CS230325B1 - Composite explosive on the basis of anorganic oxidants and/or organic nitro compounds - Google Patents

Description

The invention relates to the production of a mixed explosive and / or an explosive intermediate in which oligomers based on terephthalic acid esters are applied as a modifying component.

The importance of mixed explosives in both civilian and military applications is increasing. The most widespread oxygen donor is ammonium nitrate - ie the most widespread mixed explosives are ammonium-explosive explosives, consisting of two main groups:

I. mixtures of ammonium nitrate with fuel;

II. mixtures containing ammonium nitrate, water with the addition of a plasticizer or dispersant, an explosive substance, or a sensitizer.

Explosions of the first group can be produced by stable technological equipment, but are more often produced directly at the point of use (ie in mobile mixers or in boreholes). Ammonium nitrate is mixed with fuel, which can be a wide variety of organic compounds; however, paraffins, fuel oils or diesel are most often applied. These blends have an approximate zero oxygen bilament, which has an oily content of 94% by weight. % ammonium nitrate and 6 wt. diesel or fuel oil in an explosive; said fuel content will increase the value of the explosion heat from 1470 kj. kg ^-1 for ammonium nitrate up to 3738 kj.kg “ ¹ , which is proportionally the increase in the working ability of the explosive compared to ammonium nitrate alone. Explosives of this type are known in our country under the code designation DAP, abroad are similar mixtures called ANDK (in the GDR), ANC (in the Federal Republic of Germany), Igdanit (in the USSR), ANFO or ANBA (in the Anglo-American literature).

When the fuel is coal dust, metal powder, and the like, these mixtures are also called nitrocarbonates and are referred to as NCN code.

Ammunition explosives of the second group are characterized by relatively simple and unpretentious production technology. In our country they are known as TPV (water-plasticized explosives); in the United States and Canada, they are called "Slurry Explosives" for slurry consistency. At present, the most widely used distribution of explosives of this type is according to the method of sensitization to:

a. "Slurry Explosives" (SE), which are sensitized by an additive of an explosive nature (trinitrotoluene, hexagen, nitroesters, alkanol or allylamine nitrates, hydroxyalkyl nitrates, etc.);

b. Slurry Blasting Agents (SBA), which do not contain explosive additives and are sensitized by non-explosive components, most frequently 230325 more often with aluminum dust [for pr, Soviet Aquanals] and / or other substance (fuel oil, fibrous cellulose, polyvinyl chloride dust, sulfur, paraffin) hexamethylenetetramine, polyols, sugars and others), or aeration additives (expanded perlite, low-grade pulp or hollow beads, metal, polystyrene, ammonium nitrate adhered, etc.), or gas-releasing substances (peroxides, nitrites, carbonates, 5-endomethylene-3,7-dinitroso-1,3,5,7-tetraazacycloloctane and others).

To prevent separation of the explosive components of the TPV type, the composition includes gelling agents (plasticizers, thickeners) such as guar gum and its alkylated derivatives, polyvinyl alcohol, sodium or ammonium salts of carboxymethylcellulose, oxyethylcellulose, polyacrylamide and others. These additives simultaneously guarantee the flowability or plasticity of the respective compositions.

A newer kind of explosives Slurry are compositions of the water-in-oil emulsion type, code-named W / O in the Anglo-American literature, or the oil-in-water emulsion type code number O / W. These explosives are characterized by a lower water content (i.e. higher working capacity) compared to conventional TPV mixtures with improved flowability or plasticity; their physical stability is guaranteed by dispersants such as salts of fatty acids (e.g. deca-glycerin deca-oleate, deca-glycerin deca-stearate), partially esterified by polyols with fatty acids (eg monostearate, monooleate, monopalmitate or sorbitan tristearate, mono- or digicerides, fatty acids) ), alkyaryl sulfonates, soybean lecithin, oxyethylene-oxypropylene copolymer and others. In technical practice, the most common sensitization of W / O or O / W explosives is aeration or gas-releasing additives.

