WO2015082845A1 - Stabilised composite propellants - Google Patents

Stabilised composite propellants Download PDF

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Publication number
WO2015082845A1
WO2015082845A1 PCT/FR2014/053154 FR2014053154W WO2015082845A1 WO 2015082845 A1 WO2015082845 A1 WO 2015082845A1 FR 2014053154 W FR2014053154 W FR 2014053154W WO 2015082845 A1 WO2015082845 A1 WO 2015082845A1
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Prior art keywords
energy
epoxidized
composition according
nitric
binder
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PCT/FR2014/053154
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French (fr)
Inventor
Marie COQUILLAT
Martine GOLFIER
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Herakles
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Publication of WO2015082845A1 publication Critical patent/WO2015082845A1/en

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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
    • C06B23/006—Stabilisers (e.g. thermal stabilisers)
    • 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 is in the field of composite solid propellants whose energy binder comprises an energetic plasticizer based on nitric esters.
  • Composite solid propellants consist of a polymeric matrix coating at least one energetic solid charge and optionally a reducing solid charge.
  • the polymer matrix consists of a liquid polymer having reactive functions vis-à-vis a crosslinking system. Before curing, various additives are incorporated in the liquid polymer, then the energy charges and optionally the reducing charges.
  • the energy binder comprising the polymer, the energetic plasticizer based on nitric esters and all the additives
  • the energetic plasticizer based on nitric ester may for example comprise n-butyl-2-nitratoethylnitramine (bu-NENA), ethyl-2-nitratoethylnitramine (EthlyNENA), triethyleneglycol dinitrate (TEGDN), diethylene glycol (DEGDN), butanetriol trinitrate (BTTN), trimethylolethane trinitrate (TMETN), triethylene glycol dinitrate (TEMA), nitroglycerin and mixtures thereof.
  • bu-NENA n-butyl-2-nitratoethylnitramine
  • EthlyNENA ethyl-2-nitratoethylnitramine
  • TAGDN triethyleneglycol dinitrate
  • DEGDN diethylene glycol
  • BTTN butanetriol trinitrate
  • TMETN trimethylolethane trinitrate
  • TMETN triethylene glycol dinitrate
  • Nitric esters are not stable: they break down by cleavage of the 0-N0 2 bond and generate decomposition products. having a catalytic effect on the reaction as well as gases liable to crack the material. It is therefore necessary to add stabilizers that capture the nitrogen oxides as additives in the energy binder.
  • the conventional stabilizers used are aromatic amines (2-nitrodiphenylamine (2NDPA) for example and preferably N-methyl-para-nitroaniline (MNA)).
  • NDPA aromatic amines
  • MNA N-methyl-para-nitroaniline
  • premix contains the polymer, the nitric esters (energetic plasticizer), and the stabilizers.
  • the premix is then introduced into a kneader, then any reducing charges and energy charges.
  • the crosslinking system is added to the kneader after a mixing and drying time of the loaded dough.
  • premix should be manufactured as follows:
  • the MNA is not always soluble in the polymer and therefore can not be added in step a). It is therefore necessary to add an additional step d) adding the MNA after or before the drying step c).
  • the inventors have surprisingly found that the epoxidized fatty acid esters fulfilled these conditions and made it possible to stabilize the energetic plasticizers based on nitric esters in solid propellant composite compositions. They also found that these esters do not lead during their degradation to the formation of n-nitrosated compounds (suspected to be CMR) unlike current stabilizers.
  • the chemical stabilizers currently used with nitric esters are aromatic amines which trap nitrogen oxides by first forming the N-nitroso derivative. However, aromatic nitrosamine derivatives are known to be carcinogenic.
  • the article by Frys et al discloses the use of epoxidized fatty acid esters as stabilizers of double-base propellants containing nitroglycerin and nitrocellulose.
  • the double-base propellants have risks of auto-ignition and their stabilizers are used to limit or prevent these risks whereas, as indicated above, the problem met by the Composite propellants is the risk of cracking propellant blocks.
  • the present invention therefore relates to a solid propellant composite composition, advantageously for solid composite propellant, comprising
  • an energy binder comprising an energetic plasticizer based on nitric esters and a nitric ester stabilizer
  • the stabilizer of the nitric esters is selected from epoxidized fatty acid esters.
  • the epoxidized fatty acid esters that may be used in the context of the present invention may in particular be chosen from epoxidized oils such as epoxidized vegetable oils (epoxidized soybean oil and / or epoxidized linseed oil, for example), these oils advantageously containing mainly unsaturated long-chain fatty acid esters which have been epoxidized on one or more of their double bonds, in particular C 18 fatty acid esters, such as, for example, chosen from esters of oleic, linoleic, linolenic (especially alpha-linolenic) epoxidized acids or mixtures thereof.
  • the epoxidized fatty acid esters that may be used in the context of the present invention may also consist of a mixture of epoxidized fatty acid esters, for example of long-chain fatty acids, in particular C 14 -C 22 fatty acid esters.
  • the epoxidized fatty acid esters according to the invention may contain monoesters, diesters or triesters such as triglycerides. They generally contain at least one epoxy function but they can contain several epoxy functions (for example 3 or even 7). At least one of the ester functions may be alpha to at least one of the epoxy functions.
  • the epoxidized fatty acid esters according to the invention are chosen from epoxidized soybean oil, epoxidized linseed oil, a mixture of epoxidized C14-C22 fatty acid esters and epoxidized stearate octyl. and mixtures thereof, even more preferably from a mixture of epoxidized C14-C22 fatty acid esters, epoxidized stearate octyl and mixtures thereof.
  • epoxidized fatty acid esters are commercially available from AKCROS CHEMICALS under the name Lankroflex® L (epoxidized linseed oil), Lankroflex® E2307 (epoxidized soybean oil) and Lankroflex® ED6 (epoxidized stearate octyl).
