EP3212594B1 - Effizientes pyrotechnisches verbundprodukt ohne blei in der zusammensetzung und herstellung davon - Google Patents

Effizientes pyrotechnisches verbundprodukt ohne blei in der zusammensetzung und herstellung davon Download PDF

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Publication number
EP3212594B1
EP3212594B1 EP15808698.3A EP15808698A EP3212594B1 EP 3212594 B1 EP3212594 B1 EP 3212594B1 EP 15808698 A EP15808698 A EP 15808698A EP 3212594 B1 EP3212594 B1 EP 3212594B1
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EP
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Prior art keywords
energetic
composite pyrotechnic
charges
polymer
pyrotechnic product
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EP15808698.3A
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English (en)
French (fr)
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EP3212594A1 (de
Inventor
Fabienne Morin
Martine GOLFIER
Caroline CARAYON
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ArianeGroup SAS
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ArianeGroup SAS
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Priority to PL15808698T priority Critical patent/PL3212594T3/pl
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    • 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
    • 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
    • C06B23/007—Ballistic modifiers, burning rate catalysts, burning rate depressing agents, e.g. for gas generating

Definitions

  • the present invention relates to composite pyrotechnic products, particularly suitable as solid propellants for rocket engine propellant charges. It is more precisely composite pyrotechnic products, containing a high rate of organic energy charges in an energy binder. Said products are particularly interesting in that their composition does not contain lead, in that they are efficient, particularly in terms of the rate of combustion, and in that the pot life (see definition below) of their mixture precursor (before crosslinking) is high (their obtaining on an industrial scale is greatly facilitated).
  • the patent application FR 2 727 401 thus describes the use of bismuth salts, such as bismuth ⁇ -resorcylates, bismuth ⁇ -resorylate, bismuth salicylate, bismuth citrate, bismuth stearate, and bismuth oxide, as combustion catalyst for double base solid propellants (nitrocellulose and at least one nitric ester such as nitroglycerine) or composite double base (fillers in an energetic binder based on a nitric ester).
  • bismuth salts such as bismuth ⁇ -resorcylates, bismuth ⁇ -resorylate, bismuth salicylate, bismuth citrate, bismuth stearate, and bismuth oxide
  • the Applicant proposes a new specific energy-binding composite propellant (comprising a specific energy polymer (PAG) crosslinked with at least one polyisocyanate), containing a specific combustion catalyst (bismuth citrate) in its composition.
  • This new composite propellant whose composition does not contain lead, is energy efficient (it has a particular high speed of combustion) and its preparation process is particularly interesting.
  • the energy binder is associated with at least one energetic plasticizer.
  • the energy plasticizer (s) in question is (are) advantageously of the nitrate and / or nitramine type.
  • the energy plasticizer (s) in question is (are) very advantageously selected from diethylene glycol dinitrate (DEGDN), triethylene glycol dinitrate (TEGDN), butanetriol trinitrate (BTTN) trimethylolethane trinitrate (TMETN), a mixture of 2,4-dinitro-2,4-diaza-pentane, 2,4-dinitro-2,4-diaza-hexane and 3,5-dinitro-3, 5-diaza-heptane (and especially DNDA 5.7), nitrate ethyl nitramines (especially methyl-2-nitratoethyl nitramine (methylNENA) and ethyl-2-nitratoethyl nitramine (ethylNENA))
  • Bismuth citrate (the combustion catalyst) is generally present in the composition of the pyrotechnic products of the invention at a mass ratio of 1 to 6%, very generally at a mass ratio of 3 to 5%.
  • the composite pyrotechnic products of the invention are also likely to contain, and generally contain in their binder (crosslinked precursor polymer), besides the plasticizer (s), organic energy charges and combustion catalyst (specific), at least one additive . It is more apt to speak of at least one other additive, combustion catalysts generally constituting additives.
  • the combustion catalysts have now been isolated from the other additives insofar as they are at the basis of the technical problem currently considered and where the combustion catalyst (specific) retained constitutes a key element of the products of the invention.
  • This method may be considered as a method by analogy, but, typically, by the specific nature of the (precursor polymer of) binder and the specific nature of the combustion catalyst, its first steps are carried out at temperatures (advantageously a temperature) between 35 and 55 ° C (35 ° C ⁇ T (s) ⁇ 55 ° C) , (without cooling), without pot life problem (said polymer).
  • compositions of these propellants are presented in Table 1 below.
  • each of the prepared propellant pastes was then poured into a suitable structure and then subjected to the following heat treatment: baking for 75 hours at a temperature of 50 ° C.

