EP3515881B1 - Composite pyrotechnic product containing an anti-gleam agent of potassium salt type - Google Patents

Composite pyrotechnic product containing an anti-gleam agent of potassium salt type Download PDF

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Publication number
EP3515881B1
EP3515881B1 EP17787216.5A EP17787216A EP3515881B1 EP 3515881 B1 EP3515881 B1 EP 3515881B1 EP 17787216 A EP17787216 A EP 17787216A EP 3515881 B1 EP3515881 B1 EP 3515881B1
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energetic
potassium
agent
composite pyrotechnic
charges
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German (de)
French (fr)
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EP3515881A1 (en
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Jérôme LAFARGE
Fabienne Morin
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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
    • C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
    • C06B23/04—Compositions characterised by non-explosive or non-thermic constituents for cooling the explosion gases including antifouling and flash suppressing agents
    • 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 relates to composite pyrotechnic products, suitable in particular as solid propellants for the propellant charges of tactical missiles. They are more precisely composite pyrotechnic products, containing a high rate of organic energetic charges in an energetic binder.
  • the composition of said products is optimized with reference to the technical problem of the discretion of said products during their combustion, more precisely with reference to the technical problem of obtaining an interesting compromise in terms of discretion and energy power.
  • the technical problem of the discretion (of the solid propellants of the propellants) of the missiles is a real technical problem.
  • compositions typically contain essentially energetic fillers, nitrocellulose, cellulose acetate butyrate, an energetic plasticizer and additives. They may also contain at least one additional binder, energetic such as poly glycidylazide (PAG; uncrosslinked) or non-energetic such as polybutadiene with terminal hydroxyl functions (PBHT).
  • PAG poly glycidylazide
  • PBHT polybutadiene with terminal hydroxyl functions
  • solid double-base propellants have more modest energy performance than those of composite propellants developed in a second step.
  • Composite propellants of the Nitramite® and Azamite® type have been particularly developed, in particular for tactical missiles.
  • Composite propellants of the Nitramite® type contain energetic charges (of the RDX or HMX type) in a crosslinked binder (of the polyester, polyether or polycaprolactone type), plasticized with nitroglycerin.
  • energetic charges of the RDX or HMX type
  • a crosslinked binder of the polyester, polyether or polycaprolactone type
  • their composition has been optimized in that it does not contain metallic charges (such as aluminum charges) capable of generating primary fumes, no or few inorganic energetic charges (such as ammonium perchlorate charges) capable of generating secondary fumes and in that it contains effective anti-their agents capable of minimizing or even eliminating post-combustion phenomena (we note incidentally here that the nature and quantity of anti-glare agents should be optimized insofar as said anti-glare agents are capable of generating primary and / or secondary fumes).
  • Azamite® type composite propellants are even more energetic propellants than Nitramite® type propellants. They contain energetic charges (of RDX or HMX type) in a crosslinked energetic binder (of polyglycidyl azide (PAG) type), plasticized with at least one energetic plasticizer. They are suitably used up to firing pressures of the order of 16 MPa, in the so-called acceleration phase. Under such conditions, the anti-glare agents of the prior art (see above) have proved to be ineffective (in particular to substantially reduce the phenomenon of post combustion; more generally with reference to the technical problem of discretion).
  • the structure of the composite pyrotechnic products of the invention therefore associates, in a characteristic manner, a specific (energetic) binder and at least one specific anti-glare agent (of the potassium salt type).
  • binder that of its precursor (energy) polymer
  • that of its precursor (energy) polymer therefore constitutes one of the key elements (of the composition) of the composite pyrotechnic products of the invention.
  • Nature from to less one anti-glare agent (of potassium salt type) present therefore constitutes the other of the key elements (of the composition) of the composite pyrotechnic products of the invention.
  • potassium cryolite K 3 AlF 6
  • monobasic potassium tartrate C 4 H 5 KO 6
  • said monobasic potassium tartrate advantageously consisting of monobasic potassium L-tartrate (see above )
  • potassium cryolite K 3 AlF 6
  • the infrared signature of said potassium cryolite is more discreet than that of said monobasic potassium tartrate.
  • Said at least one original anti-glow agent is obviously expediently present in an effective but not excessive amount (the added potassium salt (s) being suitable for minimizing the phenomenon of post combustion but being likely (s) to generate primary fumes and, in any case, negatively influencing the energy capacity).
  • This effective and non-excessive amount is generally such as to ensure in the composition of the product a potassium content of 0.2 to 5% by mass, advantageously from 0.2 to 2.5% by mass.
  • This advantageous potassium content of 0.2 to 2.5% by mass corresponds approximately to a mass content, of one and / or the other of said specific potassium salts, of 1 to 5%. It is understood that at the desired equivalent potassium content, the required C 4 H 5 KO 6 content is greater than that required in K 3 AlF 6 .
  • binder With reference to the nature of the binder (therefore energetic binder), more particularly to that of its precursor polymer (polyhydroxytelechelic glycidyl azide), the following can be added.
  • the “one” poly glycidyl azide should read “at least one” poly glycidyl azide throughout the present text. Indeed, it is in no way excluded from the scope of the invention that a mixture of at least two glycidyl polyazides (having molecular masses (between 700 and 3000 g / mol) and / or different branching rates) is used. as precursor polymer for the binder of the products of the invention.
  • the precursor energetic polymer of the binder of the products of the invention is therefore a polyazide, a glycidyl polyazide (PAG) which has terminal hydroxy functions (a hydroxytelechelic PAG); hence 1) its energetic properties and 2) its ability to be crosslinked with polyisocyanate type crosslinking agents.
  • PAG glycidyl polyazide
  • Said polymer has an adequate molecular mass (in particular, with reference to its consistency (liquid) and to the consistency of its mixture with essentially the charges (organic energy) and in reference to the relative content of the crosslinked binder of crosslinking agent (s)), number-average molecular mass (Mn) of between 700 and 3000 g / mol, advantageously between 1700 and 2300 g / mol.
  • crosslinking agents of the polylsocyanate type (at least bifunctional), suitable for the crosslinking of such a hydroxytelechelic polyglycidylazide (PAG) are known per se. They may in particular be di- or triisocyanates.
  • polyisocyanates liquids, chosen from toluene diisocyanate (TDI), isophorone diisocyanate (IPDI), dicyclohexylmethylene diisocyanate (MDCI), hexamethylene diisocyanate (HDI), the trimer of said hexamethylene diisocyanate (in particular sold by the company Bayer under the trade name Desmodur® N 3300), biuret trihexane isocyanate (BTHI), 3,5,5-trimethyl-1,6-hexamethylene diisocyanate and mixtures thereof. Particularly preferably, the trimer of hexamethylene diisocyanate is used.
  • TDI toluene diisocyanate
  • IPDI isophorone diisocyanate
  • MDCI dicyclohexylmethylene diisocyanate
  • HDI hexamethylene diisocyanate
  • trimer of said hexamethylene diisocyanate in particular sold by the company Bayer under
  • Said crosslinking agents are conventionally used in the necessary and sufficient quantity, to ensure crosslinking of the polymer (not excessive so as not to pollute the crosslinked product obtained). They are conventionally used in an amount such that the bridging ratio (NCO (of the crosslinking agent) / OH (of the polymer)) is between 0.8 and 1.4, or advantageously 1.2.
  • the crosslinked energetic polymer generally represents from 9 to 14% by weight of the total composition of the composite pyrotechnic products of the invention.
  • the energetic polymer per se is generally involved for 7 to 12% by mass, the at least one crosslinking agent for about 2% by mass.
  • binder of its precursor polymer
  • interest of the invention is based on the association of such an energetic binder (precursor polymer) with at least one specific anti-glare agent (of the potassium salt type).
  • the energetic binder is associated with at least one energetic plasticizer.
  • the energetic plasticizer (s) in question is (are) advantageously of the nitrate and / or nitramine type.
  • the energetic plasticizer (s) in question is (are) very advantageously chosen 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 more particularly DNDA 5.7), nitratoethyl nitramines (in particular methyl-2-nitratoethyl nitramine (methylNENA) and ethyl-2-nitratoethyl nitramine (ethyl
  • the plasticizer (s) of the pyrotechnic products of the invention generally represent (s) from 10 to 30% by mass, more generally from 15 to 25% by mass, of the total composition of said products.
  • the energetic charges present are organic charges.
  • organic energy charges in question are not per se original. These are organic energetic fillers known per se and, for the most part, already packaged according to the prior art in crosslinked energetic polymeric binders (in particular of the PAG type). These are advantageously charges of hexogen (RDX), octogen (HMX), hexanitrohexaazaisowurtzitane (CL20), nitroguanidine (NGU), ethylene dinitramine (EDNA), N-guanylurea dinitramide (FOX 12 (GUDN)), 1,1-diamino-2,2-dinitroethylene (FOX 7 (DADE)), bis (triaminoguanidinium) 5,5'-azotetrazolate (TAGZT), 5,5'-azotetrazolate dihydrazinium (DHDZT), 5,5'-bis (tetrazolyl) hydrazine (HBT), bis (2,2-dinitropropyl) nitramine (BDNPN), a nitropyr
  • RDX and / or HMX there are energetic loads of RDX and / or HMX, more preferably energetic loads of RDX or HMX.
  • hexogen charges and / or octogen charges are particularly recommended insofar as these two types of charges offer a very satisfactory compromise: security / energy power and where it is also possible to take advantage, in within the scope of the invention, the achievements (resulting from the use of these two types of fillers in the prior art).
  • the organic energy charges are conventionally in the form of solid grains, distributed homogeneously within the plasticized crosslinked binder. These solid grains conveniently exhibit, in a manner known per se, several particle size distributions.
  • the organic energy charges of the pyrotechnic products of the invention generally represent from 50 to 70% by mass, more generally from 55 to 65% by mass, of the total composition of said products. It has been understood that said products have a high loading rate.
  • metal fillers aluminum, in particular
  • Such metal fillers are in fact capable of generating particles during their combustion, ie of generating primary fumes.
  • inorganic energetic charges of ammonium perchlorate, in particular
  • inorganic energetic charges are necessarily present, with reference to the desired discretion, in a small quantity ( ⁇ 4% by mass). They can be considered as additives (see below). Their presence may be opportune, with reference to the ballistic properties of the product.
  • the composite pyrotechnic products of the invention are moreover likely to contain, and generally contain, in their binder (crosslinked precursor polymer), in addition to the plasticizer (s), organic energy charges and specific anti-glow agent (s) , at least one additive.
  • binder crosslinked precursor polymer
  • organic energy charges and specific anti-glow agent (s)
  • anti-glare agents being able to be fully analyzed as additives.
  • Anti-glare agents have presently been isolated from other additives, insofar as they are present with reference to the technical problem presently considered and where they therefore constitute a key element of the products of the invention.
  • the composite pyrotechnic products of the invention therefore contain in their composition, in addition to the crosslinked polymer (PAG), the plasticizer (s), organic energy charges and the at least one specific anti-glow agent, at least one additive; said at least one additive comprising at least one crosslinking catalyst and / or at least one agent for stabilizing the plasticizer (s) present and / or at least one combustion catalyst.
  • Said at least one polymerization catalyst can in particular be chosen from triphenylbismuth and tin dibutyldilaurate (DBTL).
  • Said at least one agent for stabilizing the plasticizer (s) present may in particular consist of at least one aromatic amine, such as 2-nitrodiphenylamine (2-NDPA) and N-methylparanitroaniline (MNA). Present, it is generally present at a content of about 1% by mass.
  • Said at least one combustion catalyst can in particular be chosen from conventional combustion catalysts, such as lead salts and oxides, and bismuth citrate. Said bismuth citrate, in particular because of its lower toxicity, is preferred. The Applicant has described, in the patent application WO 2016/066245 , the advantageous use of said bismuth citrate as a combustion catalyst.
  • Said at least one combustion catalyst is generally present in the composition of the pyrotechnic products of the invention at a mass rate of 1 to 6%, very generally at a mass rate of 3 to 5%.
  • additives which may be present in the composition of the composite pyrotechnic products of the invention may in particular consist of inorganic energetic charges (see above) and of one or more processing agents (auxiliary (s) of manufacturing).
  • the said agent (s) is (are) generally present at a content of 1 to 2% by mass.
  • the additives optionally present generally represent a maximum of 10% by weight of the composition of the composite pyrotechnic products of the invention. They very generally represent from 0.1 to 10% by mass (often from 1.5 to 10% by mass) of the composition of said composite pyrotechnic products of the invention.
  • the composite pyrotechnic products of the invention are not of a new type but that they are new by virtue of the association, in their composition, of a specific binder (PAG crosslinked with at least one polyisocyanate) and at least one specific anti-glare agent.
  • a specific binder PAG crosslinked with at least one polyisocyanate
  • said composition is generally free of any other ingredient (in particular of any metallic filler) and therefore consists of the ingredients listed above, present in the amounts indicated above.
  • composite pyrotechnic products are suitable in particular as solid propellants for propellant charges of tactical missiles. Their use for this purpose is particularly recommended. It forms an integral part of the present invention.
  • the at least one anti-glare agent is introduced in the pulverulent state.
  • the partial vacuum mentioned is intended for degassing the medium above which it is applied. It is generally 10 mm Hg. We note incidentally that it is not necessarily of constant intensity.
  • the heat treatment (of crosslinking (of the hydroxytelechelic PAG)) is generally carried out at a temperature of between 30 and 60 ° C (30 ° C ⁇ T ⁇ 60 ° C), for several days.
  • the chemical compounds K 2 SO 4 , K 3 AlF 6 and C 4 H 5 KO 6 (monobasic potassium L-tartrate) were obtained from the company SIGMA-ALDRICH.
  • the figures 1, 2 and 3 appended represent, for each of the propellants tested (respectively that of comparative example C2 (with K 2 SO 4 (15 ⁇ m)), that of example 1 and that of example 2) the variations in temperature (temperature of equivalent black body radiation (° C)) along the axis of the jet (of gases generated) as a function of the distance (distance measured (in m) from the outlet of the nozzle); the propellant tested being at an operating pressure of 16 MPa (see point 5 below).
  • the thermal longitudinal profiles shown were obtained using IR cameras on Band II. These cameras made it possible to draw up a two-dimensional thermal profile of the jet emitted by the nozzle.
  • the anti-glow agents were present, in the compositions of the propellants (of comparative examples C1 and C2 and of examples 1 and 2 of the invention), at a quasi iso-content (approximately 0.9% by mass) of potassium.
  • compositions by weight of each of said propellants are shown in Table 1 below. We can more precisely speak of the compositions mass of the precursor paste of each of said propellants (before crosslinking). TABLE 1 Propellant (% by mass) Ex. C1 Ex. C2 Ex. 1 Ex.
  • the (binder precursor polymer the) poly glycidylazide (PAG) then the plasticizers (BTTN / TMETN) and the stabilizing agents (MNA / 2-NDPA) of said plasticizers were introduced.
  • the mixture was kneaded for 15 min at a temperature of 50 ° C.
  • the organic energy charges (RDX) were then added to said mixture, with stirring, per portion, then the combustion catalyst (bismuth citrate), the additives (other than the crosslinking agent and catalyst) and the anti- glow. Stirring was then continued for 2 h 30 min, at a temperature of 50 ° C. and under a vacuum of 10 mm Hg (which allowed the degassing of the medium), to obtain a homogeneous paste.
  • the crosslinking catalyst (DBTL (tin dibutyldilaurate) (55 ppm) was then added to said homogeneous paste and the medium was further stirred 30 min before the addition of the binder crosslinking agent (Desmodur® N 3300). Said crosslinking agent was finally added and the medium was further stirred for 15 min (still at 50 ° C. and under vacuum).
  • DBTL tin dibutyldilaurate
  • the 800 g batches of paste were used in part to assess the feasibility of the process for obtaining the propellants (to measure the pot life of the paste) and in part, after crosslinking, to evaluate the ballistic behavior of the propellant (to measure its combustion speed).
  • the pot life (which makes it possible to assess the feasibility of the process for obtaining the propellants) was determined by measuring the viscosity of the propellant paste in question (containing the crosslinking agent and the crosslinking catalyst) at over time, using a Brookfield viscometer (with body n ° 3 (mobile C) rotated at 1 revolution / min), at a temperature of 50 ° C. The time for which the viscosity reached 15 kPo was recorded in order to determine whether the propellant met the industrialization criterion, that is to say if said time recorded was greater than 10 h.
  • the burning rate was measured in a conventional manner at 20 ° C and 10 MPa.
  • firing pressure equal to 16 MPa (which corresponds to the maximum operating pressure during firing, which corresponds to the pressure during firing. so-called acceleration phase).
  • Certain characteristics of the jet were determined by optronic means, in particular by observation by IR cameras in Band II, by transmission / emission in the visible (at 632 nm), and by transmission / emission in the IR between 2 and 14 ⁇ m.
  • the thermal longitudinal profiles obtained by IR camera (Band II) make it possible to highlight black body equivalent temperature gradients in the jet.
  • the levels of transmission in the visible and in the IR make it possible to highlight the notion of transparency and therefore the effectiveness of the anti-glare agents tested.
  • a post combustion flame was present for the propellant according to comparative example C2.
  • the radiation level was high with a maximum black body equivalent temperature of 1400 ° C, located 1.2 m from the nozzle exit plane.
  • the post combustion flame was perfectly visible to the naked eye.
  • Example 1 of the invention For the propellant according to Example 1 of the invention, the composition of which contained K 3 AlF 6 , no post combustion flame was detected. The jet was considered inert. The level of radiation in band II remained low: the maximum black body equivalent temperature was 600 ° C. at the nozzle outlet (it did not exceed this value when moving away from the exit plane of said nozzle).
  • Example 2 of the invention For the propellant according to Example 2 of the invention, the composition of which contained C 4 H 5 KO 6 , in the same way, no post-combustion flame was detected.
  • the jet was considered inert.
  • the level of radiation in band II remained low: the temperature maximum black body equivalent was 650 ° C at the nozzle outlet (it did not exceed this value when moving away from the outlet plane of said nozzle). This maximum temperature is a little higher than that obtained with K 3 AlF 6 .

