Explosive and thermic compositions or charges – Structure or arrangement of component or product – Solid particles dispersed in solid solution or matrix
Reexamination Certificate
2000-03-02
2001-12-04
Jordan, Charles T. (Department: 3641)
Explosive and thermic compositions or charges
Structure or arrangement of component or product
Solid particles dispersed in solid solution or matrix
C558S483000, C558S485000, C558S487000
Reexamination Certificate
active
06325876
ABSTRACT:
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
The invention described herein may be manufactured and used by or for the government of the United States of America for governmental purposes without the payment of any royalties thereon or therefor.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to the composition of 3,3-bis(difluoroamino)-1,5-dinitratopentane, abbreviated herein as BFDNP, and the use of BFDNP as a plasticizer in energetic materials. More particularly, 3,3-bis(difluoroamino)-1,5-dinitratopentane is useful as an energetic plasticizer composition in propellants and explosives.
2. Brief Description of the Related Art
Solid propellants containing aluminum or boron fuel exhibit improved metal combustion when fluorine is present as an oxidizer in addition to oxygen. Several patents disclose difluoroamino compounds in energetic compositions. U.S. Pat. No. 3,190,894 to Logothetis discloses 9,10-bis(difluoroamino)-9,10-dihydroanthracenes. U.S. Pat. No. 3,331,867 to Smiley discloses 1,2,5,6-tetrakis(difluoroamino)-3,4-hexanediol dinitrate compounds. U.S. Pat. No. 3,337,627 to Mueller, et al. discloses gem-bis(difluoroamino), 1,3,3-tris(difluoroamino), and 1,1,4,4-tetrakis(difluoroamino) compounds. U.S. Pat. No. 3,345,398 to Rhodes discloses 1,2-bis(difluoroamino) ethane diol-1,2 compounds. U.S. Pat. No. 3,375,259 to Gibson, et al. discloses propellants such as N,N′-bis(difluoroaminomethyl)urea compounds. U.S. Pat. No. 3,410,870 to Armstrong, et al. discloses 2,3-bis(difluoroamino)-1,4-butanediol dinitrate compounds. U.S. Pat. No. 3,729,501 to Rohrback, et al. discloses 1-difluoroamino-2,3-dinitratopropane compounds. U.S. Pat. No. 3,946,085 to Adolph discloses bis(2,2,2-fluorodinitroethyl)trichloroacetal compounds. U.S. Pat. No. 3,968,160 to Reed, Jr. discloses 1,2,3-tris[difluoroamino)ethoxy]-propane compounds. U.S. Pat. No. 4,001,059 to Petry discloses 1-cyano-2,3,5,6-tetrakis(difluoroamino)hexane compounds. U.S. Pat. No. 4,075,246 to Baum, et al. discloses,1,3-bis(2,2,2-fluorodinitroethoxy)-2,2-bis(difluoroamino)propane compounds. U.S. Pat. No. 4,118,414 to Goldstein, et al. discloses tris(difluoroamino)methoxypentaerythrityl trinitrate compounds. U.S. Pat. No. 4,141,910 to Flanagan, et al. discloses 1,7-diazido-4,4-difluoroaminoheptane compounds. U.S. Pat. No. 4,341,712 to Frankel, et al. discloses bis[5,5,5-fluorodinitro-2,2-bis-(difluoroamino)-pentyl]trifluoroacetal (SYTA) compounds. U.S. Pat. No. 4,376,665 to Marcellis, et al. discloses a mixture of pentaborane and tris(difluoroamino)fluoromethane compounds. U.S. Pat. No. 4,430,514 to Schack discloses production of difluoroaminotrifluoromethane compounds. U.S. Pat. No. 5,272,249 to Archibald, et al. discloses bis-(difluoroaminomethyl)oxetanes. U.S. Pat. No. 5,420,311 to Archibald, et al. discloses bis-(difluoroaminomethyl)oxetanes. U.S. Pat. No. 5,789,617 to Archibald, et al. discloses neopentyl difluoroamino compounds.
Other energetic plasticizers, such as 1,2,3 tris(1,2-bis(difluoroamino)ethoxy)propane (TVOPA), 2,2-bis(difluoamino)-5-fluoro-5,5-dinitropentyl formal (SYFO), and 2,2-bis(difluoroamino)-1,3-bis(fluorodinitroethoxy)propane (SYEP) also have been evaluated as plasticizers in aluminized solid propellants. However, TVOPA has limited chemical and thermal stability, and SYFO and SYEP are difficult to manufacture due to laborious, low-yield, multi-step syntheses.
There is a need in the art to provide new difluoroamino compounds for use in energetic compositions. The present invention addresses this and other needs.
SUMMARY OF THE INVENTION
The present invention includes a compound comprising 3,3-bis(difluoroamino)-1,5-dinitratopentane.
The present invention also includes an energetic material comprising 3,3-bis(difluoroamino)-1,5-dinitratopentane.
