WO2016001161A1 - Pyrotechnic igniting agent - Google Patents

Abstract

The present invention relates to a pyrotechnic igniting agent, which contains basic salts of 5,5'-azotetrazole having the general empirical formula: M^m+ _n (C₂N₁₀ ^2-) _p (CO₃ ^2-) _q (OH^-) _r , wherein: M is an element of the 3rd to 12th group of the periodic table having an atomic number in the range of 21-80, (C₂N₁₀ ^2-) is an azotetrazolate dianion having the structure (AA), m is the valence of the cation, n is an integer from 1 to 6, p is an integer from 1 to 4, q is an integer from 0 to 8, r is an integer from 0 to 4, and q + r ≠ 0, wherein the fraction of the basic azotetrazolate component is 30 to 100 wt% and 0 to 70 wt% of an additive or mixtures of a plurality of additives is contained.

Description

 Pyrotechnic igniter

The present invention is a pyrotechnic ignition medium.

Pyrotechnic igniters in the context of the invention are substances or mixtures which can develop a pyrotechnic effect. In particular, the subject of the present invention is a pyrotechnic igniting agent which can be used in mechanical, electrical or opto-electric ignition systems.

From the document DE 102010025104 A1 a 5,5'-azotetrazolate explosive is known, which is an iron, cobalt, nickel, copper, cadmium or guanyl urea salt of a 5,5'-azotetrazole or a mixture of at least one 5 , 5'-azotetrazolate and at least one bistetrazolyl triazenate or at least one further metal salt or guanyl urea salt of a 5,5'-azotetrazole. The salts described therein are neutral, i. neither sour nor basic. Zinc and chromium salts of 5,5'-azotetrazole are not storage stable according to the document DE 102010025104 A1. Furthermore, there is the problem that tetracene-containing pyrotechnic mixtures are thermally not sufficiently stable, since tetrazene decomposes already at 120 ° C.

The object of the present invention was to provide a further pyrotechnic igniter. Another object of the present invention was to provide a pyrotechnic igniter which can be used in mechanical, electrical or opto-electric ignition systems.

According to the invention, this object is surprisingly achieved by the features of the main claim.

Further embodiments of the invention are set forth in the subclaims. Surprisingly, a pyrotechnic igniter was found, which basic salts of 5,5'-azotetrazole, having the general empirical formula:

M ^{iT? +} _N (C ₂ N ₁ o ² -) p (CO ₃ ² -) _q (OH-),

contains, where: an element of the 3rd-12th Group of the periodic table with an atomic number in the range of 21-80,

 Azotetrazolate dianion with the structure

m die Wertigkeit des Kations,

m the valence of the cation,

 n is an integer from 1 to 6,

 p is an integer from 1 to 4,

 q is an integer from 0 to 8,

 r is an integer from 0 to 4 and q + r 0,

wherein the proportion of the basic Azotetrazolatkomponente is 30 to 100 wt .-% and 0 to 70 wt .-% of an additive or mixtures of several additives are included. The novel basic azotetrazolate compounds according to the invention have deflagration temperatures in the range from 180 ° C. to 240 ° C.,

Friction sensitivities of 0.1 N to 1.0 N and impact sensitivity of 0.1 J to 0.5 J. The thermal stability of the basic compounds according to the invention

 Azotetrazolate is given. Storage at 71 ° C. shows no decomposition of the basic azotetrazolate compound according to the invention after 28 days, here in particular the zinc compounds.

Preferably, the pyrotechnic igniter is one which contains as an additive 10 to 60 wt .-% of an oxidizing agent selected from one or more of the nitrates of the alkali and / or alkaline earth metals and / or ammonium, the perchlorates of the alkali and / or alkaline earth metals and / or the ammonium, the peroxides of the alkali and / or alkaline earth metals and / or zinc. Particularly preferably, the pyrotechnic igniting agent contains as additive 0 to 10 wt .-% of a sensitizer, preferably tetracene. The pyrotechnic igniting agent according to the invention preferably contains as an additive 0 to 20 wt .-% of a reducing agent selected from one or more of aluminum, antimony sulfide, calcium silicide, titanium, titanium hydride, boron, borohydride, zirconium, zirconium hydride, silicon, graphite, activated carbon, carbon black or Friction agent preferably glass breakage.

Particularly preferably, the pyrotechnic igniter contains as additive

0.1 to 5% by weight of a binder selected from one or more of cellulose and its derivatives, polyvinyl butyrals, polynitropolyphenylene,

Polynitrophenyl ether, Plexigum, polyvinyl acetate and copolymers.

