EP0593479B1 - Schwer entzuendliche zuendempfindliche flexible sprengstoffzusammensetzung - Google Patents

Schwer entzuendliche zuendempfindliche flexible sprengstoffzusammensetzung Download PDF

Info

Publication number
EP0593479B1
EP0593479B1 EP91916507A EP91916507A EP0593479B1 EP 0593479 B1 EP0593479 B1 EP 0593479B1 EP 91916507 A EP91916507 A EP 91916507A EP 91916507 A EP91916507 A EP 91916507A EP 0593479 B1 EP0593479 B1 EP 0593479B1
Authority
EP
European Patent Office
Prior art keywords
composition
explosive
flame retardant
retardant material
weight
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.)
Expired - Lifetime
Application number
EP91916507A
Other languages
English (en)
French (fr)
Other versions
EP0593479A1 (de
Inventor
Martin Gerald Wagner
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.)
Ensign Bickford Co
Original Assignee
Ensign Bickford Co
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 Ensign Bickford Co filed Critical Ensign Bickford Co
Publication of EP0593479A1 publication Critical patent/EP0593479A1/de
Application granted granted Critical
Publication of EP0593479B1 publication Critical patent/EP0593479B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
    • 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
    • C06B45/12—Compositions or products which are defined by structure or arrangement of component of product having contiguous layers or zones

