US 2012029 1931A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2012/0291931 A1 Alexandrovich et al. (43) Pub. Date: Nov. 22, 2012
(54) COMPOSITE COMPOUND INCLUDING (30) Foreign Application Priority Data EXPLOSIVE AND MODIFER FOR EXPLOSIVE AND METHOD OF Oct. 16, 2006 (RU) ...... 2006136245 MANUFACTURE THEREOF Publication Classification (75) Inventors: Ivanov Yuri Alexandrovich, (51) Int. C. Moscow (RU); Frolov Alexander C06B 25/28 (2006.01) Yurievich, Moscow (RU); Osinin C06B 25/10 (2006.01) Vladimir Valerievich, Moscow (52) U.S. Cl...... 149/94; 149/101 (RU); Perevezentzev Vladimir Mikhaylovich, Mytischi (RU) (57) ABSTRACT Universal modifiers from the class of organic and inorganic (73) Assignee: McDermott Will & Emery acids and their salts of new power systems of driving force on the basis of complex complete or/and incomplete nitrates (21) Appl. No.: 13/473,369 (nitroesters) monoatomic (alcohols, alkanes), diatomic (di ols, glycols, alkanediols), triatomic (triols, glycerin), multi (22) Filed: May 16, 2012 nuclear (of absolute valence) alcohols, cellulose, as well as nitroamines (nitramines), azides (aZoimides), nitro com Related U.S. Application Data pounds and compositions with mixed groups and their mix (62) Division of application No. 12/445,387, filed on Apr. tures purposefully modifying their thermodynamic param 13, 2009, filed as application No. PCT/RU2007/ eters, mechanical, physical, chemical, biochemical 000556 on Oct. 12, 2007. properties. Patent Application Publication Nov. 22, 2012 Sheet 1 of 3 US 2012/0291931 A1
Patent Application Publication Nov. 22, 2012 Sheet 2 of 3 US 2012/0291931 A1
Patent Application Publication Nov. 22, 2012 Sheet 3 of 3 US 2012/0291931 A1
US 2012/O29 1931 A1 Nov. 22, 2012
COMPOSITE COMPOUND INCLUDING well as cellulose 1-5. Thus, it is possible to obtain dynamites EXPLOSIVE AND MODIFIER FOR with active and inactive weight 1, for example, fossil meal, EXPLOSIVE AND METHOD OF a special kind of silica (porous SiO, kieselguhr) 1-5. MANUFACTURE THEREOF 0007. With glycerine trinitrate, other nitrates of alcohols became important as explosives, such as complex complete RELATED APPLICATIONS or/and incomplete ethers of alcohols and nitric acid, for 0001. This application is a Divisional of U.S. application example, methyl nitrate, ethyl nitrate 4, ethylene glycol Ser. No. 12/445,387, filed on Apr. 13, 2009, which is the U.S. dinitrate 2.4, propylene glycol dinitrate 2, mannitol hex National Phase under 35 U.S.C. S371 of International Appli anitrate, pentaerythritol tetranitrate 1 and so on 6, 7, 8. cation No. PCT/RU2007/000556, filed on Oct. 12, 2007, These other nitrates of alcohols are safer to operate as com which in turn claims the benefit of Russian Patent Application pared to glycerine trinitrate, but are also unsuitable for use No. RU 2006136245, filed on Oct. 16, 2006, the disclosures when shooting with fire-arms. of which Applications are incorporated by reference herein. 0008. It is known that in a molecule of cellulose formed 0002 The present application relates to modifiers from the from a molecule of glucose, the alcohol hydroxyl groups of range of organic and inorganic compositions, capable to glucose persist. As such, cellulose is in the class of alcohols modify their thermodynamic parameters, physical, chemical, and has certain properties of alcohols 1-5. A molecule of biochemical properties for explosives, including gas generat cellulose contains three hydroxyl groups, therefore during its ing compositions, rocket fuels and gunpowders based interaction (etherification) with a mixture of nitric and sulfu thereon. ric acids the complex complete and incomplete nitrate ethers 0003. It is known, that when interacting, such as by etheri of cellulose are formed. For example, depending on reaction fication, monoatomic (alkanols, alcohols), diatomic (al conditions of etherification, the residues of nitric acid can kanediols, glycols, diols), triatomic (triols, glycerin), multi replace one, two or all three hydroxyls thus forming mono nuclear (absolute valence) alcohols and their possible nitrate, dinitrate and trinitrate of cellulose, respectively or isomers with a mixture of nitric and Sulfuric acids, corre mononitro, dinitro and trinitro cellulose 5. sponding complex, complete or/and incomplete ethers of 0009. It is known that trinitro cellulose or pyroxylin, in nitric acid (nitrate ethers, nitric ethers, nitrates) are readily which all three hydroxyls are replaced by residues of nitric formed. 1-5. These nitric acid ethers are to some extent acid 1-5, as well as glycerine trinitrate, is a detonating explosive. Nitrates of monoatomic alcohols are less explosive explosive featuring high energy and it is applied as a shatter than nitrates of multinuclear alcohols 3, and as such, define ing explosive in blasting works. However, trinitrocellulose is their application as brisant Substances 3, which are rapidly not applied when shooting from gun and rocket weapons as decaying Substances which release great Volumes of strongly the shattering explosion would break the installation before heated gases 2,5. These nitric acid ethers are also known as the projectile would achieve movement 1-5. To use trinitro shattering explosives 1 used in blasting operations 1-5, but cellulose in gun systems, it is necessary to slow down the are inapplicable in Small arms 1-5 as a shattering explosion speed of its combustion so as to gradually accrue the pressure capable of breaking a gunbarrel, resulting in the projectile not of formed gases to set a projectile in motion and push it out having time to leave the gun barrel 1. from the gun (1-5). To reduce the speed of its combustion, 0004 One such representative of an explosive is the com trinitro cellulose is gelled using various solvents, for example plex complete ether of triatomic alcohol (glycerin) and nitric acetone, Vinegar amyl ether and others 1. Trinitrate of cel acid, the glycerine trinitrate sometimes referred to as nitro lulose then Swells and forms dense jellylike mass; Sucha mass glycerine 1, 3-5. Glycerine trinitrate explodes from com is used for pressing tapes of various thickness and sizes which pression 1, heating 5, impact, shock, detonation, such as after drying may be applied as a Smokeless gunpowder. These explosion of a fuse of mercuric fulminate, self-decomposition explosive