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Theoretical design of novel energetic salts derived from bicyclo-HMX

  • Cong Zhang
  • Feng-Qi Zhao
  • Si-Yu Xu
  • Xue-Hai Ju
Original Paper
  • 70 Downloads

Abstract

We designed three novel cage energetic anions by introducing ionic bridges containing NΘ, N(OΘ) and N(NΘNO2) into cis-2,4,6,8-tetranitro-1H,5H-2,4,6,8- tetraazabicyclo[3.3.0] octane (bicyclo-HMX or BCMHX). The properties of 21 energetic salts, based on cage anions and ammonium-based cations, were studied by density functional theory (DFT) and volume-based thermodynamics (VBT) calculations. Compared to the parent nonionic BCHMX, most title salts have lower predicted impact sensitivities, higher predicted densities, larger predicted heats of formation (HOFs) and better predicted detonation properties. In particular, 11 energetic salts not only exhibit excellent predicted energetic properties, superior to 2,4,6,8,10,12-hexanitrohexaazaisowurtzitane (CL-20), but also have lower predicted sensitivity than CL-20. The best salt had a predicted detonation velocity of 10.06 km s−1, a predicted detonation pressure of 48.54 GPa and a predicted sensitivity (h50) of 23.99 cm. By introducing ionic bridges into highly nitrated rings, or modifying the original bridge with ionic bridges, some highly nitrated cage compounds with both excellent performance and low sensitivity can be developed strategically.

Graphical abstract

Heats of detonation, detonation velocities, and detonation pressures of salts derived from bicyclo-HMX

Keywords

Cage energetic salts DFT Design strategy Detonation pressure and velocity Sensitivity 

Supplementary material

894_2018_3835_MOESM1_ESM.docx (1.5 mb)
ESM 1 (DOCX 1577 kb)

