US20120291931A1

US20120291931A1 - Composite compound including explosive and modifier for explosive and method of manufacture thereof

Info

Publication number: US20120291931A1
Application number: US13/473,369
Authority: US
Inventors: Ivanov Yuri Alexandrovich; Frolov Alexander Yurievich; Osinin Vladimir Valerievich; Perevezentzev Vladimir Mikhaylovich
Original assignee: McDermott Will and Emery LLP
Current assignee: IFO LLC; IFOKHIM LLC; McDermott Will and Emery LLP
Priority date: 2006-10-16
Filing date: 2012-05-16
Publication date: 2012-11-22
Also published as: JP2010506821A; RU2318789C1; US20100096050A1; EP2128117A2; WO2008048146A3; EP2128117A4; WO2008048146A2

Abstract

Universal modifiers from the class of organic and inorganic acids and their salts of new power systems of driving force on the basis of complex complete or/and incomplete nitrates (nitroesters) monoatomic (alcohols, alkanes), diatomic (diols, glycols, alkanediols), triatomic (triols, glycerin), multinuclear (of absolute valence) alcohols, cellulose, as well as nitroamines (nitramines), azides (azoimides), nitro compounds and compositions with mixed groups and their mixtures purposefully modifying their thermodynamic parameters, mechanical, physical, chemical, biochemical properties.