gels burn more slowly than trinitrate of cellulose 2, and simple touch 3. However, the simplicity of synthe and enable use for shooting from gun and rocket installations. sising glycerine trinitrate, its low-stage and low-waste, as To obtain a weapon grade Smokeless gunpowder, the explo well as availability and cheapness of initial Substances or sive gels are cut in fine slices. starting materials for producing glycerine trinitrate makes its 0010. It is known that trinitrate of cellulose is also gelled manufacturing economic. The constancy of structure as a by using glycerine trinitrate. Thus, the formed mass repre target product, and insignificant quantities of impurities, sents a special kind of dynamite also used in blasting works which are very important when making compositions based under the name “blasting gelatin’ 1. The properties of trini thereon, makes glycerine trinitrate a rather promising com trate of cellulose are similar to those of similar complete or position as compared to other Substances of similar applica incomplete ethers formed during interaction of correspond tion 1-5. ing alcohols with a mixture of nitric and Sulfuric acids. Thus, 0005 For example, glycerine trinitrate is well known for the principles of the approach to purposeful modification of use in bibasic gunpowders 1-5, and various kinds of dyna thermodynamic parameters, and Stability modifications nega mite 1-5. tively influencing the properties and quality of trinitrate of 0006 Glycerine trinitrate in the pure state is not applied cellulose are authentic, as well as the Substances applied as because of its extreme instability, and during its decomposi universal modifiers of new composite structures of com tion an enormous quantity of energy is liberated as heat and a poundings of power systems of driving force based thereon. large Volume of the heated gases: nitrogen, water, carbon Some grades of Smokeless gunpowders consist of a mixture dioxide are liberated. In addition, oxygen in free condition is of trinitrate of cellulose and -30% of glycerine trinitrate 4. liberated, 1, 2 which may be used for amplification for Thus, the use of one universal modifier allows not only to explosive action of glycerine trinitrate when mixed with com improve the compatibility of components in an explosive bustible materials including ethers of nitric acid of mono mixture, but also to exclude or reduce the general contents of atomic, diatomic, triatomic and multinuclear alcohols, as various components, as the use of the universal modifier US 2012/O29 1931 A1 Nov. 22, 2012
renders the use of many other components unnecessary for natural ceresin (15%), stearin (38.8%) and orange fat-soluble obtaining required properties. Furthermore, and also to pro dye (1.2%) are cited; octogen (97.5%) and a retarder (2.5%), vide additional improvement of other properties, including, consisting of polymethyl methacrylate (1.2%), graphite bio-, radio-, light, thermal, chemical and antioxidizing stabil (0.5%), and oxysin (0.8%), and other widely used mixtures of ity may be obtained in the system when only one of our explosive compounds. proposed universal modifiers is used in the mixture. 0016. There 2,4,6,8,10,12-hexa-nitro-2,4,6,8,10,12-hexa 0011 Further to our study of materials of periodic and azo-tetracyclo (5.5,0.0',0) dodecane is a more powerful patent literature concerning the use of explosives and com explosive from the class of cyclic nitramines as compared to positions based thereon, one main drawback of the constant hexogen and octogen, and as to chemical stability and sensi and limited set of additives which do not feature sufficient tivity it is similar to octogen. 2.4.6.8, 10.12-hexa-nitro-2,4,6, efficiency and Versatility, and the compositions created from 8,10,12-hexa-azo-tetracyclo (5.5,0.0', 0') dodecane fea these additives, is that many problems related to sensitivity, tures high sensitivity to of mechanical influences and low temperature, pressure, Volume of formed Substances, their chemical stability. Patent RU No 2199540 from Apr. 26, structures and ecological compatibility, speed ofburning and 2001. Method for obtaining the 2,4,6,8,10,12-hexa-nitro-2,4, its transition to detonation are present. 6,8,10,12-hexa-azo-tetracyclo (5.5,0.0',0) dodecanes. 0012 Till now there are intensive works for creating new composite compounds of explosives having universal prop Sysoliatin S. V., Lobanova A. A., Chernikova J. T.I. (0017. In the work U.S. Pat. No. 5,587,533, High perfo erties. manse pressable explosive compositions/Braithwaite P. C., 0013. It is known that smokeless gunpowders are pro Lund O. K., Wardle R. B. explosive compositions based on duced on the basis of nitrates of cellulose in structure with 2.4.6.8,10,12-hexa-nitro-2,4,6,8,10,12-hexa-azo-tetracyclo various softeners. There are Smokeless gunpowders on the basis of glycerine trinitrate (ballistites) and pyroxylin the (5.5,0.0'''.0) dodecane and a retarder (an active binding Soviet encyclopaedic dictionary.-M.: Soviet encyclopedia, additive) in quantity of 5-10 mass %, consisting of polygly 1983, p. 119. Smokeless gunpowders, both artillery ballistite cidil nitrate, polyglycidil azide and others are discussed. and pyroxylin, and ballistite rocket firm fuel differ greatly in (0018. In the work Simpson R. L., Urtiew P.A., Ornellas raoapHTHO-mass parameters, structure, sensitivity to various D. L., et al. CL-20 performance exceeds that of HMX and its mechanical influences, power parameters, speed of burning, sensitivity is moderate//Propellants, Explosives—1997 No and sensitivity to a detonation pulse. Currently, the explosives 22 Pp. 249-255., a composition consisting of 2.4.6.8, 10. most used in the industry are hexogen and octogen. However 12-hexa-nitro-2,4,6,8,10,12-hexa-azo-tetracyclo they possess high sensitivity to mechanical influences and (5.5,0.0''',0) dodecane (CL-20) retarded by polyurethane cannot be applied without input of retarders in their structure polymer Estane-5703-P, is discussed, and this composition Patent RU No 22226522, C1. C 06 B25/00.21/00.25/24,31/ features higher sensitivity than the composition of octogen 32, C 06 D5/06, publ. Apr. 10, 2004, Bul. No 10. with the same polyurethane polymer. 