USH253H - Branch chained polynitrodiols - Google Patents

Branch chained polynitrodiols Download PDF

Info

Publication number
USH253H
USH253H US06/875,159 US87515986A USH253H US H253 H USH253 H US H253H US 87515986 A US87515986 A US 87515986A US H253 H USH253 H US H253H
Authority
US
United States
Prior art keywords
lactone
butanediol
energetic
polynitrodiols
diol
Prior art date
Legal status (The legal status 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 status listed.)
Abandoned
Application number
US06/875,159
Inventor
Michael E. Sitzmann
William H. Gilligan
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
US Department of Navy
Original Assignee
US Department of Navy
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 US Department of Navy filed Critical US Department of Navy
Priority to US06/875,159 priority Critical patent/USH253H/en
Assigned to UNITED STATES OF AMERICA, AS REPRESENTED BY THE SECRETARY OF THE NAVY THE reassignment UNITED STATES OF AMERICA, AS REPRESENTED BY THE SECRETARY OF THE NAVY THE ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: GILLIGAN, WILLIAM H., SITZMANN, MICHAEL E.
Application granted granted Critical
Publication of USH253H publication Critical patent/USH253H/en
Abandoned legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/32—Oxygen atoms
    • C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B25/00—Compositions containing a nitrated organic compound
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
    • C07C205/13—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by hydroxy groups
    • C07C205/14—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by hydroxy groups having nitro groups and hydroxy groups bound to acyclic carbon atoms
    • C07C205/15—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by hydroxy groups having nitro groups and hydroxy groups bound to acyclic carbon atoms of a saturated carbon skeleton

Definitions

  • This invention relates to alcohols and more particularly to energetic polynitroakyldiols.
  • RDX RDX or HMX
  • an energetic plasticizer and isocyanate curing agents.
  • the liquid slurry is then cast into a suitable mold and cured to form a rubbery matrix which not only binds the solid explosive and defines the shape, but also contributes energy to the final composition.
  • Energetic polymers that contain unreacted beta-nitro alcohol end groups are also subject to the reverse Henry reaction and under the conditions of isocyanate curing wherein basic urethane linkages are formed, decomposition can and does occur. This leads to poor thermal stability and aging characteristics. This is undoubtedly the reason why AFNOL, an energetic polymer, formed from pimeloyl chloride and DINOL was ultimately rejected as a candidate energetic polymer.
  • an object of this invention is to provide new energetic polynitrodiols.
  • Another object of this invention is to provide new polynitrodiols which are useful as components of energetic polymers.
  • a further object of this invention is to provide new polynitrodiols which are stable to deformylation (loss of formaldehyde).
  • Yet another object of this invention is to provide new branched chain polynitrodiols which can improve the hydrolytic stability of energetic polymers such as polyesters.
  • a still further object of this invention is to provide a method of preparing these new energetic polynitrodiols.
  • branched polynitrodiols of the formula ##STR4## wherein Z is --C(NO 2 ) 3 , --CF(NO 2 ) 2 , --C(NO 2 ) 2 CH 3 , or --N(NO 2 )CH 3 .
  • Z is --C(NO 2 ) 3 , --CF(NO 2 ) 2 , --C(NO 2 ) 2 CH 3 , or --N(NO 2 )CH 3 .
  • the energetic branched polynitroakyldiols of this invention are 2-(trinitromethyl)-1,4-butanediol, HOCH 2 CH[C(NO 2 ) 3 ]CH 2 CH 2 OH; 2-(fluorodinitromethyl)-1,4-butanediol, HOCH 2 CH[CF(NO 2 ) 2 ]CH 2 CH 2 OH; 2-(1,1-dinitroethyl)-1,4-butanediol, HOCH 2 CH[C(NO 2 ) 2 CH 3 ]CH 2 CH 2 OH; and 2-(methylnitraza)-1,4-butanediol, HOCH 2 CH[N(NO 2 )CH 3 ]CH 2 CH 2 OH.
  • These diols can be used as monomers to produce energetic polymeric binders for use in plastic-bonded explosives.
  • These energetic branched polynitroalkyldiols offer advantages over prior art diols such as 2,2-dinitropropane-1,3-diol(A-diol), C(NO 2 ) 2 [CH 2 OH] 2 , and 4,6-dioxa-2,2,8,8-tetranitrononane-1,9-diol (DINOL), CH 2 [OCH 2 C(NO 2 ) 2 CH 2 OH] 2 , in the production of energetic polymeric binders.
  • These branched polynitroalkyldiols produce polymers with end groups which do not undergo deformylation.
  • diols Another important feature of these diols is that the number of atoms in the backbone is large enough to inhibit ring formation yet, short enough so that a large number of oxygen linkages will be incorporated in the backbone of the resultant polymer.
  • These divalent oxygen linkages add flexibility to the polymer backbone and markedly enhance physical properties.
  • the fact the energetic groups are carried on branches is important from the standpoint of physical properties since nitroamino or gem-dinitro groups on the backbone of a prepolymer can markedly lower physical properties.
  • reaction of one mole of fluorodinitromethane with gamma-crotonolactone under the reaction conditions of example 2 produces 4-hydroxy-3-(fluorodinitromethyl)butric acid, gamma-lactone which is reduced by borane-tetrahydrofuran to produce 2-(fluorodinitromethyl)-1,4-butanediol as shown in example 4.
  • 1,1-dinitroethane and gamma-crotonolactone can be used to produce 2-(1,1-dinitroethyl)-1,4-butanediol and methyl nitramine and gamma-crotonolactone can be used to produce 2-(methylnitraza)-1,4-butanediol.
  • the gamma-crotonolactone starting material used in these examples was prepared by the procedure disclosed by S. Takano and K. Ogasawara in Synthesis, 1974, (1), p. 42.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Energetic branched polynitrodiols of the formula ##STR1## wherein Z is --C(NO2)3, --CF(NO2)2, --C(NO2).su CH3, or --N(NO2)CH3, and a method of preparation. These diols are useful as components of energetic binders for plastic-bonded explosives.

