EP0218511A1 - Binder-charge bonding agent and propellant composition containing it - Google Patents

Binder-charge bonding agent and propellant composition containing it Download PDF

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Publication number
EP0218511A1
EP0218511A1 EP86402055A EP86402055A EP0218511A1 EP 0218511 A1 EP0218511 A1 EP 0218511A1 EP 86402055 A EP86402055 A EP 86402055A EP 86402055 A EP86402055 A EP 86402055A EP 0218511 A1 EP0218511 A1 EP 0218511A1
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Prior art keywords
binder
adhesion agent
composition according
propellant
agent
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EP86402055A
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German (de)
French (fr)
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EP0218511B1 (en
Inventor
Bernard Finck
Gérard Doriath
Jean-Pierre Martenot
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Safran Ceramics SA
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Societe Nationale des Poudres et Explosifs
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    • CCHEMISTRY; METALLURGY
    • C06EXPLOSIVES; MATCHES
    • C06BEXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B23/00Compositions characterised by non-explosive or non-thermic constituents
    • C06B23/001Fillers, gelling and thickening agents (e.g. fibres), absorbents for nitroglycerine
    • CCHEMISTRY; METALLURGY
    • C06EXPLOSIVES; MATCHES
    • C06BEXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B45/00Compositions or products which are defined by structure or arrangement of component of product
    • C06B45/04Compositions 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
    • C06B45/06Compositions 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
    • C06B45/10Compositions 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