Definitions

  • This invention relates to a flexible explosive composition of reduced flammability. More particularly, the invention relates to a cap-sensitive flexible explosive composition containing a finely divided, cap-sensitive explosive admixed in a flame resistant polymeric binder system which includes a compatible flame retardant material. Such compositions are useful in applications which require self-supporting units rather than loose particles in environments in which the units may be subjected to ignition temperatures.
  • US-A-4861397 discloses fire-resistant explosives in which a nitramine explosive is mixed with a flame-retardant additive and a binder.
  • Chemical Abstracts, vol. 114, No. 16, Abstract No. 146427, discloses a flame-retardant explosive composition in which a flame-retarding agent is mixed with a secondary explosive and a binder component.
  • US-A-4098625 discloses an extrudable plastic-bonded explosive composition in which an explosive comprising HMX or RDX and a fluorocarbon binder are blended to form an extrudable plastic bonded composition.
  • a cap-sensitive flexible explosive composition of reduced flammability comprising a finely divided, cap-sensitive explosive in a flame resistant polymeric binder system which comprises an uncrosslinked fluorinated elastomer, or mixture of uncrosslinked fluorinated elastomers, admixed with from about 10% to about 30% by weight of the composition of a compatible flame retardant material, a drip suppressant, and the binder system remaining uncrosslinked unless exposed to heat from an ignition source in the presence of which the binder will cross-link and harden at a rate which is faster than the rate at which the explosive composition will burn.
  • the polymeric binder is chosen from flame resistant polymers and copolymers which provide a flexible explosive sheet when compounded with additional ingredients as described herein.
  • the sheet when exposed to elevated temperatures should maintain essentially its original dimensions.
  • the sheet may soften when heated but should not lose its unitary structure.
  • suitable polymeric binders are polymers and copolymers which are capable of further polymerizing or cross-linking when activated by heat from an ignition source.
  • Halogenated binders which can be formed into flexible sheets of the chlorinated and/or fluorinated polymer and copolymer families such as those containing tetrafluoroethylene, hexafluoropropylene, vinylidene fluoride, and trifluorochloroethylene are among those which are useful in this invention.
  • Fluoroelastomers of hexafluoropropylene/vinylidene fluoride sold under the Trademark viton® by E.I. du Pont de Nemours & Co. are particularly useful.
  • Polymeric compositions having a limiting oxygen index greater than 21 are preferred.
  • one or more of the polymeric materials of the type mentioned above are combined using known methods to provide an explosive containing mixture which can be formed into sheets which remain flexible under ambient conditions. It is preferable that no cross-linking occurs during normal processing or during ambient temperature storage yet occurs rapidly on exposure to high temperatures.
  • an activator which is activatable by heat from an ignition source is included in the system. When activated, the polymeric material is further polymerized or cross-linked thereby transforming it from its orginal flexible state to a hardened or thermoset state.
  • organophosphonium salts such as benzyl triphenyl phosphonium chloride, aromatic dihydroxy compounds such as bisphenol AF,and diamines or polyamines such as triethylene tetramine.
  • cap-sensitive explosives which can be used in the compositions of this invention include solid organic nitrates such as pentaerythritol tetranitrate (PETN) and nitromannite, organic nitramines such as tetryl, cyclo-trimethylenetrinitramine (RDX), cyclotetramethylene tetranitramine (HMX), nitroguanadine, TACOT and mixtures of one or more of the foregoing explosives.
  • solid organic nitrates such as pentaerythritol tetranitrate (PETN) and nitromannite
  • organic nitramines such as tetryl, cyclo-trimethylenetrinitramine (RDX), cyclotetramethylene tetranitramine (HMX), nitroguanadine, TACOT and mixtures of one or more of the foregoing explosives.
  • Compatible flame retardant materials include boron containing compounds such as zinc borate, boric acid and ammonium fluoborate; phosphorus containing compounds, especially phosphate esters such as 2-ethylhexyl diphenyl phosphate, and isodecyl diphenyl phosphate, and tricresyl phosphate; antimony oxide with a chlorine or bromine donor; hydrated materials such as alumina trihydrate, and other materials such as chlorinated or brominated hydrocarbons.
  • compatible it is meant that the flame retardant material does not react exothermically with the explosive materials when heated with the composition for a period of 24 hours at a temperature of 121°C (250°F).
  • the other ingredients comprising the flexible explosive composition must not react exothermically when incorporated in the explosives composition.
  • compositions of this invention may be added to the compositions of this invention. These include drip suppressants and/or reinforcing agents. Addition of a small amount of Teflon® polytetrafluoroethylene resin is particularly effective in suppressing dripping when the composition is subjected to ignition temperatures.
  • compositions of this invention all of the ingredients are mixed together.
  • a slurry of particles is made starting with water-wet explosive material and adding all other ingredients in a jacketed half-sigma blade mixer. Mixing is carried out at temperatures between 65.6 (150) and 93.3°C (200°F), and drying is done under vacuum in the mixer. Sheets of the combined ingredients are formed by rolling through a two-roll mill. Extrusion processes may also be used.
  • the amounts of the particular ingredients used in making the composition of the flexible explosive materials of this invention are not critical. In general the composition should contain from about 30 to 65% by weight of finely divided, cap-sensitive explosive. For most explosives purposes, amounts in the range from about 40 to 55% will produce satisfactory results. In a preferred embodiment of the invention, the cap-sensitive explosive is RDX in an amount of about 50.35 percent by weight. The amount of flame retardant material will vary depending on the particular material used. Between 10 and 30% by weight gives satisfactory results. Sufficient polymeric binder must be present to provide a flexible sheet of the combined materials. Preferably, the amount used should provide a self-supporting sheet. Amounts in the range from about 20 to about 60% by weight may be used.
  • Hot Bar Test A hot-plate is maintained at a constant temperature. A single piece of the explosive composition weighing 30 mg and roughly cubical in shape is placed in the center of the plate. The time the sample takes to ignite (in seconds) is measured and recorded. The test is conducted in triplicate, and the results are averaged. If no ignition occurs in three minutes, the results are recorded as "no ignition”.
  • Viton® C10 and LM are fluoroelastomers
  • Viton® Curatives 20 and 30 are activators for the just-mention fluoroelastomers
  • Teflon® DR is a TFE-Fluorocarbon resin all of which are sold by the E.I. du Pont de Nemours & Co.
  • This example employs RDX as the base explosive and a mixture of boric acid and phosphate esters as flame retardant.
  • This example employs a mixture of zinc borate and hydrated alumina as the flame retardant.
  • PETN 40 Viton® C10 6.2 Viton® LM 24.8 Teflon® DR 2.2 Viton® Curative No. 20 0.9 Viton® Curative No. 30 0.9 Zinc Borate 15.0 Hydrated Alumina 10.0 Specific Gravity 1.76 Detonation Velocity 5614 Hot Bar Test No ignition at 306°C(583°F) Strip Burn Test - Time to consumption 280 sec Plate Burn Test - Time until flame extinguished 1 min. 30 sec. Time until smoke generation stopped 5 min. 45 sec. Percent Remaining 98

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Molecular Biology (AREA)
  • Fireproofing Substances (AREA)
  • Casting Or Compression Moulding Of Plastics Or The Like (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Claims (15)

