CS239514B1 - Mixture of mixed explosives - Google Patents

Abstract

The invention aa relates to the use of isopropyl/or polyisopropylbiphenyls with a molecular weight of 172.2? to 575.02 as components of mixed explosives with a nitric and/or perchlorate type oxygen donor in an amount of 1 to 15 wt. % of isopropyl/or polyisopropylbiphenyls per weight of the resulting composition. It is economically advantageous to use monoisopropylbiphenyls, which are by-products of the production of technically attractive monoisopropylbiphenyls.

Description

239 514

The invention relates to the use of isopropyl and / or polyisopropylbiphenyl as a component in the manufacture of mixed explosives. The importance of mixed explosives is increasing in both civilian and military applications. The most common oxygen donor in them is ammonium nitrate - the most common explosives are ammoniacal explosives, consisting of two main groups: I. ammonium nitrate mixture with fuel; II. mixtures of ammonium nitrate, water with a plasticizer additive, and an explosive substance, or a sensitizer.

First group explosives can be produced by stable technology equipment, but are more often produced at the site of use / t. j. in mobile mixing devices or directly in boreholes /. Ammonium nitrate is mixed with fuel that can be a wide variety of organic compounds, but most often paraffins, fuel oils, or diesel are used. These mixtures have an approximate zero oxygen balance corresponding to 94% by weight. % nitric ammonium and 6 wt. said fuel will increase the explosion heat of 1470 kJ / kg for ammonium nitrate up to 3738 kJ / kg, and is proportional to an increase in the working capacity of explosives compared to ammonium nitrate alone. Explosives of this type are known in our country under the code name DAP, abroad are similar mixtures designated ANDK / in NDR /, ANC / in NSR /, Igdanite / in USSR /, ANFO or ANBA / in Anglo-American literature /. When fuel is dust, metal powder, etc., these are also referred to as nitro-carbonates and designated NCNs.

The second group amonoliad explosives are characterized by a relatively simple and inexpensive production technology. 239 514 We are known under the name TPV / explosives by plasticized water in the USA and Kaneade is a creamy consistency called "Slurry Explosives". Currently, the most usable distribution of explosives of the above type is sensitization and to: " Slurry Explosives " (code SE), which are sensitized by an additive of explosive nature / trinitrotoluene, hexogen, nitro-esters, nitrates of alkanol or alkylamines, hydroxialkyls -treats and the like /} "Slurry Hlasting Agente" (SBA code), which do not contain explosive substances and are sensitized by non-explosive components, most often aluminum dust / dust. Soviet aquariums (and / or other substance / fuel oil, fibrous cellulose, polyvinyl chloride powder, sulfur, paraffin, hexamethylene-traminine, polyols, sugars and others / aerating additives / expanded perlite, glass pulp, glass hollow) trays, cork, polystyrene, sintered ammonium nitrate and the like /, or gas / peroxide release agents, nitrites, carbonates, 1,5-endomethylene-3,7-dinitroso-1,3,5,7-tetraaza-cyclooctane and other /.

The stability of the physical stability, that is to say, the separation of the constituents of these sub-groups of "slurry" explosives while maintaining flowability or plasticity of the composition is ensured by the addition of a gel-forming substance / plasticizer such as guar gum and its alkyl derivatives, polyvinyl alcohol, sodium or ammonium salts. carboxiraethylcellulose, oxiethylcellulose, polyacrylamide and others.

The youngest type of "slurry" explosives are water-in-oil emulsion-type compositions, code-named W / 0, or oil-in-water emulsion type, code-named 0 / W}, W / O-Composites introducing aqueous solutions of blasting agent components into hydrophobic liquid / fuel oil The following emulsions are stabilized by dispersants, such as fatty acid salts (especially stearic or oily), fatty acid esters (eg, decaglycerol decaeate, decaglycerine deca stearate). partially esterified polyols with fatty acids (for monostearate, monooleate, monopalmitate or tristearate sorbate, mono- or diglycerides of fat-forming fatty acids) - 3 - 239,514 further alkylphenylsulfonates, soybean lecithin, oxyethylene-oxypropylene copolymer and Other emulsion explosives can be sensitized by nitro compounds, most often nitromethane or other nitroparafins, al The most widely used in technical practice is their sensitization by aerating agents or gas-releasing additives. Calcium nitrate and sodium perchlorate are sometimes used as oxygen donors in "Slurry" explosives, especially in aluminized compositions, but explosive mixtures are primarily characterized by low production costs, high handling safety and production and the possibility of blasting machine mechanization. This is the main reason why, in technical practice, the deposition of mixed explosives of the DAP, TPV and now W / O and G / W types is significantly dominated by the explosion of other industrial explosives. the purposes / aluminized aqueous ammonium gelling agent are, for example, processed into some secondary air bombs, the trinitrotoluene is replaced by liquid compositions based on aqueous solutions of hydrazine nitrate and the like.