Description

RELATED APPLICATIONS

This application is a Divisional of U.S. application Ser. No. 12/445,387, filed on Apr. 13, 2009, which is the U.S. National Phase under 35 U.S.C. §371 of International Application No. PCT/RU2007/000556, filed on Oct. 12, 2007, which in turn claims the benefit of Russian Patent Application No. RU 2006136245, filed on Oct. 16, 2006, the disclosures of which Applications are incorporated by reference herein.
The present application relates to modifiers from the range of organic and inorganic compositions, capable to modify their thermodynamic parameters, physical, chemical, biochemical properties for explosives, including gas generating compositions, rocket fuels and gunpowders based thereon.
It is known, that when interacting, such as by etherification, monoatomic (alkanols, alcohols), diatomic (alkanediols, glycols, diols), triatomic (triols, glycerin), multinuclear (absolute valence) alcohols and their possible isomers with a mixture of nitric and sulfuric acids, corresponding complex, complete or/and incomplete ethers of nitric acid (nitrate ethers, nitric ethers, nitrates) are readily formed. [1-5] These nitric acid ethers are to some extent explosive. Nitrates of monoatomic alcohols are less explosive than nitrates of multinuclear alcohols [3], and as such, define their application as brisant substances [3], which are rapidly decaying substances which release great volumes of strongly heated gases [2, 5]. These nitric acid ethers are also known as shattering explosives [1] used in blasting operations [1-5], but are inapplicable in small arms [1-5] as a shattering explosion capable of breaking a gun barrel, resulting in the projectile not having time to leave the gun barrel [1].
One such representative of an explosive is the complex complete ether of triatomic alcohol (glycerin) and nitric acid, the glycerine trinitrate sometimes referred to as nitroglycerine [1, 3-5]. Glycerine trinitrate explodes from compression [1], heating [5], impact, shock, detonation, such as explosion of a fuse of mercuric fulminate, self-decomposition [2], and simple touch [3]. However, the simplicity of synthesising glycerine trinitrate, its low-stage and low-waste, as well as availability and cheapness of initial substances or starting materials for producing glycerine trinitrate makes its manufacturing economic. The constancy of structure as a target product, and insignificant quantities of impurities, which are very important when making compositions based thereon, makes glycerine trinitrate a rather promising composition as compared to other substances of similar application [1-5].
For example, glycerine trinitrate is well known for use in bibasic gunpowders [1-5], and various kinds of dynamite [1-5].
Glycerine trinitrate in the pure state is not applied because of its extreme instability, and during its decomposition an enormous quantity of energy is liberated as heat and a large volume of the heated gases: nitrogen, water, carbon dioxide are liberated. In addition, oxygen in free condition is liberated, [1, 2] which may be used for amplification for explosive action of glycerine trinitrate when mixed with combustible materials including ethers of nitric acid of monoatomic, diatomic, triatomic and multinuclear alcohols, as well as cellulose [1-5]. Thus, it is possible to obtain dynamites with active and inactive weight [1], for example, fossil meal, a special kind of silica (porous SiO₂, kieselguhr) [1-5].
With glycerine trinitrate, other nitrates of alcohols became important as explosives, such as complex complete or/and incomplete ethers of alcohols and nitric acid, for example, methyl nitrate, ethyl nitrate [4], ethylene glycol dinitrate [2,4], propylene glycol dinitrate [2], mannitol hexanitrate, pentaerythritol tetranitrate [1] and so on [6, 7, 8]. These other nitrates of alcohols are safer to operate as compared to glycerine trinitrate, but are also unsuitable for use when shooting with fire-arms.
It is known that in a molecule of cellulose formed from a molecule of glucose, the alcohol hydroxyl groups of glucose persist. As such, cellulose is in the class of alcohols and has certain properties of alcohols [1-5]. A molecule of cellulose contains three hydroxyl groups, therefore during its interaction (etherification) with a mixture of nitric and sulfuric acids the complex complete and incomplete nitrate ethers of cellulose are formed. For example, depending on reaction conditions of etherification, the residues of nitric acid can replace one, two or all three hydroxyls thus forming mononitrate, dinitrate and trinitrate of cellulose, respectively [or mononitro, dinitro and trinitro cellulose] [5].
It is known that trinitro cellulose or pyroxylin, in which all three hydroxyls are replaced by residues of nitric acid [1-5], as well as glycerine trinitrate, is a detonating explosive featuring high energy and it is applied as a shattering explosive in blasting works. However, trinitrocellulose is not applied when shooting from gun and rocket weapons as the shattering explosion would break the installation before the projectile would achieve movement [1-5]. To use trinitro cellulose in gun systems, it is necessary to slow down the speed of its combustion so as to gradually accrue the pressure of formed gases to set a projectile in motion and push it out from the gun [1-5]. To reduce the speed of its combustion, trinitro cellulose is gelled using various solvents, for example acetone, vinegar amyl ether and others [1]. Trinitrate of cellulose then swells and forms dense jellylike mass; such a mass is used for pressing tapes of various thickness and sizes which after drying may be applied as a smokeless gunpowder. These explosive gels burn more slowly than trinitrate of cellulose and enable use for shooting from gun and rocket installations. To obtain a weapon grade smokeless gunpowder, the explosive gels are cut in fine slices.
It is known that trinitrate of cellulose is also gelled by using glycerine trinitrate. Thus, the formed mass represents a special kind of dynamite also used in blasting works under the name “blasting gelatin” [1]. The properties of trinitrate of cellulose are similar to those of similar complete or incomplete ethers formed during interaction of corresponding alcohols with a mixture of nitric and sulfuric acids. Thus, the principles of the approach to purposeful modification of thermodynamic parameters, and stability modifications negatively influencing the properties and quality of trinitrate of cellulose are authentic, as well as the substances applied as universal modifiers of new composite structures of compoundings of power systems of driving force based thereon. Some grades of smokeless gunpowders consist of a mixture of trinitrate of cellulose and ˜30% of glycerine trinitrate [4]. Thus, the use of one universal modifier allows not only to improve the compatibility of components in an explosive mixture, but also to exclude or reduce the general contents of various components, as the use of the universal modifier renders the use of many other components unnecessary for obtaining required properties. Furthermore, and also to provide additional improvement of other properties, including, bio-, radio-, light, thermal, chemical and antioxidizing stability may be obtained in the system when only one of our proposed universal modifiers is used in the mixture.
Further to our study of materials of periodic and patent literature concerning the use of explosives and compositions based thereon, one main drawback of the constant and limited set of additives which do not feature sufficient efficiency and versatility, and the compositions created from these additives, is that many problems related to sensitivity, temperature, pressure, volume of formed substances, their structures and ecological compatibility, speed of burning and its transition to detonation are present.
Till now there are intensive works for creating new composite compounds of explosives having universal properties.
It is known that smokeless gunpowders are produced on the basis of nitrates of cellulose in structure with various softeners. There are smokeless gunpowders on the basis of glycerine trinitrate (ballistites) and pyroxylin [the Soviet encyclopaedic dictionary.-M.: Soviet encyclopedia, 1983, p. 119]. Smokeless gunpowders, both artillery ballistite and pyroxylin, and ballistite rocket firm fuel differ greatly in
-mass parameters, structure, sensitivity to various mechanical influences, power parameters, speed of burning, and sensitivity to a detonation pulse. Currently, the explosives most used in the industry are hexogen and octogen. However they possess high sensitivity to mechanical influences and cannot be applied without input of retarders in their structure [Patent RU No 22226522, Cl. C 06 B 25/00,21/00,25/24,31/32, C 06 D 5/06, publ. Apr. 10, 2004, Bul. No 10].
There are known powder explosive compositions on the basis of smokeless pyroxylin, artillery ballistite gunpowders, ballistite solid rocket fuels, and their mixtures [Patents RU NoNo 1810321; 2021239; 2026274; 2026275; 2046117; 2074160; 2092473; 2099396; 2130446; 2176632; 2086524 C1 Aug. 10, 1997; 2122990 C1, Dec. 10, 1998; 2096396 C1, Nov. 20, 1997; GB 1265718, Mar. 8, 1992; GB 1307967, Feb. 21, 1973; U.S. Pat. No. 3,235,425; 3,186,882, Jun. 1, 1965; U.S. Pat. No. 3,713,917, Jan. 30, 1973; U.S. Pat. Nos. 4,555,276; 5,445,690; Kuk M. A. Industrial explosives science—M.: Nedra, 1980, p. 28.]. In materials of these works, as a rule, structures of explosives possess significant sensitivity to mechanical and other influences, thus the required result is not always reached.
