EP0808813A1 - 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
EP0808813A1
EP0808813A1 EP97401051A EP97401051A EP0808813A1 EP 0808813 A1 EP0808813 A1 EP 0808813A1 EP 97401051 A EP97401051 A EP 97401051A EP 97401051 A EP97401051 A EP 97401051A EP 0808813 A1 EP0808813 A1 EP 0808813A1
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EP
European Patent Office
Prior art keywords
products
binder
solid
styrene
filler
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
EP97401051A
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English (en)
French (fr)
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EP0808813B1 (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, composite propellants for rocket engines and composite explosives for ammunition loading. More precisely, the invention relates to a continuous process for the manufacture without solvent 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, o
  • the binders which can be used for the manufacture of composite pyrotechnic products can be thermoplastic binders or thermosetting binders.
  • thermoplastic binders have the advantage of being relatively easy to apply continuously thanks to the fact that they soften by temperature rise.
  • French patent application FR-A-2 723 086 describes a process for the continuous and solvent-free manufacture of composite pyrotechnic products based on thermoplastic type binders.
  • thermoplastic type binders have the drawback of leading to products which have poor temperature resistance due to the softening of the binder when the temperature rises.
  • the skilled person needs pyrotechnic products having good temperature resistance.
  • thermosetting binder offer the advantage of having good temperature resistance.
  • patent US-A-4 128 441 describes a discontinuous manufacturing process by "casting" of propellant blocks. This process is well suited for manufacturing large loads for rocket engines, but is not suitable for manufacturing industrially in series of small objects.
  • WO94 / 05607 has proposed a semi-continuous manufacturing process with solvent for such products, but the need to use a solvent which must then be eliminated limits the advantage of this process.
  • thermosetting binders When the person skilled in the art wishes to use a continuous solvent-free process with thermosetting binders, he is confronted with the problem of the short "pot life" of these compositions which means that, after mixing the ingredients of the composition, he does not have only a very short time to carry out the geometric shaping of the product before the crosslinking of the binder makes any mechanical work of the dough containing the various ingredients impossible.
  • the object of the present invention is precisely to propose such a process as well as an industrial installation 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 the composition of the intermediate products are frozen by crosslinking, the various operations are carried out at a temperature at which the binder is, chemically, almost non-evolving.
  • the formulation of the composition of the products is perfectly reproducible insofar as it is entirely carried out at the start of the process without requiring any subsequent adjustment.
  • Those skilled in the art are not confronted with any "pot life" condition and the intermediate products whose geometric dimensions are imperfect can be recycled in the manufacture.
  • thermosetting binder which can be modified during the process whose viscosity is sought to be reduced by the use of a solvent and / or a plasticizer
  • the process according to the invention uses a non-evolving liquid thermosetting binder during the process, the apparent viscosity of which is increased by the 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 from the group consisting of carbon black, colloidal silica, alumina, titanium oxide or polynorbornene.
  • the weight ratio between said thickening filler and said crosslinkable binder is between 0.05 and 0.25.
  • said solid thickening filler consists of 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 which can be used as solid thickening filler in the context of the present invention thus consists of the styrene / butadiene / styrene, styrene / isoprene / styrene, styrene / ethylene / butylene / styrene and styrene / ethylene / propylene copolymers.
  • the weight ratio between said thickening filler and said crosslinkable binder is between 10:90 and 50:50.
  • the premix constituted by the liquid binder and the said thickening charges, at least one solid reducing energy charge such as, for example, aluminum or boron powder.
  • the binder is changed by causing it to crosslink by heating to a temperature above 40 ° C. so as to obtain crosslinked finished products.
  • the method according to the invention thus makes it possible to obtain continuously, without time constraint linked to "pot life” questions and without the use of solvents or plasticizers which are undesirable from an energy standpoint, pyrotechnic products with crosslinked binder.
  • These products find their preferred applications as propellant powders in strands or in sticks for the ammunition intended for the weapons with tube, like blocks of propellants for the engines of rockets and rockets, like explosive charges for the explosive ammunition or still like pyrotechnic charges for the gas generators intended for both military and civil applications such as automotive safety.
  • the invention also relates to an installation which is particularly suitable for implementing the method according to the invention.
  • FIG. 1 schematically represents the preferred installation presented above.
  • FIG. 2 represents, for reasons of clarity, a simplified top view of the shear mill used.
  • the invention therefore consists in mixing, at room temperature, the starting constituents of a crosslinkable composite pyrotechnic composition until a homogeneous composite paste having a viscosity sufficient to be able, still at room temperature, to be formed into products. intermediates already having, in a stable manner, the final shape and dimensions of the finished product which it is desired to obtain. The form and composition of these intermediate products are then fixed by hot crosslinking so as to obtain the desired finished products.