Many of the components of mixed explosives find themselves more significant and economically more attractive to the use of various sectors of the national economy / at the same time. however, the use of some traditional sensitizers from toxicological and / or safety hydrocarbons (trinitrotoluene and nitro esters) is omitted from diesel, fuel oils and others. Such a gap can be filled with suitable, especially by-products of the chemical industry, whose further processing is still a concern. This also applies to by-products of aromatic hydrocarbon alkylation, such as, but not limited to, aromatic hydrocarbons. biphenyl isopropylation with propene. The desired homonoisopropyl biphenyl results in di- and higher isopropylated biphenyls as well as some propene oligomers.

Isopropyl- and polyisopropyl-biphenyls are oily liquids with a specific gravity of up to 1100 kg.m -1 and a flash point of 160 ° C. Their viscosity and pour point strongly depend on their composition. For example, a mixture containing about 1% by weight of isopropyl isopropylbiphenyl, 90 to 95% by weight. diisopropyl- and 4-9 wt. triisopropyl biphenyl, at 50 ° C, has a kinase value of 239,514 - 4 - tenth viscosity of 9.10 "- 10.10" - π, S - 1 and a solidification temperature of about - 15 ° C of a mixture containing 70 to 90% by weight. % diisopropyl and 10 to 30 wt. tri- and higher isopropylated biphenyls, has a kinematic viscosity of 13.5.10 to 16.10 ° C at 50 ° C. and a pour point of about -10 ° C. diisopropyl biphenyl, 80 to 85 wt. three and higher isopropylated biphenyls and 5 to 10% w / w polypropylene oil have a kinematic value of viscosity of 170.10 ° to 200.10 m at 50 ° C. s' 1 and a freezing point of -5 to 0 ° C, these yields from the refining of the crude biphenyl isopropylation product and re-espresses the highest boiling point of the operation. · Comparison - value of the kinetic viscosity at 93 ° C for a mixture of 3- and 4-aonoisopropylbif -nyl is 1.5 · 10 ~ m. s "and at the same temperature for the mixture of diisopropylbiphenyl 2,6.10" m .s ".

According to the present invention, isopropyl- and / or polyisopropyl-biphenyls having a molecular weight of 172.27 to 575.02 are applied as a component of a mixed oxygen donor of the nitrate or perchlorate type in an amount of 1 to 15% by weight, preferably at 3.78%. % to 9.50 wt. isopropyl- and / or poly-isopropylbiphenyl to the weight of the resulting composition. In doing so, it is preferred to apply the polyisopropyl biphenyls in the form of byproducts of the production of monoisopropyl biphenyl isopropylacidibiphenyl. An advantage of this invention is the technical and economic availability of polyisopropyl biphenyls in particular. The use in the sense of this invention of polyisopropyl biphenyls, resulting as mono-isopropylbiphenyls, is a contribution to the increase in the economic efficiency of said production. The application of by-products of the production of monoisopropylbiphenyls in the manufacture of mixed explosives for the purposes of the present invention leads to the savings of motor oil, fuel oil and other noble petrochemical products, so far applied as fuels and sensitizers to mixed explosives, while the utility properties of the residual gases remain. In view of the low polyisopropyl biphenylene tensile strength compared to motor oil and some other fuels used so far in the manufacture of mixed explosives, the fire hazard is reduced in the process of the present invention as well as in the storage and handling of raw materials and in the production of explosives. 514

Isopropyl and / or polyisopropyl biphenyls can be applied as a mixture after biphenyl isopropylation with propene from which the catalyst has been removed for the production of explosives. However, economically attractive mono-isopropylbiphenyls are preferably isolated from this mixture. The remainder of this isolation can be distilled to the desired viscosity fractions, i.e., according to the mode of application / the more liquid fractions for preparing the explosive directly in the wells, more viscous for the production of debris in stable process equipment.

Explosives containing isopropyl and / or polyisopropylbiphenyl are aluminizable. Their physical stability can be increased by conventional means: e.g. in the case of explosive type DAP, it is the application of admixed ammonium nitrate and / or the addition of a wooden chipboard and / or the addition of other suitable adsorbent / water-impermeable urea-formaldehyde condensates, modified fine-grained silica and the like; in the case of W / 0 or 0 / W type, a suitable dispersant.