Definitions

  • the present invention relates to a binder-filler adhesion agent, and a propellant composition with improved mechanical properties and feasibility, containing this adhesion agent.
  • It relates more particularly to a binder-filler adhesion agent for a polyurethane binder, and a composite propellant with a polyurethane binder.
  • the composite propellant compositions for rockets, missiles, or for gas generators consist of a generally non-energetic binder and reducing oxidizing charges and possibly reducing charges.
  • the oxidizing charges are generally oxidizing mineral salts such as ammonium perchlorate, for example, while the reducing charges are usually metallic charges and generally aluminum.
  • propellant compositions are preferably used to manufacture large blocks obtained by casting the composition in a mold and then polymerizing the binder.
  • the mold When the mold is formed by the casing of the propellant, it is not necessary to demold the block thus produced, which adheres directly to it, we then say that we have a molded block. In the other cases where the block is molded in an independent mold then demolded and placed in the casing of the propellant, the block is called free block.
  • the propellant must have high mechanical properties, in particular to allow its manipulation, or to withstand the stresses generated by the deformations, such as the expansion of the casing of the propellant.
  • the mechanical properties of a propellant are characterized by parameters determined by subjecting a test piece thereof to a simple tensile test and by recording the tensile curve shown in the single figure.
  • v is generally considered the product S m m .e, by analogy to the product Sm. ⁇ used for elastic materials and which represents the maximum energy admissible by the material without undergoing irreversible damage.
  • the mechanical properties of a propellant are largely determined by the nature of the binder, the degree of polymerization and crosslinking thereof. It is therefore customary to add polyols to the composite propellants with a polyurethane binder. short such as trimethylolpropane to increase the degree of bridging between the polymer chains.
  • the interaction between the binder and the filler is the phenomenon which conditions the cohesion of the propellant.
  • the separation of the charges from the binder causes voids around them which reduce the cohesion of the propellant and therefore weaken its mechanical properties.
  • These detachments can be caused in particular during the elongation of the propellant under the effect of the expansion of the casing of the propellant. This phenomenon is irreversible.
  • the most generally used compounds are compounds containing aziridinyl rings and in particular the trimethylaziridinylephosphine oxide known by the acronym MAPO.
  • MAPO derivatives have also been proposed, in particular the compounds resulting from the reaction of MAPO with a carboxylic acid.
  • the object of the present invention is to propose a new compound having improved properties for reinforcing the mechanical properties of the composition and in particular of the bond between the filler and the binder and therefore making it possible to manufacture propellant compositions having improved mechanical properties and feasibility. .
  • the invention provides a binder-filler adhesion agent between one or more fillers and a polyurethane binder, characterized in that said binder-filler adhesion agent is an aminoaziridinylphosphine oxide of general formula (I): in which: R 1 , R 2 , R 3 , R 4 which may be identical or different, represent the hydrogen atom or a methyl or ethyl radical.
  • R 1 and R 3 represent the hydrogen atom and R 2 , R 4 represent the methyl radical.
  • the subject of the invention is also a composite propellant composition with a binder based on polyurethane resin containing as main components oxidizing charges and optionally reducing charges, at least one binder-filler adhesion agent, characterized in that said agent adhesion is an aminoaziridinylphosphine oxide as defined above.
  • the weight concentration of aminoaziridinylphosphine oxide compound in the propellant composition is between 0.5 and 3% and preferably between 0.5 and 1.5% by weight of the binder.
  • the propellant composition may contain polymerization catalysts, combustion catalysts, plasticizers, antioxidants and any ballistic additive commonly used in composite propellants, in usual proportions and well known to those skilled in the art.
  • Polyurethane resins are obtained by condensation of a polyol, generally a diol, with a polyisocyanate.
  • polyesters with hydroxyl endings obtained from diethylene glycol or ethylene glycol and adipic acid or azoleic acid
  • polyethers with hydroxyl endings prepared from polyoxytetramethylene glycol, polyoxypropylene glycol or the like
  • polybutadienes with hydroxyl endings designated under the acronym PBHT and called hydroxytelechelic polybutadienes.
  • the polyurethane binder is obtained from a hydroxytelechelic polybutadiene of average molecular weight 1000 to 5000 g having a hydroxyl functionality of between 2 and 3, advantageously close to 2.3.
  • hydroxytelechelic polybutadienes of the invention mention may be made of those sold by the American company ARCO Chemical Company under the trade names R45M and R45HT.
  • polyisoyanate compounds suitable as crosslinking agent mention may be made, for example, of toluene diisocyanate (TDI), hexamethylene diisocyanate (HMDI), dimeryldiisocyanate (DDI), isophorone diisocyanate (IPDI), sorting ( isocyanato-6) -, 3.5 biuret (marketed by the Company BAYER AG under the name Desmodur N100) methylene-4,4 'bis (cyclohexyldiisocyanate) (MDCI), or the like.
  • TDI toluene diisocyanate
  • HMDI hexamethylene diisocyanate
  • DDI dimeryldiisocyanate
  • IPDI isophorone diisocyanate
  • sorting isocyanato-6) -, 3.5 biuret (marketed by the Company BAYER AG under the name Desmodur N100) methylene-4,4 'bis (cyclohex
  • Suitable oxidizing charges are, for example, ammonium perchlorate, potassium nitrate, or the like.
  • the preferred filler of the invention is ammonium perchlorate.
  • nitramines such as cyclotrimethylenetrinitramine or hexogen (RDX), cyclo-tetramethylenetetranitramine or octogen (HMX), or pentaerythritol tetranitrate (PETN), bu analog.
  • RDX cyclotrimethylenetrinitramine or hexogen
  • HMX cyclo-tetramethylenetetranitramine or octogen
  • PETN pentaerythritol tetranitrate
  • the reducing charges suitable for the invention are generally metallic powders such as aluminum, beryllium, zirconium powder or the like.
  • the preferred reducing filler of the invention is aluminum powder.
  • aminoaziridinylphosphine oxide compounds of the invention can be prepared in particular by the following two methods.
  • the first process consists in manufacturing the compound of formula (II): in which: X represents a halogen and R 1 , R 2 have the above meaning; according to the methods described in American patents 2 606 900 and 3 201 313, then reacting this compound on an amine of formula (III) to obtain the compound of formula (I): in which R 3 , R 4 have the above meaning.
  • the second method consists in carrying out the following reaction:
  • a halogenated acid sensor (X represents a halogen atom, preferably chlorine) such as triethylamine or methyl-2-aziridine.
  • the reaction is carried out at low temperature, of the order of 0 ° C to -5 ° C.
  • the aminoaziridinylphosphine oxide is recovered.
  • This compound is then purified by, for example, distillation under reduced pressure.
  • methyl-BAPO bismethylaziridinylmethylaminophosphine oxide which for further simplification will be called hereinafter methyl-BAPO
  • a slightly yellow liquid is recovered which crystallizes into a white product, with density 1.0855 kg / dm 3 and point boiling point 115 ° C at 13.3 Pa.
  • the dihaloaminophosphine can be obtained by reacting a phosphorus oxyhalide with an alkylamine halohydrate.
  • the alkyl aziridine can be obtained by, in particular, the syntheses of Wenker and Gabriel described respectively in the Journal of the American Chemical Society, vol 57 page 2328 (1935) and in Beilstein vol 21 page 1049 (1881).
  • the composite propellant composition is obtained by the usual manufacturing process which consists, summarily, in adding into the mixture of polyols, in the present example hydroxytelechelic polybutadiene, additives such as wetting plasticizers, antioxidants, crosslinking agents, then the reducing charge is introduced. Then, the mixture obtained is poured into a kneader into which will be introduced the oxidizing charge, the crosslinking agent and the various ballistic additives such as the combustion catalysts, as well as the crosslinking catalysts.
  • the propellant thus obtained is then poured to form a block with the desired dimensions and shape.
  • the composition contains:
  • composition was produced without agent reinforcing the binder-filler adhesion, and three other compositions containing respectively in the binder 1% by weight relative to the mass of the binder, of trimethylolpropane, of a condensate of MAPO with the acid. tartaric, and methyl-BAPO. This latter composition corresponds to the invention. (Table Ia)
  • composition according to the invention namely that containing as reinforcing agent mechanical or adhesion properties binder-filler, methyl BAPO, has the lowest viscosity, and secondly that the adhesion agent binder-filler according to the invention is the only one which makes it possible to obtain a composition having a high resistance to stress (S m ) and a greatly increased level of elongation (e m ).
  • compositions are produced according to the method of Example 1 with the same binder, but the propellant has the following composition:
  • Example 1 As for Example 1, three compositions are produced, the first of which does not contain a binder-filler adhesion agent, and the other two respectively contain as a binder-filler adhesion agent tri (methylaziridinyl) phosphine oxide (MAPO) ) and bis (aziridinyl) methylaminophosphine oxide (BAPO) in a concentration equal to 2% by weight relative to the mass of the binder.
  • MAPO methylaziridinyl) phosphine oxide
  • BAPO bis (aziridinyl) methylaminophosphine oxide
  • the binder-filler adhesion agent in accordance with the present invention makes it possible to obtain propellants having very advantageous mechanical properties, in particular a high tensile strength (S m ) for a level of elongation (e m ) high.
  • the known binder-filler adhesion agent namely MAPO, makes it possible to significantly increase the tensile strength (S m ) of the propellant but tends to decrease the level of elongation of the composition.
  • a propellant composition is produced according to the method of Example 1 with a binder of the following weight composition:
  • compositions 12 and 13 are known aziridinyl compounds used in composite propellants.
  • the agent of the invention also has a beneficial effect on the feasibility of the compositions by lowering the viscosity thereof.
  • binder-filler adhesion agent The optimum level of binder-filler adhesion agent must be determined for each composition. However, the results below show that this rate can be between 0.5 and 3.0% by weight of the binder and that the best results are obtained for centers between 0.5 and 1.5%.
  • the propellant has the following weight composition: Furthermore, swelling tests with binders loaded with aluminum or not have shown that the binder-alumininum adhesion is greater in the presence of an adhesion agent according to the invention.
  • the binder-filler adhesion agent of the invention namely an aminoaziridinylphosphine oxide, makes it possible to obtain composite propellants with improved mechanical properties, in particular having an equally high level of elongation for a high tensile strength. .
  • this agent makes it possible to increase the feasibility of the propellant blocks by reducing the viscosity of the compositions for the same loading rate.
  • this binder-filler adhesion agent has no effect on the ballistic properties of the propellant and in particular has no influence on the combustion rate and the specific impulse of this one.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Molecular Biology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne un agent d'adhésion liant-charge et une composition propulsive contenant cet agent d'adhésion. L'agent d'adhésion liant-charge de la présente invention permet d'améliorer la liaison entre les charges et le liant polyuréthanne d'une composition propulsive. Cet agent est un aminoaziridinylphosphine oxyde de formule générale: <IMAGE> dans laquelle R1, R2, R3 et R4 sont identiques ou différents et représentent un atome d'hydrogène ou un radical méthyl ou éthyl. La résente invention s'applique notamment dans le domaine de la fabrication de composition propulsive solide.The invention relates to a binder-charge adhesion agent and a propellant composition containing this adhesion agent. The binder-filler adhesion agent of the present invention makes it possible to improve the bond between the fillers and the polyurethane binder of a propellant composition. This agent is an aminoaziridinylphosphine oxide of general formula: <IMAGE> in which R1, R2, R3 and R4 are identical or different and represent a hydrogen atom or a methyl or ethyl radical. The present invention is particularly applicable in the field of the manufacture of solid propellant composition.

