EP2507295A1 - Procédé de préparation de polysilane-polycarbosilanes ayant une teneur réduite en carbone et fibres préparées à partir de ceux-ci - Google Patents

Procédé de préparation de polysilane-polycarbosilanes ayant une teneur réduite en carbone et fibres préparées à partir de ceux-ci

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Publication number
EP2507295A1
EP2507295A1 EP10782266A EP10782266A EP2507295A1 EP 2507295 A1 EP2507295 A1 EP 2507295A1 EP 10782266 A EP10782266 A EP 10782266A EP 10782266 A EP10782266 A EP 10782266A EP 2507295 A1 EP2507295 A1 EP 2507295A1
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EP
European Patent Office
Prior art keywords
polysilane
polycarbosilane
silicon
oligosilane
copolymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP10782266A
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German (de)
English (en)
Inventor
Juergen Clade
Arne Ruedinger
Dieter Sporn
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fraunhofer Gesellschaft zur Foerderung der Angewandten Forschung eV
Original Assignee
Fraunhofer Gesellschaft zur Foerderung der Angewandten Forschung eV
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Publication of EP2507295A1 publication Critical patent/EP2507295A1/fr
Withdrawn legal-status Critical Current

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Definitions

  • the present invention relates to polysilane-polycarbosilane copolymers, which are prepared starting from chlorine-containing silanes by targeted thermal treatment and have a significantly reduced carbon content. Ceramics produced by pyrolysis may have a molar ratio of silicon to carbon of nearly 1: 1, i. be almost or completely free of free carbon.
  • Silicon carbide materials are high for their mechanical strengths
  • Polysilanes were first synthesized by Kipping via Wurtz coupling of diphenyldichlorosilane with sodium.
  • Yajima et al For example, dodecamethylcyclohexasilane was first used as a raw material for the production of SiC ceramic fibers.
  • Polycarbosilanes takes place (Kumada rearrangement). After extraction of low molecular weight components, an infusible, high molecular weight polycarbosilane powder is obtained. Solutions of this powder in benzene or xylene can after the
  • Dry spinning process to green fibers are processed, which can be pyrolyzed without prior curing to SiC ceramic fibers.
  • the main disadvantage of this method is the complex synthesis of the starting polymer, the use of alkali metals, reactions in an autoclave and a complicated
  • Oxygen input to be connected which ultimately causes the cure.
  • Green fibers are processed, which can be pyrolyzed without prior curing to SiC ceramic fibers; However, the path to such infusible powders is costly and cumbersome.
  • WO 2005/108470 discloses a process for the preparation of a polysilane-polycarbosilane copolymer solution, from which oxygen-poor ceramic shaped bodies can be produced.
  • the starting material for this solution is inexpensive and easily accessible and can be very easily converted into an infusible material that can be converted after molding without further treatment in the corresponding ceramic material.
  • the said starting material is polysilanes, which by
  • a crosslinking aid is added, selected from
  • Arylhalosilanes and arylhaloboranes Arylhalosilanes and arylhaloboranes.
  • the polysilanes thus obtained (usually referred to as crude polysilanes / oligosilanes) can be conveniently modified by means of a subsequent, targeted thermal treatment in such a way that, although they are difficult or infusible, they are still very soluble in indifferent solvents that they can be further processed in a molding process. Solutions of these materials can be used, for example, for the production of fibers after Use dry spinning or to build ceramic matrices by the liquid phase infiltration method. Polymer fibers made from these
  • Solutions are available, can be pyrolyzed in the bundle without further form-stabilizing treatment to oxygen-poor SiC ceramic fibers.
  • the object of the present invention is to provide a method for producing
  • polysilane-containing polymers in good yield, which can be pyrolyzed to dense ceramics with a ratio of silicon to carbon in the range of 0.8: 1, 0 to 1, 1: 1, 0th This corresponds to an Si content of 44.4 to 52.4 atom%, based on the sum of carbon and silicon.
  • the same starting materials should be used as stated in WO 2005/108470, since these are readily available,
  • the object is achieved by the proposal to additionally add elemental silicon or titanium disilicide in powder form or a compound containing alkyl groups bound to silicon or to nitrogen in one of the steps of this method.
