EP0614862A1 - High-density insensitive explosives - Google Patents

High-density insensitive explosives Download PDF

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Publication number
EP0614862A1
EP0614862A1 EP93116979A EP93116979A EP0614862A1 EP 0614862 A1 EP0614862 A1 EP 0614862A1 EP 93116979 A EP93116979 A EP 93116979A EP 93116979 A EP93116979 A EP 93116979A EP 0614862 A1 EP0614862 A1 EP 0614862A1
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Prior art keywords
composition according
explosive composition
halogenated
plasticizer
cure
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Application number
EP93116979A
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German (de)
French (fr)
Inventor
Joseph Edward Flanagan
James Frederick Weber
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Boeing North American Inc
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Rockwell International Corp
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    • 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
    • C06B25/34—Compositions containing a nitrated organic compound the compound being a nitrated acyclic, alicyclic or heterocyclic amine
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B45/00—Compositions or products which are defined by structure or arrangement of component of product
    • C06B45/04—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive
    • C06B45/06—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component
    • C06B45/10—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component the organic component containing a resin
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B45/00—Compositions or products which are defined by structure or arrangement of component of product
    • C06B45/04—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive
    • C06B45/06—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component
    • C06B45/10—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component the organic component containing a resin
    • C06B45/105—The resin being a polymer bearing energetic groups or containing a soluble organic explosive

Definitions

  • This invention relates to explosive compositions of matter and is particularly directed to explosive compositions including halogenated components and organic nitramine compounds and other energetic chemical groups.
  • High energy explosives and propellants such as disclosed in U.S. Patent No. 5,045,132 are generally formulated to include a high energy binder and oxidizer, together with suitable plasticizers. These ingredients must have a favorable preferably positive heat of formation and be oxygen-rich in order for high performance to be met. Moreover, these ingredients must have thermal and shock stability in order to permit safe storage and handling.
  • the present invention contemplates performance-improved, less detonation-sensitive formulations.
  • the advantages of the present invention are realized in explosive formulations utilizing a select binder and oxidizer in combination with high-energy constituents.
  • an object of the present invention is to provide improved high-energy explosive compositions or formulations.
  • Another object of the present invention is to provide high-energy explosive compositions having a lessened detonation sensitivity and enhanced performance.
  • Figure 1 is a graph of the plate dent of the theoretical detonation velocity times the explosive mass for a selection of explosive materials.
  • new cast curable insensitive explosives comprising select oxidizers with high density binders which binder constituent replaces a portion of the sensitive explosive.
  • the binder constitutent further comprises a select halogenated polymer, a halogenated plasticizer, glycidyl azide polymer (U.S. Patent No. 4,268,450), and mixtures thereof. Additional ingredients, including a curative and a cure catalyst may be included in the explosive formulation. Substitution of all or a portion of the sensitive explosive with an elastomeric binder decreases the overall brittleness of the grain, leading to further reduced sensitivity of the explosive.
  • select levels of binder allow for production of void-free grains, further reducing the sensitivity of the explosive grain by elimination of hot-spot sources of ignition.
  • the performance of an explosive is proportional to the square of the density of the explosive grain thus, the binder fraction should have a high density in order to maintain performance.
  • a series of explosive formulations were prepared containing select halogenated ingredients to provide progressively higher density explosives. As can be seen in figure 1, a smooth linear correlation between performance improvement (related to the increase in density) and plate dent was observed.
  • the high-energy explosive compositions of the present invention include a binder and a nitramine oxidizer wherein the binder is selected from a halogenated polymer, a halogenated plasticizer and mixtures thereof with optionally a curative such as biuret trimer of hexamethylene diisocyanate (polyisocyanate curative).
  • a curative such as biuret trimer of hexamethylene diisocyanate (polyisocyanate curative).
  • Oxidizers which may be utilized in the high-energy explosive taught herein preferably include: cyclotetramethylenetetranitramine (HMX), 1,3,5-trinitro-1,3,5-triazacyclohexane (RDX), 1,7-dibromo-2,4,6-trinitrazaheptane (DBTH), 1,9-dibromo-2,4,6,8-tetranitrazanonane (DBTN), or bis(2-bromo-2,2-dinitroethyl)nitramine (BRDNEN).
  • HMX 1,3,5-trinitro-1,3,5-triazacyclohexane
  • DBTH 1,7-dibromo-2,4,6-trinitrazaheptane
  • DBTN 1,9-dibromo-2,4,6,8-tetranitrazanonane
  • BRDNEN bis(2-bromo-2,2-dinitroethyl)nitramine
  • the polymeric constituent of the binder may be selected from poly(epibromohydrin) (PEBH), 2,2-dinitro-2-bromoethyl glycidyl ether and poly(epichlorohydrin) (PECH), or mixtures thereof.
  • PEBH poly(epibromohydrin)
  • PECH poly(epichlorohydrin)
  • Plasticizers which may be utilized in the high-energy explosive compositions taught herein preferably include polybromo-aliphatic esters such as 2,3-dibromopropyl ⁇ -bromoacetate, polynitro-bromo esters such as 2-bromo-2,2-dinitroethyl ⁇ -bromoacetate, the bis(bromoacetate) ester of 2,2-dinitro-1,3-propanediol, the mono-ester of 2,2-dinitropropanol, trimethylolethane trinitrate (TMETN), bis(2-chloro-2,2-dinitroethyl) formal (CLEFO), and mixtures thereof.
  • polybromo-aliphatic esters such as 2,3-dibromopropyl ⁇ -bromoacetate
  • polynitro-bromo esters such as 2-bromo-2,2-dinitroethyl ⁇ -bromoacetate

