Modifier for explosives - european patent office ep2128117 a2

EP 2 128 117 A2
EUROPEAN PATENT APPLICATION
published in accordance with Art. 153(4) EPC 02.12.2009 Bulletin 2009/49
C06B 25/00 (2006.01)
C06B 23/00 (2006.01)
C06D 5/00 (2006.01)
(21) Application number: 07861028.4
(22) Date of filing: 12.10.2007
PCT/RU2007/000556
WO 2008/048146 (24.04.2008 Gazette 2008/17)
AT BE BG CH CY CZ DE DK EE ES FI FR GB GR
• IVANOV, Yuri Alexandrovich
HU IE IS IT LI LT LU LV MC MT NL PL PT RO SE
Moscow 107061 (RU)
• FROLOV, Alexander Yurievich
Moscow 115409 (RU)
(30) Priority: 16.10.2006 RU 2006136245
• OSININ, Vladimir Valerievich
Moscow 109518 (RU)
• PEREVEZENTZEV, Vladimir Mikhaylovich
• Obshestvo S Ogranichennoy Otvetstvennjctyu
Moskovskaya obl. 141006 (RU)
"Ifokhim"
Moscow 123-022 (RU)
(74) Representative: Fleck, Hermann-Josef
• Limited Liability Company Ifo
Klingengasse 2/1
Des Moines, IA 50309 (US)
71657 Vaihingen/Enz (DE)
MODIFIER FOR EXPLOSIVES
Universal modifiers from the class of organic and azides (azoimides), nitro compounds and compositions inorganic acids and their salts of new power systems of (substances) with mixed groups and their mixes purpose- driving force on the basis of complex complete or/and fully modifying their thermodynamic (thermochemical) incomplete nitrates (nitroesters) monoatomic (alcohols, parameters (characteristics), mechanical, physical, alkanes), diatomic (diols, glycols, alkanediols), triatomic (triols, glycerin), multinuclear (of absolute valence) alco-hols, cellulose, as well as nitroamines (nitramines), EP 2 128 117 A2
Description
kieselguhr) [1-5].
[0006]
Now alongside with glycerine trinitrate other ni- The proposed invention relates to modifiers trates of alcohols became important as explosives, that from the range of organic and inorganic compositions, is complex complete or/and incomplete ethers of alcohols capable to modify their thermodynamic parameters, and nitric acid, for example, methyl nitrate, ethyl nitrate physical, chemical, biochemical properties for explo- [4], ethylene glycol dinitrate [2,4], propylene glycol dini- sives, including gas generating compositions, rocket fu- trate [2], mannitol hexanitrate, pentaerythritol tetranitrate [1] and so on [6, 7, 8]. They are safer to operate as com- It is known, that when interacting (etherification) pared to glycerine trinitrate, but as well as the latter they with a mix of nitric and sulphuric acids the monoatomic are also unsuitable for use when shooting with fire-arms.
(alkanols, alcohols), diatomic (alkanediols, glycols, di- It is known, that in a molecule of cellulose ols), triatomic (triols, glycerin), multinuclear (absolute va- formed from a molecule of glucose, the alcohol hydroxyl lence) alcohols and their possible isomers easily form groups of glucose persist, that puts cellulose to the class corresponding complex, complete or/and incomplete of alcohols and defines its properties of alcohols [1-5], ethers of nitric acid (nitrate ethers, nitric ethers, nitrates) and a molecule of cellulose contains three hydroxyl [1-5] which are to some extent explosive, where the ni- groups, therefore during its interaction (etherification) trates of monoatomic alcohols are less explosive, than with a mix of nitric and sulphuric acids the complex com- nitrates of multinuclear alcohols [3], that defines their ap- plete, and incomplete nitrate ethers of celluloseare are plication as brisant substances [3], that is rapidly decay- formed, i.e. depending on conditions of reaction of eth- ing substances with releasing great volume of strongly erification the residues of nitric acid can replace one, two heated gases [2, 5], that is they are shattering explosives or all the three hydroxyls thus forming accordingly [1] used in blasting operations [1-5], but inapplicable in mononitrate, dinitrate and trinitrate of cellulose [or small arms [1-5] as there would be not a shot, but a shat- mononitro, dinitro and trinitro cellulose] [5].
tering explosion with break of a gun tube, and the pro- It is known, that trinitro cellulose or pyroxylin jectile would not have time to leave the gun tube[1].
where all the three hydroxyls are replaced by the residues One of such representatives for explosives is of nitric acid [1-5], as well as glycerine trinitrate, is a det- the complex complete ether of triatomic alcohol (glycerin) onating explosive featuring high energy and it is applied and nitric acid, the glycerine trinitrate incorrectly named as shattering explosive in blasting works, but it is not nitroglycerine [1, 3-5]. Glycerine trinitrate blows up from applied when shooting from gun and rocket weapon as a push [1], heating [5], impact, shock, under influence of the shattering explosion would break the installation be- detonation, for example explosion of a fuse of mercuric fore the projectile would come to movement [1-5]. For fulminate, as a result of self-decomposition [2], and sim- using the trinitro cellulose in gun systems it is necessary ple touch [3], however the simplicity of process of syn- to slow down the speed of its combustion so as to grad- thesising the glycerine trinitrate, its low-stage and low- ually accrue the pressure of formed gases to set a pro- waste, as well as availability and cheapness of initial sub- jectile in motion (to push it out) [1-5]. For reducing the stances (semi-products) for producing glycerine trinitrate speed of its combustion the trinitro cellulose is being makes its manufacturing economic, while the constancy gelled using various solvents, for example such as ace- of structure as a target product which is the glycerine tone, vinegar amyl ether and others [1], i.e. trinitrate of trinitrate itself, and insignificant quantity of impurity, that cellulose swells and forms dense jellylike mass; such a is very important when making compositions (structures, mass is used for pressing tapes of various thickness and compoundings) based thereon, makes it a rather prom- sizes which after drying may be applied as a smokeless ising composition (substance) as compared to other sub- gunpowder. They are burning down more slowly than stances of similar application (purpose, use) [1-5].
trinitrate of cellulose that enables to use them for shooting There is known application (use) of glycerine from gun and rocket installations. For obtaining a weapon trinitrate in structure of bibasic gunpowders [1-5], various smokeless gunpowder they are being cut to fine slices.
kinds (embodiments) of dynamite [1-5].