  • R 1 is chlorine, hydrogen or an alkyl radical having 1 to 4 carbon atoms and R 2 -SiR 3 3, - NH-SiR 3 3 or -N (SiR 3 3 ) 2 wherein R 3 has the same meaning as R 1 .
  • alkyl groups of a crosslinking agent which are bonded to silicon or nitrogen atoms, remain in the pyrolysis in the ceramic, so that one obtains a dense product.
  • An alternative way of solving the problem is to do one after another
  • WO 2005/108470 produced polysilane-polycarbosilane copolymer solution so much powdered silicon or titanium disilicate schliesgt that the carbon excess is reacted at high temperatures to silicon carbide and optionally titanium carbide.
  • a dense product can also be obtained in this way, because the carbon formed in the subsequent high-temperature treatment reacts off to silicon carbide or optionally in addition to titanium carbide.
  • Other powdered silicon-containing materials such as S1O2 or Si3N, however, have proved to be less suitable because they are reacted in the former case with carbon to SiC and CO, in the latter case to SiC and N 2 .
  • the powdered silicon or titanium disilicide is surface-rendered hydrophobic, for example, prior to addition to the copolymer solution.
  • the surface hydroxyl groups for trimethylsilyl ether groups by boiling with trimethylchlorosilane (based on EP 0378785) or the like.
  • trimethylchlorosilane based on EP 0378785
  • the same starting materials used for polymer production are the same silane / oligosilanes containing chlorine and hydrocarbon groups, which are also specified in WO 2005/108470 A1 as starting materials. These are mixtures of Methylchlorodisilanen with the composition Si2Me n Cl6 -n
  • the latter usually consist of a mixture of 1, 1, 2,2-tetrachloro-dimethyldisilane and 1, 1, 2-trichloro-trimethyldisilane with less than 10 mol% of other ingredients.
  • the two mentioned disilanes are preferably initially introduced in a molar ratio of 0.5: 1 to 1.5: 1.
  • the disilane mixtures mentioned are based on e.g. EP 610809 or U.
  • the reaction temperature is preferably 150 to 300 ° C, more preferably 180 to 250 ° C.
  • the catalyst used is an organic nitrogen compound having Lewis basicity but no N-H function. Preferred catalysts are nitrogen-containing
  • Heterocycles such as pyridine, quinoline, N-methylpiperidine, N-methylpyrrolidine, N-methylindole or N-methylimidazole. N-methylimidazole is particularly preferred.
  • the amount of catalyst used is preferably 1 to 2% by mass.
  • As a crosslinking aid 1,1,1-trichlorotrimethyldisilazane is very favorable, the proportion of this or another crosslinking aid of the formula (I) is preferably 5-20% by mass, more preferably 10-15% by mass.
  • the disproportionation takes place, moreover, under the conditions known in the literature; In particular, it is beneficial to keep moisture and oxygen away from the materials through the use of inert gas, such as nitrogen whiff gas, since the product is sensitive to hydrolysis and oxygen.
  • another crosslinking aid may be present, selected from arylhalosilanes and arylhaloboranes, and especially among
  • Methylchlorodisilane Lewis base and crosslinking aids.
  • Polysilane / oligosilane can be lowered. This is preferably done in one
  • chlorine is replaced by a nitrogen-containing, chlorine-free substituent, preferably with the aid of amine and / or silylamine compounds as substitution agents, i. Compounds having at least one N-Si moiety or, more preferably, at least one N-H moiety.
  • a nitrogen-containing, chlorine-free substituent preferably with the aid of amine and / or silylamine compounds as substitution agents, i. Compounds having at least one N-Si moiety or, more preferably, at least one N-H moiety.
  • these are preferably selected from ammonia and primary or secondary amines.
  • silylamines in particular silazanes of the formula Si (R 3 ) 3- [NR 3 -Si (R 3 ) 2] n -R 3 , in which n can be an integer from 1 to 6, are used.
  • Each radical R 3 is the same or different in all cases and means
  • the compounds are secondary, cyclic amines, in particular selected from pyrrole, indole, carbazole, pyrazole, piperidine and imidazole.
  • the compounds are secondary, cyclic amines, in particular selected from pyrrole, indole, carbazole, pyrazole, piperidine and imidazole.
  • the number of amino groups in R 1 and R 2 is not limited, but is preferably 0 to 6, and more preferably 0 to 4.