Description

BACKGROUND OF THE INVENTION
This invention relates to alcohols and more particularly to energetic polynitroakyldiols.
The chief promise of energetic polynitrodiols for practical explosive applications are as monomers for the synthesis of hydroxy termined prepolymers. In practice, the prepolymers are mixed with a solid explosive,
HOCH.sub.2 . . . CH.sub.2 OH+X.sub.2 R♯HO[CH.sub.2 . . . CH.sub.2 ORO--CH.sub.2 . . . CH.sub.2 ].sub.n OH
ex., RDX or HMX, an energetic plasticizer and isocyanate curing agents. The liquid slurry is then cast into a suitable mold and cured to form a rubbery matrix which not only binds the solid explosive and defines the shape, but also contributes energy to the final composition.
The most attractive diols from the standpoint of energy and availability are 2,2-dinitro-1,3-propanediol (A-diol) and 2,2,8,8-tetranitro-4,6-dioxa-1,9-nonanediol (DINOL). Both of these diols, as is the case with the majority of known polynitromonols, are substituted with nitro groups in the beta-position. Alcohols of this type are easily prepared by the addition of the respective nitrocarbanion to formaldehyde (Henry reaction). Unfortunately, however, ##STR2## this reaction is reversible in the presence of even mild bases and the resultant nitrocarbanion is subject to side reactions and decomposition over ##STR3## varying periods of time.
Energetic polymers that contain unreacted beta-nitro alcohol end groups are also subject to the reverse Henry reaction and under the conditions of isocyanate curing wherein basic urethane linkages are formed, decomposition can and does occur. This leads to poor thermal stability and aging characteristics. This is undoubtedly the reason why AFNOL, an energetic polymer, formed from pimeloyl chloride and DINOL was ultimately rejected as a candidate energetic polymer.
For this reason, a considerable effort has been expended among different groups to prepare energetic diols that are not subject to deformylation under basic conditions. These have been without exception straight chain diols, which generally, though not always, contain both nitramine and gem dinitro groups on the backbone. These structural characteristics lead to hard prepolymers with poor solubilities in the energetic plasticizers used in the explosive compositions. This type of diol appears to be of limited usefulness.
SUMMARY OF THE INVENTION
Accordingly, an object of this invention is to provide new energetic polynitrodiols.
Another object of this invention is to provide new polynitrodiols which are useful as components of energetic polymers.
A further object of this invention is to provide new polynitrodiols which are stable to deformylation (loss of formaldehyde).
Yet another object of this invention is to provide new branched chain polynitrodiols which can improve the hydrolytic stability of energetic polymers such as polyesters.
A still further object of this invention is to provide a method of preparing these new energetic polynitrodiols.
These and other objects of this invention are achieved by providing branched polynitrodiols of the formula ##STR4## wherein Z is --C(NO2)3, --CF(NO2)2, --C(NO2)2 CH3, or --N(NO2)CH3. These branched polynitrodiols may be prepared by the following method: ##STR5## wherein Z is as defined above.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The energetic branched polynitroakyldiols of this invention are 2-(trinitromethyl)-1,4-butanediol, HOCH2 CH[C(NO2)3 ]CH2 CH2 OH; 2-(fluorodinitromethyl)-1,4-butanediol, HOCH2 CH[CF(NO2)2 ]CH2 CH2 OH; 2-(1,1-dinitroethyl)-1,4-butanediol, HOCH2 CH[C(NO2)2 CH3 ]CH2 CH2 OH; and 2-(methylnitraza)-1,4-butanediol, HOCH2 CH[N(NO2)CH3 ]CH2 CH2 OH. These diols can be used as monomers to produce energetic polymeric binders for use in plastic-bonded explosives.