Description

La présente invention concerne un agent d'adhésion liant-charge, et une composition propulsive à propriétés mécaniques et faisabilité améliorées, contenant cet agent d'adhésion.The present invention relates to a binder-filler adhesion agent, and a propellant composition with improved mechanical properties and feasibility, containing this adhesion agent.

Elle concerne plus particulièrement un agent d'adhésion liant-charge pour un liant polyuréthanne, et un propergol composite à liant polyuréthanne.It relates more particularly to a binder-filler adhesion agent for a polyurethane binder, and a composite propellant with a polyurethane binder.

Les compositions propulsives composites pour fusées, missiles, ou pour générateurs de gaz sont constituées par un liant généralement non énergétique et réducteur des charges oxydantes et éventuellement des charges réductrices. Les charges oxydantes sont généralement des sels minéraux oxydants tels que le perchlorate d'ammonium, par exemple, tandis que les charges réductrices sont usuellement des charges métalliques et généralement de l'aluminium.The composite propellant compositions for rockets, missiles, or for gas generators consist of a generally non-energetic binder and reducing oxidizing charges and possibly reducing charges. The oxidizing charges are generally oxidizing mineral salts such as ammonium perchlorate, for example, while the reducing charges are usually metallic charges and generally aluminum.

Ces compositions propulsives sont, préférentiellement utilisées pour fabriquer des blocs de grandes dimensions obtenus par coulée de la composition dans un moule puis polymérisation du liant.These propellant compositions are preferably used to manufacture large blocks obtained by casting the composition in a mold and then polymerizing the binder.

Quand le moule est formé par l'enveloppe du propulseur, il n'est pas nécessaire de démouler le bloc ainsi fabriqué, qui adhère directement à celle-ci, on dit alors que l'on a un bloc moulé- collé. Dans les autres cas où le bloc est moulé dans un moule indépendant puis démoulé et disposé dans l'enveloppe du propulseur, le bloc est appelé bloc libre.When the mold is formed by the casing of the propellant, it is not necessary to demold the block thus produced, which adheres directly to it, we then say that we have a molded block. In the other cases where the block is molded in an independent mold then demolded and placed in the casing of the propellant, the block is called free block.

Dans toutes ces configurations, le propergol doit présenter des propriétés mécaniques élevées, notamment pour permettre sa manipulation, ou pour supporter les contraintes générées par les déformations, telles que la dilatation de l'enveloppe du propulseur. Ces contraintes sont importantes notamment dans le cas de blocs moulés-collés car le bloc est collé sur l'enveloppe du propulseur.In all these configurations, the propellant must have high mechanical properties, in particular to allow its manipulation, or to withstand the stresses generated by the deformations, such as the expansion of the casing of the propellant. These constraints are important in particular in the case of molded-glued blocks because the block is glued to the casing of the propellant.

Les propriétés mécaniques d'un propergol sont caractérisées par des paramètres déterminés en soumettant une éprouvette de celui-ci à un essai de traction simple et en enregistrant la courbe de traction représentée à la figure unique.The mechanical properties of a propellant are characterized by parameters determined by subjecting a test piece thereof to a simple tensile test and by recording the tensile curve shown in the single figure.

A partir de cette courbe, on détermine les paramètres suivants comme illustré à la figure unique :

  • Sm : résistance maximale à la traction (Pa)
  • ε : allongement élastique (%)
  • er : allongement à la rupture (%)
  • am : allongement minimal à la traction maximum (%)
  • E : module de Young (Pa).
From this curve, the following parameters are determined as illustrated in the single figure:
  • S m : maximum tensile strength (Pa)
  • ε: elastic elongation (%)
  • e r : elongation at break (%)
  • a m : minimum elongation at maximum traction (%)
  • E: Young's modulus (Pa).

Pour pouvoir comparer les propergols au niveau de leurs propriétés v mécaniques on considère généralement le produit Sm.em, par analogie au produit Sm. ε utilisé pour les matériaux élastiques et qui représente l'énergie maximum admissible par le matériau sans qu'il subisse un endommagement irréversible.To compare the propellants at their properties mechanical v is generally considered the product S m m .e, by analogy to the product Sm. ε used for elastic materials and which represents the maximum energy admissible by the material without undergoing irreversible damage.

Les propriétés mécaniques d'un propergol sont déterminées pour une large part par la nature du liant, le degré de polymérisation et de réticulation de celui-ci. Ainsi, il est usuel d'ajouter dans les propergols composites à liant polyuréthanne, des polyols courts tels que le triméthylolpropane pour augmenter le degré de pontage entre les chaînes de polymère.The mechanical properties of a propellant are largely determined by the nature of the binder, the degree of polymerization and crosslinking thereof. It is therefore customary to add polyols to the composite propellants with a polyurethane binder. short such as trimethylolpropane to increase the degree of bridging between the polymer chains.