  • premix 2 consisting mainly of the binder 3 thermosetting in the liquid state and by thickening solid fillers 4.
  • thermosetting binder is liquid at room temperature and that its crosslinking can only begin at a temperature above 40 ° C so as to be certain that, as long as one remains at an ambient temperature below 40 ° C, this binder will remain chemically non-evolving.
  • liquid binder means all of the liquid reactive constituents which, after crosslinking, will give the solid crosslinked binder.
  • the crosslinking reaction may be of the polycondensation reaction type, in which case the binders will in particular be of the polyurethane, polyesters or polyamides type.
  • the crosslinking reaction can be of the polyaddition reaction type with the opening of ethylenic unsaturations, in which case the binders will in particular be of the polyalkylene, polyacrylate or polymethacrylate type.
  • the composition must contain crosslinking catalysts, such as, for example, peroxides.
  • said thickening fillers can be constituted by porous solid materials of small particle size.
  • additives which are usually used as combustion modifiers such as carbon black will advantageously be used as thickening fillers; the process according to the invention offers in this case the advantage of allowing continuous production of pyrotechnic compositions already known but which were only accessible by batch processes.
  • Said thickening fillers can also be constituted by solid thermoplastic polymers of high molecular mass so as to obtain a final product whose binder is constituted by an alloy of thermoplastic polymers and of crosslinked polymers. This type of alloy makes it possible to obtain composite products having particularly high mechanical characteristics.
  • the premix 2 thus formed may also contain other additives of the final composition. It should have the consistency of a thick grease so that it can be transported continuously by means of a positive displacement pump while adhering, without sinking, to the surface of a cylinder rotating with an angular speed of a few tens of revolutions per minute.
  • This premix is therefore transported by means of a circulation pump 34, for example a gear pump, in a reserve 35 provided with a piston cover 36.
  • the premix is then taken up by a metering pump 5 to gear to be driven, in an apparatus where will be carried out the operations of mixing with the solid energetic charges and shaping of the composite paste thus obtained in the form of intermediate products already having the geometric dimensions of the finished products.
  • These two operations can be carried out in a single apparatus such as for example a twin-screw extruder whose extrusion head will be associated with a cutting device. However, preferably, these two operations will be carried out by two separate devices placed one after the other.
  • the premix 2 is transported by the pump 5 in a mixer which can be a traditional mixer such as a "BUSS" co-kneader but which, preferably and as shown in FIG. 1, is a shear rolling mill 6 constituted by two rollers cylindrical 7 and 8 of identical length and carrying helical grooves.
  • the 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.
  • the axes 9 and 10 are supported by support blocks 12 and 13, the block 12 being a motor block 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 onto the roller 7 which rotates the fastest, the premix forming on this roller a sheet which coats the latter.
  • the premix is brought to the material inlet end 14 of the rolling mill 6.
  • At least one dosing hopper 16 pours, between the material inlet end 14 and the material outlet end 15 of the rolling mill 6, the solid energy charges 17 on the premix sheet coating the roller 7. These charges solid energy are then intimately mixed with the premix 2 thanks to the shearing action of the rolling mill 6 so as to form on the roller 7 a sheet of homogeneous composite dough which already has a sufficient viscosity to be able to maintain stable geometric dimensions.
  • the solid energetic charges will mainly consist of the oxidizing charges of the composition which may be mineral charges such as for example ammonium perchlorate, potassium perchlorate or ammonium nitrate, or organic charges and in particular nitramines such as l hexogen, octogen, nitroguanidine or hexanitro-hexaazaisowurtzitane.
  • mineral charges such as for example ammonium perchlorate, potassium perchlorate or ammonium nitrate
  • organic charges and in particular nitramines such as l hexogen, octogen, nitroguanidine or hexanitro-hexaazaisowurtzitane.
  • solid oxidizing charges there may be solid reducing energy charges such as aluminum or boron and even solid additives which have not been incorporated into the premix 2.
  • the different loads may be added either as a 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 granulation device 18 located at the outlet end 15 of the rolling mill 6.
  • a granulation device 18 located at the outlet end 15 of the rolling mill 6.
  • the outlet ends of the rollers 7 and 8 do not are not grooved but are smooth.
  • the granules 19 are then taken up continuously in an extruder 20, for example a twin screw extruder, provided with an extrusion head 21 to be profiled in rods 23 driven by a conveyor belt 25.
  • a cutting device 22 cuts the profiled rods 23 leaving the extrusion head 21 into intermediate products 24 already having the final dimensions of the finished products.
  • the cutting device 22 has a movement controlled by the speed of progression of the belt 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 composite pyrotechnic products with crosslinked binder, and in particular products of small dimensions, without “pot life” constraint, without solvent and without undesirable plasticizer.
  • 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
  • the die was a cylindrical die with an outside diameter of 30mm and an inside diameter of 14mm.
  • 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)
  • Air Bags (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
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
FR9606397 1996-05-23
FR9606397A FR2749008B1 (fr) 1996-05-23 1996-05-23 Procede continu de fabrication sans solvant de produits pyrotechniques composites thermodurcissables

