Method of forming dinitramide salts

• US 5,198,204 A
• Filed: 06/18/1990
• Issued: 03/30/1993
• Est. Priority Date: 06/18/1990
• Status: Expired due to Fees

• Current Assignee: SRI International, Inc.
• Original Assignee: SRI International, Inc.
• Inventors: Ross, David S., Bottaro, Jeffrey C., Schmitt, Robert J., Penwell, Paul E.
• Primary Examiner(s): Langel, Wayne A.
• Application Number:
  US07/539,647
• Time in Patent Office: 1,016 Days
• Field of Search: 423/385, 423/387, 423/400, 564/109
• US Class Current: 423/385
• 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 method is disclosed for forming a N,N-dinitramide salt having the formula MN(NO₂)₂ where M is a cation selected form the class consisting of a metal ion and a nitrogen-containing ion, which comprises contacting a carbamate with a nitrating agent to form an acidic dinitramide intermediate reaction product, and neutralizing the acidic dinitramide with a compound selected from the class consisting of ammonia (NH₃), hydrazine (N₂ H₄), a primary amine having the formula RNH₂, a secondary amine having the formula RR'"'"'NH, and a salt having the formula AX; where R and R'"'"' are the same or different 1-6 carbon alkyls, A is a metal ion or a nitrogen-containing ion, and X is an anion selected from the class consisting of fluoride, chloride, hydroxyl, carbonate, alkoxide, and carboxyl anion, to form the corresponding dinitramide salt.

Claims

1. A method of making a N,N-dinitramide salt 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 which comprises:

a) contacting a carbamate with a nitrating agent to form an acidic dinitramide intermediate reaction product having the formula HN(NO₂)₂ ; and

b) neutralizing the acidic dinitramide intermediate reaction product by contacting it with a compound selected from the class consisting of ammonia (NH₃), hydrazine (N₂ H₄), a primary amine having the formula RNH₂, a secondary amine having the formula RR'"'"'NH, and a salt having the formula AX;

where R and R'"'"' are the same or different 1-6 carbon alkyls, A is a metal ion or a nitrogen-containing ion, and X is an anion selected from the class consisting of a fluoride, chloride, hydroxyl, carbonate, alkoxide, and carboxyl.

2. The method of claim 1 wherein said step of contacting a carbamate with a nitrating agent further comprises contacting with a nitrating agent a carbamate selected from the class consisting of ammonium carbamate having the formula NH₄⁺ CO₂ NH₂^-, a 1-4 carbon di, tri, or tetra alkyl ammonium carbamate, and an alkali metal carbamate.

3. The method of claim 2 wherein said carbamate is selected from the class consisting of ammonium carbamate, trimethyl ammonium carbamate, tetramethyl ammonium carbamate, triethyl ammonium carbamate, lithium carbamate, sodium carbamate, and potassium carbamate.

4. The method of claim 2 wherein said step of contacting a carbamate with a nitrating agent further comprises contacting ammonium carbamate with a nitrating agent.

5. The method of claim 2 wherein said step of contacting a carbamate with a nitrating agent further comprises contacting said carbamate with a nitrating agent selected from the class consisting of nitronium tetrafluoroborate, (NO₂⁺)₂ (S₂ O₇^-2), NO₂⁺ AlCl₄^-, N₂ O₃, NO₂ F, NO₂⁺ PF₆^-, NO₂⁺ AsF₆^-, NO₂ ⁺ SbF₆^-, acetylnitrate, trifluoroacetylnitrate, trifluoroacetylnitrate in combination with catalytic BF₃, acetonecyanohydrin nitrate in combination with catalytic BG₃, and any one of said nitrating agents in combination with nitric acid.

6. The method of claim 2 wherein said step of contacting a carbamate with a nitrating agent further comprises contacting said carbamate with nitronium tetrafluoroborate.

7. The method of claim 2 wherein said carbamate is contacted with a mixture of said nitrating agent and a solvent.

8. The method of claim 7 wherein said solvent is selected from the class consisting of acetonitrile, sulfolane, chloroform, ethyl acetate, nitromethane, ether, dichloromethane, and combinations thereof.