Description

La présente invention concerne des produits pyrotechniques composites, convenant notamment comme propergols solides pour chargements propulsifs de missiles tactiques. Il s'agit plus précisément de produits pyrotechniques composites, renfermant un fort taux de charges énergétiques organiques dans un liant énergétique. La composition desdits produits est optimisée en référence au problème technique de la discrétion desdits produits lors de leur combustion, plus précisément en référence au problème technique de l'obtention d'un compromis intéressant en termes de discrétion et de pouvoir énergétique.The present invention relates to composite pyrotechnic products, suitable in particular as solid propellants for the propellant charges of tactical missiles. They are more precisely composite pyrotechnic products, containing a high rate of organic energetic charges in an energetic binder. The composition of said products is optimized with reference to the technical problem of the discretion of said products during their combustion, more precisely with reference to the technical problem of obtaining an interesting compromise in terms of discretion and energy power.

Le problème technique de la discrétion (des propergols solides des chargements propulsifs) des missiles est un réel problème technique.The technical problem of the discretion (of the solid propellants of the propellants) of the missiles is a real technical problem.

Il est bien connu de l'homme du métier :

  • qu'ils existent deux phases de tir, lors du tir d'un missile tactique : une phase dite d'accélération où la pression de fonctionnement est maximale (la valeur de cette pression de fonctionnement maximale étant évidemment liée au pouvoir énergétique du propergol en combustion) et une phase dite de croisière où la pression de fonctionnement est minimale (généralement de l'ordre de 2 à 3 MPa) ;
  • que la discrétion d'un missile tactique, i.e. celle de son chargement de propergol s'apprécie à l'aptitude dudit chargement, lors de sa combustion, à émettre des fumées (fumées primaires (résultant de la combustion, dans le jet de gaz produit, des particules solides également produites) et/ou fumées secondaires (si du perchlorate d'ammonium est présent dans la composition du propergol)) et à engendrer des lueurs (dues au phénomène de post combustion, i.e. à la ré-inflammation des gaz de combustion) ; et
  • que ladite discrétion est évidemment plus difficile à gérer en phase dite d'accélération.
It is well known to those skilled in the art:
  • that there are two firing phases, when firing a tactical missile: a so-called acceleration phase where the operating pressure is maximum (the value of this maximum operating pressure being obviously linked to the energetic power of the burning propellant ) and a so-called cruising phase where the operating pressure is minimal (generally of the order of 2 to 3 MPa);
  • that the discretion of a tactical missile, i.e. that of its propellant charge is assessed by the ability of said charge, during its combustion, to emit fumes (primary fumes (resulting from combustion, in the gas jet produced , solid particles also produced) and / or secondary fumes (if ammonium perchlorate is present in the composition of the propellant)) and to generate glows (due to the phenomenon of post combustion, ie to the re-ignition of the combustion gases); and
  • that said discretion is obviously more difficult to manage in the so-called acceleration phase.

Dans ce contexte de la combustion des propergols, en référence au problème technique de la discrétion, voire à un problème technique de nature différente, il a été préconisé d'incorporer divers types d'additifs dans la composition de propergols.In this context of the combustion of propellants, with reference to the technical problem of discretion, or even to a technical problem of a different nature, it has been recommended to incorporate various types of additives in the composition of propellants.

Dans un premier temps, pour notamment les missiles tactiques, des propergols double base (nitrocellulose/nitroglycérine) ont été développés. De tels propergols, économiques à produire et très discrets (grâce à la présence, au sein de leur composition, d'additifs (agents anti-lueurs) performants), sont toujours d'actualité.Initially, for tactical missiles in particular, dual-base propellants (nitrocellulose / nitroglycerin) were developed. Such propellants, economical to produce and very discreet (thanks to the presence, within their composition, of high-performance additives (anti-glare agents)), are still relevant today.

Dans ce contexte des propergols solides double base, il a notamment été décrit :

  • l'utilisation de cryolite (Na3AlF6) et de fluorure de potassium et d'aluminium (= de cryolithe de potassium ; (K3AlF6)), comme additifs réduisant le flash émis au moment d'un tir d'arme à feu (voir la partie introductive du brevet US 4 078 955 ). De tels additifs, efficaces, présentent toutefois l'inconvénient (dans ce contexte) de générer, lors de la combustion, de l'alumine et des fluorures, qui provoquent usure et corrosion dans le canon ;
  • l'utilisation de cryolite de potassium (K3AlF6), comme catalyseur de combustion et celle de sels alcalins, tels le sulfate de potassium (K2SO4), le nitrate de potassium, le fluorure de potassium et d'aluminium (= la cryolithe de potassium ; (K3AlF6)), le tartrate de potassium hydrogéné, comme additifs anti-lueurs (voir l'enseignement du brevet US 4 381 270 ) ;
  • l'utilisation de ces mêmes sels alcalins : le sulfate de potassium (K2SO4), le nitrate de potassium, le fluorure de potassium et d'aluminium (= la cryolithe de potassium ; (K3AlF6)), le tartrate de potassium hydrogéné, comme additifs anti-lueurs (voir les enseignements du brevet US 3 960 621 et de la demande de brevet EP 0 219 431 ) ;
  • l'utilisation de cryolite de potassium (K3AlF6), comme co-catalyseur (voir l'enseignement de la demande de brevet GB 2 258 230 ).
In this context of solid double-base propellants, it has been described in particular:
  • the use of cryolite (Na 3 AlF 6 ) and potassium and aluminum fluoride (= potassium cryolite; (K 3 AlF 6 )), as additives reducing the flash emitted when firing a weapon fire (see the introductory part of the patent US 4,078,955 ). Such additives, which are effective, however, have the drawback (in this context) of generating, during combustion, alumina and fluorides, which cause wear and corrosion in the barrel;
  • the use of potassium cryolite (K 3 AlF 6 ), as a combustion catalyst and that of alkaline salts, such as potassium sulphate (K 2 SO 4 ), potassium nitrate, potassium aluminum fluoride ( = potassium cryolite; (K 3 AlF 6 )), hydrogenated potassium tartrate, as anti-glare additives (see the teaching of the patent US 4,381,270 );
  • the use of these same alkaline salts: potassium sulfate (K 2 SO 4 ), potassium nitrate, potassium aluminum fluoride (= potassium cryolite; (K 3 AlF 6 )), tartrate of hydrogenated potassium, as anti-glare additives (see the teachings of the patent US 3,960,621 and the patent application EP 0 219 431 );
  • the use of potassium cryolite (K 3 AlF 6 ) as a co-catalyst (see the teaching of the patent application GB 2 258 230 ).

