EP3164375B1 - Pyrotechnic igniting agent - Google Patents

Description

The present invention is a pyrotechnic igniter.

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 comprises 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, ie neither acidic nor basic. Zinc and chromium salts of 5,5'-azotetrazole are according to the document DE 102010025104 A1 not storable. Furthermore, there is the problem that tetracene-containing pyrotechnic mixtures are thermally not sufficiently stable, since tetrazene decomposes already at 120 ° C.

DE 10 2010 036 950 A1 discloses the use of basic 5,5'-azotetrazolate salts of general formula ([ML _m X _n ] ^{p +} ) _q (C ₁ N ₄ R ₁ ^- ) _r , where M is an element of the third-twelfth group of the periodic table in the range of 21-80, as initial explosive.

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.

wobei der Anteil der basischen Azotetrazolatkomponente 30 bis 100 Gew.-% beträgt und 0 bis 70 Gew.-% eines Zusatzstoffes oder Mischungen mehrerer Zusatzstoffe enthalten sind. Die erfindungsgemäßen neuen basischen Azotetrazolatverbindungen besitzen Verpuffungstemperaturen im Bereich von 180 °C bis 240 °C, Reibempfindlichkeiten von 0,1 N bis 1,0 N und Schlagempfindlichkeit von 0,1 J bis 0,5 J. Die thermische Stabilität der erfindungsgemäßen basischen Azotetrazolatverbindungen ist gegeben. Lagerungen bei 71 °C zeigen nach 28 Tagen keine Zersetzung der erfindungsgemäßen basischen Azotetrazolatverbindung.
Vorzugsweise ist das pyrotechnische Anzündmittel eines, welches als Zusatzstoff 10 bis 60 Gew.-% eines Oxidationsmittels enthält, ausgewählt aus einem oder mehreren der Nitrate der Alkali- und/oder Erdalkalimetalle und/oder des Ammoniums, der Perchlorate der Alkali- und/oder Erdalkalimetalle und/oder des Ammoniums, der Peroxide der Alkali- und/oder Erdalkalimetalle und/oder des Zinks.Surprisingly, a pyrotechnic igniter was found, wherein
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- ) (OH ^- ) ₂ , Zn ²⁺ ₂ (C ₂ N ₁₀ ^2- ) (OH ^- ) ₂ or Zn ²⁺ ₃ (C ₂ N ₁₀ ^2- ) ₂ (OH ^- ) _{2 ,}
contains, where:
(C ₂ N ₁₀ ^2- ) azotetrazolate dianion having the structure

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 defoaming 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 Azotetrazolatverbindungen invention given. Storage at 71 ° C show no decomposition of the basic Azotetrazolatverbindung invention after 28 days.
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 igniting agent contains as 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.

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

1. 1. Oxidationsmittel (einzeln oder in Mischungen) ausgewählt aus der Gruppe bestehend aus:
   Nitrate der Alkali- oder Erdalkalimetalle oder des Ammoniums wie Natrium-, Kalium- oder Ammoniumnitrat, Perchlorate der Alkali- oder Erdalkalimetalle oder des Ammoniums, Peroxide der Alkali- oder Erdalkalimetalle oder des Zinks.
2. 2. Energiereiche Zuschläge (einzeln oder in Mischungen) von Hexogen, Oktogen , Nitrocellulose.
3. 3. Reduktionsmittel (einzeln oder in Mischungen) ausgewählt aus der Gruppe bestehend aus:
   Aluminium, Titan, Titanhydrid, Bor, Borhydrid, Zirkon, Zirkonhydrid, Silicium, Gra-phit, Aktivkohle, Ruß.
4. 4. Bindemittel (einzeln oder in Mischungen) ausgewählt aus der Gruppe bestehend aus:
   Cellulose sowie deren Derivate, Polyvinylbutyrale, Polynitropolyphenylen, Polynitrophenylether, Plexigum, Polyvinylacetat, Copolymere.
5. 5. Abbrandmoderatoren, Stabilisatoren und Verarbeitungshilfen (einzeln oder in Mischungen) ausgewählt aus der Gruppe bestehend aus:
   Zinkoxid, Zinkcarbonat, Silikate, Kieselgele, Kieselsäuren, beispielsweise Aerosil (Fa. Degussa), Bornitrid.

As additives can be used:

1. 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. 2. High-energy supplements (individually or in mixtures) of hexogen, octogen, nitrocellulose.
3. 3. Reducing agent (individually or in mixtures) selected from the group consisting of:
   Aluminum, titanium, titanium hydride, boron, borohydride, zirconium, zirconium hydride, silicon, graphite, activated carbon, carbon black.
4. 4. Binders (individually or in mixtures) selected from the group consisting of:
   Cellulose and its derivatives, polyvinyl butyrals, Polynitropolyphenylen, Polynitrophenylether, Plexigum, polyvinyl acetate, copolymers.
5. 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 the friction and impact sensitivities was carried out according to methods of the Federal Institute for Materials Research (BAM) in the BAM Report 142 (1987), while the measurement of the decomposition temperatures by differential scanning calorimetry (DSC) (Mettler) at a heating rate of 10 K. per minute took place.