These energetic branched polynitroalkyldiols offer advantages over prior art diols such as 2,2-dinitropropane-1,3-diol(A-diol), C(NO2)2 [CH2 OH]2, and 4,6-dioxa-2,2,8,8-tetranitrononane-1,9-diol (DINOL), CH2 [OCH2 C(NO2)2 CH2 OH]2, in the production of energetic polymeric binders. These branched polynitroalkyldiols produce polymers with end groups which do not undergo deformylation.
Another important feature of these diols is that the number of atoms in the backbone is large enough to inhibit ring formation yet, short enough so that a large number of oxygen linkages will be incorporated in the backbone of the resultant polymer. These divalent oxygen linkages add flexibility to the polymer backbone and markedly enhance physical properties. Moreover, the fact the energetic groups are carried on branches is important from the standpoint of physical properties since nitroamino or gem-dinitro groups on the backbone of a prepolymer can markedly lower physical properties.
The reaction sequences for preparing these branched polynitroalkyl diols can be summarized as follows: ##STR6## where Z is --C(NO2)3, --CF(NO2)2, --C(NO2)2 CH3, or --N(NO2)CH3. The reaction of one mole of trinitromethane with one mole of gamma-crotonolactone under the reaction conditions of example 1 produces 4-hydroxy-3-(trinitromethyl)butyric acid, gamma-lactone which is reduced by borane-tetrahydrofuran to produce 2-(trinitromethyl)-1,4-butanediol as shown in example 3. Similarly, the reaction of one mole of fluorodinitromethane with gamma-crotonolactone under the reaction conditions of example 2 produces 4-hydroxy-3-(fluorodinitromethyl)butric acid, gamma-lactone which is reduced by borane-tetrahydrofuran to produce 2-(fluorodinitromethyl)-1,4-butanediol as shown in example 4. Using the same procedure, 1,1-dinitroethane and gamma-crotonolactone can be used to produce 2-(1,1-dinitroethyl)-1,4-butanediol and methyl nitramine and gamma-crotonolactone can be used to produce 2-(methylnitraza)-1,4-butanediol.
The general nature of the invention having been set forth, the following examples are presented as specific illustrations thereof. It will be understood that the invention is not limited to these examples but is susceptible to various modifications that will be recognized by one skilled in the art.
The gamma-crotonolactone starting material used in these examples was prepared by the procedure disclosed by S. Takano and K. Ogasawara in Synthesis, 1974, (1), p. 42.
EXAMPLE 1 4-Hydroxy-3-(trinitromethyl)butyric acid, gamma-lactone ##STR7##
A mixture of 7.5 g (0.089 mole) of gamma-crotonolactone, 56.7 g (0.124 mole) of 33% aqueous nitroform and 32 ml of methanol was stirred in an oil bath at 72°-75° C. for 5 hr. The mixture was then cooled in an ice bath to precipitate an oil which turned to a solid and was removed by filtration and washed with cold water to give 13.7 g, mp 103°-105° C. The water wash precipitated more oil from the filtrate. After extraction into methylene chloride, the oil was crystallyzed from methanol-water to give an additional 1.55 g of product [total yield of 15.25 g (73%)]. Recrystallization from methanol-water raised the mp to 105°-106° C.; 1 H NMR(CD2 Cl2): 2.74-3.36 (m,2H); 4.25-4.60 (m, 2H); 4.75-4.97 (m, 1H); IR (KBr): 1775 (shoulder at 1787) (C=0); 1600, 1590 (NO2) cm-1.
Anal. Calcd for C5 H5 N3 O8 : C, 25.54; H, 2.14; N, 17.87. Found: C, 25.63; H, 2.13; N, 17.81.
EXAMPLE 2 4-Hydroxy-3-(fluorodinitromethyl)butyric acid, gamma-lactone ##STR8##
