WO1999048842A1

WO1999048842A1 - Primary explosives and primers which can be ignited by electric triggering

Info

Publication number: WO1999048842A1
Application number: PCT/EP1999/001906
Authority: WO
Inventors: Rainer Hagel; Klaus Redecker
Original assignee: Dynamit Nobel Gmbh Explosivstoff- Und Systemtechnik
Priority date: 1998-03-20
Filing date: 1999-03-22
Publication date: 1999-09-30
Also published as: EP1064241B1; EP1064241A1; DE59914443D1; DE19912622A1; ATE369327T1

Abstract

The invention relates to primary explosives and primers for igniting boosters or propellant charges or for generating compressed gas, whereby the primary explosives and the primers can be electrically ignited.

Description

1

Initial explosives and primers ignitable by electrical triggering

The invention relates to initial explosives and primers for igniting boosters or propellant charges or for generating compressed gas.

DE-A 33 21 943 describes ignition charges which contain special initial explosives and peroxides which can be used to ignite thermal charges. Because of their composition, they are preferably ignited by mechanical action. Electrical ignition of these sets is only possible under special conditions.

It is an object of the invention to provide initial explosives which can be ignited electrically, optionally in combination with ignition mixtures.

The invention is based on a further object of providing ignition charges which can be ignited electrically, if appropriate in combination with ignition mixtures.

Another object was to provide initial explosives and primers that can be ignited electrically, possibly in combination with igniter mixtures, and in which the vapors contain a reduced proportion of toxic compounds and are as free from aggressive gases as possible.

According to the invention, to solve a problem, initial explosives are provided in a first embodiment, which are selected from 2-diazo-4,6-dinitrophenol, 4-diazo-2,6-dinitrophenol, dipicrylditetrazole, salts of 2-diazo-4,6-dinitroresorzine , 4-Diazo-2,6-dinitroresorzins, Dinitrobenzofuroxans, the Trinitrophenol and the Trinitroresorzins or mixtures of these initial explosives. Examples of salts which can be used with preference are the potassium salt of dinitrobenzofuroxane, the potassium

ESTÄTSGUNGSKOPIE 2

called lium and strontium salts of trinitrophenol and trinitroresorzine. If a small proportion of lead can be tolerated in the swaths, the lead salts of trinitroresorzine can also be contained in normal or basic form.

According to the invention, in one embodiment, ignition kits are provided in order to achieve a further object, which, in addition to at least one initial explosive, contain at least one oxidizing agent and optionally binders, reducing agents, secondary explosives, components which contribute to the implementation and / or contain inert substances.

The initial explosives which can be used for this purpose according to the invention are selected from 2-diazo-4,6-dinitrophenol, 4-diazo-2,6-dinitrophenol, dipicrylditetrazole, from the salts of 2-diazo-4,6-dinitroresorzine, 4-diazo-2, 6-dinitroresorzins, Dinitrobenzofuroxans, the Trinitrophenol and / or the Trinitroresorzins. Examples of salts which can be used with preference are the potassium salt of dinitrobenzofuroxane, the potassium and strontium salts of trinitrophenol and trinitroresorzine. If a small proportion of lead can be tolerated in the swaths, the lead salts of trinitroresorzine in normal or basic form can also be present in the mixture in amounts of up to 20% by weight.

The initial explosives can be present here in amounts of 20 to 70% by weight. Mixtures of these initial explosives can also be used. They can be used in both fine-grained and coarse-grained condition.

According to the invention, the oxidizing agent is selected from zinc peroxide, potassium nitrate and / or potassium perchlorate. Zinc peroxide is preferably used with an active oxygen content of more than 12.3% (cf. DE-PS 29 52 069).

According to the invention, the oxidizing agent is used in amounts of 5 to 50% by weight. The oxidizing agent can be used both in a fine-grained state and in coarse-grained form. 3

Furthermore, the primers according to the invention can also contain binders, reducing agents, secondary explosives, components which contribute to the implementation and / or contain inert substances.

Suitable reducing agents are the reducing agents known per se in ignition kits which improve the ignition ability. Boron, titanium, zirconium, magnesium, cerium magnesium, cerium silicon, aluminum / magnesium or calcium silicide powders are suitable, for example. Mixtures of these reducing agents can also be used. According to the invention, the proportion of the reducing agent can make up to 20% by weight.

