EP3656753B1 - Herstellungsverfahren von pyrotechnischen verbunderzeugnissen - Google Patents

Herstellungsverfahren von pyrotechnischen verbunderzeugnissen Download PDF

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Publication number
EP3656753B1
EP3656753B1 EP19211106.0A EP19211106A EP3656753B1 EP 3656753 B1 EP3656753 B1 EP 3656753B1 EP 19211106 A EP19211106 A EP 19211106A EP 3656753 B1 EP3656753 B1 EP 3656753B1
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fillers
type
energetic
cross
advantageously
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French (fr)
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EP3656753A1 (de
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Jérôme LAFARGE
Nancy Desgardin
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ArianeGroup SAS
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ArianeGroup SAS
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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

Definitions

  • the present invention falls within the field of solid propulsion. More specifically, it relates to a process for preparing composite pyrotechnic products (composite solid propellants) and composite pyrotechnic products (composite solid propellants) capable of being obtained by said process. Said composite pyrotechnic products (composite solid propellants) are particularly suitable for the propellant loadings of strategic or tactical missiles.
  • the composite pyrotechnic products in question contain a high rate of energetic charges (of nitramine type) in an energetic binder (comprising an energetic polymer (of the polyglycidyl azide (PAG) type) crosslinked and plasticized with at least one energetic plasticizer.
  • an energetic binder comprising an energetic polymer (of the polyglycidyl azide (PAG) type) crosslinked and plasticized with at least one energetic plasticizer.
  • the process in question is a process by analogy, the products in question are of known type. However, said products retain the signature of their preparation process which involves an original crosslinking system. Despite the substitution of this original crosslinking system for the crosslinking system of the prior art, they exhibit interesting mechanical properties and the thermal protection (PT) / binder / product assemblies also exhibit interesting peel properties (they are sufficiently robust. to respond to firing requests).
  • PT thermal protection
  • EP 0 576 326 discloses a pyrotechnic composition comprising a polyhydroxyl terminated glycidyl azide, at least one polyisocyanate, an energetic plasticizer and an oxidizing filler. It also discloses that the preferred polyisocyanates are a mixture of an aliphatic trimer with an aromatic polymer, showing an average NCO group functionality of 2.7 and an NCO: OH ratio close to 1: 1.
  • CMR substance Carcinogenic, Mutagenic (or genotoxic) and toxic for Reproduction (or reprotoxic)
  • the inventors wished to find a substitute for it; more precisely, they wished to identify an efficient crosslinking system (leading to a composite propellant with suitable properties, with the same constituent ingredients, except therefore the crosslinking system, and this under the same preparation conditions), free of CMR substance.
  • the overall functionality corresponds to the functionality of the crosslinking system consisting of a mixture of polyisocyanates aliphatic.
  • the overall functionality of the crosslinking system is equal to: [(average functionality (di-NCO) * mol number (di-NCO)) / (mol number (di-NCO) + mol number (tri-NCO) )] + [(average functionality (tri-NCO) * mol number (tri-NCO)) / (mol number (di-NCO) + mol number (tri-NCO)].
