US2415001A - Explosive compounds - Google Patents

Description

Patented Jan. 28, 1947 NITED STATES PATENT EXPLOSIVE COMPOUNDS John D. Brandner, West 'Walker Township,

Schuylkill County, Pa., assignor to Atlas 'Powder Company, Wilmington, DeL, a. corporation of Delaware No Drawing. Application October 21, 1944,

Serial No. 559,831

The present application relates to explosives.

An object of the present invention is the provi sion of diisopropanolamine trinitrate.

Another object of the present invention is the provision of a method for the preparation of diisopropanolamine trinitrate.

A further object of the present invention is the provision of an improved detonator.

It has been found that the new compound, diisopropanolamine trinitrate, has unusual properties as an explosive and that it is particularly applicable as an explosive compound in detonators.

A preferred method for the preparation of diisopropanolamine trinitrate according to the present invention includes first reacting diisopropanolamine with dilute nitric acid with the resultant production of the nitrate salt of diisopropanolamine, concentrating the nitrate salt solution, reacting the concentrated solution with a concentrated nitric acid solution, drowning the reacted nitration mixture in cold water, and

separating the precipitated crude diisopropanol- This crude product may be itin hot water, cooling the solution, and separating the purified precipitated diisopropanolamine trinitrate.

The equations for these reactions may be represented as follows:

H H H O H H O H HC-G-O HC-C-C H H H H H H NH+HNOa NHg N03- H H H H H H HCC-C HC-C-C H O H H O H H H Dilute Diisopropanolnitric Nitrate salt of amine acid diisopropanolamine H v H H HCCC H H H\ /NH2 N0 -+2HNO H H H Concentrated HCCC nitric acid H O H H 02 N H O H HC-CC H H H /NH N03+2H2O H H H HO-C-O H O H N 02 Diisopropanolamine 'trate Itis readily seen from the above description 3 Claims. (Cl. 260-467) 2 of its process of preparationthat 'diisopropanolamine trinitrate possesses the valuable property of solubility in 'hot water and relative insolubility in cold water. This property readily distinguishesit from such other alkylol amine nitrates asdiethanolamine trinitrate and monoethanolamine 'dinitrate which. are water soluble compounds, as is also monopropanolamine dinitrate. Consequently, all of these compounds require complex solvent drowning procedures to separate them from nitrationmixtures.

Diisopropanolamine trinitrate is obtained as a white crystalline solid having a melting point of 119.6" C. It dissolves readily in hot water without decomposition. It is a powerful secondary explosive material, highly resistant to shock and friction, but it is readily initiated by the common primary detonator compositions. Stability tests show it to have satisfactory heat stability. In the standard Abel heat test at 160'F., diiso propanolamine trinitrate produced no effect on the starch-jpotassiumiodide test paper during a test period of 60 minutes.

- Diisopr'opanolam-ine trinitrate may be employed to .particular advantage as an explosive ingredient in detonators, and it finds especial utility as asecondary detonating, or base charge,

material.

A number of specific embodiments of the invention are contained in the following examples:

Example ,I

This example shows a preparation of diisopropanolamine trinitrate.

100 grams of diisopropanolamine, a soft, white, waxy solid, were dissolved in 2'7 grams of water with slight warming. 67.1 grams of nitric acid wereplaced in a beakersurrounded by icesalt bath and equipped witha thermometer and a mechanical stirrer. The amount of water in the diisopropanolamine solution and in the nitric acid solution was sumcient to give a concentration of 50% nitric acid on mixing, The diisopropanola-mine solution was slowly run into the nitric acid solution from a dropping funnel. The reaction progressed smoothly. The maximum temperature reached was 12 C., and the total time of addition was 1 hour and 35 minutes. The reacted'mixture was evaporated on a steam bath for two hours. The theoretical yield of nitrate salt of diisopropanolamine was 143.7 grams and the actual yield of product was 151 grams, indicating the presence of residual water. The product was'in the form of a thick yellow syrup.

604 grams of 96.8% nitric acid in a 1 liter beaker were cooled in an ice-salt bath. With rapid agitation, the nitrate salt of diisopropanolamine was run into the-acid through a dropping funnel. The viscosity of the nitrat'e salt made the feed rather slow. The time of nitration was 1 hour and 23 minutes. The maximum temperature reached was 7 C., but the average temperature was about 5.5 C. The nitration mixture was drownedin 1335 cc. of water contained in a beaker surrounded by an ice-salt mixture. The time of drowning was 53 minutes andthe maximum temperature was 9 C. .Diisopropanolamine trinitrate came down as a fine white precipitate which was filtered and washed with 500 cc. of water at a temperature of 8 to 9 C. The excess liquid was sucked out, and the diisopropanolamine trinitrate was spread out to dry. The dried product was a white chalky material. 167.6 grams were obtained amounting to 77.5% of the theoretical yield.

