EP0808813B1 - Kontinuierliches Verfahren zur lösungsmittelfreien Herstellung von Zusammensetzungen für Pyrotechnische Erzeugnisse mit wärmehärtbarem Bindemittel - Google Patents

Kontinuierliches Verfahren zur lösungsmittelfreien Herstellung von Zusammensetzungen für Pyrotechnische Erzeugnisse mit wärmehärtbarem Bindemittel Download PDF

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Publication number
EP0808813B1
EP0808813B1 EP97401051A EP97401051A EP0808813B1 EP 0808813 B1 EP0808813 B1 EP 0808813B1 EP 97401051 A EP97401051 A EP 97401051A EP 97401051 A EP97401051 A EP 97401051A EP 0808813 B1 EP0808813 B1 EP 0808813B1
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Prior art keywords
process according
binder
products
styrene
solid
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Expired - Lifetime
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EP97401051A
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English (en)
French (fr)
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EP0808813A1 (de
Inventor
Alain Lefumeux
Dominique Wiencek
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Societe Nationale des Poudres et Explosifs
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Societe Nationale des Poudres et Explosifs
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    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B21/00—Apparatus or methods for working-up explosives, e.g. forming, cutting, drying
    • C06B21/0008—Compounding the ingredient
    • C06B21/0025—Compounding the ingredient the ingredient being a polymer bonded explosive or thermic component
    • 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
    • C06B23/001—Fillers, gelling and thickening agents (e.g. fibres), absorbents for nitroglycerine