La demande de brevet US 2011/0284140 décrit l'éventuelle présence d'additifs anti-lueurs (notamment choisis parmi une cryolite, l'oxalate de sodium, le sulfate de potassium, le nitrate de potassium, un autre sel de potassium et leurs mélanges) dans des compositions double-base composites pour armes à tubes (armes légères). Lesdites compositions renferment typiquement essentiellement des charges énergétiques, de la nitrocellulose, du butyrate d'acétate de cellulose, un plastifiant énergétique et des additifs. Elles sont susceptibles de renfermer en outre au moins un liant supplémentaire, énergétique tel que le polyazoture de glycidyle (PAG ; non réticulé) ou non énergétique tel que le polybutadiène à fonctions hydroxyle terminales (PBHT).The patent application US 2011/0284140 describes the possible presence of anti-glare additives (in particular chosen from a cryolite, sodium oxalate, potassium sulphate, potassium nitrate, another potassium salt and their mixtures) in composite double-base compositions for tube guns (small arms). Said compositions typically contain essentially energetic fillers, nitrocellulose, cellulose acetate butyrate, an energetic plasticizer and additives. They may also contain at least one additional binder, energetic such as poly glycidylazide (PAG; uncrosslinked) or non-energetic such as polybutadiene with terminal hydroxyl functions (PBHT).

Les propergols solides double base présentent toutefois des performances énergétiques plus modestes que celles des propergols composites développés dans un deuxième temps. Ont tout particulièrement été développés, notamment pour les missiles tactiques, des propergols composites de type Nitramite® et Azamite®.However, solid double-base propellants have more modest energy performance than those of composite propellants developed in a second step. Composite propellants of the Nitramite® and Azamite® type have been particularly developed, in particular for tactical missiles.

Les propergols composites de type Nitramite® renferment des charges énergétiques (de type RDX ou HMX) dans un liant réticulé (de type polyester, polyéther ou polycaprolactone), plastifié avec de la nitroglycérine. En référence au problème technique de leur discrétion, leur composition a été optimisée en ce qu'elle ne renferme pas de charges métalliques (telles des charges d'aluminium) aptes à générer des fumées primaires, pas ou peu de charges énergétiques inorganiques (telles des charges de perchlorate d'ammonium) aptes à générer des fumées secondaires et en ce qu'elle renferme des agents anti-leurs efficaces aptes à minimiser, voire supprimer les phénomènes de post combustion (on note incidemment ici que les nature et quantité d'agents anti-lueurs sont à optimiser dans la mesure où lesdits agents anti-lueurs sont susceptibles de générer des fumées primaires et/ou secondaires). A titre d'agents anti-lueurs efficaces, il a été proposé des composés à base de métaux alcalins, sodium (Na2SO4,...) et surtout potassium (K2SO4, KNO3, K3AlF6, ...). A ce propos, on peut se référer à l'enseignement du livre « Technologie des propergols solides » par Alain DAVENAS (Editeur Masson), 1988, page 549 . Des résultats très satisfaisants ont ainsi été obtenus (notamment avec utilisation de K2SO4, comme agent anti-lueur) dans les conditions d'utilisation de ces propergols composites de type Nitramite® (pressions de tir jusqu'à 10-12 MPa, en phase dite d'accélération).Composite propellants of the Nitramite® type contain energetic charges (of the RDX or HMX type) in a crosslinked binder (of the polyester, polyether or polycaprolactone type), plasticized with nitroglycerin. With reference to the technical problem of their discretion, their composition has been optimized in that it does not contain metallic charges (such as aluminum charges) capable of generating primary fumes, no or few inorganic energetic charges (such as ammonium perchlorate charges) capable of generating secondary fumes and in that it contains effective anti-their agents capable of minimizing or even eliminating post-combustion phenomena (we note incidentally here that the nature and quantity of anti-glare agents should be optimized insofar as said anti-glare agents are capable of generating primary and / or secondary fumes). As effective anti-glow agents, it has been proposed compounds based on alkali metals, sodium (Na 2 SO 4 , ...) and especially potassium (K 2 SO 4 , KNO 3 , K 3 AlF 6 , ...). In this regard, we can refer to the teaching of the book “Solid propellant technology” by Alain DAVENAS (Publisher Masson), 1988, page 549 . Very satisfactory results were thus obtained (in particular with the use of K 2 SO 4 , as an anti-glare agent) under the conditions of use of these composite propellants of the Nitramite® type (firing pressures up to 10-12 MPa, in the so-called acceleration phase).

Les propergols composites de type Azamite® sont des propergols encore plus énergétiques que ceux de type Nitramite®. Ils renferment des charges énergétiques (de type RDX ou HMX) dans un liant énergétique réticulé (de type polyazoture de glycidyle (PAG)), plastifié avec au moins un plastifiant énergétique. Ils sont opportunément utilisés jusqu'à des pressions de tir de l'ordre de 16 MPa, en phase dite d'accélération. Dans de telles conditions, les agents anti-lueurs de l'art antérieur (voir ci-dessus) se sont révélés inefficaces (pour notamment réduire de façon substantielle le phénomène de post combustion ; plus généralement en référence au problème technique de la discrétion). Les inventeurs ont tout particulièrement mis en évidence (au sein donc de propergols de type Azamite®) l'inefficacité de K2SO4 (d50 = 285 µm) conventionnellement utilisé au sein des propergols de type Nitramite®. Ils ont testé (au sein de propergols de type Azamite®) ce même agent anti-lueur de l'art antérieur, en l'utilisant à plus faible granulométrie (d50 = 15 µm). Ils ont alors constaté que le phénomène de post combustion demeurait, malgré une amélioration sensible de la transmission dans le visible. Ils ont constaté qu'une flamme de post combustion était toujours présente (voir l'exemple comparatif C2 ci-après ainsi que la figure 1 annexée). L'homme du métier conçoit parfaitement que, dans un tel contexte, d'utilisation d'un propergol plus énergétique (Azamite®/Nitramite®) avec volonté d'optimiser les performances du moteur (pression en phase d'accélération : jusqu'à 16 MPa/10-12 MPa)), les problèmes de post combustion sont exacerbés. Il conçoit parfaitement que le problème technique de la discrétion est plus difficile à gérer.Azamite® type composite propellants are even more energetic propellants than Nitramite® type propellants. They contain energetic charges (of RDX or HMX type) in a crosslinked energetic binder (of polyglycidyl azide (PAG) type), plasticized with at least one energetic plasticizer. They are suitably used up to firing pressures of the order of 16 MPa, in the so-called acceleration phase. Under such conditions, the anti-glare agents of the prior art (see above) have proved to be ineffective (in particular to substantially reduce the phenomenon of post combustion; more generally with reference to the technical problem of discretion). Inventors have it all particularly highlighted (therefore within Azamite® type propellants) the ineffectiveness of K 2 SO 4 (d 50 = 285 µm) conventionally used in Nitramite® type propellants. They tested (in Azamite® type propellants) this same anti-glare agent of the prior art, using it with a smaller particle size (d 50 = 15 μm). They then observed that the post-combustion phenomenon remained, despite a significant improvement in transmission in the visible range. They found that a post combustion flame was still present (see comparative example C2 below as well as figure 1 annexed). Those skilled in the art understand perfectly that, in such a context, the use of a more energetic propellant (Azamite® / Nitramite®) with the desire to optimize engine performance (pressure in the acceleration phase: up to 16 MPa / 10-12 MPa)), post combustion problems are exacerbated. He fully understands that the technical problem of discretion is more difficult to manage.

De manière générale, l'homme du métier conçoit que la discrétion d'un produit pyrotechnique composite est d'autant plus problématique que les performances énergétiques dudit produit pyrotechnique composite sont élevées.In general, those skilled in the art understand that the discretion of a composite pyrotechnic product is all the more problematic the higher the energy performance of said composite pyrotechnic product.

Il est du mérite des inventeurs de proposer, dans un contexte particulier (de propergols très énergétiques, destinés à être mis en combustion à haute pression (en phase d'accélération)), des agents anti-lueurs efficaces (lesdits agents anti-lueurs sont présents conventionnellement dans la composition des propergols à l'état de poudres ; ils sont introduits, conventionnellement, à l'état de poudres, lors de la préparation desdits propergols). Il est du mérite des inventeurs de proposer un nouveau propergol composite à liant énergétique spécifique (liant = un polymère énergétique spécifique (de type polyazoture de glycidyle (PAG) hydroxytéléchélique) réticulé avec au moins un polyisocyanate), renfermant au moins un agent anti-lueur spécifique dans sa composition. Ce nouveau propergol composite est performant sur le plan énergétique (il présente notamment une haute vitesse de combustion) et reste discret (même en phase d'accélération, à des pressions jusqu'à 16 MPa).It is to the inventors' merit to propose, in a particular context (very energetic propellants, intended to be combusted at high pressure (in the acceleration phase)), effective anti-glare agents (said anti-glare agents are conventionally present in the composition of propellants in the state of powders; they are introduced, conventionally, in the state of powders, during the preparation of said propellants). It is to the inventors' merit to propose a new composite propellant with a specific energetic binder (binder = a specific energetic polymer (of the polyazide type of hydroxytelechelic glycidyl (PAG) crosslinked with at least one polyisocyanate), containing at least one specific anti-glare agent in its composition. This new composite propellant is energy efficient (it has a high combustion speed in particular) and remains discreet (even in the acceleration phase, at pressures up to 16 MPa).

Selon son premier objet, la présente invention concerne donc de nouveaux produits pyrotechniques composites, fortement énergétiques. Ils sont du type à liant énergétique réticulé renfermant des charges énergétiques organiques. Ils renferment, plus précisément, dans un liant plastifié, comprenant un polymère énergétique réticulé et au moins un plastifiant énergétique, des charges énergétiques organiques et au moins un agent anti-lueur de type sel de potassium. De façon caractéristique :

  • ledit polymère énergétique réticulé consiste en un polyazoture de glycidyle (PAG), ayant une masse moléculaire moyenne en nombre (Mn) comprise entre 700 et 3000 g/mol, réticulé, via ses fonctions terminales hydroxyles, avec au moins un agent de réticulation de type polyisocyanate ; et
  • ledit au moins un agent anti-lueur de type sel de potassium est choisi parmi la cryolite de potassium (K3AlF6), le tartrate de potassium monobasique (C4H5KO6) et leurs mélanges.
According to its first object, the present invention therefore relates to novel, highly energetic, composite pyrotechnic products. They are of the type with a crosslinked energy binder containing organic energy charges. They contain, more precisely, in a plasticized binder, comprising a crosslinked energetic polymer and at least one energetic plasticizer, organic energetic fillers and at least one anti-glare agent of the potassium salt type. Characteristically:
  • said crosslinked energetic polymer consists of a polyglycidylazide (PAG), having a number-average molecular mass (Mn) of between 700 and 3000 g / mol, crosslinked, via its terminal hydroxyl functions, with at least one crosslinking agent of the type polyisocyanate; and
  • said at least one anti-glare agent of potassium salt type is chosen from potassium cryolite (K 3 AlF 6 ), monobasic potassium tartrate (C 4 H 5 KO 6 ) and mixtures thereof.