It is known that till now hexogen and octogen are applied as brisant explosives which possess high sensitivity and consequently cannot be applied in the pure state. To lower their sensitivity and maintaining safe handling, hexogen and octogen are used only in combination with various unexplosive additives or retarders, for example, unsaturated and saturated solid hydrocarbons, such as wax, paraffin, ceresin and other chemical substances similar to such compositions as stearin, and also various rubbers and polymers plasticized by inactive and active softeners. Powerful explosives usually contain in their structure retarders from 2.5 up to 10 mass % [Patent RU 2252925 CL. C 06 B 25/34, 45/22, Oct. 28, 2003, publ. May 27, 2006. Bul. No 15]. In this work [LLNL Explosive Handbook. Properties of Chemical Explosive and Explosive Simlants/Dobratz B. M., Livermore, Calif., 1981.] explosive structures containing hexogen (95-93.5%) and a retarder (5-6.5%), consisting of a mixture of synthetic ceresin (45%), natural ceresin (15%), stearin (38.8%) and orange fat-soluble dye (1.2%) are cited; octogen (97.5%) and a retarder (2.5%), consisting of polymethyl methacrylate (1.2%), graphite (0.5%), and oxysin (0.8%), and other widely used mixtures of explosive compounds.
There 2,4,6,8,10,12-hexa-nitro-2,4,6,8,10,12-hexa-azo-tetracyclo (5,5,0,0^3,11, 0^5,9) dodecane is a more powerful explosive from the class of cyclic nitramines as compared to hexogen and octogen, and as to chemical stability and sensitivity it is similar to octogen. 2,4,6,8,10,12-hexa-nitro-2,4,6,8,10,12-hexa-azo-tetracyclo (5,5,0,0^3,11, 0^5,9) dodecane features high sensitivity to of mechanical influences and low chemical stability. [Patent RU No 2199540 from Apr. 26, 2001. Method for obtaining the 2,4,6,8,10,12-hexa-nitro-2,4,6,8,10,12-hexa-azo-tetracyclo (5,5,0,0^3,11,0^5,9) dodecanes. Sysoliatin S. V., Lobanova A. A., Chernikova J. T.].
In the work [U.S. Pat. No. 5,587,533, High perfomanse pressable explosive compositions/Braithwaite P. C., Lund O. K., Wardle R. B.] explosive compositions based on 2,4,6,8,10,12-hexa-nitro-2,4,6,8,10,12-hexa-azo-tetracyclo (5,5,0,0^1,11,0^5,9) dodecane and a retarder (an active binding additive) in quantity of 5-10 mass %, consisting of polyglycidil nitrate, polyglycidil azide and others are discussed.
In the work [Simpson R. L., Urtiew P. A., Ornellas D. L., et al. CL-20 performance exceeds that of HMX and its sensitivity is moderate//Propellants, Explosives—1997—No 22—Pp. 249-255.], a composition consisting of 2,4,6,8,10,12-hexa-nitro-2,4,6,8,10,12-hexa-azo-tetracyclo (5,5,0,0^1,11,0^5,9) dodecane (CL-20) retarded by polyurethane polymer Estane-5703-P, is discussed, and this composition features higher sensitivity than the composition of octogen with the same polyurethane polymer.
In the work [Patent RU 2252925, C1. C06 B 25/34, 45/22, Oct. 28, 2003, publ. May 27, 2006. Bul. No 15] a composition based on 2,4,6,8,10,12-hexa-nitro-2,4,6,8,10,12-hexa-azo-tetracyclo (5,5,0,0,^3,11,0^5,9) dodecanes (98.5-97 mass %) and a retarder (1.5-3 mass %) is discussed and consists of stearic acid and/or paraffin and/or ceresin or their mixtures. Works for improving the properties of explosive compositions on the basis of these compounds (substances) are still in progress and there is some success. However, it is rather difficult to apply them safely according to their intended purpose because of their instability.
It is known that application of liquid explosive compositions and their composite structures of compoundings is one important and promising direction for solving certain tasks of various special-purpose designations. Consistent solutions on their being liquid or heterogeneous under usual conditions are easier to produce as compared to solid explosives. [Patent RU 2063944, C1. C 06 B 25/10, 1996, publ. in Bul. No 20 from Jul. 20, 1996].
However, the use of liquid explosives such as glycerine trinitrate or compositions based thereon is seriously limited because of their very high sensitivity to various mechanical influences. However, high-energy substances, in particular glycerine trinitrate, are used widely in explosive compositions of various purpose. To reduce their sensitivity to various influences, some retarding additives are used. Tri-nitro-glycerin explosive compositions for various special-purpose designations, including industrial explosives, such as pobedits, detonites and similar compounds are created by using such retarding additives. Though these compositions feature rather low sensitivity to mechanical influences due to low content (approximately 10%) of glycerine trinitrate, for the same reason they feature low energy characteristics.
A number of compositions on the basis of glycerine trinitrate are known [U.S. Pat. No. 3,108,916, C1. C 06 B 19/02, 1963. U.S. Pat. No. 2,988,436, C1. C 06 D 5/04 1961. U.S. Pat. No. 4,011,114, C1. C 06 B 45/10, 1976]. These compositions feature rather high sensitivity to mechanical influences and low energy properties because of low oxygen factor. Trimethylolethane trinitrate is a known retarder for glycerine trinitrate. [U.S. Pat. No. 3,423,256, C1. C 06 B 3/001969.] However, an essential decrease in sensitivity of liquid explosive composition is reached only in case of introducing a large amount of retarder in glycerine trinitrate, and as a result, its explosive characteristics decrease sharply. In view of the above, the problem of creating high-energy explosive heterogeneous solutions featuring enough low sensitivity to various mechanical influences is rather urgent and the problem is not yet solved because the common drawback of the described explosive compositions is the high sensitivity to various mechanical influences. Therefore creating new explosive compositions using modifiers described in the present disclosure that were unknown earlier for the given purpose, with mechanical and other properties set depending on the object in view, is novel.
The common drawback of explosive compositions described in the above-mentioned references is their high sensitivity to various mechanical influences.
The task of creating explosives designed for manufacturing extended and sheet charges, detonating tape and other similar materials for special explosive works is rather urgent and promising. There are known plastic explosive substances hexoplasts HP-74; HP -87; HP -87K [<<The list of recommended industrial explosive materials.>> M: Nedra, 1977, page 28.] and elastic explosives [U.S. Pat. No. 3,723,204, C1. 149-19 C 06B 3/00, C 06C 1/100, 1973; Patent UK No 1297706, C1. C 06B 15/01, 1970], such explosives in the class of efficient crystal explosives, including hexogen in a combination with various binding substances, for example, rubbers which content in composite materials ranges from 13 to 30%. These compositions are used for special explosive works. However they feature high sensitivity to various mechanical influences, thus the frequency of explosions during phasic test is 70% and the transition of burning of these compositions to their explosions is quick and fast.
There is a known explosive composition containing colloxylin as a basis, plasticized by liquid nitroesters of multinuclear alcohols, for example, glycerine trinitrate, as well as a stabilizer for chemical stability. [Svetlov B. Ya. and Yaremenko N. E. The theory and properties of industrial explosives. M.: Nedra, 1973, p. 185]. This explosive composition features high explosibility.
There is a known explosive composition also containing colloxylin as a basis, and plasticized by liquid nitroesters of multinuclear alcohols, for example, by glycerine trinitrate, stabilizer for chemical stability and fine-dyspersated particles of high density substance. The stabilizer for chemical stability is centralite. [Patent RU 2105746, C1. C 06 B 25/18. Publ. 27.02.1998 in Bul. No 6].
Till now creating the gas generating compositions, including those for fire extinguishers, safety bags and other pneumatic devices is rather urgent and promising. There is a known gas generating composition for fire extinguishers on the basis of ether of cellulose which contains 30 to 40% of softener substance (composition) with the formula
[U.S. Pat. No. 3,873,579, C1. C 06 D 5/06, 1975]. The temperature of burning of this composition is 2000 to 2500° K. Another gas generating composition for fire extinguishers contains in mass % dibutyl phthalate (17), acetate of cellulose (7.6), N-methyl-p-nitroaniline (1), nitrate of cellulose (30.4), trinitrate of pentaeritrit (37), ethyl centralite (2), tin oxides (5) while the temperature of its burning is 1700° K. [U.S. Pat. No. 3,639,183, C1. C 06 D 5/06, 1972]. The purpose of improvement of such compositions is lowering the sensitivity to various mechanical influences and lowering the temperature of burning; and the main components of such compositions remain almost without qualitative and quantitative changes. Thus there is known a gas generating composition consisting in mass % of ratio of nitrate of cellulose (59-69) bases, 1,6-diazido-2-acetoxy-4-oxa-hexane (30-40) as softener, while the other additives are dimethyl diphenyl urea (0.5-0.6) and vaseline (0.4-0.5), and the temperature of burning of this composition is 1450° K [Copyright certificate RU No 918289, M C1. C 06 D 5/06. UDC 662.16 (088.8), publ. Apr. 7, 1982. Bul. No 13. date of publication of the description Apr. 10, 1982], however all these compositions feature higher sensitivity to mechanical influences, high temperature and high speed of burning.
Earlier it was considered that acids promote decomposition of many explosives [L. A. Smirnov <<The equipment for manufacturing ballistite gunpowders using auger technology and charges made of them>>, edited by L. V. Zabelina. M.: 1997]. However, there is known a stabilizer of chemical stability of gunpowder, solid rocket fuel and gas generating composition on the basis of nitrocellulose, a boric or phosphorous acid, or an organic acid or its salt having the formula (I)