In slurry explosives, calcium nitrate (especially in cyapal corrodes) or sodium perchlorate is sometimes applied as oxygen donors - the latter mainly in aluminized compositions. However, low production costs, high production and handling safety and the possibility of mechanization of blasting machines are characterized by explosive mixtures mainly based on ammonium nitrate. This is the main reason why in technical practice the exploitation of explosives of DAP, TPV and now W / O and O / W types highly prevails over exploitation of other types of industrial explosives. An analogous trend can also be seen in the field of explosives for military purposes For example, the prepared aqueous ammonium nitrate gels are laboratory-tested in some types of aviation bombs, the trinitrotoluene is being replaced by more powerful quaipal compositions based on aqueous solutions of hydrazine nitrate, etc.).

Many of the blend explosive components themselves find themselves becoming increasingly important and economically attractive to use in various sectors of the national economy (eg diesel, fuel oils, ethylene glycol and others); on the other hand, some traditional sensitizers for toxicological and / or safety reasons (trinitrotoluene and nitroesters) are dispensed with. The gap thus formed can be filled with suitable, in particular by-products of the chemical industry, whose further processing is still a burden. This also applies to residues from the manufacture of terephthalic acid polyesters which, by virtue of their composition, could, to some extent, replace ethylene glycol in explosive Slurry compositions; ethylene glycol and some other lower polyols, as is known, are applied as fuel and / or sensitizers in compositions characterized by relatively high explosion energy, good detonator sensitivity, good patronity, good water resistance, and good physical stability.

The essence of a zinc explosive based on> organic oxidants and / or organic nitro compounds containing modifiers according to the invention is that it contains at least one of the oligomers of the general formula as a modifying component

HO-X-0

X-OW wherein n is 1 to 5 and X is —CH ₂ CH ₂ - or —CH ₂ CH ₂ —O — CH ₂ CH ₂ -, in an amount of 0.1 to 70% by weight, preferably in an amount of 7 04 to 51.28% by weight of oligomers based on the weight of the resulting composition.

An advantage of the present invention is the ease of availability of modifiers; application of residues from the production of terephthalic acid polyesters will increase the economic efficiency of this production due to the advantageous use of oligomers which are a burden for other processing. A further advantage of the process according to the invention is the savings of ethylene glycol and other lower polyols so far used as sensitizers and / or plasticizers of some types of mixed explosives, characterized in particular by good sensitivity to detonator initiation, good physical stability and good resistance to 230325 or water; terephthalic acid-based oligomers can largely replace ethylene glycol and lower polyols. An advantage of the modifier of the present invention over ethylene glycol and / or lower polyols is that terephthalic acid ester-based oligomers are good solvents for aromatic polynitro compounds, which can therefore act as plasticizers in compositions containing these nitro compounds. In addition, solutions of polynitroaromatics in terephthalic acid-based oligomer esters can be applied as phlegmatizers and / or hydrophobizing components of mixed explosives.

The most suitable application of the oligomers to the terephthalic acid ester base is in the form of a solution and / or suspension thereof in polyols, such as e.g. in ethylene glycol, diethylene glycol, glycerine and the like, or in polynitroaromatics such as dinitrotoluene, nitrated solvontafta and others; these solutions and / or suspensions may be liquid, but may also have a grease to solid paste consistency.

Explosives containing terephthalic acid ester oligomers are aluminizable. Their physical stability, especially composition! with low water content is good - in this respect they are undemanding for special additives. In anhydrous compositions, terminal hydroxy groups of the oligomers can be utilized to improve the physical properties of the corresponding charges, in particular by reacting them with a suitable crosslinking agent, such as e.g. isocyanates.

Physical properties of the composition! The type of TPV, W / O or O / W can be influenced by the established methods, in which the presence of terephthalic acid ester oligomers in the com position can favorably influence the effect of which method.

The application of terephthalic acid ester-based oligomers in the present invention has not been described in the literature to date; is illustrated by the following examples, which in no way exclude the possible variability of the modes of application.