It is known, that trinitrate of cellulose is also being gelled Glycerine trinitrate in the pure state is not ap- by using glycerine trinitrate thus the formed mass repre- plied because of its extreme instability, and, during its sents a special kind of dynamite also used in blasting decomposition not only enormous quantity of energy is works under the name "blasting gelatin" [1]. As the prop- liberated as heat and huge volume of the heated gases: erties of trinitrate of cellulose are similar to those of similar nitrogen, water, carbon dioxide, but also oxygen in free complete or incomplete ethers formed during interaction condition [1, 2] which may be used for amplification for (etherification) of our proposed corresponding alcohols explosive action of glycerine trinitrate in its mix with com- with a mix of nitric and sulfuric acids the principles of the bustible materials including ethers of nitric acid of mono- approach to the decision of tasks for purposeful modifi- atomic, diatomic, triatomic and multinuclear alcohols, as cation of thermodynamic (thermochemical) parameters well as cellulose [1-5], thus it is possible to obtain dyna- and stability influences negatively influencing the prop- mites with active and inactive weight [1], for example, erties and quality of trinitrate of cellulose are authentic, with fossil meal, a special kind of silica (porous SiO2, as well as the substances (compositions) applied (used) EP 2 128 117 A2
as universal modifiers of new composite structures of Nedra, 1980, p.28.], in materials of these works, as a compoundings of power systems of driving force based rule, structures of explosives, possess significant sensi- thereon. And some grades of smokeless gunpowders tivity a different sort to mechanical and other influences, consist of a mix containing at the same time trinitrate of thus the required result is not always reached.
cellulose and ∼30% of glycerine trinitrate [4], thus the use It is known that till now hexogen, octogen are (application) of the only and the same universal modifier applied (are used) as brisant explosives which possess allows not only to improve the compatibility of compo- high sensitivity and consequently cannot be applied nents in a somewhat componental system, but also to (used) in the pure state. For lowering their sensitivity and exclude or reduce the general contents of each of its maintaining safe handling they are used (applied) only components as the use (application) of the universal in a combination with various unexplosive additives (re- modifier allows to reject the use of many other compo- tarders), as additives (retarders) are used unsaturated nents necessary for obtaining required properties, and and saturated solid hydrocarbons, such as wax, paraffin, also to provide additional improvement of other proper- ceresin and other chemical substances (compositions) ties, including, bio-, radio-, light, thermal, chemical and similar to such compositions as stearin, and also various antioxidizing stability which the system gets when use rubbers and polymers plasticized by inactive and active only one of our proposed universal modifiers.
(explosive) softeners. Powerful explosives usually con- Further to our study of materials of periodic and tain in their structure retarders from 2,5 up to 10 mas. % patent literature concerning the use (application) of ex- [Patent RU 2252925 CL. C 06 B 25/34, 45/22, plosives and compositions based thereon, intended for 28.10.2003, publ. 27.05.2006. Bul. NT 15]. In this work the various purposes, we defined the main drawback, [LLNL Explosive Handbook. Properties of Chemical Ex- namely, the constant and limited set of additives which plosive and Explosive Simlants/Dobratz B.M., Livermore, are not featuring sufficient efficiency and versatility, and, California, 1981.] explosive structures containing hexo- the compositions created on their basis (structures, com- gen (95-93,5 %) and a retarder (5-6,5 %), consisting of poundings) do not solve many problems related to sen- a mix of synthetic ceresin (45 %), natural ceresin (15 %), sitivity, temperature, pressure, volume of formed sub- stearin (38,8 %) and orange fat-soluble dye (1,2 %) are stances, to their structures and ecological compatibility, cited; octogen (97,5 %) and a retarder (2,5 %), consisting speed of burning and its transition to detonation.
of polymethyl methacrylate (1,2 %), graphite (0,5 %), and Till now there are intensive works for creating oxysin (0,8 %), and other widely used mix explosive com- new composite compounds of explosives having univer- It is known, that smokeless gunpowders are (composition) from the class of cyclic nitramines produced on the basis of nitrates of cellulose in structure 2,4,6,8,10,12-hexa-nitro- 2,4,6,8,10,12-hexa- azo-tetra- with various softeners. There are smokeless gunpow- cyclo (5,5,0,03,11, 05,9) dodecane as compared to hexo- ders on the basis of glycerine trinitrate (ballistites) and gen and octogen, and as to chemical stability and sen- pyroxylin [the Soviet encyclopaedic dictionary.-M.: Sovi- sitivity it is similar to octogen, it features high sensitivity et encyclopedia, 1983, p.119]. Smokeless gunpowders, to different sort of mechanical influences and low chem- both artillery ballistite and pyroxylin, and ballistite rocket ical stability. [Patent RU NT 2199540 from 26.04.2001.
