DE1111079B - Explosives or propellants - Google Patents

Description

The present invention relates to explosives and propellants containing inorganic substances Nitrate with increased detonation stability and transmission. In the case of plastic explosives, a lower plastic viscosity and a lower yield point and, in the case of powdery explosives, one get higher density.

The plastic ammonium nitrate explosives contain crystallized ammonium nitrate, which in a liquid or a gel phase is suspended. To accommodate the detonation from the Oxygen released from nitrate, various flammable components, such as wood flour, aluminum, Nitro hydrocarbons, added. The medium in which ammonium nitrate is suspended contains im generally an explosive mixture, e.g. B. nitroglycerin, nitroglycol and cellulose nitrate, but can also a non-explosive mixture, e.g. B. cellulose nitrate in nitrobenzene. To make a Propellant, the mixture is made so that it burns quickly but does not detonate. The ammonium nitrate can be partially replaced by other inorganic nitrates, such as sodium nitrate.

To produce plastic ammonium nitrate explosive mixtures, the components are mixed with one another kneaded. The homogeneous product can be used directly; but it will generally go through squeezed out an opening and sheathed or inserted into a suitable container. It was a long unsolved problem to find squeezable explosives with a high content of ammonium nitrate to manufacture. This problem has been solved so far by adding compounds which give low-melting mixtures with ammonium nitrate, e.g. B. carbamide, or by Compounds have been added that prevent the wetting of ammonium nitrate by gelatin (the viscous phase), e.g. B. paratertiary octylphenyl diethyl phosphate.

The present invention relates to improved explosives and propellants containing inorganic nitrate, especially ammonium nitrate, where they contain nitrate as a component or from it are made that with 0.001 to 1.5 g of alkylamine having at least 6 carbon atoms in the alkyl group treated per 100 g of nitrate. Fatty amines, d. H. Long carbon chain alkylamines, 12 to 20 carbon atoms, such as. B. dodecylamine, hexadecylamine and octadecylamine were found to be special suitable.

The alkylamines, e.g. B. Hexadecylamine, are so strongly basic that they have the property with ammo-explosives or propellants

Applicant:

Nitroglycerin Aktiebolaget,
Gyttorp (Sweden)

Representative:

Dr. F. Zumstein, Dipl.-Chem. Dr. rer. nat. E. Assmann and Dipl.-Chem. Dr. R. Koenigsberger, patent attorneys,

Munich 2, Bräuhausstr. 4th

Claimed priority:
Sweden October 31 and December 4, 1958

Bertil Petrus Enoksson, Gyttorp (Sweden),
has been named as the inventor

to react with the development of ammonia. The reaction takes place on the surface of the Crystals instead, whereby the alkylamine is connected to the crystals through the amino group.

Primary amines were tried first because they are readily available commercially, but also secondary and tertiary amines, such as. B. stearindimethylamine can be used.

Generally about 0.1 g of alkylamine per 100 g of ammonium nitrate was added. Lower Amounts than 0.005 g per 100 g of ammonium nitrate did not show sufficient effect on nitrate crystals less than 0.1 mm. In the case of coarse ammonium nitrate, i.e. H. granulated ammonium nitrate, As little as 0.001 g per 100 g of ammonium nitrate may be of interest. The addition can be carried out with a small part of ammonium nitrate, which then with the mass of ammonium nitrate is mixed.

The best effect is achieved when the amine is added to an already crystallized nitrate which has a higher temperature than the melting point of the compound added, and the salt is then allowed to cool while stirring. But the amine can also be in a solution

109 647/202

3 4

or melt of ammonium nitrate before or during example 1

rend to be added to the crystallization. Since the _{Es became a dynamite of the} following composition