D'autres composants du propergol ont une influence sur ses propriétés mécaniques. Ainsi, la nature du plastifiant est importante.Other components of the propellant have an influence on its mechanical properties. Thus, the nature of the plasticizer is important.

Toutefois, l'interaction entre le liant et la charge est le phénomène qui conditionnne la cohésion du propergol. En effet, le décollement des charges du liant provoque autour de celles-ci des vides qui diminuent la cohésion du propergol et donc affaiblissent ses propriétés mécaniques. Ces décollements peuvent être provoqués notamment lors de l'élongation du propergol sous l'effet de la dilation de l'enveloppe du propulseur. Ce phénomène est irréversible.However, the interaction between the binder and the filler is the phenomenon which conditions the cohesion of the propellant. In fact, the separation of the charges from the binder causes voids around them which reduce the cohesion of the propellant and therefore weaken its mechanical properties. These detachments can be caused in particular during the elongation of the propellant under the effect of the expansion of the casing of the propellant. This phenomenon is irreversible.

Pour améliorer la liaison liant-charge, il est ajouté des composés présentant d'une part une certaine affinité pour la charge et d'autre part des fonctions chimiques permettant une fixation sur les chaînes macromoléculaires du liant.To improve the binder-filler bond, compounds are added which have, on the one hand, a certain affinity for the filler and, on the other hand, chemical functions allowing attachment to the macromolecular chains of the binder.

Les composés les plus généralement utilisés sont des composés contenant des cycles aziridinyles et notamment le triméthylaziridi- nylephosphine oxyde connu sous le sigle MAPO.The most generally used compounds are compounds containing aziridinyl rings and in particular the trimethylaziridinylephosphine oxide known by the acronym MAPO.

Il a également été proposé des dérivés du MAPO, notamment les composés provenant de la réaction du MAPO avec un acide carboxylique.MAPO derivatives have also been proposed, in particular the compounds resulting from the reaction of MAPO with a carboxylic acid.

La présente invention a pour but de proposer un nouveau composé ayant des propriétés améliorées de renforcement des propriétés mécaniques de la composition et notamment de la liaison entre la charge et le liant et permettant donc de fabriquer des compositions propulsives ayant des propriétés mécaniques et une faisabilité améliorées.The object of the present invention is to propose a new compound having improved properties for reinforcing the mechanical properties of the composition and in particular of the bond between the filler and the binder and therefore making it possible to manufacture propellant compositions having improved mechanical properties and feasibility. .

A cet effet, l'invention propose un agent d'adhésion liant-charge entre une ou plusieurs charges et un liant polyuréthanne caractérisé en ce que ledit agent d'adhésion liant-charge est un aminoaziridinylphosphine oxyde de formule générale (I) :

Figure imgb0001
dans laquelle : Rl, R2, R3, R4 qui peuvent être identiques ou différents, représentent l'atome d'hydrogène ou un radical méthyl ou éthyl.To this end, the invention provides a binder-filler adhesion agent between one or more fillers and a polyurethane binder, characterized in that said binder-filler adhesion agent is an aminoaziridinylphosphine oxide of general formula (I):
Figure imgb0001
in which: R 1 , R 2 , R 3 , R 4 which may be identical or different, represent the hydrogen atom or a methyl or ethyl radical.

Selon une caractéristique préférentielle de l'invention, R1 et R3 représentent l'atome d'hydrogène et R2, R4 représentent le radical méthyl.According to a preferred characteristic of the invention, R 1 and R 3 represent the hydrogen atom and R 2 , R 4 represent the methyl radical.

L'invention a également pour öbjet une composition propulsive composite à liant à base de résine polyuréthanne contenant comme composants principaux des charges oxydantes et éventuellement des charges réductrices, au moins un agent d'adhésion liant-charge, caractérisé en ce que ledit agent d'adhésion est une aminoaziridinylphosphine oxyde telle que définie ci-dessus.The subject of the invention is also a composite propellant composition with a binder based on polyurethane resin containing as main components oxidizing charges and optionally reducing charges, at least one binder-filler adhesion agent, characterized in that said agent adhesion is an aminoaziridinylphosphine oxide as defined above.

Selon une autre caractéristique de l'invention, la concentration pondérale en composé aminoaziridinylphosphine oxyde dans la composition propulsive est comprise entre 0,5 et 3 % et de préférence entre 0,5 et 1,5 % du poids du liant.According to another characteristic of the invention, the weight concentration of aminoaziridinylphosphine oxide compound in the propellant composition is between 0.5 and 3% and preferably between 0.5 and 1.5% by weight of the binder.

La composition propulsive peut contenir des catalyseurs de polymérisation, des catalyseurs de combustion, des plastifiants, des anti-oxydants et tout additif balistique usuellement utilisé dans les propergols composites, dans des proportions habituelles et bien connues de l'homme de métier.The propellant composition may contain polymerization catalysts, combustion catalysts, plasticizers, antioxidants and any ballistic additive commonly used in composite propellants, in usual proportions and well known to those skilled in the art.

Les résines polyuréthannes sont obtenues par condensation d'un polyol, généralement un diol, avec un polyisocyanate.Polyurethane resins are obtained by condensation of a polyol, generally a diol, with a polyisocyanate.

Comme polyols les plus souvent utilisés, on peut citer les polyesters à terminaisons hydroxyles obtenus à partir du diéthylène glycol ou de l'éthylène glycol et de l'acide adipique ou acide azé- laïque, les polyethers à terminaisons hydroxyles préparés à partir du polyoxytétraméthylèneglycol, polyoxypropylèneglycol ou analogue, les polybutadiènes à terminaisons hydroxyles désignées sous le sigle PBHT, et appelés polybutadiènes hydroxytéléchéliques.As polyols most often used, mention may be made of polyesters with hydroxyl endings obtained from diethylene glycol or ethylene glycol and adipic acid or azoleic acid, polyethers with hydroxyl endings prepared from polyoxytetramethylene glycol, polyoxypropylene glycol or the like, polybutadienes with hydroxyl endings designated under the acronym PBHT, and called hydroxytelechelic polybutadienes.