Most preferably, the pyrotechnic igniter contains

Zn 2 ⁺ 2 (C ₂ N ₁₀ ² -) (CO ^{3 2} -),

Zn ²⁺ ₃ (C ² N ₁₀ ² -) 2 (CO ₃ ² -),

Zn ²⁺ ₄ (C ₂ N ₁₀ ² -) 2 (CO ^{3 2} -) (OFr) ₂ ,

Zn 2 ⁺ 2 (C ₂ Nio ^{2 "} ) (OH-) ₂ and / or

Zn ²⁺ ₃ (C2N ₁₀ ² -) 2 (OH-) 2.

The pyrotechnic igniting agents according to the invention are used in mechanical, electrical or opto-electric ignition systems.

As additives can be used:

1. Oxidizing agent (individually or in mixtures) selected from the group

 consisting of:

Nitrates of alkali or alkaline earth metals or ammonium such as sodium, potassium or ammonium nitrate, perchlorates of alkali or alkaline earth metals or of ammonium, peroxides of alkali or alkaline earth metals or zinc.

2. High-energy supplements (individually or in mixtures) of hexogen, octogen, nitrocellulose.

3. Reducing agents (individually or in mixtures) selected from the group

consisting of: Aluminum, titanium, titanhydride, boron, borohydride, zirconium, zirconium hydride, silicon, graphite, activated carbon, carbon black.

4. Binders (individually or in mixtures) selected from the group consisting of: cellulose and derivatives thereof, polyvinyl butyrals, polynitropolyphenylene, polynitrophenyl ethers, plexigum, polyvinyl acetate, copolymers.

5. burnout moderators, stabilizers and processing aids (singly or in mixtures) selected from the group consisting of:

Zinc oxide, zinc carbonate, silicates, silica gels, silicas, for example Aerosil (Degussa), boron nitride.

The substances are characterized by lead and barium freedom, a high ignition power, short reaction times and corresponding sensitivities. These features enable a reduction in the mass of explosives needed for safe ignition.

Table 1 shows decomposition temperatures, friction and impact sensitivities of selected examples. The measurement of friction and

Impact sensitivities were carried out according to methods of the Federal Institute for

Material research (BAM) in the BAM report 142 (1987), while the

Measurement of the decomposition temperatures with the differential scanning calorimetry (DSC) (Mettler) at a heating rate of 10 K per minute was carried out.

 More specifically, the subject matter of the present invention is a pyrotechnic igniter which comprises basic salts of 5,5'-azotetrazole having the general empirical formula:

M ^{iT? +} _N (C ₂ N ₁ o ² -) _p (CO ₃ ² -) _q (OH-),

 contains, where:

 M is an element of the 3rd-12th Group of the periodic table with a

 Atomic number in the range of 21 -80,

(C ₂ Nio ^{2 ~} ) Azotetrazolate dianion with the structure

m the valence of the cation,

n is an integer from 1 to 6,

p is an integer from 1 to 4,

q is an integer from 0 to 8,

r is an integer from 0 to 4 and q + r 0,

wherein the proportion of the basic azotetrazolate component is 30 to 100% by weight and 0 to 70% by weight of an additive or mixtures of several additives are included; a pyrotechnic igniting agent containing as an additive 10 to 60 wt .-% of an oxidizing agent selected from one or more of the nitrates of the alkali and / or alkaline earth metals and / or ammonium, the perchlorates of the alkali and / or alkaline earth metals and / or the ammonium, the peroxides of the alkali and / or alkaline earth metals and / or zinc;

a pyrotechnic igniting agent containing as an additive 0 to 10 wt .-% of a sensitizer, preferably tetracene; a pyrotechnic igniting agent containing as an additive 0 to 20 wt .-% of a reducing agent selected from one or more of aluminum, antimony sulfide, calcium silicide, titanium, titanium hydride, boron, borohydride, zirconium, zirconium hydride, silicon, graphite, activated carbon, carbon black or Friction agent preferably glass breakage; a pyrotechnic igniter containing, as an additive, 0.1 to 5% by weight of a binder selected from one or more of cellulose and derivatives thereof, polyvinyl butyrals, polynitropolyphenylene, polynitrophenyl ether, plexigum, polyvinyl acetate and copolymers; a pyrotechnic igniter comprising Zn ²⁺ ₂ (C2Ni ₀ ² XCO3 ^2); a pyrotechnic igniter containing Zn ²⁺ ₃ (C ₂ Ni ₀ ² MCOs ² );

- a pyrotechnic igniter which Zn ²⁺ ₄ (C2Ni ₀ ^{2 ")} 2 (CO3 ^2") (OH ^") ₂

 contains;

a pyrotechnic igniter containing Zn ²⁺ ₂ (C ₂ Nio ^{2 ~} ) (OH ^" ) ₂ ;

- A pyrotechnic igniter containing Zn ²⁺ 3 (C ₂ Nio ^{2 ~} ) ₂ (OH ^" ) ₂ .