  • the number of carbon atoms in R 1 , R 2 and R 3 is also not limited, but is preferably 1 to 6 for aliphatic and 5 to 20 for aromatic and aliphatic-aromatic radicals.
  • the amines are selected from ammonia, ethylenediamine, diethylamine, dimethylamine, methylamine, aniline, ethylamine, hexamethyldisilazane, heptamethyldisilazane and tris (trimethylsilyl) amine.
  • amines of the abovementioned which carry short-chain alkyl radicals, in particular methyl and ethyl radicals.
  • Dimethylamine is particularly favorable.
  • Secondary amines have the advantage that the resulting polymers carry -NR 2 groups, that is, are free of NH functions.
  • the chlorine reduction / substitution usually takes place as follows:
  • the raw material, ie, the hydrocarbon group-carrying / containing raw polysilane / oligosilane obtained by the above-described disproportionation is dissolved in a suitable inert and aprotic solvent.
  • the solvents used are, in particular, aprotic, non-polar solvents, such as aliphatic hydrocarbons (eg n-pentane, n-hexane, cyclohexane, n-heptane, n-octane), halogenated
  • Hydrocarbons e.g., methylene chloride, chloroform, carbon tetrachloride,
  • aromatic hydrocarbons eg benzene, toluene, o-xylene, sym-mesitylene
  • further ethereal solvents eg diethyl ether, diisopropyl ether, tetrahydrofuran, 1, 4-dioxane or a higher or non-symmetric ether.
  • the solvent is preferably a halogen-free
  • Hydrocarbon particularly preferably an aromatic hydrocarbon from the group benzene, toluene, o-xylene.
  • the substitution agent (amine) is added in a molar excess, which is preferably at least 2: 1, based on the bound chlorine atoms in the starting material.
  • the substitution agent is added neat or dissolved in an inert and aprotic solvent as indicated above.
  • the adding can e.g. by dropping; In this case, preferably a temperature between room temperature and the boiling point of the amine or its solution should be maintained.
  • a salt is formed which is insoluble in the solvent or, in the case of substitution with silylamines, trimethylchlorosilane.
  • the suspension is allowed to stand for some time, often several hours, or refluxed to the boiling point of the solvent. It is then optionally cooled to room temperature, and if salt has formed, this is filtered off. Subsequently, the solvent and optionally formed trimethylchlorosilane is completely removed, for example in vacuo.
  • Reaction vessel condensed or filled under pressure as a liquid in this, in the case of liquefied amines optionally under dilution with a suitable solvent as indicated above. Subsequently, the starting material, dissolved again in the same solvent as possible, added. After complete addition, the batch is allowed to stand for a similar period of time as described above or refluxed and then worked up as described above.
  • the chlorine content of the starting material thus treated can be reduced by the process step according to the invention at least to not more than 3% by mass, usually less than 1% by mass and generally to less than 0.2% by mass.
  • the crude polysilane / oligosilane is then subjected to a further thermal treatment, as described in WO 2005/108470, in which on the one hand it is made difficult or infusible by increasing the average molecular weight and, on the other hand, by the rearrangement reactions taking place in this process
  • Polysilane-polycarbosilane copolymer is transferred. Another inventively intended effect of this thermal treatment is a repeated
  • the thermal aftertreatment usually takes place under atmospheric pressure, whereby it is highly recommended to work under moisture and oxygen exclusion. Therefore, the material is conveniently treated under inert gas, in a particularly advantageous manner under a pure nitrogen atmosphere, wherein the
  • the heating is preferably carried out continuously, for example at a rate of 1-5 K / min., Preferably 2-4 K / min.
  • low molecular weight methylsilylamines and z.T. Methylchlorosilylamines are continuously distilled off.
  • the end point of the thermal aftertreatment is noticeable by a steep increase in the torque at the agitator.
  • the last volatiles can be removed in vacuo in a temperature range around 100 ° C.
  • the infusible but soluble copolymer according to the invention can thus be prepared in a single step from the dechlorinated crude polysilane / oligosilane, which usually no further separation steps (extractions, filtrations) are required. By dissolving this copolymer in an inert solvent, a polysilane-polycarbosilane solution according to the invention is obtained.