where R═—H, —OH, —COOH, —COONa
R₁═—H, —OH, —COOH; —COONH₄, —COONa,
R₂═—H, —OH, —COOH, —COONa, the residue of composition having the formula

where R₁or R have above-stated values,

or having the formula (II):

where R═—OH, —OK, —ONH₄, —ONa,
R₁=−bond or-C₂H₄,
R₂is absent or means H₂O or 2H₂O [Patent RU 2244703, C1. C06 B 25/18, 21/00, 25/28 C06 D 5/00, Dec. 2, 2003, publ. Jan. 20, 2005 Bul. No 2].

An engineering problem discussed in the present disclosure consists in creating a universal modifier for explosives from a range of composite complete or incomplete nitrates of monoatomic, diatomic, triatomic or multinuclear alcohols, nitrocelluloses, nitroamines, azides, nitrobenzenes or nitroalkanes. Introducing such a modifier in these explosives allows one to modify their thermodynamic parameters, physical, chemical, and biochemical properties and to create on the basis of these explosives, with the introduced modifiers, explosive and unexplosive composite compounds having liquid, heterogeneous or solid aggregate state depending on objects in view with required properties that may vary upon the ratio of components included in the composition.
The technical result of the present disclosure is the inhibition of premature decomposition of explosives at all the initial stages of development of this process, with its subsequent initiation as a result of smooth and fast growth of temperature thus leading to explosive decomposition or burning depending on the sufficient surplus of oxygen in the system, both due to oxygen-containing compounds, and as a result of emission of oxygen in a pure state when decomposing the substances included in explosive composition, i.e. controlling the rate of their decomposition, as well as decrease in sensitivity of explosives to various mechanical influences, and improvement of the degree of compression.
The technical result is reached by using known, cheap and accessible compositions belonging to inorganic acids, organic acids and their salts as a universal modifier for explosives from the range of complex complete or incomplete nitrates of monoatomic, diatomic, triatomic or multinuclear alcohols, nitrocellulose, nitroamines, nitroanilines, azides, nitrobenzenes, nitroalkanes and their mixtures, where the compositions belonging to inorganic or organic acids or their salts are chosen from the following group: orthoboric acid, phosphorous acid or orthophosphoric acid, or a composition having the formula (1):

where R═—H, —OH, —COOH, COONa,
R₁═—H, —OH, —COOH, —COONH₄, —COONa,
R₂═—H, —OH, —COOH, —COONa, and R₁and R have
the above-stated values, formula (2):

where R═—OH, —OK, —ONH₄, —ONa,
- R₁=−single bond or —C₂H₄,
- R₂is absent or H₂O or 2H₂O,
or formula (3):

where if R═—NO₂; R₁═R₂═—H, it is 2-nitrobenzoic acid (o-nitrobenzoic acid),
if R₁═—NO₂; R═R₂═—H, it is 3-nitrobenzoic acid (m-nitrobenzoic acid),
if R₂═—NO₂; R═R₁═—H, it is 4-nitrobenzoic acid (p-nitrobenzoic acid).
Specific examples of acids and salts of the above mentioned formulas include the following:

The composition having the formula (1) where R═—OH, R₁═—COOH, R₂═
is the 5,5′-methylenedisalicylic acid.
The composition having the formula (1) where R═—OH, R₁═—COONH₄, R₂═
is the diammonium salt of 5,5′-methylenedisalicylic acid.
The composition having the formula (1) where R═H, R₁═—COOH, R₂═—H is orthophthalic acid.
The composition having the formula (1) where R═H, R₁═—COOH, R₂═—COOH is isophthalic acid.
The composition having the formula (1) where R═—COOH, R₁═H, R₂═—COOH is terephthalic acid.
The composition having the formula (1) where R═—COONa, R₁═H, R₂═—COONa is the disodium salt of terephthalic acid.
The composition having the formula (1) where R═H, R₁═—COONa, R₂═—COONa is the disodium salt of metaphthalic acid.
The composition having the formula (1) where R═—COOH, R₁═—OH, R₂═—H is salicylic acid.
The composition having the formula (1) where R═—OH, R₁═—COONa, R₂═—H is the sodium salt of salicylic acid.
The composition having the formula (1) where R═—COOH, R₁═—H, R₂═—H═—H is benzoic acid.
The composition having the formula (1) where R═—COONa, R₁═—H, R₂═—H is the sodium salt of benzoic acid.
The composition having the formula (1) where R═—COOH, R₁═—H, R₂═—OH is para-oxybenzoic acid.
The composition having the formula (1) where R═—H, R₁═—COOH, R₂═—OH is meta-oxybenzoic acid.
The composition having the formula (2) where R═—OH, R₁=single bond, R₂— absent, is oxalic acid.
The composition having the formula (2) where R═—OH, R₁=single bond, R₂=2H₂O is oxalic acid dihydrate.
The composition having the formula (2) where R═—OK, R₁=single bond, R₂— absent, is lemon salt.
The composition having the formula (2) where R═—ONa, R₁=single bond, R₂— absent, is sodium oxalate.
The composition having the formula (2) where R═—ONH₄, R₁=single bond, R₂— absent, is ammonium oxalate.
The composition having the formula (2) where R═—OH, R₁═—C₂H₄, R₂— absent, is succinic acid.
The listed compositions have, basically, rather low temperature of decomposition and rather high temperature of ignition, thus, a part of thermal energy will be spent for decomposing these substances when introducing them into the specified explosives. Thus, there will be a decrease of general temperature of formed gases with simultaneous increase in their volumes and there will be a proportional development of pressure due to gases formed as a result of decomposition and/or burning of the listed compositions.
Explosives from the range of complex complete or incomplete nitrates of monoatomic, diatomic, triatomic or multinuclear alcohols, nitrocelluloses, nitroamines, nitroanilines, azides, nitrobenzenes or nitroalkanes, where it is offered to introduce the above modifiers, may be the following explosives:
Explosives having the formula:

where R or/and R₁═—CH₃, —H,

n=1−4;
if R═R₁═—CH₂—O—NO₂; n=1, is glycerol trinitrate (nitroglycerine);
if R═R₁═—H; n=1, is methyl nitrate;
if R═—CH₃; R₁═—H; n=1, is ethyl nitrate
if R═—CH₂—O—NO₂; R₁═—H; n=1, is ethylene glycol dinitrate;
if R═—CH₃; R₁═—CH₂—O—NO₂; n=1, is propylene glycol dinitrate;
if R═R₁═—CH₂—O—NO₂; n=4, is mannitol hexanitrate (nitromannitol);
if R═—CH₂CL; R₁═—CH₂—O—NO₂; n=1, is monochlorhydrin dinitrate;
if R═—H; R₁═

it is pentaerythritol tetranitrate (penthrite);
Explosives including:

Nitroisobutyl glycerinetrinitrate having the formula:

Diethanol-N-nitroamine dinitrate (DINA) having the formula

Diglycerin tetranitrate having the formula

Diethyleneglycol dinitrate (diglycol dinitrate, dinitrodiglycol) having the formula

Trinitrate of cellulose (trinitro cellulose, trinitrate of cellulose, trinitrate) —[C₆H₇O₂(O—NO₂)₃]n;
Ethylene-N,N′-dinitramine (EDNA)
NO₂NH—(CH₂)₂—NHNO₂;
Nitroguanidine (NH₂)₂C═NNO₂
Nitrourea NH₂CONHNO₂;
N,N′-bis(β,β,β-trinitroethyl)carbamide, or N,N′-bis(β,β,β-trinitroethyl)urea (BTNEM)