  • the process in question is a process by analogy which is implemented, in a conventional manner (see the above steps) with the majority of the conventional constituent ingredients of a composite pyrotechnic product of the type sought (see above), except therefore for the crosslinking system.
  • this difference is in no way insignificant with regard to the properties sought for the final product and the bonding properties of said final product.
  • the oligomers of the crosslinking agents of the aliphatic polyisocyanate type of the invention are advantageously homopolymers and / or oligomerization products of the urethdione and / or allophanate type.
  • the crosslinking agents consist of a mixture of aliphatic polyisocyanates, based on the one hand on polyisocyanates without or with urethdione or allophanate structural units having an average functionality greater than 2.1 and less than 3.0, and based, on the other hand, on polyisocyanates having an average functionality greater than 3.0, and preferably greater than 3.0 and less than 4.0.
  • the aliphatic polyisocyanates of the invention advantageously have the same isocyanate unit.
  • said same isocyanate unit is hexamethylene 1,6-diisocyanate (HMDI or HDI) or isophoronediisocyanate (IPDI), and more preferably hexamethylene 1,6-diisocyanate (HMDI or HDI) ).
  • said crosslinking agents consist of a mixture of aliphatic polyisocyanates, based on the one hand on polyisocyanates with units of urethdione or allophanate structure having a functionality of approximately 2.5 and based, on the other hand, on polyisocyanates of homopolymers of hexamethylene 1,6-diisocyanate (HMDI or HDI) having a functionality of about 3.5.
  • HMDI hexamethylene 1,6-diisocyanate
  • the bridging ratio Rp (NCO / OH) of said crosslinking agents corresponds to the ratio by number of isocyanate functions (NCO) and of hydroxy functions (OH) originating from PAG.
  • This bridging ratio Rp (NCO / OH) preferably varies from 1.0 to 1.4, more preferably from 1.1 to 1.3, and even more preferably is equal to 1.2.
  • the overall functionality of said crosslinking system preferably varies from 2.5 to 3.0, and even more preferably from 2.6 to 3.0.
  • the energetic polymer selected as precursor of the binder of the products of the invention is therefore a polyazide, a poly glycidyl azide (PAG) which has terminal hydroxyl functions (a hydroxytelechelic PAG); hence 1) its energetic properties and 2) its ability to be crosslinked with polyisocyanate type crosslinking agents.
  • Said polymer has an adequate molecular weight (in particular, with reference to its consistency (liquid) and to the consistency of its mixture with essentially the fillers and with reference to the relative content of the crosslinked binder in crosslinking agents, number-average molecular weight included between 700 and 3000 g / mol, advantageously between 1700 and 2300 g / mol.
  • the organic energy charges are of the nitramine type. They are advantageously chosen from charges of hexogen (RDX), octogen (HMX), hexanitrohexaazaisowurtzitane (CL 20), and mixtures thereof. Very advantageously they consist of hexogen charges (RDX).
  • the at least one energetic plasticizer very advantageously consists of a mixture of butanetriol trinitrate (BTTN) and trimethylolethane trinitrate (TMETN).
  • Said at least one stabilizer of said at least one energy plasticizer is generally chosen from aromatic amines, epoxidized fatty acid esters and mixtures thereof. It is advantageously chosen from 2-nitrodiphenylamine (2-NDPA), N-methylparanitroaniline (MNA) and their mixtures.
  • oxidizing charges can in particular consist of potassium perchlorate charges.
  • fillers can be present, in the absence of reducing fillers, at a low content. More generally, they are present with reducing fillers, such as aluminum fillers.
