US20100096050A1 - Modifier for explosives - Google Patents

Modifier for explosives Download PDF

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Publication number
US20100096050A1
US20100096050A1 US12/445,387 US44538707A US2010096050A1 US 20100096050 A1 US20100096050 A1 US 20100096050A1 US 44538707 A US44538707 A US 44538707A US 2010096050 A1 US2010096050 A1 US 2010096050A1
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Prior art keywords
modifier
composition
formula
acid
cooh
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Ivanov Yuri Alexandrovich
Frolov Alexander Yurievich
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IFO LLC
IFOKHIM LLC
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IFO LLC
IFOKHIM LLC
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Publication of US20100096050A1 publication Critical patent/US20100096050A1/en
Assigned to LIMITED LIABILITY COMPANY IFO, IFOKHIM LLC reassignment LIMITED LIABILITY COMPANY IFO ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: IVANOV, YURI ALEXANDROVICH, OSININ, VLADIMIR VALERIEVICH, PEREVEZENTZEV, VLADIMIR MIKHAYLOVICH, FROLOV, ALEXANDER YURIEVICH
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    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
    • C06B23/006—Stabilisers (e.g. thermal stabilisers)
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
    • C06B23/005—Desensitisers, phlegmatisers

Definitions

  • the proposed invention relates to modifiers from the range of organic and inorganic compositions, capable to modify their thermodynamic parameters, physical, chemical, biochemical properties for explosives, including gas generating compositions, rocket fuels and gunpowders based thereon.
  • Glycerine trinitrate in the pure state is not applied because of its extreme instability, and, during its decomposition not only enormous quantity of energy is liberated as heat and huge volume of the heated gases: nitrogen, water, carbon dioxide, but also oxygen in free condition [1, 2] which may be used for amplification for explosive action of glycerine trinitrate in its mix with combustible materials including ethers of nitric acid of monoatomic, diatomic, triatomic and multinuclear alcohols, as well as cellulose [1-5], thus it is possible to obtain dynamites with active and inactive weight [1], for example, with fossil meal, a special kind of silica (porous SiO 2 , kieselguhr) [1-5].
  • glycerine trinitrate other nitrates of alcohols became important as explosives, that is complex complete or/and incomplete ethers of alcohols and nitric acid, for example, methyl nitrate, ethyl nitrate [4], ethylene glycol dinitrate [2,4], propylene glycol dinitrate [2], mannitol hexanitrate, pentaerythritol tetranitrate [1] and so on [6, 7, 8]. They are safer to operate as compared to glycerine trinitrate, but as well as the latter they are also unsuitable for use when shooting with fire-arms.
  • trinitro cellulose or pyroxylin where all the three hydroxyls are replaced by the residues of nitric acid [1-5], as well as glycerine trinitrate is a detonating explosive featuring high energy and it is applied as shattering explosive in blasting works, but it is not applied when shooting from gun and rocket weapon as the shattering explosion would break the installation before the projectile would come to movement [1-5].
  • trinitro cellulose in gun systems it is necessary to slow down the speed of its combustion so as to gradually accrue the pressure of formed gases to set a projectile in motion (to push it out) [1-5].
  • trinitro cellulose For reducing the speed of its combustion the trinitro cellulose is being gelled using various solvents, for example such as acetone, vinegar amyl ether and others [1], i.e. trinitrate of cellulose swells and forms dense jellylike mass; such a mass is used for pressing tapes of various thickness and sizes which after drying may be applied as a smokeless gunpowder. They are burning down more slowly than trinitrate of cellulose that enables to use them for shooting from gun and rocket installations. For obtaining a weapon smokeless gunpowder they are being cut to fine slices.
  • solvents for example such as acetone, vinegar amyl ether and others [1]