  • the epoxidized fatty acid esters are generally present in the composition in a content of between 0.25 and 1% by weight relative to the total weight of the composition. They generally represent between 1 and 5% by weight relative to the mass of the mixture of nitric esters / epoxidized fatty acid esters.
  • the term "energetic plasticizer based on nitric esters” means any energetic plasticizer comprising nitric esters, in particular consisting of nitric esters.
  • the nitric esters are chosen from n-butyl-2-nitratoethylnitramine (bu-NENA) and ethyl-2-nitratoethylnitramine.
  • EthlyNENA triethylene glycol dinitrate
  • DEGDN diethylene glycol dinitrate
  • BTTN butanetriol trinitrate
  • TMETN trimethylethane trinitrate
  • TMETN triethylene glycol dinitrate
  • TEMA triethylene glycol dinitrate
  • nitroglycerin especially among butanetriol trinitrate, trimethylethane trinitrate, trioxyethylene glycol dinitrate and mixtures thereof, more particularly it is butanetriol trinitrate.
  • Nitric esters are generally present in the composition in a content of between 6 and 30% by weight relative to the total mass of the composition. They generally represent 30 to 75% by weight of the energy binder.
  • the energy binder comprises a polymer.
  • This polymer can be inert or energetic.
  • the polymer is inert, it may be, for example, a polyester having a hydroxy terminus or a polyether having a hydroxy terminus. It is advantageously chosen from polyoxypropylene glycol, polybutyleneoxide, polytetramethylene oxide, polyethylene oxide, diethylene glycol polyadipate (PADEG) and mixtures thereof. In particular, it is diethylene glycol polyadipate.
  • the polymer is energetic, it may be a glycidyl polyazide (PAG) or a glycidyl polynitrate. In particular it is glycidyl polyazide.
  • PAG glycidyl polyazide
  • the polymer is generally present in the composition in a content of between 5 and 30% by weight relative to the total weight of the composition. It generally represents 25 to 70% by weight of the energy binder.
  • the energy load that can be used in the composition according to the present invention is generally pulverulent and is advantageously chosen from the group formed by ammonium perchlorate (PA), ammonium nitrate (NA), hexogen (DX) octogen (HMX), hexanitrohexaazaisowurtzitane (CL20) or mixtures thereof.
  • the energy charges are generally present in the composition in a content of between 60 and 80% by weight relative to the total mass of the composition.
  • the optional reducing charge that can be used in the composition according to the present invention is generally pulverulent and is advantageously chosen from the group formed by aluminum, boron, zirconium or their mixtures.
  • the reducing charge if it is present, is generally present in the composition in a content of between 1 and 20% by weight relative to the total mass of the composition.
  • the crosslinking system that can be used in the composition according to the present invention is advantageously liquid and in particular chosen from polyisocyanates such as toluene diisocyanate, in particular alicyclic polyisocyanates, such as dicyclohexylmethylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate or biuret triisocyanate.
  • polyisocyanates such as toluene diisocyanate
  • alicyclic polyisocyanates such as dicyclohexylmethylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate or biuret triisocyanate.
  • the crosslinking system is generally present in the composition in a content of between 0.4 and 5% by weight relative to the total mass of the composition.
  • the composition according to the present invention further comprises additives, advantageously chosen from other stabilizers (such as 2-nitrodiphenylamine), antioxidants, chain extenders, polymerization catalysts, combustion modifiers (accelerators or retarders), ballistic additives (for example cooling), binder-load adhesion and bridging.
  • additives are usually present in the energy binder.
  • the additives, if present, are generally present in the composition in a content of between 0.1 and 10% by weight relative to the total weight of the composition.
  • the present invention further relates to a solid composite propellant characterized in that it is at least partly made of a composite composition according to the present invention.
  • a pyrotechnic charge characterized in that it comprises a solid propellant, in particular composite, according to the present invention in a structure.
  • the loads can be full or channel.
  • the structures are conventional structures like propellant structure.
  • the propellants are manufactured according to the methods conventionally used for composite compositions for solid propellants. For example by mixing in a kneader in which the various ingredients are introduced in an appropriate order and carefully and thoroughly kneaded under given pressure and temperature conditions. This mixture, which is in the form of a paste, is cast in a mold with shaping tools. The whole is baked to ensure the hardening of the dough. The mold is in some cases the same envelope of the engine.
  • the present invention also relates to a method of manufacturing the composite composition according to the present invention, characterized in that it comprises the prior step of manufacturing the energy binder before the addition of the energy charge, the possible reducing charge and of the crosslinking system.
  • the prior step of manufacturing the energy binder is carried out in two stages, the second stage consisting of the addition of the nitric esters in the energy binder.
  • the present invention relates to the use of an epoxidized fatty acid ester, in particular as defined above, as a stabilizer for the nitric esters of the energetic plasticizer of the energy binder of a solid propellant composite composition, particular as defined above, more particularly for composite solid propellant.
  • the stabilizing effect of epoxidized fatty acid esters was first validated in a BTTN + 1% Lankroflex model mixture by Vacuum Test (ESV, NFT 70-717) and microcalorimetry tests. Microcalorimetry makes it possible to measure the heat flux generated or absorbed by a sample of the order of 1 g in a thermoregulated chamber of a microcalorimeter. The results are summarized in the following table: Volume of gas released, final level and total energy at 80 ° C
  • the ESV show a good compatibility between the nitric esters and the different Lankroflex tested.
  • the energies obtained in microcalorimetry show the stabilizing effect provided by Lankroflex grades which strongly limit the runaway of the reaction observed on pure nitric esters.
  • Lankroflex® ED6 showed the best results.
  • a critical edge greater than 50 mm at 80 ° C on an Oxalane® X mix was measured in a cracking aging test.
  • the protocol consists in following the integrity of an edge cube defined by X-ray analysis over a period of 21 days at 80 ° C.
