Theoretical study on the mechanisms of the decomposition of nitrate esters and the stabilization of aromatic amines
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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.
KeywordsNitrate esters Decomposition Stabilizers Rate constants
This work was supported by the fund of key technology research and development projects (20190302130GX), Jilin Province Science and Technology Department.
- 5.Bohn MA (2002) Kinetic description of mass loss data for the assessment of stability, compatibility and aging of energetic components and formulations exemplified with ε-Cl20. Propellants Explos Pyrotech 27(3):125–135. https://doi.org/10.1002/1521-4087(200206)27:3<125::AID-PREP125>3.0.CO;2-4 CrossRefGoogle Scholar
- 8.Monoruzzaman M, Bellerby JM, Bohn MA (2014) Activation energies for the decomposition of nitrate ester groups at the anhydroglucopyranose ring positions C2, C3 and C6 of nitrocellulose using the nitration of a dye as probe. Polym Degrad Stab 102:49–58. https://doi.org/10.1016/j.polymdegradstab.2014.02.002 CrossRefGoogle Scholar
- 13.Venter A, Ifa DR, Cooks RG, Poehlein SK, Chin A, Ellison D (2006) A desorption electrospray ionization mass spectrometry study of aging products of diphenylamine stabilizer in double-base propellants. Propellants Explos Pyrotech 31(6):472–476. https://doi.org/10.1002/prep.200600064 CrossRefGoogle Scholar
- 26.Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Mennucci B, Petersson GA, Nakatsuji H, Caricato M, Li X, Hratchian HP, Izmaylov AF, Bloino J, Zheng G, Sonnenberg JL, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Vreven T, Montgomery Jr JA, Peralta JE, Ogliaro F, Bearpark M, Heyd JJ, Brothers E, Kudin KN, Staroverov VN, Kobayashi R, Normand J, Raghavachari K, Rendell A, Burant JC, Iyengar SS, Tomasi J, Cossi M, Rega N, Millam NJ, Klene M, Knox JE, Cross JB, Bakken V, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Martin RL, Morokuma K, Zakrzewski VG, Voth GA, Salvador P, Dannenberg JJ, Dapprich S, Daniels AD, Farkas Ö, Foresman JB, Ortiz JV, Cioslowski J, Fox DJ (2009) Gaussian 09, revision A.1. Gaussian Inc., WallingfordGoogle Scholar
- 31.Shehata AB, Hassan MA, Nour MA (2003) Effect of new poly 2-acryloyl-N,N′-bis (4-nitrophenyl) propandiamide and poly 2-acryloyl-N,N′-bis (4-methylphenyl) propandiamide and their synergistic action on the stability of nitrocellulose. J Hazard Mater 102(2):121–136. https://doi.org/10.1016/S0304-3894(03)00138-9 CrossRefPubMedGoogle Scholar