EP0072276A1 - Giessbare pyrotechnische Rauchzusammensetzung mit gefärbter oder nicht gefärbter Flamme, die ein Chloriertes Bindmittel enthält - Google Patents

Giessbare pyrotechnische Rauchzusammensetzung mit gefärbter oder nicht gefärbter Flamme, die ein Chloriertes Bindmittel enthält Download PDF

Info

Publication number
EP0072276A1
EP0072276A1 EP82401344A EP82401344A EP0072276A1 EP 0072276 A1 EP0072276 A1 EP 0072276A1 EP 82401344 A EP82401344 A EP 82401344A EP 82401344 A EP82401344 A EP 82401344A EP 0072276 A1 EP0072276 A1 EP 0072276A1
Authority
EP
European Patent Office
Prior art keywords
chlorinated
binder
mass
pyrotechnic composition
composition according
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.)
Granted
Application number
EP82401344A
Other languages
English (en)
French (fr)
Other versions
EP0072276B1 (de
Inventor
Georges Sedat
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.)
Direction General pour lArmement DGA
Etat Francais
Original Assignee
Direction General pour lArmement DGA
Etat Francais
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 Direction General pour lArmement DGA, Etat Francais filed Critical Direction General pour lArmement DGA
Publication of EP0072276A1 publication Critical patent/EP0072276A1/de
Application granted granted Critical
Publication of EP0072276B1 publication Critical patent/EP0072276B1/de
Expired 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
    • 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
    • C06D—MEANS FOR GENERATING SMOKE OR MIST; GAS-ATTACK COMPOSITIONS; GENERATION OF GAS FOR BLASTING OR PROPULSION (CHEMICAL PART)
    • C06D3/00—Generation of smoke or mist (chemical part)
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S149/00—Explosive and thermic compositions or charges
    • Y10S149/116—Flare contains resin
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S149/00—Explosive and thermic compositions or charges
    • Y10S149/117—Smoke or weather composition contains resin