The alkylammmolecule is considerably larger than the am- jo e

is monium nitrate, it will rise to the surface of the ^s

Crystals forced and in this case also gives the 5! Nitroglycerin 24.1%

desired protection. One can also use a nitroglycol 11.8% salt

Alkylamine or a solution thereof, e.g. B. Hexa- ^A ??? !! T5 ', ^treat with

decylammonium chloride or -acetal at the control of _ ° ^'16 ^ dodecylamm 54.4%

Alkylamine itself. Cyclic nitro hydrocarbons 6.0 »/ ο

When using this treated ammonium- io nitrocellulose 1.4%

nitrates in plastic explosives are ir vwi, "ηΛ nlj, °

plastic viscosity and the yield point of the mixed chalk U, 2%

When squeezing the dynamite with a moderate force, and squeezing the average shear rate of 8.27 per mixture can be a higher shear chip at a lower pressure or at 15 seconds (cm / cm second) Speed happen. The maximum voltage of 2.3 · 10 * dynes / cm ^{2 is} required. The same amount of solid substances in the mix can also be increased required dynamite that did not contain dodecylamine. It is technically very convenient, at the same rate of shear, a thrust treatment of ammonium nitrate before its tension of 2.8 · 10 ⁴ dynes / cm ² . After dividing in the viscous phase for 24 hours and storing it for 20 hours, the dynamite, which did not contain any dodecylamine, was therefore easier to handle and also easily contained, could not be distributed in the extruder used. But it is also possible to squeeze it out, that is, a higher shear stress desired result than 9.2 · 10 ⁴ dynes / cm ^{2 was} required by adding the alkylamine, while this was to bring about the plastic mixture. Dynamite containing a dodecylamine

The plastic ammonium nitrate explosives 25 shear stress of 2.5 · 10 ⁴ dyn / cm ² at a shear

often show annoying old things. To achieve a high rate of 8.27 seconds - ¹ required.

Detonation rate of aged explosives. .

becomes a stronger initial impulse and solid confinement Example 2

or the use of larger diameters is necessary. A dynamite of the following composition was produced

agile. The detonation transfer, i.e. H. the maxi- 30 manufactured:

distance over which the detonation of a nitroglycerin 241%

Cartridge is propagated to another is vermin- Nitroelvkol 118 ° /

changes. This is especially true when blasting at low levels of ammonium nitrate ''.'.'.'.'.'.'.'.'.'.'.'.'.'.'. 54.4%

Temperatures very disadvantageous. These disadvantages are Cyclic nitro hydrocarbons 6.0 «/ ο

in the process according to the invention by the 35 nitrocellulose 1 4%

Use of alkylamine additives to the explosive wood flour 21%

substance significantly reduced. The chalk too 02%

Baking of the explosive during storage is reduced. '

The improvements resulting from these additives were used.

conditions reduce the wetting of the salt surfaces 40 composition of a 0.1% octadecylamine

through the liquid phase, and therefore air-bubble-traded ammonium nitrate are produced. The two

suitable dimensions on the salt crystals, even dynamites were extruded in a laboratory

after prolonged storage, retained. The emp- apparat with an average shear

The sensitivity of the stored explosive is not compared to a speed of 4.56 sec. cm- ¹ . 3 hours

only received, but also the freshly made 45 den after making the dynamite required that

Explosive has higher detonation transmission and contained the octadecylamine treated salt, one

better detonation stability at lower temperature shear stress of 2.8 · 10 ⁴ dyn / cm ² , while the

ratures. These mentioned properties of the alkyl dynamite without octadecylamine have a shear stress

Amine additives are not required for plastic explosives of 4.1 · 10 ⁴ dynes / cm ² . 24 hours after the

limited, but are also used for powdery am- 50 production required dynamite, octadecylamine

get monium nitrate explosives; the last one contained a shear stress of 3.0-10 ⁴ dynes / cm ² ,

In addition, a higher density and better density are achieved, while dynamite without octadecylamine cannot be used.

Storage properties. was compressible, d. H. a higher shear stress than

The explosives produced according to the invention required ^{9.2 · 10 4} dynes / cm ^2,

may also contain other ingredients that 55.

commonly used in such products, for example

the; e.g. sensitizers, carbonaceous fuel 100g dynamite according to Example 1, which contains 0.1% octa-

substances and finely divided, flammable metal powder. Containing foidecylamine, were treated with more ammonium

Gentle sensitizers can be used, for example, mixed nitrate containing 0.1% octadecylamine,

den: explosive nitric acid esters, such as nitroglycerin, 60 until the same compressibility as

Nitroglycol and nitrated hydrocarbons, e.g. B. with a dynamite of the same composition as in

Nitrotoluene. As examples, carbonaceous burning example 1, but without octadecylamine. To this

materials are coal and wood flour. The fine-purpose was an addition of 7 g of ammonium nitrate

scattered, flammable metal powder can be powdered required.

Be aluminum or ferro-silicon. 65.

