研究所, 陕西 西安 710065)

作者简介:

唐望(1982-),男,助理研究员,主要从事含能材料及无机材料制备研究。e-mail: tangwang1982@163.com 通信联系人: 邱少君(1971-),男,研究员,主要从事含能材料及无机材料制备研究。e-mail: qiu_shaojun@163.com

通讯作者:

邱少君(1971-),男,研究员,主要从事含能材料及无机材料制备研究。e-mail: qiu_shaojun@163.com

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Noval Lead Complex of 4-(2,4,6-Trinitroanilino)benzoic Acid (TABA): Synthesis, Crystal Structure and Thermal Decomposition Properties
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(Xi′an Modern Chemistry Research Institute, Xi′an 710065, China)

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    摘要:

    以4-(2, 4, 6-三硝基苯胺基)苯甲酸(TABA)为配体, 采用溶剂挥发法合成出了一种新型铅配合物: {[PbL2(DMF)H2O]·2(DMF)H2O}n(1)(L=4-(2, 4, 6-三硝基苯胺基)苯甲酸根, DMF=N, N-二甲基甲酰胺)。用X-射线单晶衍射仪测定了它的单晶结构。用TG-DSC测定了其热分解过程。在不同升温速率下测试了配合物1与RDX(质量比1:1)混合物的DSC曲线。计算了该混合物热分解反应的动力学参数。结果表明, 该配合物属于单斜晶系, P2(1)/c空间群, 晶体参数为: a=6.900(2)Å, b=19.162(6)Å, c=34.866(11)Å, β=94.261(4)°, V=4597(3)Å3, Z=4。以Pb(Ⅱ)为桥联离子与4-(2, 4, 6-三硝基苯胺基)苯甲酸根配位形成一维配位聚合物链。配合物1的热分解主要经历四个阶段。第一阶段发生在58~84 ℃, 主要失去结晶态、配位态水分子及部分结晶状态的DMF。第二阶段为84~231 ℃, 主要是剩余DMF分子的失去。231~320 ℃和320~415 ℃为第三和第四阶段, 主要是有机含能配体TABA2-的放热分解, 在296 ℃及335 ℃出现放热峰。配合物1可促进了RDX的热分解。

    Abstract:

    Using 4-(2, 4, 6-trinitroanilino)benzoic acid (TABA) as the ligand, a noval lead complex, {[PbL2(DMF)H2O]·2(C3H7NO)H2O}n(1) (L=4-(2, 4, 6-trinitroanilino) benzoate, DMF=N, N′-dimethylformamide), was synthesized by a solvent evaporation method. Its structure was determined by a X-ray single crystal diffractometer. Its thermal decomposition process was determined by TG-DSC. DSC curves of the 50/50-complex 1 /RDX mixture at different heating rate were determined and the kinetic parameters of the thermal decomposition reaction of the mixture were calculated. Results show that the crystal is monoclinic, its space group is P2(1)/c with crystal parameters a=6.900(2)Å, b =19.162(6)Å, c=34.866(11)Å, β=94.261(4)°, V=4597(3)Å3, Z=4. Pb(Ⅱ) ions are connected by 4-(2, 4, 6-trinitroanilino) benzoate and 1-D coordination polymer chains are formed. The thermal decomposition of complex 1 mainly undergoes four stages. The first stage occurs between 58 ℃ to 84 ℃ and complex 1 mainly loses its crystallized and coordinated water molecules and part of crystallized DMF molecules. The temperature range of 84 ℃ to 231 ℃ is the second thermal decomposition stage with complete loss of the rest DMF molecules.The energetic organic ligand TABA2-decomposes mainly at stages 3 and 4 of the process and exothermal peaks appear at 296 ℃ and 335 ℃, respectively. The thermal decomposition of RDX was accelerated by complex 1.

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唐望,常佩,郑晓东,等.4-(2,4,6-三硝基苯胺基)苯甲酸(TABA)的新型铅配合物: 制备、晶体结构及热分解性质[J].含能材料, 2016, 24(5):444-450. DOI:10.11943/j. issn.1006-9941.2016.05.005.
TANG Wang, CHANG Pei, ZHENG Xiao-dong, et al. Noval Lead Complex of 4-(2,4,6-Trinitroanilino)benzoic Acid (TABA): Synthesis, Crystal Structure and Thermal Decomposition Properties[J]. Chinese Journal of Energetic Materials, 2016, 24(5):444-450. DOI:10.11943/j. issn.1006-9941.2016.05.005.

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  • 收稿日期: 2015-06-16
  • 最后修改日期: 2015-08-02
  • 录用日期: 2015-08-25
  • 在线发布日期: 2016-05-05
  • 出版日期: 2016-05-20