  • At least one additive can in particular be chosen from crosslinking catalysts, ballistic catalysts, processing aids, anti-glare and binder / fillers binding agents. Such additives conventionally enter into the composition of propellants.
  • a second subject of the invention relates to a composite pyrotechnic product containing organic energetic charges of nitramine type in a plasticized binder, said plasticized binder comprising at least one polyazide of glycidyl with terminal hydroxyl functions, the number-average molecular mass of which is between 700 and 3000 g / mol, crosslinked via its hydroxyl functions by aliphatic polyisocyanates, at least one energetic plasticizer and at least one stabilizer of said at least one energetic plasticizer, capable of being obtained by the preparation process of the invention.
  • the binder crosslinking system (“diisocyanate” + “triisocyanate”) (see the tested crosslinking systems described below) was then added to said homogeneous paste according to the protocol described below.
  • the "diisocyanate” was introduced first, then left stirring for 10 minutes at 40 ° C, then the “triisocyanate” was then added, stirring the medium for 20 minutes.
  • a sample of each of the propellant pastes thus prepared was taken for the determination of pot life.
  • the pot life of a propellant paste is evaluated by measuring the change in the viscosity of said paste over time. It is expressed as the time (in hours) to reach a viscosity of 1.5 kPa.s. It is more or less critical depending on the quantities of dough prepared.
  • each of the prepared propellant pastes was then poured into a suitable structure and then subjected to the following heat treatment: baking for 21 days at a temperature of 40 ° C. At the end of the heat treatment, crosslinked propellants were obtained.
  • the mechanical properties of said propellants were determined by subjecting a series of five test pieces (a long CRB test piece (of the "JANAF” type, having the following measurements: useful thickness 6.9 mm, total length 91.3 mm, length of the narrowed portion 83 mm, thickness of said narrowed portion 9.1 mm)) of said propellants to simple tensile tests and recording the corresponding tensile curves.
  • the precursor paste of the Azalane® propellant of the prior art was obtained according to the above protocol using the crosslinking system below.
  • Cross-linking system Isonate® M143 (Dow Chemical): aromatic isocyanate (CMR), marketed by the company Covestro, containing a high percentage of 4,4'-diphenylmethane diisocyanate (MDI) (monomer (free) (70% free MDI), exhibiting a average functionality of 2.17 and a low viscosity of 39 mPa.s at 25 ° C according to standard MDI-01-02), + Desmodur® N3300 (Covestro): aliphatic isocyanate, marketed by the company COVESTRO, containing homopolymers of hexamethylene 1,6-diisocyanate (HMDI or HDI), containing an amount of free HMDI less than 0.15% by mass, exhibiting an average functionality of 3.5, and a viscosity of 3000 mPa s at 23 ° C according to DIN EN ISO 3219.
  • MDI 4,4'-diphenylmethane diisocyanate
  • Table 2 The results presented in Table 2 are comparative results with respect to the Azalane® reference. All these results are lower than the Azalane® reference made up of the mixture of Isonate® M143 and Desmodur® N3300. The% negative for the elongation tests and for the stress tests correspond to the percentage of level losses compared to the Azalane® reference, these degradations are low when it is indicated "in the dispersion", which means that they do not differ from the results obtained for the Azalane® reference (except for the uncertainty).
  • the pot life of the propellant pastes of the invention with Desmodur® N3400 and Desmodur® XP2860 is greater than 24 hours.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Molecular Biology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Claims (16)