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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)
  • Adhesives Or Adhesive Processes (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (9)

  1. Pyrotechnisches Verbundprodukt, das in einem plastifizierten Bindemittel, das ein vernetztes energetisches Polymer und mindestens einen energetischen Plastifizierer umfasst, organische energetische Ladungen und einen Verbrennungskatalysator enthält, dadurch gekennzeichnet, dass:
    - das vernetzte energetische Polymer aus einem Glycidylpolyazid (PAG) besteht, das ein zahlenmittleres Molekulargewicht (Mn) zwischen 700 und 3000 g/mol aufweist und über seine Hydroxylendgruppen mit mindestens einem Vernetzungsmittel vom Typ Polyisocyanat vernetzt ist, und
    - der Verbrennungskatalysator aus Wismutzitrat besteht.
  2. Pyrotechnisches Verbundprodukt gemäß Anspruch 1, dadurch gekennzeichnet, dass das Glycidylpolyazid (PAG) ein zahlenmittleres Molekulargewicht (Mn) zwischen 1700 und 2300 g/mol aufweist.
  3. Pyrotechnisches Verbundprodukt gemäß Anspruch 1 oder 2, dadurch gekennzeichnet, dass der mindestens eine energetische Plastifizierer vom Typ Nitrat und/oder Nitramin ist.
  4. Pyrotechnisches Verbundprodukt gemäß einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass die organischen energetischen Ladungen ausgewählt sind aus Ladungen von Hexogen, Octogen, Hexanitrohexaazaisowurtzitan, Nitroguanidin, Ethylendinitramin, N-Guanylharnstoffdinitramid, 1,1-Diamino-2,2-dinitroethylen, Bis(triaminoguanidinium)-5,5'-azotetrazolat, Dihydrazinium-5,5'-azotetrazolat, 5,5'-Bis(tetrazolyl)hydrazin, Bis(2,2-dinitropropyl)nitramin, einem Nitropyrazol und Mischungen dieser Ladungen.
  5. Pyrotechnisches Verbundprodukt gemäß einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass es 1 bis 6 Masse-%, vorzugsweise 3 bis 5 Masse-% des Wismutzitrats enthält.
  6. Pyrotechnisches Verbundprodukt gemäß einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass es ferner mindestens einen Zusatzstoff enthält.
  7. Pyrotechnisches Verbundprodukt gemäß Anspruch 6, dadurch gekennzeichnet, dass der mindestens eine Zusatzstoff mindestens einen Vernetzungskatalysator und/oder mindestens ein Stabilisierungsmittel für den mindestens einen energetischen Plastifizierer umfasst.
  8. Pyrotechnisches Verbundprodukt gemäß einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass seine Zusammensetzung, ausgedrückt in Massenprozenten, enthält:
    - 50 bis 70 %, vorzugsweise 55 bis 65 %, der organischen energetischen Ladungen,
    - 10 bis 14 % des vernetzten energetischen Polymers,
    - 10 bis 30 %, vorzugsweise 15 bis 25 %, des mindestens einen energetischen Plastifizierers,
    - 1 bis 6 %, vorzugsweise 3 bis 5 %, des Wismutzitrats und
    - 0 bis 4 %, vorzugsweise 0,1 bis 4 %, des Zusatzstoffes.
  9. Verfahren zur Herstellung eines pyrotechnischen Verbundprodukts gemäß einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass es umfasst:
    - Bilden einer homogenen Paste durch
    a) Einarbeiten des mindestens einen energetischen Plastifizierers, der organischen energetischen Ladungen und der anderen Bestandteile des gewünschten pyrotechnischen Verbundprodukts bei einer Temperatur zwischen 35 und 55 °C in das Glycidylpolyazid, mit Ausnahme jeglicher Vernetzungsmittel und jeglicher Vernetzungskatalysatoren, und
    (b) Rühren des resultierenden Gemisches unter Teilvakuum bei einer Temperatur zwischen 35 und 55 °C,
    - Einarbeiten des mindestens einen Vernetzungsmittels und gegebenenfalls mindestens eines Vernetzungskatalysators in die homogene Paste unter Teilvakuum bei einer Temperatur zwischen 35 und 55 °C, und anschließendes Rühren der gebildeten Mischung,
    - Gießen der gerührten gebildeten Mischung in mindestens eine Struktur und
    - Wärmebehandeln der in die mindestens eine Struktur gegossenen gerührten gebildeten Mischung.
EP15808698.3A 2014-10-28 2015-10-27 Effizientes pyrotechnisches verbundprodukt ohne blei in der zusammensetzung und herstellung davon Active EP3212594B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL15808698T PL3212594T3 (pl) 2014-10-28 2015-10-27 Kompozytowy wyrób pirotechniczny o dużej efektywności, niezawierający w swojej kompozycji ołowiu i sposób jego wytwarzania