Explosive having the formula:

where if R₁═—NO₂; R₂═R₃═R₄═R₅═—H, it is an N-nitroaniline;
if R₁═R₄═—NO₂; R₂═—CH₃; R₃═R₅═—H, it is 4-nitrophenyl-N-methylnitroamine (N-nitro-N-methyl 4-nitroamine);
if R₁═R₅═—H; R₂═—CH₃; R₃═R₄═—NO₂, it is 2,4-dinitro-N-methylaniline;
if R₁═R₃═R₄═—NO₂; R₂═—CH₃; R₅═—H, it is 2,4-dinitrophenyl-N-methylnitroamine (N-nitro-N-methyl-2,4-dinitroaniline);
if R₁═—H; R₂═—CH₃; R₃═R₄═R₅—NO₂, it is N-methyl-2,4,6-trinitroaniline;
if R₁═R₃═R₄═R₅═—NO₂; R₂═—CH₃, it is N-methyl-N,2,4,6-tetranitroaniline (N-methyl-N-nitro-2,4,6-trinitroaniline);
if R₁═—H; R₂═—CH₃; R₃═R₄═R₅—NO₂, it is N-methyl-2,4,6-trinitroaniline;
if R₁═R₃═R₄═R₅═—NO₂; R₂═—CH₃, it is N-methyl-N,2,4,6-tetranitroaniline (N-methyl-N-nitro-2,4,6-trinitroaniline or 2,4,6-trinitroaniline-N-methylnitroamine, tetryl);
if R₁═—H; R₂═—CH₃; R₃═R₄═R₅—NO₂, it is N-methyl-2,4,6-trinitroaniline;
R₁═R₃═R₄═R₅═—NO₂; R₂═—CH₃, it is N-methyl-N-methyl-N-2,4,6-tetranitroaniline (N-methyl-N-nitro-2,4,6-trinitroaniline or 2,4,6-trinitroaniline-N-methylnitroamine, tetryl);
If R₁═R₂═—H; R₃═R₄═R₅═—NO₂, -it is 2,4,6-trinitroaniline;
Explosive having the formula:

if R₁═—OH; R₂═R₄═R₆═—NO₂; R₃═R₅═—H, it is 2,4,6-trinitrophenol (picric acid);
if R₁═Cl; R₂═R₄═R₆═—NO₂; R₃═R₅═—H, it is 2,4,6-trinitrochlorbenzene;
if R₁═R₃═—OH; R₂═R₄═R₆═—NO₂; R₅═—H, it is 2,4,6-trinitroresorcinol (TNR, stifnine acid);
if R₁═—OCH₃; R₂═R₄═R₆═—NO₂; R₅═—H, it is 2,4,6-trinitroanisol (2,4,6-trinitro methoxybenzene);
if R₁═R₃═NH₂; R₂═R₄═R₆═—NO₂; R₅═—H, it is 1,3-diamino-2,4,6-trinitrobenzene (2,4,6-trinitrophenylenediamine);
if R₁═R₃═R₅═NH₂; R₂═R₄═R₆═—NO₂, it is 1,3,5-triamino-2,4,6-trinitrobenzene;
if R₁═CH₃; R₂═R₄═R₆═—NO₂; R₃═R₅═—H, it is 2,4,6-trinitrotoluene (trotyl, a TNT);
if R₁═—CH₃; R₂═R₄═R₆═—NO₂; R₃═OH; R₅═—H, it is trinitrocreosol;
if R₁═R₃═R₆═—NO₂; R₂═R₄═R₆═H, it is 1,3,5-trinitrobenzene;
if R₁═—CH₃; R₂═R₄═R₆═—NO₂; R₃═

R₅═—H, is 1-methyl-3-tert-butyl-2,4,6-trinitrobenzene;

if R₁═R₃—CH₃; R₂═R₄═R₆═—NO₂;
R₅═

is 1,3-dimethyl-5-tert-butyl-2,4,6-trinitrobenzene;

if R₁═R₃—CH₃; R₂═R₄═R₆═—NO₂; R₅═—H, it is 2,4,6-trinitro meta-xylene (1,3-dimethyl-2,4,6-trinitrobenzene);

Isomers of Tetranitrobenzene;

1,3,5-trinitro-1,3,5-triazacyclo-hexane (hexogen)

1,3,5,7-tetranitro-1,3,5,7-tetraazocyclooctane (cyclotetramethylene-tetranitroamine, octogen)

2,2′,4,4′,6,6′-hexanitrodiphenyl;
2,2′,4,4′,6,6′-hexanitrodiphenylsulfide (hexyd);
2,2′,4,4′,6,6′-hexanitrodiphenylsulfone;
2,2′,4,4′,6,6′-hexanitrostilbene;
3,3′-diamino-2,2′,4,4′,6,6′-hexanitro-diphenyl;
2,4,6,-hexanitrodiphenylamin;
Isomers of trinitronaphthalene;
Isomers of tetranitronaphthalene;
Nitroalkanes:
C(NO₂)_4-tetranitromethane;
CH₂(NO₂)CH₂NO₂-1,2-dinitroethane;
CH₃CH(NO₂)₂-1,1-dinitroethane;
CH₃C(NO₂)₃-1,1,1-trinitroethane;
C₂(NO₂)₆-hexanitroethane;
C₆(NO₂)₃(N₃)₃-trinitrotriazidobenzene;
C₃N₃(N₃)₃-cyanurtriazide,

The above cited explosives and their mixtures do not limit the possible assortment of various other explosives that in combination with the described modifiers from between organic acids, inorganic acids and their salts or other of substances, featuring similar properties and used as universal modifiers. The above explosives may also similarly influence various parameters and properties having new energy systems of driving force created on their basis with characteristics required for any specific purpose. The same explosive composition may feature different speeds of decomposition depending on the method of its activation. The composition may also exhibit the properties of simple burning, and not passing to detonation or brisances, i.e. to be applied in two-component explosive compositions on the basis of the cited obtained explosives in a combination with the modifiers described herein, as an active principle of a new composite structure of monobasic gunpowders, gas generating compositions with or without using pyroxylin in their composition.
The operating principle of the disclosed modifiers in various composite structures of compounds for the specified classes of explosives is essentially the same. The modifiers and substances having similar properties under certain conditions may decay and emit gaseous products. In the presence of enough oxygen in the system may result not only in decomposition, but also burning or a combination of these processes. Thus, there may be a thermodynamic effect of significant decrease in temperature and increase in volume of the formed gases, and incidental proportional development of certain pressure. The effect of decrease in temperature of gases is most pronounced in cases where the compositions having the temperature of decomposition that is lower or coincides with the temperature of ignition are used as modifiers. Creating explosive and unexplosive energy systems of driving force with the properties set depending on the object in view is general and universal for all such systems. Using such an effect is rather urgent when creating low erosion, low-kindle or cold gunpowders. When the properties of substances do not satisfy these conditions there may be an increase in total temperature effect. The modifier for our offered explosives may be used in case of the ratio modifier/explosive equal to (0.1-99.9: 99.9-0.1).
To increase the energy characteristics of the described composite structures it is possible to introduce metallic power additives to the compositions.
To provide various consistent properties including plasticity to explosive and unexplosive composite structures, it is possible to use binding, gelatinizing (swelling) and polymeric compositions.

