Elsevier

Journal of Hazardous Materials

Volume 68, Issue 3, 10 September 1999, Pages 155-178
Journal of Hazardous Materials

Review
Studies on energetic compounds: Part XI: Preparation and thermolysis of polynitro organic compounds

https://doi.org/10.1016/S0304-3894(99)00056-4Get rights and content

Abstract

The thermolysis of high energetic polynitro organic compounds has been reviewed in the present communication.

Introduction

The chemistry of polynitro compounds have been described in a good number of publications 1, 2, 3. Kamlet [4], Kamlet and Adolph [5] and Bliss et al. [6] have investigated the relationship between structure of organic compounds with impact sensitivity. The early thermal decomposition reactions are very important from the view point of understanding the mechanism of explosion. Thus, the thermolysis of polynitro compounds have been undertaken using TG/DTA/DTG/DSC techniques in the last decade and most of the work is scattered and, hence, it was thought to review these studies. Further, the data on density, oxygen balance (OB), velocity of detonation (VOD) and impact sensitivity (h50% cm applying 2 kg weight) are also available in literature for some cases and this has also been included in the manuscript. The preparation and mechanistic aspects of thermolysis of polynitro compounds have been described critically in the present review.

Section snippets

Aliphatic nitro compounds

Aliphatic nitro compounds with nearly zero or even positive OB having high melting points are desirable explosives and useful oxidizers for solid propellants. New processes have been discovered to prepare polynitro aliphatic derivatives, in which an additional electronegative moiety has been incorporated into the molecule at the methyl group. This class of compounds have the general formula: RC(NO2)2X, where X=NO2 (trinitromethyl), F (fluorodinitromethyl, Ref. [7]), CN (cyanodinitromethyl) and N

Aromatic nitro compounds

Aromatic nitro compounds are obtained mostly either by the nitration of corresponding aromatic compound or by the oxidation of corresponding amines. Presence of even one nitro group is sufficient to increase the thermal decomposition of aromatic compounds. Nevertheless, aromatic compounds which have two or more nitro groups, exhibit distinctly marked explosive properties. Zeman et al. [15] and Zeman [16] have correlated the thermal decomposition kinetics of polynitro aromatic explosives at

Homocyclic nitro compounds

There is a considerable current interest in the synthesis 43, 44, 45, 46, 47 and thermolysis of polynitrohomocyclic (“cage”) compounds [48]. These are relatively highly strained molecules, that contain several –NO2 substituents, and emerging as high-density energetic materials [49]. Recently, Eaton et al. [50] have developed a systematic methodology for the syntheses of 1,3,5-trinitrocubane and 1,3,5,7-tetranitrocubane as superior high energy shock insensitive explosives. The thermal behaviour

Heterocyclic nitro compounds

Heterocyclic nitro compounds may be aliphatic or aromatic in character, depending upon the electronic constitution. These compounds represent explosives of higher performance compared with analogous aromatic systems, regarding their elemental composition, OB, density, standard heat of formation and VOD. Reactions of a polyatomic substituents with an ortho –NO2 group in an aromatic ring are now widely used to synthesise many heterobicyclic molecules 55, 56, 57. In general, the reactions between

Metal salts of nitro compounds

Metal salts of nitro compounds have long been of interest as energetic additives and/or as burning rate modifiers in composite solid rocket propellants and in explosive compositions. Recently, Rao et al. [139] have prepared Cu(II), Ag(I), Pb(II) salts of 2,4,N-trinitroanilinoacetic acid (2,4,N-TNAAA) and 2,4,6-trinitroanilino acetic acid (2,4,6-TNAAA). The order of thermal stability of salts of 2,4,N-TNAAA is reported to be Ag>Pb>Cu, while for salts of 2,4,6-TNAAA, it is Cu>Ag>Pb.

Metal salts of

Concluding remarks

The thermolysis of energetic compounds is a very complex process. The thermal decomposition of several polynitro organic compounds involve simple bond scission prior to explosion. A notable feature of these reactions is the fact that the aromatic ring remains intact. The next stage of thermolysis involves propagation reaction which involve exothermic oxidation/reduction reactions leading to the formation of low molecular weight and thermodynamically stable gaseous products. It has also been

Acknowledgements

Thanks are due to the Head of Chemistry Department, D.D.U. Gorakhpur University, Gorakhpur for library facilities. The financial assistance by ISRO and DST is also acknowledged.