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1402431A FR3027597B1 (fr) 2014-10-28 2014-10-28 Produit pyrotechnique composite performant sans pb dans sa composition et sa preparation
PCT/FR2015/052888 WO2016066945A1 (fr) 2014-10-28 2015-10-27 PRODUIT PYROTECHNIQUE COMPOSITE PERFORMANT SANS Pb DANS SA COMPOSITION ET SA PREPARATION

Publications (2)

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EP3212594A1 EP3212594A1 (de) 2017-09-06
EP3212594B1 true EP3212594B1 (de) 2018-07-18

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EP15808698.3A Active EP3212594B1 (de) 2014-10-28 2015-10-27 Effizientes pyrotechnisches verbundprodukt ohne blei in der zusammensetzung und herstellung davon

Country Status (8)

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US (1) US20180290945A1 (de)
EP (1) EP3212594B1 (de)
JP (1) JP6510640B2 (de)
KR (1) KR102621576B1 (de)
FR (1) FR3027597B1 (de)
IL (1) IL251766B (de)
PL (1) PL3212594T3 (de)
WO (1) WO2016066945A1 (de)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3056583B1 (fr) * 2016-09-26 2018-10-19 Airbus Safran Launchers Sas Produit pyrotechnique composite renfermant un agent anti-lueur de type sel de potassium
FR3090629B1 (fr) * 2018-12-20 2021-07-23 Arianegroup Sas Procédé de préparation de produits pyrotechniques composites
FR3096680B1 (fr) 2019-06-03 2021-09-24 Arianegroup Sas produit pyrotechnique composite
CN112500253B (zh) * 2020-12-02 2022-04-12 湖北航天化学技术研究所 一种温敏时变高能固体推进剂

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FR2648809B1 (fr) * 1989-06-21 1991-09-13 Livbag Snc Composition solide generatrice de gaz et son utilisation dans les generateurs de gaz pour coussins gonflables destines a proteger les passagers d'un vehicule automobile
JPH075425B2 (ja) * 1989-10-06 1995-01-25 防衛庁技術研究本部長 ガス発生組成物
JPH07165483A (ja) * 1993-12-13 1995-06-27 Daicel Chem Ind Ltd ガス発生剤組成物
FR2727401B1 (fr) * 1994-11-29 1996-12-27 Poudres & Explosifs Ste Nale Compositions modificatrices de proprietes balistiques et propergols contenant de telles compositions
US6168677B1 (en) * 1999-09-02 2001-01-02 The United States Of America As Represented By The Secretary Of The Army Minimum signature isocyanate cured propellants containing bismuth compounds as ballistic modifiers
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CA2351002C (en) * 2000-06-27 2009-04-07 The Minister Of National Defence Insensitive melt cast explosive compositions containing energetic thermoplastic elastomers
EP1186582A1 (de) * 2000-09-08 2002-03-13 Her Majesty in Right of Canada, as represented by the Minister of National Defence Nichtempfindliche Treibsatzzusammensetzungen, welche energetische thermoplastische Elastomere auf Basis von Copolyuerethanen enthalten
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GB2512346B (en) * 2013-03-27 2021-06-30 Bae Systems Plc Non-phthalate propellants

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Also Published As

Publication number Publication date
IL251766A0 (en) 2017-06-29
FR3027597B1 (fr) 2016-12-09
FR3027597A1 (fr) 2016-04-29
KR102621576B1 (ko) 2024-01-05
JP6510640B2 (ja) 2019-05-08
EP3212594A1 (de) 2017-09-06
US20180290945A1 (en) 2018-10-11
KR20170101897A (ko) 2017-09-06
JP2017538648A (ja) 2017-12-28
IL251766B (en) 2020-04-30
WO2016066945A1 (fr) 2016-05-06
PL3212594T3 (pl) 2019-01-31

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