  • trinitrate of cellulose swells and forms dense jellylike mass
  • such a mass is used for pressing tapes of various thickness and sizes which after drying may be applied as a smokeless gunpowder. They are burning down more slowly than trinitrate of cellulose that enables to use them for shooting from gun and rocket installations. For obtaining
  • trinitrate of cellulose is also being gelled by using glycerine trinitrate thus the formed mass represents a special kind of dynamite also used in blasting works under the name “blasting gelatin” [1].
  • the properties of trinitrate of cellulose are similar to those of similar complete or incomplete ethers formed during interaction (etherification) of our proposed corresponding alcohols with a mix of nitric and sulfuric acids
  • the principles of the approach to the decision of tasks for purposeful modification of thermodynamic (thermochemical) parameters and stability influences negatively influencing the properties and quality of trinitrate of cellulose are authentic, as well as the substances (compositions) applied (used) as universal modifiers of new composite structures of compoundings of power systems of driving force based thereon.
  • smokeless gunpowders are produced on the basis of nitrates of cellulose in structure with various softeners.
  • smokeless gunpowders on the basis of glycerine trinitrate (ballistites) and pyroxylin [the Soviet encyclopaedic dictionary.-M.: Soviet encyclopedia, 1983, p. 119].
  • Smokeless gunpowders, both artillery ballistite and pyroxylin, and ballistite rocket firm fuel differ the big variety on -mass parameters (characteristics), structure, sensitivity a various sort to mechanical influences, power parameters, speed of burning, sensitivity a detonation pulse.
  • composition consisting of a basis of 2,4,6,8,10,12-hexa-nitro-2,4,6,8,10,12-hexa-azo-tetracyclo (5,5,0,0, 1,11 , 0 5,9 ) dodecane (CL-20) retarded by polyurethane polymer Estane-5703-P, is offered, and this composition features higher sensitivity than the composition of octogen with the same polyurethane polymer.
  • liquid explosives such as glycerine trinitrate or compositions (structures, compoundings) based thereon
  • high-energy substances in particular glycerine trinitrate
  • compositions are constant objects for creating on the basis thereon explosive compositions for various purpose.
  • retarding additives are used (applied).
  • tri-nitro-glycerin explosive compositions substances, compoundings
  • special-purpose designations including industrial (commercial) explosives, such as pobedits, detonites and similar compounds are created.
  • these compositions (compounds) feature rather low sensitivity to mechanical influences due to low contents (approximately 10%) of glycerine trinitrate and at the same time, and for the same reason they feature low energy characteristic (response).
  • compositions on the basis of glycerine trinitrate [U.S. Pat. No. 3,108,916, Cl. C 06 B 19/02, 1963. U.S. Pat. No. 2,988,436, Cl. C 06 D 5/04 1961. U.S. Pat. No. 4,011,114, Cl. C 06 B 45/10, 1976].
  • These compositions feature rather high sensitivity to mechanical influences and low energy properties because of low (small) oxygen factor.
  • use (application) of trimethylolethane trinitrate as a retarder for glycerine trinitrate. [U.S. Pat. No. 3,423,256, Cl.
  • Another gas generating composition for fire extinguishers contains in mass. % dibutil phthalate (17), acetate of cellulose (7.6), N-methyl-p-nitroaniline (1), nitrate of cellulose (30.4), trinitrate of pentaeritrit (37), ethyl centralite (2), tin oxides (5) while the temperature of its burning makes 1700° K. [U.S. Pat. No. 3,639,183, Cl. C 06 D 5/06, 1972].
  • R 1 —H, —OH, —COOH; —COONH 4 , —COONa,
  • R 2 —H, —OH, —COOH, —COONa, the residue of composition having the formula
  • R 1 or R have above-stated values, or having the formula (II):
  • R —OH, —OK, —ONH 4 , —ONa
  • R 1 -bond or —C 2 H 4
  • R 2 is absent or means H 2 O or 2H 2 O
