WO1994005643A1 - Neopentyl difluoroamino compounds for use in energetic formulations - Google Patents

Neopentyl difluoroamino compounds for use in energetic formulations Download PDF

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Publication number
WO1994005643A1
WO1994005643A1 PCT/US1993/008224 US9308224W WO9405643A1 WO 1994005643 A1 WO1994005643 A1 WO 1994005643A1 US 9308224 W US9308224 W US 9308224W WO 9405643 A1 WO9405643 A1 WO 9405643A1
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WO
WIPO (PCT)
Prior art keywords
ono
group
compounds
energetic
neopentyl
Prior art date
Application number
PCT/US1993/008224
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English (en)
French (fr)
Inventor
Thomas G. Archibald
Gerald E. Manser
Original Assignee
Aerojet-General Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Aerojet-General Corporation filed Critical Aerojet-General Corporation
Priority to AU48431/93A priority Critical patent/AU4843193A/en
Publication of WO1994005643A1 publication Critical patent/WO1994005643A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C247/00—Compounds containing azido groups
    • C07C247/02—Compounds containing azido groups with azido groups bound to acyclic carbon atoms of a carbon skeleton
    • C07C247/04—Compounds containing azido groups with azido groups bound to acyclic carbon atoms of a carbon skeleton being saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C239/00—Compounds containing nitrogen-to-halogen bonds; Hydroxylamino compounds or ethers or esters thereof
    • C07C239/02—Compounds containing nitrogen-to-halogen bonds
    • C07C239/04—N-halogenated amines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C243/00—Compounds containing chains of nitrogen atoms singly-bound to each other, e.g. hydrazines, triazanes
    • C07C243/02—N-nitro compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D205/00—Heterocyclic compounds containing four-membered rings with one nitrogen atom as the only ring hetero atom
    • C07D205/02—Heterocyclic compounds containing four-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings
    • C07D205/04—Heterocyclic compounds containing four-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/04—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having no double bonds between ring members or between ring members and non-ring members