Definitions

  • the present invention relates to the field of composite pyrotechnic products and in particular composite powders for tube weapons, propellants composites for rocket engines and explosives composites for ammunition loading. More precisely the invention relates to a continuous process for solvent-free manufacturing of such pyrotechnic products comprising a thermosetting binder.
  • a pulverulent energy charge which can be a mineral charge such as for example ammonium nitrate, ammonium perchlorate or potassium perchlorate or else an organic charge and in particular a nitramine such as for example hexogen, oct
  • Binders usable for the manufacture of composite pyrotechnics can be thermoplastic binders or binders thermosetting.
  • thermoplastic binders have the advantage of relatively easily lend themselves to implementation continuously due to the fact that they soften by temperature rise. So the patent application French FR-A-2 723 086 describes a manufacturing process continuous and solvent-free of pyrotechnic products composites based on thermoplastic type binders.
  • thermoplastic type binders have the disadvantage of leading to products that have a poor temperature resistance due to the very softening of the binder when the temperature.
  • the man of profession needs pyrotechnic products presenting good temperature resistance.
  • thermosetting binder offer the advantage of presenting good temperature resistance.
  • US-A-4,405,534 describes a process for manufacturing composite explosives by cold compression of granules of explosives coated with a polyurethane film made plastic thanks to the presence of plasticizers. This process, apart from the fact that it is discontinuous, has the disadvantage additional to require the presence of a strong plasticizer content which is not always favorable to the energy plan.
  • thermosetting binders When the skilled person wants to implement with thermosetting binders a continuous process solvent-free it faces the problem of short "pot life" of these compositions which means that after mixture of the ingredients of the composition, it does have only a very short time to perform the shaping geometry of the product before the crosslinking of the binder does not make any mechanical work of the dough containing the different ingredients.
  • thermosetting binder Nevertheless the possibilities of application of these techniques are limited and the skilled person does not have not a general continuous manufacturing process and solvent-free composite pyrotechnic products to thermosetting binder.
  • the object of the present invention is precisely to propose such a process as well as an installation industrial allowing the implementation of this process.
  • the major originality of the process according to the invention lies in the fact that with the exception of the final phase during which the structure and composition of intermediate products are fixed by crosslinking, the different operations are carried out at a temperature at which the binder is, chemically, almost non-scalable. So the formulation of the product composition is perfectly reproducible insofar as it is fully carried out in start of the process without requiring any adjustment ulterior. The skilled person is not confronted with any condition of "pot life" and intermediate products whose geometric dimensions are imperfect can be recycled in manufacturing.
  • the process according to the invention uses a liquid thermosetting binder non-evolving during the process of which the apparent viscosity by use of fillers thickeners.
  • said solid thickening filler consists of a porous material whose particle size is between 0.1 and 10 ⁇ m (microns) and whose specific surface is between 60 and 500 m 2 / g .
  • this material will also have combustion modifying properties and will be chosen in the group consisting of carbon black, the colloidal silica, alumina, titanium oxide or polynorbornene.
  • the weight ratio between said thickening filler and said binder crosslinkable is between 0.05 and 0.25.
  • said solid thickening filler is constituted by a thermoplastic polymer with hydrocarbon units which may contain, in addition to carbon and hydrogen atoms, oxygen and nitrogen atoms and whose molecular mass weight average is between 3x10 5 and 3x10 6 .
  • thermoplastic polymers usable as solid thickening filler in the framework of the present invention is thus constituted by styrene / butadiene / styrene, styrene / isoprene / styrene copolymers, styrene / ethylene / butylene / styrene and styrene / ethylene / propylene.
  • thermoplastic polymers usable as solid thickening fillers in the framework of the present invention is constituted by the polyurethanes with polyether and polycarbonate patterns and by polyether / polyamide block copolymers.
  • the weight ratio between said thickening filler and said binder crosslinkable is between 10:90 and 50:50.
  • solid oxidizing energy charges we can also incorporate into the premix, consisting by the liquid binder and said thickening fillers, at least one solid reducing energy charge like, for example, aluminum or boron powder.
  • the method according to the invention thus makes it possible to obtain continuously, without time constraints linked to "pot life” issues and no use of solvents or energy-unwanted plasticizers, Composite pyrotechnic products with crosslinked binder. These products find their preferred applications as propellant powders in strands or in sticks for ammunition intended for the weapons with tube, like blocks of propellants for rocket and rocket engines, as explosive charges for ammunition explosives or as pyrotechnic charges for gas generators intended for both military applications than civil applications like automotive safety.
  • the invention also relates to an installation particularly suitable for the implementation of method according to the invention.
  • Figure 1 shows, so schematic, the preferred installation presented above.
  • Figure 2 shows, for reasons of clarity, a simplified top view of the rolling mill shear used.
  • the invention therefore consists in mixing, at temperature ambient the starting constituents of a composition composite pyrotechnic crosslinkable until obtained a homogeneous composite paste with a viscosity sufficient to be able, always at temperature ambient, be in the form of products intermediaries who already have a stable shape and final dimensions of the finished product that we want to get.
  • the form and composition of these intermediate products are then frozen by hot crosslinking so as to obtain the products desired completions.
  • thermosetting binder is liquid to room temperature and that its crosslinking cannot start only at a temperature above 40 ° C so as to be certain that as long as we stay at one ambient temperature below 40 ° C, this binder will remain chemically non-evolving.