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Molecular Biology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

High-density insensitive explosives including a binder and an oxidizer wherein the binder is selected from a halogenated polymer, a halogenated plasticizer and mixtures thereof. Such explosives display enhanced performance with decreased sensitivity.

Description

    BACKGROUND OF THE INVENTION 1. Field of the Invention
  • This invention relates to explosive compositions of matter and is particularly directed to explosive compositions including halogenated components and organic nitramine compounds and other energetic chemical groups.
    • 2. Description of Related Art
  • High energy explosives and propellants such as disclosed in U.S. Patent No. 5,045,132 are generally formulated to include a high energy binder and oxidizer, together with suitable plasticizers. These ingredients must have a favorable preferably positive heat of formation and be oxygen-rich in order for high performance to be met. Moreover, these ingredients must have thermal and shock stability in order to permit safe storage and handling.
  • The disadvantages of known explosive compositions such as thermal and shock instability are overcome with the new explosive compositions of the present invention.
    • BRIEF SUMMARY AND OBJECTS OF THE INVENTION
  • To improve the high energy potential and improve insensitivity of explosive compositions when the heat release factor is reduced, the present invention contemplates performance-improved, less detonation-sensitive formulations.
  • The advantages of the present invention are realized in explosive formulations utilizing a select binder and oxidizer in combination with high-energy constituents.
  • Accordingly, an object of the present invention is to provide improved high-energy explosive compositions or formulations.
  • Another object of the present invention is to provide high-energy explosive compositions having a lessened detonation sensitivity and enhanced performance.
  • These and other objects and features of the present invention will be apparent from the following detailed description.
    • BRIEF DESCRIPTION OF THE DRAWINGS
  • Figure 1 is a graph of the plate dent of the theoretical detonation velocity times the explosive mass for a selection of explosive materials.
    • DETAILED DESCRIPTION OF THE INVENTION
  • According to the present invention, new cast curable insensitive explosives are provided comprising select oxidizers with high density binders which binder constituent replaces a portion of the sensitive explosive. The binder constitutent further comprises a select halogenated polymer, a halogenated plasticizer, glycidyl azide polymer (U.S. Patent No. 4,268,450), and mixtures thereof. Additional ingredients, including a curative and a cure catalyst may be included in the explosive formulation. Substitution of all or a portion of the sensitive explosive with an elastomeric binder decreases the overall brittleness of the grain, leading to further reduced sensitivity of the explosive. In addition, select levels of binder allow for production of void-free grains, further reducing the sensitivity of the explosive grain by elimination of hot-spot sources of ignition.
  • The performance of an explosive is proportional to the square of the density of the explosive grain thus, the binder fraction should have a high density in order to maintain performance. A series of explosive formulations were prepared containing select halogenated ingredients to provide progressively higher density explosives. As can be seen in figure 1, a smooth linear correlation between performance improvement (related to the increase in density) and plate dent was observed.
  • The high-energy explosive compositions of the present invention include a binder and a nitramine oxidizer wherein the binder is selected from a halogenated polymer, a halogenated plasticizer and mixtures thereof with optionally a curative such as biuret trimer of hexamethylene diisocyanate (polyisocyanate curative).
  • Oxidizers which may be utilized in the high-energy explosive taught herein preferably include:
       cyclotetramethylenetetranitramine (HMX),
       1,3,5-trinitro-1,3,5-triazacyclohexane (RDX),
       1,7-dibromo-2,4,6-trinitrazaheptane (DBTH),
       1,9-dibromo-2,4,6,8-tetranitrazanonane (DBTN), or
       bis(2-bromo-2,2-dinitroethyl)nitramine (BRDNEN).
  • The polymeric constituent of the binder may be selected from poly(epibromohydrin) (PEBH), 2,2-dinitro-2-bromoethyl glycidyl ether and poly(epichlorohydrin) (PECH), or mixtures thereof.
  • Plasticizers which may be utilized in the high-energy explosive compositions taught herein preferably include polybromo-aliphatic esters such as 2,3-dibromopropyl α-bromoacetate, polynitro-bromo esters such as 2-bromo-2,2-dinitroethyl α-bromoacetate, the bis(bromoacetate) ester of 2,2-dinitro-1,3-propanediol, the mono-ester of 2,2-dinitropropanol, trimethylolethane trinitrate (TMETN), bis(2-chloro-2,2-dinitroethyl) formal (CLEFO), and mixtures thereof.
  • Specific formulations of high-energy explosive compostions and their physical characteristics such as density, electrostatic detonation (ESD), and the like, according to the present invention are provided in the TABLE I and II respectively.
    Figure imgb0001
  • Obviously, numerous variations and modifications may be made without departing from the present invention. Accordingly, it should be clearly understood that the embodiments of the present invention disclosed hereinabove are not intended to limit the scope of the present invention.