  • the copolymer becomes as follows
  • WO 2005/108470 known dissolved in an inert organic solvent.
  • the solvents used are, in particular, non-polar solvents, such as aliphatic hydrocarbons (for example n-pentane, n-hexane, cyclohexane, n-heptane, n-octane), aromatic hydrocarbons (for example n-pentane, n-hexane, cyclohexane, n-heptane, n-octane), aromatic
  • Hydrocarbons eg benzene, toluene, o-xylene, sym-mesitylene
  • halogenated Hydrocarbons eg methylene chloride, chloroform, carbon tetrachloride, 1,1,1-trichloroethane, chlorobenzene
  • ethers eg diethyl ether, diisopropyl ether
  • the solvent is preferably a halogenated or halogen-free hydrocarbon, more preferably a halogen-free aromatic hydrocarbon from the group benzene, toluene, o-xylene.
  • the proportion of the polysilane-polycarbosilane copolymer in the polymer solution may be adjusted depending on the purpose of use of the solution. If the solution is for the production of fibers by the dry-spinning method, polymer contents of 50-90% by mass, preferably 60-75% by mass, are advantageous. If the solution is to prepare ceramic matrices by the liquid phase infiltration method, the polymer content may be significantly lower due to the low viscosity required, e.g. 20% by mass.
  • the second embodiment of the invention is limited to those variants in which the polysilane-polycarboxylic acid copolymer is solubilized and does not interfere with a solid content in the solution, e.g. if the solution is to be spun into fibers as mentioned above.
  • the polysilane-polycarboxylic acid copolymer is solubilized and does not interfere with a solid content in the solution, e.g. if the solution is to be spun into fibers as mentioned above.
  • the further process steps then take place as described above for the first variant, i. with or without
  • Particle diameter of about 1 -2 ⁇ added, which was preferably hydrophobicized as described above, to prevent the sedimentation of the added particles and to keep them in suspension.
  • the proportion of silicon or titanium disilicide powder is calculated so that the excess carbon in the subsequent high-temperature treatment to silicon carbide and optionally titanium carbide
  • the powder content used for this purpose is preferably 20-60% by mass, more preferably 35-50% by mass, based on the copolymer used.
  • the (spinning) solution thus obtained has one for spinning or other Processing processes suitable consistency and this also suitable flow properties.
  • the polysilane-polycarbosilane copolymer solution according to the invention is generally suitable for the production of ceramic silicon carbide materials having a silicon to carbon ratio in the range from 0.8: 1, 0 to 1, 1: 1, 0.
  • the polysilane-polycarbosilane is converted from said solution into the desired form. Unless the solvent is already evaporated, it is removed and the remaining material is pyrolyzed under inert gas or reducing atmosphere.
  • the production of polymer fibers is carried out by the dry spinning process; this is prior art (F. Fourne, "Synthetic Fibers", Carl Hauser Verlag 1995, p 183; V.B. Gupta, V. K. Kothari (ed.), "Manufactured Fiber Technology", Chapman & Hall 1997, p.
  • Preferred parameters for the spinning process are the use of a nozzle package with nozzles diameter 50 to 300 ⁇ and a capillary length of 0.2 to 0.5 mm, a shaft temperature of 20 to 50 ° C at a length of 2 m and a take-off speed of 100 up to 300 m / min.
  • the polymer fibers according to the invention can without previous
  • form stabilizing treatment are pyrolyzed.
  • the preferred parameters for pyrolysis are a heating rate between 5 and 50 K / min and a
  • the pyrolysis can be carried out under inert (N 2 , argon) or reducing (argon / H 2 , N 2 / CO, etc.) atmosphere.
  • inert N 2 , argon
  • reducing argon / H 2 , N 2 / CO, etc.
  • Atmosphere for the pyrolysis is nitrogen or forming gas (argon with 10 vol .-% H 2 ).
  • an oven for example, an electric oven is suitable.
  • the ceramic fibers may be subjected to a further thermal treatment resulting in their compaction and partial or complete
  • the thermal treatment is preferably carried out at temperatures between 1500 and 2200 ° C, more preferably between 1700 and 1900 ° C.
  • the thermal treatment is preferably carried out at temperatures between 1500 and 2200 ° C, more preferably between 1700 and 1900 ° C.