firm fuel differ the big variety on ra ap THO-mass pa- Method for obtaining the 2,4,6,8,10,12-hexa-nitro- rameters (characteristics), structure, sensitivity a various 2,4,6,8,10,12-hexaazo-tetracyclo (5,5,0,03,11,05,9) do- sort to mechanical influences, power parameters, speed decanes. Sysoliatin S.V., Lobanova A.A., Chernikova of burning, sensitivity a detonation pulse. Now the explo- sives most used in the industry are the hexogen and an In the work [Patent US NT 5587533, High per- octogen, however they possess high sensitivity a differ- fomanse pressable explosive compositions/Braithwaite ent sort to mechanical influences and cannot be applied P. C., Lund O. K., Wardle R. B.] explosive compositions without input in their structure of retarders [Patent RU based on 2,4,6,8,10,12-hexa-nitro-2,4,6,8,10,12-hexa- NT2226522, Cl. C 06 B 25/00,21/00,25/24,31/32, C 06 azo-tetracyclo (5,5,0,0,1,11, 05,9) dodecane and a retard- er (an active binding additive) in quantity of 5-10 mas.%, There are known powder explosive composi- consisting of polyglycidil nitrate, polyglycidil azide and tions (structures, compoundings) on the basis of smoke- less pyroxylin, artillery ballistite gunpowders, ballistite In the work [Simpson R.L., Urtiew P.A., Ornellas solid rocket fuels, their mixes [Patents RU NTNT D.L., et al. CL-20 performance exceeds that of HMX and 1810321; 2021239; 2026274; 2026275; 2046117; its sensitivity is moderate // Propellants, Explosives - 2074160; 2092473; 2099396; 2130446, 2176632; 1997 - NT 22 - Pp. 249-255.] a composition consisting of 2086524 C1 10.08.1997; 2122990 C1, 10.12.1998; a basis of 2,4,6,8,10,12-hexa-nitro-2,4,6,8,10,12-hexa- 2096396 C1, 20.11,1997; GB 1265718, 08.03.1992; GB azo-tetracyclo (5,5,0,0,1,11, 05,9) dodecane (CL-20) re- 1307967, 21.02.1973; Patents US NTNT 3235425; tarded by polyurethane polymer Estane-5703-P, is of- 3186882, 01.06.1965; 3713917, 30.01.1973; 4555276; fered, and this composition features higher sensitivity 5445690; Kuk M.A. Industrial explosives science - M.: than the composition of octogen with the same poly- EP 2 128 117 A2
lutions) featuring enough low sensitivity to various me- In the work [Patent RU 2252925, Cl. C06 B chanical influences is rather urgent till now and it is not 25/34, 45/22, 28.10.2003, publ. 27.05.2006. Bul. NT 15] yet solved because the common drawback of the de- a composition based on 2,4,6,8,10,12-hexa-nitro- scribed explosive compositions is the high sensitivity to 2,4,6,8,10,12-hexa-azo-tetracyclo (5,5,0,0,3,11,05,9) do- various mechanical influences. Therefore creating new decanes (98,5-97 mas.%) and a retarder (1,5-3 mas.%) explosive compositions using our offered modifiers that is offered, it consists of stearin acid and-or paraffin and- were unknown earlier for the given purpose, with me- or ceresin or their mixes though works for improving the chanical and other properties set depending on the object properties of explosive compositions on the basis of these compounds (substances) are still in progress and The common drawback of explosive composi- there is some success, however it is rather difficult to tions described in these patents materials is their high reach the results allowing to apply (to use) them safely sensitivity to various mechanical influences.
according to their intended purpose because of their in- Till now the task of creating explosives de- signed for manufacturing extended and sheet charges, It is known, that application (use) of liquid ex- detonating tape and other similar materials (products) for plosive compositions (substances) and their composite special explosive works is rather urgent and promising.
structures of compoundings is one of important and There are known plastic explosive substances hexo- promising directions for solving certain tasks of various plasts HP-74; HP -87; HP -87K [« The list of recommend- special-purpose designations, and the consistent solu- ed industrial explosive materials.» M: Nedra, 1977, page tions on their basis being liquid or heterogeneous, under 28.] and elastic explosives [Patent US 3723204, Cl.
usual conditions are easier to produce as compared to 149-19 C 06B 3/00, C 06C 1/100, 1973; Patent UK NT solid explosives (compositions). [Patent RU 2063944, Cl.
1297706, Cl, C 06B 15/01, 1970], such explosives belong C 06 B 25/10, 1996, publ. in Bul. NT 20 from 20.07.96].
to mix of efficient crystal explosives, as a rule it is hexogen However, the use (application) of liquid explo- in a combination with various binding substances, for ex- sives such as glycerine trinitrate or compositions (struc- ample, rubbers which content in composite materials tures, compoundings) based thereon is seriously limited ranges from 13 to 30%. These compositions are used because of their very high sensitivity to various mechan- (applied) for special explosive works. However they fea- ical influences, however high-energy substances (com- ture high sensitivity to various mechanical influences, positions), in particular glycerine trinitrate, are constant thus the frequency of explosions during phasic test objects for creating on the basis thereon explosive com- makes 70% and the transition of burning of these com- positions for various purpose. For reducing (decreasing) positions to their explosions is quick and fast.
their sensitivity to various influences some retarding ad- There is a known explosive composition con- ditives are used (applied). Using such additives a lot of taining colloxylin as a basis, plasticized by liquid nitro- so-called, tri-nitro-glycerin explosive compositions (sub- esters of multinuclear alcohols, for example, glycerine stances, compoundings) for various special-purpose trinitrate, as well as the stabilizer for chemical stability.
designations, including industrial (commercial) explo- [Svetlov B.Ya. and Yaremenko N.E. The theory and prop- sives, such as pobedits, detonites and similar com- erties of industrial explosives. M.: Nedra, 1973, p.185.].
pounds are created. Though these compositions (com- This explosive composition features high explosibility.
pounds) feature rather low sensitivity to mechanical in- There is a known explosive composition also fluences due to low contents (approximately 10 %) of containing colloxylin as a basis, and plasticized by liquid glycerine trinitrate and at the same time, and for the same nitroesters of multinuclear alcohols, for example, by glyc- reason they feature low energy characteristic (response).
erine trinitrate; stabilizer for chemical stability and fine- There is known a number of compositions (sub- dyspersated particles of high density substance. The sta- stances, compoundings) on the basis of glycerine trini- bilizer for chemical stability is centralite. [Patent RU trate [Patent US 3108916, Cl. C 06 B 19/02, 1963. Patent 2105746, Cl. C 06 B 25/18. Publ. 27.02.1998 in Bul. NT 6].