Claims (22)

  1. An explosive composition including a binder and an oxidizer wherein the binder is selected from a halogenated polymer, a halogenated plasticizer, and mixtures thereof.
  2. An explosive composition according to Claim 1 wherein the halogenated polymer is a brominated polymer.
  3. An explosive composition according to claim 1 wherein the halogenated plasticizer is a brominated plasticizer.
  4. An explosive composition according to Claim 1 wherein the oxidizer is:
       cyclotetramethylenetetranitramine (HMX),
       1,3,5-trinitro-1,3,5-triazacyclohexane (RDX),
       1,7-dibromo-2,4,6-trinitrazaheptane (DBTH),
       1,9-dibromo-2,4,6,8-tetranitrazanonane (DBTN), or
       bis(2-bromo-2,2-dinitroethyl)nitramine (BRDNEN).
  5. An explosive composition according to Claim 1 wherein the halogenated polymer is poly(epibromohydrin) (PEBH).
  6. An explosive composition according to Claim 1 wherein the halogenated polymer is poly(2,2-dinitro-2-bromoethyl glycidyl ether).
  7. An explosive composition according to Claim 1 wherein the halogenated plasticizer is a polybromo-aliphatic ester.
  8. An explosive composition according to Claim 1 wherein the halogenated plasticizer is a polynitro-bromo ester.
  9. An explosive composition according to Claim 1 wherein the halogenated plasticizer is 2,3-dibromopropyl-α-bromoacetate.
  10. An explosive composition according to Claim 1 wherein the halogenated plasticizer is the bis(bromoacetate)ester of 2,2-dinitro-1,3-propanediol.
  11. An explosive composition according to Claim 1 wherein the halogenated plasticizer is the mono-bromoacetate ester of 2,2-dinitropropanol.
  12. A cast-cure insensitive explosive composition including a binder and an oxidizer wherein the binder is selected from a halogenated polymer, a halogenated plasticizer, and mixtures thereof.
  13. A cast-cure insensitive explosive composition according to Claim 12 wherein the halogenated polymer is a brominated polymer.
  14. A cast-cure insensitive explosive composition according to claim 12 wherein the halogenated plasticizer is a brominated plasticizer.
  15. A cast-cure insensitive explosive composition according to Claim 12 wherein the oxidizer is:
       cyclotetramethylenetetranitramine (HMX),
       1,3,5-trinitro-1,3,5-triazacyclohexane (RDX),
       1,7-dibromo-2,4,6-trinitrazaheptane (DBTH),
       1,9-dibromo-2,4,6,8-tetranitrazanonane (DBTN), or
       bis(2-bromo-2,2-dinitroethyl)nitramine (BRDNEN).
  16. A cast-cure insensitive explosive composition according to Claim 12 wherein the halogenated polymer is poly(epibromohydrin) (PEBH).
  17. A cast-cure insensitive explosive composition according to Claim 12 wherein the halogenated polymer is poly(2,2-dinitro-2-bromoethyl glycidyl ether).
  18. A cast-cure insensitive explosive composition according to Claim 12 wherein the halogenated plasticizer is a polybromo-aliphatic ester.
  19. A cast-cure insensitive explosive composition according to Claim 12 wherein the halogenated plasticizer is a polynitro-bromo ester.
  20. A cast-cure insensitive explosive composition according to Claim 12 wherein the halogenated plasticizer is 2,3-dibromopropyl-α-bromoacetate.
  21. A cast-cure insensitive explosive composition according to Claim 12 wherein the halogenated plasticizer is the bis(bromoacetate)ester of 2,2-dinitro-1,3-propanediol.
  22. A cast-cure insensitive explosive composition according to Claim 12 wherein the halogenated plasticizer is the mono-bromoacetate ester of 2,2-dinitropropanol.
EP93116979A 1993-03-12 1993-10-20 High-density insensitive explosives Withdrawn EP0614862A1 (en)