  • the minimum edge for which cracking is obtained is the critical edge.
  • the composition of the kneaded mixture studied is described in the table below:
  • the mixtures were made in centrifuge tubes and homogenized with a spatula.
  • the tubes were exposed to temperatures of either 50 ° C in an oven or at room temperature (23.6 ° C) for about 72 hours and then observed.
  • the details of the observations are given in Table 2 below.
  • Table 1 Details of the Premix / Lankroflex mixtures.

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
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Abstract

The invention relates to a composite composition for solid propellant comprising a) an energy charge, b) a possible reducing charge, c) an energetic binder comprising an energetic plasticiser based on nitric esters and a stabiliser of the nitric esters, and d) a cross-linking system, characterised in that the stabiliser of the nitric esters is selected from the epoxidised fatty acid esters.

Description

PROPERGOLS COMPOSITES STABILISES  STABILIZED COMPOSITE PROPERGOLS
La présente invention est dans le domaine des propergols solides composites dont le liant énergétique comprend un plastifiant énergétique à base d'esters nitriques. The present invention is in the field of composite solid propellants whose energy binder comprises an energetic plasticizer based on nitric esters.
Les propergols solides composites sont constitués d'une matrice polymérique enrobant au moins une charge solide énergétique et éventuellement une charge solide réductrice. La matrice polymérique est constituée à partir d'un polymère liquide ayant des fonctions réactives vis- à-vis d'un système réticulant. Avant durcissement on incorpore dans le polymère liquide divers additifs, puis les charges énergétiques et éventuellement les charges réductrices. Composite solid propellants consist of a polymeric matrix coating at least one energetic solid charge and optionally a reducing solid charge. The polymer matrix consists of a liquid polymer having reactive functions vis-à-vis a crosslinking system. Before curing, various additives are incorporated in the liquid polymer, then the energy charges and optionally the reducing charges.
Par convention nous distinguerons quatre groupes de constituants pour un propergol solide:  By convention we will distinguish four groups of constituents for a solid propellant:
- le liant énergétique comprenant le polymère, le plastifiant énergétique à base d'esters nitriques et l'ensemble des additifs,  the energy binder comprising the polymer, the energetic plasticizer based on nitric esters and all the additives,
- le système réticulant  - the crosslinking system
- les charges énergétiques,  - the energy charges,
- et éventuellement les charges réductrices. - and possibly the reducing charges.
Le plastifiant énergétique à base d'ester nitrique peut par exemple comprendre du n-butyl-2-nitratoéthylnitramine (bu-NENA), de l'éthyl-2- nitratoéthylnitramine (EthlyNENA), du dinitrate de triéthylèneglycol (TEGDN), du dinitrate de diéthylèneglycol (DEGDN), du trinitrate de butanetriol (BTTN), du trinitrate de triméthyloléthane (TMETN), du dinitrate de triéthylène glycol (TEMA), de la nitroglycérine et leurs mélanges.  The energetic plasticizer based on nitric ester may for example comprise n-butyl-2-nitratoethylnitramine (bu-NENA), ethyl-2-nitratoethylnitramine (EthlyNENA), triethyleneglycol dinitrate (TEGDN), diethylene glycol (DEGDN), butanetriol trinitrate (BTTN), trimethylolethane trinitrate (TMETN), triethylene glycol dinitrate (TEMA), nitroglycerin and mixtures thereof.
Or les esters nitriques ne sont pas stables : ils se décomposent par coupure de la liaison 0-N02 et génèrent des produits de décomposition ayant un effet catalytique sur la réaction ainsi que des gaz susceptibles de fissurer le matériau. Il est donc nécessaire de rajouter des stabilisants qui captent les oxydes d'azote en tant qu'additifs dans le liant énergétique. Les stabilisants conventionnels utilisés sont des aminés aromatiques (la 2- nitrodiphénylamine (2NDPA) par exemple et préférentiellement la N- méthyl-para-nitroaniline (MNA)). La mise en œuvre des esters nitriques nécessite leur désensibilisation « flegmatisation » à l'aide des ingrédients du liant. Nitric esters are not stable: they break down by cleavage of the 0-N0 2 bond and generate decomposition products. having a catalytic effect on the reaction as well as gases liable to crack the material. It is therefore necessary to add stabilizers that capture the nitrogen oxides as additives in the energy binder. The conventional stabilizers used are aromatic amines (2-nitrodiphenylamine (2NDPA) for example and preferably N-methyl-para-nitroaniline (MNA)). The use of nitric esters requires their desensitization "phlegmatization" using the ingredients of the binder.
Pour ce faire un mélange homogène appelé « prémix » est réalisé. Ce prémix contient le polymère, les esters nitriques (plastifiant énergétique), et les stabilisants.  To do this a homogeneous mixture called "premix" is realized. This premix contains the polymer, the nitric esters (energetic plasticizer), and the stabilizers.
Le prémix est ensuite introduit dans un malaxeur, puis les éventuelles charges réductrices et les charges énergétiques. Le système réticulant est ajouté dans le malaxeur après un temps de mélange et séchage de la pâte chargée.  The premix is then introduced into a kneader, then any reducing charges and energy charges. The crosslinking system is added to the kneader after a mixing and drying time of the loaded dough.
Normalement le prémix devrait être fabriqué de la façon suivante :  Normally the premix should be manufactured as follows:
a) mélange du polymère et des stabilisants + éventuellement des additifs (extenseur de chaînes, polyol, autres polymères...) ; a) mixing the polymer and the stabilizers + optionally additives (chain extender, polyol, other polymers, etc.);
b) ajout des esters nitriques b) addition of nitric esters
c) séchage. c) drying.
Toutefois la MNA n'est pas toujours soluble dans le polymère et ne peut donc pas être ajouté à l'étape a). Il est donc nécessaire de rajouter une étape supplémentaire d) d'ajout de la MNA après ou avant l'étape de séchage c).  However, the MNA is not always soluble in the polymer and therefore can not be added in step a). It is therefore necessary to add an additional step d) adding the MNA after or before the drying step c).