0014. There are known powderexplosive compositions on 0019. In the work Patent RU 2252925, C1. C06 B25/34, the basis of Smokeless pyroxylin, artillery ballistite gunpow 45/22, Oct. 28, 2003, publ. May 27, 2006. Bul. No 15 a ders, ballistite solid rocket fuels, and their mixtures Patents composition based on 2,4,6,8,10,12-hexa-nitro-2,4,6,8,10. RU NoNo 1810321; 2021239; 2026274; 2026275; 2046117; 12-hexa-azo-tetracyclo (5.5,0,0,'',0) dodecanes (98.5-97 2074160; 2092473; 20993.96; 2130446; 2176632; 2086524 mass %) and a retarder (1.5-3 mass %) is discussed and C1 Aug. 10, 1997: 2122990 C1, Dec. 10, 1998: 2096396 C1, consists of Stearic acid and/or paraffin and/or ceresin or their Nov. 20, 1997: GB 1265718, Mar. 8, 1992; GB 1307967, Feb. mixtures. Works for improving the properties of explosive 21, 1973: U.S. Pat. No. 3,235,425; 3,186,882, Jun. 1, 1965; compositions on the basis of these compounds (Substances) U.S. Pat. No. 3,713,917, Jan. 30, 1973: U.S. Pat. Nos. 4,555, are still in progress and there is some Success. However, it is 276; 5,445,690; Kuk M. A. Industrial explosives science— rather difficult to apply them safely according to their M.: Nedra, 1980, p. 28...In materials of these works, as a rule, intended purpose because of their instability. structures of explosives possess significant sensitivity to 0020. It is known that application of liquid explosive com mechanical and other influences, thus the required result is positions and their composite structures of compoundings is not always reached. one important and promising direction for Solving certain 0015. It is known that till now hexogen and octogen are tasks of various special-purpose designations. Consistent applied as brisant explosives which possess high sensitivity Solutions on their being liquid or heterogeneous under usual and consequently cannot be applied in the pure state. To lower conditions are easier to produce as compared to Solid explo their sensitivity and maintaining safe handling, hexogen and sives. Patent RU 2063944, C1. C 06 B25/10, 1996, publ. in octogen are used only in combination with various unexplo Bul. No 20 from Jul. 20, 1996. sive additives or retarders, for example, unsaturated and Satu 0021 However, the use of liquid explosives such as glyc rated Solid hydrocarbons, such as wax, paraffin, ceresin and erine trinitrate or compositions based thereon is seriously other chemical Substances similar to Such compositions as limited because of their very high sensitivity to various Stearin, and also various rubbers and polymers plasticized by mechanical influences. However, high-energy Substances, in inactive and active softeners. Powerful explosives usually particular glycerine trinitrate, are used widely in explosive contain in their structure retarders from 2.5 up to 10 mass % compositions of various purpose. To reduce their sensitivity Patent RU 2252925 CL. C 06 B25/34, 45/22, Oct. 28, 2003, to various influences, some retarding additives are used. Tri publ. May 27, 2006. Bul. No 15. In this work LLNL Explo nitro-glycerin explosive compositions for various special sive Handbook. Properties of Chemical Explosive and Explo purpose designations, including industrial explosives, such as sive Simlants/Dobratz B.M., Livermore, Calif., 1981. explo pobedits, detonites and similar compounds are created by sive structures containing hexogen (95-93.5%) and a retarder using such retarding additives. Though these compositions (5-6.5%), consisting of a mixture of synthetic ceresin (45%), feature rather low sensitivity to mechanical influences due to US 2012/O29 1931 A1 Nov. 22, 2012 low content (approximately 10%) of glycerine trinitrate, for the same reason they feature low energy characteristics. R-CH-N-CH-N 0022. A number of compositions on the basis of glycerine NO 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 D5/04 1961. U.S. Pat. No. 3,873,579, C1. C 06 D5/06, 1975. The tem U.S. Pat. No. 4,011,114, C1. C 06 B 45/10, 1976). These perature of burning of this composition is 2000 to 2500 K. compositions feature rather high sensitivity to mechanical Another gas generating composition for fire extinguishers influences and low energy properties because of low oxygen contains in mass % dibutyl phthalate (17), acetate of cellulose (7.6), N-methyl-p-nitroaniline (1), nitrate of cellulose (30.4), factor. Trimethylolethane trinitrate is a known retarder for trinitrate of pentaeritrit (37), ethyl centralite (2), tin oxides (5) glycerine trinitrate. U.S. Pat. No. 3,423.256, C1. C 06 B while the temperature of its burning is 1700°K. U.S. Pat. No. 37001969. However, an essential decrease in sensitivity of 3,639,183, C1. C 06 D5/06, 1972). The purpose of improve liquid explosive composition is reached only in case of intro ment of such compositions is lowering the sensitivity to vari ducing a large amount of retarder in glycerine trinitrate, and ous mechanical influences and lowering the temperature of as a result, its explosive characteristics decrease sharply. In burning; and the main components of Such compositions view of the above, the problem of creating high-energy explo remain almost without qualitative and quantitative changes. sive heterogeneous Solutions featuring enough low sensitivity Thus there is known a gas generating composition consisting to various mechanical influences is rather urgent and the in mass % of ratio of nitrate of cellulose (59-69) bases, 1.6- problem is not yet solved because the common drawback of diazido-2-acetoxy-4-oxa-hexane (30-40) as softener, while the described explosive compositions is the high sensitivity to the other additives are dimethyl diphenyl urea (0.5-0.6) and various mechanical influences. Therefore creating new explo vaseline (0.4-0.5), and the temperature of burning of this sive compositions using modifiers described in the present composition is 1450° K Copyright certificate RU No disclosure that were unknown earlier for the given purpose, 918289, MC1. C 06 D5/06. UDC 662.16 (088.8), publ. Apr. with mechanical and other properties set depending on the 7, 1982. Bul. No 13. date of publication of the description object in view, is novel. Apr. 10, 1982, howeverall these compositions feature higher 0023 The common drawback of explosive compositions sensitivity to mechanical influences, high temperature and described in the above-mentioned references is their high high speed of burning. sensitivity to various mechanical influences. 0028. Earlier it was considered that acids promote decom 0024. The task of creating explosives designed for manu position of many explosives L. A. Smirnov <
