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偏二甲肼制备低熔点胺基酰亚胺的实验研究
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Preparation of Low Melting Points Aminimide from Unsymmetrical Dimethylhydrzine
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    摘要:

    为了解决报废偏二甲肼再利用问题,使偏二甲肼经烷基化、酰基化、脱氢,合成了八种具有较低熔点的饱和脂肪族胺基酰亚胺化合物。研究了胺基酰亚胺的结构、熔点和热分解温度。红外分析表明,酰亚胺基团N-上的LP与酰基π轨道产生共轭效应,形成 两个共振结构N=C—O-和N-—C=O。酰基上的取代烷基给电诱导能力的强弱对酰亚胺基团这两个共振结构的特征吸收峰位置有明显影响,给电诱导能力越弱,则N=C—O--和N-—C=O红外吸收的频率越高。动态DSC分析表明,胺基碳链对饱和脂肪族胺基酰亚胺热分解活性的影响不明显,而延长酰基碳链可显著提高热分解活性。

    Abstract:

    Aiming at the problem of recycling scraps unsymmetrical dimethylhydrzine (UDMH), eight saturated aliphatic aminimides with low melting points were synthesized after UDMH was alkylated, acidylated and dehydrogenated. The structures, melting points and pyrolysis activities of aminimides were studied. FTIR spectra show that the resonance structure N=C—O- and N-—C=O is formed resulting from delocalization of the electron pair in the p-orbital of the imide nitrogen with the π-orbital of the carbonyl. The positions of the characteristic absorption peak frequencies of the two resonance structures are influenced obviously by the inductive effect of the substituent in carbonyl. The carbonyl substituent with a weaker inductive effects cause the IR absorption peak to shift toward higher frequencies. Dynamic DSC results show that the carbochain of amine group presents a little effect on the pyrolysis activities of aminimide among the aliphatic saturated aminimides. The aminimide with a longer carbonyl carbochain presents higher pyrolysis activity.

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张有智,李正莉,王煊军.偏二甲肼制备低熔点胺基酰亚胺的实验研究[J].含能材料, 2009, 17(4):478-481. DOI:10.3969/j. issn.1006-9941.2009.04.025.
ZHANG You-zhi, LI Zheng-li, WANG Xuan-jun. Preparation of Low Melting Points Aminimide from Unsymmetrical Dimethylhydrzine[J]. Chinese Journal of Energetic Materials, 2009, 17(4):478-481. DOI:10.3969/j. issn.1006-9941.2009.04.025.

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  • 收稿日期: 2008-12-02
  • 最后修改日期: 2009-03-12
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  • 在线发布日期: 2011-11-04
  • 出版日期: 2009-08-25