US 2988436, CI. C 06 D 5/04 1961. Patent US 4011114, Till now creating the gas generating composi- CI. C 06 B 45/10, 1976]. These compositions (compound- tions, including those for fire extinguishers, safety bags ings) feature rather high sensitivity to mechanical influ- and other pneumatic devices is rather urgent and prom- ences and low energy properties because of low (small) ising. There is a known gas generating composition for oxygen factor. There is known use (application) of tri- fire extinguishers on the basis of ether of cellulose which methylolethane trinitrate as a retarder for glycerine trin- contains 30 to 40 % of softener substance (composition) itrate. [Patent US 3423256, CI. C 06 B 3/001969.] How- ever an essential decrease in sensitivity of liquid explo-sive composition is reached only in case of introducing a lot of retarder in glycerine trinitrate, thus its explosivecharacteristics (parameters) go down sharply. On the ba-sis of the above-stated it follows, that the problem of cre-ating a high-energy explosive heterogeneous bodies (so- [Patent US 3873579, Cl. C 06 D 5/06, 1975]. The tem- EP 2 128 117 A2
perature of burning of this composition makes 2000 to2500°K. Another gas generating composition for fire ex-tinguishers contains in mass.% dibutil phthalate (17),acetate of cellulose (7,6), N-methyl-p-nitroaniline (1), ni- trate of cellulose (30,4), trinitrate of pentaeritrit (37),ethyl centralite (2), tin oxides (5) while the temperatureof its burning makes 1700°K. [Patent US 3639183, Cl.
C 06 D 5/06, 1972]. The purpose of improvement of such compositions is lowering the sensitivity to various me- chanical influences and lowering the temperature of R 2 is absent or means H2O or 2H2O [Patent RU burning; and the main components of such composi- 2244703, Cl. C06 B 25/18, 21/00, 25/28 C06 D 5/00, tions remain almost without qualitative and quantitative 02.12.2003, publ. 20.01.2005 Bul. NT 2].
changes. Thus there is known a gas generating compo- The engineering problem of the invention con- sition consisting in mass.% of ratio of nitrate of cellulose sists in creating a universal modifier for explosives from (59-69) bases, 1,6-diazido-2-acetoxy-4-oxa-hexane a range of composite complete or incomplete nitrates of (30-40) as softener, while the other additives are dime- monoatomic, diatomic, triatomic or multinuclear alcohols, thyl diphenyl urea (0,5-0,6) and vaseline (0,4-0,5), and nitrocelluloses, nitroamines, azides, nitrobenzenes or ni- the temperature of burning of this composition makes troalkanes; introducing such a modifier in these explo- 1450°K [Copyright certificate RU NT 918289, M Cl. C 06 sives allows to modify their thermodynamic parameters, D 5/06. UDC 662.16 (088.8), publ. 07.04.82. Bul. NT13.
physical, chemical, biochemical properties and to create date of publication of the description 10.04.82], however on the basis of these explosives, with the introduced mod- all these compositions feature higher sensitivity to me- ifiers, explosive and unexplosive composite compounds chanical influences, high temperature and high speed having liquid (consistent), heterogeneous or solid aggre- gate state depending on objects in view (tasks) with re- Earlier it was considered, that acids promote quired properties that may vary, by varying the ratio of decomposition of many explosives (compositions) components included in the composition.
[L.A.Smirnov «The equipment for manufacturing ballis- The technical result of the invention is the inhi- tite gunpowders using auger technology and charges bition of premature decomposition of explosives (com- made of them», edited by L.V.Zabelina. M.: 1997]. How- pounds) at all the initial stages of development of this ever, there is known a stabilizer of chemical stability of process, with its subsequent initiation (activation) as a gunpowder, solid rocket fuel and gas generating compo- result of smooth and fast growth (increase) of tempera- sition on the basis of nitrocellulose, a boric or phospho- ture thus leading to explosive decomposition or burning rous acid, or an organic acid or its salt having the formula depending on sufficiency surplus of oxygen in the sys- tem, both due to oxygen-containing compounds (sub- stances), and as a result of emission of oxygen in a purestate when decomposing the substances (compounds)included in explosive composition, i.e. controlling the rateof their decomposition, as well as decrease in sensitivityof explosives to various mechanical influences, improve- The technical result is reached by using known, cheap and accessible compositions (substances) be- R2 =-H, -OH, -COOH, -COONa, the residue of composi- longing to inorganic, organic acids and their salts as a universal modifier for explosives from the range of com- plex complete or incomplete nitrates of monoatomic, di-atomic, triatomic or multinuclear alcohols, nitrocellulose,nitroamines, nitroanilines, azides, nitrobenzenes, nitro-alkanes and their mix, where the compositions belongingto inorganic or organic acids or their salts, are chosen from the following group: orthoboric acid, phosphorous acid or orthophosphoric acid, or composition having the EP 2 128 117 A2
R1 = - H, - OH, - COOH, - COONH4, - COONa, The composition having the formula (1) at R= R2 = - H, - OH, - COOH, - COONa, and R1 and R have H, R1= - COONa, R2= - COONa is the disodium salt of The composition having the formula (1) at R= - COOH, R1= - OH, R2 = -H is the salicylic acid.
[0038]
The composition having the formula (1) at R= - OH, R1= - COONa, R2= -H is the sodium salt of salicylicacid.
The composition having the formula (1) at R= - COOH, R1= - H, R2= -H =-H is the benzoic acid.
The composition having the formula (1) at R= - COONa, R1= - H, R2= -H is the sodium salt of benzoic The composition having the formula (1) at R= - COOH, R1= - H, R2= - OH is the para- oxybenzoic acid.
[0042]
The composition having the formula (1) at R= - H, R1= - COOH, R2= - OH is the meta-oxybenzoic acid.
[0043]
The composition having the formula (2) at R =- OH, R1 = single bond, R2 - absent, is the oxalic acid is.