  • binder liquid all of the liquid reactive constituents which, after crosslinking, will give the crosslinked binder solid.
  • the crosslinking reaction can be of the type polycondensation reaction, in which case the binders will in particular be of the polyurethane, polyesters or polyamides.
  • the crosslinking reaction can be of the type polyaddition reaction with opening of unsaturations ethylenic, in which case the binders will in particular be polyalkylenes, polyacrylates or polymethacrylates. In the latter case, the composition must contain crosslinking catalysts, such as for example peroxides.
  • said thickening fillers can be made of porous solid materials of small particle size.
  • certain additives usually used as modifiers of combustion like carbon black the process according to the invention in this case offers the advantage of allowing continuously obtaining pyrotechnic compositions already known but which were only accessible by discontinuous processes.
  • Said thickening fillers can also be made up of thermoplastic polymers high molecular weight solids so as to get a final product whose binder consists of a alloy of thermoplastic polymers and polymers cross-linked. This type of alloy allows obtaining composite products with characteristics particularly high mechanical properties.
  • the premix 2 thus formed may also contain other additives of the final composition. he should have the consistency of a thick fat of so that it can be transported continuously using a positive displacement pump while adhering, without sinking, on the surface of a cylinder rotating with a speed angular of a few tens of revolutions per minute.
  • This premix is therefore transported by means of a circulation pump 34, for example a gear, in a reserve 35 provided with a piston cover 36.
  • the premix is then taken up by a pump doser 5 with gear to be driven, in a equipment where the operations of mixing with solid energy charges and setting in the form of the composite paste thus obtained in the form of intermediate products that already have the ratings geometries of finished products.
  • These two operations can be carried out in a single device like for example a twin screw extruder whose head extrusion will be associated with a cutting device. But, preferentially, these two operations will be carried out by two separate devices, one placed following each other.
  • the premix 2 is transported by the pump 5 in a mixer which can be a traditional mixer as a "BUSS" co-kneader but which, preferably and as shown in Figure 1, is a rolling mill shear 6 consisting of two cylindrical rollers 7 and 8 of identical length and having grooves helical. Axes 9 and 10 of these two cylinders are parallel and located in the same horizontal plane being spaced so as to leave a slot 11 between the two rollers. Axes 9 and 10 are supported by support blocks 12 and 13, block 12 being a block engine driving in rotation the two cylinders 7 and 8 which rotate in opposite directions to each other at different speeds.
  • Such a shear rolling mill is known to those skilled in the art and described in numerous publications, for example in the patent application FR-A-2 723 086 already cited.
  • the pump 5 thus brings the premix 2 to the roller 7 which turns the fastest, the premix forming on this roll a sheet which coats this latest.
  • the premix is brought to the end 14 material inlet of the rolling mill 6.
  • At least one dosing hopper 16 pours between the material inlet end 14 and the end of material outlet 15 from rolling mill 6, the loads solid energy 17 on the premix sheet coating the roller 7. These solid energy charges are then intimately mixed with premix 2 thanks to the shearing action of the rolling mill 6 so as to form on roll 7 a sheet of composite dough homogeneous which already has sufficient viscosity to ability to maintain stable geometric dimensions.
  • Solid energy charges will mainly constituted by the oxidizing charges of the composition which can be mineral fillers such as ammonium perchlorate, potassium perchlorate or ammonium nitrate, or organic fillers and in particular nitramines such as hexogen, octogen, nitroguanidine or hexanitro-hexaazaisowurtzitane.
  • mineral fillers such as ammonium perchlorate, potassium perchlorate or ammonium nitrate
  • organic fillers and in particular nitramines such as hexogen, octogen, nitroguanidine or hexanitro-hexaazaisowurtzitane.
  • the different charges may be brought either in mixture by a single hopper, or separately by a succession of hoppers.
  • the composite dough sheet thus obtained is recovered in the form of granules 19 by a device for granulation 18 located at the outlet end 15 of the rolling mill 6.
  • a device for granulation 18 located at the outlet end 15 of the rolling mill 6.
  • the outlet ends of rollers 7 and 8 are not grooved but are smooth.
  • the granules 19 are then taken up continuously in an extruder 20, for example a twin extruder screw, fitted with an extrusion head 21 to be profiled in rods 23 driven by a conveyor belt 25.
  • an extruder 20 for example a twin extruder screw, fitted with an extrusion head 21 to be profiled in rods 23 driven by a conveyor belt 25.
  • a cutting device 22 cuts the rods profiles 23 leaving the extrusion head 21 in 24 intermediate products already with the ratings final of finished products.
  • the device cutting 22 has a movement controlled by the speed of progression of the mat 25 on which the rods rest 23.
  • the finished products 27 leaving the oven 26 can then be packaged in their packaging 28.
  • the method according to the invention thus makes it possible to manufacture in continuous series of products composite pyrotechnics with crosslinked binder, and in particular products of small dimensions, without constraint of "pot life", solvent-free and plasticizer-free undesirable.
  • the 7-hole and 19-hole multi-perforated cylindrical powder strands were produced by the continuous process according to the invention from the following three compositions: Composition 1 Composition 2 Composition 3 binder PBHT: 9% PBHT: 10.5% PAG: 13% thickening filler SIS 6% PE-PA: 4.5% PE-PA: 7% oxidizing charge RDX 85% RDX 85% RDX 80% particle size of the oxidizing charge 100 ⁇ m 150 ⁇ m 80 ⁇ m reducing load 0 0 0 0
  • Example 4 On 10 meters of propellant extruded continuously for each of the compositions, the dimensional variations obtained after hot cutting and crosslinking are as follows: Example 4 Example 5 Example 6 outer diameter in mm 30.5 ⁇ 0.002 30.0 ⁇ 0.02 29.9 ⁇ 0.02 inside diameter in mm 13.8 ⁇ 0.003 13.9 ⁇ 0.02 14.05 ⁇ 0.02 length in mm 121 ⁇ 0.1 120.5 ⁇ 0.15 120.4 ⁇ 0.1