References

  1. 1.
    Gutowski L, Trzciński W, Szala M (2018) 5,5′,6,6′-Tetranitro-2,2′-bibenzimidazole: a thermally stable and insensitive energetic compound. ChemPlusChem 83:87–91CrossRefGoogle Scholar
  2. 2.
    Snyder CJ, Myers TW, Imler GH, Chavez DE, Parrish DA, Veauthier JM, Scharff RJ (2017) Tetrazolyl triazolotriazine: a new insensitive high explosive. Propell Explos Pyrot 42:238–242CrossRefGoogle Scholar
  3. 3.
    Tang Y, Mitchell LA, Imler GH, Parrish DA, Shreeve JM (2017) Ammonia oxide as a building block for high-performance and insensitive energetic materials. Angew Chem Int Ed 56:5894–5898CrossRefGoogle Scholar
  4. 4.
    Wu Q, Zhu W, Xiao H (2014) Searching for a new family of insensitive high explosives by introducing N hybridization and N-oxides into a cage cubane. J Mol Model 20:2483–2491CrossRefGoogle Scholar
  5. 5.
    Gao H, Shreeve JM (2011) Azole-based energetic salts. Chem Rev 111:7377–7436CrossRefGoogle Scholar
  6. 6.
    Ghule VD (2012) Computational studies on energetic properties of trinitro-substituted imidazole-triazole and pyrazole-triazole derivatives. J Phys Chem A 116:9391–9397CrossRefGoogle Scholar
  7. 7.
    Zhang X, Yang J, Gong X (2015) Theoretical studies on the stability of the salts formed by DTDO with HNO3 and HN(NO2)2. J Chem Sci 127:761–769CrossRefGoogle Scholar
  8. 8.
    Zhang J, Zhang Q, Vo TT, Parrish DA, Shreeve JM (2015) Energetic salts with pi-stacking and hydrogen-bonding interactions lead the way to future energetic materials. J Am Chem Soc 137:1697–1704CrossRefGoogle Scholar
  9. 9.
    Zhang X, Gong X (2015) Theoretical studies on the energetic salts of substituted 3,3′-amino-N,N′-azo-1,2,4-triazoles: the role of functional groups. J Chem Eng Data 60:2869–2878CrossRefGoogle Scholar
  10. 10.
    He P, Zhang JG, Yin X, Wu JT, Wu L, Zhou ZN, Zhang TL (2016) Energetic salts based on tetrazole N-oxide. Chem Eur J 22:7670–7685CrossRefGoogle Scholar
  11. 11.
    Huang H, Shi Y, Liu Y, Yang J (2016) 1,2,4,5-Dioxadiazine-functionalized [N-NO2] furazan energetic salts. Dalton Trans 45:15382–15389CrossRefGoogle Scholar
  12. 12.
    Liu W, Liu WL, Pang SP (2017) Structures and properties of energetic cations in energetic salts. RSC Adv 7:3617–3627CrossRefGoogle Scholar
  13. 13.
    Talawar MB, Sivabalan R, Mukundan T, Muthurajan H, Sikder AK, Gandhe BR, Rao AS (2009) Environmentally compatible next generation green energetic materials (GEMs). J Hazard Mater 161:589–607CrossRefGoogle Scholar
  14. 14.
    Sikder AK, Sikder N (2004) A review of advanced high performance, insensitive and thermally stable energetic materials emerging for military and space applications. J Hazard Mater 112:1–15CrossRefGoogle Scholar
  15. 15.
    Xu XJ, Xiao HM, Gong XD, Ju XH, Chen ZX (2005) Theoretical studies on the vibrational spectra, thermodynamic properties, detonation properties, and pyrolysis mechanisms for polynitroadamantanes. J Phys Chem A 109:11268–11274CrossRefGoogle Scholar
  16. 16.
    Pan Y, Zhu W (2017) Theoretical design on a series of novel bicyclic and cage nitramines as high energy density compounds. J Phys Chem A 121:9163–9171CrossRefGoogle Scholar
  17. 17.
    Wu Q, Tan L, Hang Z, Wang J, Zhang Z, Zhu W (2015) A new design strategy on cage insensitive high explosives: symmetrically replacing carbon atoms by nitrogen atoms followed by the introduction of N-oxides. RSC Adv 5:93607–93614CrossRefGoogle Scholar
  18. 18.
    He P, Mei H, Wu L, Yang J, Zhang JG, Cohen A, Gozin M (2018) Design of new bridge-ring energetic compounds obtained by diels-alder reactions of tetranitroethylene dienophile. J Phys Chem A 122:3320–3327CrossRefGoogle Scholar
  19. 19.
    Zhang MX, Eaton PE, Gilardi R (2000) Hepta- and octanitrocubanes. Angew Chem Int Ed 39:401–404CrossRefGoogle Scholar
  20. 20.
    Ghule VD, Sarangapani R, Jadhav PM, Pandey RK (2011) Computational design and structure-property relationship studies on heptazines. J Mol Model 17:2927–2937CrossRefGoogle Scholar
  21. 21.
    Shen C, Wang P, Lu M (2015) Molecular design and property prediction for a series of novel dicyclic cyclotrimethylene trinitramines (RDX) derivatized as high energy density materials. J Phys Chem A 119:8250–8255CrossRefGoogle Scholar
  22. 22.
    Pan Y, Zhu W (2017) Designing and looking for novel cage compounds based on bicyclo-HMX as high energy density compounds. RSC Adv 8:44–52CrossRefGoogle Scholar
  23. 23.
    Ye CC, An Q, Goddard WA, Cheng T, Zybin S, Ju XH (2015) Initial decomposition reactions of bicyclo-HMX [BCHMX or cis-1,3,4,6-tetranitrooctahydroimidazo-[4,5-d]imidazole] from quantum molecular dynamics simulations. J Phys Chem C 119:2290–2296Google Scholar
  24. 24.
    Yan QL, Zeman S, Zhang XH, Málek J, Xie WX (2015) The mechanisms for desensitization effect of synthetic polymers on BCHMX: physical models and decomposition pathways. J Hazard Mater 294:145–157CrossRefGoogle Scholar
  25. 25.
    Ghule VD, Deswal S, Devi A, Kumar TR (2016) Computer-aided design of energetic tris(tetrazolyl)amine derivatives and salts. Ind Eng Chem Res 55:875–881CrossRefGoogle Scholar
  26. 26.
