HMX and Related Compounds

HMX has usually been associated with the better known explosive RDX (242, R = N02), with which it has usually been admixed. RDX has been regarded as a somewhat more powerful explosive (67MI1), but HMX is 

R1 - R4 = COEt) which was useful as a dispersant and a suspending and blending agent (76USP3978047). 

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These examples of crystal studies in the expl field are but a few of many applications that have been reported. Propellants, primers, pyrotechnics many HE s have been greatly improved by the development of processes which control crystal growth stability of the individual fnaterials. Some further info may be found in the Refs listed below. See also Crystallography, Crystals, etc Refs 1)J.R.Johnson, "Crystallographic Studies of RDX, HMX and Related Compounds OSRD Rept 694 (July 1942) 2)J.R.Johnson,... 

G.B. Kistiakowdcy G.P. Baxter, "The Mechanism of Formation of Cyclonite, OSRD Rept 950 (Oct 1942) 35) J-R- Johnson, Cryst-allographic Studies of RDX, HMX, and Related Compounds , OSRD Rept 694 July 1942)... 

HMX, Octagen, Octahydro-l,3,5,7-tetranitro-l,3,5,7-tetrazine under Secondary Aliphatic Amines HxCDF Hexachlorodibenzofurans under Dioxin and Related Compounds Hydrazine under Ions with Nitrogen Hydrazine Derivatives... 

Refs 1) W.E. Bachmann, "Studies on the Preparation and Properties of RDX" OSRD 82D(Aug 1942)(Structure of HMX BSX 2) W.E. Bachmann, "Studies on RDX(B) and Related Compounds", OSRD 5l86(June 1945) p 156 3) Anon, Summary Technical Report... 

Although many other explosives and explosives-related compounds exist, only the data for 2,4,6-trinitrotoluene (TNT) and its breakdown products, the cyclic nit-ramines (RDX and HMX), tetryl, trinitrobenzene, and nitroglycerin will be reviewed in this chapter. Two dinitrotoluene isomers are also included, as they are still used as explosives in addition to being side-products of TNT synthesis. 

Density plays an important role in the behavior of energetic materials. The pressure in explosions and the impulse produced by the same compound when used as a propellant are related. The shockwave pressure behind the detonation front is proportional to the density squared [3] times the specific impulse [4). The specific impulse itself depends on the volume of gas produced and the heat of combustion per gram of propellant which leads to a further complex dependence on density [5). Thus, the overall dependency of the detonation pressure on the density is greater than quadratic. Two examples of dense energetic materials are the widely used /9-HMX and RDX [6,7], shown in Fig. 1. 

Varied nitrocompounds ranging from such Onitrocompounds as TNT to N-nitrocompounds such as RDX and HMX to 0-nitrocompounds such as trinitroglycerol play a most significant role in energetic compounds. Their preparation is thus of substantial importance. This chapter reviews the most frequently used electrophilic nitration chemistry with particular emphasis on the use of superacidic systems, nitronium salts, and related complexes on which my research group for 30 years has continued to cairv out intensive research. 

G. A. Olah in Chapter 7 reviews some of the most useful methods in preparing nitro compounds (i.e., electrophilic nitrations with superacid systems, nitronium salts, and related Friedel-Crafts type complexes). Polynitro compounds were traditionally and still are the most widely used explosives [e.g., nitroglycerol, trinitrotoluene (TNT), and Af-nitramines (RDX and HMX)]. Methods of preparing nitro compounds thus remain a key part of the synthesis of energetic materials. 

Thirty-four explosives and related materials were analyzed by both GC-MS and LC [23]. The analyzed compounds included nitro derivatives of benzene, toluene, xylene, phenol and naphthalene, as well as TNB, TNT, picric acid, EGDN, NG, PETN, nitroguanidine, RDX, HMX and tetiyl. 

Sullivan, J.H., Jr. Putnam, H.D. Keirn, M.A. Pruitt, B.C., Jr. Nichols, J.C. McClave, J.T. "A Summary and Evaluation of Aquatic Environmental Data in Relation to Establishing Water Quality Criteria for Munitions-unique Compounds. Part 4 RDX and HMX," Final Report, Contract DAMD 17-77-C-7027., Water and Air Research, Inc.,... 

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