- the use of a pyrotechnic igniting agent in mechanical,

 electric or opto-electric ignition systems.

The invention is further illustrated by, but not limited to, the following examples: Table 1 lists the compositions of 5 different basic salts of 5,5'-azotetrazole.

Table 1 Compositions, deflagration temperatures and friction and impact sensitivities of selected basic salts of 5,5'-azotetrazole.

No. Molecular Formula 'Verp.

 in ° C in N in J

1 Zn ²⁺ 2 (C ₂ Nio ² -) (CO ₃ ² -) 227 0.7 0.3

2 Zn ²⁺ ₃ (C2N ₁₀ ² -) 2 (CO ₃ ² -) 223 0.5 0.1

3 Zn ²⁺ ₄ (C ₂ N ₁₀ ² -) 2 (CO ^{3 2} -) 215 0.7 0.3

4 Zn ²⁺ 2 (C ₂ Nio ² -) (OH-) ₂ 210 0.5 0.2

5 Zn ²⁺ ₃ (C2N ₁₀ ² -) 2 (OH-) 2 207 0.3 0.1

[a]: deflagration temperature; [b]: friction sensitivity; [c]: impact sensitivity.

Claims

 claims Pyrotechnic igniter, characterized in that it comprises basic salts of 5,5'-azotetrazole having the general empirical formula: M ^{iT? +} _N (C ₂ N ₁ o ² -) _p (CO ^{3 2} -) _q (OH-), where: M is an element of the 3rd-12th Group of the periodic table with an atomic number in the range of 21-80, (C ₂ Nio ^{2 ~} ) Azotetrazolate dianion with the structure

m the valence of the cation,  n is an integer from 1 to 6,  p is an integer from 1 to 4,  q is an integer from 0 to 8,  r is an integer of 0 to 4 and q + r 0, wherein the proportion of the basic Azotetrazolatkomponente is 30 to 100% by weight and 0 to 70 wt .-% of an additive or mixtures of several additives are included. Pyrotechnic igniter according to claim 1, characterized in that it contains as an additive 10 to 60 wt .-% of an oxidizing agent selected from one or more of the nitrates of the alkali and / or alkaline earth metals and / or ammonium, the perchlorates of the alkali and / or alkaline earth metals and / or ammonium, the peroxides of the alkali and / or alkaline earth metals and / or zinc. Pyrotechnic igniter according to claim 1, characterized in that it contains as additive 0 to 10 wt .-% of a sensitizer, preferably tetracene. 4. Pyrotechnic igniting agent according to claim 1, characterized in that it contains as an additive 0 to 20 wt .-% of a reducing agent selected from one or more of aluminum, antimony sulfide, calcium silicide, titanium, titanium hydride, boron, borohydride, zirconium, zirconium hydride , Silicon, graphite, activated carbon, carbon black or friction agents preferably glass breakage. 5. Pyrotechnic igniter according to claim 1, characterized in that it contains as an additive 0.1 to 5 wt .-% of a binder selected from one or more of cellulose and derivatives thereof, polyvinyl butyrals, Polynitropolyphenylen, Polynitrophenylether, Plexigum, polyvinyl acetate and copolymers , 6. Pyrotechnic igniter according to one or more of claims 1 to 5, characterized in that it contains Zn ²⁺ ₂ (C2Ni ₀ ^{2 "} ) (CO3 ^2" ). 7. Pyrotechnic igniter according to one or more of claims 1 to 5, characterized in that it contains Zn ²⁺ ₃ (C2Ni ₀ ^{2 "} ) 2 (CO3 ^2" ). 8. Pyrotechnic igniter according to one or more of claims 1 to 5, characterized in that it contains Zn ²⁺ ₄ (C2Ni ₀ ^{2 "} ) 2 (CO3 ^2" ) (OH ^" ) ₂ . 9. Pyrotechnic igniter according to one or more of claims 1 to 5, characterized in that it contains Zn ²⁺ ₂ (C ₂ Ni ₀ ^{2 "} ) (OH ^" ) ₂ . 10. Pyrotechnic igniter according to one or more of claims 1 to 5, characterized in that it contains Zn ²⁺ ₃ (C ₂ Ni ₀ ^{2 "} ) ₂ (OH ^" ) ₂ . 1 1. Use of a pyrotechnic igniting agent according to one or more of claims 1 to 10 in mechanical, electrical or opto-electric ignition systems.