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Air Bags (AREA)

Claims (11)

  1. Kontinuierliches Verfahren zur lösemittelfreien Herstellung pyrotechnischer Endprodukte in Form von Verbundmaterialien, deren Ausgangsbestandteile insbesondere ein flüssiges Bindemittel, das bei einer Temperatur oberhalb von 40 °C vernetzbar ist, und mindestens einen festen, energetischen, oxidierenden Füllstoff umfassen, wobei das Verfahren insbesondere darin besteht,
    i) die Ausgangsbestandteile dieser Produkte unter Erhalt einer homogenen Masse aus den Bestandteilen des Verbundmaterials mit einer Viskosität, die so groß ist, daß die geometrischen Maße stabil erhalten bleiben können, zu vermischen,
    ii) die so erhaltene Masse zu Zwischenprodukten mit den geometrischen Maßen der Endprodukte zu formen,
    iii) die Form und die Zusammensetzung der so erhaltenen Zwischenprodukte durch Vernetzung des Bindemittels zu fixieren,
    dadurch gekennzeichnet, daß
    iv) das als Ausgangsbestandteil verwendete flüssige Bindemittel zunächst mit einem festen, pulverförmigen verdickenden Füllstoff vermischt wird, um ein Vorgemisch mit fettartiger Konsistenz zu erhalten, das anschließend mit den energetischen Füllstoffen vermischt wird,
    v) das Vermischen der Ausgangsbestandteile und die Verformung der Masse zu den Zwischenprodukten bei einer Temperatur unterhalb von 40 °C durchgeführt werden.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß der feste, verdickende Füllstoff aus einem porigen Material besteht, dessen Korngröße im Bereich von 0,1 bis 10 µm und dessen spezifische Oberfläche im Bereich von 60 bis 500 m2/g liegt.
  3. Verfahren nach Anspruch 2, dadurch gekennzeichnet, daß das Material unter Ruß, kolloidaler Kieselsäure, Aluminiumoxid, Titandioxid, Polynorbornen ausgewählt wird.
  4. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß der feste verdickende Füllstoff aus einem thermoplastischen Polymer mit Kohlenwasserstoffeinheiten besteht, das/die Sauerstoff- und Stickstoffatome enthalten kann/können, dessen Gewichtsmittel des Molekulargewichts im Bereich von 3 · 105 bis 3 · 106 liegt.
  5. Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß der verdickende Füllstoff unter den Styrol-Butadien-Styrol-Copolymeren, Styrol-Isopren-Styrol-Copolymeren, Styrol-Ethylen-Butylen-Styrol-Copolymeren, Styrol-Ethylen-Propylen-Copolymeren ausgewählt wird.
  6. Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß der verdickende Füllstoff unter den Polyurethanen auf der Basis von Polyethern und Polycarbonaten und unter den Polyether/Polyamid-Blockcopolymeren ausgewählt wird.
  7. Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß das Gewichtsverhältnis des verdickenden Füllstoffs zu dem vernetzbaren Bindemittel im Bereich von 10:90 bis 50:50 liegt.
  8. Verfahren nach Anspruch 2, dadurch gekennzeichnet, daß das Gewichtsverhältnis des verdickenden Füllstoffs zu dem vernetzbaren Bindemittel im Bereich von 0,05 bis 0,25 liegt.
  9. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß zusätzlich zu den festen, oxidierenden energetischen Füllstoffen mindestens ein fester, reduzierender energetischer Füllstoff verwendet wird.
  10. Verfahren nach Anspruch 9, dadurch gekennzeichnet, daß der feste, reduzierende, energetische Füllstoff aus pulverförmigem Aluminium oder Bor besteht.
  11. Vorrichtung zur Durchführung des Verfahrens nach einem der Ansprüche 1 bis 10,
    dadurch gekennzeichnet, daß sie in der Richtung, in der das Material gefördert wird, umfaßt:
    i) ein Walzwerk (6), das aus zwei mit Rillen versehenen zylindrischen Walzen (7, 8) gleicher Länge besteht, die helikal angeordnete Rillen aufweisen und deren Achsen parallel verlaufen und in der gleichen horizontalen Ebene angeordnet sind und dabei solch einen Abstand voneinander aufweisen, daß zwischen den Walzen ein Spalt (11) bleibt, die sich in entgegengesetzter Richtung drehen,
    ii) eine Zumeßpumpe (5), die an dem Ende (14) des Walzwerks (6), an dem die Materialzufuhr erfolgt, das Vorgemisch (2) zuführt, das aus dem flüssigen Bindemittel und dem verdickenden Füllstoff besteht,
    iii) mindestens einen Dosiertrichter (16), der zwischen dem Ende (14) des Walzwerks (6), an dem die Materialzufuhr erfolgt, und dem Ende, an dem das Material das Walzwerk (6) verläßt, die festen energetischen Füllstoffe (17) auf die Walzen des Walzwerks (6) aufgibt,
    iv) eine Vorrichtung (18) zur Granulierung der so hergestellten Masse, die an dem Ende (15) des Walzwerks, an dem das Material das Walzwerk verläßt, angeordnet ist,
    v) einen Extrudcr (20), der das Granulat aufnimmt, das aus der Granuliervorrichtung stammt,
    vi) eine Zerschneidevorrichtung (22), die die aus dem Extruder austretenden extrudierten Stränge (23) in die Zwischenprodukte (24) zerschneidet,
    vii) ein Transportband (25), das für den Transport und die Weiterleitung der zerschnittenen Zwischenprodukte in einen Wärmeofen (26) sorgt.
EP97401051A 1996-05-23 1997-05-12 Kontinuierliches Verfahren zur lösungsmittelfreien Herstellung von Zusammensetzungen für Pyrotechnische Erzeugnisse mit wärmehärtbarem Bindemittel Expired - Lifetime EP0808813B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9606397A FR2749008B1 (fr) 1996-05-23 1996-05-23 Procede continu de fabrication sans solvant de produits pyrotechniques composites thermodurcissables
FR9606397 1996-05-23