9. The method of claim 2 wherein said carbamate is contacted with a mixture of said nitrating agent and acetonitrile to form said intermediate reaction product having the formula HN(NO₂)₂.

10. The method of claim 9 wherein said carbamate is contacted with a mixture of nitronium tetrafluoroborate and acetonitrile to form said intermediate reaction product having the formula HN(NO₂)₂.

11. The method of claim 9 wherein ammonium carbamate is contacted with a mixture of nitronium tetrafluoroborate and acetonitrile to form said intermediate reaction product having the formula HN(NO₂)₂.

12. The method of claim 1 wherein said step of neutralizing said intermediate reaction product comprises contacting it with a salt having the formula AX where A is a mono, di, or trivalent metal cation selected from the class 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.

13. A method of making a N,N-dinitramide salt 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 which comprises:

a) contacting a carbamate selected from the class consisting of ammonium carbamate having the formula NH₄⁺ CO₂ NH₂^-, a 1-4 carbon di, tri, or tetra alkyl ammonium carbamate, and an alkali metal carbamate with a nitrating agent selected from the class consisting of nitronium tetrafluoroborate, (NO₂⁺)₂ (S₂ O₇^-2), NO₂⁺, N₂ O₅, AlCl₄^-, 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 of said nitrating agents in combination with nitric acid to form an acidic dinitramide intermediate reaction product having the formula HN(NO₂)₂ ; and

b) neutralizing the acidic dinitramide intermediate reaction product by contacting it with a compound selected from the class consisting of ammonia (NH₃), hydrazine (N₂ H₄), a primary amine having the formula RNH₂, a secondary amine having the formula RR'"'"'NH, and a salt having the formula AX;

where R and R'"'"' are the same or different 1-6 carbon alkyls, A is a metal ion or a nitrogen-containing ion, and X is an anion selected from the class consisting of fluoride, chloride, hydroxyl, carbonate, alkoxide, and carboxyl.

14. The method of claim 13 wherein said step of neutralizing said intermediate reaction product comprises contacting it with a salt having the formula AX where A is a mono, di, or trivalent metal cation selected from the class 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.

15. The method of claim 14 wherein A is a metal cation selected from the class consisting of Li, Na, K, Be, and Mg.

16. The method of claim 13 wherein A is a 1-8 nitrogen-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=2+n+z-k, and each R" is the same or different 1-6 carbon straight chain or branched alkyl.

17. The method of claim 13 wherein A is a nitrogen-containing cation selected from the class consisting of cubane-1,4-bis ammonium ion;

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

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

cubane-1,2,3,4-tetraammonium ion;

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

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

guanidium (C(NH₂)₃⁺);

triaminoguanidinium (C(N₂ H₃)₃⁺);

nitronium (O═

N═

O⁺);

nitrosonium (N.tbd.O⁺); and

a 1-10,000 nitrogen polymer of ethyleneimine.

18. A method of making a N,N-dinitramide salt 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 which comprises:

a) contacting ammonium carbamate with a nitronium tetrafluoroborate nitrating agent in acetonitrile to form an acidic dinitramide intermediate reaction product having the formula HN(NO₂)₂ ; and

b) neutralizing the acidic dinitramide intermediate reaction product by contacting it with ammonia (NH₃) to form ammonium dinitramide having the formula NH₄⁺ N(NO₂)₂^-.

19. The method of claim 18 wherein said ammonium carbamate/nitronium tetrafluoroborate/acetonitrile solution is maintained within a temperature range of from about -30°

c to about 20°

C. during said nitrating step.

20. The method of claim 18 wherein said nitrating step is carried out for a period of from about 1/2 hour to about 1 day.

21. The method of claim 18 wherein said neutralizing step is carried out at a temperature of from about -40°

C. to about 150°

C. at ambient pressure for a time period ranging from about 1 minute to about 168 hours.

22. The method of claim 18 wherein said neutralizing step is carried out at a temperature of from about 0°

C. to about 20°

C. at ambient pressure for a time period ranging from about 1 hour to about 2 hours.