  1. Herstellungsverfahren eines pyrotechnischen Verbunderzeugnisses, umfassend:
    a) Bereitstellen der konstituierenden Bestandteile des pyrotechnischen Verbunderzeugnisses, wobei die konstituierenden Bestandteile umfassen:
    - mindestens ein Glycidylpolyazid mit endständigen Hydroxylgruppen und einer zahlenmittleren Molmasse zwischen 700 und 3000 g/mol,
    - mindestens einen energetischen Weichmacher,
    - mindestens einen Stabilisator des mindestens einen energetischen Weichmachers,
    - organische energetische Ladungen vom Nitramintyp,
    - Vernetzungsmittel vom Polyisocyanattyp,
    - gegebenenfalls zusätzliche Ladungen, ausgewählt aus oxidierenden Ladungen und Mischungen aus oxidierenden und reduzierenden Ladungen,
    - gegebenenfalls mindestens ein Additiv, einschließlich mindestens eines Vernetzungskatalysators,
    b) Bilden einer homogenen Paste, die alle konstituierenden Bestandteile des gewünschten pyrotechnischen Erzeugnisses enthält,
    c) Gießen der erhaltenen homogenen Paste in mindestens eine Struktur, und
    d) Wärmebehandeln der in die mindestens eine Struktur gegossenen homogenen Paste,
    dadurch gekennzeichnet, dass die Vernetzungsmittel aus aliphatischen Polyisocyanaten bestehen, die:
    - für mehr als 99,6 % Massenanteil, vorteilhafterweise mehr als 99,7 % Massenanteil, in Form von Oligomeren und für weniger als 0,4 % Massenanteil, vorteilhafterweise weniger als 0,3 % Massenanteil, in Form von mindestens einem Monomer vorliegen,
    - eine globale Funktionalität von 2,1 bis 3,0 aufweisen, und
    - in einer Menge verwendet werden, die ein Verbrückungsverhältnis Rp(NCO/OH) von 0,9 bis 1,5 gewährleistet.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass es sich bei den Oligomeren um Homopolymere und/oder Oligomerisierungsprodukte vom Typ Urethdion und/oder Allophanat handelt.
  3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass die Vernetzungsmittel aus einer Mischung von aliphatischen Polyisocyanaten auf der Basis von einerseits Polyisocyanaten ohne oder mit Urethdion- oder Allophanat-Struktureinheiten mit einer mittleren Funktionalität von mehr als 2,1 und weniger als 3,0 und auf der Basis von andererseits Polyisocyanaten mit einer mittleren Funktionalität von mehr als 3,0 und vorzugsweise mehr als 3,0 und weniger als 4,0 bestehen.
  4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass die aliphatischen Polyisocyanate die gleiche Isocyanateinheit aufweisen.
  5. Verfahren nach Anspruch 4, dadurch gekennzeichnet, dass es sich bei der gleichen Isocyanateinheit um Hexamethylen-1,6-diisocyanat (HMDI oder HDI) oder Isophorondiisocyanat (IPDI), und vorzugsweise um Hexamethylen-1,6-diisocyanat (HMDI oder HDI) handelt.
  6. Verfahren nach Anspruch 4 oder 5, dadurch gekennzeichnet, dass die Vernetzungsmittel aus einer Mischung von aliphatischen Polyisocyanaten auf der Basis von einerseits Polyisocyanaten mit Urethdion- oder Allophanat-Struktureinheiten mit einer mittleren Funktionalität von etwa 2,5 und auf der Basis von andererseits Polyisocyanaten von Homopolymeren des Hexamethylen-1,6-diisocyanats (HMDI oder HDI) mit einer mittleren Funktionalität von etwa 3,5 bestehen.
  7. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass das Verbrückungsverhältnis Rp(NCO/OH) der Vernetzungsmittel 1,0 bis 1,4, vorzugsweise 1,1 bis 1,3 und besonders bevorzugt gleich 1,2 beträgt.
  8. Verfahren nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass die globale Funktionalität der Vernetzungsmittel zwischen 2,5 und 3,0 und vorzugsweise zwischen 2,6 und 3,0 liegt.
  9. Verfahren nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass die zahlenmittlere Molmasse (Mn) des Glycidylpolyazids mit endständigen Hydroxylgruppen zwischen 1700 und 2300 g/mol liegt.
  10. Verfahren nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, dass die organischen energetischen Ladungen ausgewählt sind aus Ladungen von Hexogen (RDX), Octogen (HMX), Hexanitrohexaazaisowurtzitan (CL 20) und Mischungen davon, und dass sie vorteilhafterweise aus Ladungen von Hexogen (RDX) bestehen.