10

Secondary explosives, for example octogen, amino compounds of nitrated aromatics, for example of trinitrobenzene such as mono-, di- or triaminotrinitrobenzene or diaminohexanitrodiphenyl, and furthermore the acylation products, furthermore preferably further components which make a contribution to the reaction,

15 water compounds, for example hexanitrooxanilide or hexanitrodiphenylurea, hexanitrostilbene, hexanitrodiphenyloxide, hexanitrodiphenylsulfide, hexanitrodiphenylsulfone, hexanitrodiphenylamine, tetranitrocarbazole, tetranitroacridone, polyvinylnitrate, nitrocellulose nitrate, nitrocellulose nitrate, nitrocellulose nitrate, nitrocellulose nitrate, nitrocellulose nitrate, nitrocellulose nitrate, nitrocellulose nitrate, nitrocellulose nitrate, nitrocellulose nitrate, nitrocellulose nitrate, nitrocellulose nitrate, nitrocellulose nitrate, nitrocellulose nitrate, nitrocellulose nitrate, nitrocellulose nitrate, nitrocellulose nitrate, nitrocellulose nitrate are used. Secondary explosives that act as binders are preferred. Especially before

20 moves is nitrocellulose. These components can be contained in amounts of up to 30% by weight.

Both the initial explosives according to the invention and the ignition charges according to the invention are referred to and used as the so-called 1st charge. You can

25 NEN preferably combined with a so-called 2nd charge (ignition mixture). This second charge preferably contains a mixture of metal powder as a reducing agent and potassium perchlorate as an oxidizing agent. Titanium or zirconium powder is preferred as the metal powder. The metal powder is in the redox system in amounts of 30 to 80 wt .-% and the potassium perchlorate in amounts of 20 to

30 70 wt .-% used. 4

Moderators in amounts of up to 10% by weight can also be used. Ca resinate, for example, can serve as a moderator.

Materials made of conductive material can also be used. Both carbon and a metal or an alloy, for example brass, which conducts the electrical current can serve as the conductive material. The fabrics are preferably used in fiber form. Metal fibers that can be used are, for example, iron or copper. The proportion of fibers can vary between 0.5 and 20% by weight.

Suitable inert substances are the substances known per se in ignition systems, which are also used to match the properties of these phrases to the respective intended use. Tin dioxide is an example. The inert substances also include other binders, for example PVB, waxes or PE, adhesives and dyes. The proportion of the inert substances in the primers according to the invention can make up to 20% by weight.

The ignition kits according to the invention or the ignition mixtures are produced by methods known per se by mixing the individual constituents with the binder dissolved in a solvent or the secondary explosive which has binder properties. This mixing can be done by methods known per se by stirring, kneading or similar distribution methods. The ignition charges according to the invention or the ignition mixtures are obtained as a pulpy mass.

The first charges according to the invention not only fulfill the function of a standard ignition charge, but can also be used directly without an additional booster charge. This is generally done by directly applying a first charge according to the invention with the aid of a metering device, such as pipettes, syringes or the like. 5

A stamp can also be used to apply the charges, with which the mixture adhering to the stamp can be applied after immersion in the charges.

In a further preferred embodiment, the primers according to the invention are portioned into perforated plates by carefully brushing in the substances or mixtures moistened with water. After ejection from the mold, drying and, if necessary, slight pressing of the ignition set according to the invention thus formed.

The first charges according to the invention can, optionally in combination with a second charge, for example by an ignition / ignition element according to DE-A 19637587, but also by ignition / ignition elements of the type of a split, glow wire or metal layer element igniter and all by sparks or ignitions triggered by laser light are ignited.

The invention relates in detail to:

Initial explosives for igniting boosters or propellant charges or for generating pressurized gas, in which the initial explosives can be ignited electrically and are selected from 2-diazo-4,6-dinitrophenol, 4-diazo-2,6-dinitrophenol, dipyrylditetrazole the salts of 2-diazo-4,6-dinitroresorzins, 4-diazo-2,6-dinitroresorzins, dinitrobenzofuroxane, trinitrophenol or trinitroresorzins or from mixtures of these initial explosives.

The potassium dinitrobenzofuroxane can preferably be selected as the salt of dinitrobenzofuroxane, the potassium and / or strontium salts as the trinitrophenol salt, the potassium and / or strontium salts as the trinitroresorcinol salt and the lead salts in normal and / or basic form as the trinitroresorcinol salt.

In the case of the initial explosives according to the invention, the initial explosive can be compressed and / or a dam made of inert substance can be provided. 6

Furthermore, the invention relates to ignition charges for igniting boosters or propellant charges or for generating pressurized gas, in which the ignition charge can be ignited electrically and contains at least one oxidizing agent in addition to at least one initial explosive.