The following examples illustrate the invention. Example 4

All percentages given are 280 kg by weight of plastic explosive according to Example 1

percent. were with 292 kg explosives with ammonium

nitrate containing 0.1% octadecylamine, ie with a mixture of 280 kg of the same composition as the other sample and 12 kg of ammonium nitrate containing 0.1% octadecylamine. Despite the larger amount of this salt, the latter explosive required slightly less energy to knead than the other sample. When pressed out at a shear rate of 4.56 sec- ¹ , the amine-containing dynamite required a shear stress of 3.5 · 10 ⁴ dynes / cm ² , while the comparative sample required a shear stress of 4.1 · 10 ⁴ dynes / cm ² . The drop hammer values, the tear sensitivity, the detonation temperature, the chemical stability and the detonation speed were very similar in both samples. The detonation transmission from cartridge to cartridge (22 mm diameter) was 10% higher for the dynamite containing octadecylamine than for the comparative sample.

20th

Example 5

Ammonium nitrate stored for 1 year was dried and ground. Half of the sample was made mixed with an addition of 0.1% oleylamine and the other half without this addition as a comparison sample used. Explosives with the same composition as mentioned in Example 1 were made from these two salts. The comparison sample could not use 25 mm cartridges squeezed out, while the amine-treated sample gave a product that was squeezed out by itself was too soft for 20mm cartridges. After a week of storage the detonation transmission was from cartridge to cartridge (22 mm diameter) 425 mm for the explosive that is treated with amine Ammonium nitrate contained, during the transfer in the comparison sample, that which was not treated Contained nitrate, was 165 mm.

40

Example 6

Crystallized ammonium nitrate was mixed with 0.1% isopropylamine lauryl sulfate dissolved in water to a concentration of 33% with stirring. The salt was dried in vacuo at 30 ° C. 210 g of this salt were kneaded together with 100 g of a 4% strength solution of nitrocellulose in dibutyl phthalate. When pressed out at a shear rate of 4.56 sec. ^-1 , the plastic mass required a shear stress of 2.8 · 10 ⁴ dynes / cm ² . The comparison sample without isopropylamine lauryl sulfate required a shear stress of 6.5 · 10 ⁴ dynes / cm2 at the same shear rate.

Example 7

A plastic explosive (A) was produced with the following composition:

Nitroglycerin - nitroglycol

(70:30) 35.9%

Cyclic nitro hydrocarbons

(nitrated toluene) 6.0%

Nitrocellulose 1.4%

Ammonium nitrate 54.4%

Wood flour 2.1%

Chalk 0.2%

Another explosive (B) of the following composition with the same expressing properties was obtained manufactured:

Nitroglycerin - nitroglycol

(70:30) 35.9%

Cyclic nitro hydrocarbons 2.0%

Nitrocellulose 1.4%

Ammonium nitrate 58.4%

Wood flour 2.1%

Chalk 0.2%

Hexadecylamine 0.02%

Octadecylamine 0.02%

The detonation speed and the detonation transmission (transmission value) were at these two explosives.

The speed of detonation, m / sec. with a column of explosive 25 mm in diameter, detonated by a standard no. 8 detonator, after storage, was:

Explosive 6605 A. 6535 24 hours, 6225 solid inclusion 6410 5810 no inclusion 6110 5930 1 week, no inclusion 7335 6190 1 month, no inclusion 3305 3 months, no inclusion 3650 6 months, no inclusion 3065

Transfer value, mm for a column of explosive 22 mm in diameter

After storage Tempe
rature C. Explosive
AIB 210 480 to 490 24 hours 17 ° C. 200 to 210 500 to 510 1 week 17 ° C. 200 to 210 460 to 470 1 month 17 ° C. 200 to 210 400 to 410 3 months .... 17 ° C. 200 to 210 430 to 440 6 months .... 18 ° C. 200 to 60 430 to 440 72 hours 20 ° C. 50 to 40 200 to 210 216 hours 20 ° C. 30 to 60 260 to 270 1 month 20 ° C. 50 to 80 250 to 260 3 months .... 20 ° C. 70 to 80 320 to 330 6 months .... 20 ° 70 to

60

65

Example 8

A dynamite of the following composition was produced:

Nitroglycerin — nitroglycol (50:50) 35.9% Cyclic nitro hydrocarbon 6.0%

Nitrocellulose 1.4%

Wood flour 2.1%

Ammonium nitrate 54.5%

Chalk 0.05%

Iron oxide (red pigment) 0.05%

The dynamite mentioned was mixed with increasing amounts of stearic amine. The compressibility was determined at a shear rate of 4.56 sec. ^-1 after storage for 3 hours.