Publications (2)

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

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EP97401051A Expired - Lifetime EP0808813B1 (de) 1996-05-23 1997-05-12 Kontinuierliches Verfahren zur lösungsmittelfreien Herstellung von Zusammensetzungen für Pyrotechnische Erzeugnisse mit wärmehärtbarem Bindemittel

Country Status (8)

Country Link
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)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2995432A (en) * 1958-08-04 1961-08-08 Phillips Petroleum Co Solid composite rubber base propellants containing reinforcing agent of resinous aldehyde condensate
US4375522A (en) * 1980-07-21 1983-03-01 The United States Of America As Represented By The Secretary Of The Navy Thixotropic restrictor, curable at room temperature, for use on solid propellant grains
US4650617A (en) * 1985-06-26 1987-03-17 Morton Thiokol Inc. Solvent-free preparation of gun propellant formulations
US4726919A (en) * 1985-05-06 1988-02-23 Morton Thiokol, Inc. Method of preparing a non-feathering nitramine propellant
WO1989006258A1 (en) * 1987-12-24 1989-07-13 The University Of Manchester Institute Of Science Polymer compositions
EP0417912A2 (de) * 1989-08-25 1991-03-20 Idemitsu Petrochemical Company Limited Formmasse auf der Basis eines thermoplastischen Harzes
DE19528052A1 (de) * 1994-07-29 1996-02-01 Poudres & Explosifs Ste Nale Kontinuierliches Verfahren zur lösungsmittelfreien Herstellung von pyrotechnischen Composit-Produkten

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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
US4177227A (en) * 1975-09-10 1979-12-04 The United States Of America As Represented By The Secretary Of The Air Force Low shear mixing process for the manufacture of solid propellants
US4098627A (en) * 1976-12-15 1978-07-04 The United States Of America As Represented By The Secretary Of The Navy Solvolytic degradation of pyrotechnic materials containing crosslinked polymers
DE3010052C2 (de) * 1980-03-15 1982-09-09 Friedrich-Ulf 8899 Rettenbach Deisenroth Verfahren zur Herstellung von kunststoffgebundenen Explosivstoffen
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
US4889571A (en) * 1986-09-02 1989-12-26 Morton Thiokol, Inc. High-energy compositions having castable thermoplastic binders
DE3635296C2 (de) * 1986-10-16 1995-12-21 Nitrochemie Gmbh Verfahren zum Herstellen von Treibladungspulver
SE465572B (sv) * 1989-06-21 1991-09-30 Nobel Kemi Ab Saett och anordning foer framstaellning av explosiva substanser
US4994212A (en) * 1990-05-24 1991-02-19 Trw Vehicle Safety Systems Inc. Process for manufacturing a gas generating material
US5486248A (en) * 1994-05-31 1996-01-23 Morton International, Inc. Extrudable gas generant for hybrid air bag inflation system

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2995432A (en) * 1958-08-04 1961-08-08 Phillips Petroleum Co Solid composite rubber base propellants containing reinforcing agent of resinous aldehyde condensate
US4375522A (en) * 1980-07-21 1983-03-01 The United States Of America As Represented By The Secretary Of The Navy Thixotropic restrictor, curable at room temperature, for use on solid propellant grains
US4726919A (en) * 1985-05-06 1988-02-23 Morton Thiokol, Inc. Method of preparing a non-feathering nitramine propellant
US4650617A (en) * 1985-06-26 1987-03-17 Morton Thiokol Inc. Solvent-free preparation of gun propellant formulations
WO1989006258A1 (en) * 1987-12-24 1989-07-13 The University Of Manchester Institute Of Science Polymer compositions
EP0417912A2 (de) * 1989-08-25 1991-03-20 Idemitsu Petrochemical Company Limited Formmasse auf der Basis eines thermoplastischen Harzes
DE19528052A1 (de) * 1994-07-29 1996-02-01 Poudres & Explosifs Ste Nale Kontinuierliches Verfahren zur lösungsmittelfreien Herstellung von pyrotechnischen Composit-Produkten
FR2723086A1 (fr) * 1994-07-29 1996-02-02 Poudres & Explosifs Ste Nale Procede continu de fabrication sans solvant de produits pyrotechniques composites

Also Published As

Publication number Publication date
DE69706228T2 (de) 2002-05-16
NO972318L (no) 1997-11-24
IL120670A0 (en) 1997-08-14
US5831339A (en) 1998-11-03
CA2204840C (fr) 2002-01-08
JPH1053484A (ja) 1998-02-24
FR2749008A1 (fr) 1997-11-28
NO972318D0 (no) 1997-05-21
MX9703466A (es) 1997-11-29
IL120670A (en) 2000-07-26
JP3826226B2 (ja) 2006-09-27
DE69706228D1 (de) 2001-09-27
FR2749008B1 (fr) 1998-06-26
EP0808813B1 (de) 2001-08-22
CA2204840A1 (fr) 1997-11-23
NO307084B1 (no) 2000-02-07

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