N,N'-azobis-nitroazoles and analogs thereof as igniter compounds for use in energetic compositions

• US 6,156,136 A
• Filed: 12/22/1998
• Issued: 12/05/2000
• Est. Priority Date: 05/13/1998
• Status: Expired due to Fees

• Current Assignee: SRI International, Inc.
• Original Assignee: SRI International, Inc.
• Inventors: Bottaro, Jeffrey C., Schmitt, Robert J., Penwell, Paul E.
• Primary Examiner(s): Miller, Edward A.
• Application Number:
  US09/220,098
• Time in Patent Office: 714 Days
• Field of Search: 149/36, 149/92, 149/19.1
• US Class Current: 149/19.1
• CPC Class Codes: C06B 25/04 the nitrated compound being an aromatic
• CPC Class Codes: C06B 25/34 the compound being a nitrated acyclic, alicyclic or heterocyclic amine
• CPC Class Codes: C06C 7/00 Non-electric detonators; Blasting caps; Primers
• CPC Class Codes: C06C 9/00 Chemical contact igniters; Chemical lighters
• CPC Class Codes: C06D 5/06 by reaction of two or more solids
• CPC Class Codes: C07D 207/50 Nitrogen atoms
• CPC Class Codes: C07D 231/16 Halogen atoms or nitro radicals
• CPC Class Codes: C07D 249/10 with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
• CPC Class Codes: C07D 401/12 linked by a chain containing hetero atoms as chain links
• CPC Class Codes: C07D 403/12 linked by a chain containing hetero atoms as chain links
• CPC Class Codes: C07D 403/14 containing three or more hetero rings
• CPC Class Codes: C07D 487/14 Ortho-condensed systems

Abstract

Novel energetic compounds are provided comprising N,N'"'"'-azobis-nitroazoles or analogs thereof. The compounds are useful as igniter materials in a variety of energetic compositions, particularly gas-generating compositions for inflating automobile or aircraft occupant restraint devices. The compounds are also useful in solid rocket propellant compositions, and as primary explosives to be used as detonators, blasting caps, firearms, and the like. Methods for synthesizing the compounds and manufacturing energetic compositions therewith are provided as well.

Claims

1. A solid composition for generating gases when ignited, comprising a secondary explosive, an oxidizer, and a compound having the structural formula (I) ##STR13## wherein:

R is a monocyclic nitrogen-containing heterocycle or a bicyclic aromatic substituent;

R¹, R², R³ and R⁴ are independently selected from the group consisting of N, N→

O, (N⁺ --R^a)Z^-, CH, C--R^b, C--NR^c R^d, and C--NO₂ in which R^a and R^b are independently C₁ -C₂₄ alkyl, or fluoro, R^c and R^d are independently H or C₁ -C₂₄ alkyl, and Z^- is a counterion, or wherein R⁴ is bound to an atom contained within R and beta to J², with the proviso that at least one of R¹, R², R³ and R⁴ is C--NO₂ ; and

J¹ and J² are independently either N or N→

O, with the proviso that J¹ and J² are not both N→

O.

2. The composition of claim 1, wherein the secondary explosive is selected from the group consisting of TNT, RDX, HMX, picric acid, and combinations thereof.

3. The composition of claim 1, wherein the oxidizer is selected from the group consisting of ammonium nitrate, phase-stabilized ammonium nitrate, ammonium dinitramide, potassium nitrate, potassium dinitramide, sodium peroxide, ammonium perchlorate, cocrystallized potassium dinitramide and ammonium nitrate (KDN-AN), and combinations thereof.

4. The composition of claim 2, wherein the oxidizer is selected from the group consisting of ammonium nitrate, phase-stabilized ammonium nitrate, ammonium dinitramide, potassium nitrate, potassium dinitramide, sodium peroxide, ammonium perchlorate, cocrystallized potassium dinitramide and ammonium nitrate (KDN-AN), and combinations thereof.

5. The composition of claim 1, further including a gas-generating fuel.

6. The composition of claim 5, wherein the gas-generating fuel is selected from the group consisting of triaminoguanidine nitrate (TAGN), diaminoguanidine nitrate (DAGN), monoaminoguanidine nitrate (MAGN), 3-nitro-1,2,4-triazole-5-one (NTO), salts of NTO, urazole, triazoles, tetrazoles, guanidine nitrate, oxamide, oxalyldihydrazide, melamine, semicarbazide, azodicarbonamide, and mixtures thereof.