  • the engineering problem of the invention consists in creating a universal modifier for explosives from a range of composite complete or incomplete nitrates of monoatomic, diatomic, triatomic or multinuclear alcohols, nitrocelluloses, nitroamines, azides, nitrobenzenes or nitroalkanes; introducing such a modifier in these explosives allows to modify their thermodynamic parameters, physical, chemical, biochemical properties and to create on the basis of these explosives, with the introduced modifiers, explosive and unexplosive composite compounds having liquid (consistent), heterogeneous or solid aggregate state depending on objects in view (tasks) with required properties that may vary, by varying the ratio of components included in the composition.
  • the technical result of the invention is the inhibition of premature decomposition of explosives (compounds) at all the initial stages of development of this process, with its subsequent initiation (activation) as a result of smooth and fast growth (increase) of temperature thus leading to explosive decomposition or burning depending on sufficiency surplus of oxygen in the system, both due to oxygen-containing compounds (substances), and as a result of emission of oxygen in a pure state when decomposing the substances (compounds) included in explosive composition, i.e. controlling the rate of their decomposition, as well as decrease in sensitivity of explosives to various mechanical influences, improvement of the degree of compression.
  • compositions belonging to inorganic, organic acids and their salts as a universal modifier for explosives from the range of complex complete or incomplete nitrates of monoatomic, diatomic, triatomic or multinuclear alcohols, nitrocellulose, nitroamines, nitroanilines, azides, nitrobenzenes, nitroalkanes and their mix, where the compositions belonging to inorganic or organic acids or their salts, are chosen from the following group: orthoboric acid, phosphorous acid or orthophosphoric acid, or composition having the formula (1):
  • R 1 —H, —OH, —COOH, —COONH 4 , —COONa,
  • R 2 —H, —OH, —COOH, —COONa, and R 1 and R have the above-stated values, or formula (2):
  • the listed compositions have, basically, rather low temperature of decomposition and rather high temperature of ignition, thus, a part of thermal energy will be spent for decomposing these substances when introducing them into the specified explosives, thus there will be a decrease of general (total) temperature of formed gases with simultaneous increase in their volumes and there will be a proportional development of pressure due to gases formed as a result of decomposition and-or burning of these compositions.
  • the explosives from the range of complex complete or incomplete nitrates of monoatomic, diatomic, triatomic or multinuclear alcohols, nitrocelluloses, nitroamines, nitroanilines, azides, nitrobenzenes or nitroalkanes, where it is offered to introduce the above modifiers, may be the following explosives:
  • R or/and R 1 —CH 3 , —H
  • pentaerythritol tetranitrate penthrite
  • DINA Diethanol-N-nitroamine dinitrate
  • Diethyleneglycol dinitrate (diglycol dinitrate, dinitrodiglycol) having the formula
  • Trinitrate of cellulose (trinitro cellulose, trinitrate of cellulose, trinitrate) —[C 6 H 7 O 2 (O—NO 2 ) 3 ] n ;
  • Ethylene-N,N′-dinitramine EDNA
  • R 5 —H, is 1-methyl-3-tert-butyl-2,4,6-trinitrobenzene
  • compositions As the operating principle of our offered modifiers in various composite structures of compounds for the specified classes of explosives (compositions) is essentially the same, and it consists in that these modifiers and substances (compositions) having similar properties under certain conditions may decay with emitting gaseous products, and in presence of enough of oxygen in the system may occur not only their decomposition, but also burning or a combination of these processes, thus there may be a thermodynamic (thermochemical) effect of significant decrease in temperature and increase in volume of the formed gases, and incidental proportional development of certain pressure [and the effect of decrease in temperature of gases is most pronounced in case when the compositions (substances) having the temperature of decomposition that is lower or coincides with the temperature of ignition are used (are applied) as modifiers], our approach to creating explosive and unexplosive energy systems of driving force with the properties set depending on the object in view is general and universal for all such systems.