  1. Zündempfindliche flexible Explosivstoffzusammensetzung mit verringerter Entflammbarkeit, umfassend einen fein zerteilten zündempfindlichen Explosivstoff in einem feuerbeständigen Polymerbindemittelsystem, umfassend ein nicht vernetztes fluoriertes Elastomer oder ein Gemisch von nicht vernetzten fluorierten Elastomeren, gemischt mit von etwa 10% bis etwa 30% bezüglich des Gewichts der Zusammensetzung eines kompatiblen Flammverzögerungsmaterials, ein Tropfunterdrückungsmittel, und worin das Bindemittelsystem unvernetzt bleibt, es sei denn es wird Hitze von einer Zündquelle ausgesetzt, bei deren Vorliegen sich das Bindemittel vernetzen und aushärten wird, mit einer Geschwindigkeit, die höher als die Geschwindigkeit ist, mit der die Explosivstoffzusammensetzung brennen wird.
  2. Zusammensetzung nach Anspruch 1, worin die Zusammensetzung von 30 bis etwa 65 Gew.-% des Explosivstoffs enthält und das Bindemittelsystem von etwa 20 bis etwa 60 Gew.-% der Zusammensetzung umfaßt.
  3. Zusammensetzung nach Anspruch 1 oder 2, worin der Explosivstoff aus Pentaerithritoltetranitrat oder Cyclotrimethylentrinitramin ausgewählt ist.
  4. Zusammensetzung nach einem der vorhergehenden Ansprüche, worin das Flammverzögerungsmaterial aus Zinkborat oder Borsäure ausgewählt ist.
  5. Zusammensetzung nach einem der vorhergehenden Ansprüche, welche ein Vernetzungsaktivierungsmittel für das fluorierte Elastomer umfaßt.
  6. Zündempfindliche flexible Explosivstoffzusammensetzung mit verringerter Entflammbarkeit, umfassend von etwa 30 bis etwa 65 Gew.-% eines fein zerteilten zündempfindlichen Explosivstoffs und von etwa 10 bis etwa 30 Gew.-% kompatiblen Flammverzögerungsmaterials, gemischt mit einemunvernetzten Fluorelastomerbindemittel, wobei das Bindemittel bei Umgebungstemperatur unvernetzt bleibt, aber in der Lage ist wenn es durch intensive Hitze von einer Zündquelle aktiviert wird, zu vernetzen und auszuhärten, mit einer Geschwindigkeit, die höher als die Geschwindigkeit ist, mit der die Explosivstoffzusammensetzung brennen wird.
  7. Zusammensetzung nach Anspruch 6, in der Form eines Blatts.
  8. Zusammensetzung nach Anspruch 6, worin der Explosivstoff Pentaerithritoltetranitrat ist, das Flammverzögerungsmaterial Zinkborat ist und das Flourelastomer Hexafluorpropylen/Vinylidenfluorid ist.
  9. Zusammensetzung nach Anspruch 8, worin das Explsivstoffmaterial in einer Menge von etwa 40 bis etwa 50 Gew.-% und das Flammverzögerungsmaterial in einer Menge von etwa 10 bis etwa 20 Gew.-% vorliegt.
  10. Zusammensetzung nach Anspruch 8 in der Form eines Blatts.
  11. Zusammensetzung nach Anspruch 1, worin das Flammverzögerungsmaterial ein Gemisch von Phosphatestern umfaßt.
  12. Zusammensetzung nach Anspruch 6, worin der Explosivstoff Cyclotrimethylentrinitramin, das Flammverzögerungsmaterial Borsäure und das Flourelastomer Hexafluorpropylen/vinylidenfluorid ist.
  13. Zusammensetzung nach Anspruch 6, worin der Explosivstoff Cyclotrimethylentrinitramin, das Flammverzögerungsmaterial Zinkborat und das Flourelastomer Hexafluorpropylen/vinylidenfluorid ist.
  14. Zusammensetzung nach Anspruch 1, worin das Flammverzögerungsmaterial ein Gemisch von Borsäure und Phosphatestern umfaßt.
  15. Zusammensetzung nach Anspruch 1, worin das Flammverzögerungsmaterial ein Gemisch von Zinkborat und Phosphatestern umfaßt.
EP91916507A 1991-08-27 1991-08-27 Schwer entzuendliche zuendempfindliche flexible sprengstoffzusammensetzung Expired - Lifetime EP0593479B1 (de)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1991/005901 WO1993004020A1 (en) 1991-08-27 1991-08-27 Low flammability cap-sensitive flexible explosive composition

Publications (2)

Publication Number Publication Date
EP0593479A1 EP0593479A1 (de) 1994-04-27
EP0593479B1 true EP0593479B1 (de) 1996-09-18

Family

ID=22225749

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91916507A Expired - Lifetime EP0593479B1 (de) 1991-08-27 1991-08-27 Schwer entzuendliche zuendempfindliche flexible sprengstoffzusammensetzung

Country Status (5)

Country Link
EP (1) EP0593479B1 (de)
CZ (1) CZ285383B6 (de)
DE (1) DE69122270T2 (de)
SK (1) SK22694A3 (de)
WO (2) WO1993004020A1 (de)