Grams of stearic amine
per gram of dynamite Shear force, dyn / cm ² 0.0004
0.00055
0.0016
0.0032 4.00 10 *
2.70 · 10 *
3.06 · 10 *
2.70 · 10 *
2.55 10 *

Example 9

A mixture of the following composition was prepared:

Ammonium nitrate 20 g

A 4% solution of nitrocellulose in dibutyl phthalate 10 g

This mixture was mixed with increasing amounts of stearic amine. Complete pressing was at _go a shear rate of 4.56 sec.! certainly.

Diameter was 2,800 m / sec. and the detonation transmission 60 to 70 mm. A corresponding one Explosive without stearic amine gave a detonation speed of 2,500 m / sec. and a detonation transfer from 50 to 60 mm.

Example 12

An ammonium nitrate explosive powder of the following composition was produced:

Nitroglycerin — Nitroglycol (60:40) 6.0%
Ammonium nitrate, which contains 0.08%

Stearinamine treated was 85.3%

Silicon 3.0%

Wood flour 2.8%

Paraffin 2.9%

A sample of this showed a detonation transmission of 40 to 70 mm at 20 ° C, 25 mm diameter, but a sample without stearic amine only showed a detonation transmission from 0 to 20 mm below the same conditions.

Stearinamine, ° / o Shear stress, dyn / cm ² not squeezable 0.008 9.8 0.03 3.29 0.07 3.26 0.09 2.88 0.3 2.12 0.7 2.23

Example 10

A powdery explosive was produced with the following composition:

Nitroglycerin — Nitroglycol (60:40) 6.3 ⁰ Zo ammonium nitrate, which contains 0.05%

Stearinamine was treated ... 76.1%

Trotyl (trinitrotoluene) 11.5%

Silicon 2.0%

Kieselguhr 1.2 «/»

Wood flour 2.7%

Paraffin 0.2%

This explosive, enclosed in an iron pipe, had a detonation speed of 5,400 m / sec. The detonation transmission (transmission value [gap test]) at a diameter of 22 mm was 230 to 240 mm. A corresponding explosive without stearic amine resulted in a detonation transmission from 150 to 160 mm.

Example 11

An explosive powder of the following composition was produced:

Nitroglycerin 6%

Wood flour 5 <y ₀

Aluminum 4%

Ammonium nitrate, which contains 0.1%

Stearinamine treated was 85%

The explosive had a density of 1.25 g / cm ² . A corresponding explosive without stearic amine had a density of only 1.14 g / cm ^s . The speed of detonation in a paper cylinder of 25 mm

Example 13

A powdery explosive was produced with the following composition:

Nitroglycerin — Nitroglycol (60:40) 6%

Wood flour 2%

Paraffin 3%

Silicon 2%

Ammonium nitrate, which contains 0.08%

Stearinamine treated was 87%

The transfer of detonation in a column of explosives of 22 mm diameter, ignited with a standard no. 8 detonator at 20 ° C 40 to 70 mm, and the transfer number was only slightly lower at lower temperatures.

The detonation transfer of the same explosive without stearic amine at 20 ° C was 0 to 30 mm.

Example 14

93 g of crystallized ammonium nitrate were mixed with 4 g of wood flour and 0.1 g of laurylamine at 60 ° C. After cooling, 3 g of fuel oil were added and the product in paper cylinders Cartridges packed. When packing was a 10% higher density than with similar methods with no treated ammonium nitrate achieved.

Example 15

A 4% solution of nitrocellulose in dibutyl phthalate was prepared. 1 part by weight of the gel mentioned was mixed with 2 parts by weight of ammonium nitrate which had been treated with 0.0003 mol of an amine mentioned in the following table per 100 g of ammonium nitrate. The shear stress was determined at a shear rate of 2.28 sec. - ^x .

6o addition

Stearic amine
Stearic amine acetate
Stearin dimethylamine
C ₁₈ H ₃₇ NH (CHo) ₃ NH ₂

Shear stress, dyn cm ²

9.40

3.41 ·

3.76

5.65

3.76

10 *
10 *
ΙΟ ⁴
10 *
10 *

Claims (9)

9 10 Claims: 2. Explosives or propellants according to 1. explosives or propellants with a language 1, characterized in that the nitrate stop at inorganic nitrate, especially with dodecylamine, hexadecylamine and / or Ammonium nitrate, characterized in that octadecylamine has been treated. they contain nitrate as a component or from a 5 Nitrate are produced that contain 0.001 to 1.5 g. Publications considered: Alkylamine with at least 6 carbon atoms in German Patent Nos. 334 547, 380 888, the alkyl group per 100 g of nitrate treated 581814, 750 641; became. Swiss patent specification No. 181254. © 109 647/202 7. 61