DE1167238B - Sensitized nitro paraffin explosives - Google Patents

Description

Sensitized Nitroparaffin Explosives The invention relates on explosives mixtures and in particular on nitro-paraffin explosives that are carried out by Addition of an organic amine are sensitized.

The nitroparaffin explosives according to the invention are particularly suitable for breaking rocks where a powerful explosive with a high detonation speed is required. The nitroparaffin explosives sensitized according to the invention Contact with water or aqueous salt solutions does not lose their effectiveness and can, for example, run through water and then be ignited. Due to their advantageous properties, the explosives are according to the invention for use in mines, for military purposes, for the manufacture of Oil drilling and other uses, especially where there is an impact of water or saline solutions is particularly valuable.

Explosives that can be used in liquid form are known. These explosives show, however. often serious disadvantages by For example, they are very sensitive to shock and only in this sensitive state be available. Such explosives are dangerous to manufacture, and the transport of such explosives is very difficult and extremely demanding Caution.

An improvement in mechanical shock sensitivity was found in the case of nitroparaffin explosives achieved by adding paraffins, such as n-octane or n-dodecane, to tetranitromethane or hexanitroethane can be obtained. A use of sensitizers from Amine type, as used according to the invention, comes with these known explosives out of consideration. Any benefit in terms of maintaining effectiveness in contact with or in the presence of water or aqueous salt solutions not taken or derived from the information on these known explosives will.

Also is a foamable liquid explosive composition known, which consists essentially of a liquid nitroparaffin, a metal stearate and a sensitizer in the form of ethylene diamine or morpholine. The composition can contain a stabilizer such as methanol, ethanol, isopropanol, Isobutanol, dibutyltin diacetate or silicon dioxide, preferably will the sensitizer dissolved in a lower aliphatic alcohol. These foam-producing Compositions serve in particular to form a foam blanket from the disintegrant above the ground, for example to clear minefields. Apart from this, that the special physical form of the foam state is only for very specific areas of application is appropriate, these known explosive compositions are sensitive to Leaching by water or aqueous salt solutions.

The invention makes the above-mentioned disadvantages more known Explosives eliminated. The sensitized by adding an organic amine Nitroparaffin explosives according to the invention are characterized in that the sensitizing amine from a monoarylalkyleneamine, alkylaryldiamine and / or aminopyridine and in an amount of about 0.2 to 20 percent by weight in the nitroparaffin is incorporated.

Nitroparaffin explosives based on them are particularly preferred of nitromethane, which consists of 20 to 0.5 percent by weight of benzylamine, toluenediamine or Diaminopyridine and 80 to 99.5 percent by weight nitromethane exist.

As can be seen from the experiments below, the explosive compositions according to the invention for long periods of time with water or aqueous salt solutions in intense touch without losing their effectiveness. The explosives compositions can be in the place where the explosives are to be used, prepares be by adding the sensitizer or a mixture of said sensitizers is mixed with a nitro paraffin.

Below are qualitative tests with sensitized nitroparaffins described, from which the inventive explosives compositions formed with the achieved advantages are evident.

Sensitized nitromethane was used for the experiment. The leaching attempts were performed by making mixtures of approximately equal volumes of solutions of the sensitizer in nitromethane and water or aqueous saline solutions are common were shaken to prepare the aqueous sodium chloride solutions, to imitate lake water. After frequent shaking during the periods indicated in the table The mixtures were allowed to settle for time so that two layers formed. The nitromethane layers were examined for their explosive properties.

In the ignition or blasting operation No. 1, 15 cc samples of the sensitized Put nitromethane solution in 20 - 150 mm test tubes made of Pyrex glass. The test tubes were placed behind a protective shield and fitted with a No. 6 primer or 8 or an intermediate igniter Chestnut Booster (hereinafter referred to as C. B.) detonated. This intermediate igniter is an electric primer that has a two-part detonator, is about 5 to 7 '/ 2 cm long, and is attached to his Sides is wrapped ("Primacord" by Ensign-Brickford). The ends of the detonator are at an angle of approximately 30 ° to the longitudinal axis of the detonator cut off. The cut surfaces are then wrapped together. At the ignition a very strong one arises at the junction between the two detonators Push. The use of these intermediate igniters (boosters) is sometimes necessary, when the cargo of the sensitized nitroparaffin is not firmly entrapped.