EXAMPLES, ILLUSTRATING THE INVENTION

Research of mixtures of various modifiers and explosives regarding the compatibility and influence of modifiers on heat-resistant characteristics of explosives was performed. It is marked, that introduction of modifiers not only does not reduce the heat-resistant parameters of explosives, but also makes an inhibitory effect on their autocatalytic decomposition. Research was carried out using an installation for defining the temperature of the beginning of intensive decomposition (Tbid) and phase transformations of polymeric materials using the DTC method (differential thermocouple) according to OST B-84-615-72.

Example 1

A thematic example of influence of the offered acids is the influence of oxalic acid (crystalline hydrate) on glycerine trinitrate. In FIG. 1 and FIG. 2 there are the diagrams of decomposition of mixtures of oxalic acids (crystalline hydrate) with glycerine trinitrate in mass ratio 1:2 and 1:5 accordingly. It was found that introducing oxalic acids (crystalline hydrate) does not worsen the heat-resistant characteristics of glycerine trinitrate. It is also determined that the composition is not susceptible to transition of burning to explosion or detonation.
Mixtures of glycerine trinitrate (OST B 84-2386) and oxalic acids (crystalline hydrate) TY standard 2642-001-07500602-97 were prepared from their solutions in ethyl alcohol GOST 18300-87 by mixing at a room temperature and further removal of ethyl alcohol by keeping in exhaust case until a film is formed. The mixing did not cause changes of temperature, color and sedimentation. The compositions have been investigated using a microscope and a significant decrease in heterogeneity was marked with increase of oxalic acid (crystalline hydrate) content. The density of structures was ρ=1.7-1.75 g/cm³(high density compositions).

Example 2

A thematic example of influence of the proposed salts of organic acids is the influence of ammonium oxalate (crystalline hydrate) on glycerine trinitrate. In FIG. 3 there is a diagram of decomposition of a mixture of ammonium oxalate (crystalline hydrate) with glycerine trinitrate in mass ratio 1:1 accordingly. It was found that introducing ammonium oxalate (crystalline hydrate) does not worsen the heat-resistant characteristics of glycerine trinitrate, but also renders inhibitory action on its autocatalytic decomposition. It is also determined, that the composition is not susceptible to transition of burning to explosion or detonation. The mixtures were prepared similarly to those of Example 1.

Example 3

Thematic examples are mixtures of oxalic acids (crystalline hydrate) with glycerine trinitrate, thus the mixtures prepared in mass ratio: composition No 1—1:5, composition No 2—1:2, composition No 3—1:1, composition No 4—2:1 accordingly. The mixtures were been tested for explosive characteristics using a Kast's impact machine OST B 84-892-74 (Sensitivity impact using an impact machine at the bottom limit with instr. No 1 and instr. No 2) and the following results are received:

Composition No 1 with a load of 2 kg and height Ho=250 mm (instr. No 2). The percent of explosions made 80%,
Structure No 2 with a load of 2 kg and height Ho=250 mm (instr. No 2). The percent of explosions made 55%,
Composition No 3 with a load of 10 kg and height Ho=250 mm (instr. No 2). The percent of explosions made 68%,
Composition No 4 with a load of 10 kg and height Ho=250 mm (instr. No 2). The percent of explosions made 0%.

The detonation of glycerine trinitrate is caused when dropping a 2 kg load from a height of Ho=40 mm [9].

Composition No 3 with a load of 10 kg Ho>500 mm (instr. No 1),

Composition No 4 with a load of 10 kg. Ho>500 mm (instr. No 1).
The compositions have been tested for sensitivity to shock-free friction at the bottom limit (OST B 84-894-74) at a speed of disk rotation (friction) of 520 rev/min. Thus, the sensitivity to shock-free friction at the bottom limit of composition No 3 makes Po=>3000 kilogram-force/cm²and of composition No 4−Po=>3000 kilogram-force/cm². The tests were carried out at a temperature of 18° C.
The compositions have been tested for sensitivity to friction at a shock shift at the bottom limit (OST B 84-895-83). Thus, the sensitivity to friction at a shock shift at the bottom limit of composition No 3 was equal to Po=750 kilogram-force/cm²and of composition No 4 Po=1750 kilogram-force/cm².
As a result of tests of samples with various percentage of glycerine trinitrate and oxalic acid (crystalline hydrate), it is possible to obtain the mixture of 50%-60% of glycerine trinitrate and 50%-40% oxalic acid (crystalline hydrate) accordingly, among substances featuring low sensitivity to mechanical influences. Thus, it is possible to operate with them while observing conventional security measures.
The compositions have been tested for speed of explosive transformation (detonation) OST B 84-90074, susceptibility to transition of burning to explosion or detonation—the character of destruction of a pipe with indicating its dimensions and estimating the explosive process according to OST B 84-90074. Thus, the composition with the content of oxalic acid (crystalline hydrate) with glycerine trinitrate of 40%-60% accordingly, has shown the following characteristics: the density ρ=1.75 g/cm³, the speed of detonation D=6370 m/s, the composition is not susceptible to transition of burning to explosion or detonation; the composition with the content of oxalic acids (crystalline hydrate) with glycerine trinitrate of 60%-40% accordingly, has shown the following characteristics: the density ρ=1.7 g/cm³, the speed of detonation D=880-2230 m/s, the composition is not susceptible to transition of burning to explosion or detonation.
For giving various consistent properties including plasticity to such explosive and unexplosive compositions, gelatinating (swelling) and polymeric compositions were used, such as pyroxylin, colloxylin and other compositions in monobasic and bibasic composite materials with the described modifiers. Thematic examples are the obtained structures: oxalic acid (crystalline hydrate) 72%,
CT-30 21%, glycerine trinitrate 7% with speed of burning 0.5 mm/s and temperature of burning ˜800° K. (at P=40 and temperature 20° C.)—the product is plastic, it is susceptible to molding; and oxalic acid (crystalline hydrate) 42%, glycerine trinitrate 42%, PVR (polyvinyl butyral resin) 16% with speed of burning 5 mm/s and temperature of burning ˜1500° K. (at P=40 and temperature 20° C.). The product is plastic, it is susceptible to molding, there is also an expressed influence of the modifier on the speed of burning and temperature of the obtained gases.