Il est donc nécessaire de trouver un nouveau stabilisant capable de remplacer les stabilisants classiques et qui soit miscible avec le polymère de façon à éviter la nécessité d'une étape supplémentaire dans le procédé de fabrication du prémix et donc dans le procédé de fabrication des propergols. It is therefore necessary to find a new stabilizer capable of replacing conventional stabilizers and which is miscible with the polymer so as to avoid the need for an additional step in the process manufacturing the premix and therefore in the process of manufacturing propellants.
Les inventeurs se sont aperçus de façon surprenante que les esters d'acide gras époxydés remplissaient ces conditions et permettaient de stabiliser les plastifiants énergétiques à base d'esters nitriques dans des compositions composites pour propergol solide. Ils se sont en outre aperçus que ces esters ne conduisent pas lors de leur dégradation à la formation de composé n-nitrosés (suspectés d'être CMR) contrairement aux stabilisants actuels. Les stabilisants chimiques utilisés actuellement avec les esters nitriques sont des aminés aromatiques qui piègent les oxydes d'azote en formant en premier lieu le dérivé N-nitroso. Or, les dérivés nitrosamines aromatiques sont connus pour être cancérigènes.  The inventors have surprisingly found that the epoxidized fatty acid esters fulfilled these conditions and made it possible to stabilize the energetic plasticizers based on nitric esters in solid propellant composite compositions. They also found that these esters do not lead during their degradation to the formation of n-nitrosated compounds (suspected to be CMR) unlike current stabilizers. The chemical stabilizers currently used with nitric esters are aromatic amines which trap nitrogen oxides by first forming the N-nitroso derivative. However, aromatic nitrosamine derivatives are known to be carcinogenic.
L'article de Frys et al (propellants, explosives, pyrotechnies, 2011, 36, pages 347-355) décrit l'utilisation d'esters d'acide gras époxydés en tant que stabilisants de propergols double-bases contenant de la nitroglycérine et de la nitrocellulose. The article by Frys et al (propellants, explosives, pyrotechnics, 2011, 36, pages 347-355) discloses the use of epoxidized fatty acid esters as stabilizers of double-base propellants containing nitroglycerin and nitrocellulose.
Or les propergols double-bases n'ont rien à voir avec les propergols composites selon la présente invention.  But double-base propellants have nothing to do with composite propellants according to the present invention.
En effet les problèmes de stabilisation ne sont pas les mêmes : les propergols double-bases ont des risques d'auto-inflammation et leurs stabilisants sont utilisés pour limiter ou prévenir ces risques alors que, comme indiqué ci-dessus, le problème rencontré par les propergols composites est le risque de fissuration des blocs de propergols. Indeed the problems of stabilization are not the same: the double-base propellants have risks of auto-ignition and their stabilizers are used to limit or prevent these risks whereas, as indicated above, the problem met by the Composite propellants is the risk of cracking propellant blocks.
II ne s'agit donc pas du même effet de stabilisation et ce n'est pas parce qu'un produit est un stabilisant pour les propergols double-base qu'il peut être stabilisant pour les propergols composites. Ceci est d'autant plus vrai qu'il est nécessaire, dans le cas des stabilisants des propergols composites, que le stabilisant se disperse bien dans le prémix. On ne peut donc transposer l'enseignement de ce document aux propergols composites. It is not therefore the same stabilizing effect and it is not because a product is a stabilizer for double-base propellants that it can be stabilizing for composite propellants. This is all the more true as it is necessary, in the case of stabilizers of composite propellants, that the stabilizer disperses well in the premix. We can not therefore, translate the teaching of this document to composite propellants.
La présente invention concerne donc une composition composite pour propergol solide, avantageusement pour propergol composite solide, comprenant The present invention therefore relates to a solid propellant composite composition, advantageously for solid composite propellant, comprising
a) une charge énergétique a) an energy load
b) une éventuelle charge réductrice b) a possible reducing load
c) un liant énergétique comprenant un plastifiant énergétique à base d'esters nitriques et un stabilisant des esters nitriques et c) an energy binder comprising an energetic plasticizer based on nitric esters and a nitric ester stabilizer and
d) un système réticulant, d) a crosslinking system,
caractérisée en ce que le stabilisant des esters nitriques est choisi parmi les esters d'acide gras époxydés. Les esters d'acide gras époxydés utilisables dans le cadre de la présente invention peuvent en particulier être choisis parmi les huiles époxydées telles que les huiles végétales époxydées (l'huile de soja époxydée et/ou l'huile de lin époxydée par exemple), ces huiles contenant avantageusement principalement des esters d'acides gras à longue chaîne insaturés qui ont été époxydés sur une ou plusieurs de leurs doubles liaison, en particulier des esters d'acides gras en Cie, tels que par exemple choisis parmi les esters de l'acide oléiques, linoléique, linolénique (en particulier alpha-linolénique) époxydé ou leurs mélanges. characterized in that the stabilizer of the nitric esters is selected from epoxidized fatty acid esters. The epoxidized fatty acid esters that may be used in the context of the present invention may in particular be chosen from epoxidized oils such as epoxidized vegetable oils (epoxidized soybean oil and / or epoxidized linseed oil, for example), these oils advantageously containing mainly unsaturated long-chain fatty acid esters which have been epoxidized on one or more of their double bonds, in particular C 18 fatty acid esters, such as, for example, chosen from esters of oleic, linoleic, linolenic (especially alpha-linolenic) epoxidized acids or mixtures thereof.