La structure des produits pyrotechniques composites de l'invention associe donc, de façon caractéristique, un liant spécifique (énergétique) et au moins un agent anti-lueur (de type sel de potassium) spécifique.The structure of the composite pyrotechnic products of the invention therefore associates, in a characteristic manner, a specific (energetic) binder and at least one specific anti-glare agent (of the potassium salt type).

La nature du liant (celle de son polymère précurseur (énergétique)) constitue donc l'un des éléments clés (de la composition) des produits pyrotechniques composites de l'invention. La nature du au moins un agent anti-lueur (de type sel de potassium) présent constitue donc l'autre des éléments clés (de la composition) des produits pyrotechniques composites de l'invention.The nature of the binder (that of its precursor (energy) polymer) therefore constitutes one of the key elements (of the composition) of the composite pyrotechnic products of the invention. Nature from to less one anti-glare agent (of potassium salt type) present therefore constitutes the other of the key elements (of the composition) of the composite pyrotechnic products of the invention.

Ledit au moins un agent anti-lueur présent dans la composition des produits pyrotechniques composites de l'invention consiste donc en la cryolite de potassium (= le fluorure de potassium et d'aluminium ; (K3AlF6)), le tartrate de potassium monobasique (C4H5KO6) (ledit tartrate de potassium monobasique consistant lui-même en le L-tartrate de potassium monobasique, le D-tartrate de potassium monobasique ou en un mélange de ces deux formes énantiomères ; il consiste avantageusement en le L-tartrate de potassium monobasique (moins onéreux que le D-tartrate de potassium monobasique)) ou un de leurs mélanges. Il consiste avantageusement en la cryolite de potassium (K3AlF6) ou en le tartrate de potassium monobasique (C4H5KO6) (ledit tartrate de potassium monobasique consistant avantageusement en le L-tartrate de potassium monobasique (voir ci-dessus)). Il consiste très avantageusement en la cryolite de potassium (K3AlF6) (la signature en infra-rouge de ladite cryolite de potassium est plus discrète que celle dudit tartrate de potassium monobasique). Ces sels spécifiques de potassium, dont il est proposé, dans le cadre de l'invention, une utilisation originale (comme agents anti-lueurs pour propergols très énergétiques du type précisé (destinés à être mis en combustion à haute pression (en phase d'accélération))), sont des composés connus, disponibles commercialement, à des granulométries conventionnelles (poudres avec des grains présentant généralement un d50 entre 1 et 300 µm).Said at least one anti-glare agent present in the composition of the composite pyrotechnic products of the invention therefore consists of potassium cryolite (= potassium aluminum fluoride; (K 3 AlF 6 )), potassium tartrate monobasic (C 4 H 5 KO 6 ) (said monobasic potassium tartrate itself consisting of monobasic potassium L-tartrate, monobasic potassium D-tartrate or a mixture of these two enantiomeric forms; it advantageously consists of Monobasic potassium L-tartrate (less expensive than monobasic potassium D-tartrate)) or a mixture thereof. It advantageously consists of potassium cryolite (K 3 AlF 6 ) or of monobasic potassium tartrate (C 4 H 5 KO 6 ) (said monobasic potassium tartrate advantageously consisting of monobasic potassium L-tartrate (see above )). It very advantageously consists of potassium cryolite (K 3 AlF 6 ) (the infrared signature of said potassium cryolite is more discreet than that of said monobasic potassium tartrate). These specific potassium salts, for which it is proposed, within the framework of the invention, an original use (as anti-glare agents for very energetic propellants of the specified type (intended to be put in combustion at high pressure (in phase of acceleration))), are known compounds, available commercially, with conventional particle sizes (powders with grains generally having an d 50 between 1 and 300 μm).

Ledit au moins un agent anti-lueur original est évidemment opportunément présent en une quantité efficace mais non excessive (le(s) sel(s) de potassium ajouté(s) convenant pour minimiser le phénomène de post combustion mais étant susceptible(s) de générer des fumées primaires et, en tout état de cause, influant, de façon négative, sur le pouvoir énergétique). Cette quantité efficace et non excessive est généralement telle qu'elle assure dans la composition du produit une teneur en potassium de 0,2 à 5 % en masse, avantageusement de 0,2 à 2,5 % en masse. Cette teneur avantageuse en potassium de 0,2 à 2,5 % en masse correspond environ à une teneur massique, en l'un et/ou l'autre desdits sels spécifiques de potassium, de 1 à 5 %. On conçoit qu'à teneur équivalente en potassium recherchée, la teneur en C4H5KO6 requise est supérieure à celle requise en K3AlF6.Said at least one original anti-glow agent is obviously expediently present in an effective but not excessive amount (the added potassium salt (s) being suitable for minimizing the phenomenon of post combustion but being likely (s) to generate primary fumes and, in any case, negatively influencing the energy capacity). This effective and non-excessive amount is generally such as to ensure in the composition of the product a potassium content of 0.2 to 5% by mass, advantageously from 0.2 to 2.5% by mass. This advantageous potassium content of 0.2 to 2.5% by mass corresponds approximately to a mass content, of one and / or the other of said specific potassium salts, of 1 to 5%. It is understood that at the desired equivalent potassium content, the required C 4 H 5 KO 6 content is greater than that required in K 3 AlF 6 .

En référence à la nature du liant (liant énergétique donc), plus particulièrement à celle de son polymère précurseur (polyazoture de glycidyle hydroxytéléchélique), on peut ajouter ce qui suit.With reference to the nature of the binder (therefore energetic binder), more particularly to that of its precursor polymer (polyhydroxytelechelic glycidyl azide), the following can be added.

Notons tout d'abord que le « un » polyazoture de glycidyle doit se lire « au moins un » polyazoture de glycidyle dans tout le présent texte. En effet, il est nullement exclu du cadre de l'invention qu'un mélange d'au moins deux polyazotures de glycidyle (présentant des masses moléculaires (entre 700 et 3000 g/mol) et/ou des taux de ramification différents) soit utilisé comme polymère précurseur du liant des produits de l'invention.It should be noted first of all that the “one” poly glycidyl azide should read “at least one” poly glycidyl azide throughout the present text. Indeed, it is in no way excluded from the scope of the invention that a mixture of at least two glycidyl polyazides (having molecular masses (between 700 and 3000 g / mol) and / or different branching rates) is used. as precursor polymer for the binder of the products of the invention.

Le polymère énergétique précurseur du liant des produits de l'invention est donc un polyazoture, un polyazoture de glycidyle (PAG) qui présente des fonctions terminales hydroxy (un PAG hydroxytéléchélique) ; d'où 1) ses propriétés énergétiques et 2) sa capacité à être réticulé avec les agents de réticulation de type polyisocyanate.The precursor energetic polymer of the binder of the products of the invention is therefore a polyazide, a glycidyl polyazide (PAG) which has terminal hydroxy functions (a hydroxytelechelic PAG); hence 1) its energetic properties and 2) its ability to be crosslinked with polyisocyanate type crosslinking agents.

Ledit polymère a une masse moléculaire adéquate (notamment, en référence à sa consistance (liquide) et à la consistance de son mélange avec essentiellement les charges (énergétiques organiques) et en référence à la teneur relative du liant réticulé en agent(s) de réticulation), masse moléculaire moyenne en nombre (Mn) comprise entre 700 et 3000 g/mol, avantageusement entre 1700 et 2300 g/mol.Said polymer has an adequate molecular mass (in particular, with reference to its consistency (liquid) and to the consistency of its mixture with essentially the charges (organic energy) and in reference to the relative content of the crosslinked binder of crosslinking agent (s)), number-average molecular mass (Mn) of between 700 and 3000 g / mol, advantageously between 1700 and 2300 g / mol.

Les agents de réticulation, de type polylsocyanate (au moins bifonctionnels), convenant à la réticulation d'un tel polyazoture de glycidyle (PAG) hydroxytéléchélique sont connus per se. Il peut notamment s'agir de di- ou triisocyanates. Il s'agit avantageusement de polyisocyanates, liquides, choisis parmi le toluène diisocyanate (TDI), l'isophorone diisocyanate (IPDI), le dicyclohexylméthylène diisocyanate (MDCI), l'hexaméthylène diisocyanate (HDI), le trimère dudit hexaméthylène diisocyanate (notamment commercialisé par la société Bayer sous la dénomination commerciale Desmodur® N 3300), le biuret trihexane isocyanate (BTHI), le 3,5,5-triméthyl-1,6-hexaméthylène diisocyanate et leurs mélanges. De façon particulièrement préférée, on utilise le trimère de l'hexaméthylène diisocyanate.The crosslinking agents, of the polylsocyanate type (at least bifunctional), suitable for the crosslinking of such a hydroxytelechelic polyglycidylazide (PAG) are known per se. They may in particular be di- or triisocyanates. They are advantageously polyisocyanates, liquids, chosen from toluene diisocyanate (TDI), isophorone diisocyanate (IPDI), dicyclohexylmethylene diisocyanate (MDCI), hexamethylene diisocyanate (HDI), the trimer of said hexamethylene diisocyanate (in particular sold by the company Bayer under the trade name Desmodur® N 3300), biuret trihexane isocyanate (BTHI), 3,5,5-trimethyl-1,6-hexamethylene diisocyanate and mixtures thereof. Particularly preferably, the trimer of hexamethylene diisocyanate is used.

Lesdits agents de réticulation sont conventionnellement utilisés en quantité nécessaire et suffisante, pour assurer la réticulation du polymère (non excessive pour ne pas polluer le produit réticulé obtenu). Ils sont conventionnellement utilisés en une quantité telle que le rapport de pontage (NCO (de l'agent de réticulation) /OH (du polymère)) soit compris entre 0,8 et 1,4, soit avantageusement de 1,2.Said crosslinking agents are conventionally used in the necessary and sufficient quantity, to ensure crosslinking of the polymer (not excessive so as not to pollute the crosslinked product obtained). They are conventionally used in an amount such that the bridging ratio (NCO (of the crosslinking agent) / OH (of the polymer)) is between 0.8 and 1.4, or advantageously 1.2.

Le polymère énergétique réticulé représente généralement de 9 à 14 % en masse de la composition totale des produits pyrotechniques composites de l'invention. Le polymère énergétique per se est généralement intervenu pour 7 à 12 % en masse, le au moins un agent de réticulation pour environ 2 % en masse.The crosslinked energetic polymer generally represents from 9 to 14% by weight of the total composition of the composite pyrotechnic products of the invention. The energetic polymer per se is generally involved for 7 to 12% by mass, the at least one crosslinking agent for about 2% by mass.

On a bien compris que la nature du liant (de son polymère précurseur) n'est pas per se originale mais que l'intérêt de l'invention repose sur l'association d'un tel (polymère précurseur de) liant, énergétique, avec au moins un agent anti-lueur (de type sel de potassium) spécifique.It has been understood that the nature of the binder (of its precursor polymer) is not per se original but that the interest of the invention is based on the association of such an energetic binder (precursor polymer) with at least one specific anti-glare agent (of the potassium salt type).