Example 4

Another thematic example are the obtained compositions of pyroxylin with salt of methylenedisalicylic acid. Thus when introduting it up to 0.5% of mass, the stability of gunpowders made 3.5 to 4.5 kPa, at a norm of 8 kPa. When introducing the diammonium salt of methylenedisalicylic acid up to 20% of mass, essential decrease in temperature of the formed gases down by 700-800° K. was marked, while maintaining acceptable power of gunpowders.

Example 5

The obtained compositions of pyroxylin with lemon salt may also servea thematic example, because when introducing it up to 0.5% mass, the stability of gunpowders made 3.5-4.5 kPa, at a norm of 8 kPa. When introducing lemon salt up to 20% mass, the obtained compositions had the power of gunpowder comparable to the normal one at a level of 1030 to 1060 kJ/kg.
The obtained data as to characteristics of compositions in the Examples 1 and 2 allow to assume the possibility of their application for modifying the properties of gunpowders, including control of temperature, of the structure of obtained gases.
Alongside with experimental data, thermodynamic calculated values of obtained compositions had good convergence of results and completely confirmed the experimental data.
On the basis that the principle of action of the proposed modifiers for new power systems of driving force for all classes of explosives though essentially the same, however each individual explosive, as well as any other composition possesses certain unique inherent properties (physical, chemical, mechanical and others), that is each new power system of driving force on their basis has its own “know-how” having certain information value, but not influencing on essence of the invention as a whole and that are sometimes inexpedient to open with a view of the further preservation of priority of the trend itself and of the time of research process. Therefore, the obtained data and some results, having certain dependence and convergence in application conditions of our proposed modifiers in a combination with the cited explosive compositions are not always outlined in the description of materials in the text or restricted.

LITERATURE

The List of Documents Quoted and Taken into Account During Examination

1. E. S. Hotinsky. The course of organic chemistry.—Kharkov.: Publishing house of the Kharkov Red Labour Banner Award A. M. Gorky National University, 1959.-724 pp.
2. B. A. Pavlov and A. P. Terentyev. The course of organic chemistry.—Moscow.: National scientific and technical publishing house of chemical literature, 1961.-592 pp.
3. A. E. Chichibabin. Principles of organic chemistry. Volume I.—Moscow.: National scientific and technical publishing house of chemical literature, 1963.-912 pp.
4. A. N. Nesmeyanov, N. A. Nesmeyanov. Principles of organic chemistry. Book one.—Moscow.: Publishing house “Khimiya”, 1974.-624 pp.
5. B. N. Stepanenko. The course of organic chemistry Part I. Aliphatic compositions.—Moscow.: Publishing house “Vysschaya shkola”, 1976.-448 pp.
6. E. Ju. Orlova. Chemistry and technology of brisant substances.—Moscow.: Scientific and technical publishing house OBORONGIZ, 1960.-396 pp.
7. E. Ju. Orlova. Chemistry and technology of brisant substances.—Leningrad.: Publishing house “Khimiya”, 1973.-688 pp.
8. Ju. A. Lebedev, E. A. Miroshnichenko, Ju. K. Knobel. Thermochemistry of nitro compounds. Publishing house “Nauka”. Moscow. 1970.-168 pp.
9. Orlova E. Ju. Chemistry and technology of brisant substances: Textbook for high schools—Ed.,—3rd ed., rev.—L.: Khimiya, 1981.-312 pp.

Claims

1-30. (canceled)

31. A composite compound comprising:

an explosive selected from the group of complex complete or incomplete nitrates of monoatomic, diatomic, triatomic or multinuclear alcohols, nitrocelluloses, nitroamines, azides, nitrobenzenes, nitroanilines, nitroalkanes and mixtures thereof; and

a modifier selected from:

an inorganic acid consisting of at least one from the following group: orthoboric acid, phosphorous acid, or orthophosphoric acid,

an organic acid consisting of at least one from the following group: 2-nitrobenzoic acid, 3-nitrobenzoic acid, 4-nitrobenzoic acid, or

a composition of formula (1)

where R═—H, —OH, —COOH, —COONa,

R₁═—H, —OH, —COOH, 'COONH₄, —COONa,

R₂═—H, —OH, —COOH, —COONa,

and R₁and R have the above-stated values, or

a composition of formula (2):

where R═—OH, —OK, —ONH₄, —ONa, R₁=a single bond or —C₂H₄, and R₂=is absent or H₂O or 2H₂O.

32. The composite compound according to claim 31, wherein the modifier has the composition of formula (1) and is at least one selected from the group consisting of: 5,5′-methylenedisalicylic acid, diammonium salt of 5,5′-methylenedisalicylic acid, orthophthalic acid, isophthalic acid, terephthalic acid, disodium salt of terephthalic acid, disodium salt of metaphthalic acid, salicylic acid, sodium salt of salicylic acid, benzoic acid, sodium salt of benzoic acid, para-oxybenzoic acid, and meta-oxybenzoic acid.

33. The composite compound according to claim 31, wherein the modifier has the composition of formula (2) and is at least one selected from the group consisting of oxalic acid, oxalic acid dihydrate, lemon salt, sodium oxalate, ammonium oxalate, and succinic acid.

34. The composite compound according to any of claims 31 to 33, wherein the explosive is at least one selected from the group consisting of: glycerol trinitrate, methyl nitrate, ethyl nitrate, ethylene glycol dinitrate, propylene glycol dinitrate, mannitol hexanitrate, monochlorhydrin dinitrate, pentaerythritol tetranitrate.

35. The composite compound according to any of claims 31 to 33, wherein the explosive is at least one selected from the group consisting of: nitroisobutyl glycerinetrinitrate, diethanol-N-nitroamine dinitrate, diglycerin tetranitrate, and diethyleneglycol dinitrate.

36. The composite compound according to any of claims 31 to 33, wherein the explosive is trinitrate of cellulose.

37. The composite compound according to any of claims 31 to 33, wherein the explosive is at least one selected from the group consisting of: ethylene-N,N′-dinitramine, nitroguanidine, nitrourea, N,N′-bis(β,β,β-trinitroethyl)carbamide, N,N′-bis(β,β,β-trinitroethyl)urea, N-nitroaniline, 4-nitrophenyl-N-methylnitroamine, 2,4-dinitro-N-methylaniline, 2,4-dinitrophenyl-N-methylnitroamine, N-methyl-2,4,6-trinitroaniline, N-methyl-N, 2,4,6-tetranitroaniline, N-methyl-N, 2,4,6-tetranitroaniline, and 2,4,6-trinitroaniline.