Dans un mode de réalisation préféré de l'invention, le liant polyuréthanne est obtenu à partir d'un polybutadiène hydroxytéléchélique de poids moléculaire moyen 1000 à 5000 g ayant une fonctionnalité en hydroxyle comprise entre 2 et 3, avantageusement voisine de 2,3.In a preferred embodiment of the invention, the polyurethane binder is obtained from a hydroxytelechelic polybutadiene of average molecular weight 1000 to 5000 g having a hydroxyl functionality of between 2 and 3, advantageously close to 2.3.

Comme polybutadiènes hydroxytéléchéliques préférés de l'invention on peut citer ceux commercialisés par la Société américaine ARCO Chemical Company sous les dénominations commerciales R45M et R45HT.As preferred hydroxytelechelic polybutadienes of the invention, mention may be made of those sold by the American company ARCO Chemical Company under the trade names R45M and R45HT.

Comme composés polyisoyanates convenables comme agent de réticulation, on peut citer à titre d'exemple, le toluène diisocyanate (TDI), l'hexaméthylène diisocyanate (HMDI), le dimeryldiisocyanate (DDI), l'isophorone diisocyanate (IPDI), le tri(isocyanato-6)-,3,5 biuret (commercialisé par la Société BAYER A.G sous la dénomination Desmodur N100) le méthylène-4,4' bis (cyclohexyldiisocyanate) (MDCI), ou analogues.As polyisoyanate compounds suitable as crosslinking agent, mention may be made, for example, of toluene diisocyanate (TDI), hexamethylene diisocyanate (HMDI), dimeryldiisocyanate (DDI), isophorone diisocyanate (IPDI), sorting ( isocyanato-6) -, 3.5 biuret (marketed by the Company BAYER AG under the name Desmodur N100) methylene-4,4 'bis (cyclohexyldiisocyanate) (MDCI), or the like.

Les charges oxydantes convenables sont, par exemple, le perchlorate d'ammonium, le nitrate de potassium, ou analogue. La charge préférée de l'invention est le perchlorate d'ammonium.Suitable oxidizing charges are, for example, ammonium perchlorate, potassium nitrate, or the like. The preferred filler of the invention is ammonium perchlorate.

Par ailleurs, il est possible d'ajouter à ces charges oxydantes des nitramines, telles que la cyclotriméthylènetrinitramine ou hexogène (RDX), la cyclo-tétraméthylènetétranitramine ou octogène (HMX), ou du tétranitrate de pentaérythritol (PETN), bu analogue.Furthermore, it is possible to add to these oxidizing charges nitramines, such as cyclotrimethylenetrinitramine or hexogen (RDX), cyclo-tetramethylenetetranitramine or octogen (HMX), or pentaerythritol tetranitrate (PETN), bu analog.

Les charges réductrices convenables pour l'invention sont généralement des poudres métalliques telles que la poudre d'aluminium, de béryllium, de zirconium ou analogues.The reducing charges suitable for the invention are generally metallic powders such as aluminum, beryllium, zirconium powder or the like.

La charge réductrice préférée de l'invention est la poudre d'aluminium.The preferred reducing filler of the invention is aluminum powder.

Les composés aminoaziridinylphosphine oxydes de l'invention peuvent être préparés notamment par les deux procédés suivants.The aminoaziridinylphosphine oxide compounds of the invention can be prepared in particular by the following two methods.

Le premier procédé consiste à fabriquer le composé de formule (II) :

Figure imgb0002
dans laquelle : X représente un halogène et R1, R2 ont la signification ci-dessus; selon les procédés décrits dans les brevets américains n° 2 606 900 et 3 201 313, puis à faire réagir ce composé sur une amine de formule (III) pour obtenir le composé de formule (I) :
Figure imgb0003
dans laquelle R3, R4 ont la signification ci-dessus.The first process consists in manufacturing the compound of formula (II):
Figure imgb0002
in which: X represents a halogen and R 1 , R 2 have the above meaning; according to the methods described in American patents 2 606 900 and 3 201 313, then reacting this compound on an amine of formula (III) to obtain the compound of formula (I):
Figure imgb0003
in which R 3 , R 4 have the above meaning.

Le second procédé consiste à mettre en oeuvre la réaction suivante :

Figure imgb0004
The second method consists in carrying out the following reaction:
Figure imgb0004

On utilise comme solvant le toluène, et un capteur de l'acide halogéné (X représente un atome d'halogène, de préférence le chlore) tel que la triéthylamine ou la méthyl-2-aziridine.Toluene is used as solvent, and a halogenated acid sensor (X represents a halogen atom, preferably chlorine) such as triethylamine or methyl-2-aziridine.

La réaction est effectuée à basse température, de l'ordre de 0°C à -5° C.The reaction is carried out at low temperature, of the order of 0 ° C to -5 ° C.

Après séparation de l'halogénohydrate formé,'par exemple, par filtration et évaporation du solvant, on récupère l'aminoaziridinylphosphine oxyde.After separation of the halohydrate formed, for example, by filtration and evaporation of the solvent, the aminoaziridinylphosphine oxide is recovered.

Ce composé est ensuite purifié par, par exemple, distillation sous pression réduite.This compound is then purified by, for example, distillation under reduced pressure.

Dans le cas de la synthèse du bisméthylaziridinylméthylaminophos- phine oxyde qui pour plus de simplification sera appelé ci-après méthyl-BAPO, on récupère un liquide légèrement jaune qui cristallise en un produit blanc, de masse volumique 1,0855 kg/dm3 et point d'ébullition 115° C sous 13,3 Pa.In the case of the synthesis of bismethylaziridinylmethylaminophosphine oxide which for further simplification will be called hereinafter methyl-BAPO, a slightly yellow liquid is recovered which crystallizes into a white product, with density 1.0855 kg / dm 3 and point boiling point 115 ° C at 13.3 Pa.