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US3099493A 1993-03-12 1993-03-12
US30994 1993-03-12

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1876161A1 (en) * 2006-07-04 2008-01-09 Diehl BGT Defence GmbH & Co.KG Pyrotechnical charge
US8318959B1 (en) * 2012-01-04 2012-11-27 Flurochem, Inc. Synthesis and polymerization of glycidyl ethers
WO2014008986A1 (en) * 2012-07-13 2014-01-16 Diehl Bgt Defence Gmbh & Co. Kg Insensitive explosive active substance

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3399235A (en) * 1964-06-08 1968-08-27 Aerojet General Co Polynitro trifluoromethyl amines
US3488396A (en) * 1967-07-10 1970-01-06 North American Rockwell Dinitrohalo compounds
GB1195558A (en) * 1967-09-25 1970-06-17 North American Rockwell Explosive Compounds
US3590067A (en) * 1963-11-26 1971-06-29 Aerojet General Co Polynitro halo compounds useful as antibiotics,fungicides and explosives
US3808182A (en) * 1972-06-16 1974-04-30 Us Navy 2,2-dinitroalkyl vinyl ethers and polymers thereof
US3907907A (en) * 1968-05-16 1975-09-23 Rockwell International Corp 2-Fluoro-2,2-dinitroethyl substituted polyethers
US4341712A (en) * 1977-02-17 1982-07-27 Rockwell International Corporation Fluorodinitro compounds
US4988397A (en) * 1986-04-30 1991-01-29 The United States Of America As Represented By The Secretary Of The Navy Energetic binders for plastic bonded explosives
US5049213A (en) * 1985-10-10 1991-09-17 The United States Of America As Represented By The Secretary Of The Navy Plastic bonded explosives using fluorocarbon binders

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3590067A (en) * 1963-11-26 1971-06-29 Aerojet General Co Polynitro halo compounds useful as antibiotics,fungicides and explosives
US3399235A (en) * 1964-06-08 1968-08-27 Aerojet General Co Polynitro trifluoromethyl amines
US3488396A (en) * 1967-07-10 1970-01-06 North American Rockwell Dinitrohalo compounds
GB1195558A (en) * 1967-09-25 1970-06-17 North American Rockwell Explosive Compounds
US3907907A (en) * 1968-05-16 1975-09-23 Rockwell International Corp 2-Fluoro-2,2-dinitroethyl substituted polyethers
US3808182A (en) * 1972-06-16 1974-04-30 Us Navy 2,2-dinitroalkyl vinyl ethers and polymers thereof
US4341712A (en) * 1977-02-17 1982-07-27 Rockwell International Corporation Fluorodinitro compounds
US5049213A (en) * 1985-10-10 1991-09-17 The United States Of America As Represented By The Secretary Of The Navy Plastic bonded explosives using fluorocarbon binders
US4988397A (en) * 1986-04-30 1991-01-29 The United States Of America As Represented By The Secretary Of The Navy Energetic binders for plastic bonded explosives

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1876161A1 (en) * 2006-07-04 2008-01-09 Diehl BGT Defence GmbH & Co.KG Pyrotechnical charge
US8318959B1 (en) * 2012-01-04 2012-11-27 Flurochem, Inc. Synthesis and polymerization of glycidyl ethers
WO2014008986A1 (en) * 2012-07-13 2014-01-16 Diehl Bgt Defence Gmbh & Co. Kg Insensitive explosive active substance

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CA2107256A1 (en) 1994-09-13
NO940872D0 (en) 1994-03-11

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