  • thermodynamic thermochemical
  • the modifier for our offered explosives may be used in case of the ratio modifier/explosive equal to (0.1-99.9: (99.9-0.1).
  • FIG. 1 and FIG. 2 there are the diagrams of decomposition of mixes of oxalic acids (crystalline hydrate) with glycerine trinitrate in mass ratio 1:2 and 1:5 accordingly; it was been found that introducting oxalic acids (crystalline hydrate) does not worsen the heat-resistant characteristics of glycerine trinitrate. It is also determined, that the composition is not susceptible to transition of burning to explosion or detonation.
  • FIG. 3 there is a diagram of decomposition of a mix of ammonium oxalate (crystalline hydrate) with glycerine trinitrate in mass ratio 1:1 accordingly, it was been found that introducing ammonium oxalate (crystalline hydrate) does not worsen the heat-resistant characteristics of glycerine trinitrate, but also renders inhibitory action on its autocatalytic decomposition. It is also determined, that the composition is not susceptible to transition of burning to explosion or detonation.
  • the mixes were prepared similarly to those of Example 1.
  • Thematic examples are mixes of oxalic acids (crystalline hydrate) with glycerine trinitrate, thus the mixes prepared in mass ratio: composition No.1-1:5, composition No.2-1:2, composition No.3-1:1, composition No.4-2:1 accordingly, have been tested for explosive characteristics using a Kast's impact machine OST B 84-892-74 (Sensitivity impact using an impact machine at the bottom limit with instr. No.1 and instr. No.2) and the following results are received:
  • compositions have been tested for sensitivity to shock-free friction at the bottom limit (OST B 84-894-74) at a speed of disk rotation (friction) of 520 rev/min.
  • the tests were carried out at a temperature of 18° C.
  • compositions have been tested for sensitivity to friction at a shock shift at the bottom limit (OST B 84-895-83).
  • gelatinating (swelling) and polymeric compositions (substances) were used, such as pyroxylin, colloxylin and other compositions in monobasic and bibasic composite materials with our offered modifiers.
  • Thematic examples are the obtained structures: oxalic acid (crystalline hydrate) 72%, CT-30 21%, glycerine trinitrate 7% with speed of burning 0.5 mm/s and temperature of burning ⁇ 800° K.
  • the thematic example are also the obtained compositions of pyroxylin with salt of methylenedisalicylic acid.
  • the stability of gunpowders made 3.5 to 4.5 kPa, at a norm of 8 kPa.
  • the diammonium salt of methylenedisalicylic acid up to 20% of mass. essential decrease in temperature of the formed gases down by 700-800° K. was marked, while maintaining acceptable power of gunpowders.
  • compositions of pyroxylin with lemon salt may also serve a thematic example, because when introducing it up to 0.5% mass., the stability of gunpowders made 3.5-4.5 kPa, at a norm of 8 kPa. When introducing the lemon salt up to 20% mass., the obtained compositions had the power of gunpowder comparable to the normal one at a level of 1030 to 1060 kJ/kg.
  • thermodynamic calculated values of obtained compositions which had good convergence of results and completely confirmed the experimental data and the Claims.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US12/445,387 2006-10-16 2007-10-12 Modifier for explosives Abandoned US20100096050A1 (en)

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RU2006136245 2006-10-16
RU2006136245/02A RU2318789C1 (ru) 2006-10-16 2006-10-16 Модификатор взрывчатых веществ
PCT/RU2007/000556 WO2008048146A2 (fr) 2006-10-16 2007-10-12 Modificateur pour substances explosives

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CN115709075A (zh) * 2022-11-15 2023-02-24 西安近代化学研究所 一种纳米二氧化锡负载单原子燃烧催化剂及其制备方法

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CN114045039B (zh) * 2021-12-09 2022-10-04 湖南卫航科技有限公司 一种炸药模拟物及其制备方法、应用
CN116283452A (zh) * 2023-03-03 2023-06-23 西南科技大学 基于pickering乳液法制备炸药/HNS核壳结构球形复合物的方法

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RU2318789C1 (ru) 2008-03-10
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WO2008048146A2 (fr) 2008-04-24

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