  • Pyrolysis and / or optionally the thermal treatment can be carried out under the same conditions as described above for the fibers.
  • Silicon tetrachloride is added, and the mixture is stirred at 60 ° C for 10 h.
  • the subsequent fractional distillation in vacuo gives 135 g of pure 1,1,1-trichloro-trimethyldisilazane.
  • Another fraction containing 1, 1, 1, 3,3-pentachloro-trimethyltrisilazane as high boilers, can be worked up by a further fractional distillation.
  • a methylchlorodisilane mixture (disilane fraction" from the Müller-Rochow process, consisting of in each case 45 mol% of CI 2 MeSiSiMeCl 2 and Cl 2 MeSiSiMe 2 CI and 10 mol% of CIMe 2 SiSiMe 2 CI, bp 150-155 ° C) are mixed with 25 g of N-methylimidazole and 100 g of 1,1,1-trichloro-trimethyldisilazane as crosslinking assistant and heated at 0.5 K / min to 180 ° C.
  • disilane fraction from the Müller-Rochow process, consisting of in each case 45 mol% of CI 2 MeSiSiMeCl 2 and Cl 2 MeSiSiMe 2 CI and 10 mol% of CIMe 2 SiSiMe 2 CI, bp 150-155 ° C
  • a distillate consists of MeSiCb, Me 2 SiCl 2 and Me 2 CISiSiMe 2 CI and 153 g of a dark brown, hydrolysis-sensitive crude polysilane / oligosilane solid at room temperature with a chlorine content of about 30% by mass Dissolved 60 wt% solution containing crude polysilane / oligosilane.
  • Example 2 was repeated except that phenyltrichlorosilane was used instead of 1,1,1-trichloro-trimethyldisilazane.
  • phenyltrichlorosilane was used instead of 1,1,1-trichloro-trimethyldisilazane.
  • Polysilane / oligosilane contains a maximum of 0.2% by mass of chlorine (lower detection limit).
  • volume flow should be adjusted so that the gas is completely absorbed when it enters the liquid;
  • the contents of the reaction vessel should be stirred vigorously.
  • the temperature is measured by means of an internal thermometer; the consumption of dimethylamine is monitored by means of a balance.
  • the reaction is terminated; the end can also be recognized by a decrease in the internal temperature.
  • the reaction mixture is filtered through a pressure filter and the filtrate in vacuo at 65 ° C from the solvent freed.
  • the resulting modified polysilane / oligosilane contains less than 0.2 mass% chlorine (lower detection limit).
  • Example 5 was repeated, but using 1, 5 I of a 60% by mass solution of the crude polysilane / oligosilane according to Comparative Example 1.
  • 151 g of a polysilane according to Example 2 are heated in a round bottom flask with 3 K / min to 400 ° C and 50 min. kept at this temperature. During the subsequent cooling, the temperature is maintained at 100 ° C. for 1 h, during which time the last volatiles are removed by applying a vacuum. 16 ml of a yellow distillate consisting of various mono-, di- and oligomethyl-chlorosilanes and 108.5 g of a dark brown polysilane-polycarbosilane copolymer are obtained
  • Example 6 was repeated except that the polysilane according to Comparative Example 1 was thermally crosslinked.
  • Distillation apparatus slowly heated to a final temperature of about 330 ° C. During the heating, about 200 ml of a yellowish distillate are obtained, which in the
  • Consists essentially of various dimethylamino-methylmonosilanes; the end point of the cross-linking can be recognized by the solidification of the mass.
  • Example 8 0.5 mass%, dissolved in a solution of about 70% by mass in toluene or xylene.
  • the solution has a suitable viscosity (about 20-40 Pas) in order to be spun into fibers based on the patent application DE 10 2004 04 531 A1.
  • Example 8
  • average particle size of ⁇ 5 ⁇ was refluxed in 500 ml of trimethylchlorosilane for 1 h, filtered through a pressure filter, washed with dry n-pentane and dried in vacuo.
  • Copolymer whose chlorine content is now only about 0.5% by mass, is prepared about 65% by mass solution in toluene and 45% by mass of the
  • the solution has a suitable viscosity (about 20-40 Pas) in order to be spun into fibers based on the patent application DE 10 2004 04 531 A1.