  11. Verfahren nach einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, dass der mindestens eine energetische Weichmacher vom Typ Nitrat und/oder Nitramin ist, dass der mindestens eine energetische Weichmacher vorteilhafterweise ausgewählt ist aus:
    - Salpetersäureestern, wie Diethylenglykoldinitrat (DEGDN), Triethylenglykoldinitrat (TEGDN), Butantrioltrinitrat (BTTN), Trimethylolethantrinitrat (TMETN), Nitroglycerin und Mischungen davon,
    - Nitraminen, wie einer Mischung aus 2,4-Dinitro-2,4-diazapentan, 2,4-Dinitro-2,4-diaza-hexan und 3,5-Dinitro-3,5-diazaheptan, Nitratoethylnitraminen, einschließlich Methyl-2-nitratoethylnitramin (methylNENA) und Ethyl-2-nitratoethylnitramin (ethylNENA), und Mischungen davon, und
    - Mischungen aus diesen Salpetersäureestern und Nitraminen,
    und dass der mindestens eine energetische Weichmacher sehr vorteilhafterweise aus einer Mischung von Butantrioltrinitrat (BTTN) und Trimethylolethantrinitrat (TMETN) besteht.
  12. Verfahren nach einem der Ansprüche 1 bis 11, dadurch gekennzeichnet, dass der mindestens eine Stabilisator des mindestens einen energetischen Weichmachers ausgewählt ist aus aromatischen Aminen, epoxidierten Fettsäureestern und Mischungen davon, und dass der mindestens eine Stabilisator des mindestens einen energetischen Weichmachers vorteilhafterweise ausgewählt ist aus 2-Nitrodiphenylamin (2-NDPA), N-Methylparanitroanilin (MNA) und Mischungen davon.
  13. Verfahren nach einem der Ansprüche 1 bis 12, dadurch gekennzeichnet, dass die konstituierenden Bestandteile oxidierende Ladungen, vorteilhafterweise Ammoniumperchloratladungen, und reduzierende Ladungen, vorteilhafterweise Aluminiumladungen, umfassen.
  14. Verfahren nach einem der Ansprüche 1 bis 13, dadurch gekennzeichnet, dass die konstituierenden Bestandteile mindestens ein Additiv umfassen, insbesondere ausgewählt aus Vernetzungskatalysatoren, ballistischen Katalysatoren, Herstellungshilfsmitteln, Antiglow-Agenzien und Bindemitteln für Binder/Ladungen.
  15. Pyrotechnisches Verbunderzeugnis, enthaltend organische energetische Ladungen vom Nitramintyp in einem plastifizierten Binder, wobei der plastifizierte Binder mindestens ein Glycidylpolyazid mit endständigen Hydroxylgruppen, dessen zahlenmittlere Molmasse zwischen 700 und 3000 g/mol liegt, das über seine Hydroxylgruppen durch aliphatische Polyisocyanate vernetzt ist, mindestens einen energetischen Weichmacher und mindestens einen Stabilisator für den mindestens einen energetischen Weichmacher umfasst, erhältlich durch das Herstellungsverfahren nach einem der vorhergehenden Ansprüche.
  16. Pyrotechnisches Verbunderzeugnis nach Anspruch 15, wobei es sich bei dem mindestens einen vernetzten Glycidylpolyazid mit endständigen Hydroxylgruppen um ein dreidimensionales Netzwerk handelt, das im Wesentlichen aus folgenden Struktureinheiten gebildet wird:
    - vom Typ A: wobei die Vorstufe aus dem mindestens einen Glycidylpolyazid mit endständigen Hydroxylgruppen besteht, und
    - vom Typ B: wobei die Vorstufen aus den Oligomeren von aliphatischem (aliphatischen) Polyisoicyanat(en) bestehen.
EP19211106.0A 2018-11-26 2019-11-25 Herstellungsverfahren von pyrotechnischen verbunderzeugnissen Active EP3656753B1 (de)

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FR1871772A FR3088929B1 (fr) 2018-11-26 2018-11-26 Procédé de préparation de produits pyrotechniques composites

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EP3656753B1 true EP3656753B1 (de) 2021-05-12

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Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2692257B1 (fr) * 1992-06-12 1995-05-05 Divbag Snc Composition pyrotechnique génératrice de gaz chauds non toxiques et son utilisation dans un dispositif de protection des occupants d'un véhicule automobile.
FR3027598B1 (fr) 2014-10-28 2018-05-04 Arianegroup Sas Produit pyrotechnique composite avec charges d'adn et de rdx dans un liant de type pag et sa preparation
FR3059725B1 (fr) * 2016-12-02 2019-01-25 Airbus Safran Launchers Sas Chargement de propergol, avec adhesion lieur/propergol renforcee, et sa preparation

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EP3656753A1 (de) 2020-05-27
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