References (153)

  • S. Zeman et al.

    Thermochim. Acta

    (1984)
  • S. Zeman

    Thermochim. Acta

    (1980)
  • H. Ostmark et al.

    Thermochim. Acta

    (1993)
  • G.K. Williams et al.

    Combust. Flame

    (1994)
  • T.B. Brill et al.

    Combust. Flame

    (1993)
  • R.T. Spear, J. Dagley, J. Org. Energ. Compounds (1996)...
  • P.L. Marinkas, Organic Energetic Compounds, Nova Science Publishers, New York,...
  • T. Urbanski, Chemistry and Technology of Explosives, Vol. 1, Pergamon, PWN — Polish Scientific Publishers, Warzawa,...
  • M.J. Kamlet, The relationship between impact sensitivity with structure of organic high explosives: I. Polynitro...
  • M.J. Kamlet et al.

    Propellants Explos.

    (1979)
  • D.E. Bliss et al.

    J. Energ. Mater.

    (1991)
  • M.J. Kamlet et al.

    J. Org. Chem.

    (1968)
  • J.P. Weber et al.

    Propellants, Explos., Pyrotech.

    (1990)
  • J. Stals et al.

    Aust. J. Chem.

    (1975)
  • F. Volk

    Propellants, Explos., Pyrotech.

    (1985)
  • A.F. McKay

    Nitroguanidines

    Chem. Rev.

    (1952)
  • Y.Y. Zhong et al.

    Propellants, Explos., Pyrotech.

    (1989)
  • K.O. Christe et al.

    J. Energ. Mater.

    (1987)
  • Y. Oyumi et al.

    Propellants, Explos., Pyrotech.

    (1987)
  • T.B. Brill et al.

    Chem. Rev.

    (1993)
  • E.E. Gilbert et al.

    Propellants Explos.

    (1976)
  • A.T. Nielson, R.L. Atkins, W.P. Norris, Hexanitrobenzene, US Pat. 113 (1981)...
  • A.T. Nielson et al.

    J. Org. Chem.

    (1980)
  • M.F. Foltz et al.

    J. Mater. Sci.

    (1996)
  • M. Warman et al.

    J. Org. Chem.

    (1961)
  • D.G. Ott et al.

    J. Energ. Mater.

    (1987)
  • C.D. Hutchinson et al.

    Propellants, Explos., Pyrotech.

    (1984)
  • T.B. Brill et al.

    J. Phys. Chem.

    (1993)
  • J.N. Ayres et al.

    Small scale gap test date compilation

    NOLTR

    (1973)
  • G.A. Luper et al.

    Propellants, Explos., Pyrotech.

    (1996)
  • G.E. Clarkson, T.G. Holden, P.W. Millar, J. Chem. Soc. (1950)...
  • C.D. Hutchinson et al.

    Propellants, Explos., Pyrotech.

    (1984)
  • M. Chayovsky et al.

    J. Energ. Mater.

    (1990)
  • M.J. Kamlet et al.

    J. Org. Chem.

    (1969)
  • G. Om Reddy et al.

    Propellants, Explos., Pyrotech.

    (1983)
  • Y. Hara et al.

    Ind. Explos. Soc. Jpn.

    (1973)
  • T.B. Brill et al.

    J. Phys. Chem.

    (1993)
  • A.T. Nielsen et al.

    J. Org. Chem.

    (1994)
  • R.L. Atkins et al.

    J. Org. Chem.

    (1986)
  • B.M. Cartwright et al.

    J. Energ. Mater.

    (1996)
  • C.P. Achuthan et al.

    J. Sci. Ind. Res.

    (1984)
  • M. Kony et al.

    J. Phys. Chem.

    (1992)
  • F. Zene-guo et al.

    Propellants, Explos., Pyrotech.

    (1992)
  • F. Zene-guo et al.

    Propellants, Explos., Pyrotech.

    (1992)
  • E.E. Gilbert

    Propellants, Explos., Pyrotech.

    (1980)
  • A.P. Marchand et al.

    J. Org. Chem.

    (1984)
  • A.P. Marchand et al.

    J. Org. Chem.

    (1984)
  • G.P. Sollott et al.

    J. Org. Chem.

    (1980)
  • L.A. Paquette et al.

    J. Org. Chem.

    (1985)
  • P.E. Eaton et al.

    J. Org. Chem.

    (1984)
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