    Devi A, Deswal S, Dharavath S, Ghule VD (2015) Molecular design and screening of energetic nitramine derivatives. J Mol Model 21:298–305CrossRefGoogle Scholar
  27. 27.
    Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Zakrzewski VG, Montgomery JA, Stratmann RE, Burant JC, Dapprich S, Millam JM, Daniels AD, Kudin KN, Strain MC, FarkasO TJ, BaroneV CM, Cammi R, Mennucci B, Pomelli C, Adamo C, Clifford S, Ochterski J, Petersson GA, Ayala PY, Cui Q, Morokuma K, Malick DK, Rabuck AD, Raghavachari K, Foresman JB, Cioslowski J, Ortiz JV, Baboul AG, Stefanov BB, Liu G, Liashenko A, Piskorz P, Komaromi I, Gomperts R, Martin RL, Fox DJ, Keith T, Al-Laham MA, Peng CY, Nanayakkara A, Gonzalez C, Challacombe M, Gill PMW, Johnson B, Chen W, Wong MW, Andres JL, Gonzalez C, Head-Gordon M, Replogle ES, Pople JA (2009) Gaussian 09, revision a. 01. Gaussian Inc, Wallingford, CTGoogle Scholar
  28. 28.
    Namazian M (2003) Density functional theory response to the calculation of electrode potentials of quinones in non-aqueous solution of acetonitrile. J Mol Struct THEOCHEM 664:273–278CrossRefGoogle Scholar
  29. 29.
    Pan JF, Lee YW (2004) Crystal density prediction for cyclic and cage compounds. Phys Chem Chem Phys 6:471–473CrossRefGoogle Scholar
  30. 30.
    Bouhmaida N, Ghermani NE (2005) Elusive contribution of the experimental surface molecular electrostatic potential and promolecule approximation in the empirical estimate of the crystal density. J Chem Phys 122:114101–114109CrossRefGoogle Scholar
  31. 31.
    Rice BM, Hare JJ, Byrd EF (2007) Accurate predictions of crystal densities using quantum mechanical molecular volumes. J Phys Chem A 111:10874–10879CrossRefGoogle Scholar
  32. 32.
    Politzer P, Martinez J, Murray JS, Concha MC (2010) An electrostatic correction for improved crystal density predictions of energetic ionic compounds. Mol Phys 108:1391–1396CrossRefGoogle Scholar
  33. 33.
    Lu T, Chen F (2012) Multiwfn: a multifunctional wavefunction analyzer. J Comput Chem 33:580–592CrossRefGoogle Scholar
  34. 34.
    Jenkins HD, Tudela D, Glasser L (2002) Lattice potential energy estimation for complex ionic salts from density measurements. Inorg Chem 41:2364–2367CrossRefGoogle Scholar
  35. 35.
    Byrd EF, Rice BM (2006) Improved prediction of heats of formation of energetic materials using quantum mechanical calculations. J Phys Chem A 110:1005–1013CrossRefGoogle Scholar
  36. 36.
    Zhu W, Yan Q, Li J, Cheng B, Shao Y, Xia X, Xiao H (2012) Prediction of the properties and thermodynamics of formation for energetic nitrogen-rich salts composed of triaminoguanidinium cation and 5-nitroiminotetrazolate-based anions. J Comput Chem 33:1781–1789CrossRefGoogle Scholar
  37. 37.
    Rayne S, Forest K (2010) Estimated gas-phase standard state enthalpies of formation for organic compounds using the gaussian-4 (G4) and W1BD theoretical methods. J Chem Eng Data 55:5359–5364CrossRefGoogle Scholar
  38. 38.
    Kamlet MJ, Dickinson C (1968) Chemistry of detonations. III. Evaluation of the simplified calculational method for chapman-jouguet detonation pressures on the basis of available experimental information. J Chem Phys 48:43–50CrossRefGoogle Scholar
  39. 39.
    Keshavarz MH (2013) A new general correlation for predicting impact sensitivity of energetic compounds. Propell Explos Pyrot 38:754–760CrossRefGoogle Scholar
  40. 40.
    Xiang F, Zhu W, Xiao H (2013) Theoretical studies of energetic nitrogen-rich ionic salts composed of substituted 5-nitroiminotetrazolate anions and various cations. J Mol Model 19:3103–3118CrossRefGoogle Scholar
  41. 41.
    Glasser L, Jenkins HD (2004) Standard absolute entropies, S°298, from volume or density. Thermochim Acta 414:125–130CrossRefGoogle Scholar
  42. 42.
    Meng ZY, Zhao FQ, Xu SY, Ju XH (2017) Computational study of azole salts as high-energy materials. Can J Chem 95:691–696CrossRefGoogle Scholar
  43. 43.
    Jing M, Li H, Wang J, Shu Y, Zhang X, Ma Q, Huang Y (2014) Theoretical investigation on the structure and performance of N, N′-azobis-polynitrodiazoles. J Mol Model 20:2155–2163CrossRefGoogle Scholar
  44. 44.
    Schmidt MW, Gordon MS, Boatz JA (2005) Triazolium-based energetic ionic liquids. J Phys Chem A 109:7285–7295CrossRefGoogle Scholar
  45. 45.
    Yang G (2010) Amine salt–catalyzed synthesis of 5-substituted 1-tetrazoles from nitriles. Synth Commun 40:2624–2632CrossRefGoogle Scholar
  46. 46.
    Li J (2010) Relationships for the impact sensitivities of energetic C-nitro compounds based on bond dissociation energy. J Phys Chem B 114:2198–2202CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  • Cong Zhang
    • 1
  • Feng-Qi Zhao
    • 2
  • Si-Yu Xu
    • 2
  • Xue-Hai Ju
    • 1
  1. 1.Key Laboratory of Soft Chemistry and Functional Materials of MOE, School of Chemical EngineeringNanjing University of Science and TechnologyNanjingPeople’s Republic of China
  2. 2.Laboratory of Science and Technology on Combustion and ExplosionXi’an Modern Chemistry Research InstituteXi’anPeople’s Republic of China

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