Le dihalogénoaminophosphine peut être obtenu par réaction d'un oxyhalogénure de phosphore sur un halogénohydrate d'alkylamine.The dihaloaminophosphine can be obtained by reacting a phosphorus oxyhalide with an alkylamine halohydrate.

L'alkyle aziridine peut être obtenu par, notamment, les synthèses de Wenker et Gabriel décrites respectivement dans le Journal of the American Chemical Society, vol 57 page 2328 (1935) et dans le Beilstein vol 21 page 1049 (1881).The alkyl aziridine can be obtained by, in particular, the syntheses of Wenker and Gabriel described respectively in the Journal of the American Chemical Society, vol 57 page 2328 (1935) and in Beilstein vol 21 page 1049 (1881).

Les exemples ci-dessous qui sont donnés uniquement à titre indicatif et n'ont aucun caractère limitatif, illustrent clairement l'invention et montrent les détails, buts et avantages de celle-ci.The examples below, which are given for information only and are in no way limiting, clearly illustrate the invention and show the details, aims and advantages thereof.

Exemple 1Example 1

La composition propulsive composite est obtenue par le procédé usuel de fabrication qui consiste, sommairement, à ajouter dans le mélange des polyols, dans le présent exemple le polybutadiène hydroxytéléchélique, des additifs tels que plastifiants mouillants, antioxydants, agents de réticulation, puis la charge réductrice est introduite. Ensuite, le mélange obtenu est coulé dans un malaxeur où seront introduits la charge oxydante, l'agent réticulant et les différents additifs balistiques tels que les catalyseurs de combustion, ainsi que les catalyseurs de réticulation.The composite propellant composition is obtained by the usual manufacturing process which consists, summarily, in adding into the mixture of polyols, in the present example hydroxytelechelic polybutadiene, additives such as wetting plasticizers, antioxidants, crosslinking agents, then the reducing charge is introduced. Then, the mixture obtained is poured into a kneader into which will be introduced the oxidizing charge, the crosslinking agent and the various ballistic additives such as the combustion catalysts, as well as the crosslinking catalysts.

Le propergol ainsi obtenu est ensuite coulé pour former un bloc aux dimensions et à la forme désirées.The propellant thus obtained is then poured to form a block with the desired dimensions and shape.

Selon ce procédé on a réalisé un propergol ayant la composition pondérale suivante :

Figure imgb0005
la composition contient :
Figure imgb0006
According to this process, a propellant having the following weight composition was produced:
Figure imgb0005
the composition contains:
Figure imgb0006

On a réalisé une composition sans agent renforçateur de l'adhésion liant-charge, et trois autres compositions contenant respectivement dans le liant 1 % en poids par rapport à la masse du liant, de triméthylolpropane, d'un condensat du MAPO avec l'acide tartrique, et du méthyl-BAPO. Cette dernière composition correspond à l'invention. (Tableau I.a)

Figure imgb0007
A composition was produced without agent reinforcing the binder-filler adhesion, and three other compositions containing respectively in the binder 1% by weight relative to the mass of the binder, of trimethylolpropane, of a condensate of MAPO with the acid. tartaric, and methyl-BAPO. This latter composition corresponds to the invention. (Table Ia)
Figure imgb0007

On a testé la faisabilité de ces compositions et mesuré leurs propriétés mécaniques rassemblées dans le tableau I.b ci-après :

Figure imgb0008
We tested the feasibility of these compositions and measured their mechanical properties collected in Table Ib below:
Figure imgb0008

Ces résultats montrent premièrement que la composition conforme à l'invention, à savoir celle contenant comme agent renforçateur des propriétés mécaniques ou d'adhésion liant-charge, le méthyl BAPO, a la plus faible viscosité, et deuxièmement que l'agent d'adhésion liant-charge conforme à l'invention est le seul qui permette d'obtenir une composition ayant une résistance à la contrainte (Sm) élevée et un niveau d'allongement (em) fortement augmenté.These results show firstly that the composition according to the invention, namely that containing as reinforcing agent mechanical or adhesion properties binder-filler, methyl BAPO, has the lowest viscosity, and secondly that the adhesion agent binder-filler according to the invention is the only one which makes it possible to obtain a composition having a high resistance to stress (S m ) and a greatly increased level of elongation (e m ).

Ce résultat apparait clairement par la comparaison des produits em x sm.This result is clear from the comparison of the products e m xs m .

Exemple 2Example 2

On réalise des compositions selon le procédé de l'exemple 1 avec le même liant, mais le propergol a la composition suivante :

Figure imgb0009
Compositions are produced according to the method of Example 1 with the same binder, but the propellant has the following composition:
Figure imgb0009

Comme pour l'exemple 1, on réalise trois compositions dont la première ne contient pas d'agent d'adhésion liant-charge, et les deux autres contiennent respectivement comme agent d'adhésion liant-charge le tri(méthylaziridinyl) phosphine oxyde (MAPO) et le bis (aziridinyl)méthylaminophosphine oxyde (BAPO)dans une concentration égale à 2 % en poids par rapport à la masse du liant. (Tableau II.a)

Figure imgb0010
As for Example 1, three compositions are produced, the first of which does not contain a binder-filler adhesion agent, and the other two respectively contain as a binder-filler adhesion agent tri (methylaziridinyl) phosphine oxide (MAPO) ) and bis (aziridinyl) methylaminophosphine oxide (BAPO) in a concentration equal to 2% by weight relative to the mass of the binder. (Table II.a)
Figure imgb0010

La viscosité et les propriétés mécaniques des compositions obtenues sont rassemblées dans le tableau II.b.