[0044]
The composition having the formula (2) at R = - OH, R1 = single bond, R2 = 2H2O is the 2-water oxalic if R= -NO2; R1= R2= -H, it is a 2-nitrobenzoic acid (o- The composition having the formula (2) at R = if R1=-NO2; R=R2=-H, it is a 3-nitrobenzoic acid (m-ni- - OK, R1 = single bond, R2 - absent, is the lemon salt.
The composition having the formula (2) at R = if R2= -NO2; R= R1= -H, it is a 4-nitrobenzoic acid (p- - ONa, R1 = single bond, R2 - absent, is the sodium The preferable acids and salts of the above mentioned The composition having the formula (2) at R = - ONH4, R1 = single bond, R2 - absent, is the ammonium The composition having the formula (1) at R=- The composition having the formula (2) at R= - OH, R1 = - C2H4, R2 - absent, is the succinic acid.
[0049]
The listed compositions have, basically, rather low temperature of decomposition and rather high tem-perature of ignition, thus, a part of thermal energy will bespent for decomposing these substances when introduc- is the 5,5’- methylenedisalicylic acid.
ing them into the specified explosives, thus there will be The composition having the formula (1) at R= - a decrease of general (total) temperature of formed gas- es 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 burn-
ing of these compositions.
[0050]
The explosives from the range of complex com- plete or incomplete nitrates of monoatomic, diatomic, tri-atomic or multinuclear alcohols, nitrocelluloses, nitroam-ines, nitroanilines, azides, nitrobenzenes or nitroalkanes,where it is offered to introduce the above modifiers, may is the diammonium salt of 5,5 ’-methylenedisalicylic acid.
The composition having the formula (1) at R= H, R1= - COOH, R1= - COOH, R2= - H is the orthophthalic acid.
[0033]
The composition having the formula (1) at R = H, R1 = - COOH, R2 = - COOH is the isophthalic acid.
The composition having the formula (1) at R= - COOH, R1= H, R2= - COOH is the terephthalic acid.
[0035]
The composition having the formula (1) at R= - COONa, R1= H, R2= - COONa is the disodium salt of EP 2 128 117 A2
1 = -CH2O-NO2; n=1, is a glycerol trinitrate Trinitrate of cellulose (trinitro cellulose, trinitrate of cellulose, trinitrate) - [C6H7O2 if R= -CH2-O-NO2; R1 = -H; n =1, is an ethylene glycol 3; R1= -CH2-O-NO2; n=1, is a propylene gly- K N, N’-bis (K,K,K,-trinitroethyl) car- if R=R1 = -CH2-O-NO2; n=4, is a mannitol hexanitrate bamide, or N, N’-bis(K,K,K - trinitroethyl) if R= -CH2CL; R1= -CH2-O-NO2; n=1, is a monochlo-rhydrin dinitrate;if R=-H; it is pentaerythritol tetranitrate (penthrite); Nitroisobutyl glycerinetrinitrate having the for-mula if R1= -NO2; R2=R3=R4=R5= -H, it is an N-nitroaniline;if R1=R4= -NO2; R2 = -CH3; R3=R5= -H, itis a 4-nitrophenyl-N-methylnitroamine (N-nitro - N-methyl 4-nitroamine); if R1=R5= -H; R2= -CH3, R3=R4= -NO2, it isa 2,4-dinitro-N-methylaniline;if R1= R3=R4= -NO2; R2 = -CH3; R5= -H, it is a 2,4-di-nitrophenil-N-methylnitroamine (N-nitro - N-methyl - 2,4-dinitro - aniline); if R1 -H; R2 = -CH3; R3=R4=R5 -NO2, it isN-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 K Diglycerin tetranitrate having the formula N-methyl - 2,4,6-trinitroaniline;if R1=R3=R4 = R5 = - NO2; R2 = - CH3, itis 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 K Diethyleneglycol dinitrate (diglycol dini- trate, dinitrodiglycol) having the formula methyl - N, 2,4,6-tetranitroaniline (N-methyl- N-nitro - 2,4,6-trinitroaniline or 2,4,6-trini-troaniline - N-methylnitroamine, tetryl);If R1=R2= -H; R3=R4= R5= - NO2, - it is a EP 2 128 117 A2
K .1,3,5,7-tetranitro-1,3,5,7-tetraazocy- clooctane(cyclotetramethylene - tetrani-troamine, octogen) it is 2,4,6-trinitrophenol (picric acid);if R .2,2’,4,4’,6,6’ - hexanitrodiphenyl; K .2,2’,4,4’,6,6’ - hexanitrodiphenylsul- it is 2,4,6-trinitroresorcin (TNR, stifnine ac- K .2,2’,4,4’,6,6’ - hexanitrodiphenylsulfone; K .2,2’,4,4’,6,6’ - hexanitrostylbene; .3,3’-diamino-2,2’,4,4’,6,6’ - hexanitro- it is 2,4,6-trinitroanisol (2,4,6-trinitro meth- it is 2,4,6-trinitrotoluene (trotyl, a TNT); K .C6(NO2)3(N3)3- trinitrotriazidobenzene; The above cited (designated) explosives (com- positions) and their mixes do not limit the possible as-sortment of various other explosives (copositions) that incombination (mix) with our proposed compositions (sub-stances) from between organic, inorganic acids and their salts or other of substances (compositions), featuringsimilar properties and used as universal modifiers, may R5 = - H, is 1-methyl - 3-tert - butyl - 2,4,6- also similarly (purposefully) influence various parame- ters and properties of new energy systems of driving force created on their basis with characteristics required for any specific purpose, where, the same explosive com-position may feature different speed of decompositiondepending on the way (method) of its activation, and mayalso show the properties of simple burning not passingto detonation or brisances, i.e. to carry out the possibility is 1,3-dimethyl - 5-tert-butyl - 2,4,6-trini- of application (use) of two-component explosive compo- sition on basis of the cited obtained explosives in a com- if R1 = R1= R3 -CH3; R2=R4=R6= -NO2; R5=- bination (mix) with our offered modifiers in an individual H, it is 2,4,6-trinitro meta-xylene (1,3-dime- kind of each of them, as an active principle of a new composite structure of compoundings of monobasic gun- powders, gas generating compositions with or without K . 1,3,5-trinitro- 1,3,5-triazacyclo-hexane using (application) pyroxylin (pyroxylin-free gunpow- ders) in their composition.