De façon conventionnelle, au liant énergétique, est associé au moins un plastifiant énergétique. Le(s) plastifiant(s) énergétique(s) en cause est(sont) avantageusement de type nitrate et/ou nitramine. Le(s) plastifiant(s) énergétique(s) en cause est(sont) très avantageusement choisi(s) parmi le dinitrate de diéthylène glycol (DEGDN), le dinitrate de triéthylène glycol (TEGDN), le trinitrate de butanetriol (BTTN), le trinitrate de triméthyloléthane (TMETN), un mélange de 2,4-dinitro-2,4-diaza-pentane, de 2,4-dinitro-2,4-diaza-hexane et de 3,5-dinitro-3,5-diaza-heptane (et tout particulièrement le DNDA 5,7), les nitrato éthyl nitramines (notamment le méthyl-2-nitratoéthyl nitramine (méthylNENA) et l'éthyl-2-nitratoéthyl nitramine (éthylNENA)) et leurs mélanges.Conventionally, the energetic binder is associated with at least one energetic plasticizer. The energetic plasticizer (s) in question is (are) advantageously of the nitrate and / or nitramine type. The energetic plasticizer (s) in question is (are) very advantageously chosen 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 more particularly DNDA 5.7), nitratoethyl nitramines (in particular methyl-2-nitratoethyl nitramine (methylNENA) and ethyl-2-nitratoethyl nitramine (ethylNENA)) and their mixtures.

Le(s) plastifiant(s) des produits pyrotechniques de l'invention représente(nt) généralement de 10 à 30 % en masse, plus généralement de 15 à 25 % en masse, de la composition totale desdits produits.The plasticizer (s) of the pyrotechnic products of the invention generally represent (s) from 10 to 30% by mass, more generally from 15 to 25% by mass, of the total composition of said products.

Les charges énergétiques présentes sont des charges organiques.The energetic charges present are organic charges.

Les charges énergétiques organiques en cause ne sont pas per se originales. Il s'agit de charges énergétiques organiques connues per se et, pour la plupart, déjà conditionnées selon l'art antérieur dans des liants polymériques énergétiques réticulés (notamment de type PAG). Il s'agit avantageusement de charges d'hexogène (RDX), d'octogène (HMX), d'hexanitrohexaazaisowurtzitane (CL20), de nitroguanidine (NGU), d'éthylène dinitramine (EDNA), de dinitramide de N-guanylurée (FOX 12 (GUDN)), de 1,1-diamino-2,2-dinitro éthylène (FOX 7 (DADE)), de 5,5'-azotétrazolate de bis(triaminoguanidinium) (TAGZT), de 5,5'-azotétrazolate de dihydrazinium (DHDZT), de 5,5'-bis(tétrazolyl)hydrazine (HBT), de bis(2,2-dinitropropyl) nitramine (BDNPN), d'un nitropyrazole ou d'un mélange de ces charges (énergétiques organiques).The organic energy charges in question are not per se original. These are organic energetic fillers known per se and, for the most part, already packaged according to the prior art in crosslinked energetic polymeric binders (in particular of the PAG type). These are advantageously charges of hexogen (RDX), octogen (HMX), hexanitrohexaazaisowurtzitane (CL20), nitroguanidine (NGU), ethylene dinitramine (EDNA), N-guanylurea dinitramide (FOX 12 (GUDN)), 1,1-diamino-2,2-dinitroethylene (FOX 7 (DADE)), bis (triaminoguanidinium) 5,5'-azotetrazolate (TAGZT), 5,5'-azotetrazolate dihydrazinium (DHDZT), 5,5'-bis (tetrazolyl) hydrazine (HBT), bis (2,2-dinitropropyl) nitramine (BDNPN), a nitropyrazole or a mixture of these fillers (organic energy ).

Au sein des produits pyrotechniques composites de l'invention, on trouve donc un type de charge énergétique, avantageusement choisi parmi la liste ci-dessus, ou un mélange d'au moins deux types de charge énergétique, avantageusement choisis parmi la liste ci-dessus.Within the composite pyrotechnic products of the invention, there is therefore a type of energy charge, advantageously chosen from the above list, or a mixture of at least two types of energy charge, advantageously chosen from the above list. .

De façon préférée, on y trouve des charges énergétiques de RDX et/ou HMX, de façon plus préférée, des charges énergétiques de RDX ou de HMX.Preferably, there are energetic loads of RDX and / or HMX, more preferably energetic loads of RDX or HMX.

L'utilisation de charges d'hexogène et/ou de charges d'octogène est particulièrement préconisée dans la mesure où ces deux types de charges offrent un très satisfaisant compromis : sécurité/pouvoir énergétique et où il est aussi possible de mettre à profit, dans le cadre de l'invention, des acquis (résultant de l'utilisation de ces deux types de charges dans l'art antérieur).The use of hexogen charges and / or octogen charges is particularly recommended insofar as these two types of charges offer a very satisfactory compromise: security / energy power and where it is also possible to take advantage, in within the scope of the invention, the achievements (resulting from the use of these two types of fillers in the prior art).

Les charges énergétiques organiques se présentent conventionnellement sous la forme de grains solides, répartis de façon homogène au sein du liant réticulé plastifié. Ces grains solides présentent opportunément, de façon connue per se, plusieurs distributions granulométriques.The organic energy charges are conventionally in the form of solid grains, distributed homogeneously within the plasticized crosslinked binder. These solid grains conveniently exhibit, in a manner known per se, several particle size distributions.

Les charges énergétiques organiques des produits pyrotechniques de l'invention représentent généralement de 50 à 70 % en masse, plus généralement de 55 à 65 % en masse, de la composition totale desdits produits. On a compris que lesdits produits sont à fort taux de charge.The organic energy charges of the pyrotechnic products of the invention generally represent from 50 to 70% by mass, more generally from 55 to 65% by mass, of the total composition of said products. It has been understood that said products have a high loading rate.

En référence à la discrétion recherchée, la présence de charges métalliques (d'aluminium, notamment), au sein du liant plastifié des produits pyrotechniques de l'invention, est, elle, généralement exclue. De telles charges métalliques sont en effet susceptibles de générer des particules lors de leur combustion, i.e. de générer des fumées primaires.With reference to the desired discretion, the presence of metal fillers (aluminum, in particular), within the plasticized binder of the pyrotechnic products of the invention, is itself generally excluded. Such metal fillers are in fact capable of generating particles during their combustion, ie of generating primary fumes.

La présence de charges énergétiques inorganiques (de perchlorate d'ammonium, notamment), au sein du liant plastifié des produits pyrotechniques de l'invention, n'est pas souhaitée mais ne saurait être totalement exclue. En tout état de cause, de telles charges énergétiques inorganiques, présentes, le sont obligatoirement, en référence à la discrétion recherchée, en faible quantité (< 4 % en masse). Elles peuvent être considérées comme des additifs (voir ci-après). Leur présence peut être opportune, en référence aux propriétés balistiques du produit.The presence of inorganic energetic charges (of ammonium perchlorate, in particular), within the plasticized binder of the pyrotechnic products of the invention, is not desired but cannot be totally excluded. In any event, such inorganic energetic charges, present, are necessarily present, with reference to the desired discretion, in a small quantity (<4% by mass). They can be considered as additives (see below). Their presence may be opportune, with reference to the ballistic properties of the product.

Les produits pyrotechniques composites de l'invention sont par ailleurs susceptibles de renfermer, et renferment généralement, dans leur liant (polymère précurseur réticulé), outre les plastifiant(s), charges énergétiques organiques et agent(s) anti-lueur spécifique(s), au moins un additif. On peut plus justement parler d'au moins un autre additif, les agents anti-lueur pouvant tout à fait s'analyser comme des additifs. Les agents anti-lueur ont été présentement isolés des autres additifs, dans la mesure où ils sont présents en référence au problème technique présentement considéré et où ils constituent donc un élément clé des produits de l'invention.The composite pyrotechnic products of the invention are moreover likely to contain, and generally contain, in their binder (crosslinked precursor polymer), in addition to the plasticizer (s), organic energy charges and specific anti-glow agent (s) , at least one additive. We can more accurately speak of at least one other additive, the anti-glare agents being able to be fully analyzed as additives. Anti-glare agents have presently been isolated from other additives, insofar as they are present with reference to the technical problem presently considered and where they therefore constitute a key element of the products of the invention.

Parmi les additifs opportunément présents, on privilégie les additifs conventionnels ci-après : les catalyseurs de réticulation, les agents de stabilisation du(des) plastifiant(s) énergétique(s) présent(s) et les catalyseurs de combustion. Ainsi, selon une variante avantageuse, les produits pyrotechniques composites de l'invention renferment donc dans leur composition, outre le polymère (PAG) réticulé, les plastifiant(s), charges énergétiques organiques et le au moins un agent anti-lueur spécifique, au moins un additif ; ledit au moins un additif comprenant au moins un catalyseur de réticulation et/ou au moins un agent de stabilisation du(des) plastifiant(s) présent(s) et/ou au moins un catalyseur de combustion. Ledit au moins un catalyseur de polymérisation peut notamment être choisi parmi le triphénylbismuth et le dibutyldilaurate d'étain (DBTL). Présent, il l'est généralement à une teneur ne dépassant pas 100 ppm. Ledit au moins un agent de stabilisation du(des) plastifiant(s) présent(s) peut notamment consister en au moins une amine aromatique, telle la 2-nitrodiphénylamine (2-NDPA) et la N-méthylparanitroaniline (MNA). Présent, il l'est généralement à une teneur d'environ 1 % en masse. Ledit au moins un catalyseur de combustion peut notamment être choisi parmi les catalyseurs de combustion conventionnels, tels les sels et oxydes de plomb, et le citrate de bismuth. Ledit citrate de bismuth, en raison notamment de sa moindre toxicité, est préféré. La Demanderesse a décrit, dans la demande de brevet WO 2016/066245 , l'utilisation avantageuse dudit citrate de bismuth comme catalyseur de combustion. Ledit au moins un catalyseur de combustion est généralement présent dans la composition des produits pyrotechniques de l'invention à un taux massique de 1 à 6 %, très généralement à un taux massique de 3 à 5 %.Among the additives suitably present, the following conventional additives are preferred: crosslinking catalysts, stabilizers for the energetic plasticizer (s) present and combustion catalysts. Thus, according to an advantageous variant, the composite pyrotechnic products of the invention therefore contain in their composition, in addition to the crosslinked polymer (PAG), the plasticizer (s), organic energy charges and the at least one specific anti-glow agent, at least one additive; said at least one additive comprising at least one crosslinking catalyst and / or at least one agent for stabilizing the plasticizer (s) present and / or at least one combustion catalyst. Said at least one polymerization catalyst can in particular be chosen from triphenylbismuth and tin dibutyldilaurate (DBTL). Present, it is usually present at a level not exceeding 100 ppm. Said at least one agent for stabilizing the plasticizer (s) present may in particular consist of at least one aromatic amine, such as 2-nitrodiphenylamine (2-NDPA) and N-methylparanitroaniline (MNA). Present, it is generally present at a content of about 1% by mass. Said at least one combustion catalyst can in particular be chosen from conventional combustion catalysts, such as lead salts and oxides, and bismuth citrate. Said bismuth citrate, in particular because of its lower toxicity, is preferred. The Applicant has described, in the patent application WO 2016/066245 , the advantageous use of said bismuth citrate as a combustion catalyst. Said at least one combustion catalyst is generally present in the composition of the pyrotechnic products of the invention at a mass rate of 1 to 6%, very generally at a mass rate of 3 to 5%.

D'autres additifs susceptibles d'être présents dans la composition des produits pyrotechniques composites de l'invention peuvent notamment consister en des charges énergétiques inorganiques (voir ci-dessus) et en un ou plusieurs agents de mise en œuvre (auxiliaire(s) de fabrication). Le(s)dit(s) agent(s) est(sont) généralement présent(s) à une teneur de 1 à 2 % en masse.Other additives which may be present in the composition of the composite pyrotechnic products of the invention may in particular consist of inorganic energetic charges (see above) and of one or more processing agents (auxiliary (s) of manufacturing). The said agent (s) is (are) generally present at a content of 1 to 2% by mass.