A solution containing 16.5 g (0.196 mole) of gamma-crotonolactone and 31.8 g (0.256 mole) of fluorodinitromethane in 100 ml of methylene chloride (protected by a drierite drying tube) was stirred in an ice bath while 30.8 ml of pyridine was added in 3 ml portions over 5 min. The solution was stirred at ice bath temperature for 3 hr. before an additional 8.9 ml of pyridine was added in 3 portions over 2 min. After an additional 3 hr. at 0° C., the solution was poured into a solution containing 85 ml conc. hydrochloric acid diluted with 170 ml of water. The mixture was stirred vigorously at ambient temperature for 15 min. before the methylene chloride layer was separated, washed with water and dried over sodium sulfate. Removal of the methylene chloride gave 28.4 g of tan solid which was dissolved in 120 ml of hot chloroform. The hot solution was stirred with 10 g of silica gel 60, then filtered and the silica gel was washed with 120 ml of hot chloroform. Hexane was added to the filtrate (at room temperature) to the cloud point. Cooling to -15° C. gave 21.9 g of white crystals, mp 58°-60° C. A second crop (4.6 g, mp 57°-59° C.) raised the yield to 26.5 g (65%); 1 H NMR (CDCl3): 2.55-3.14 (m, 2H); 3.97-4.88 (m, 3H); IR(KBr): 1800, 1766 (C=0), 1609, 1600 (shoulder) (NO2) cm-1.
Anal. Calcd for C5 H5 N2 FO6 : C, 28.86; H, 2.42; N, 13.46; F, 9.13. Found: C, 28.95; H, 2.45; N, 13.18; F, 9.12.
EXAMPLE 3 2-(Trinitromethyl)-1,4-butanediol ##STR9##
A 1M solution of borane-THF (10 ML, 10 mmole) was stirred under a nitrogen atmosphere in a cold water bath (15° C.) while 2.1 g (8.94 mmole) of 4-hydroxy-3-(trinitromethyl)butyric acid, gamma-lactone was added. The solution was stirred at 25° C. for 1 hr. and then at 35°-37° C. for 3 days before it was cooled to room temperature and 1 ml of water was slowly added dropwise. Most of the THF was removed and the residue was stirred with ether. The insoluble material (boric acid) was removed by filtration and the ether filtrate was extracted twice with water to remove remaining boric acid. The ether was removed to give 2.10 g (98%) of an oil which was essentially pure by TLC. An analytical sample was obtained by chromatography on silica gel 60 with methylene chloride-acetone (80/20) as eluent: 1 H NMR (CD2 Cl2) 1.90-2.12 (m, 2H), 2.44 (broad OH), 3.60 (broad m, 1H), 3.93 (t, 2H), 4.23 (d, 2H); IR (film) 3700-3050 (OH), 1600 (NO2) cm-1.
Anal. Calcd for C5 H9 N3 O8 : C, 25.11; H, 3.79; N, 17.57. Found C, 25.00; H, 3.86; N, 17.34.
EXAMPLE 4 2-(Fluorodinitromethyl)-1,4-butanediol ##STR10##
To a 1M solution of borane-THF (5 ml, 5 mmole) stirred under a nitrogen atmosphere in an ice bath was added 1.0 g (4.8 mmole) of 4-hydroxy-3-(fluorodinitromethyl)butyric acid, gamma-lactone. The solution was then held in a water bath at 25°-28° C. for 24 hr. before 1 ml of water was slowly added dropwise. The solution was poured into 15 ml of water and extracted with ether to give 1.02 g (100%) of an oil which was essentially pure by TLC. Chromatography on silica gel 60 using methylene chloride-acetone (80/20) as eluent gave an analytical sample. 1 H NMR (CDCl3) 1.70-1.93 (m, 2H), 2.36(OH), 3.34-3.97 (m, 5H); IR (film) 3700-3050 (OH), 1605 (NO2) cm-1.
Anal Calcd for C5 H9 N2 FO6 : C, 28.31; N, 4.28; N, 13.21: F, 8.96. Found: C, 28.04; H, 4.44; N, 12.81; F, 8.50.
Obviously many numerous modifications and variations of this invention are possible in light of the above teachings. It is therefore to be understood that within the scope of the appended claims the invention may be practiced otherwise than as specifically described.