• ein pyrotechnisches Anzündmittel, wobei es
  Zn²⁺ ₂(C₂N₁₀ ^2-)(CO₃ ^2-), Zn²⁺ ₃(C₂N₁₀ ^2-)₂(CO₃ ^2-), Zn²⁺ ₄(C₂N₁₀ ^2-)₂(CO₃ ^2-)(OH^-)₂, Zn²⁺ ₂(C₂N₁₀ ^2-)(OH^-)₂ oder Zn²⁺ ₃(C₂N₁₀ ^2-)₂(OH^-)₂.
  enthält, wobei gilt:
  (C₂N₁₀ ^2-) Azotetrazolatdianion mit der Struktur
  
  wobei der Anteil der basischen Azotetrazolatkomponente 30 bis 100 Gew.-% beträgt und 0 bis 70 Gew.-% eines Zusatzstoffes oder Mischungen mehrerer Zusätzstoffe enthalten sind.
• ein pyrotechnisches Anzündmittel, welches als Zusatzstoff 10 bis 60 Gew.-% eines Oxidationsmittels enthält, ausgewählt aus einem oder mehreren der Nitrate der Alkali- und/oder Erdalkalimetalle und/oder des Ammoniums, der Perchlorate der Alkali- und/oder Erdalkalimetalle und/oder des Ammoniums, der Peroxide der Alkali- und/oder Erdalkalimetalle und/oder des Zinks;
• ein pyrotechnisches Anzündmittel, welches als Zusatzstoff 0 bis 10 Gew.-% eines Sensibilisators, vorzugsweise Tetrazen enthält;
• ein pyrotechnisches Anzündmittel, welches als Zusatzstoff 0 bis 20 Gew.-% eines Reduktionsmittels enthält, ausgewählt aus einem oder mehreren von Aluminium, Antimonsulfid, Calciumsilicid, Titan, Titanhydrid, Bor, Borhydrid, Zirkon, Zirkonhydrid, Silicium, Graphit, Aktivkohle, Ruß oder Friktionsmittel vorzugsweise Glasbruch;
• ein pyrotechnisches Anzündmittel, welches als Zusatzstoff 0,1 bis 5 Gew.-% eines Bindemittels enthält, ausgewählt aus einem oder mehreren von Cellulose und deren Derivaten, Polyvinylbutyrale, Polynitropolyphenylen, Polynitrophenylether, Plexigum, Polyvinylacetat und Copolymeren;
• die Verwendung eines pyrotechnischen Anzündmittels in mechanischen, elektrischen oder opto-elektrischen Anzündsystemen.

The subject of the present invention is in detail:

• a pyrotechnic igniter, wherein it
  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- ) (OH ^- ) ₂ , Zn ²⁺ ₂ (C ₂ N ₁₀ ^2- ) (OH ^- ) ₂ or Zn ²⁺ ₃ (C ₂ N ₁₀ ^2- ) ₂ (OH ^- ) ₂ ,
  contains, where:
  (C ₂ N ₁₀ ^2- ) azotetrazolate dianion having the structure
  
  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.
• 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 of 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;
• 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;
• the use of a pyrotechnic igniter in mechanical, electrical or opto-electric ignition systems.

The invention is explained in more detail by the following examples, without limiting them:
Table 1 lists the compositions of 5 different basic salts of 5,5'-azotetrazole. <b> Table 1 </ b> Compositions, deflagration temperatures and friction and impact sensitivities of selected basic salts of 5,5'-azotetrazole. No. Molecular formula T _Verp . ^[a] in ° C F _friction ^[b] in N E _stroke ^[c] in J 1 Zn ²⁺ ₂ (C ₂ N ₁₀ ^2- ) (CO ₃ ^2- ) 227 0.7 0.3 2 Zn ²⁺ ₃ (C ₂ N 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 N ₁₀ ^2- ) (OH ^- ) ₂ 210 0.5 0.2 5 Zn ²⁺ ₃ (C ₂ N ₁₀ ^2- ) ₂ (OH ^- ) ₂ 207 0.3 0.1 [a]: deflagration temperature; [b]: friction sensitivity; [c]: impact sensitivity.

Claims (6)

1. A pyrotechnic igniting agent, characterized in that it contains
   Zn²⁺ ₂(C₂N₁₀ ^2-)(CO₃ ^2-), Zn²⁺ ₃(C₂N₁₀ ^2-)₂(CO₃ ^2-),Zn²⁺ ₄(C₂N₁₀ ^2-)₂(CO₃ ^2-)(OH^-)₂, Zn²⁺ ₂(C₂N₁₀ ^2-)(OH^-)₂ or Zn²⁺ ₃(C₂N₁₀ ^2-)₂(OH^-)₂,
   wherein:
   (C₂N₁₀) is azotetrazolate dianion having the structure

   

   wherein the proportion 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.
2. A pyrotechnic igniting agent according to claim 1, characterized in that it contains, as 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 of ammonium, the perchlorates of the alkali and/or alkaline earth metals and/or of ammonium, the peroxides of the alkali and/or alkaline earth metals and/or of zinc.
3. A pyrotechnic igniting agent according to claim 1, characterized in that it contains, as additive, 0 to 10 wt% of a sensitizer, preferably tetrazene.
4. A pyrotechnic igniting agent according to claim 1, characterized in that it contains, as additive, 0 to 20 wt% of a reducing agent selected from one or more of aluminum, antimony sulfide, calcium silicide, titanium, titanium hydride, boron, boron hydride, zirconium, zirconium hydride, silicon, graphite, activated carbon, carbon black or friction modifiers, preferably cullet.
5. A pyrotechnic igniting agent according to claim 1, characterized in that it contains, as additive, 0.1 to 5 wt% of a binder selected from one or more of cellulose and derivatives thereof, polyvinyl butyrals, polynitropolyphenylene, polynitrophenyl ether, plexigum, polyvinyl acetate and copolymers.
6. The use of a pyrotechnic igniting agent according to one or more of claims 1 to 5 in mechanical, electrical or optoelectrical ignition systems.