[0052]
As the operating principle of our offered modi- fiers in various composite structures of compounds for the specified classes of explosives (compositions) is es-sentially the same, and it consists in that these modifiersand substances (compositions) having similar propertiesunder certain conditions may decay with emitting gase- EP 2 128 117 A2
ous products, and in presence of enough of oxygen in and oxalic acids (crystalline hydrate) Ty standard the system may occur not only their decomposition, but 2642-001-07500602-97 were prepared from their solu- also burning or a combination of these processes, thus tions in ethyl alcohol GOST 18300-87 by mixing at a room there may be a thermodynamic (thermochemical) effect temperature and further removal of ethyl alcohol by keep- of significant decrease in temperature and increase in ing in exhaust case until a film is formed. The mixing did volume of the formed gases, and incidental proportional not cause changes of temperature, color and sedimen- development of certain pressure [and the effect of de- tation. The compositions have been investigated using crease in temperature of gases is most pronounced in a microscope and a significant decrease in heterogeneity case when the compositions (substances) having the was marked with increase of the oxalic acids (crystalline temperature of decomposition that is lower or coincides hydrate) content. The density of structures made ρ = with the temperature of ignition are used (are applied) as 1,7-1,75 g/cm3 (high density compositions).
modifiers], our approach to creating explosive and unex-plosive energy systems of driving force with the proper- Example 2
ties set depending on the object in view is general and universal for all such systems. Using such an effect is A thematic example of influence of the pro- rather urgent when creating low erosion, low-kindle or posed salts of organic acids is the influence of ammonium «cold gunpowders». When the properties of substances oxalate (crystalline hydrate) on glycerine trinitrate. In Fig.
do not satisfy these conditions there may be an increase 3 there is a diagram of decomposition of a mix of ammo- in total temperature effect. The modifier for our offered nium oxalate (crystalline hydrate) with glycerine trinitrate explosives may be used in case of the ratio modifier/ in mass ratio 1:1 accordingly, it was been found that in- explosive equal to (0,1-99,9 : (99,9-0,1).
troducing ammonium oxalate (crystalline hydrate) does For increasing (raising) the enrgy characteris- not worsen the heat-resistant characteristics of glycerine tics (properties) of our offered composite structures trinitrate, but also renders inhibitory action on its auto- (compositions) it is possible to introduce in them metallic catalytic decomposition. It is also determined, that the composition is not sucseptible to transition of burning to For giving various consistent properties includ- explosion or detonation. The mixes were prepared sim- ing the plasticity to such explosive and unexplosive com- posite structures it is possible to use binding, gelatinizing(swelling) and polymeric compositions (substances).
Example 3
Examples, illustrating the invention.
Thematic examples are mixes of oxalic acids (crystalline hydrate) with glycerine trinitrate, thus the mix- Researches of mixes of each of modifiers and es prepared in mass ratio: composition NT1 - 1:5, com- each of explosives regarding the compatibility and influ- position NT2 - 1:2, composition NT3 - 1:1, composition ence of modifiers on heat-resistant characteristics of ex- NT4 - 2:1 accordingly, have been tested for explosive plosives. It is marked, that introduction of modifiers not characteristics using a Kast’s impact machine OST B only does not reduce the heat-resistant parameters of 84-892-74 (Sensitivity impact using an impact machine explosives, but also makes an inhibitory effect on their at the bottom limit with instr. NT1 and instr. NT2) and the autocatalytic decomposition. Researches were carried out using an installation for defining the temperature ofthe beginning of intensive decomposition (Tbid) and Composition NT1 with a load of 2 kg. and height phase transformations of polymeric materials using the Ho=250 mm. (instr. NT2). The percent of explosions DTC method (differential thermocouple) according to Structure NT2 with a load of 2 kg. and height Ho=250 mm. (instr. NT2). The percent of explosions made Example 1
55 %,Composition NT3 with a load of 10 kg. and height A thematic example of influence of the offered Ho=250MM. (instr. NT2). The percent of explosions acids is the influence of oxalic acid (crystalline hydrate) on glycerine trinitrate. In Fig. 1 and Fig. 2 there are the Composition NT4 with a load of 10 kg. and height diagrams of decomposition of mixes of oxalic acids (crys- Ho=250MM. (instr. NT2). The percent of explosions talline hydrate) with glycerine trinitrate in mass ratio 1:2 and 1:5 accordingly; it was been found that introducting The detonation of glycerine trinitrate is caused when oxalic acids (crystalline hydrate) does not worsen the dropping a 2 kg. load from a height of Ho=40mm [9].
heat-resistant characteristics of glycerine trinitrate. It is Composition NT3 with a load of 10 kg. Ho> 500 mm.
also determined, that the composition is not susceptible to transition of burning to explosion or detonation.
Composition NT4 with a load of 10 kg. Ho> 500 mm.