Les esters d'acide gras époxydés utilisables dans le cadre de la présente invention peuvent également consister en un mélange d'esters d'acides gras époxydés, par exemple d'acides gras à longues chaînes, en particulier en C14-C22 (ester de l'acide myristoléique, palmitoléique, sapiénique, oléique, élaidique, vaccenique, linoléique, linoelaidique, alpha-linolénique, arachidonique, eicosapentaenoique, ericique et/ou docosahexaénoique époxydé par exemple), ou de l'octyle de stéarate époxydé et leurs mélanges. The epoxidized fatty acid esters that may be used in the context of the present invention may also consist of a mixture of epoxidized fatty acid esters, for example of long-chain fatty acids, in particular C 14 -C 22 fatty acid esters. myristoleic, palmitoleic, sapenic, oleic, elaidic, vaccenic, linoleic, linolenic, alpha-linolenic, arachidonic, eicosapentaenoic, ericic and / or docosahexaenoic acids epoxidized for example), or octyl epoxidized stearate and mixtures thereof.
Les esters d'acide gras époxydés selon l'invention peuvent contenir des monoesters, des diesters ou des triesters tels que des triglycérides. Ils contiennent en général au moins une fonction époxy mais ils peuvent en contenir plusieurs (par exemple 3, ou même 7). Au moins une des fonctions ester peut se trouver en alpha d'au moins une des fonctions époxy.  The epoxidized fatty acid esters according to the invention may contain monoesters, diesters or triesters such as triglycerides. They generally contain at least one epoxy function but they can contain several epoxy functions (for example 3 or even 7). At least one of the ester functions may be alpha to at least one of the epoxy functions.
Avantageusement les esters d'acide gras époxydés selon l'invention sont choisis parmi l'huile de soja époxydée, l'huile de lin époxydée, un mélange d'esters d'acides gras en C14-C22 époxydés, l'octyle de stéarate époxydé et leurs mélanges, de façon encore plus avantageuse parmi un mélange d'esters d'acides gras en C14-C22 époxydés, l'octyle de stéarate époxydé et leurs mélanges. Ces esters d'acide gras époxydés sont disponibles commercialement auprès de la société AKCROS CHEMICALS sous la dénomination Lankroflex® L (huile de lin époxydée), Lankroflex® E2307 (huile de soja époxydée) et Lankroflex® ED6 (octyle de stéarate époxydé).  Advantageously, the epoxidized fatty acid esters according to the invention are chosen from epoxidized soybean oil, epoxidized linseed oil, a mixture of epoxidized C14-C22 fatty acid esters and epoxidized stearate octyl. and mixtures thereof, even more preferably from a mixture of epoxidized C14-C22 fatty acid esters, epoxidized stearate octyl and mixtures thereof. These epoxidized fatty acid esters are commercially available from AKCROS CHEMICALS under the name Lankroflex® L (epoxidized linseed oil), Lankroflex® E2307 (epoxidized soybean oil) and Lankroflex® ED6 (epoxidized stearate octyl).
Les esters d'acide gras époxydés sont en général présents dans la composition en une teneur comprise entre 0,25 et 1 % en masse par rapport à la masse totale de la composition. Ils représentent en général entre 1 et 5 % en masse par rapport à la masse du mélange esters nitriques/esters d'acide gras époxydés. Au sens de la présente invention on entend par « plastifiant énergétique à base d'esters nitriques », tout plastifiant énergétique comprenant des esters nitriques, en particulier constitué par des esters nitriques. De façon avantageuse les esters nitriques sont choisies parmi la n-butyl-2- nitratoéthylnitramine (bu-NENA), l'éthyl-2-nitratoéthylnitramine (EthlyNENA), le dinitrate de triéthylèneglycol (TEGDN), le dinitrate de diéthylèneglycol (DEGDN), le trinitrate de butanetriol (BTTN), le trinitrate de triméthyloéthane (TMETN), le dinitrate de triéthylène glycol (TEMA), la nitroglycérine et leurs mélanges, en particulier parmi le trinitrate de butanetriol, le trinitrate de triméthyloéthane, le dinitrate de trioxyéthylène glycol et leurs mélanges, plus particulièrement il s'agit du trinitrate de butanetriol. The epoxidized fatty acid esters are generally present in the composition in a content of between 0.25 and 1% by weight relative to the total weight of the composition. They generally represent between 1 and 5% by weight relative to the mass of the mixture of nitric esters / epoxidized fatty acid esters. For the purposes of the present invention, the term "energetic plasticizer based on nitric esters" means any energetic plasticizer comprising nitric esters, in particular consisting of nitric esters. Advantageously, the nitric esters are chosen from n-butyl-2-nitratoethylnitramine (bu-NENA) and ethyl-2-nitratoethylnitramine. (EthlyNENA), triethylene glycol dinitrate (TEGDN), diethylene glycol dinitrate (DEGDN), butanetriol trinitrate (BTTN), trimethylethane trinitrate (TMETN), triethylene glycol dinitrate (TEMA), nitroglycerin and mixtures thereof , especially among butanetriol trinitrate, trimethylethane trinitrate, trioxyethylene glycol dinitrate and mixtures thereof, more particularly it is butanetriol trinitrate.
Les esters nitriques sont en général présents dans la composition en une teneur comprise entre 6 et 30 % en masse par rapport à la masse totale de la composition. Ils représentent en général 30 à 75 % en masse du liant énergétique.  Nitric esters are generally present in the composition in a content of between 6 and 30% by weight relative to the total mass of the composition. They generally represent 30 to 75% by weight of the energy binder.
Le liant énergétique comprend un polymère. Ce polymère peut être inerte ou énergétique. The energy binder comprises a polymer. This polymer can be inert or energetic.