The primers according to the invention can additionally optionally contain binders, reducing agents, secondary explosives, components which contribute to the implementation, moderators, substances made of conductive material and / or inert substances.

The initial explosives that can be used can be ignited electrically and are selected from 2-diazo-4,6-dinitrophenol, 4-diazo-2,6-dinitrophenol, dipicrylditetrazole, from the salts of 2-diazo-4,6-dinitroresorzine, 4-diazo- 2,6-dinitroresorzins, Dinitrobenzofuroxans, the Trinitrophenol or the Trinitroresorzins or from mixtures of these initial explosives, the oxidizing agents can be selected from zinc peroxide, potassium nitrate and / or potassium perchlorate, the reducing agents can be selected from boron, titanium, zirconium, magnesium -, cermagnesium, cerium silicon, aluminum / magnesium and / or calcium silicide powder, the secondary explosive can be selected from octogen, from amino compounds of nitrated aromatics, preferably mono-, di- and / or triaminotrinitrobenzene or diaminohexanitodiphenyl, from acylation products of these compounds, preferably hexanitrooxanilide and / or hexanitrodiphenylurea, from hexanitrostilbene, hexanitodiphenylox id, hexanitrodiphenyl sulfide, hexanitrodiphenyl sulfone, hexanitrodiphenylamine, tetranitrocarbazole, tetranitroacridone, polyvinyl nitrate, nitrocellulose and / or pentaerythritol tetranitrate, the inert substance can be selected from tin dioxide, PV or / and dyes, glue, and., as Ca resinate selected and / or fibers made of conductive material, preferably carbon fibers, can be selected as the conductive substance.

The proportion of initial explosives can be 20 to 70% by weight, the proportion of oxidizing agents 5 to 50% by weight, the proportion of reducing agents up to 20% by weight, the proportion of secondary explosives up to 30% by weight, the proportion of moderators up to 7

10% by weight, the proportion of conductive substances up to 20% by weight and / or the proportion of inert substances up to 20% by weight.

The present invention further relates to charges which consist of a combination of one of the initial explosives described above or of an ignition charge (1st charge) as described above with an ignition mixture (2nd charge).

The initial explosives according to the invention can be used in processes for igniting boosters or propellant charges or for generating compressed gas electrically, the initial explosive being ignited electrically.

Furthermore, the ignition charges according to the invention can be used in methods for igniting boosters or propellant charges or for the electrical generation of compressed gas, the ignition charge being ignited electrically.

The invention is described in more detail below by means of examples, without any intention that it should restrict it:

Manufacture of explosives

2-Diazo-4,6-dinitrophenol (diazodinitrophenol or diazole) is made by diazotizing sodium picramate.

Sodium picramate can be obtained from picric acid by selective reduction with sodium hydrogen sulfide.

Potassium dinitrobenzofuroxanate (potassium benzanate) is produced by neutralizing dinitrobenzofuroxane with potassium hydrogen carbonate in an aqueous medium.

Potassium picrate is precipitated by reaction of magnesium picrate with potassium nitrate or potassium sulfate in aqueous solution, filtered and free of magnesium salt with water 8th

washed and the water displaced with alcohol. Potassium picrate is stored in this form (alcohol moisture approx. 30 to 40% by weight).

embodiments

example 1

While small masses of diazodinitrophenol (diazole) or dipicrylditetrazole, e.g. B. 5 mg, do not ignite when using a metal layer element, sensitization is achieved by adding 30% potassium dinitrobenzofuroxanate, thereby ensuring reliable ignition.

Larger diazodinitrophenol masses ignite due to self-insulation, but there is then a risk of detonation.

Reliable ignition of even small diazodinitrophenol masses is achieved by a barrier layer made of inert material or by thermal charging.

Example 2

An ignition charge made of 30% diazodinitrophenol, 50% zinc peroxide, 10% calcium silicide and 10% NC spherical powder ignites reliably only when using a metal layer element with an insulation layer.

Example 3

Layers of potassium dinitrobenzofuroxanate, compressed with a pressure of up to 10,000 bar, ignite reliably when using a metal layer element without damaging.

Example 4

An ignition charge made of 50% potassium dinitrobenzofuroxanate, 45% zinc peroxide and 5% titanium or boron will ignite reliably when using a metal layer element without an insulation layer. 9

Example 5

A layer of NC-bonded potassium picrate with carbon fibers ignites safely when using a split igniter with self-insulation.