0036 An engineering problem discussed in the present 0047 where if R = NO, R=R_-H, it is 2-ni disclosure consists in creating a universal modifier for explo trobenzoic acid (o-nitrobenzoic acid), sives from a range of composite complete or incomplete 0048 if R = NO; R=R_-H, it is 3-nitrobenzoic nitrates of monoatomic, diatomic, triatomic or multinuclear acid (m-nitrobenzoic acid), alcohols, nitrocelluloses, nitroamines, azides, nitrobenzenes or nitroalkanes. Introducing Such a modifier in these explo 0049 if R = NO; R=R= H, it is 4-nitrobenzoic sives allows one to modify their thermodynamic parameters, acid (p-nitrobenzoic acid). physical, chemical, and biochemical properties and to create Specific examples of acids and salts of the above mentioned on the basis of these explosives, with the introduced modifi formulas include the following: ers, explosive and unexplosive composite compounds having 0050. The composition having the formula (1) where liquid, heterogeneous or Solid aggregate State depending on = -OH, R= -COOH, R= objects in view with required properties that may vary upon the ratio of components included in the composition. R 0037. The technical result of the present disclosure is the inhibition of premature decomposition of explosives at all the -CH initial stages of development of this process, with its Subse R quent initiation as a result of Smooth and fast growth of temperature thus leading to explosive decomposition or burn ing depending on the Sufficient Surplus of oxygen in the is the 5.5'-methylenedisalicylic acid. system, both due to oxygen-containing compounds, and as a 0051. The composition having the formula (1) where result of emission of oxygen in a pure state when decompos = -OH, R= -COONH R = ing the Substances included in explosive composition, i.e. R controlling the rate of their decomposition, as well as decrease in sensitivity of explosives to various mechanical -CH influences, and improvement of the degree of compression. R 0038. 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 is the diammonium salt of 5,5'-methylenedisalicylic acid. explosives from the range of complex complete or incomplete 0.052 The composition having the formula (1) where nitrates of monoatomic, diatomic, triatomic or multinuclear R—H, R= -COOH, R= H is orthophthalic acid. alcohols, nitrocellulose, nitroamines, nitroanilines, azides, 0053. The composition having the formula (1) where nitrobenzenes, nitroalkanes and their mixtures, where the R—H, R= -COOH, R= -COOH is isophthalic acid. compositions belonging to inorganic or organic acids or their 0054 The composition having the formula (1) where salts are chosen from the following group: orthoboric acid, = -COOH, R=H, R= -COOH is terephthalic acid. phosphorous acid or orthophosphoric acid, or a composition 0055. The composition having the formula (1) where having the formula (1): —COONa, R=H, R= COONa is the disodium salt of terephthalic acid. R R2 0056. The composition having the formula (1) where R—H, R= COONa, R = COONa is the disodium salt of metaphthalic acid. R 0057 The composition having the formula (1) where 0039 where R= H, OH, -COOH, COONa, —COOH, R= -OH, R= H is salicylic acid. 0040 R= H, OH, -COOH, -COONH 0058. The composition having the formula (1) where COONa, —OH, R= COONa, R= H is the sodium salt of 0041) R-H, -OH,-COOH,-COONa, and R and salicylic acid. Rhave 0059. The composition having the formula (1) where 0042 the above-stated values, formula (2): —COOH, R= H, R= H = H is benzoic acid. 0060. The composition having the formula (1) where O O V M —COONa, R= H, R= H is the sodium salt of C-R1-C, R, benzoic acid. V 0061 The composition having the formula (1) where R R —COOH, R= H, R= -OH is para-oxybenzoic 0043 where R= -OH, - OK, ONH - ONa, acid. 0044) R=-single bond or —CH, 0062. The composition having the formula (1) where 0045 R is absent or HO or 2HO, R—H, R= -COOH, R= -OH is meta-oxybenzoic 0046 or formula (3): acid. 0063. The composition having the formula (2) where H-O-CO =—OH. R. Single bond, R - absent, is oxalic acid. R 0064. The composition having the formula (2) where —OH, R=single bond, R-2H2O is oxalic acid dihy drate. R 0065. The composition having the formula (2) where =—OK. R. Single bond, R - absent, is lemon salt. 0066. The composition having the formula (2) where =—ONa, R. Single bond, R-absent, is sodium oxalate. US 2012/O29 1931 A1 Nov. 22, 2012
0067. The composition having the formula (2) where I0084 Diethanol-N-nitroamine dinitrate (DINA) having =—ONH R Single bond, R - absent, is ammonium the formula oxalate. 0068. The composition having the formula (2) where H. H. H. H. =—OH, R=—CH, R - absent, is Succinic acid. 0069. The listed compositions have, basically, rather low on-o------0-0, temperature of decomposition and rather high temperature of o, . . 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 I0085 Diglycerin tetranitrate having the formula general temperature of formed gases with simultaneous CH-CHONO2-CHONO increase in their volumes and there will be a proportional development of pressure due to gases formed as a result of O decomposition and/or burning of the listed compositions. CH-CHONO-CHONO; 0070 Explosives from the range of complex complete or incomplete nitrates of monoatomic, diatomic, triatomic or I0086 Diethyleneglycol dinitrate (diglycol dinitrate, dini multinuclear alcohols, nitrocelluloses, nitroamines, nitroa trodiglycol) having the formula nilines, azides, nitrobenzenes or nitroalkanes, where it is offered to introduce the above modifiers, may be the follow CH-CH-ONO ing explosives: O 0071 Explosives having the formula: CH-CH2-ONO2:
I0087 Trinitrate of cellulose (trinitro cellulose, trinitrate of al-i-o-o: cellulose, trinitrate) —CHO(O—NO)n: R I0088. Ethylene-N,N'-dinitramine (EDNA) I0089 NONH (CH). NHNO; 0072 where R or/and R= -CH, -H, 0090 Nitroguanidine (NH)C=NNO (0091 Nitrourea NHCONHNO; 0092 N,N'-bis(B.B.B-trinitroethyl)carbamide, or N,N'-bis (B. B. B-trinitroethyl)urea (BTNEM) ----. NHCH2C(NO) OC 0073. n=1-4; V 0074) if R—R= CH-O NO; n=1, is glycerol NHCH2C(NO2)3: trinitrate (nitroglycerine); 0075 if R=R= H; n=1, is methyl nitrate; (0093 Explosive having the formula: 0076) if R= -CH: R=-H; n=1, is ethyl nitrate 0077 if R = CH-O NO; R = H; n=1, is ethyl R-N-R ene glycol dinitrate; Rs R3 0078 if R= -CH: R= -CH O NO; n=1, is pro pylene glycol dinitrate; 0079 if R=R= -CH O NO; n=4, is mannitol hexanitrate (nitromannitol); 0080 if R= -CHCL; R = CH-O NO; n=1, is R4 monochlorhydrin dinitrate; 0081 if R = H; R = (0094) where if R = NO: R=R-R-Rs= H, it is an N-nitroaniline; (0095 if R=R - NO; R = CH; R =Rs= H, it -C- = 4, is 4-nitrophenyl-N-methylnitroamine (N-nitro-N-methyl 4-nitroamine); 0096 if R=Rs—H; R = CH: R=R - NO, it it is pentaerythritol tetranitrate (penthrite); is 2,4-dinitro-N-methylaniline; 0082 Explosives including: (0097 if R=R-R-NO; R = CH; R = H, it 0083) Nitroisobutyl glycerinetrinitrate having the for is 2,4-dinitrophenyl-N-methylnitroamine (N-nitro-N-me mula: thyl-2,4-dinitroaniline); 0098 if R = H; R = CH: R=R-R, NO, it is CHONO N-methyl-2,4,6-trinitroaniline; 0099] if R=R-R-R= NO; R = CH, it is ON-C-CHONO; N-methyl-N,2,4,6-tetranitroaniline (N-methyl-N-nitro-2, CHONO 4,6-trinitroaniline); 0100 if R = H; R = CH; R =R Rs NO, it is N-methyl-2,4,6-trinitroaniline; US 2012/O29 1931 A1 Nov. 22, 2012
0101 if R=R =R=Rs—NO; R = CH, it is Isomers of Tetranitrobenzene: N-methyl-N,2,4,6-tetranitroaniline (N-methyl-N-nitro-2, 4,6-trinitroaniline or 2,4,6-trinitroaniline-N-methylni 0119) 1,3,5-trinitro-1,3,5-triazacyclo-hexane (hexogen) troamine, tetryl); 0102 if R = H; R = CH; R =R Rs NO, it is N-methyl-2,4,6-trinitroaniline; o 0103 R=R =Ra–Rs—NO; R = CH, it is N-methyl-N-methyl-N-2,4,6-tetranitroaniline (N-methyl N N-nitro-2,4,6-trinitroaniline or 2,4,6-trinitroaniline-N- N N methylnitroamine, tetryl); oN1 N1 YNo. 0104. If R=R —H; R =R=Rs—NO, -it is 2.4. 6-trinitroaniline; I0120) 1,3,5,7-tetranitro-1,3,5,7-tetraazocyclooctane (cy 0105 Explosive having the formula: clotetramethylene-tetranitroamine, octogen) R R6 R2
Rs R3 ON- r -NO R4 0106 if R= -OH: R=R RE NO, R=Rs— s H. it is 2,4,6-trinitrophenol (picric acid); NO 0107 if R=Cl; R=R-R-NO, R=Rs—H, it is 2,4,6-trinitrochlorbenzene: I0121 2.2'44", 6,6'-hexanitrodiphenyl: 0108 if R=R= -OH: R=R-R-NO; Rs— 0.122 2.2'44", 6,6'-hexanitrodiphenylsulfide (hexyd); H, it is 2,4,6-trinitroresorcinol (TNR, stifnine acid); I0123 2.2'44", 6,6'-hexanitrodiphenylsulfone; 0109 if R= -OCH: R=R-R-NO; R = H, 0.124 2.2'44", 6,6'-hexanitrostilbene: it is 2,4,6-trinitroanisol (2,4,6-trinitro methoxybenzene); 0.125 3,3'-diamino-2,2'44".6,6'-hexanitro-diphenyl: 0110 if R=R NH; R =R=R NO; Rs— 0.126 2.4.6.-hexanitrodiphenylamin; H, it is 1,3-diamino-2,4,6-trinitrobenzene (2,4,6-trinitro I0127. Isomers of trinitronaphthalene; phenylenediamine); I0128 Isomers of tetranitronaphthalene; 0111 if R=R-R=NH: R=R. R. —NO, it is 0129. Nitroalkanes: 1,3,5-triamino-2,4,6-trinitrobenzene: 0.130 C(NO) tetranitromethane: 0112 if R=CH: R=R RE NO, R=Rs— I0131 CH(NO)CHNO-1,2-dinitroethane; H, it is 2,4,6-trinitrotoluene (trotyl, a TNT); (0132 CH-CH(NO)-1,1-dinitroethane; 0113 if R = CH: R=R-R-NO; R =OH: 0.133 CHC(NO)-1,1,1-trinitroethane; Rs—H, it is trinitrocreosol: 0.134 C(NO)-hexanitroethane: 0114 f R—R—R= NO; R=R-R-H, it is I0135 C(NO)(N)-trinitrotriazidobenzene: 1,3,5-trinitrobenzene: 0.136 CN(N)-cyanurtriazide, 0115 if R = CH: R=R-R-NO; R = 0.137 The above cited explosives and their mixtures do not limit the possible assortment of various other explosives that CH3 in combination with the described modifiers from between organic acids, inorganic acids and their salts or other of Sub - -CH: stances, featuring similar properties and used as universal ch, modifiers. The above explosives may also similarly influence various parameters and properties having new energy sys tems of driving force created on their basis with characteris Rs—H, is 1-methyl-3-tert-butyl-2,4,6-trinitrobenzene: tics required for any specific purpose. The same explosive 0116 if R=R CH; R =R=R= NO; composition may feature different speeds of decomposition 0117 R= depending on the method of its activation. The composition may also exhibit the properties of simple burning, and not CH3 passing to detonation or brisances, i.e. to be applied in two component explosive compositions on the basis of the cited --CH, obtained explosives in a combination with the modifiers ch, described herein, as an active principle of a new composite structure of monobasic gunpowders, gas generating compo sitions with or without using pyroxylin in their composition. is 1,3-dimethyl-5-tert-butyl-2,4,6-trinitrobenzene: 0.138. The operating principle of the disclosed modifiers in 0118 if R=R CH; R=R R=—NO; Rs— various composite structures of compounds for the specified H, it is 2,4,6-trinitro meta-xylene (1,3-dimethyl-2,4,6- classes of explosives is essentially the same. The modifiers trinitrobenzene); and Substances having similar properties under certain con US 2012/O29 1931 A1 Nov. 22, 2012 ditions may decay and emit gaseous products. In the presence acid (crystalline hydrate) content. The density of structures of enough oxygen in the system may result not only in decom was p=1.7-1.75 g/cm (high density compositions). position, but also burning or a combination of these pro cesses. Thus, there may be a thermodynamic effect of signifi Example 2 cant decrease in temperature and increase in Volume of the 0144. A thematic example of influence of the proposed formed gases, and incidental proportional development of salts of organic acids is the influence of ammonium oxalate certain pressure. The effect of decrease in temperature of (crystalline hydrate) on glycerine trinitrate. In FIG.3 there is gases is most pronounced in cases where the compositions a diagram of decomposition of a mixture of ammonium having the temperature of decomposition that is lower or oxalate (crystalline hydrate) with glycerine trinitrate in mass coincides with the temperature of ignition are used as modi ratio 1:1 accordingly. It was found that introducing ammo fiers. Creating explosive and unexplosive energy systems of nium oxalate (crystalline hydrate) does not worsen the heat driving force with the properties set depending on the object resistant characteristics of glycerine trinitrate, but also ren in view is general and universal for all such systems. Using ders inhibitory action on its autocatalytic decomposition. It is Such an effect is rather urgent when creating low erosion, also determined, that the composition is not Susceptible to low-kindle or cold gunpowders. When the properties of sub transition ofburning to explosion or detonation. The mixtures stances do not satisfy these conditions there may be an were prepared similarly to those of Example 1. increase in total temperature effect. The modifier for our offered explosives may be used in case of the ratio modifier/ Example 3 explosive equal to (0.1-99.9: 99.9-0.1). 