  • Example 8 is repeated without the addition of surface-modified silicon powder, with the amount of toluene chosen to give the solution a suitable viscosity for spinning.
  • the spinning mass obtained according to Example 7 is filled under inert conditions (glove box) in a spinning apparatus consisting of a storage container, a spinning pump and a nozzle package consisting of filter and nozzle plate.
  • Polymer threads are dropped after passing through a 40 ° C heated shaft are wound up on a galette.
  • the solvent evaporates in the spinning shaft.
  • the delay can be varied continuously and thus the
  • Green fiber diameter can be adjusted.
  • Example 9 is repeated, but using the silicon powder filled dope of Example 8.
  • Example 9 is repeated, but using the dope of the
  • the green fibers prepared according to Example 9 are pyrolyzed in a vertical tube furnace under an inert gas atmosphere (N 2 ) at a rate of 12 K / min to a final temperature of 1200 ° C.
  • N 2 inert gas atmosphere
  • the upper X-ray diagram of FIG. 1 is obtained. It gives no indication
  • the green fibers prepared according to Example 10 are first pyrolyzed as described in Example 1 1. They are then heated under argon atmosphere at 1500 ° C for 5 min. By this high-temperature treatment, the free carbon in the fibers is reacted with the silicon powder, and the resulting ceramic fibers consist solely of crystallized silicon carbide (atomic ratio of silicon to carbon 1: 1).

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Abstract

La présente invention a pour objet un procédé de préparation d'une solution de copolymère polysilane-polycarbosilane, à partir de laquelle on peut obtenir, après élimination du solvant et pyrolyse, un matériau céramique ayant un rapport silicium/carbone compris dans la gamme allant de 0,8/1,0 à 1,1/1,0. Le procédé comprend les étapes suivantes : la production d'un polysilane/oligosilane brut contenant des groupes hydrocarbures chlorés par dismutation d'un méthylchlorodisilane ou d'un mélange de plusieurs méthylchlorodisilanes de la composition Si2MenCl6-n, dans laquelle n est compris entre 1 et 4, la dismutation s'effectuant avec une base de Lewis en tant que catalyseur ; la post-réticulation thermique du polysilane/oligosilane brut en un copolymère polysilane-polycarbosilane infusible, soluble dans des solvants inertes ; ainsi que - la préparation de ladite solution par dissolution du polysilane-polycarbosilane dans un solvant inerte. L'invention est caractérisée en ce que, dans une étape de ce procédé, du silicium élémentaire ou du siliciure de titane est en outre ajouté en quantité appropriée sous forme de poudre ou sous la forme d'un composé qui contient des groupes alkyle liés au silicium ou à l'azote, cet ajout étant réalisé (a) du fait que le polysilane/oligosilane brut est produit en présence d'un agent de réticulation choisi parmi les composés de la formule Cl2R1Si-R2 qui ont un point d'ébullition supérieur à 100 °C et dans laquelle formule R1 représente le chlore, l'hydrogène ou un radical alkyle ayant de 1 à 4 atomes de carbone et R2 est -SiR3 3, -NH-SiR3 3 ou -N(SiR3 3)2, R3 ayant la même signification que R1, ou (b) du fait que du silicium ou du siliciure de titane pulvérulent est ajouté à la solution de polysilane-polycarbosilane. A partir de la solution de copolymère, des fibres vertes ou des matériaux sous une autre forme peuvent être préparés, lesquels peuvent être transformés à leur tour en matériaux de carbure de silicium céramiques. Ils peuvent en outre être utilisés pour la fabrication de matrices céramiques.
EP10782266A 2009-11-30 2010-11-22 Procédé de préparation de polysilane-polycarbosilanes ayant une teneur réduite en carbone et fibres préparées à partir de ceux-ci Withdrawn EP2507295A1 (fr)

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DE102009056371A DE102009056371A1 (de) 2009-11-30 2009-11-30 Polysilan-Polycarbonsilane mit reduziertem Kohlenstoffgehalt auf Basis von Methylchlorpolysilanen sowie daraus hergestellte Keramiken
PCT/EP2010/067954 WO2011064174A1 (fr) 2009-11-30 2010-11-22 Procédé de préparation de polysilane-polycarbosilanes ayant une teneur réduite en carbone et fibres préparées à partir de ceux-ci

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