Mixes of glycerine trinitrate (OST B 84-2386) EP 2 128 117 A2
The compositions have been tested for sensi- tivity to shock-free friction at the bottom limit (OST B84-894-74) at a speed of disk rotation (friction) of 520 Example 4
rev/min. Thus the sensitivity to shock-free friction at the bottom limit of composition NT3 makes Po > 3000 kilo- The thematic example are also the obtained gram-force/cm2 and of composition NT4 - Po = > 3000 compositions of pyroxylin with salt of methylenedisalicyl- kilogram-force/cm2-The tests were carried out at a tem- ic acid. Thus when introduting it up to 0,5 % of mass., the stability of gunpowders made 3,5 to 4,5 kPa, at a The compositions have been tested for sensi- norm of 8 kPa. When introducing the diammonium salt tivity to friction at a shock shift at the bottom limit (OST of methylenedisalicylic acid up to 20% of mass. essential B 84-895-83). Thus the sensitivity to friction at a shock decrease in temperature of the formed gases down by shift at the bottom limit of composition NT3 was equal to 700-800 °K was marked, while maintaining acceptable Po=750 kilogram-force/cm2 and of composition NT4 As a result of tests of samples with various per- Example 5
centage of glycerine trinitrate and oxalic acid (crystallinehydrate), it is possible to reckon the mix of 50%-60% of The obtained compositions of pyroxylin with glycerine trinitrate and 50%-40% oxalic acid (crystalline lemon salt may also servea thematic example, because hydrate) accordingly, among substances featuring low when introducing it up to 0,5 % mass., the stability of sensitivity to mechanical influences thus it is possible to gunpowders made 3,5-4,5 kPa, at a norm of 8 kPa. When operate with them while observing conventional security introducing the lemon salt up to 20 % mass., the obtained compositions had the power of gunpowder comparable The compositions have been tested for speed to the normal one at a level of 1030 to 1060 kJ/kg.
of explosive transformation (detonation) OST B The obtained data as to characteristics of com- 84-90074, susceptibility to transition of burning to explo- positions in the Examples 1 and 2 allow to assume the sion or detonation - the character of destruction of a pipe possibility of their application for modifying the properties with indicating its dimensions and estimating the explo- of gunpowders, including control of temperature, of the sive process according to OST B 84-90074, thus the com- position with the content of oxalic acid (crystalline hy- Alongside with experimental data we have also drate) with glycerine trinitrate of 40%-60 % accordingly, obtained thermodynamic calculated values of obtained has shown the following characteristics: the density ρ = compositions which had good convergence of results and 1,75 g/cm3, the speed of detonation D = 6370 m/s, the completely confirmed the experimental data and the composition is not susceptible to transition of burning to explosion or detonation; the composition with the content On the basis of that the principle of action of our of oxalic acids (crystalline hydrate) with glycerine trini- first proposed modifiers for new power systems of driving trate of 60%-40 % accordingly, has shown the following force for all classes of explosives (compositions) though characteristics: the density ρ = 1,7 g/cm3, the speed of essentially the same, however each individual explosive, detonation D = 880-2230 m/s, the composition is not sus- as well as any other composition (substance) possesses ceptible to transition of burning to explosion or detona- certain unique inherent properties (physical, chemical, mechanical and others), that is each new power system For giving various consistent properties includ- of driving force on their basis has its own "know-how" ing plasticity to such explosive and unexplosive compo- having certain information value, but not influencing on sitions, gelatinating (swelling) and polymeric composi- essence of the invention as a whole and that are some- tions (substances) were used, such as pyroxylin, colloxy- times inexpedient to open with a view of the further pres- lin and other compositions in monobasic and bibasic ervation of priority of the trend itself and of the time of composite materials with our offered modifiers. Thematic research process, therefore our obtained data and some examples are the obtained structures: oxalic acid (crys- results, having certain dependence and convergence in application conditions of our proposed modifiers in a 7 % with speed of burning 0,5 mm/s and temperature of combination (mix) with the cited explosive compositions burning ∼800°K (at P=40 and temperature 20°C) - the (substances) are not always outlined in the description product is plastic, it is susceptible to molding; and oxalic of materials in the text or being restricted.
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 (The list of documents quoted and taken into The product is plastic, it is susceptible to mold- ing, there is also an expressed influence of the modifieron the speed of burning and temperature of the obtained 1. E.S. Hotinsky. The course of organic chemistry. - EP 2 128 117 A2
Kharkov.: Publishing house of the Kharkov Red La- bour Banner Award A.M.Gorky National University, 2. B.A.Pavlov and A.P.Terentyev. The course of or-ganic chemistry. - Moscow.: National scientific andtechnical publishing house of chemical literature,1961. - 592 pp.
3. A.E. Chichibabin. Principles of organic chemistry.
Volume I. - Moscow.: National scientific and techni- cal publishing house of chemical literature, 1963. -912 pp.
4. A.N. Nesmeyanov, N.A. Nesmeyanov. Principlesof organic chemistry. Book one.-Moscow.: Publish-ing house "Khimiya", 1974.-624 pp.
5. B.N. Stepanenko. The course of organic chemistry Part I. Aliphatic compositions. - Moscow.: Publishinghouse "Vysschaya shkola", 1976. - 448 pp.
where R= - OH, - OK, - ONH4, - ONa,R1 = a single bond or - C2H4, 6. E.Ju. Orlova. Chemistry and technology of brisant substances. - Moscow.: Scientific and technical pub- lishing house OBORONGIZ, 1960 - 396 pp.
2. Modifier as claimed in Claim 1 whereas the com-
position having the formula (1) at R= - OH, R1 = -
7. E.Ju. Orlova. Chemistry and technology of brisant substances. - Leningrad.: Publishing house "Khimi-ya", 1973. - 688 pp.
8. Ju.A. Lebedev, E.A.Miroshnichenko, Ju.K. Kno-bel. Thermochemistry of nitro compounds. Publish-ing house "Nauka". Moscow. 1970. - 168 pp.
is 5,5’-methylenedisalicylic acid.
9. Orlova E.Ju.Chemistry and technology of brisant 3. Modifier as claimed in Claim 1 whereas the com-
substances: Textbook for high schools - Ed., - 3rd position having the formula (1) at R= - OH, R1= - ed., rev. - L.: Khimiya, 1981.-312 pp.
1. Modifier for explosives from a range of complex
complete or incomplete nitrates of monoatomic, di-
is diammonium salt of 5,5’-methylenedisalicylic ac- atomic, triatomic or multinuclear alcohols, nitrocel- luloses, nitroamines, azides, nitrobenzenes, ni-troanilines, nitroalkanes and their mixes being an in- 4. Modifier as claimed in Claim 1 whereas the com-
organic acid chosen from the following group: or- position having the formula (1) at R= - COOH, R1= thoboric acid, phosphorous acid, orthophosphoric - COOH, R2= - H is orthophthalic acid.
acid or organic acid chosen from the following group: 2-nitrobenzoic acid, 3-nitrobenzoic acid, 4-nitroben- 5. Modifier as claimed in Claim 1 whereas the com-
zoic acid, or composition having the formula (1) position having the formula (1) at R= H, R1= - COOH,R2= - COOH is isophthalic acid.