Figure imgb0011
The viscosity and the mechanical properties of the compositions obtained are collated in Table II.b.
Figure imgb0011

Ces résultats montrent que l'agent d'adhésion liant-charge conforme à la présente invention permet d'obtenir des propergols présentant des propriétés mécaniques très intéressantes, notamment une résistance à la traction (Sm) élevée pour un niveau d'allongement (em) élevé. Au contraire, l'agent d'adhésion liant-charge connu, à savoir le MAPO, permet d'augmenter sensiblement la résistance à la traction (Sm) du propergol mais a tendance à diminuer le niveau d'allongement de la composition.These results show that the binder-filler adhesion agent in accordance with the present invention makes it possible to obtain propellants having very advantageous mechanical properties, in particular a high tensile strength (S m ) for a level of elongation (e m ) high. On the contrary, the known binder-filler adhesion agent, namely MAPO, makes it possible to significantly increase the tensile strength (S m ) of the propellant but tends to decrease the level of elongation of the composition.

Compte tenu de la viscosité faible de la composition, l'addition d'un agent d'adhésion liant-charge n'a que peu d'influence sur celle-ci.Given the low viscosity of the composition, the addition of a binder-filler adhesion agent has little influence thereon.

Exemple 3Example 3

On réalise une composition propulsive selon le procédé de l'exemple 1 avec un liant de composition pondérale suivante :

Figure imgb0012
A propellant composition is produced according to the method of Example 1 with a binder of the following weight composition:
Figure imgb0012

De manière identique aux exemples 1 et 2, trois compositions ont été fabriquées contenant respectivement : pas d'agent d'adhésion liant-charge, 1,5 % en poids de bisaziridinylméthylaminophosphine oxyde et 0,5 % en poids de bisaziridinyldiméthylaminophosphine oxyde. (Tableau III.a) (les condensations sont exprimées en % du poids du liant)

Figure imgb0013
In an identical manner to Examples 1 and 2, three compositions were produced containing respectively: no binder-filler adhesion agent, 1.5 % by weight of bisaziridinylmethylaminophosphine oxide and 0.5% by weight of bisaziridinyldimethylaminophosphine oxide. (Table III.a) (the condensations are expressed in% of the weight of the binder)
Figure imgb0013

La viscosité et les propriétés mécaniques de ces compositions sont rassemblées dans le tableau III.b.

Figure imgb0014
The viscosity and the mechanical properties of these compositions are collated in Table III.b.
Figure imgb0014

Ces résultats montrent également que les deux aminoaziridinylphosphine oxydes conformes à l'invention ont une influence bénéfique sur les propriétés mécaniques des propergols obtenus.These results also show that the two aminoaziridinylphosphine oxides in accordance with the invention have a beneficial influence on the mechanical properties of the propellants obtained.

Exemple 4Example 4

On réalise plusieurs propergols avec le liant décrit à l'exemple 1 mais contenant d'autres charges oxydantes.Several propellants are produced with the binder described in Example 1 but containing other oxidizing charges.

La composition des propergols est la suivante :

Figure imgb0015
Comme dans les précédents exemples, on réalise plusieurs compositions contenant comme agent d'adhésion liant-charge avec une concentration de 0,5 % en poids du liant, respectivement :

  • - du méthyl BAPO, (Composition 11)
  • - du NN,N'N',1-2 dipropylène isophtalamide (Composition 12) :
    Figure imgb0016
  • - du NN,N'N',N"N" 1-2 tripropylène trimésamide (Composition 13) :
    Figure imgb0017
The composition of the propellants is as follows:
Figure imgb0015
As in the previous examples, several compositions are produced containing as binder-filler adhesion agent with a concentration of 0.5% by weight of the binder, respectively:
  • - methyl BAPO, (Composition 11)
  • - NN, N'N ', 1-2 dipropylene isophthalamide (Composition 12):
    Figure imgb0016
  • - NN, N'N ', N "N" 1-2 tripropylene trimesamide (Composition 13):
    Figure imgb0017

Les agents des compositions 12 et 13 sont des composés aziridinyles connus et utilisés dans des propergols composites.The agents of compositions 12 and 13 are known aziridinyl compounds used in composite propellants.

De manière identique aux exemples précédents, la viscosité et les propriétés mécaniques des compositions obtenues sont rassemblées dans le tableau IV

Figure imgb0018
In an identical manner to the previous examples, the viscosity and the mechanical properties of the compositions obtained are collated in Table IV
Figure imgb0018

Ces résultats montrent que l'agent d'adhésion liant-charge de l'invention permet d'obtenir un niveau d'allongement supérieur aux autres agents pour une résistance à la traction sensiblement identique.These results show that the binder-filler adhesion agent of the invention makes it possible to obtain a level of elongation greater than the other agents for a substantially identical tensile strength.

L'agent de l'invention a également un effet bénéfique pour la faisabilité des compositions par l'abaissement de la viscosité de celles-ci.The agent of the invention also has a beneficial effect on the feasibility of the compositions by lowering the viscosity thereof.

Exemple 5Example 5

Le taux optimum d'agent d'adhésion liant-charge doit être déterminé pour chaque composition. Toutefois les résultats ci-après montrent que ce taux peut être compris entre 0,5 et 3,0 % en poids du liant et que les meilleurs résultats sont obtenus pour des con- centrations comprises entre 0,5 et 1,5 %.The optimum level of binder-filler adhesion agent must be determined for each composition. However, the results below show that this rate can be between 0.5 and 3.0% by weight of the binder and that the best results are obtained for centers between 0.5 and 1.5%.

Ces essais ont été réalisés avec le même liant que l'exemple 1 à l'exception que le polybutadiène hydroxytéléchélique est celui commercialisé par la Société ARCO Chemical sous la dénomination R45HT.These tests were carried out with the same binder as Example 1, except that the hydroxytelechelic polybutadiene is that sold by the company ARCO Chemical under the name R45HT.