0145 Thematic examples are mixtures of oxalic acids 0.139. To increase the energy characteristics of the (crystalline hydrate) with glycerine trinitrate, thus the mix described composite structures it is possible to introduce tures prepared in mass ratio: composition No 1—1:5, com metallic power additives to the compositions. position No 2–1:2, composition No.3—1:1, composition No 0140. To provide various consistent properties including 4—2:1 accordingly. The mixtures were been tested for explo plasticity to explosive and unexplosive composite structures, sive characteristics using a Kast's impact machine OST B it is possible to use binding, gelatinizing (Swelling) and poly 84-892-74 (Sensitivity impact using an impact machine at the meric compositions. bottom limit with instr. No 1 and instr. No 2) and the following results are received: 0146 Composition No 1 with a load of 2 kg and height EXAMPLES, ILLUSTRATING THE INVENTION Ho-250 mm (instr. No 2). The percent of explosions made 80%, 0141 Research of mixtures of various modifiers and 0147 Structure No 2 with a load of 2 kg and height explosives regarding the compatibility and influence of modi Ho-250 mm (instr. No 2). The percent of explosions made fiers on heat-resistant characteristics of explosives was per 55%, formed. It is marked, that introduction of modifiers not only 0148 Composition No 3 with a load of 10 kg and height does not reduce the heat-resistant parameters of explosives, Ho-250 mm (instr. No 2). The percent of explosions made but also makes an inhibitory effect on their autocatalytic 68%, decomposition. Research was carried out using an installa 0149 Composition No 4 with a load of 10 kg and height tion for defining the temperature of the beginning of intensive Ho-250 mm (instr. No 2). The percent of explosions made decomposition (Tbid) and phase transformations of poly O%. meric materials using the DTC method (differential thermo 0150. The detonation of glycerine trinitrate is caused couple) according to OST B-84-615-72. when dropping a 2 kg load from a height of Ho=40 mm 9. 0151. Composition No 3 with a load of 10 kg Hod-500 mm Example 1 (instr. No 1), 0152 Composition No 4 with a load of 10kg. Ho>500mm 0142. A thematic example of influence of the offered acids (instr. No 1). is the influence of oxalic acid (crystalline hydrate) on glyc 0153. The compositions have been tested for sensitivity to erine trinitrate. In FIG. 1 and FIG. 2 there are the diagrams of shock-free friction at the bottom limit (OST B 84-894-74) at decomposition of mixtures of oxalic acids (crystalline a speed of disk rotation (friction) of 520 rev/min. Thus, the hydrate) with glycerine trinitrate in mass ratio 1:2 and 1:5 sensitivity to shock-free friction at the bottom limit of com accordingly. It was found that introducing oxalic acids (crys position No 3 makes Po=>3000 kilogram-force/cm and of talline hydrate) does not worsen the heat-resistant character composition No 4-Po=>3000 kilogram-force/cm. The tests istics of glycerine trinitrate. It is also determined that the were carried out at a temperature of 18°C. composition is not susceptible to transition of burning to 0154 The compositions have been tested for sensitivity to explosion or detonation. friction at a shock shift at the bottom limit (OST B 84-895 0143 Mixtures of glycerine trinitrate (OST B 84-2386) 83). Thus, the sensitivity to friction at a shock shift at the and oxalic acids (crystalline hydrate)TY standard 2642-001 bottom limit of composition No 3 was equal to Po=750 kilo 07500602-97 were prepared from their solutions in ethyl gram-force/cm and of composition No 4 Po=1750 kilogram alcohol GOST 18300-87 by mixing at a room temperature force/cm. and further removal of ethyl alcohol by keeping in exhaust 0.155. As a result of tests of samples with various percent case until a film is formed. The mixing did not cause changes age of glycerine trinitrate and oxalic acid (crystalline of temperature, color and sedimentation. The compositions hydrate), it is possible to obtain the mixture of 50%-60% of have been investigated using a microscope and a significant glycerine trinitrate and 50%-40% oxalic acid (crystalline decrease in heterogeneity was marked with increase of oxalic hydrate) accordingly, among Substances featuring low sensi US 2012/029 1931 A1 Nov. 22, 2012 tivity to mechanical influences. Thus, it is possible to operate (0162. On the basis that the principle of action of the pro with them while observing conventional security measures. posed modifiers for new power systems of driving force for all 0156 The compositions have been tested for speed of classes of explosives though essentially the same, however explosive transformation (detonation) OST B 84-90074, sus each individual explosive, as well as any other composition ceptibility to transition of burning to explosion or detona possesses certain unique inherent properties (physical, tion—the character of destruction of a pipe with indicating its chemical, mechanical and others), that is each new power dimensions and estimating the explosive process according to system of driving force on their basis has its own “know-how” OST B 84-90074. Thus, the composition with the content of having certain information value, but not influencing on oxalic acid (crystalline hydrate) with glycerine trinitrate of essence of the invention as a whole and that are sometimes 40%-60% accordingly, has shown the following characteris inexpedient to open with a view of the further preservation of tics: the density p=1.75 g/cm, the speed of detonation priority of the trend itself and of the time of research process. D=6370 m/s, the composition is not susceptible to transition Therefore, the obtained data and some results, having certain of burning to explosion or detonation; the composition with dependence and convergence in application conditions of our the content of oxalic acids (crystalline hydrate) with glycer proposed modifiers in a combination with the cited