Definitions

  • the technical sector of the present invention is that of flowable pyrotechnic compositions of the smoke smoke type with or without a colored flame.
  • the binder is a resin with a high chlorine content.
  • white smoke or colored flame pyrotechnic compositions are mixtures of pulverulent constituents or dry granules, consolidated by compression at high pressure, with a small proportion of agglomerating binder.
  • a chlorine-donating substance generally a chlorinated organic compound, with a high chlorine content, the role of which is to allow the abundant formation of sublimable metal chlorides intended to produce either white (or gray) smoke or a flame color.
  • compositions of this type in which the chlorine donor consists of hexachloroethane; a low percentage plastic binder of less than 10% ensures the cohesion of the whole.
  • Compositions of this type present risks of fragmentation of the charge by impact during their use.
  • their permeability to humidity changes their characteristics and makes them unsuitable for proper operation.
  • French patent 2 153 431 has also proposed a pyrotechnic composition containing polyvinyl chloride and optionally an additional chlorine donor consisting of a salt of the ammonium chloride type.
  • the polyvinyl chloride must be dissolved in a plasticizer, but in this case, the acceptable proportion of plasticizer can hardly exceed 15% by mass of the total of the composition. Beyond this value, the plasticizer acts as an excessive diluent and the performance of the composition is: all the more reduced.
  • the plasticizer being the only liquid constituent of the composition, its low percentage makes problematic the mixing and the flowability of this composition.
  • the binder obtained is relatively poor in halogen 30% of the total binder and 10% of the composition) whereas the optimal yield of the composition requires about 30% by mass of the composi-Lion of which 12 to 13% come from the oxidizing perchlorate (ammonium perchlorate), the rest to be supplied by the binder.
  • the "setting" of this binder requires a "baking" due several hours at 150 ° C, too high a temperature for a pyrotechnic composition whose reaction begins to manifest from about 200 ° C. The risk in manufacturing is therefore significant.
  • the object of the present invention is to provide a new smoke-producing pyrotechnic composition and a new improved pyrotechnic composition with a colored flame, the operating temperature of which can be adapted as required from 350 ° C. to 500 ° C. to produce smoke with a combustion without flame, up to around 1000 ° C or more to produce combustions with colored flame.
  • Another object of the present invention is also to provide a new smoke or colored flame pyrotechnic composition which can be easily kneaded and poured (or extruded) at ordinary temperature or close to 0 ° C., to obtain by the polymerization of a resin , a load of great compactness and great structural cohesion in order to avoid its fragmentation by shocks or vibrations.
  • Another object of the invention is also to provide a pyrotechnic composition free from any solvent, which would adversely affect the conservation of its properties by modifying its pyrotechnic behavior in an undesirable manner over time, and capable of being cast in various forms and in all capabilities.
  • Another object of the invention is also to provide a pyrotechnic composition in which the binder constitutes, in addition to its role of charge consolidator and regulator of combustion rate, an abundant chlorine donor necessary for obtaining the desired effects , this halogen being able to constitute from 30% to at least up to 70% by mass of the binder.
  • Another object of the invention is also to provide a pyrotechnic composition, the binder of which can be hardened by polymerization at ordinary temperature or at a moderately high temperature not exceeding 80 ° C. maximum.
  • the subject of the invention is therefore a flowable pyrotechnic composition
  • a flowable pyrotechnic composition comprising in particular an oxide-reducing couple and a chlorinated binder, characterized in that the binder is constituted by the combination of a polymerizable chlorinated monomer and a chlorinated polymer copolymerized or not , the resulting mixture being subjected to polymerization at moderate temperature, said binder then containing approximately 30 to 70% by mass of chlorine.
  • the monomer may be a chlorine alkylene, the number of carbon atoms of which is between 2 and 5, the chlorinated polymer being of the perchlorinated type.
  • the chlorinated alklylene can be dichloro - 1,1 - ethylene, and the chlorinated polymer polypropylene, polyethylene perchlorinated.
  • the binder can comprise 50 to 80% by mass of chlorinated monomer, the rest being constituted by the chlorinated polymer.
  • the binder can comprise approximately 70% of chlorinated monomer and 30% of chlorinated polymer.
  • the binder can also comprise approximately 50 to 60% by mass of chlorinated monomer, 20 to 25% by mass of chlorinated polymer and 15 to 20% by mass of another monomer such as allyldiglycol carbonate.
  • the binder may further comprise a hardener of the organic peroxide type in a proportion of approximately 3 to 4% of the total mass of binder.
  • the pyrotechnic composition can comprise approximately 30 to 35% by mass of zinc oxide, 25 to 35% by mass of ammonium perchlorate and 30 to 40% by mass of binder.
