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化学学报
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化学学报 ›› 2007, Vol. 65 ›› Issue (18): 2034-2038. 上一篇    下一篇

研究论文

N,N'-二(二乙氧基硫代磷酰基)-1,4-苯二胺的合成、晶体结构及热性能研究

任元林*, 程博闻, 张金树, 藏洪俊, 康卫民, 丁长坤   

  1. (天津工业大学天津市纤维改性及功能纤维重点实验室 天津 300160)
  • 投稿日期:2006-12-28 修回日期:2007-03-05 发布日期:2007-09-28
  • 通讯作者: 任元林

Synthesis, Crystal Structure and Thermal Properties of N,N'-Di(diethoxythiophosphoryl)-1,4-phenylenediamine

REN Yuan-Lin*; CHENG Bo-Wen; ZHANG Jin-Shu; ZANG Hong-Jun; KANG Wei-Min; DING Chang-Kun   

  1. (Tianjin Municipal Key Laboratory of Fiber Modification and Functional Fiber, Tianjin Polytechnic University, Tianjin 300160)
  • Received:2006-12-28 Revised:2007-03-05 Published:2007-09-28
  • Contact: REN Yuan-Lin

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通过二乙氧基硫代磷酰氯与对苯二胺反应生成了标题化合物N,N'-二(二乙氧基硫代磷酰基)-1,4-苯二胺，并应用元素分析, FTIR及1H NMR对标题化合物进行了表征. 利用X射线单晶衍射测定了其晶体结构, 同时应用TG分析法对其热性能进行了分析. 标题化合物的相对分子质量Mr＝412.42, 为正交晶系, Pbca空间群, 晶胞参数为a＝0.86936(16) nm, b＝1.2787(2) nm, c＝1.8897(3) nm, β＝90°, V＝2.1006(7) nm3, Z＝8, Dc＝1.304 g/cm3, μ(Mo Kα)＝0.425 mm－1, F(000)＝872, S＝1.052. 最终偏离因子R＝0.0628, wR＝0.1860, 可观测衍射点1852个[I＞2σ(I)]. 该晶体通过对苯二胺连接并以中心对称分布, 并形成层状结构, 且存在弱的分子内氢键N—H…S. TG分析表明该化合物有很好的热稳定性及成炭性, 通过其阻燃聚丙烯腈表明, 该物质是一种高效能的膨胀型阻燃剂.

关键词: O,O-二乙基硫代磷酰氯, 对苯二胺, N,N'-二(二乙氧基硫代磷酰基)-1,4-苯二胺, 晶体结构, 热性能, 膨胀型阻燃剂

The title compound N,N'-di(diethoxythiophosphoryl)-1,4-phenylenediamine was synthesized by the reaction of diethoxythiophosphoryl chloride and p-phenylenediamine and characterized by elemental analysis, IR and 1H NMR spectra. Its crystal structure was determined by single crystal X-ray diffraction analysis and the thermal property was studied by TG analysis. The relative molecular weight of the title compound is 412.42, the crystal structure belongs to orthorhombic, Pbca space group, with a＝0.86936(16) nm, b＝1.2787(2) nm, c＝1.8897(3) nm, β＝90°, V＝2.1006(7) nm3, Z＝8, Dc＝1.304 g/cm3, μ(Mo Kα)＝0.425 mm－1, F(000)＝872, S＝1.052, the final R＝0.0628 and wR＝0.1860 for 1852 observed reflections with I＞2σ(I). The X-ray single crystal diffraction analysis demonstrates that the crystal structure is centrosymmetric. The weak N—H…S intramolecular hydrogen bonds were observed to link the molecules into sheets. The TG analysis shows that the title compound has good thermal stability and char forming capability, and its retarding the fire by polyacrylonitrile reveals that the compound is an excellent intumescent fire retardant.

Key words: diethoxythiophosphoryl chloride, p-phenylenediamine, N,N'-di(diethoxythiophosphoryl)-1,4- phenylenediamine, crystal structure, thermal property, intumescent fire retardant