38. The composite compound according to any of claims 31 to 33, wherein the explosive is at least one selected from the group consisting of: 2,4,6-trinitrophenol, 2,4,6-trinitrochlorbenzene, 2,4,6-trinitroresorcin, 2,4,6-trinitroanisol, 1,3-diamino-2,4,6-trinitrobenzene, 1,3,5-triamino-2,4,6-trinitrobenzenes, 2,4,6-trinitrotoluene, trinitrocreosol, 1,3,5-trinitrobenzene, 1-methyl-3-tert-butyl-2,4,6-trinitrobenzene, 1,3-dimethyl-5-tert-butyl-2,4,6-trinitrobenzene, 2,4,6-trinitro-meta-xylene, and an isomer of tetranitrobenzene.

39. The composite compound according to any of claims 31 to 33, wherein the explosive is at least one selected from the group consisting of: 1,3,5-trinitro-1,3,5-triazacyclohexane and 1,3,5,7-tetranitro-1,3,5,7-tetraazocyclooctane.

40. The composite compound according to any of claims 31 to 33, wherein the explosive is at least one selected from the group consisting of: 2,2′,4,4′,6,6′-hexanitrodiphenyl, 2,2′,4,4′,6,6′-hexanitrodiphenylsulfide, 2,2′,4,4′,6,6′-hexanitrodiphenylsulfone, 2,2′,4,4′, 6,6′-hexanitrostilbene, 3,3′-diamino-2,2′,4,4′,6,6′-hexanitrodiphenyl, 2,4,6-hexanitrodiphenylamine, an isomer of trinitronaphthalene, and an isomer of tetranitronaphthalene.

41. The composite compound according to any of claims 31 to 33, wherein the explosive is at least one selected from the group consisting of: tetranitromethane, 1,2-dinitroethane, 1,1-dinitroethane, 1,1,1-trinitroethane, hexanitroethane.

42. The composite compound according to any of claims 31 to 33, wherein the explosive is at least one selected from the group consisting of: trinitrotriazidobenzene or cyanurtriazide.

43. A method of manufacturing an explosive composition comprising the step of:

combining an explosive selected from the group of complex complete or incomplete nitrates of monoatomic, diatomic, triatomic or multinuclear alcohols, nitrocelluloses, nitroamines, azides, nitrobenzenes, nitroanilines, nitroalkanes and mixtures thereof; and

a modifier selected from:

an inorganic acid consisting of at least one from the following group: orthoboric acid, phosphorous acid, and orthophosphoric acid,

an organic acid consisting of at least one from the following group: 2-nitrobenzoic acid, 3-nitrobenzoic acid, and 4-nitrobenzoic acid, or

a composition of formula (1)

where R═—H, —OH, —COOH, or —COONa

R₁═—H, —OH, —COOH, —COONH₄, or —COONa,

R₂′—H, —OH, —COOH, —COONa, or

and R₁and R have the above-stated values, or

a composition of formula (2):

where R═—OH, —OK, —ONH₄, or —ONa,

R₁=a single bond or —C₂H₄,

R₂=is absent or H₂O or 2H₂O.

44. The method according to claim 43, wherein the modifier has the composition of formula (1) and is at least one selected from the group consisting of: 5,5′-methylenedisalicylic acid, diammonium salt of 5,5′-methylenedisalicylic acid, orthophthalic acid, isophthalic acid, terephthalic acid, disodium salt of terephthalic acid, disodium salt of metaphthalic acid, salicylic acid, sodium salt of salicylic acid, benzoic acid, sodium salt of benzoic acid, para-oxybenzoic acid, and meta-oxybenzoic acid.

45. The method according to claim 43, wherein the modifier has the composition of formula (2) and is at least one selected from the group consisting of oxalic acid, oxalic acid dihydrate, lemon salt, sodium oxalate, ammonium oxalate, and succinic acid.

46. The method according to any of claims 43 to 45, wherein the explosive is at least one selected from the group consisting of: glycerol trinitrate, methyl nitrate, ethyl nitrate, ethylene glycol dinitrate, propylene glycol dinitrate, mannitol hexanitrate, monochlorhydrin dinitrate, and pentaerythritol tetranitrate.

47. The method according to any of claims 43 to 45, wherein the explosive is at least one selected from the group consisting of: nitroisobutyl glycerinetrinitrate, diethanol-N-nitroamine dinitrate, diglycerin tetranitrate, and diethyleneglycol dinitrate.

48. The method according to any of claims 43 to 45, wherein the explosive is trinitrate of cellulose.

49. The method according to any of claims 43 to 45, wherein the explosive is at least one selected from the group consisting of: ethylene-N,N′-dinitramine, nitroguanidine, nitrourea, N,N′-bis(β,β,β-trinitroethyl)carbamide, N,N′-bis(β,β,β-trinitroethyl)urea, N-nitroaniline, 4-nitrophenyl-N-methylnitroamine, 2,4-dinitro-N-methylaniline, 2,4-di-nitrophenyl-N-methylnitroamine, N-methyl-2,4,6-trinitroaniline, N-methyl-N, 2,4,6-tetranitroaniline, N-methyl-N, 2,4,6-tetranitroaniline, and 2,4,6-trinitroaniline.

50. The method according to any of claims 43 to 45, wherein the explosive is at least one selected from the group consisting of: 2,4,6-trinitrophenol, 2,4,6-trinitrochlorbenzene, 2,4,6-trinitroresorcin, 2,4,6-trinitroanisol, 1,3-diamino-2,4,6-trinitrobenzene, 1,3,5-triamino-2,4,6-trinitrobenzenes, 2,4,6-trinitrotoluene, trinitrocreosol, 1,3,5-trinitrobenzene, 1-methyl-3-tert-butyl-2,4,6-trinitrobenzene, 1,3-dimethyl-5-tent-butyl-2,4,6-trinitrobenzene, 2,4,6-trinitro-meta-xylene, and an isomer of tetranitrobenzene.

51. The method according to any of claims 43 to 45, wherein the explosive is at least one selected from the group consisting of: 1,3,5-trinitro-1,3,5-triazacyclohexane and 1,3,5,7-tetranitro-1,3,5,7-tetraazocyclooctane.

52. The method according to any of claims 43 to 45, wherein the explosive is at least one selected from the group consisting of: 2,2′,4,4′,6,6′-hexanitrodiphenyl, 2,2′,4,4′,6,6′-hexanitrodiphenylsulfide, 2,2′,4,4′,6,6′-hexanitrodiphenylsulfone, 2,2′,4,4′,6,6′-hexanitrostilbene, 3,3′-diamino-2,2′,4,4′,6,6′-hexanitrodiphenyl, 2,4,6-hexanitrodiphenylamine, an isomer of trinitronaphthalene, and an isomer of tetranitronaphthalene.

53. The method according to any of claims 43 to 45, wherein the explosive is at least one selected from the group consisting of: tetranitromethane, 1,2-dinitroethane, 1,1-dinitroethane, 1,1,1-trinitroethane, and hexanitroethane.

54. The method according to any of claims 43 to 45, wherein the explosive is at least one selected from the group consisting of: trinitrotriazidobenzene and cyanurtriazide.