Les additifs éventuellement présents (au vu des propos ci-dessus, on a compris que généralement plusieurs types d'additif sont présents) représentent généralement au maximum 10 % en masse de la composition des produits pyrotechniques composites de l'invention. Ils représentent très généralement de 0,1 à 10 % en masse (souvent de 1,5 à 10 % en masse) de la composition desdits produits pyrotechniques composites de l'invention.The additives optionally present (in view of the above comments, it has been understood that generally several types of additive are present) generally represent a maximum of 10% by weight of the composition of the composite pyrotechnic products of the invention. They very generally represent from 0.1 to 10% by mass (often from 1.5 to 10% by mass) of the composition of said composite pyrotechnic products of the invention.

Au vu des propos ci-dessus, on comprend que les produits pyrotechniques composites de l'invention ne sont pas d'un type nouveau mais qu'ils sont nouveaux de par l'association, dans leur composition, d'un liant spécifique (PAG réticulé par au moins un polyisocyanate) et d'au moins un agent anti-lueur spécifique.In view of the above comments, it is understood that the composite pyrotechnic products of the invention are not of a new type but that they are new by virtue of the association, in their composition, of a specific binder (PAG crosslinked with at least one polyisocyanate) and at least one specific anti-glare agent.

Dans le cadre d'une variante avantageuse, la composition des produits pyrotechniques composites de l'invention, exprimée en pourcentages massiques, renferme donc :

  • de 50 à 70 %, avantageusement de 55 à 65 %, de charges énergétiques organiques, et
  • de 9 à 14 % du polymère énergétique (de type PAG hydroxytéléchélique) réticulé (via ses fonctions terminales hydroxy par au moins un polyisocyanate),
  • de 10 à 30 %, avantageusement de 15 à 25 %, d'au moins un plastifiant énergétique,
  • de 0 à 10 %, avantageusement de 0,1 à 10 %, d'au moins un additif, et
  • ledit au moins un agent anti-lueur de type sel de potassium choisi parmi la cryolite de potassium (K3AlF6), le tartrate de potassium monobasique (C4H5KO6) et leurs mélanges, en une quantité assurant une teneur en potassium dudit propergol de 0,2 % à 2,5 % en masse.
In the context of an advantageous variant, the composition of the composite pyrotechnic products of the invention, expressed in percentages by mass, therefore contains:
  • from 50 to 70%, advantageously from 55 to 65%, of organic energy charges, and
  • from 9 to 14% of the energetic polymer (of the hydroxytelechelic PAG type) crosslinked ( via its terminal hydroxy functions by at least one polyisocyanate),
  • from 10 to 30%, advantageously from 15 to 25%, of at least one energetic plasticizer,
  • from 0 to 10%, advantageously from 0.1 to 10%, of at least one additive, and
  • said at least one anti-glow agent of the potassium salt type chosen from potassium cryolite (K 3 AlF 6 ), monobasic potassium tartrate (C 4 H 5 KO 6 ) and their mixtures, in an amount ensuring a content of potassium of said propellant from 0.2% to 2.5% by mass.

On comprend que les plages avantageuses indiquées ci-dessus peuvent tout à fait être considérées indépendamment les unes des autres. De préférence, elles le sont en combinaison les unes avec les autres.It is understood that the advantageous ranges indicated above can quite be considered independently of one another. Preferably, they are in combination with each other.

Dans le cadre de cette variante avantageuse, ladite composition est généralement exempte de tout autre ingrédient (notamment de toute charge métallique) et consiste donc en les ingrédients listés ci-dessus, présents en les quantités indiquées ci-dessus.In the context of this advantageous variant, said composition is generally free of any other ingredient (in particular of any metallic filler) and therefore consists of the ingredients listed above, present in the amounts indicated above.

Le grand intérêt des produits de l'invention ressort à l'évidence des propos ci-dessus.The great interest of the products of the invention is evident from the above comments.

On rappelle, à toutes fins utiles, que lesdits produits pyrotechniques composites conviennent notamment comme propergols solides pour chargements propulsifs de missiles tactiques. Leur utilisation à cette fin est particulièrement préconisée. Elle fait partie intégrante de la présente invention.It is recalled, for all practical purposes, that said composite pyrotechnic products are suitable in particular as solid propellants for propellant charges of tactical missiles. Their use for this purpose is particularly recommended. It forms an integral part of the present invention.

La préparation desdits produits ne pose pas de difficultés particulières. Elle peut notamment être mise en oeuvre par le procédé précisé ci-après, qui constitue un autre objet de l'invention. Il s'agit d'un procédé par analogie, qui, de façon caractéristique, fait intervenir le au moins un agent anti-lueur spécifique, dans la préparation d'un propergol avec liant de type PAG hydroxytéléchélique réticulé.The preparation of said products does not pose any particular difficulties. It can in particular be implemented by the method specified below, which constitutes another subject of the invention. This is a process by analogy, which characteristically involves the at least one specific anti-glow agent in the preparation of a propellant with a crosslinked hydroxytelechelic PAG type binder.

La présente invention concerne donc aussi un procédé de préparation d'un produit pyrotechnique composite, tel que décrit ci-dessus. Ce procédé comprend :

  • la constitution d'une pâte homogène par
    1. a) incorporation, avec agitation, à une température comprise entre 35 et 55°C, dans un polyazoture de glycidyle adéquat (PAG hydroxytéléchélique présentant une masse moléculaire en nombre telle que précisée ci-dessus), d'au moins un plastifiant énergétique, des charges énergétiques organiques et des autres ingrédients constitutifs du produit pyrotechnique composite recherché (incluant le au moins un agent anti-lueur (de type sel de potassium) spécifique) à l'exception d'un quelconque agent de réticulation et d'un quelconque catalyseur de réticulation, et
    2. b) agitation du mélange résultant, sous vide partiel, à une (avantageusement ladite) température comprise entre 35 et 55°C ;
  • sous vide partiel, à une (avantageusement ladite) température comprise entre 35 et 55°C, l'incorporation, dans ladite pâte homogène constituée, d'éventuellement au moins un catalyseur de réticulation et, dudit au moins un agent de réticulation, suivie d'une agitation du mélange constitué ;
  • la coulée dudit mélange constitué (ayant été) agité (= du mélange obtenu) dans au moins une structure ; et
  • le traitement thermique dudit mélange constitué (ayant été) agité coulé dans ladite au moins une structure.
The present invention therefore also relates to a process for preparing a composite pyrotechnic product, as described above. This process includes:
  • the constitution of a homogeneous paste by
    1. a) incorporation, with stirring, at a temperature between 35 and 55 ° C, in a suitable poly glycidylazide (hydroxy-telechelic PAG having a number molecular mass as specified above), of at least one energetic plasticizer, organic energetic charges and other constituent ingredients of the desired composite pyrotechnic product (including the at least one specific anti-glow agent (of potassium salt type)) with the exception of any crosslinking agent and any catalyst of crosslinking, and
    2. b) agitation of the resulting mixture, under partial vacuum, at a (advantageously said) temperature of between 35 and 55 ° C;
  • under partial vacuum, at a (advantageously) temperature of between 35 and 55 ° C, the incorporation, in said homogeneous paste consisting of optionally at least one crosslinking catalyst and, of said at least one crosslinking agent, followed by 'agitation of the mixture formed;
  • casting said mixture consisting of (having been) stirred (= of the mixture obtained) into at least one structure; and
  • heat treatment of said mixture consisting of (having been) stirred cast into said at least one structure.

Le au moins un agent anti-lueur est introduit à l'état pulvérulent.The at least one anti-glare agent is introduced in the pulverulent state.

Le vide partiel mentionné est destiné au dégazage du milieu au-dessus duquel il est appliqué. Il est généralement de 10 mm Hg. On note incidemment qu'il n'est pas forcément d'intensité constante.The partial vacuum mentioned is intended for degassing the medium above which it is applied. It is generally 10 mm Hg. We note incidentally that it is not necessarily of constant intensity.

Le traitement thermique (de réticulation (du PAG hydroxytéléchélique)) est généralement mis en œuvre à une température comprise entre 30 et 60°C (30°C ≤ T ≤ 60°C), pendant plusieurs jours.The heat treatment (of crosslinking (of the hydroxytelechelic PAG)) is generally carried out at a temperature of between 30 and 60 ° C (30 ° C ≤ T ≤ 60 ° C), for several days.

On propose maintenant d'illustrer l'invention par les exemples et figures ci-après. On propose plus précisément deux exemples comparatifs (exemple comparatif C1 avec K2SO4 de forte granulométrie (d50 = 285 µm), comme agent anti-lueur et exemple comparatif C2 avec K2SO4 de faible granulométrie (d50 = 15 µm), comme agent anti-lueur) et deux exemples de l'invention (exemple 1 (avec K3AlF6 (d50 ≈ 30 µm), comme agent anti-lueur) et exemple 2 (avec C4H5KO6 (d50 ≈ 50 µm), comme agent anti-lueur)).It is now proposed to illustrate the invention by the examples and figures below. More precisely, two comparative examples are proposed (comparative example C1 with K 2 SO 4 of large particle size (d 50 = 285 μm), as anti-glare agent and comparative example C2 with K 2 SO 4 of small particle size (d 50 = 15 µm), as anti-glare agent) and two examples of the invention (example 1 (with K 3 AlF 6 (d 50 ≈ 30 µm), as anti-glare agent ) and example 2 (with C 4 H 5 KO 6 (d 50 ≈ 50 µm), as anti-glare agent)).

Les composés chimiques K2SO4, K3AlF6 et C4H5KO6 (L-tartrate de potassium monobasique) ont été obtenus auprès de la société SIGMA-ALDRICH.The chemical compounds K 2 SO 4 , K 3 AlF 6 and C 4 H 5 KO 6 (monobasic potassium L-tartrate) were obtained from the company SIGMA-ALDRICH.

Les figures 1, 2 et 3 annexées représentent, pour chacun des propergols testés (respectivement celui de l'exemple comparatif C2 (avec K2SO4 (15 µm)), celui de l'exemple 1 et celui de l'exemple 2) les variations de la température (température de rayonnement équivalente corps noir (°C)) selon l'axe du jet (de gaz générés) en fonction de la distance (distance mesurée (en m) à partir de la sortie de la tuyère) ; le propergol testé l'étant à une pression de fonctionnement de 16 MPa (voir le point 5 ci-après). Les profils longitudinaux thermiques montrés ont été obtenus à l'aide de caméras IR sur la Bande II. Ces caméras ont permis de dresser un profil thermique bidimensionnel du jet émis par la tuyère.The figures 1, 2 and 3 appended represent, for each of the propellants tested (respectively that of comparative example C2 (with K 2 SO 4 (15 μm)), that of example 1 and that of example 2) the variations in temperature (temperature of equivalent black body radiation (° C)) along the axis of the jet (of gases generated) as a function of the distance (distance measured (in m) from the outlet of the nozzle); the propellant tested being at an operating pressure of 16 MPa (see point 5 below). The thermal longitudinal profiles shown were obtained using IR cameras on Band II. These cameras made it possible to draw up a two-dimensional thermal profile of the jet emitted by the nozzle.