Si le polymère est inerte, il peut s'agir par exemple d'un polyester ayant une terminaison hydroxy ou d'un polyéther ayant une terminaison hydroxy. Il est avantageusement choisi parmi le polyoxypropylène glycol, polybutylèneoxyde, polytétraméthylène oxyde, le polyoxyde d'éthylène, le polyadipate de diéthylène glycol (PADEG) et leurs mélanges. En particulier il s'agit du polyadipate de diéthylène glycol. If the polymer is inert, it may be, for example, a polyester having a hydroxy terminus or a polyether having a hydroxy terminus. It is advantageously chosen from polyoxypropylene glycol, polybutyleneoxide, polytetramethylene oxide, polyethylene oxide, diethylene glycol polyadipate (PADEG) and mixtures thereof. In particular, it is diethylene glycol polyadipate.
Si le polymère est énergétique, il peut s'agir d'un polyazoture de glycidyle (PAG) ou d'un polynitrate de glycidyle. En particulier il s'agit du polyazoture de glycidyle.  If the polymer is energetic, it may be a glycidyl polyazide (PAG) or a glycidyl polynitrate. In particular it is glycidyl polyazide.
Le polymère est en général présent dans la composition en une teneur comprise entre 5 et 30 % en masse par rapport à la masse totale de la composition. Il représente en général 25 à 70 % en masse du liant énergétique. La charge énergétique utilisable dans la composition selon la présente invention est en général pulvérulente et est avantageusement choisie dans le groupe formé par le perchlorate d'ammonium (PA), le nitrate d'ammonium (NA), l'hexogène ( DX), l'octogène (HMX), l'hexanitrohexaazaisowurtzitane (CL20) ou leurs mélanges. The polymer is generally present in the composition in a content of between 5 and 30% by weight relative to the total weight of the composition. It generally represents 25 to 70% by weight of the energy binder. The energy load that can be used in the composition according to the present invention is generally pulverulent and is advantageously chosen from the group formed by ammonium perchlorate (PA), ammonium nitrate (NA), hexogen (DX) octogen (HMX), hexanitrohexaazaisowurtzitane (CL20) or mixtures thereof.
Les charges énergétiques sont en générale présentes dans la composition en une teneur comprise entre 60 à 80 % en masse par rapport à la masse totale de la composition. L'éventuelle charge réductrice utilisable dans la composition selon la présente invention est en général pulvérulente et est avantageusement choisie dans le groupe formé par l'aluminium, le bore, le zirconium ou leurs mélanges.  The energy charges are generally present in the composition in a content of between 60 and 80% by weight relative to the total mass of the composition. The optional reducing charge that can be used in the composition according to the present invention is generally pulverulent and is advantageously chosen from the group formed by aluminum, boron, zirconium or their mixtures.
La charge réductrice si elle est présente, est en générale présente dans la composition en une teneur comprise entre 1 à 20 % en masse par rapport à la masse totale de la composition.  The reducing charge, if it is present, is generally present in the composition in a content of between 1 and 20% by weight relative to the total mass of the composition.
Le système réticulant utilisable dans la composition selon la présente invention est avantageusement liquide et en particulier choisi parmi les polyisocyanates tels que le toluène diisocyanate, en particulier les polyisocyanates alicycliques, tels que le dicyclohexylméthylène diisocyanate, l'isophorone diisocyanate, l'hexaméthylène diisocyanate ou le biuret triisocyanate. The crosslinking system that can be used in the composition according to the present invention is advantageously liquid and in particular chosen from polyisocyanates such as toluene diisocyanate, in particular alicyclic polyisocyanates, such as dicyclohexylmethylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate or biuret triisocyanate.
Le système réticulant est en générale présent dans la composition en une teneur comprise entre 0,4 et 5 % en masse par rapport à la masse totale de la composition.  The crosslinking system is generally present in the composition in a content of between 0.4 and 5% by weight relative to the total mass of the composition.
Dans un mode de réalisation particulier, la composition selon la présente invention comprend en outre des additifs, avantageusement choisis parmi d'autres stabilisants (tels que la 2-nitrodiphénylamine), des anti-oxydants, des extenseurs de chaîne, des catalyseurs de polymérisation, des modificateurs de combustion (accélérateurs ou ralentisseurs), des additifs balistiques (refroidissants par exemple), des agents d'adhésion liant- charges et des pontants. Les additifs sont en général présents dans le liant énergétique. Les additifs, s'ils sont présents, sont en général présents dans la composition en une teneur comprise entre 0,1 et 10 % en masse par rapport à la masse totale de la composition. La présente invention concerne en outre un propergol solide composite caractérisé en ce qu'il est au moins en partie constitué d'une composition composite selon la présente invention. In a particular embodiment, the composition according to the present invention further comprises additives, advantageously chosen from other stabilizers (such as 2-nitrodiphenylamine), antioxidants, chain extenders, polymerization catalysts, combustion modifiers (accelerators or retarders), ballistic additives (for example cooling), binder-load adhesion and bridging. Additives are usually present in the energy binder. The additives, if present, are generally present in the composition in a content of between 0.1 and 10% by weight relative to the total weight of the composition. The present invention further relates to a solid composite propellant characterized in that it is at least partly made of a composite composition according to the present invention.
Elle concerne de plus un chargement pyrotechnique caractérisé en ce qu'il comprend un propergol solide, en particulier composite, selon la présente invention dans une structure. Les chargements peuvent être pleins ou à canal. Les structures sont des structures classiques type structure à propulseur. It further relates to a pyrotechnic charge characterized in that it comprises a solid propellant, in particular composite, according to the present invention in a structure. The loads can be full or channel. The structures are conventional structures like propellant structure.