  • the pyrotechnic composition may comprise approximately 40 to 60% of nitrate or ammonium perchlorate of strontium or barium, 10 to 20% by mass of a thermogenic agent chosen from the group consisting of magnesium, boron, calcium disilicide, 30 to 40% the mass of binder.
  • the pyrotechnic compositions according to the invention may comprise a plasticizer chosen for example from the family of phthalic esters, in small proportion.
  • the combination of a chlorinated polymer belonging to the family known as chlorinated rubbers surprisingly produces a binder or resin usable in pyrotechnic compositions, whose mechanical resistance is considerably improved and makes it capable of consolidating a charge and with less shrinkage.
  • the binder must be added in sufficient quantity.
  • Dichloro 1,1 - ethylene with vinylidene chloride is a very mobile liquid with a low boiling point (31.6 ° C at normal pressure). Used as it is, it is not very capable of allowing a flowable composition to be obtained because its viscosity is practically zero and therefore. does not act as a lubricant for solid particles during con composition.
  • the mass polymerization of the monomer alone gives a friable and cracked polymer as a result of significant shrinkage and of which. the properties are very bad and make this product capable of playing a role of consolidating charge, at least if the polymerization is carried out at atmospheric pressure.
  • the desired viscosity is then obtained by dissolving in the monomer the chlorinated soluble polymer such as polypropylene, polyethylene, perchlorinated, more generally a compound of the family of "chlorinated rubbers".
  • the mixture of vinylidene chloride and perchlorinated polymer is produced in the preferred proportion of 70% by mass of monomer and 30% of polymer.
  • the hardening is obtained by dissolving in the resin a suitable proportion, 3 to 4% approximately, of a hardener of the family of organic peroxides, such as benzoyl peroxide or better, isopropyl or butyl percarbonate -cychohexyl.
  • a hardener of the family of organic peroxides such as benzoyl peroxide or better, isopropyl or butyl percarbonate -cychohexyl.
  • the constituents of the pyrotechnic charge such as nitrates, perchlorates, metal oxides, powdered metal, are incorporated into the liquid resin at a temperature below 20 ° C, if possible close to 10 ° C, the whole being kneaded for a few moments and then poured into molds.
  • the curing of the composition is carried out at ordinary temperature, around 20 to 25 ° C, in a closed envelope or under a protective liquid layer in order to avoid significant losses of monomer by evaporation.
  • a solid and compact pyrotechnic composition is thus obtained, the binder of which is a resin with a high chlorine content, containing approximately 70% of this halogen.
  • the binder thus obtained can be modified in its composition in various ways depending on the desired effect.
  • a modification of the resin may be desired in order to increase the consolidation and to regulate the rate of combustion of the composition.
  • This modification can consist in adding to the resin before hardening another conventional resin compatible with it, to obtain a copolymerization.
  • a low viscosity liquid monomer such as allyldiglycol carbonate.
  • the monomer is perfectly soluble and compatible with the chlorinated resin and hardens with the same catalyst.
  • the desired proportion of this monomer was 15 to 20% by mass of the total resin, but may vary beyond these limits.
  • the polymerization is carried out under the same conditions at the same temperature. However, it may be desired to improve the hardening by terminating the polymerization phase at a significantly higher temperature, from 30 to 80 ° C. for a period of 2 to 4 hours.
  • a plasticizer from the family of substituted phthalic esters compatible with the resin, in particular butyl glycol phthalate compatible with chlorinated rubbers
  • the modified resin has the preferred composition as follows:
  • the catalyst is added to the vinylidene dichloride at a temperature between 0 ° C and 10 ° C with gentle stirring.
  • the dissolution is immediate.
  • the chlorinated polymer is then added with stirring. Dissolution is rapid at first and then becomes slightly slower as the viscosity of the solution increases.
  • the second monomer is optionally added with stirring. The dissolution is practically immediate.
  • This resin can thus be stored ready for use for several weeks at a temperature below 0 ° C, or for a few days at a temperature between 0 ° C and 10 ° C.
  • the chlorine content of this resin is approximately 56% by mass, the equivalent of pure polyvinyl chloride.
  • the solid constituents nitrates, perchlorates, oxides are previously ground and sieved to 0.2 mm and are cooled to 0 ° C with the powdered metal which must be used if necessary.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Molecular Biology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Botany (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
EP82401344A 1981-08-10 1982-07-20 Giessbare pyrotechnische Rauchzusammensetzung mit gefärbter oder nicht gefärbter Flamme, die ein Chloriertes Bindmittel enthält Expired EP0072276B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8115468A FR2510987A1 (fr) 1981-08-10 1981-08-10 Composition pyrotechnique coulable du type fumigene a flamme coloree ou non comprenant un liant chlore
FR8115468 1981-08-10