Claims (11)

What is claimed is:
1. A diol of the formula ##STR11## wherein Z is selected from the group consisting of --C(NO2)3, --CF(NO2)2, --C(NO2)2 CH3, and --N(NO2)CH3.
2. The diol of claim 1 which is 2-(trinitromethyl)-1,4-butanediol.
3. The diol of claim 1 which is 2-(fluorodinitromethyl)-1,4-butanediol.
4. The diol of claim 1 which is 2-(1,1-dinitroethyl)-1,4-butanediol.
5. The diol of claim 1 which is 2-(methylnitraza)-1,4-butanediol.
6. A lactone of the formula ##STR12## wherein Z is selected from the group consisting of --C(NO2)3 --CF(NO2)2, --C(NO2)2 CH3, and --N(NO2)CH3.
7. The lactone of claim 6 wherein Z is --C(NO2)3.
8. The lactone of claim 6 wherein Z is --CF(NO2)2.
9. The lactone of claim 6 wherein Z is --C(NO2)2 CH3.
10. The lactone of claim 6 wherein Z is --N(NO2)CH3.
11. A process for preparing a branched polynitrodiol comprising the following steps in order:
(1) reacting one mole of a compound of the formula Z--H with one mole of gamma-crotonolactone to produce a lactone of the formula ##STR13## (2) reducing the lactone produced in step (1) with borane-tetrahydrofuran to produce the desired branched polynitrodiol of the formula ##STR14## (3) isolating the product branched polynitrodiol; wherein Z is selected from the group consisting of --C(NO2)3, --CF(NO2)2, --C(NO2)2 CH3, and --N(NO2)CH3.
US06/875,159 1986-06-17 1986-06-17 Branch chained polynitrodiols Abandoned USH253H (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US06/875,159 USH253H (en) 1986-06-17 1986-06-17 Branch chained polynitrodiols