In the ignition or blasting process No. 2, 15 cc samples of the sensitized nitromethane solution were placed in 20-150 mm tubes made of Pyrex glass. The test tubes were inserted into a piece of steel tubing just large enough inside diameter to accommodate the test tube. The containers containing the sensitized nitromethane were placed behind a safety shield and detonated with detonators or a CB. The results of the qualitative tests are shown in the table below. Test results Concentration Ignition I Leaching Sensitizer tration process detonator number of the number of leaching times Weight attempts blasting solution percent no hours Propylenediamine ........... 2 1 No. 6 1 1 none - Ethylenediamine ............ 2 1 No. 8 1 1 none - Ethylenimine .............. 4 1 No. 8 5 0 distilled 4 water Ethylenimine .............. 4 2 No. 8 5 1 aqueous cooking 4 Saline solution N, N'-diethyl-p-phenylene- diamine ................. 8 2 No. 8 5 1 none - N, N'-diethyl-p-phenylene- diamine ................. 10 2 No. 8 8 0 aqueous cooking 24 Saline solution None ................... - 1 number 8 5 0 none - None ................... - 2 No. 8 5 0 none - None ................... - 2 CB 5 0 none - Pyrrole .................... 2 1 No. 8 3 0 none - 2,3-Dimethylaniline ......... 4 1 No. 8 3 0 none - Dibenzylamine ............. 4 1 No. 8 3 0 none - p-Toluidine ................ 4 1 No. 8 3 0 none - 1-naphthylamine ........... 4 1 No. 8 3 0 none - Benzidine .................. 4 1 No. 8 3 0 none - Benzylamine ............... 2 1 No. 8 5 2 none - Benzylamine ............... 4 1 No. 8 6 4 none - Benzylamine ............... 6 1 No. 8 16 13 none - Benzylamine ............... 8 1 No. 8 11 10 none - Benzylamine ............... 6 1 No. 8 10 7 distilled 4 water Concentration Ignition Leaching Sensitizer tration yorgang detonator number of the number of leaching time Weight attempts blasting solution percent no hours Benzylamine ............... 8 1 No. 8 6 4 distilled 4 water Benzylamine ............... 6 1 No. 8 8 7 aqueous cooking 24 saline solution Benzylamine ............... 8 1 No. 8 8 7 aqueous cooking 24 saline solution Benzylamine ............... 6 1 No. 8 8 6 distilled 72 water Benzylamine ............... 8 1 No. 8 8 6 aqueous cooking 72 saline solution Benzylamine ............... 6 2 No. 8 8 8 none - Benzylamine ............... 6 2 No. 8 5 5 distilled 4 water Benzylamine ............... 6 2 No. 8 5 5 aqueous cooking 24 saline solution Benzylamine ............... 6 2 No. 8 5 5 aqueous cooking 72 saline solution Benzylamine ............... 8 2 No. 8 5 5 distilled 72 water 2,4-diaminotoluene ......... 4 1 No. 8 12 8 none - 2,4-diaminotoluene ......... 6 1 No. 8 12 10 none - 2,4-diaminotoluene ......... 6 1 No. 8 6 3 distilled 4 water 2,4-diaminotoluene ......... 6 1 No. 8 8 5 aqueous cooking 24 saline solution 2,4-diaminotoluene ......... 6 1 No. 8 7 5 distilled 24th water 2,4-diaminotoluene ......... 6 1 No. 8 10 9 distilled 72 water 2,4-diaminotoluene ......... 6 1 No. 8 10 8 aqueous cooking 72 saline solution 2,4-diaminotoluene ......... 6 2 No. 8 8 8 none - 2,4-diaminotoluene ......... 6 2 No. 8 5 5 aqueous cooking 24 saline solution 2,4-diaminotoluene ......... 6 2 No. 8 5 5 distilled 24 water 2,4-diaminotoluene ......... 6 2 No. 8 5 4 aqueous Kodh- 72 saline solution 2,4-diaminotoluene ......... 6 2 No. 8 5 5 distilled 72 water 2,6-diaminopyridine ........ 4 1 No. 8 18 12 none - 2,6-diaminopyridine ........ 6 1 No. 8 8 7 none - 2,6-diaminopyridine ........ 6 1 No. 8 9 9 aqueous cooking 4 saline solution 2,6-diaminopyridine ........ 6 2 No. 8 8 8 none - 2,6-diaminopyridine ........ 6 2 No. 8 5 5 distilled 4 water 2,6-diaminopyridine ........ 6 2 No. 8 5 5 aqueous cooking 4 saline solution 2,6-diaminopyridine ........ 6 2 No. 8 5 5 distilled 24 water Concentration Ignition Leaching Sensitizer tration process detonator number of number of leaching time Weight tests blasting solution percent no hours 2,6-diaminopyridine ........ 6 2 No. 8 5 4 aqueous cooking 24 Saline solution 2,6-diaminopyridine ........ 6 2 No. 8 3 3 distilled 72 water 2,6-diaminopyridine ........ 6 2 No. 8 3 3 aqueous cooking 72 saline solution As can be seen from the table above, nitro-paraffin explosives can be sensitized by adding organic amines, but the special organic amines used according to the invention, ie monoarylalkyleneamines, alkylaryldiamines and / or aminopyridines, produce sensitized nitroparaffins with particularly advantageous properties, namely those which themselves after extended contact with water are effective. This represents a surprising and considerable improvement over the previously known sensitized nitroparaffin explosives. In particular, the above table shows that nitromethane sensitized by benzylamine, toluenediamine and / or diaminopyridine retains its effectiveness even after prolonged and intensive contact and leaching with water or aqueous salt solutions.