Publications (2)

Publication Number Publication Date
EP0072276A1 true EP0072276A1 (de) 1983-02-16
EP0072276B1 EP0072276B1 (de) 1984-11-28

Family

ID=9261333

Family Applications (1)

Application Number Title Priority Date Filing Date
EP82401344A Expired EP0072276B1 (de) 1981-08-10 1982-07-20 Giessbare pyrotechnische Rauchzusammensetzung mit gefärbter oder nicht gefärbter Flamme, die ein Chloriertes Bindmittel enthält

Country Status (6)

Country Link
US (1) US4447278A (de)
EP (1) EP0072276B1 (de)
AU (1) AU550775B2 (de)
CA (1) CA1187705A (de)
DE (1) DE3261373D1 (de)
FR (1) FR2510987A1 (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2134097A (en) * 1982-12-11 1984-08-08 Diehl Gmbh & Co Incendiary agent composition
FR3049598A1 (fr) * 2016-04-04 2017-10-06 Nexter Munitions Composition fumigene efficace dans les domaines visible et infrarouge

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SE8703743L (sv) * 1987-09-29 1989-03-30 Bofors Ab Pyroteknisk foerdroejningssats
US5565645A (en) * 1995-04-24 1996-10-15 Thiokol Corporation High-intensity infrared decoy flare
US5886293A (en) * 1998-02-25 1999-03-23 The United States Of America As Represented By The Secretary Of The Navy Preparation of magnesium-fluoropolymer pyrotechnic material
DE102009049003A1 (de) * 2009-10-09 2011-06-16 Rheinmetall Waffe Munition Gmbh Kunststoffgebundene pyrotechnische Mischung zur Erzeugung von Alkalimetallchlorid- bzw. Erdalkalimetallchlorid-Aerosolen als Tarnnebel

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1078608A (fr) * 1953-04-02 1954-11-19 France Etat Compositions fumigènes
FR2153431A1 (de) * 1971-09-23 1973-05-04 Ensign Bickford Co
FR2249590A5 (en) * 1972-11-02 1975-05-23 France Etat Smoke generating compsn. contg. PVC binder - hexachloroethane and zinc oxide, for camouflage operations
DE2451701A1 (de) * 1974-10-31 1976-05-06 Feistel Pyrotech Fab Rauch- oder nebelsatz und verfahren zu seiner herstellung
FR2351378A1 (fr) * 1976-05-10 1977-12-09 France Etat Artifice de signalisation de fonctionnement d'une mine d'exercice
FR2403984A1 (fr) * 1977-09-27 1979-04-20 Nico Pyrotechnik Charge fumigene et son procede de preparation

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3246053A (en) * 1958-01-29 1966-04-12 Exxon Research Engineering Co Slurry casting process for solid rocket propellants
US3520742A (en) * 1962-12-31 1970-07-14 Aerojet General Co Encapsulation of particulate nitronium oxidizer salts with polymerization of ethylenically unsaturated monomers
US3728172A (en) * 1970-12-15 1973-04-17 Thiokol Chemical Corp Product and process for producing a container cured illuminant composition
US3761329A (en) * 1971-09-23 1973-09-25 Ensign Bickford Co Color flare including polyvinyl chloride color intensifier

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1078608A (fr) * 1953-04-02 1954-11-19 France Etat Compositions fumigènes
FR2153431A1 (de) * 1971-09-23 1973-05-04 Ensign Bickford Co
FR2249590A5 (en) * 1972-11-02 1975-05-23 France Etat Smoke generating compsn. contg. PVC binder - hexachloroethane and zinc oxide, for camouflage operations
DE2451701A1 (de) * 1974-10-31 1976-05-06 Feistel Pyrotech Fab Rauch- oder nebelsatz und verfahren zu seiner herstellung
FR2351378A1 (fr) * 1976-05-10 1977-12-09 France Etat Artifice de signalisation de fonctionnement d'une mine d'exercice
FR2403984A1 (fr) * 1977-09-27 1979-04-20 Nico Pyrotechnik Charge fumigene et son procede de preparation

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2134097A (en) * 1982-12-11 1984-08-08 Diehl Gmbh & Co Incendiary agent composition
FR3049598A1 (fr) * 2016-04-04 2017-10-06 Nexter Munitions Composition fumigene efficace dans les domaines visible et infrarouge
WO2017174895A1 (fr) * 2016-04-04 2017-10-12 Nexter Munitions Composition fumigène efficace dans les domaines visible et infrarouge
US11414360B2 (en) 2016-04-04 2022-08-16 Nexter Munitions Efficient smoke composition in visible and infrared ranges