7. The composition of claim 5, further including a binder.

8. The composition of claim 7, wherein the binder comprises an organic polymeric material.

9. The composition of claim 8, wherein the organic polymeric material is selected from the group consisting of polycarbonates, polyesters, polyurethanes and combinations thereof.

15. The composition of claim 1, wherein R¹, R², R³ and R⁴ are selected from the group consisting of N, CH and C--NO₂.

16. The composition of claim 1, wherein J¹ and J² are N.

17. The composition of claim 16, wherein one of R¹ and R² is N and the substituent R contains two adjacent nitrogen atoms, one of which is directly bound to J².

18. The composition of claim 1, wherein R is a monocyclic nitrogen-containing heterocycle.

19. The composition of claim 18, having the structural formula (II) ##STR15## in which R⁵, R⁶, R⁷ and R⁸ are independently selected from the group consisting of N, N→

O, (N⁺ R^a)Z^-, CH, C--R^b, C--NR^c R^d, and C--NO₂ in which R^a and R^b are independently C₁ -C₂₄ alkyl or fluoro, R^c and R^d are independently H or C₁ -C₂₄ alkyl, and Z^- is a counterion.

20. The composition of claim 19, wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ are selected from the group consisting of N, CH and C--NO₂.

21. The composition of claim 19, having the structural formula ##STR16##

22. The composition of claim 19, having the structural formula

23. The composition of claim 18, having the structural formula (III) in which R⁵, R⁶, R⁷, R⁸, and R⁹ are independently selected from the group consisting of N, N→

O, (N⁺ R^a)Z^-, CH, C--R^b, C--NR^c R^d, and C--NO₂ in which R^a and R^b are independently C₁ -C₂₄ alkyl or fluoro, R^c and R^d are independently H or C₁ -C₂₄ alkyl, and Z^- is a counterion, with the proviso that at least one of R⁵, R⁶, R⁷ , R⁸, and R⁹ is N, N→

O, or (N⁺ R^a)Z^-.

24. The composition of claim 1, wherein R is a bicyclic aromatic substituent.

25. The composition of claim 24, wherein the bicyclic aromatic substituent comprises two fused aromatic rings which may or may not be heterocyclic.

26. The composition of claim 25, having the structural formula (V) ##STR17## wherein R¹ through R⁸ and R¹⁴ through R¹⁷ are independently selected from the group consisting of N, N→

O, (N⁺ --R^a)Z^-, CH, C--R^b, C--NR^c R^d, and C--NO₂ in which R^a and R^b are independently C₁ -C₂₄ alkyl or fluoro, R^c and R^d are independently H or C₁ -C₂₄ alkyl, n is 0 or 1, and Z^- is a counterion.

27. The composition of claim 24, wherein the bicyclic aromatic substituent comprises two five-membered nitrogen-containing heterocycles joined through an azo linkage.

28. The composition of claim 27, having the structural formula (IV) ##STR18## wherein J³ is C, J⁴ and J⁵ are independently N or N→

O, with the proviso that J⁴ and J⁵ are not both N→

O, and R⁵, R⁶, R⁸, R¹⁰, R¹¹, R¹², and R¹³ are independently selected from the group consisting of N, N→

O, N⁺ --R^a, CH, C--R^b, C--NR^c R^d, and C--NO₂ in which R^a and R^b are independently C₁ -C₂₄ alkyl, and R^c and R^d are independently H or C₁ -C₂₄ alkyl.

29. The composition of claim 28, wherein J⁴ and J⁵ are both N.

30. The composition of claim 29, wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁸, R⁹, R¹⁰, R¹¹, R¹², and R¹³ are independently selected from the group consisting of N, CH and C--NO₂.

10. A solid rocket propellant composition comprising a binder composition, fuel, and a compound having the structural formula (I) ##STR14## wherein:

R is a monocyclic nitrogen-containing heterocycle or a bicyclic aromatic substituent;

R¹, R², R³ and R⁴ are independently selected from the group consisting of N, N→

O, (N⁺ --R^a)Z^-, CH, C--R^b, C--NR^c R^d, and C--NO₂ in which R^a and R^b are independently C₁ -C₂₄ alkyl, or fluoro, R^c and R^d are independently H or C₁ -C₂₄ alkyl, and Z^- is a counterion, or wherein R⁴ is bound to an atom contained within R and beta to J², with the proviso that at least one of R¹, R², R³ and R⁴ is C--NO₂ ; and

J¹ and J² are independently either N or N→

O, with the proviso that J¹ and J² are not both N→

O.