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1239968B (de) * 1963-03-14 1967-05-03 Delet Selbsttragende Sprengstoffmasse mit viskos-elastischem Bindemittel, sowie Verfahren zu deren Herstellung
US4098625A (en) * 1968-05-08 1978-07-04 The United States Of America As Represented By The Secretary Of The Navy Explosive compositions bonded with fluorocarbon polymers
US4355126A (en) * 1974-12-06 1982-10-19 General Electric Company Flame retardant, non-dripping compositions of polyphenylene ether and acrylonitrile-butadiene-styrene
DE2632741B2 (de) * 1976-07-21 1979-05-03 Hoechst Ag, 6000 Frankfurt Gummimischung und daraus hergestellte, gewebeverstärkte Formkörper
US4861397A (en) * 1988-03-09 1989-08-29 The United States Of America As Represented By The Secretary Of The Army Fire-resistant explosives
JPH075422B2 (ja) * 1989-05-02 1995-01-25 防衛庁技術研究本部長 難燃性爆薬組成物
DE3925791A1 (de) * 1989-08-04 1991-02-07 Bayer Ag Flammgeschuetzte, nicht tropfende polyamidformmassen

Also Published As

Publication number Publication date
DE69122270D1 (de) 1996-10-24
EP0593479A1 (de) 1994-04-27
WO1993004020A1 (en) 1993-03-04
SK22694A3 (en) 1994-11-09
CZ285383B6 (cs) 1999-07-14
DE69122270T2 (de) 1997-01-30
CZ41894A3 (en) 1994-12-15
WO1993004021A1 (en) 1993-03-04

Similar Documents

Publication Publication Date Title
EP2552860B1 (de) Nicht toxische, schwermetallfreie, sensibilisierte und explosive perkussionszünder und verfahren zu ihrer herstellung
US4861397A (en) Fire-resistant explosives
Elbeih et al. Effect of different polymeric matrices on some properties of plastic bonded explosives
Steinhauser et al. Using the chemistry of fireworks to engage students in learning basic chemical principles: a lesson in eco-friendly pyrotechnics
JPS60219249A (ja) ポリ塩化ビニル樹脂混和物
DE69513251T2 (de) Nichtgiftige Materialien enthaltende, schlagempfindliche Zündmittelzusammensetzung und deren Verwendung für Perkussionszündsatzpatronen
US8277584B2 (en) Extremely insensitive detonating substance and method for its manufacture
US20020137875A1 (en) Fire suppressing gas generator composition
US5080735A (en) Low flammability cap-sensitive flexible explosive composition
CN105601457B (zh) 一种etn‑dnt低共熔含能材料及其制备方法
EP0593479B1 (de) Schwer entzuendliche zuendempfindliche flexible sprengstoffzusammensetzung
RU2616943C1 (ru) Автономное средство пожаротушения
JPH02293388A (ja) 難燃性爆薬組成物
IL100230A (en) Low flammability flexible explosive composition
US4952341A (en) Mechanical enhancement of the burning rate of solid propellants by means of shrink tubes or spheres
IE913258A1 (en) Low flammability cap-sensitive flexible explosive¹composition
RU2214848C1 (ru) Аэрозольгенерирующий энергетический полимерный композит для систем объемного пожаротушения
US3325317A (en) Lead azide-elastomer explosives in film and sheet form
PT98940B (pt) Processo para a preparacao de composicoes explosivas flexiveis sensiveis e capsulas, de reduzida inflamabilidade, contendo um elastomero fluorado ou uma mistura de elastomeros fluorados
EP1440958B1 (de) Nicht-toxische, bleifreie Zündmittelzusammensetzung
Zecheru Biopolymers for military use: opportunities and environment implications-a review
KR20230086246A (ko) 벌크폭약의 전폭약용 에멀젼 폭약 조성물
JP2634285B2 (ja) 放射性物質取扱所の被覆材用非灰分性樹脂組成物
RU2291141C1 (ru) Замедлительный пиротехнический состав (варианты)
Wilkinson Evaluation of novel propellants manufactured from commercially available Thermoplastic Elastomers (TPE) using resonant acoustic mixing

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19940218

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): DE FR GB

RIN1 Information on inventor provided before grant (corrected)

Inventor name: WAGNER, MARTIN GERALD

17Q First examination report despatched

Effective date: 19950123

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: THE ENSIGN BICKFORD COMPANY

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE FR GB

ET Fr: translation filed
REF Corresponds to:

Ref document number: 69122270

Country of ref document: DE

Date of ref document: 19961024

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

REG Reference to a national code

Ref country code: FR

Ref legal event code: TP

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20050817

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20050930

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20060825

Year of fee payment: 16

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070301

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20070430

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20070827

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20060831

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070827