Furthermore, the present invention further includes a compound of 3,3-bis(difluoroamino)-1,5-dinitratopentane made by the process comprising the steps of difluoroamination and nitration.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The present invention is an improved energetic plasticizer containing difluoroamino groups, more specifically the composition of 3,3-bis(difluoroamino)-1,5-dinitratopentane (BFDNP). BFDNP of the present invention can be used as a plasticizer in energetic compositions, such as propellants and explosives. The 3,3-bis(difluoroamino)-1,5-dinitratopentane is manufactured through a process of difluoroamination and nitration.
The compound of 3,3-bis(difluoroamino)-1,5-dinitratopentane of the present invention comprises a structure as shown in formula (I), below:
BFDNP (O
2
NO(CH
2
)
2
C(NF
2
)
2
(CH
2
)
2
ONO
2
) comprises a mobile liquid at room temperature. Differential Scanning Calorimeter (DSC) characterization showed a glass transition temperature of −87° C. and an onset decomposition temperature of 186° C., peaking at 196° C. BFDNP has a density of 1.56 g/cm
3
. The heat of formation is estimated to be −76 kcal/mol. Based on this data, the performance calculations for BFDNP by the Kamlet Short Method (KSM/GAB) method revealed a Specific Impulse (Isp) of 278.9 seconds. Compared to 262.3 seconds for BTTN, 258.6 seconds for SYFO, and 266.5 seconds for SYEP, BFDNP provides an improved plasticizer with excellent performance potential.
The present invention provides the compound 3,3-bis(difluoroamino)-1,5-dinitratopentane (BFDNP) as an improved energetic plasticizer containing difluoroamino and nitrato groups as oxidizer functions. This compound is synthesized in one embodiment from a known compound of 1,5-dichloropentanone-3 in approximately 3 or 4 steps by replacing the chlorines with trifluoroacetoxy groups; reacting with difluoroamine in oleum; and, replacing the trifluoroacetoxy by nitrato groups either directly or via the parent diol.
The process of manufacturing the 3,3-bis(difluoroamino)-1,5-dinitratopentane comprises the steps of difluoroamination and nitration, as detailed in Examples 1-3, below. As seen in the examples, the step difluoroamination comprises reacting 1,5-bis(trifluoroacetoxy)pentan-3-one ((CF
3
C(═O)OCH
2
CH
2
)
2
C═O) with difluoroamine reactant, preferably containing oleum, to form 3,3-bis(difluoroamino)-1,5-bis(trifluoroacetoxy)pentane. The 3,3-bis(difluoroamino)-1,5-bis(trifluoroacetoxy)pentane ((CF
3
C(═O)OCH
2
CH
2
)
2
C(NF
2
)
2
) reacted with methanol to form 3,3-bis(difluoroamino)pentanediol-1,5(HO(CH
2
)
2
C(NF
2
)
2
(CH
2
)
2
OH) followed by nitration with a mixture of sulfric acid and nitric acid (H
2
SO
4
/HNO
3
) to form the 3,3-bis(difluoroamino)-1,5-dinitratopentane. In an alternative embodiment, the nitration of 3,3-bis(difluoroamino)-1,5-bis(trifluoroacetoxy)pentane can be directly performed with a mixture of sulfuric acid and nitric acid. In another embodiment, difluoroamination and nitration of the 1,5-bis(trifluoroacetoxy)pentan-3-one is accomplished directly with a difluoroamine reactant in oleum followed by a reaction with nitric acid.
The synthesis of 1,5-dichloropentan-3-one (Cl(CH
2
)
2
C(═O)(CH
2
)
2
Cl) is known, as described in the Journal of the Chemical Society (C) 1970, 2401 by O. R. Owen and C. B. Reese, the disclosure of which is herein incorporated by reference. Generally a reaction of 3-chloropropionyl chloride (Cl(CH
2
)
2
C(═O)Cl), ethylene (CH
2
═CH
2
) and aluminum chloride (AlCl
3
) is performed. The 1,5-dichloropentan-3-one is reacted with sodium trifluoroacetate (NaOC(═O)CF
3
) to produce 1,5-bis(trifluoroacetoxy)pentan-3-one (CF
3
C(═O)OCH
2
CH
2
)
2
C═O).
Schematically, the synthesis of the 3,3-bis(difluoroamino)-1,5-dinitratopentane of the present invention may be shown as:
REFERENCES:
patent: 3190894 (1965-06-01), Logothetis
patent: 3331867 (1967-07-01), Smiley
patent: 3337627 (1967-08-01), Mueller et al.
patent: 3345398 (1967-10-01), Rhodes
patent: 3352914 (1967-11-01), Perry et al.
patent: 3375259 (1968-03-01), Gibson et al.
patent: 3410870 (1968-11-01), Armstrong et al.
patent: 3729501 (1973-04-01), Rohrback et al.
patent: 3946
Adolph Horst G.
Trivedi Nirupam J.
Baker Aileen J.
Homer Mark
Jordan Charles T.
The United States of America as represented by the Secretary of
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