Dinitramide salts and method of making same

• US 5,254,324 A
• Filed: 06/18/1990
• Issued: 10/19/1993
• Est. Priority Date: 06/18/1990
• Status: Expired due to Term

• Current Assignee: SRI International, Inc.
• Original Assignee: SRI International, Inc.
• Inventors: Penwell, Paul E., Ross, David S., Bottaro, Jeffrey C., Schmitt, Robert J.
• Primary Examiner(s): Langel, Wayne
• Assistant Examiner(s): Hendrickson, Stuart L.
• Application Number:
  US07/540,020
• Time in Patent Office: 1,219 Days
• Field of Search: 423/263, 423/385, 423/249, 423/250, 423/252, 423/253, 423/251, 423/387, 149/45, 564/107, 564/109
• US Class Current: 423/263
• CPC Class Codes: C01B 21/082 Compounds containing nitrogen and non-metals and optionally metalsC01B21/06, C01B21/08 take precedence
• CPC Class Codes: C06B 25/00 Compositions containing a nitrated organic compound
• CPC Class Codes: C06B 31/00 Compositions containing an inorganic nitrogen-oxygen salt
• CPC Class Codes: C06B 41/00 Compositions containing a nitrated metallo-organic compound

Abstract

A N,N-dinitramide salt is disclosed having the formula MN(NO₂)₂ where M is a cation selected from the class consisting of a metal ion and a nitrogen-containing ion. The dinitramide salt exhibits high temperature stability, high energy density, and an absence of smoke generating halogens, rendering it useful as an oxidizer in rocket fuels. The dinitramide salts are meltable and pumpable oxidizers which may be used in start-stop rocket engines instead of other less stable oxidizers.

Claims

1. A N,N-dinitramide salt having the formula M^+r [N(NO₂)₂^- ]_r where M is a cation selected from the group consisting of a metal ion and a nitrogen-containing ion, and r is the cationic charge of M.

2. The N,N-dinitramide salt of claim 1 wherein M is a mono, di, or trivalent metal cation selected from the group consisting of Li, Na, K, Rb, Cs, Ca, Ba, Sr, Mg, Cu, Ag, Au, Zn, Cd, Hg, Al, Sc, Y, Ga, In, Lanthanide elements (57-71), Ti, Zr, Hf, Ge, Sn, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, and Pt.

3. The N,N-dinitramide salt of claim 2 wherein M is a metal cation selected from the group consisting of Li, Na, K, Be, and Mg.

4. The N,N-dinitramide salt of claim 1 wherein M is a 1-8 nitrogen-atom containing cation.

5. The N,N-dinitramide salt of claim 1 wherein M is a 1-8 nitrogen-atom containing cation having the formula R_k H_m N_n^+z, wherein n=1 to 8, k=0 to 2+n, z=1 to n, m=n+2+z-k, and each R is the same or different 1-6 carbon straight chain or branched alkyl.

6. The N,N-dinitramide salt of claim 1 wherein M is a nitrogen-atom containing cation selected from the group consisting of guanidinium;

triaminoguanidinium;

nitronium;

nitrosonium;

an ionic polymer of ethyleneimine containing 1-10,000 nitrogen atoms;

cubane-1,4-bis ammonium ion;

cubane-1,2,4,7-tetra ammonium ion;

cubane-1,2,3,4-tetra ammonium ion;

cubane-1,3,5,7-tetra ammonium ion;

cubane-1,2,3,4,7-penta ammonium ion; and

cubane-1,2,4,6,8-penta ammonium ion.

7. The N,N-dinitramide salt of claim 1 wherein said salt is the reaction product of a dinitramine compound with a compound selected from the group consisting of ammonia, hydrazine, and a salt having the formula MX wherein X is an ion selected from the group consisting of fluoride, chloride, hydroxyl, carbonate, alkoxide, and carboxylate.

8. The N,N-dinitramide salt of claim 7 wherein said salt is the reaction product of a dinitramine having the formula L_n ZR'"'"'N(NO₂)₂ with said MX compound, wherein n is 1 to 3;

L is the same or different 1-6 carbon alkyl, aryl, hydrogen, halogen, amine, or ether group;

Z is an element selected from the group consisting of Si, Sn, Ge, As, B, Sb, Bi, Pb, and Hg; and

R'"'"' is a 1 to 6 carbon alkylene group;

the M⁺ ion is selected from the group consisting of a metal cation, a substituted ammonium cation, an ammonium cation, a substituted hydrazinium cation, and a hydrazinium cation; and

the ^- X anion is a halogen ion selected from the group consisting of fluoride and chloride ions.

9. The N,N-dinitramide salt of claim 7 wherein said dinitramide salt is the reaction product of a nitramine compound having the formula NH₂ NO₂ with a nitrating agent selected from the group consisting of nitronium tetrafluoroborate, (NO₂⁺)₂ (S₂ O₇^-2), NO₂⁺ AlCl₄^-, N₂ O₅, NO₂ F, NO₂⁺ PF₆^-, NO₂⁺ AsF₆^-, NO₂⁺ SbF₆^-, acetylnitrate, trifluoroacetylnitrate, trifluoroacetylnitrate in combination with catalytic BF₃, acetonecyanohydrin nitrate in combination with catalytic BF₃, and any one of these in combination with nitric acid, and to form an acid having the formula HN(NO₂)₂ which is then reacted with a compound selected from the group consisting of a metal-containing compound and a nitrogen-containing compound to form said dinitramide salt having the formula MN(NO₂)₂.

10. The N,N-dinitramide salt of claim 1 wherein said salt is the reaction product of a nitramine compound having the formula NH₂ NO₂ with nitronium tetrafluoroborate to form an acid having the formula HN(NO₂)₂, which is then reacted with a compound selected from the group consisting of a metal-containing compound and a nitrogen-containing compound to form said dinitramide salt having the formula MN(NO₂)₂.