1. COMPOSITION MASSIQUE1. MASSIC COMPOSITION

Les exemples 1 et 2 sont relatifs à des propergols selon l'invention comprenant, dans leur composition :

  • des charges d'hexogène (RDX). La charge oxydante d'hexogène est conventionnelle : elle est constituées à 60 % en masse d'un RDX d'une classe granulométrique 0 - 100 µm et à 40 % en masse d'un RDX d'une classe granulométrique 2,5 µm - 5 µm ;
  • un liant à base d'un polymère énergétique de type PAG hydroxytéléchélique (commercialisé par la société EURENCO (Mn (masse moléculaire moyenne en nombre) = 1900 g/mol) réticulé (par le trimère de l'hexaméthylène diisocyanate commercialisé par la société Bayer sous la dénomination commerciale Desmodur® N 3300), plastifié par un mélange de deux plastifiants énergétiques (BTTN (trinitrate de butanediol)/TMETN (trinitrate de triméthyloléthane) : 50/50 (% massiques)) ;
  • des agents de stabilisation desdits plastifiants (MNA (N-méthylparanitroaniline)/2-NDPA (2-nitrodiphénylamine) ; 68/32 (% massiques)),
  • du citrate de bismuth en tant que catalyseur balistique ; et
  • un agent anti-lueur (K2AlF6 pour l'exemple 1 de l'invention et C4H5KO6 pour l'exemple 2 de l'invention).
Examples 1 and 2 relate to propellants according to the invention comprising, in their composition:
  • hexogen charges (RDX). The oxidizing charge of hexogen is conventional: it consists of 60% by mass of an RDX of a particle size class 0 - 100 µm and 40% by mass of an RDX of a particle size class of 2.5 µm - 5 µm;
  • a binder based on an energetic polymer of hydroxytelechelic PAG type (marketed by the company EURENCO (Mn (mass number-average molecular) = 1900 g / mol) crosslinked (by the trimer of hexamethylene diisocyanate sold by the company Bayer under the trade name Desmodur® N 3300), plasticized with a mixture of two energetic plasticizers (BTTN (butanediol trinitrate ) / TMETN (trimethylolethane trinitrate): 50/50 (% by mass));
  • agents for stabilizing said plasticizers (MNA (N-methylparanitroaniline) / 2-NDPA (2-nitrodiphenylamine); 68/32 (% by mass)),
  • bismuth citrate as a ballistic catalyst; and
  • an anti-glare agent (K 2 AlF 6 for example 1 of the invention and C 4 H 5 KO 6 for example 2 of the invention).

Lesdits propergols des exemples 1 et 2 de l'invention ont donc été comparés à des propergols (de composition similaire) renfermant K2SO4 à titre d'agent anti-lueur (les inventeurs ont donc testé l'utilisation, à titre d'agent anti-lueur, de K2SO4 dont le diamètre médian était de 285 µm et celle de K2SO4 dont le diamètre médian était de 15 µm. Dans les deux cas, ils ont observé une flamme de post combustion. La figure 1 montre les résultats obtenus avec le K2SO4 de faible granulométrie (d50 = 15 µm) ; celle obtenue avec le K2SO4 de forte granulométrie (d50 = 285 µm) était tout à fait similaire).Said propellants of Examples 1 and 2 of the invention were therefore compared with propellants (of similar composition) containing K 2 SO 4 as anti-glare agent (the inventors therefore tested the use, as anti-glare agent, of K 2 SO 4 whose median diameter was 285 µm and that of K 2 SO 4 whose median diameter was 15 µm. In both cases, they observed a post combustion flame. figure 1 shows the results obtained with K 2 SO 4 of small particle size (d 50 = 15 µm); that obtained with the K 2 SO 4 of large particle size (d 50 = 285 μm) was quite similar).

Les agents anti-lueurs étaient présents, dans les compositions des propergols (des exemples comparatifs C1 et C2 et des exemples 1 et 2 de l'invention), à quasi iso-teneur (environ 0,9 % en masse) en potassium.The anti-glow agents were present, in the compositions of the propellants (of comparative examples C1 and C2 and of examples 1 and 2 of the invention), at a quasi iso-content (approximately 0.9% by mass) of potassium.

Les compositions massiques de chacun desdits propergols (qui comprennent en outre des auxiliaires de fabrication) sont indiquées dans le Tableau 1 ci-après. On peut plus précisément parler des compositions massiques de la pâte précurseur de chacun desdits propergols (avant réticulation). TABLEAU 1 Propergol (% en masse) Ex. C1 Ex. C2 Ex. 1 Ex. 2 Ingrédients (% en masse) Liant plastifié Polymère énergétique PAG 7,9 7,9 7,9 7,9 Agent de réticulation Desmodur® N 3300 2 2 2 2 Plastifiants BTTN/TMETN 21,4 21,4 21,4 21,4 Agents de stabilisation du plastifiant (additif) MNA/2-NDPA 0,7 0,7 0,7 0,7 Charges Charges énergétiques organiques RDX 60 60 60 57,7 « Additif » de combustion Catalyseur de combustion Citrate de Bi 4 4 4 4 Additif anti lueur K2SO4 (285 µm) 2 K2SO4 (15 µm) 2 K3AlF6 2 C4H5KO6 4,3 Autre additif Auxiliaires de fabrication 2 2 2 2 The compositions by weight of each of said propellants (which further comprise processing aids) are shown in Table 1 below. We can more precisely speak of the compositions mass of the precursor paste of each of said propellants (before crosslinking). TABLE 1 Propellant (% by mass) Ex. C1 Ex. C2 Ex. 1 Ex. 2 Ingredients (% by mass) Plasticized binder Energetic polymer PAG 7.9 7.9 7.9 7.9 Crosslinking agent Desmodur® N 3300 2 2 2 2 Plasticizers BTTN / TMETN 21.4 21.4 21.4 21.4 Plasticizer stabilizers (additive) MNA / 2-NDPA 0.7 0.7 0.7 0.7 Charges Organic energy loads RDX 60 60 60 57.7 Combustion "additive" Combustion catalyst Bi citrate 4 4 4 4 Anti glow additive K 2 SO 4 (285 µm) 2 K 2 SO 4 (15 µm) 2 K 3 AlF 6 2 C 4 H 5 KO 6 4.3 Other additive Manufacturing auxiliaries 2 2 2 2

2. MODE OPERATOIRE DE PREPARATION DES PATES DE PROPERGOL ET DES PROPERGOLS2. PROCEDURE FOR PREPARING PROPERGOL PASTA AND PROPERGOLS

Dans un malaxeur, on a introduit le (polymère précurseur du liant = le) polyazoture de glycidyl (PAG) puis les plastifiants (BTTN/TMETN) et les agents de stabilisation (MNA/2-NDPA) desdits plastifiants. Le mélange a été malaxé durant 15 min à une température de 50°C.In a kneader, the (binder precursor polymer = the) poly glycidylazide (PAG) then the plasticizers (BTTN / TMETN) and the stabilizing agents (MNA / 2-NDPA) of said plasticizers were introduced. The mixture was kneaded for 15 min at a temperature of 50 ° C.

On a ensuite ajouté audit mélange, sous agitation, les charges énergétiques organiques (RDX), par portion, puis le catalyseur de combustion (citrate de bismuth), les additifs (autres que les agent et catalyseur de réticulation) et l'agent anti-lueur. L'agitation a alors été poursuivie pendant 2 h 30, à la température de 50°C et sous un vide de 10 mm de Hg (qui a permis le dégazage du milieu), pour l'obtention d'une pâte homogène.The organic energy charges (RDX) were then added to said mixture, with stirring, per portion, then the combustion catalyst (bismuth citrate), the additives (other than the crosslinking agent and catalyst) and the anti- glow. Stirring was then continued for 2 h 30 min, at a temperature of 50 ° C. and under a vacuum of 10 mm Hg (which allowed the degassing of the medium), to obtain a homogeneous paste.

Le catalyseur de réticulation (DBTL (dibutyldilaurate d'étain) (55 ppm)) a alors été ajouté à ladite pâte homogène et le milieu a encore été agité 30 min avant l'addition de l'agent de réticulation du liant (Desmodur® N 3300). Ledit agent de réticulation a enfin été ajouté et le milieu a encore été agité 15 min (toujours à 50°C et sous vide).The crosslinking catalyst (DBTL (tin dibutyldilaurate) (55 ppm)) was then added to said homogeneous paste and the medium was further stirred 30 min before the addition of the binder crosslinking agent (Desmodur® N 3300). Said crosslinking agent was finally added and the medium was further stirred for 15 min (still at 50 ° C. and under vacuum).

On a ainsi préparé des lots de 800 g et des lots de 5 kg de pâte de propergol.There were thus prepared batches of 800 g and batches of 5 kg of propellant paste.

Les lots de 800 g de pâte ont été en partie utilisés pour apprécier la faisabilité du procédé d'obtention des propergols (pour mesurer la vie de pot de la pâte) et en partie, après réticulation, pour évaluer le comportement balistique du propergol (pour mesurer la vitesse de combustion de celui-ci).The 800 g batches of paste were used in part to assess the feasibility of the process for obtaining the propellants (to measure the pot life of the paste) and in part, after crosslinking, to evaluate the ballistic behavior of the propellant (to measure its combustion speed).

Les lots de 5 kg, partagés en deux, ont été réticulés. En fait, deux blocs de propergols (pour chacune des compositions) ont été préparés : deux blocs de diamètre 90 mm et de longueur 150 mm. Ils ont été testés (au banc d'essai : voir le point 5 ci-après).The 5 kg batches, divided in two, were crosslinked. In fact, two blocks of propellants (for each of the compositions) were prepared: two blocks with a diameter of 90 mm and a length of 150 mm. They have been tested (on the test bench: see point 5 below).

Quelle que soit la pâte en cause, pour sa réticulation, elle a été coulée dans une structure adaptée puis soumise au traitement thermique ci-après : cuisson pendant 14 jours à une température de 50°C.Whatever the paste in question, for its crosslinking, it was cast in a suitable structure and then subjected to the following heat treatment: baking for 14 days at a temperature of 50 ° C.

3. DETERMINATION DE LA VIE DE POT DES PATES3. DETERMINATION OF THE POT LIFE OF PASTA

La vie de pot (qui permet d'apprécier la faisabilité du procédé d'obtention des propergols) a été déterminée par la mesure de la viscosité de la pâte de propergol en cause (renfermant l'agent de réticulation et le catalyseur de réticulation) au cours du temps, au moyen d'un viscosimètre Brookfield (avec le corps n°3 (mobile C) mis en rotation à 1 tour/min), à une température de 50°C. On a relevé le temps pour lequel la viscosité a atteint 15 kPo, afin de déterminer si le propergol répondait au critère d'industrialisation, c'est-à-dire si ledit temps relevé était supérieur à 10 h.The pot life (which makes it possible to assess the feasibility of the process for obtaining the propellants) was determined by measuring the viscosity of the propellant paste in question (containing the crosslinking agent and the crosslinking catalyst) at over time, using a Brookfield viscometer (with body n ° 3 (mobile C) rotated at 1 revolution / min), at a temperature of 50 ° C. The time for which the viscosity reached 15 kPo was recorded in order to determine whether the propellant met the industrialization criterion, that is to say if said time recorded was greater than 10 h.

4. DETERMINATION DE LA VITESSE DE COMBUSTION DES PROPERGOLS4. DETERMINATION OF THE BURNING SPEED OF PROPERGOLS

La vitesse de combustion a été mesurée de façon conventionnelle à 20 °C et 10 MPa.The burning rate was measured in a conventional manner at 20 ° C and 10 MPa.