Les propergols sont fabriqués selon les procédés classiquement utilisés pour les compositions composites pour propergols solides. Par exemple par mélange dans un malaxeur dans lequel les différents ingrédients sont introduits selon un ordre approprié et soigneusement et longuement malaxés dans des conditions de pression et de température données. Ce mélange, qui se présente sous la forme d'une pâte, est coulé dans un moule avec des outillages de mise en forme. L'ensemble subit une cuisson pour assurer le durcissement de la pâte. Le moule constitue dans certains cas l'enveloppe même du moteur. La présente invention concerne également un procédé de fabrication de la composition composite selon la présente invention, caractérisé en ce qu'il comprend l'étape préalable de fabrication du liant énergétique avant l'ajout de la charge énergétique, de l'éventuelle charge réductrice et du système réticulant. The propellants are manufactured according to the methods conventionally used for composite compositions for solid propellants. For example by mixing in a kneader in which the various ingredients are introduced in an appropriate order and carefully and thoroughly kneaded under given pressure and temperature conditions. This mixture, which is in the form of a paste, is cast in a mold with shaping tools. The whole is baked to ensure the hardening of the dough. The mold is in some cases the same envelope of the engine. The present invention also relates to a method of manufacturing the composite composition according to the present invention, characterized in that it comprises the prior step of manufacturing the energy binder before the addition of the energy charge, the possible reducing charge and of the crosslinking system.
Dans un mode de réalisation avantageux, l'étape préalable de fabrication du liant énergétique est réalisée en deux étapes, la deuxième étape consistant en l'ajout des esters nitriques dans le liant énergétique. In an advantageous embodiment, the prior step of manufacturing the energy binder is carried out in two stages, the second stage consisting of the addition of the nitric esters in the energy binder.
Enfin la présente invention concerne l'utilisation d'un ester d'acide gras époxydé, en particulier tel que défini ci-dessus, en tant que stabilisant des esters nitriques du plastifiant énergétique du liant énergétique d'une composition composite pour propergol solide, en particulier telle que définie ci-dessus, plus particulièrement pour propergol solide composite. Finally, the present invention relates to the use of an epoxidized fatty acid ester, in particular as defined above, as a stabilizer for the nitric esters of the energetic plasticizer of the energy binder of a solid propellant composite composition, particular as defined above, more particularly for composite solid propellant.
L'invention sera mieux comprise à la lumière des exemples qui suivent qui ne sont indiqués qu'à titre d'illustration de l'invention. The invention will be better understood in the light of the examples which follow, which are only given by way of illustration of the invention.
Exemple 1 : Example 1
L'effet stabilisant des esters d'acide gras époxydés a d'abord été validé en mélange modèle BTTN+1% Lankroflex par des essais en Epreuve sous vide (ESV, norme NFT 70-717) et microcalorimétrie. La microcalorimétrie permet de mesurer le flux thermique généré ou absorbé par un échantillon de l'ordre de lg dans une enceinte thermorégulée d'un microcalorimètre. Les résultats sont rassemblés dans le tableau suivant : Volume de gaz dégagé, niveau final et énergie totale à 80° C The stabilizing effect of epoxidized fatty acid esters was first validated in a BTTN + 1% Lankroflex model mixture by Vacuum Test (ESV, NFT 70-717) and microcalorimetry tests. Microcalorimetry makes it possible to measure the heat flux generated or absorbed by a sample of the order of 1 g in a thermoregulated chamber of a microcalorimeter. The results are summarized in the following table: Volume of gas released, final level and total energy at 80 ° C
Figure imgf000011_0001
Figure imgf000011_0001
(*) 4-nitrotriphénylamine  (*) 4-nitrotriphenylamine
Les ESV montrent une bonne compatibilité entre les esters nitriques et les différents Lankroflex testés. Les énergies obtenues en microcalorimétrie montrent l'effet stabilisant apporté par les grades Lankroflex qui limitent fortement l'emballement de la réaction observée sur les esters nitriques purs. Le Lankroflex® ED6 a montré les meilleurs résultats.  The ESV show a good compatibility between the nitric esters and the different Lankroflex tested. The energies obtained in microcalorimetry show the stabilizing effect provided by Lankroflex grades which strongly limit the runaway of the reaction observed on pure nitric esters. Lankroflex® ED6 showed the best results.
Exemple 2 : Example 2
Une arête critique supérieure à 50 mm à 80°C sur une malaxée type Oxalane® X a été mesurée lors d'un essai de vieillissement fissurant. Le protocole consiste à suivre l'intégrité d'un cube d'arête défini par analyses aux rayons X sur une durée de 21 jours à 80°C. L'arête minimale pour laquelle on obtient une fissuration est l'arête critique. La composition de la malaxée étudiée est décrite dans le tableau ci-dessous :  A critical edge greater than 50 mm at 80 ° C on an Oxalane® X mix was measured in a cracking aging test. The protocol consists in following the integrity of an edge cube defined by X-ray analysis over a period of 21 days at 80 ° C. The minimum edge for which cracking is obtained is the critical edge. The composition of the kneaded mixture studied is described in the table below:
Huiles nitrées 17,5%  Nitrated oils 17,5%
Lankroflex ED6 0,6%  Lankroflex ED6 0.6%
Charges 75%  75% Charges
Polymère, réticulant, additifs 6,9% Ce résultat signifie que sur un cube de propergol d'arête 50mm soumis à une température de 80°C on ne voit pas de fissure sur un temps de 3 semaines. Le bloc est donc sain, c'est-à-dire que le lankroflex joue son rôle de stabilisant car il évite la formation de fissure, en limitant la génération de gaz susceptibles de se former lorsque les esters nitriques ne sont pas stabilisés. Polymer, crosslinker, additives 6.9% This result means that on a propellant cube of 50mm edge subjected to a temperature of 80 ° C one does not see crack on a time of 3 weeks. The block is therefore healthy, that is to say that the lankroflex plays its role of stabilizer because it avoids the formation of crack, limiting the generation of gas likely to form when the nitric esters are not stabilized.
Exemple 3 : Example 3
La solubilité des LANKROFLEX L / E2307 / ED6 a été testée dans des Prémix A dont le polymère est du PAG ou du PADEG à 50°C et à température ambiante à une teneur de 2,5 % en masse par rapport à la masse totale du prémix.  The solubility of LANKROFLEX L / E2307 / ED6 was tested in Premix A whose polymer is PAG or PADEG at 50 ° C. and at room temperature at a content of 2.5% by weight relative to the total mass of premixes.