Since explosives of the type under consideration are often found in boreholes that reach below a water level and water-containing zones are used penetrate, in practice it is not uncommon for such explosives come into contact with water or aqueous salt solutions. Also is at different Applications often an ingress of water or moisture during storage or not to avoid shortly before use, or only with difficulty. the Explosives according to the invention are insensitive to such external influences, which increases their range of application considerably and opens up new areas of application. The previously known nitroparaffin explosives containing an organic amine have no comparable resistance to the effects of moisture.

In addition to the compounds mentioned in the examples, inter alia the following substances within the scope of the invention as sensitizers, either alone or in admixture with each other.

Monoarylalkyleneamines such as 1-amino-2-phenylethane, p-tolylenediamine, p-methylenediamino benzene. Aminopyridines such as 2-aminopyridine, 2,4,6-triaminopyridine.

Alkyldiaminobenzenes such as 1-ethyl-2,4-diaminobenzene, N, N-dimethyl-1,3-diaminobenzene, N-propyl-o-phenylenediamine. Nitroparaffins, alone or mixed together can be used with advantage are, for. E.g .: mononitromethane, 1- or 2-nitropropane, symmetrical dinitroethanes, 1,3-dinitropropane, 1,1,3-trinitrobutane, nitroethane, 1,1,2-trinitroethane. The nitro paraffins used in the invention preferably have a slightly negative oxygen balance. In the case of mixtures of nitro paraffins, it is therefore it is advisable to select the nitroparaffins in this way and in such proportions add that the mixture has a slightly negative oxygen balance.

The preferred nitroparaffin is mononitromethane because it has an oxygen content which allows relatively safe handling prior to sensitization. It has a low freezing point and can be stored safely; when it sensitizes it can be ignited with a normal primer.

The sensitizers are according to the invention in concentrations from about 0.2 to 20 percent by weight is incorporated into the nitroparaffin. Preferably the sensitizer is in amounts of about 2 to 10 percent by weight in the solution from the sensitizer and the nitroparaffin, larger amounts can under Certain conditions lead to segregation and the explosive power of nitroparaffin to decrease.

The sensitizer and the nitroparaffin are preferably used for the Handling stored and transported in separate containers and only at the time and mixed together in the place where they are to be used. this is a very safe method of working with the very powerful explosives, there the unsensitized nitroparaffin can be handled without danger, with only the usual safety measures when handling flammable liquids must be observed. The sensitizers for their part do not require a higher level in care than the nitro paraffins. However, the nitro paraffins can optionally also be sensitized before storage or dispatch. Because the sensitized Nitroparaffins are very stable against vibrations, it is almost impossible to You can detonate them without using an intermediate detonator, if that is the case with explosives normal safety precautions are observed, safely handled and stored will.

The sensitizer and the nitroparaffin can be in any one Way and in any desired way Containers are mixed together. Of course, the use of equipment that easily generates sparks must be avoided and the materials should be kept cool before, during, and after mixing will.

Various fillers can be the sensitized nitroparaffin can be added before and after sensitization. Such fillers consist of Sawdust, powdered coal or carbon, starch and the like, such fillers are known in the art.

As the nitroparaffins and sensitizers alone or with each other mixed with very low freezing points are the sensitized explosives according to the invention advantageous for use in cold weather and in places where the material has to be stored in unheated places. The sensitized Nitroparaffins can, once they are frozen, almost without any danger thawed in a premature explosion. Although preferably neither the sensitized Nitroparaffins nor the separate sensitizer or nitroparaffins excessively are to be heated, it is possible both sensitized and unsensitized Materials at temperatures up to about 50 ° C for an indefinite period of time without damage to store.

The ignition of the sensitized nitroparaffin can be known by Intermediate igniters, such as electric detonators or a chestnut booster, are carried out. Multiple intermediate igniters can be used if desired. For large loads a small charge of another explosive such as dynamite, find application as an intermediate igniter. The sensitized nitroparaffins can at any temperature between the freezing point and the boiling point of the explosive be used. The ignition can be carried out under any desired pressure of the explosive are executed.

The sensitized nitroparaffins can be found at the place of use using conventional containers made of metal, plastic, wood; Paper and the like be kept. If the cargo is to be brought into a hole, that into a Rock, for example granite, is drilled, the liquid sensitized nitroparaffin can can be poured directly into the hole without the use of any other container. The sensitized nitroparaffins can be packed in containers that act as storage containers and also serve to pick up the cargo at the place of use.

Claims (2)

Claims: 1. Sensitized by adding an organic amine Nitroparaffin explosives, which do not indicate that the sensitizing Amine is a monoarylalkyleneamine, alkylaryldiamine and / or aminopyridine and in one An amount of about 0.2 to 20 percent by weight is incorporated into the nitroparaffin. 2. Nitroparaffin explosive based on nitromethane according to claim 1, characterized characterized in that it consists of 20 to 0.5 percent by weight benzylamine, toluenediamine or Diaminopyridine and 80 to 99.5 percent by weight nitromethane. Into consideration Drawn pamphlets: U.S. Patents Nos. 2,560,439, 2,967,099.