11. The composition of claim 10, wherein the binder composition is selected from the group consisting of polyoxetanes, polyglycidyl azide, hydroxyl-terminated polybutadiene, polybutadiene-acrylonitrileacrylic acid terpolymer, polyethers, polyglycidyl nitrate, polycaprolactone, and mixtures thereof.

12. The composition of claim 10, wherein the fuel comprises a metallic component comprising aluminum, beryllium, boron, magnesium, zirconium, or mixtures or alloys thereof.

13. The composition of claim 11, wherein the fuel comprises a metallic component comprising aluminum, beryllium, boron, magnesium, zirconium, or mixtures or alloys thereof.

14. The composition of claim 10, further including one or more additional components selected from the group consisting of plasticizers, burn rate modifiers and ballistic additives.

31. The composition of claim 10, wherein R¹, R², R³ and R⁴ are selected from the group consisting of N, CH and C--NO₂.

32. The composition of claim 10, wherein J¹ and J² are N.

33. The composition of claim 32, wherein one of R¹ and R² is N and the substituent R contains two adjacent nitrogen atoms, one of which is directly bound to J².

34. The composition of claim 11, wherein R is a monocyclic nitrogen-containing heterocycle.

35. The composition of claim 34, having the structural formula (II) ##STR19## in which R⁵, R⁶, R⁷ and R⁸ are independently selected from the group consisting of N, N→

O, (N⁺ R^a)Z^-, CH, C--R^b, C--NR^c R^d, and C--NO₂ in which R^a and R^b are independently C₁ -C₂₄ alkyl or fluoro, R^c and R^d are independently H or C₁ -C₂₄ alkyl, and Z^- is a counterion.

36. The composition of claim 35, wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ are selected from the group consisting of N, CH and C--NO₂.

37. The composition of claim 35, having the structural formula ##STR20##

38. The composition of claim 35, having the structural formula

39. The composition of claim 34, having the structural formula (III) in which R⁵, R⁶, R⁷, R⁸, and R⁹ are independently selected from the group consisting of N, N→

O, (N⁺ R^a)Z^-, CH, C--R^b, C--NR^c R^d, and C--NO₂ in which R^a and R^b are independently C₁ -C₂₄ alkyl or fluoro, R^c and R^d are independently H or C₁ -C₂₄ alkyl, and Z^- is a counterion, with the proviso that at least one of R⁵, R⁶, R⁷ , R⁸, and R⁹ is N, N→

O, or (N⁺ R^a)Z^-.

40. The composition of claim 34, wherein R is a bicyclic aromatic substituent.

41. The composition of claim 40, wherein the bicyclic aromatic substituent comprises two fused aromatic rings which may or may not be heterocyclic.

42. The composition of claim 41, having the structural formula (V) ##STR21## wherein R¹ through R⁸ and R¹⁴ through R¹⁷ are independently selected from the group consisting of N, N→

O, (N⁺ --R^a)Z^-, CH, C--R^b, C--NR^c R^d, and C--NO₂ in which R^a and R^b are independently C₁ -C₂₄ alkyl or fluoro, R^c and R^d are independently H or C₁ -C₂₄ alkyl, n is 0 or 1, and Z³¹ is a counterion.

43. The composition of claim 40, wherein the bicyclic aromatic substituent comprises two five-membered nitrogen-containing heterocycles joined through an azo linkage.

44. The composition of claim 43, having the structural formula (IV) ##STR22## wherein J³ is C, J⁴ and J⁵ are independently N or N→

O, with the proviso that J⁴ and J⁵ are not both N→

O, and R⁵, R⁶, R⁸, R¹⁰, R¹¹, R¹², and R¹³ are independently selected from the group consisting of N, N→

O, N⁺ --R^a, CH, C--R^b, C--NR^c R^d, and C--NO₂ in which R^a and R^b are independently C₁ -C₂₄ alkyl, and R^c and R^d are independently H or C₁ -C₂₄ alkyl.

45. The composition of claim 44, wherein J⁴ and J⁵ are both N.

46. The composition of claim 45, wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁸, R⁹, R¹⁰, R¹¹, R¹², and R¹³ are selected from the group consisting of N, CH and C--NO₂.