explosive ine trinitrate of 60%-40% accordingly, has shown the follow compositions are not always outlined in the description of ing characteristics: the density p=1.7 g/cm, the speed of materials in the text or restricted. detonation D-880-2230 m/s, the composition is not suscep tible to transition of burning to explosion or detonation. LITERATURE 0157 For giving various consistent properties including plasticity to such explosive and unexplosive compositions, The List of Documents Quoted and Taken into gelatinating (Swelling) and polymeric compositions were Account During Examination used. Such as pyroxylin, colloxylin and other compositions in (0163 1. E. S. Hotinsky. The course of organic chemis monobasic and bibasic composite materials with the try. Kharkov.: Publishing house of the Kharkov Red described modifiers. Thematic examples are the obtained Labour Banner Award A. M. Gorky National University, structures: oxalic acid (crystalline hydrate) 72%, CT-30 1959.-724 pp. 21%, glycerine trinitrate 7% with speed of burning 0.5 mm/s (0164. 2. B. A. Pavlov and A. P. Terentyev. The course of and temperature of burning ~800°K. (at P-40 and tempera organic chemistry. Moscow. National scientific and ture 20°C.)—the product is plastic, it is susceptible to mold technical publishing house of chemical literature, 1961.- ing; and oxalic acid (crystallinehydrate) 42%, glycerine trini 592 pp. trate 42%, PVR (polyvinyl butyral resin) 16% with speed of (0165 3. A. E. Chichibabin. Principles of organic chemis burning 5 mm/s and temperature of burning ~1500 K. (at try. Volume I. Moscow.: National scientific and technical P-40 and temperature 20° C.). The product is plastic, it is publishing house of chemical literature, 1963.-912 pp. Susceptible to molding, there is also an expressed influence of (0166 4. A. N. Nesmeyanov, N.A. Nesmeyanov. Principles the modifier on the speed of burning and temperature of the of organic chemistry. Book one. Moscow.: Publishing obtained gases. house “Khimiya', 1974-624 pp. (0167 5. B. N. Stepanenko. The course of organic chem Example 4 istry Part I. Aliphatic compositions. Moscow. Publish ing house "Vysschayashkola”, 1976.-448 pp. 0158 Another thematic example are the obtained compo (0168 6. E. Ju. Orlova. Chemistry and technology of sitions of pyroxylin with salt of methylenedisalicylic acid. brisant substances. Moscow.: Scientific and technical Thus when introduting it up to 0.5% of mass, the stability of publishing house OBORONGIZ, 1960.-396 pp. gunpowders made 3.5 to 4.5 kPa, at a norm of 8 kPa. When (0169. 7. E. Ju. Orlova. Chemistry and technology of introducing the diammonium salt of methylenedisalicylic brisant substances.—Leningrad.: Publishing house acid up to 20% of mass, essential decrease in temperature of “Khimiya”, 1973.-688 pp. the formed gases down by 700-800°K. was marked, while 0170 8. Ju. A. Lebedev. E. A. Miroshnichenko, Ju. K. maintaining acceptable power of gunpowders. Knobel. Thermochemistry of nitro compounds. Publishing house “Nauka’. Moscow. 1970-168 pp. Example 5 (0171 9. Orlova E. Ju. Chemistry and technology of brisant 0159. The obtained compositions of pyroxylin with lemon substances: Textbook for high schools Ed., 3rd ed., salt may also serveathematic example, because when intro rev. L.: Khimiya, 1981.-312 pp. ducing it up to 0.5% mass, the stability of gunpowders made 1-30. (canceled) 3.5-4.5 kPa, at a norm of 8 kPa. When introducing lemon salt 31. A composite compound comprising: up to 20% mass, the obtained compositions had the power of an explosive selected from the group of complex complete gunpowder comparable to the normal one at a level of 1030 to or incomplete nitrates of monoatomic, diatomic, tri 1060 kJ/kg. atomic or multinuclear alcohols, nitrocelluloses, (0160 The obtained data as to characteristics of composi nitroamines, azides, nitrobenzenes, nitroanilines, tions in the Examples 1 and 2 allow to assume the possibility nitroalkanes and mixtures thereof; and of their application for modifying the properties of gunpow a modifier selected from: ders, including control of temperature, of the structure of an inorganic acid consisting of at least one from the fol obtained gases. lowing group: orthoboric acid, phosphorous acid, or (0161 Alongside with experimental data, thermodynamic orthophosphoric acid, calculated values of obtained compositions had good conver an organic acid consisting of at least one from the following gence of results and completely confirmed the experimental group: 2-nitrobenzoic acid, 3-nitrobenzoic acid, 4-ni data. trobenzoic acid, or US 2012/O29 1931 A1 Nov. 22, 2012
a composition of formula (1) 38. The composite compound according to any of claims 31 to 33, wherein the explosive is at least one selected from (1) R R2 the group consisting of 2,4,6-trinitrophenol. 2,4,6-trinitro chlorbenzene, 2,4,6-trinitroresorcin, 2,4,6-trinitroanisol. 1.3- diamino-2,4,6-trinitrobenzene, 1,3,5-triamino-2,4,6-trini trobenzenes, 2,4,6-trinitrotoluene, trinitrocreosol, 1,3,5- R trinitrobenzene, 1-methyl-3-tert-butyl-2,4,6-trinitrobenzene, where R= -H, -OH, -COOH, -COONa, 1,3-dimethyl-5-tert-butyl-2,4,6-trinitrobenzene, 2,4,6-trini R= H, OH, -COOH, COONH COONa, tro-meta-xylene, and an isomer of tetranitrobenzene. R= H, -OH,-COOH,-COONa, 39. The composite compound according to any of claims 31 to 33, wherein the explosive is at least one selected from R CH the group consisting of 1,3,5-trinitro-1,3,5-triazacyclohex ane and 1,3,5,7-tetranitro-1,3,5,7-tetraazocyclooctane. 40. The composite compound according to any of claims R 31 to 33, wherein the explosive is at least one selected from and R and Rhave the above-stated values, or the group consisting of 2.2.4.4.6,6'-hexanitrodiphenyl, 2.2". a composition of formula (2): 4,4,6,6'-hexanitrodiphenylsulfide, 2,2',4,4,6,6'-hexani trodiphenylsulfone, 2,2'44", 6,6'-hexanitrostilbene, 3,3'-di (2) amino-2,2',4,4,6,6'-hexanitrodiphenyl, 2.4.6- hexanitrodiphenylamine, an isomer of trinitronaphthalene, R 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 where R—OH, - OK, —ONH —ONa, R=a single bond the group consisting of tetranitromethane, 1,2-dinitroethane, or —CH, and R is absent or HO or 2H2O. 1,1-dinitroethane, 1,1,1-trinitroethane, hexanitroethane. 