6. Modifier as claimed in Claim 1 whereas the com-
position having the formula (1) at R= - COOH, R1=H, R2= - COOH is terephthalic acid.
7. Modifier as claimed in Claim 1 whereas the com-
EP 2 128 117 A2
position having the formula (1) at R= - COONa, R1= trate, methyl nitrate, ethyl nitrate, ethylene glycol din- H, R2= - COONa is disodium salt of terephthalic acid.
itrate, propylene glycol dinitrate, mannitol hexani-trate, monochlorhydrin dinitrate, pentaerythritol 8. Modifier as claimed in Claim 1 whereas the com-
position having the formula (1) at R= H, R1= - COO-Na, R2= - COONa is disodium salt of metaphthalic 23. Modifier as claimed in Claim 1 whereas it is a
modifier for explosive from the range: nitroisobutylglycerinetrinitrate or diethanol-N-nitroamine dini- 9. Modifier as claimed in Claim 1 whereas the com-
trate, either diglycerin tetranitrate, or diethylenegly- position having the formula (1) at R= - COOH, R1= 24. Modifier as claimed in Claim 1 whereas it is a
10. Modifier as claimed in Claim 1 whereas the com-
modifier of trinitrate of cellulose.
position having the formula (1) at R= - OH, R1= - COONa, R2= -H is sodium salt of salicylic acid.
25. Modifier as claimed in Claim 1 whereas it is a
modifier for explosive from the range: ethylene - N,
11. Modifier as claimed in Claim 1 whereas the com-
N ’-dinitramine or nitroguanidine, or nitrourea, or N, position having the formula (1) at R= - COOH, R1= N’-bis (b, b, b trinitroethyl) carbamide, or N, N ’-bis (b, b, b trinitroethyl) urea, or N-nitroaniline, or 4-ni- trophenyl-N-methylnitroamine, or 2,4-di-nitro - N- 12. Modifier as claimed in Claim 1 whereas the com-
methylaniline, or 2,4-dinitrophenyl - N-methylni- position having the formula (1) at R=- COONa, R1=- troamine, or N-methyl-2,4,6-trinitroaniline, or N-me- H, R2= -H is sodium salt of benzoic acid.
thyl-N, 2,4,6-tetranitroaniline, or N-methyl-N, 2,4,6-tetranitroaniline, or 2,4,6-trinitroaniline.
13. Modifier as claimed in Claim 1 whereas the com-
position having the formula (1) at R= - COOH, R1=
26. Modifier as claimed in Claim 1 whereas it is a
- H, R2= - OH is para-oxybenzoic acid.
modifier for explosive from the range: 2,4,6-trinitro-phenol, or 2,4,6-trinitrochlorbenzene, or 2,4,6-trini- 14. Modifier as claimed in Claim 1 whereas the com-
troresorcin, or 2,4,6-trinitroanisol, or 1,3-diamino- position having the formula (1) at R= - H, R1= - 2,4,6-trinitrobenzene, or 1,3,5-triamino-2,4,6-trini- COOH, R2= - OH is meta-oxybenzoic acid.
trobenzenes, or 2,4,6-TNT, or trinitrocreosol, or1,3,5-trinitrobenzene, or 1-methyl-3-tert-butyl-2,4,6- 15. Modifier as claimed in Claim 1 whereas the com-
trinitrobenzene, or 1,3-dimethyl-5-tert-butyl-2,4,6- position having the formula (2) at R= -OH, R1= single trinitrobenzene, or 2,4,6-trinitro-meta-xylene, or an 16. Modifier as claimed in Claim 1 whereas the com-
27. Modifier as claimed in Claim 1 whereas it is a
position having the formula (2) at R= - OH, R1= single modifier for explosive from the range: 1,3,5-trinitro- bond, R2= 2H2O is oxalic acid dihydrate.
1,3,5-triazacyclohexane or 1,3,5,7-tetranitro- 17. Modifier as claimed in Claim 1 whereas the com-
position having the formula (2) at R= - OK, R1= single
28. Modifier as claimed in Claim 1 whereas it is a
modifier for explosive from the range: 2,2’, 4,4’, 6,6’-hexanitrodiphenyl, 2,2’, 4,4’, 6,6’-hexanitrodiphenyl- 18. Modifier as claimed in Claim 1 whereas the com-
sulphide, 2,2’, 4,4’, 6,6’-hexanitrodiphenylsulfone, position having the formula (2) at R= - ONa, R1 = 2,2’, 4,4’, 6,6’-hexanitrostylbene, 3,3’-diamino-2,2’, single bond, R2 - absent, is sodium oxalate.
4,4’, 6,6’-hexanitrodiphenyl, 2,4,6-hexanitrodiphe-nylamine, an isomer of trinitronaphthalene, an iso- 19. Modifier as claimed in Claim 1 whereas the com-
position having the formula (2) at R= - ONH4, R1=single bond, R2 - absent, is ammonium oxalate.
29. Modifier as claimed in Claim 1 whereas it is a
modifier for explosive from the range: tetranitrometh-
20. Modifier as claimed in Claim 1 whereas the com-
ane, 1,2-dinitroethane, 1,1-dinitroethane, 1,1,1-trin- position having the formula (2) at R= - OH, R1= - C2H4, R2 - absent, is succinic acid.
30. Modifier as claimed in Claim 1 whereas it is a
21. Modifier as claimed in Claim 1 whereas it is a
modifier for explosive from the range: trinitrotriazi- modifier for explosive from the range: glycerol trini- EP 2 128 117 A2
EP 2 128 117 A2
EP 2 128 117 A2
EP 2 128 117 A2
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