Example 1

Residues from the production of polyethylene terephthalate having the consistency of a flowing suspension and containing 10 wt. % ethylene glycol, 0.4 wt. water and a total of 15.7 wt. hydroxyl groups. Of these residues and industrial ammonium nitrate containing 0,6% by weight. of water is a semi-paste mixture prepared by atmospheric pressure at atmospheric pressure having the composition (w / w): 10.21% of terephthalic acid ester oligomers, 1.54% of ethylene glycol, 0.59% of water and 87.66% of ammonium nitrate . Said mixture is approximately zero oxygen balance and for a specific charge weight of 1000 kg. m ^-3 is characterized by:

explosion heat (kj.kg ^-1 ) 3700 explosion gas volume (l.kg ^_1 j 940 complete ideal explosion work íkj, kg ¹ ) 3200 detonation velocity (km.s ^-1 ) 3,1—3,2

Using a non-isothermal differential thermal analysis (DTAj) operating at a linear temperature rise rate of 5 ° C. Min ¹ , sample weights of 0.08 to 0.09 g and a measuring range of 1 mV per scale of temperature differential recorder were found:

DTA Data For Composition For Starting Ammonium Nitrate

melting start (° G) hardly specif. 154.8 melting peak (° C) 119.0 160.5 the origin of the exothermic ; ^ .1; F decomposition (° C) 152.7 180.2

The DTA-recording of the composition and its visual observation on heating showed that the applied residues from polyethylene terephthalate production dissolve ammonium nitrate to a clear, water-soluble liquid.

The composition is useful as an explosive, but it is preferable to treat it by aluminization, if necessary by adding an additional amount of oxygen donor and other auxiliary components, so as to increase the performance of the resulting explosive.

EXAMPLE 2

There are residues from the production of polyethylene terephthalate and technical ammonium nitrate, the same quality as in Example 1. Of these components, gel-forming substance "guar gum" and aluminum powder with specific surface area of about 0.7 nť.g malaxérovacím ¹ is produced, the polosypká Composition (% by weight): 7.04% terephthalic acid ester oligomers, 0.8% ethylene glycol, 1.0% guar gum, 0.69% water, 3.0% aluminum and 87.47% ammonium nitrate. For a charge specific gravity of 1000 kg. m ~ ³ is a composition characterized by:

oxygen balance (%) +3,9 explosion heat (k.kg ¹ ) 3890 explosion volume (l.kg ¹ ) 910 complete ideal explosion work (kkg.kg ¹ ) 3150 detonation rate (km.s ^-1 ) 3, 2 to 3.3

239325

Using DTA as in Example 1, for this composition it is found:

melting point (° C) difficult to specify melting peak (° C) 120.1 exo-decomposition start ( ^Q C) 150.2

The composition is useful as an explosive, but more preferably, the evacuation of evolutionary oxygen, e.g. aluminum dust, which increases the working ability.

Example 3

From technical ammonium nitrate as in Example 1, from technical bis (5-hydroxy-3-oxapentyl) terephthalate containing 2.8% w / w diethylene glycol, it is a malaxer process at atmospheric pressure, heated to 30-33 ° in the malaxer. C, prepared semi-loose mixture with weight (%): 11.66% bis (5-hydroxy-3-oxapentyl) terephthalate, 0.34% diethylene glycol, 0.5% water and

87.5% ammonium nitrate. Said composition for a specific charge weight of 1000 kg.nr ^{3 is} characterized by:

oxygen balance (%) —3,7 explosion heat (kjkg ^-1 ) 3600 explosion volume (l.kg ') 955 complete ideal explosion work (kj.kg ^- ') 3100 detonation velocity (km.s ” ¹ ) 2.9-3.0

Using DTA as in Example 1, this composition found:

melting point (° C) 131.0 melting peak (° C) 152.0 exo-decomposition start (° CJ 170.0

The composition is useful as a mixed explosive with good physical stability and good sensitivity to detonator initiation, but treatment with aluminum and other additives (especially oxygen donors) to a more powerful composition is more preferred.

Example 4

Glycolized residues from the production of polyethylene terephthalate containing 5.8 why are available. % of hydroxyl groups and having a full melting temperature range of 110 to 130 ° C. With DTA as in Example 1, these residues are found: as early as 27 ° C, a very elongated endotherm begins with a fuzzy peak at 36 ° C, with another smaller peak at 88.5 ° C and reaching a zero line at 113 ° C, beginning 116 ° C and its peak at 126 ° C, reaching the zero line at 139 ^and G.

wt. parts of said glycolized residues are added to 110 wt. % by volume of an 81.3% aqueous ammonium nitrate solution of 80 ° C warm, presented in the malaxer. The halogenation of this mixture is carried out with moderate cooling and the malaxer content. This results in a plastics material which is very good moldable in the temperature range of 45-55 ° C, but good moldable even at 20-25 ° C. This material, suitable for further processing e.g. for water-plasticized explosive compositions, has a composition (% by weight): 26.7% terephthalic acid ester-based oligomers), 13.66% water and 59.64 pens. ammonium nitrate.