Le propergol a la composition pondérale suivante :

Figure imgb0019
Figure imgb0020
Par ailleurs, des essais de gonflement avec des liants chargés en aluminium ou non ont montré que l'adhésion liant-alumininum est plus grande en présence d'un agent d'adhésion conforme à l'invention.The propellant has the following weight composition:
Figure imgb0019
Figure imgb0020
Furthermore, swelling tests with binders loaded with aluminum or not have shown that the binder-alumininum adhesion is greater in the presence of an adhesion agent according to the invention.

Ces mêmes essais réalisés avec des compositions de propergol tels que décrits dans l'exemple 1 montre un accroissement notable de l'adhésion en présence d'agent d'adhésion conforme à l'invention et notamment en présence de méthyl BAPO.These same tests carried out with propellant compositions as described in Example 1 show a significant increase in adhesion in the presence of adhesion agent in accordance with the invention and in particular in the presence of methyl BAPO.

L'agent d'adhésion liant-charge de l'invention, à savoir un aminoaziridinylphosphine oxyde permet d'obtenir des propergols composites à propriétés mécaniques améliorées, notamment présentant pour une résistance à la traction élevée, un niveau du taux d'élongation également élevé.The binder-filler adhesion agent of the invention, namely an aminoaziridinylphosphine oxide, makes it possible to obtain composite propellants with improved mechanical properties, in particular having an equally high level of elongation for a high tensile strength. .

En outre, cet agent permet d'augmenter la faisabilité des blocs de propergol en diminuant la viscosité des compositions pour un même taux de charge.In addition, this agent makes it possible to increase the feasibility of the propellant blocks by reducing the viscosity of the compositions for the same loading rate.

Par ailleurs, compte tenu des faibles taux utilisés cet agent d'adhésion liant-charge n'a pas d'effet sur les propriétés balistiques du propergol et notamment n'a pas d'influence sur la vitesse de combustion et l'impulsion spécifique de celui-ci.Furthermore, given the low rates used, this binder-filler adhesion agent has no effect on the ballistic properties of the propellant and in particular has no influence on the combustion rate and the specific impulse of this one.

Claims (9)

1. Agent d'adhésion liant-charge entre une ou plusieurs charges et un liant polyuréthanne caractérisé en ce qu'il est un aminoaziridinylphosphine oxyde de formule générale I :
Figure imgb0021
dans laquelle Rl,R2, R3, R4 sont identiques ou différents et représentent l'atome d'hydrogène ou un radical méthyl ou éthyl.
1. Bonding-filler adhesion agent between one or more fillers and a polyurethane binder, characterized in that it is an aminoaziridinylphosphine oxide of general formula I:
Figure imgb0021
in which R 1 , R 2 , R 3 , R 4 are identical or different and represent the hydrogen atom or a methyl or ethyl radical.
2. Agent selon la revendication 1, caractérisé en ce que R1 et R3 représentent l'atome d'hydrogène et R2, R4 représentent le radical méthyl.2. Agent according to claim 1, characterized in that R 1 and R 3 represent the hydrogen atom and R2 , R 4 represent the methyl radical. 3. Composition propulsive à liant polyuréthanne contenant comme composants principaux des charges oxydantes et réductrices, au moins un agent d'adhésion liant-charge, caractérisée en ce que le dit agent est un agent d'adhésion liant-charge selon les revendications 1 ou 2.3. propellant composition with polyurethane binder containing as main components oxidizing and reducing fillers, at least one binder-filler adhesion agent, characterized in that said agent is a binder-filler adhesion agent according to claims 1 or 2 . 4. Composition selon la revendication 3, caractérisée en ce que la concentration pondérale en composé aminoaziridinylphosphine oxyde est comprise entre 0,5 % et 3 % de la masse du liant.4. Composition according to claim 3, characterized in that the concentration by weight of aminoaziridinylphosphine oxide compound is between 0.5% and 3% of the mass of the binder. 5. Composition selon la revendication 4, caractérisée en ce que la concentration précitée est comprise entre 0,5 % et 1,5 % de la masse du liant.5. Composition according to claim 4, characterized in that the above concentration is between 0.5% and 1.5% of the mass of the binder. 6. Composition selon l'une des revendications 3 à 5, caractérisée en ce que le liant polyuréthanne précité est un produit de la condensation entre un polybutadiène hydroxytéléchélique et un diisocyanate aromatique, aliphatique ou cycloaliphatique.6. Composition according to one of claims 3 to 5, characterized in that the above-mentioned polyurethane binder is a product of the condensation between a hydroxytelechelic polybutadiene and an aromatic, aliphatic or cycloaliphatic diisocyanate. 7. Composition selon l'une des revendications 3 à 6, caractérisée en ce que les charges oxydantes sont choisies dans le groupe consistant en perchlorate d'ammonium, perchlorate de potassium, perchlorate de sodium, nitrate d'ammonium, nitrate de potassium; les charges réductrices étant choisies dans le groupe consistant en aluminium, zirconium, beryllium.7. Composition according to one of claims 3 to 6, characterized in that the oxidizing charges are chosen from the group consisting of ammonium perchlorate, potassium perchlorate, sodium perchlorate, ammonium nitrate, potassium nitrate; the reducing charges being chosen from the group consisting of aluminum, zirconium, beryllium. 8. Composition selon l'une des revendications 3 à 7, caractérisée en ce qu'elle contient des charges énergétiques choisies dans le groupe comprenant l'octogène, l'hexogène, le tétranitrate de pentaérythritol.8. Composition according to one of claims 3 to 7, characterized in that it contains energy charges selected from the group comprising octogen, hexogen, pentaerythritol tetranitrate. 9. Composition selon l'une des revendications 3 à 8, caractérisée en ce que la charge oxydante est du perchlorate d'ammonium et la charge réductrice de l'aluminium.9. Composition according to one of claims 3 to 8, characterized in that the oxidizing charge is ammonium perchlorate and the reducing charge of aluminum.
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JPH0759694B2 (en) 1995-06-28
JPS6289779A (en) 1987-04-24
NO863707D0 (en) 1986-09-17
CA1285771C (en) 1991-07-09
EP0218511B1 (en) 1989-09-06

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