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Theoretical study on the mechanisms of the decomposition of nitrate esters and the stabilization of aromatic amines

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Abstract

The nitrate esters are important components of double-base propellants. Aromatic amines are recommended as the stabilizers to delay the decomposition of nitrate esters and increase their storage time. The decomposition mechanisms of alkyl, alkoxy dinitrate, and poly-fluoride nitrate esters and the stabilizing effect of aromatic amines including new designed phenols are studied at the level of B3LYP/6-31G**. Alkyl and alkoxyl dinitrate esters are likely to be transformed by hydrogen abstraction, which is consistent with that of mononitrate and trinitrate esters. However, for poly-fluoride nitrate esters, NO2 catalyzed self-decomposition is preferred. In addition, comparing with mononitrate and trinitrate esters, the order of their stability is mononitrates > dinitrates > trinitrates. Poly-fluoride nitrate esters have a poorer stability than non-fluorinated nitrate esters. Comparing with parent nitrate esters, the stability of new designed poly-fluoride oxygen-containing nitrate esters is slightly improved. Aromatic amines including new designed phenols are effective stabilizers of nitrate esters, especially when introduced hydroxyl in the para position, can enhance the effects of stabilizers. The rate constants for the decomposition of nitrate esters and the bimolecular reaction between stabilizers and NO2 are calculated by using traditional transition state theory.

Comparison between the reaction energy barrier of nitrate esters and stabilizers with NO2

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Funding

This work was supported by the fund of key technology research and development projects (20190302130GX), Jilin Province Science and Technology Department.

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Authors and Affiliations

  1. Institute of Functional Material Chemistry, National & Local United Engineering Lab for Power Battery, Faculty of Chemistry, Northeast Normal University, Changchun, 130024, People’s Republic of China

    Yang Sun, Shuang Ni & Xiu-mei Pan

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  1. Yang Sun
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  2. Shuang Ni
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  3. Xiu-mei Pan
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Correspondence to Xiu-mei Pan.

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Highlights

• Mechanisms of decompositions for dinitrate esters are elaborated.

• Mechanisms of the reactions between stabilizers and NO2 are elucidated.

• New nitrate esters containing fluoride/oxygen and stabilizers are designed.

• Relevant kinetic studies of stabilizers and nitrate esters are investigated.

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Sun, Y., Ni, S. & Pan, Xm. Theoretical study on the mechanisms of the decomposition of nitrate esters and the stabilization of aromatic amines. J Mol Model 25, 346 (2019). https://doi.org/10.1007/s00894-019-4245-7

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  • DOI: https://doi.org/10.1007/s00894-019-4245-7

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