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US06/875,159 USH253H (en) 1986-06-17 1986-06-17 Branch chained polynitrodiols

Publications (1)

Publication Number Publication Date
USH253H true USH253H (en) 1987-04-07

Family

ID=25365302

Family Applications (1)

Application Number Title Priority Date Filing Date
US06/875,159 Abandoned USH253H (en) 1986-06-17 1986-06-17 Branch chained polynitrodiols

Country Status (1)

Country Link
US (1) USH253H (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5859264A (en) * 1995-03-13 1999-01-12 Croda International, Plc Explosive compositions
US20160168317A1 (en) * 2014-12-11 2016-06-16 Orbital Atk, Inc. Methods of producing energetic polymers, energetic binders, and energetic compositions

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5859264A (en) * 1995-03-13 1999-01-12 Croda International, Plc Explosive compositions
US20160168317A1 (en) * 2014-12-11 2016-06-16 Orbital Atk, Inc. Methods of producing energetic polymers, energetic binders, and energetic compositions
US10696786B2 (en) * 2014-12-11 2020-06-30 Northrop Grumman Innovation Systems, Inc. Methods of producing energetic polymers, energetic binders, and energetic compositions

Similar Documents

Publication Publication Date Title
US4268450A (en) Energetic hydroxy-terminated azido polymer
USH253H (en) Branch chained polynitrodiols
CA2008154C (en) Synthesis of a diazido terminated energetic plasticizer
SU837326A3 (en) Method of preparing 4"-desoxy-4"-oxoeritromycin a
US4472311A (en) Method of preparing 1,1,1-azidodinitro compounds
US4522756A (en) Alkyl, azido, nitro ethers and method of preparation
EP1144473B1 (en) Synthesis of energetic thermoplastic elastomers containing both polyoxirane and polyoxetane blocks
US5186770A (en) Bis(2-nitro-2-azapropyl) ether
US4323518A (en) Polynitroethylthionocarbonates and method of preparation
US4229576A (en) Anthranilates of oxyalkylated cyanuric acid
US5773551A (en) Method of utilizing isocyanate linkages for forming multi-tier cascade polymers
US4567296A (en) 1-Fluoro-1,1,5-trinitro-3-oxa-5-azahexane and method of preparation
JPH0525161A (en) Novel cyclic ether compound
US4340755A (en) Biguanide diperchlorate and process for preparation thereof
CN116903427B (en) A nitrate functionalized ionic liquid plasticizer and its application
US5532390A (en) Energetic azide plasticizer
US4452739A (en) 1,3,3,5,7,7-Hexanitroperhydro-1,5-diazocine, N-nitroso analogs thereof, and processes for their preparation
US4311649A (en) N,N-Bis(2-fluoro-2,2-dinitroethyl)carbamate esters
US4683086A (en) Azido derivatives of pentaerythritol
JPH0475878B2 (en)
CN117285466B (en) 3,3', 5' -Tetranitro-1, 1' -di (trinitromethyl) -1H,1' H-4,4' -bipyrazole energetic compound and preparation method and application thereof
US4546200A (en) 2,2-Dinitrobutane-1,4-diol and monoesters
WO2011162859A1 (en) Synthesis of an azido energetic alcohol
EP0618893A1 (en) Energetic polymers and process for preparation thereof
US4317928A (en) N,N,N',N'-Tetrakis(2-fluoro-2,2-dinitroethyl) oxamide and a method of preparation thereof

Legal Events

Date Code Title Description
AS Assignment

Owner name: UNITED STATES OF AMERICA, AS REPRESENTED BY THE SE

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:SITZMANN, MICHAEL E.;GILLIGAN, WILLIAM H.;REEL/FRAME:004566/0439

Effective date: 19860616

STCF Information on status: patent grant

Free format text: PATENTED CASE