Example 6

70 mg of a two-stage charge consisting of 25 mg of potassium benzanate and 45 mg of potassium perchlorate / titanium ignite safely when ignited electrically.

Claims

10 patent claims:

1. Initial explosives for igniting boosters or propellant charges or for generating compressed gas, characterized in that the initial explosives are ignitable and are selected from 2-diazo-4,6-dinitrophenol, 4-

Diazo-2,6-dinitrophenol, dipicrylditetrazole, from the salts of 2-diazo-4,6-dinitroresorzine, 4-diazo-2,6-dinitroresorzine, dinitrobenzofuroxane, trinitrophenol or trinitroresorzine or from mixtures of these initial explosives.

2. Initial explosives according to claim 1, characterized in that as the salt of dinitrobenzofuroxane, the potassium dinitrobenzofuroxanate, as the salt of trinitrophenol, the potassium and / or strontium salts, as the salt of trinitroresorcinol, the potassium and / or strontium salts, and as the salt of trinitroresorcinol, the normal lead isomer salts and / or basic form are selected.

3. Initial explosives according to claim 1 or 2, characterized in that the initial explosive is compressed.

4. Initial explosives according to claim 1 or 2, characterized in that a dam is provided from inert material.

5. Ignition charge for igniting boosters or propellant charges or for generating compressed gas, characterized in that the ignition charge is electrically ignitable and contains at least one oxidizing agent in addition to at least one initial explosive.

6. Ignition charge according to claim 5, characterized in that it additionally contains binders, reducing agents, secondary explosives, components which make a contribution to the implementation, moderators, substances made of conductive material and / or inert substances. 11

7. Ignition charge according to claim 5 or 6, characterized in that the initial explosives are ignitable electrically and are selected from 2-diazo-4,6-dinitrophenol, 4-diazo-2,6-dinitrophenol, dipicrylditetrazole, from the salts of 2- Diazo-4,6-dinitroresorzins, 4-diazo-2,6-dinitroresorzins, dinitrobenzofuroxans, trinitrophenol or trinitroresorzins or mixtures of these initial explosives, that the oxidizing agents are selected from zinc peroxide, potassium nitrate and / or potassium perchlorate, that the reducing agents are selected from boron, titanium, zirconium, magnesium, cerium magnesium, cerium silicon, aluminum / magnesium and / or calcium silicide powder, that the secondary explosive is selected from octogen, from amino compounds of nitrated aromatics, preferably mono-, di- and / or triaminotrinitrobenzene or diaminohexanitrodiphenyl, from acylation products of these compounds, preferably hexanitrooxanilide and / or hexanitrodiphenylurea Hexanitrostilbene, hexanitrodiphenyl oxide, hexanitrodiphenyl sulfide, hexanitrodiphenyl sulfone, hexanitrodiphenylamine, tetranitrocarbazole, tetranitroacridone, polyvinyl nitrate,

Nitrocellulose and / or pentaerythritol tetranitrate, that the inert substance is selected from tin dioxide, PVB, waxes, adhesives and / or dyes and / or PE, that Ca resinate is selected as moderator and / or that fibers made of conductive material, preferably, are used as the conductive substance Carbon fibers are selected.

8. Ignition charge according to one or more of claims 5 to 7, characterized in that the proportion of initial explosives 20 to 70 wt .-%, the proportion of oxidizing agents 5 to 50 wt .-%, the proportion of reducing agents up to 20 wt. -%, the proportion of secondary explosives up to 30% by weight, the proportion of moderators up to 10% by weight, the proportion of conductive substances up to

20% by weight and / or the proportion of inert substances makes up to 20% by weight.

9. Charging, characterized in that it consists of a combination of an initial explosive according to one or more of claims 1 to 4 or of an ignition charge according to one or more of claims 5 to 8 (1st loading) with an ignition mixture (2nd Charge). 12

10. A method for igniting boosters or propellant charges or for the electrical generation of compressed gas, characterized in that an initial explosive according to one or more of claims 1 to 4 is ignited electrically.

11. A method for igniting boosters or propellant charges or for the electrical generation of compressed gas, characterized in that an ignition charge according to one or more of claims 5 to 7 is electrically ignited.

12. Use of an initial explosive according to one or more of claims 1 to 4 for the electrical ignition of boosters or propellant charges or for the electrical generation of compressed gas.

13. Use of an ignition charge according to one or more of claims 5 to 7 for the electrical ignition of boosters or propellant charges or for the electrical generation of compressed gas.