The application within the meaning of the present invention to isopropyl- and / or poly-isopropylbiphenyls has not yet been described in the literature and documented by the following examples. Example 1 28 wt. parts of a 50% aqueous sodium hydroxide solution are added to 925 wt. 80 ° C warm aqueous solution containing 69.9% wt. ammonium nitrate, 16.6% by weight of sodium nitrate and 13.7% by weight of sodium nitrate; water. This mixture is slowly and mixed into a mixture of 28 wt. % of 71.43% oleic acid and 40 wt. parts of diisopropyl biphenyl containing 19.7 wt. monoisopropylbiphenyls. The resulting emulsion is cooled to 47-50 ° C and 40 wt. part-spun microspheres / glass crumb. The result is an explosive of type W / 0 composition /% w / w: 58.25% ammonium nitrate, 17.28% sodium nitrate, 3.78% diisopropyl- and monoisopropylbiphenyl, 2.0% ammonium oil, 0.3% % free ammonia, 3.76% glass microspheres and 14.63% water. This emulsion type tr-havine has the following explosive characteristics: -6-239,514 oxygen balance (%). · ....................... +4,9 explosion heat Q /kj.kg “* ^ / ...... · .... ......... 3400 volume of explosion gases /l.kg"l / ............ 845 complete ideal work of explosion /kJ.kg"1 / ...... ..... 2850 charge weight /kg.m”^/................1150 detonation speed /km.s~l / ........ 4.4 Example 2 A polyisopropyl biphenyl fraction containing 8.4% by weight diisopropyl biphenyl, 84.8% by weight is available. tri-and higher isopropylated biphenyls and 6.8% propene oligomers; this fraction at 50 ° C has a kinematic value of viscosity of 180.10 ° C / m 2. To 7.8 wt. 1 part by weight of chlorobutane monohydrate in malaxier is added 1 wt. part of the polyisopropylbiphenyl fraction, 0.21 wt. of atomic aluminum and 0.14 wt. works ”guar-gumw. After homogenization, 1.35 wt. 70.5% aqueous ammonium nitrate solution of 75 ° C warm. After careful homogenization and cooling to a laboratory temperature, a TPV-type gel (explosive /% w / w): 9.5% polyisopropalbiphenyl, 64.7% sodium chlorate, 9.1% ammonium nitrate, 2, 0% aluminum, 1.3% "guar-gum" and 13.4% water. For charge density 1700kg.m "^ this gel has the following characteristics: oxygen balance /% / ......... ................. -0,5 explosion heat Q /kJ.kg ”^ / ................... 5000 5000 explosion rate /l.kg "" ^ / ... 520 full ideal explosion /kj.kg"1/...........3600 detonation velocity? /km.s”^/.................···· 2,46 Example 3 There are three different fractions obtained by distilling the mixture after isopropylation biphenyl: - a technically pure mixture of 3- and 4-monoisopropylbiphenyls, hereinafter referred to as IPD, - a fraction containing 92.4% by weight of diisopropylbiphenyl / the remainder being tri- and higher isopropylated derivatives /, - 7 ~ 239,514 6 9 1 at 50 ° C, kinematical value of viscosity 14,97 * 10 "m ', s, hereinafter referred to as DIPD; the fraction of Example 2, hereinafter referred to as TIPD. From these fractions, the DAis explosives are prepared to approximate zero oxygen balance. The standard diesel was a DAE explosive with fuel oil as fuel. The characteristics of the individual mixtures are presented in Table 1.

Table 1

Components and Pointers Explosive Type DAP AB c Standard Composition /% w / w: Ammonium Nitrate 93.8 94.0 94.4 94.0 Diesel - - - 5.5 IPD 5.9 - - - DIPD - 5 , 7 - TIPD - - 5.3 - water / max./ 0.3 0.3 0.3 0.5

Ané £... Q k k /kj.kg 1 1 / / kg 26 kg kg 26 26 26 kg kg 26 26 26 26 26 26 26 26 26 26 26 26 26 l l l ^ / 780 790 790 800-900 detonation velocity /km.s"1/ 2,2-29 2,2-29 2,2-2,9 2,2-2,9

Notes: Q is the explosive heat; V is the volume of post-explosion fumes; W is a complete ideal explosion job; the detonation velocity values are based on the mass density of 1100 kg.m -1;

Using a non-isothermal differential thermal analysis (DTA), operating at 0.08 to 0.09 g of sample, a linear temperature rise rate of 5 ° C.min, and recording a temperature di-239 of S14 - 8 - ference with a range of 0 , 5 mV on the scale of the recorder scale, the data presented in Table 2 were found in Table 1 mixtures.

Table 2

Type of data from DTA KomDOdition with your explosives DAP ABC Standard melting starts Z ° C / 158.0 157.0 159.0 154.2 Melting peak / ° C / 162.3 161.6 164.1 160.5 Exodus origin / ° C / 175.1 175.5 174.8 176.0

For comparison, the DTA method for starting ammonium nitrate values:

Melting point ....... 158.6 ° C

melting peak .............. 163.7 ° C

exo-decomposition start, 184.0 ° C, the results show that the application of isopropyl- and / or poly-isopropylbiphenyls as a DAP type explosive fuel is practically equivalent to motor diesel application in terms of stability and performance of the resulting explosives.

Claims (1)

SUBJECT INVENTION 23S 514 Use of isopropyl and / or polyisopropyl biphenyls having a molecular weight of 172.27 to 575.02 as a mixed explosive component with an oxygen donor of the nitrate and / or perchlorate type, in an amount of 1 to 15% by weight, preferably in an amount of 3.78 to 9, 5 wt. isopropyl and / or polyisopropyl biphenyls by weight of the resulting composition.