The dry crude diisopropanolamine trinitrate was then dissolved in 3 liters of boiling water, filtered and slowly cooled to 30 C. during the course of an hour. The solution was then placed in an ice salt bath and chilled to a temperature of 7 C. The diisopropanolamine trinitrate precipitated and was then filtered ofi and washed with water to remove acidity. The final purified product obtained was snow white and in the form of uniform, free flowing crystals. The yield obtained amounted to 76.6 grams, Since there is some loss due to the product's dissolving in the mother liquor and wash water, this yield may be considerably increased on subsequent batches of product by successive reuse of the mother liquor and wash water.

Example II This example reports tests made to determine the sensitivity of the material.

A 10 kilogram weight was dropped repeatedly from a height of 64 inches onto the material lying on a steel anvil. No detonations were obtained.

A rod weighing 10%, pounds, and having a hemispherical nose, was let slide down a trough set at various angles so as to impinge upon the material placed on an anvil. The angles used and the corresponding vertical height of fall were as follows, the angle being measured between the trough and the horizontal:

Angle: Vertical height 45 inches 45 60 do 55 75 do 65 Using both a steel nose and a brass nose on the rod at each angle and both a brass and steel anvil with each nose, no detonations were obtained in any case.

These tests indicate that diisopropanolamine trinitrate is less sensitive than tetryl to impact, and to a combination of impact and friction.

Example III This example shows the preparation and testing of fuse caps containing base charges of diisopropanolamine trinitrate. Fuse cap shells, 0.222 inch in diameter, were each charged with 0.23 gram of diisopropanolamine trinitrate, and this charge was pressed at 150 pounds pin pressure. Over the base charge, a primer charge of 0.17 gram of nitromannite and a flash charge of 0.06 gram of a mixture of 75% diazodinitrophenol and 25% nitromannite were pressed together at 30 pounds pin pressure.

These caps were given sand tests in a 200 gram bomb, and an average of 55.6 grams of sand was crushed by each cap.

Example IV 25 fuse caps were made similarly to those described in Example III except that they contained 0.29 gram of diisopropanolamine trinitrate pressed at 150 pounds for a base charge, 0.10 gram of nitromannite primer charge, and 0.06 gram of diazodinitrophenol and nitromannite flash charge pressed together at 25 pounds. These caps all produced A plates in the lead plate test.

10 more fuse caps similar to these last but containing only 0.08 gram of nitromannite primer charge were prepared, and these also all produced A lead plates.

Example V 25 electric blasting caps were made up by loading shells 0.260 inch in diameter each with 0.29 gram of diisopropanolamine trinitrate base charge and 0.125 gram of nitromannite primer charge pressed together under a inch inner capsule at pounds pin pressure and sealing conventional match head assemblies into the tops of the shells. These caps also all produced A lead plates.

The diisopropanolamine trinitrate which was prepared according to Example I and used in all the above tests was a free-flowing crystalline powder showing admirable charging characteristics.

In its particular use as a base charge in detonators, diisopropanolamine trinitrate may be used in combination with any primary detonator compositions such as, for example, mercury fulminate, lead azide and diazodinitrophenol. Diisopropanolamine trinitrate is also a useful material for incorporation with primary detonator compositions. Also, diisopropanolamine trinitrate base charges may be superimposed over or under other base charge materials such as, for example, tetryl, .pentaerythritol tetranitrate and trinitrotoluene, or it may be employed mixed with such materials.

Its property of relative insolubility in water and its high degree of stability give diisopropanolamine trinitrate an important advantage over other isopropanolamine nitrates. Monoisopropanolamine dinitrate is very soluble in water. Triisopropanolamine tetranitrate hydrolytically decomposes under all but acid conditions. Furthermore, this salt is only obtained in low yields and is too unstable for effective use.

It is readily seen from the above description that diisopropanolamine trinitrate is a highly useful compound having valuable properties which distinguish it from other alkylol amine nitrates. Diisopropanolamine trinitrate is a practical explosive not only for detonators, but also for general explosive uses such as, as an ingredient in blasting explosives.

What is claimed is:

1. Diisopropanolamine trinitrate.

2. A process of preparing diisopropanolamine trinitrate which comprises reacting diisopropanolamine with dilute nitric acid, concentrating the resulting solution of nitrate salt of the diisopropanola-mine, reacting the concentrated product with concentrated nitric acid, drowning the nitration mixture in cold water and separating the precipitated diisopropanolamine trinitrate product.

3. A process according to claim 2 which further comprises dissolving the diisopropanolamine trinitrate product in hot water, cooling the solution, and separating the reprecipitated product.

JOHN D. BRANDNER.