13. The N,N-dinitramide salt of claim 2 wherein M is a mono or divalent metal cation selected from the group consisting of Li, Na, K, Rb, Cs, Cu, Ag, Au, and Hg.

14. The N,N-dinitramide salt of claim 13 wherein M is a metal cation selected from the group consisting of Li, Na, and K.

11. A N,N-dinitramide salt having the formula M^+r [N(NO₂)₂^- ]_r where r is the cationic charge of M and M is a cation selected from the group consisting of:

a) mono, di, and trivalent metal ions elected from the group consisting of Li, Na, K, Rb, Cs, Ca, Ba, Sr, Mg, Cu, Ag, and Au, Zn, Cd, Hg, Al, Sc, Y, Ga, In, Lanthanide elements (57-71), Ti, Zr, Hf, Ge, Sn, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, and Pt;

b) a cation having the formula R_k H_m N_n^+z, wherein n=1 to 8, k=0 to 2+n, z=1 to n, m=n+2+z-k, and each R is the same or different 1-6 carbon straight chain or branched alkyl; and

c) a nitrogen-containing cation selected from the group consisting of guanidinium;

triaminoguanidinium;

nitronium;

nitrosonium;

an ionic polymer of ethyleneimine containing 1-10,000 nitrogen atoms;

cubane-1,4-bis ammonium ion;

cubane-1,2,4,7-tetra ammonium ion;

cubane-1,2,3,4-tetra ammonium ion;

cubane-1,3,5,7-tetra ammonium ion;

cubane-1,2,3,4,7-penta ammonium ion; and

cubane-1,2,4,6,8- penta ammonium ion.

12. A N,N-dinitramide salt having the formula M^+- N(NO₂)₂ where M is a monovalent cation selected from the group consisting of a metal ion and a nitrogen-containing ion.

15. The N,N-dinitramide salt of claim 12 wherein M is a cation having the formula R_k H_m N_n⁺, wherein n=1 to 8, k=0 to 2+n, m=n+3-k, and each R is the same or different 1-6 carbon straight chain or branched alkyl.

16. The N,N-dinitramide salt of claim 12 wherein said salt is the reaction product of a dinitramine compound with a compound selected from the group consisting of ammonia, hydrazine, and a salt having the formula MX wherein M is a metal ion and X is an ion selected from the group consisting of fluoride, chloride, hydroxyl, carbonate, alkoxide, and carboxylate.

17. The N,N-dinitramide salt of claim 12 wherein the M⁺ ion in said salt has the formula R_k H_m N_n⁺, wherein n=1 to 2, k=0 to 3+n, m=3+n-31 k, and each R is the same or different 1-6 carbon straight chain or branched alkyl.

18. The N,N-dinitramide salt of claim 17 wherein the M⁺ ion in said salt is selected from the group consisting of NH₄⁺, Ch₃ NH₃⁺, (CH₃)₂ NH₂⁺, (CH₃)₃ NH⁺, CH₃)₄ N⁺, C₂ H₅ NH₃⁺, (C₂ H₅)₂ NH₂⁺, (C₂ H₅)₃ NH⁺, (C₂ H₅)₄ N⁺, (C₂ H₅)(CH₃)NH₂⁺, (C₂ H₅)(CH₃)₂ NH⁺, (C₂ H₅)₂ (CH₃)₂ N⁺, (C₃ H₇)₄ N⁺, (C₄ H₉)₄ N⁺, N₂ H₅⁺, Ch₃ N₂ H₄⁺, (CH₃)₂ N₂ H₃⁺, (CH₃)₃ N₂ H₂⁺, (CH₃)₄ N₂ H⁺, and (CH₃)₅ N₂⁺.

19. The N,N-dinitramide salt of claim 12 wherein said salt is the reaction product of a dinitramine having the formula L_a ZR'"'"'N(NO₂)₂ with said MX compound, wherein n is 1 to 3;

L is the same or different 1-6 carbon alkyl, aryl, hydrogen, halogen, amine, or ether group;

Z is an element selected from the group consisting of Si, Sn, Ge, As, B, Sb, Bi, Pb, and Hg; and

R'"'"' is a 1 to 6 carbon alkylene group;

the M⁺ ion is selected from the group consisting of a metal cation, a substituted ammonium cation, an ammonium cation, a substituted hydrazinium cation, and a hydrazinium cation; and

the ^- X anion is a halogen ion selected from the group consisting of fluoride and chloride ions.

20. The N,N-dinitramide salt of claim 12 wherein said salt is selected from the group consisting of ammonium dinitramide, tetramethylammoniumdinitramide, tetrabutyl ammonium dinitramide, potassium dinitramide, and cesium dinitramide.

21. A N,N-dinitramide salt having the formula MN(NO₂)₂ where M is a cation selected from the group consisting of:

a) monovalent metal ions elected from the group consisting of Li, Na, K, Rb, Cs, Cu, Ag, Au, and Hg;

b) a cation having the formula R_k H_m N_n⁺, wherein n=1 to 8 , k=0 to 2+n, m=n+3-k, and each R is the same or different 1-6 carbon straight chain or branched alkyl; and

c) a nitrogen-containing cation selected from the group consisting of guanidinium;

triaminoguanidinium;

nitronium;

nitrosonium;

cubane-1,4-bis ammonium ion;

cubane-1,2,4,7-tetra ammonium ion;

cubane-1,2,3,4-tetra ammonium ion;

cubane-1,3,5,7-tetra ammonium ion;

cubane-1,2,3,4,7-penta ammonium ion; and

cubane-1,2,4,6,8-penta ammonium ion.