32. The composite compound according to claim 31, 42. The composite compound according to any of claims wherein the modifier has the composition of formula (1) and 31 to 33, wherein the explosive is at least one selected from is at least one selected from the group consisting of 5.5'- the group consisting of trinitrotriazidobenzene or cyanurtri methylenedisalicylic acid, diammonium salt of 5.5'-methyl azide. enedisalicylic acid, orthophthalic acid, isophthalic acid, 43. A method of manufacturing an explosive composition terephthalic acid, disodium salt ofterephthalic acid, disodium comprising the step of salt of metaphthalic acid, salicylic acid, sodium salt of Sali combining an explosive selected from the group of com cylic acid, benzoic acid, sodium salt of benzoic acid, para plex complete or incomplete nitrates of monoatomic, oxybenzoic acid, and meta-oxybenzoic acid. diatomic, triatomic or multinuclear alcohols, nitrocellu 33. The composite compound according to claim 31, loses, nitroamines, azides, nitrobenzenes, nitroanilines, wherein the modifier has the composition of formula (2) and nitroalkanes and mixtures thereof, and is at least one selected from the group consisting of oxalic a modifier selected from: acid, oxalic acid dihydrate, lemon salt, Sodium oxalate, an inorganic acid consisting of at least one from the fol ammonium oxalate, and Succinic acid. lowing group: orthoboric acid, phosphorous acid, and 34. The composite compound according to any of claims orthophosphoric acid, 31 to 33, wherein the explosive is at least one selected from an organic acid consisting of at least one from the following the group consisting of glycerol trinitrate, methyl nitrate, group: 2-nitrobenzoic acid, 3-nitrobenzoic acid, and ethyl nitrate, ethylene glycol dinitrate, propylene glycol dini 4-nitrobenzoic acid, or trate, mannitol hexanitrate, monochlorhydrin dinitrate, pen taerythritol tetranitrate. a composition of formula (1) 35. The composite compound according to any of claims (1) 31 to 33, wherein the explosive is at least one selected from R R 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. where R= H, OH, -COOH, or -COONa 37. The composite compound according to any of claims 31 to 33, wherein the explosive is at least one selected from R= H, -OH,-COOH, -COONH, or -COONa, the group consisting of ethylene-N,N'-dinitramine, R. H. -OH,-COOH, -COONa, or nitroguanidine, nitrourea, N,N'-bis(B.B.B-trinitroethyl)car R CH bamide, N,N'-bis(B.B.B-trinitroethyl)urea, N-nitroaniline, 4-nitrophenyl-N-methylnitroamine, 2,4-dinitro-N-methyla niline, 2,4-dinitrophenyl-N-methylnitroamine, N-methyl-2, 4,6-trinitroaniline, N-methyl-N, 2,4,6-tetranitroaniline, R N-methyl-N, 2,4,6-tetranitroaniline, and 2,4,6-trinitroa niline. and R and Rhave the above-stated values, or US 2012/O29 1931 A1 Nov. 22, 2012 10
a composition of formula (2): 49. The method according to any of claims 43 to 45, wherein the explosive is at least one selected from the group (2) consisting of ethylene-N,N'-dinitramine, nitroguanidine, O O nitrourea, N,N'-bis(B.B.B-trinitroethyl)carbamide, N,N'-bis (B.B.B-trinitroethyl)urea, N-nitroaniline, 4-nitrophenyl-N- R 1. C-R1-C, R methylnitroamine, 2,4-dinitro-N-methylaniline, 2,4-di-nitro phenyl-N-methylnitroamine, N-methyl-2,4,6-trinitroaniline, N-methyl-N, 2,4,6-tetranitroaniline, N-methyl-N, 2,4,6-tet where R= -OH, - OK, ONH, or - ONa, ranitroaniline, and 2,4,6-trinitroaniline. R=a single bond or —CH 50. The method according to any of claims 43 to 45, R is absent or HO or 2H2O. wherein the explosive is at least one selected from the group 44. The method according to claim 43, wherein the modi consisting of 2,4,6-trinitrophenol. 2,4,6-trinitrochlorben fier has the composition of formula (1) and is at least one Zene, 2,4,6-trinitroresorcin, 2.4.6-trinitroanisol. 1,3-di selected from the group consisting of 5.5'-methylenedisali amino-2,4,6-trinitrobenzene, 1,3,5-triamino-2,4,6-trini trobenzenes, 2,4,6-trinitrotoluene, trinitrocreosol, 1,3,5- cylic acid, diammonium salt of 5,5'-methylenedisalicylic trinitrobenzene, 1-methyl-3-tert-butyl-2,4,6-trinitrobenzene, acid, orthophthalic acid, isophthalic acid, terephthalic acid, 1,3-dimethyl-5-tent-butyl-2,4,6-trinitrobenzene, 2,4,6-trini disodium salt of terephthalic acid, disodium salt of metaph tro-meta-xylene, and an isomer of tetranitrobenzene. thalic acid, salicylic acid, Sodium salt of Salicylic acid, ben 51. The method according to any of claims 43 to 45, Zoic acid, Sodium salt of benzoic acid, para-oxybenzoic acid, wherein the explosive is at least one selected from the group and meta-oxybenzoic acid. consisting of 1,3,5-trinitro-1,3,5-triazacyclohexane and 1.3, 45. The method according to claim 43, wherein the modi 5,7-tetranitro-1,3,5,7-tetraazocyclooctane. fier has the composition of formula (2) and is at least one 52. The method according to any of claims 43 to 45, selected from the group consisting of oxalic acid, oxalic acid wherein the explosive is at least one selected from the group dihydrate, lemon salt, sodium oxalate, ammonium oxalate, consisting of 2.2.4.4.6,6'-hexanitrodiphenyl, 2.2.4.4.6,6'- and Succinic acid. hexanitrodiphenylsulfide, 2.2',4,4,6,6'-hexanitrodiphenyl 46. The method according to any of claims 43 to 45, sulfone, 2,2,4,4,6,6'-hexanitrostilbene, 3,3'-diamino-2,2',4, wherein the explosive is at least one selected from the group 4,6,6'-hexanitrodiphenyl, 2.4.6-hexanitrodiphenylamine, an consisting of glycerol trinitrate, methyl nitrate, ethyl nitrate, isomer of trinitronaphthalene, and an isomer of tetrani ethylene glycol dinitrate, propylene glycol dinitrate, mannitol tronaphthalene. hexanitrate, monochlorhydrin dinitrate, and pentaerythritol 53. The method according to any of claims 43 to 45, tetranitrate. wherein the explosive is at least one selected from the group 47. The method according to any of claims 43 to 45, consisting of tetranitromethane, 1,2-dinitroethane, 1,1-dini wherein the explosive is at least one selected from the group troethane, 1,1,1-trinitroethane, and hexanitroethane. consisting of nitroisobutyl glycerinetrinitrate, diethanol-N- 54. The method according to any of claims 43 to 45, nitroamine dinitrate, diglycerintetranitrate, and diethyleneg wherein the explosive is at least one selected from the group lycol dinitrate. consisting of trinitrotriazidobenzene and cyanurtriazide. 48. The method according to any of claims 43 to 45, wherein the explosive is trinitrate of cellulose. c c c c c