Definitions

  • This invention relates to novel neopentyl difluoroamino compounds.
  • the compounds of the present invention are useful as plasticizers and oxidizers in high-energy formulations, such as propellants, explosives, gasifiers, or the like.
  • High-energy solid formulations such as propellants, explosives, and gasifiers, generally consist of paniculate solids, such as fuel material, oxidizers, or both, held together by an elastomeric binder. These high-energy formulations also often include a plasticizer, such as a nitrate ester, which is a liquid prior to its incorporation into the formulation.
  • a plasticizer such as a nitrate ester
  • Organic compounds which contain nitrogen and fluorine are frequently used as fuel material and/or paniculate oxidizers. These compounds are most suitable for making high-energy propellants because such compounds form gaseous HF as a decomposition product. During decomposition, the high heat of formation of HF is liberated to the surroundings, thereby doing mechanical work. Additionally, during the course of decomposition, fluorine is present as an oxidizing agent, and thus, no external source is required to complete oxidation.
  • Plasticizers are used in solid propellants and explosives to facilitate processing and increase flexibility and toughness, in addition to providing other benefits which vary with the nature and use of the formulation.
  • Energetic or high-energetic plasticizers are those that provide energy in addition to flexibility and toughness, and their inclusion therefore does not lessen the performance of the formulation.
  • Considerations involved in the selection and use of plasticizers include compatibility with the other components of the formulation, including the primary energetic compounds and any binders present, the oxygen balance of the plasticizer, energy content, safety (i.e. , stability with regard to detonation), and melting point.
  • Plasticizers with melting points in a range which causes them to crystallize readily are of limited utility, since crystallization is detrimental to the plasticizer function and can adversely affect the mechanical properties of the propellant or explosive.
  • the binder is an important means of maintaining the uniformity of the formulation and of holding it together, the binder material burns with substantially lower energy than the fuel. The binder thus imposes a limit on the energy content of the fuel material.
  • One way of minimizing this limitation is to use a binder which release as much energy as possible when burning with the fuel. It is desirable, therefore, that the elastomeric binder have pendant groups which themselves are relatively high in energy.
  • the polyethers and the elastomers formed therefrom should contain pendant groups which impart miscibility of the elastomer with the nitrate ester plasticizers.
  • Nitro, nitrato, nitramino and cyano groups are examples of pendant groups which impart nitrate ester- miscibility to the polymer and which have relatively high energies so as to contribute to the performance of the propellant.
  • a difluoroamino (NF ⁇ group) Compounds containing two fluorine atoms bonded to nitrogen, i.e. , a difluoroamino (NF ⁇ group, have been extensively studied as ingredients for propellants and explosives.
  • the difluoroamino group has higher energy, higher positive heat of formation and greater thermal stability than the other frequently used pendant groups (e.g. the nitrato group).
  • the difluoroamino group strongly enhances the performance of formulations containing boron and aluminum as fuels.
  • difluoroamino group Practical use of the difluoroamino group in propellants and explosives has been limited, however. In compounds known to date, the difluoroamino group was found to impart unacceptably high impact sensitivity or chemical instability to the compound. Due to the strong electron-withdrawing nature of the difluoroamino group, NF 2 -containing compounds have been found to be unstable and readily lose HF to form nitriles when alpha hydrogens are present.
  • NF 2 -containing compounds in explosives and propellants has been limited to those compounds containing difluoroamino groups on a tertiary center prepared from tetrafluorohydrazine, or geminal di-difluoroamino groups prepared from strong acid solutions of difluoroamine. In both cases the resulting products are shock sensitive and expensive to prepare.
  • the present invention provides a variety of high-energy, neopentyl difluoroamino compounds which are useful as oxidizers and plasticizers in energetic formulations.
  • These neopentyl difluoroamino compounds can be prepared either:
  • NF 2 -derivatives (2) by first preparing NF 2 -derivatives and then substituting these derivatives with energetic pendant groups. More specifically, mono-NF 2 and bis-NF 2 -oxetanes are synthesized and further reacted to yield the corresponding dinitrate esters. It has been discovered that these NF 2 -dinitrate esters are very useful as energetic plasticizers in high-energy formulations.
  • the plasticizer compounds of the present invention are particularly compatible with binders containing the NF 2 group prepared from NF 2 -containing oxetanes, i.e. , from mono-NF 2 -oxetane and/or bis-NF 2 -oxetane.
  • R 1 , R 2 , R 3 may be the same or different, and are selected from functional groups including, but not limited to, H, lower alkyl, NF 2 , NO 2 , ONO 2 , N 3 , or N(R 4 )NO 2 where R 4 is H or a lower alkyl; or R 1 and R 2 may be combined as a single divalent radical and may be, for example, -N NOj)- or -N(NO 2 )-CH 2 -N(NO 2 )-; and, when R 1 and R 2 are so combined, R 3 may be, for example, NF 2 , ONO 2 , NO 2 , or N 3 .
  • alkyl is used herein to refer to substituents which are fully saturated hydrocarbon chains.
  • the alkyl groups may be either straight-chain or branched-chain, limited only by steric hinderance.
  • lower alkyl is used herein as it is used in the art, designating alkyl groups of a relatively small number of carbon atoms. Additionally, since alkyl groups do not add to the energetic character of the molecule, shorter alkyl groups (i.e. , 1-4 carbons) are preferred. Within the scope of Formula I, certain embodiments are preferred, namely those in which R 1 , R 2 , and R 3 are the same or different, and are selected from the following functional groups: H, CH 3 , C 2 H 5 , NF 2 , ONO 2 , NO 2 , N 3 , N(CH 3 )NO 2 and N(C 2 H 5 )NO 2 .
  • R 1 , R 2 , and R 3 are selected from the following functional groups: H, NF 2 and ONO 2 . Even more preferred are those compounds in which R 1 is either H or NF 2 ; R 2 is ONO 2 ; and R 3 is ONO 2 .
  • the energy content and physical properties of the compounds represented by Formula I vary. Table I lists the properties of several neopentyl-NF 2 -nitrate plasticizers. Mixtures of these compounds give eutectics with useful plasticizer melting ranges. These compounds are particularly compatible with binders containing the NF 2 group prepared from NF 2 -containing oxetanes, i.e. , from mono-NF 2 -oxetane and/or bis-NF 2 -oxetane.
  • the invention further resides in the preparation of compounds represented by
  • R 1 is a functional group including, but not limited to, H, lower alkyl
  • R 4 is H or a lower alkyl
  • R 2 is ONO 2
  • R 3 is
  • the process of the present invention involves: (a) combining a solution of a compound having the formula:
  • R 1 is a functional group including, but not limited to, H, lower alkyl, NF 2 , ONO 2 , NO 2 , N 3 and N(R 2 )NO 2 where R 2 is H or a lower alkyl, with nitric acid to form a product mixture; and (b) recovering the compound represented by Formula I from said product mixture.
  • step (a) is an organic solution.
  • a solution of the compound represented by Formula II in methylene chloride is the presently preferred solution.
  • the nitric acid used in the above process should have a concentration of at least about 95%, with a concentration of about 98% to about 100% being preferred.
  • Compounds prepared using the above process are recovered using standard methods and procedures known in the art.
  • Compounds corresponding to Formula I can be synthesized, for example, using mono- and bis-NF 2 -oxetanes as starting materials. Reaction of the mono- and bis- NFj-oxetanes with 100% nitric acid in methylene chloride gives a quantitative yield of the corresponding dinitrate esters. Mono-NF 2 -oxetane gives 2-difluoroaminomethyl-2-methyl- propane-l,3-diol dinitrate, an oil, and bis-NF 2 -oxetane gives 2,2-bis(difluoroaminomethyl) propane- 1,3-diol dinitrate, a solid. These difluoroneopentyl amine plasticizers may also be synthesized by direct fluorination of amine dinitrates or by fluorination of amine diols followed by nitration.
  • neopentyl difluoroamino compounds can be prepared either: (1) by the direct fluorination of amine derivatives containing energetic groups; or (2) by first preparing NF 2 derivatives and then substituting these derivatives with energetic groups.
  • Energetic groups which are useful as substituents in these neopentyl difluoroamino compounds include, but are not limited to, NF 2 , NO 2 , ONO 2 , N(R 4 )NO 2 , where R 4 is H or a lower alkyl, and N 3 .
  • Examples of these compounds include, but are not limited to, the following: 2-difluoroaminomethyl-2- nitratomethylpropane-l,3-diol dinitrate; tris(difluoroamino methyl)ethanol nitrate; and tetrakis(difluoroaminomethyl)methane.
  • Table II shows the structures of some additional high-energy difluoroneopentyl amine plasticizers and/or oxidizers that can be prepared using the methods of the present invention.
  • EXAMPLE ⁇ This example illustrates the preparation and properties of 2,2-bis- (difluoroaminomethyl)propane-l,3-diol dinitrate.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
PCT/US1993/008224 1992-09-02 1993-09-01 Neopentyl difluoroamino compounds for use in energetic formulations WO1994005643A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU48431/93A AU4843193A (en) 1992-09-02 1993-09-01 Neopentyl difluoroamino compounds for use in energetic formulations