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EP0808813A1 EP0808813A1 (de) 1997-11-26
EP0808813B1 true EP0808813B1 (de) 2001-08-22

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US (1) US5831339A (de)
EP (1) EP0808813B1 (de)
JP (1) JP3826226B2 (de)
CA (1) CA2204840C (de)
DE (1) DE69706228T2 (de)
FR (1) FR2749008B1 (de)
IL (1) IL120670A (de)
NO (1) NO307084B1 (de)

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US6315930B1 (en) * 1999-09-24 2001-11-13 Autoliv Asp, Inc. Method for making a propellant having a relatively low burn rate exponent and high gas yield for use in a vehicle inflator
US6736913B1 (en) * 2000-10-31 2004-05-18 Alliant Techsystems Inc. Method for processing explosives containing 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazatetracyclo [5.5.0.05,903,11]-dodecan (CL-20) with naphthenic and paraffinic oils
GB0205559D0 (en) * 2002-03-11 2002-04-24 Bae Systems Plc Improvements in and relating to the filling of explosive ordnance
JP2006044975A (ja) * 2004-08-03 2006-02-16 Ihi Aerospace Co Ltd 固体推進薬
US7854811B1 (en) * 2009-07-11 2010-12-21 Kemzecur, Inc. Mouldable plastic explosives and inert simulants for mouldable plastic explosives
CN109704892A (zh) * 2019-03-03 2019-05-03 浏阳市浏河机械有限公司 烟火药混合潮料造粒工艺

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US4776993A (en) * 1974-05-14 1988-10-11 The United States Of America As Represented By The Secretary Of The Navy Extrusion method for obtaining high strength composite propellants
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FR2577919B1 (fr) * 1985-02-27 1987-02-20 Poudres & Explosifs Ste Nale Procede de fabrication sans solvant de produits pyrotechniques composites a liant thermodurcissable et produits ainsi obtenus, notamment poudres propulsives composites
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NO972318D0 (no) 1997-05-21
EP0808813A1 (de) 1997-11-26
MX9703466A (es) 1997-11-29
JP3826226B2 (ja) 2006-09-27
NO307084B1 (no) 2000-02-07
CA2204840C (fr) 2002-01-08
IL120670A0 (en) 1997-08-14
FR2749008B1 (fr) 1998-06-26
JPH1053484A (ja) 1998-02-24
US5831339A (en) 1998-11-03
FR2749008A1 (fr) 1997-11-28
CA2204840A1 (fr) 1997-11-23
DE69706228T2 (de) 2002-05-16
IL120670A (en) 2000-07-26
NO972318L (no) 1997-11-24
DE69706228D1 (de) 2001-09-27

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