Process for forming ammonium dinitramide salt by reaction between ammonia and a nitronium-containing compound

• US 5,316,749 A
• Filed: 07/30/1991
• Issued: 05/31/1994
• Est. Priority Date: 07/30/1991
• Status: Expired due to Fees

• Current Assignee: SRI International, Inc.
• Original Assignee: SRI International, Inc.
• Inventors: Schmitt, Robert J., Bottaro, Jeffrey C., Penwell, Paul E., Bomberger, David C.
• Primary Examiner(s): LANGEL, WAYNE A
• Application Number:
  US07/737,757
• Time in Patent Office: 1,036 Days
• Field of Search: 423/385
• 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: C01B 21/20 Nitrogen oxides; Oxyacids of nitrogen; Salts thereof
• CPC Class Codes: C06B 31/00 Compositions containing an inorganic nitrogen-oxygen salt

Abstract

A method for forming an ionically bonded ammonium dinitramide salt having the formula NH₄³⁰ N(NO₂)₂ - useful as a stable oxidizer for solid fuel rocket propellant or explosive formulations is disclosed. The ammonium dinitramide salt is formed by the reaction of ammonia and a nitronium-containing compound, such as a nitronium salt or a covalently bonded compound containing a NO₂ - group, at a temperature of from about - 20° C. to about 120° C. The nitronium-containing compound may be either a covalently bonded compound containing a NO₂ - group or a nitronium salt having the formula (NO₂⁺)_n X^-n, where X is the anion of the nitronium salt and n= 1-2.

Claims

1. A process for the formation of ammonium dinitramide salt which comprises reacting ammonia with a nitronium-containing compound at a temperature at which ionically bonded ammonium dinitramide salt will form.

2. The process of claim 1 wherein said reaction temperature to form said ammonium dinitramide salt ranges from about -20°

C. to about -120°

C.

3. The process of claim 2 wherein said reaction temperature to form said ammonium dinitramide salt ranges from about -30°

C. to about -90°

C.

4. The process of claim 2 wherein said reaction temperature to form said ammonium dinitramide salt ranges from about -40°

C. to about -80°

C.

5. The process of claim 2 wherein said nitronium-containing compound comprises a nitronium salt.

6. The process of claim 5 wherein said nitronium salt has the formula (NO₂⁺)_n X^-n where X is any anion capable of forming a salt with the nitronium cation and n=1-2.

7. The process of claim 6 wherein said anion X reacts with said ammonia and protons liberated in said reaction to form a byproduct which may be separated from said dinitramide salt reaction product.

8. The process of claim 6 wherein said anion is selected from the group consisting of BF₄^-, NO₃^- HS₂ O₇^-, AlCl₄^-, F^-, PF₆^-, ClS₂ O₆^-, F₂ PO₂^-, AsF₆^-, SbF₆^-, FS₂ O₆^-, ClO₄^-, S₂ O₇^-2, SiF₆^-2, and SO₃ F^-.

9. The process of claim 2 wherein said nitronium-containing compound comprises a covalently bonded compound containing a NO₂ --group.

10. The process of claim 2 wherein said process further comprises the step of forming a solution, dispersion, or mixture of said nitronium-containing compound and an aprotic liquid.

11. The process of claim 10 wherein said aprotic liquid is selected from the group consisting of diethyl ether, methylene chloride (CH₃ Cl₂), chloroform (CHCl₃), carbon tetrachloride (CCl₄), methyl ether ((CH₃)₂ O), a freon gas, acetonitrile, ethyl acetate, sulfolane, and mixtures of same.

12. The process of claim 10 wherein the amount of nitronium-containing compound dissolved, dispersed, or mixed with said aprotic liquid comprises from about 1 to about 50 wt.% of the total weight of the resulting solution, dispersion, or mixture.

13. The process of claim 2 wherein said process is a batch process and includes the further step of permitting said reaction mass to warm up to room temperature at the end of said reaction time period.

14. The process of claim 13 wherein step of permitting said reaction mass to warm up at the end of said reaction time period further includes stirring said reaction mass while said reaction mass is warming up, and maintaining said reaction mass under a basic condition.

15. The process of claim 2 including the further step of separating said ammonium dinitramide salt product from said reaction mass.

16. The process of claim 2 wherein said ammonia is dissolved in an aprotic liquid to form a solution and said solution is mixed with a solid nitronium-containing compound during said reaction to form said ammonium dinitramide salt.

17. The process of claim 2 wherein said nitronium-containing compound is in a solid state at said reaction temperature having the formula NO₂⁺ X^-, and said nitronium-containing compound is reacted with said ammonia by contacting said solid nitronium-containing compound with ammonia gas in the absence of solvents to form said ammonium dinitramide salt.

18. The process of claim 2 wherein said process is carried out on a continuous basis.

19. The process of claim 2 wherein said process is carried out on a continuous basis by continuously contacting said nitronium-containing compound with ammonia and continuously removing said ammonium dinitramide salt product.

20. A process for the formation of ammonium dinitramide salt having the formula NH₄⁺ N(NO₂)₂^- which comprises:

a) forming a solution, dispersion, or mixture of an aprotic liquid and a nitronium-containing compound selected from the group consisting of a covalently bonded compound containing a NO₂ --group and a nitronium salt having the formula (NO₂⁺)_n X^-n, where X is the anion of the salt and n=1-2; and

b) contacting said nitronium-containing compound with ammonia at a temperature within a range of from about -20°

C. to about -120°

C. to form said ammonium dinitramide salt.

21. The process of claim 20 wherein the pressure is maintained between about 700 and 800 Torr during said reaction.

22. The process of claim 20 wherein a stoichiometric excess of ammonia is used during said reaction.

23. The process of claim 20 wherein said reaction is a batch reaction carried out at said temperature for a period of from about 0.5 to about 8 hours.

24. The process of claim 20 including the further step of permitting said reaction mass to warm up to room temperature at the end of said reaction time period while stirring said reaction mass, and maintaining said reaction mass under an ammonia atmosphere.

25. The process of claim 20 including the further step of separating said ammonium dinitramide salt product from said reaction mass.

26. A process for the formation of ammonium dinitramide salt having the formula NH₄⁺ N(NO₂)₂^- which comprises:

a) forming a solution, dispersion, or mixture of an aprotic liquid and a nitronium-containing compound selected from the group consisting of a covalently bonded compound containing a NO₂ -group and a nitronium salt having the formula (NO₂⁺)_n X^-n, where X is the anion of the salt and n=1-2; and

b) contacting said nitronium-containing compound with a stoichiometric excess of ammonia at a temperature within a range of from about -20°

C. to about -120°

C., while maintaining the pressure within a range of between about 700 and 800 Torr for a period of from about 0.5 to about 8 hours;

c) permitting said reaction mass to warm up to room temperature at the end of said reaction time period while stirring said reaction mass, and maintaining said reaction mass under an ammonia atmosphere; and

d) separating said ammonium dinitramide salt product from said reaction mass.