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US07/939,172 US5789617A (en) 1992-09-02 1992-09-02 Neopentyl difluoroamino compounds for use in energetic formulations
US07/939,172 1992-09-02

Publications (1)

Publication Number Publication Date
WO1994005643A1 true WO1994005643A1 (en) 1994-03-17

Family

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Application Number Title Priority Date Filing Date
PCT/US1993/008224 WO1994005643A1 (en) 1992-09-02 1993-09-01 Neopentyl difluoroamino compounds for use in energetic formulations

Country Status (4)

Country Link
US (1) US5789617A (en, 2012)
AU (1) AU4843193A (en, 2012)
TW (1) TW247901B (en, 2012)
WO (1) WO1994005643A1 (en, 2012)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6325876B1 (en) 2000-03-02 2001-12-04 The United States Of America As Represented By The Secretary Of The Navy Energetic plasticizers containing 3,3-bis(difluoroamino)-1,5-dinitratopentane and method of preparation
US8008527B1 (en) 2009-07-02 2011-08-30 The United States Of America As Represented By The Secretary Of The Navy Octafluoropentaerythrityltetramine (octafluoro-peta) and process for its preparation

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3350453A (en) * 1964-04-14 1967-10-31 Rohm & Haas Alkyl compounds containing nitrogen and fluorine
US3729501A (en) * 1961-08-25 1973-04-24 Gen Electric Difluoroamino aliphatic compounds
US4820859A (en) * 1982-07-15 1989-04-11 Secretary Of State For Defence In Her Majesty's Government Of The United Kingdom Process for the production of high energy material
US4985584A (en) * 1982-07-15 1991-01-15 Secretary Of State For Defence Process for the production of high energy materials

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4118414A (en) * 1966-03-28 1978-10-03 Exxon Research & Engineering Co. Difluoramino compounds and perfluoroguanidine-pentaerythrityl nitrates

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3729501A (en) * 1961-08-25 1973-04-24 Gen Electric Difluoroamino aliphatic compounds
US3350453A (en) * 1964-04-14 1967-10-31 Rohm & Haas Alkyl compounds containing nitrogen and fluorine
US4820859A (en) * 1982-07-15 1989-04-11 Secretary Of State For Defence In Her Majesty's Government Of The United Kingdom Process for the production of high energy material
US4985584A (en) * 1982-07-15 1991-01-15 Secretary Of State For Defence Process for the production of high energy materials

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
TETRAHEDRON, Volume 24, issued 1968, S.F. REED JR. et al., "Radical Reactions of Tetrafluorohydrazine Saturated Hydrocarbons and Ethers", pages 5089-5098. *

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Publication number Publication date
AU4843193A (en) 1994-03-29
TW247901B (en, 2012) 1995-05-21
US5789617A (en) 1998-08-04

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