Les résultats de vie de pot et de vitesse de combustion figurent dans le Tableau 2 ci-après. Tableau 2 Propergol Agent anti lueur Vie de pot (50°C) Vitesse de combustion (10 MPa, 20°C) Ex. C2 K2SO4 13 h 14,1 mm/s Ex 1 K3AlF6 23 h* 13,5 mm/s** Ex 2 C4H5KO6 41 h* 13,3 mm/s** *Au vu des résultats de vie de pot indiqués, on voit que le critère d'industrialisation est largement satisfait.
**On note que les agents anti-lueurs de l'invention ont tendance à abaisser la vitesse de combustion. Cela dépend bien évidemment, des quantités utilisées. Il est opportun de minimiser ces quantités pour conserver des vitesses de combustion supérieures à 12 mm/s à 10 MPa. The pot life and burn rate results are shown in Table 2 below. Table 2 Propellant Anti glare agent Pot life (50 ° C) Burning rate (10 MPa, 20 ° C) Ex. C2 K 2 SO 4 1 p.m. 14.1 mm / s Ex 1 K 3 AlF 6 11 p.m. * 13.5 mm / s ** Ex 2 C 4 H 5 KO 6 41 h * 13.3 mm / s ** * In view of the pot life results indicated, it can be seen that the industrialization criterion is largely satisfied.
** It is noted that the anti-glow agents of the invention tend to lower the combustion rate. This obviously depends on the quantities used. It is advisable to minimize these quantities in order to maintain combustion speeds greater than 12 mm / s at 10 MPa.

5. TESTS AU BANC D'ESSAI5. TESTS AT THE TEST BENCH

Des blocs obtenus ont été testés au banc d'essai dans des conditions de fonctionnement « sévères » : pression de tir égale à 16 MPa (ce qui correspond à la pression maximale de fonctionnement lors du tir, ce qui correspond à la pression lors de la phase dite d'accélération).The blocks obtained were tested on the test bench under "severe" operating conditions: firing pressure equal to 16 MPa (which corresponds to the maximum operating pressure during firing, which corresponds to the pressure during firing. so-called acceleration phase).

Pour vérifier la discrétion d'un moteur, on s'est volontairement placé à la pression de fonctionnement la plus élevée soit à, donc, 16 MPa (i.e. dans les conditions où cette discrétion est la plus difficile à gérer).To check the discretion of an engine, we voluntarily placed ourselves at the highest operating pressure, i.e. at 16 MPa (i.e. in conditions where this discretion is the most difficult to manage).

Certaines caractéristiques du jet (gaz émis en sortie de tuyère) ont été déterminées par des moyens optroniques, notamment par observation par caméras IR en Bande II, par transmission/émission dans le visible (à 632 nm), et par transmission/émission dans l'IR entre 2 et 14 µm. Les profils longitudinaux thermiques obtenus par caméra IR (Bande II) permettent de mettre en évidence dans le jet des gradients en température équivalent corps noir. Les niveaux de transmission dans le visible et dans l'IR permettent de mettre en évidence la notion de transparence et donc l'efficacité des agents anti-lueurs testés.Certain characteristics of the jet (gas emitted at the nozzle outlet) were determined by optronic means, in particular by observation by IR cameras in Band II, by transmission / emission in the visible (at 632 nm), and by transmission / emission in the IR between 2 and 14 µm. The thermal longitudinal profiles obtained by IR camera (Band II) make it possible to highlight black body equivalent temperature gradients in the jet. The levels of transmission in the visible and in the IR make it possible to highlight the notion of transparency and therefore the effectiveness of the anti-glare agents tested.

Sur les figures 1, 2 et 3 annexées, on a donc montré les résultats de l'observation par caméra IR (Bande II), i.e. les profils longitudinaux thermiques pour, respectivement, le propergol selon l'exemple comparatif C2 avec K2SO4 (15 µm), le propergol selon l'exemple 1 de l'invention et le propergol selon l'exemple 2 de l'invention.On the figures 1, 2 and 3 appended, we have therefore shown the results of the observation by IR camera (Band II), ie the longitudinal thermal profiles for, respectively, the propellant according to comparative example C2 with K 2 SO 4 (15 μm), the propellant according to Example 1 of the invention and the propellant according to Example 2 of the invention.

Pour le propergol selon l'exemple comparatif C2, dont la composition contenait du K2SO4 (faible granulométrie), une flamme de post combustion était présente. Le niveau de rayonnement était élevé avec une température maximale équivalent corps noir de 1400°C, située à 1,2 m du plan de sortie de tuyère. La flamme de post combustion était parfaitement visible à l'œil nu.For the propellant according to comparative example C2, the composition of which contained K 2 SO 4 (small particle size), a post combustion flame was present. The radiation level was high with a maximum black body equivalent temperature of 1400 ° C, located 1.2 m from the nozzle exit plane. The post combustion flame was perfectly visible to the naked eye.

Pour le propergol selon l'exemple 1 de l'invention, dont la composition contenait du K3AlF6, aucune flamme de post combustion n'a été décelée. Le jet a été considéré comme inerte. Le niveau de rayonnement en bande II est resté faible : la température maximale équivalent corps noir était de 600°C en sortie de tuyère (elle n'a pas dépassé cette valeur en s'éloignant du plan de sortie de ladite tuyère).For the propellant according to Example 1 of the invention, the composition of which contained K 3 AlF 6 , no post combustion flame was detected. The jet was considered inert. The level of radiation in band II remained low: the maximum black body equivalent temperature was 600 ° C. at the nozzle outlet (it did not exceed this value when moving away from the exit plane of said nozzle).

Pour le propergol selon l'exemple 2 de l'invention, dont la composition contenait du C4H5KO6, de la même façon, aucune flamme de post combustion n'a été décelée. Le jet a été considéré comme inerte. Le niveau de rayonnement en bande II est resté faible : la température maximale équivalent corps noir était de 650°C en sortie de tuyère (elle n'a pas dépassé cette valeur en s'éloignant du plan de sortie de ladite tuyère). Cette température maximale est un peu plus élevée que celle obtenue avec K3AlF6.For the propellant according to Example 2 of the invention, the composition of which contained C 4 H 5 KO 6 , in the same way, no post-combustion flame was detected. The jet was considered inert. The level of radiation in band II remained low: the temperature maximum black body equivalent was 650 ° C at the nozzle outlet (it did not exceed this value when moving away from the outlet plane of said nozzle). This maximum temperature is a little higher than that obtained with K 3 AlF 6 .

Il n'a pas été observé, en présence de K3AlF6 (renfermant pourtant de l'aluminium) ou en présence de C4H5KO6, de fumées primaires (la transmission dans le visible à 632 nm était très élevée).Primary fumes were not observed in the presence of K 3 AlF 6 (however containing aluminum) or in the presence of C 4 H 5 KO 6 (transmission in the visible range at 632 nm was very high). .

Claims (11)

  1. Composite pyrotechnic product containing, in a plasticized binder comprising a cross-linked energetic polymer and at least one energetic plasticizer, organic energetic charges and at least one anti-glare agent of the potassium salt type, characterized in that:
    - said cross-linked energetic polymer consists of a glycidyl azide polymer (GAP) having a number average molecular weight (Mn) in the range 700 g/mol to 3000 g/mol, cross-linked via its hydroxyl terminal functions with at least one cross-linking agent of the polyisocyanate type; and
    - said at least one anti-glare agent of the potassium salt type is selected from potassium cryolite (K3AlF6), monobasic potassium tartrate (C4H5KO6) and mixtures thereof.
  2. The composite pyrotechnic product of claim 1, characterized in that said at least one anti-glare agent of the potassium salt type is present in an amount which ensures a potassium content of 0.2 % to 2.5 % by weight.
  3. The composite pyrotechnic product of claim 1 or 2, characterized in that said glycidyl azide polymer (GAP) has a number average molecular weight (Mn) between 1700 and 2300 g/mol.
  4. The composite pyrotechnic product of any one of claims 1 to 3, characterized in that said at least one energetic plasticizer is of the nitrate and/or nitramine type.
  5. The composite pyrotechnic product of any one of claims 1 to 4, characterized in that said energetic charges are selected from hexogen charges, octogen charges, and mixtures of such charges.
  6. The composite pyrotechnic product of any one of claims 1 to 5, characterized in that it further comprises at least one additive.
  7. The composite pyrotechnic product of claim 6, characterized in that said at least one additive is selected from at least one cross-linking catalyst, at least one agent for stabilizing said at least one energetic plasticizer, at least one combustion catalyst and mixtures thereof.
  8. The composite pyrotechnic product of claim 6 or 7, characterized in that it comprises bismuth citrate as the combustion catalyst.
  9. The composite pyrotechnic product of any one of claims 1 to 8, characterized in that that its composition, expressed in percentages by weight, contains:
    - 50 to 70 %, advantageously 55 to 65 %, of said organic energetic charges,
    - 9 to 14 % of said cross-linked energetic polymer,
    - 10 to 30 %, advantageously 15 to 25 %, of said at least one energetic placticizer,
    - 0 to 10 %, advantageously 0.1 to 10 %, of at least one additive; and
    - said at least one anti-glare agent of the potassium salt type selected from potassium cryolite (K3AlF6), monobasic potassium tartrate (C4H5KO6) and mixtures thereof, in an amount ensuring a potassium content of said propellant of 0.2 % to 2,5 % by weight.
  10. The composite pyrotechnic product of any one of claims 1 to 9, for use as a solid propellant of a propulsive load of a tactical missile.
  11. A method for preparing a composite pyrotechnic product of any one of claims 1 to 9, characterized in that it comprises:
    - constituting a homogeneous paste by:
    a) adding to said glycidyl azide polymer, at a temperature between 35 and 55°C, said at least one energetic plactiiczer, energetic charges and other ingredients constituting the looked-for composite pyrotechnic product with the exception of any cross-linking agent and of any cross-linking catalyst; and
    b) stirring the resulting mixture, under a partial vacuum, at a temperature between 35 and 55°C ;
    - under a partial vacuum, at a temperature between 35 and 55°C , adding to said resulting homogeneous paste, said at least one cross-linking agent and optionally at least one cross-linking catalyst, then stirring the resulting mixture;
    - casting said stirred resulting mixture in at least one structure; and
    - heat treating said stirred resulting mixture cast in said at least one structure.
EP17787216.5A 2016-09-26 2017-09-25 Composite pyrotechnic product containing an anti-gleam agent of potassium salt type Active EP3515881B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1601396A FR3056583B1 (en) 2016-09-26 2016-09-26 COMPOSITE PYROTECHNIC PRODUCT COMPRISING A POTASSIUM SALT-TYPE ANTI-LIGHT AGENT
PCT/FR2017/052573 WO2018055312A1 (en) 2016-09-26 2017-09-25 Composite pyrotechnic product containing an anti-gleam agent of potassium salt type

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EP3515881B1 true EP3515881B1 (en) 2021-02-17

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FR3096680B1 (en) 2019-06-03 2021-09-24 Arianegroup Sas composite pyrotechnic product

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Publication number Priority date Publication date Assignee Title
US3960621A (en) * 1957-03-12 1976-06-01 Imperial Chemical Industries Limited Propellents
SE7408998L (en) * 1974-07-09 1976-01-12 Bofors Ab FLASH DAMPER FOR POWDER.
SE437511B (en) * 1979-04-24 1985-03-04 Bofors Ab WANTED TO MAKE CONSOLIDATED BODY OF DOUBLE BASKET SHEETS
GB2258230B (en) 1982-06-25 1993-10-13 Poudres & Explosifs Ste Nale Production of double-base propergol propellant blocks
FR2588551B1 (en) * 1985-10-14 1987-11-20 Poudres & Explosifs Ste Nale PROCESS FOR PRODUCING A DOUBLE-BASED PROPULSIVE COMPOSITION WITH LOW FLAME LIGHT EMISSION, AND PROPULSIVE COMPOSITION THUS OBTAINED
DE102010020776B4 (en) * 2010-05-18 2015-03-05 Diehl Bgt Defence Gmbh & Co. Kg Propellant charge and method for its production
FR3027597B1 (en) * 2014-10-28 2016-12-09 Herakles PERFORMANT COMPOSITE PYROTECHNIC PRODUCT WITHOUT PB IN ITS COMPOSITION AND PREPARATION
DE102014016223B3 (en) 2014-10-31 2016-02-18 Audi Ag Method for operating a communication system and communication system

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WO2018055312A1 (en) 2018-03-29
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EP3515881A1 (en) 2019-07-31

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