Les mélanges réalisés sont détaillés dans le tableau 1 ci-dessous.  The mixtures made are detailed in Table 1 below.
Les mélanges ont été effectués dans des tubes à centrifuger et homogénéisés à la spatule. Les tubes ont été exposés à des températures soit de 50°C en étuve ou à température ambiante (soit 23,6°C) durant environ 72h puis observés. Le détail des observations est donné dans le tableau 2 ci-dessous. The mixtures were made in centrifuge tubes and homogenized with a spatula. The tubes were exposed to temperatures of either 50 ° C in an oven or at room temperature (23.6 ° C) for about 72 hours and then observed. The details of the observations are given in Table 2 below.
La solubilité de trois grades de Lankroflex à 20 et 50°C est donc confirmée dans les polymères et les prémix. The solubility of three grades of Lankroflex at 20 and 50 ° C is therefore confirmed in polymers and premixes.
Tableau 1: Détails des masses des mélanges Prémix / Lankroflex.
Figure imgf000013_0001
Table 1: Details of the Premix / Lankroflex mixtures.
Figure imgf000013_0001
Tableau 2 : Détails des observations faites sur les mélanges précédents.
Figure imgf000013_0002
Table 2: Details of observations made on previous mixtures.
Figure imgf000013_0002

Claims

REVENDICATIONS
1. Composition composite pour propergol solide comprenant 1. Composite composition for solid propellant comprising
a) une charge énergétique a) an energy charge
b) une éventuelle charge réductrice b) a possible reducing charge
c) un liant énergétique comprenant un plastifiant énergétique à base d'esters nitriques et un stabilisant des esters nitriques et c) an energy binder comprising an energy plasticizer based on nitric esters and a nitric ester stabilizer and
d) un système réticulant, d) a crosslinking system,
caractérisée en ce que le stabilisant des esters nitriques est choisi parmi les esters d'acide gras époxydés. characterized in that the nitric ester stabilizer is chosen from epoxidized fatty acid esters.
2. Composition selon la revendication 1, caractérisé en ce que le stabilisant est choisi parmi l'huile de soja époxydée, l'huile de lin époxydée, un mélange d'esters d'acides gras en C14-C22 époxydés, l'octyle de stéarate époxydé et leurs mélanges. 2. Composition according to claim 1, characterized in that the stabilizer is chosen from epoxidized soybean oil, epoxidized linseed oil, a mixture of epoxidized C14-C22 fatty acid esters, octyl of epoxidized stearate and mixtures thereof.
3. Composition selon l'une quelconque des revendications 1 ou 2, caractérisée en ce que le liant comprend un polymère inerte, avantageusement le polyadipate de diéthylène glycol. 3. Composition according to any one of claims 1 or 2, characterized in that the binder comprises an inert polymer, advantageously diethylene glycol polyadipate.
4. Composition selon l'une quelconque des revendications 1 ou 2, caractérisée en ce que le liant comprend un polymère énergétique, avantageusement le polyazoture de glycidyle. 4. Composition according to any one of claims 1 or 2, characterized in that the binder comprises an energetic polymer, advantageously glycidyl polyazide.
5. Composition selon l'une quelconque des revendications 1 à 4, caractérisée en ce que les esters nitriques sont choisis parmi le trinitrate de butanetriol, le trinitrate de triméthylo éthane, le dinitrate de trioxyéthylène glycol et leurs mélanges 5. Composition according to any one of claims 1 to 4, characterized in that the nitric esters are chosen from butanetriol trinitrate, trimethylethane trinitrate, trioxyethylene glycol dinitrate and their mixtures.
..
6. Composition selon l'une quelconque des revendications 1 à 5, caractérisée en ce qu'elle comprend des additifs, avantageusement choisis parmi d'autres stabilisants tels que la 2-nitrodiphénylamine, des antioxydants et des pontants tels que des polyols. 6. Composition according to any one of claims 1 to 5, characterized in that it comprises additives, advantageously chosen among other stabilizers such as 2-nitrodiphenylamine, antioxidants and bridging agents such as polyols.
7. Propergol solide composite caractérisé en ce qu'il est au moins en partie constitué d'une composition selon l'une quelconque des revendications 1 à 6. 7. Composite solid propellant characterized in that it is at least partly made up of a composition according to any one of claims 1 to 6.
8. Chargement pyrotechnique caractérisé en ce qu'il comprend un propergol solide composite selon la revendication 7 dans une structure. 8. Pyrotechnic charge characterized in that it comprises a composite solid propellant according to claim 7 in a structure.
9. Procédé de fabrication de la composition selon l'une quelconque des revendications 1 à 6, caractérisé en ce qu'il comprend l'étape préalable de fabrication du liant énergétique avant l'ajout de la charge énergétique, de l'éventuelle charge réductrice et du système réticulant. 9. Process for manufacturing the composition according to any one of claims 1 to 6, characterized in that it comprises the preliminary step of manufacturing the energy binder before adding the energy charge, the possible reducing charge and the crosslinking system.
10. Procédé selon la revendication 8, caractérisé en ce que l'étape préalable de fabrication du liant énergétique est réalisée en deux étapes, la deuxième étape consistant en l'ajout des esters nitriques dans le liant énergétique. 10. Method according to claim 8, characterized in that the preliminary step of manufacturing the energy binder is carried out in two stages, the second stage consisting of the addition of nitric esters in the energy binder.
11. Utilisation d'un ester d'acide gras époxydé en tant que stabilisant des esters nitriques du plastifiant énergétique du liant énergétique d'une composition composite pour propergol solide. 11. Use of an epoxidized fatty acid ester as a stabilizer of the nitric esters of the energy plasticizer of the energy binder of a composite composition for solid propellant.
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