Also Published As

Publication number Publication date
EP0072276B1 (de) 1984-11-28
AU550775B2 (en) 1986-04-10
DE3261373D1 (en) 1985-01-10
CA1187705A (fr) 1985-05-28
AU8657482A (en) 1983-02-17
FR2510987B1 (de) 1983-12-23
FR2510987A1 (fr) 1983-02-11
US4447278A (en) 1984-05-08

Similar Documents

Publication Publication Date Title
EP0125166B1 (de) Kalt formbare explosive Zusammensetzung und Verfahren zu ihrer Herstellung
US10125057B2 (en) Use of a solid for the production of a propellant powder
EP3172274B1 (de) Verwendung von monoperoxycarbonat- peroxid gemischen zum vernetzen und zusammensetzungen von vernetzbaren polymeren
EP0072276B1 (de) Giessbare pyrotechnische Rauchzusammensetzung mit gefärbter oder nicht gefärbter Flamme, die ein Chloriertes Bindmittel enthält
FR2714374A1 (fr) Compositions pyrotechniques solides à liant thermoplastique et plastifiant polybutadiène silylferrocénique.
EP1604963A2 (de) Pyrotechnische Zusammensetzung mit verbesserter Festigkeit
WO2016066945A1 (fr) PRODUIT PYROTECHNIQUE COMPOSITE PERFORMANT SANS Pb DANS SA COMPOSITION ET SA PREPARATION
US4445947A (en) Low cost fluorocarbon flare compositions
EP0814069B1 (de) Schmelzbare/giessbare Sprengstoffzusammensetzung mit verminderter Empfindlichkeit
FR2526418A1 (fr) Composition propulsive contenant de la nitrocellulose, de la nitroglycerine, du benzoate de cuivre et du plomb ou ses derives, notamment pour fusees
EP0002418B1 (de) Verfahren zur Herstellung von extrudierten Formteilen auf der Basis von Olefinpolymerisaten
EP3515881B1 (de) Pyrotechnisches verbundprodukt mit einem antiglimmmittel vom kaliumsalztyp
FR2471959A1 (fr) Composition pyrotechnique eclairante coulable comportant une poudre metallique
FR2857359A1 (fr) Composition pyrotechnique generatrice de gaz destinee a la securite automobile et brulant a des temperatures de combustion inferieures a 2200 k
EP1364931B1 (de) Treibladungspulver für Rohrwaffen mit höher Leistung und reduzierter erodierender Wirkung
WO2023156729A1 (fr) Procede d'obtention de pates d'allumage en melangeur a resonance acoustique.
FR2681065A2 (fr) Procede de moulage pour la fabrication d'un bloc de propergol double base a taux eleve de nitramine et bloc de propergol obtenu par ce procede.
BE607150A (de)
EP0013850A2 (de) Körnige Treibstoffe auf der Basis von Nitrocellulose, Nitroöl und Polyvinylnitrat und Verfahren zu deren Herstellung
FR2868774A1 (fr) Composition explosive
EP0032080B1 (de) Gefärbte pyrotechnische Leuchtzusammensetzung mit einem hohen Gehalt einer Ausstrahlungskomponente
FR2680782A1 (fr) Procede de moulage pour la fabrication d'un bloc de propergol double base a taux eleve de nitramine et bloc de propergol obtenu par ce procede.
US1302202A (en) Process for preparing gelatinized propellent explosives.
CA2930488A1 (fr) Produit pyrotechnique composite a liant reticule et son procede de preparation
WO2024062190A1 (fr) Propergol composite a vitesse de combustion reduite

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: 19820810

AK Designated contracting states

Designated state(s): DE GB

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Designated state(s): DE GB

REF Corresponds to:

Ref document number: 3261373

Country of ref document: DE

Date of ref document: 19850110

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

Ref country code: GB

Payment date: 19930709

Year of fee payment: 12

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

Ref country code: DE

Payment date: 19930921

Year of fee payment: 12

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

Ref country code: GB

Effective date: 19940720

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

Effective date: 19940720

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

Ref country code: DE

Effective date: 19950401