Example 5

Following the procedure of Example 4, only 102 wt. % of an 87.7% aqueous ammonium nitrate solution and 50 wt. parts of glycolized residues from the production of polyethylene terephthalate, a composition (% by weight) of 32.9% terephthalic acid oligomers, 8.25% water and 58.85% ammonium nitrate is prepared. The entire amount of this composition, at a temperature of 20 to 25 ° C of a significantly stiffer mass than the composition of Example 4, is homogenized at 150 to 40 ° C by a malaxer method. parts of technical ammonium nitrate and 10 wt. parts of the gelling agent guar gum; then 150 wt. parts by weight of sodium perchlorate monohydrate and 25 wt. parts of aluminum dust having a specific surface area of about 0.7 rnr.g ^-1 and homogenization is complete after 15 minutes. This results in a semi-flowable, very compressible (up to a specific gravity of 1800 kg. M ³ ) composition having a loading (% by weight): .1.2,26% of terephthalic acid ester oligomers), 48.97% ammonium nitrate, 27.1% sodium perchlorate, 5.13% aluminum, 6.49% water and 2.05% guan gum. For a specific charge weight of 1500 kg. m ^-3 is a composition characterized by:

oxygen balance (%) +3.2 explosion heat (kj.kg ^-1 ) 4980 the volume of afterbursts (1 kg- ¹ ) 700 complete Ideal explosion work (k) .kg ^-1 3650 detonation velocity (km.s ^-1 ) 2.9-3.1 Example 6

K 330 wt. 1000 parts by weight of technical dinitrotoluene are added. parts of the glycolized residues from the production of polyethylene terephthalate (quality see Example 4) and the mixture is heated to 60 ° C with stirring. Then 620 wt. parts of technical dinitronaphthalene (approximately half of this amount is dissolved in the melting furnace), resulting in a costly mass having a paste-like cosiness at 30 ° C. This composition has

230323 composition (wt.%): 51.28% terephthalic acid ester-based oligomers and 48.72% polynitroaromatics.

Using DTA as in Example 1, the composition found: melt endotherm onset at 27 ^° C _: melt endotherm peak at 38 ° C, endotherm elongation at 57 ° C with peak at 94 ° C and exothermic onset at 175 ° C.

The composition is suitable for application as a phlegmatizer, a hydrophobizing component, a fuel and a mixed explosive sensitizer, especially NCN explosives, with the possibility of improving the physical stability of the resulting explosive by crosslinking with a suitable agent, e.g. toluene diisocyanate and the like.

Claims (2)

Composition (% by weight): 51.28% of oligomers yields terephthalic acid esters and 48.72% of polynitroaromatics. With DTA as in Example 1, the following is found in the com- position: beginning of heating furnace endotherm at 27 ° C: peak melting endotherm at 38 ° C, beginning of further elongated endotherm at 57 ° C with peak at 94 ° C and initial exothermic decomposition at 175 ° C. The composition is suitable for application to an acoflegmatizer, a hydrophobic component, a fuel and a mixed explosive sensitizer, most notably NCN type explosives, with the possibility of improving the physical stability of the resulting flux by crosslinking with a suitable reagent, e.g., toluene diisocyanate and the like. PŘEĎME 1. An inorganic oxidant and / or modifier-containing organic nitrile flux explosive, characterized in that it comprises at least one of the oligomers of the general formula HO- —X — O — C— —C as the modifying component. In which n is 1-5 and X is -CH 2 CH 2 - or -CH 2 CH 2 -O-CH 2 CH 2 - in an amount of 0.1 to 70% by weight, preferably in an amount of 7.04 to 51% 28% by weight, oligomer mass of the resulting composition. '2. Mixed explosive according to claim 1, characterized in that it contains residues from the production of terephthalic acid polyester as a modifying component.