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WO2003018649A1 - Complexes de cobalt utiles pour la polymerisation de 1,3-butadiene - Google Patents

Complexes de cobalt utiles pour la polymerisation de 1,3-butadiene Download PDF

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Publication number
WO2003018649A1
WO2003018649A1 PCT/EP2002/008450 EP0208450W WO03018649A1 WO 2003018649 A1 WO2003018649 A1 WO 2003018649A1 EP 0208450 W EP0208450 W EP 0208450W WO 03018649 A1 WO03018649 A1 WO 03018649A1
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Prior art keywords
general formula
process according
aluminum
cobalt
cocl
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PCT/EP2002/008450
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English (en)
Inventor
Giovanni Ricci
Francesco Masi
Anna Sommazzi
Roberto Santi
Marco Battistella
Sandra Righi
Giuseppe Savini
Original Assignee
Eni S.P.A.
Polimeri Europa S.P.A.
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Publication of WO2003018649A1 publication Critical patent/WO2003018649A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F136/06—Butadiene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/06—Cobalt compounds
    • C07F15/065—Cobalt compounds without a metal-carbon linkage

Definitions

  • the present invention relates to cobalt complexes with particular phosphines and their use in the polymerization of 1, 3-butadiene to give branched polybutadienes with a high content of 1,4-cis units.
  • Catalysts based on cobalt salts and phosphinic ligands are cited as providing polybutadienes with a high content of
  • 1,2 units for example US-A-5, 986, 026; US-A-5, 548, 045; US-A-
  • phinic ligands having well-defined ⁇ steric parameter values, combined with cobalt salts and organo-derivatives of aluminum, are capable of producing branched polybutadienes with a high content of 1,4-cis units, not only in aromatic
  • the ⁇ parameter is a measurement of the steric hindrance of phos- phine and is described by CA. Tolman in Chemical Reviews 77, 313, (1977).
  • the present invention relates to a process for the preparation of branched polybutadiene with a high content of 1,4-cis units by means of the polymerization of 1, 3-butadiene, carried out in the presence of one or more solvents and a catalytic system which comprises a Cobalt complex, preformed or formed in situ, having general formula (I) Co x+ -L ⁇ (I) wherein x is one, two or three, preferably 2; n ranges from 1 to 3; L is selected from one or more ligands of Co; the positive charge of the cobalt complex having general formula (I) being neutralized by one or more mono- or polyvalent anions; characterized in that the ligand L is selected from phosphorous derivatives having general formula (la)
  • eral formula (la) having a theta ( ⁇ ) steric hindrance value greater than 145°, preferably greater than 150°.
  • polybutadiene with a high content of 1,4-cis units refers to polybutadiene in which at least 80% of the butadiene units is concatenated in 1,4-cis position.
  • branched polybutadiene refers to a polybutadiene having a g value (defined further on in the experimental part) ⁇ 0.90, preferably ⁇ 0.85.
  • anions suitable for neutralizing the positive charge of the compound having general formula (I) are concerned, typical but non-limiting examples are halides, sulfo- cyanide, isocyanate, sulfate, acid sulfate, phosphate, acid phosphate, carboxylates, dicarboxylates .
  • the above anions are chlorides.
  • (I) is CoCl 2 -2L.
  • the catalytic system of the present invention also comprises, in addition to the cobalt complex having general formula (I) , one or more cocatalysts selected from organo- derivatives of aluminum selected from:
  • the organo-derivative of aluminum is selected from aluminoxanes and relative derivatives (a2) .
  • organo-derivatives of aluminum (al) are concerned, in the compounds having general formula (II) Al ( R a ) ( R b ) ( R c ) , R a is selected from alkyl (cycloalkyl included), aryl, alkylaryl, alkoxyl, hydrogen, fluorine; R b and R c , the same or different, are selected from alkyl (cycloal- kyl included) , aryl , alkylaryl , arylalkyl .
  • Typical organo- derivatives of aluminum are diethylaluminum hydride, di- n-propyl aluminum hydride, di-n-butylaluminum hydride, diiso- butyl aluminum hydride, diphenyl aluminum hydride, di-p-tolyl aluminum hydride, dibenzyl aluminum hydride, diethyl aluminum hydride, phenyl-n-propyl aluminum hydride, p-tolyl ethyl aluminum hydride, p-tolyl isopropyl aluminum hydride, benzyl ethyl aluminum hydride, benzyl n-propyl aluminum hydride, benzyl isopropyl aluminum hydride, diethylaluminum ethoxide, diisobutyl aluminum ethoxide, dipropyl aluminum ethoxide, trimethyl aluminum, triethyl aluminum, tri-n-propyl aluminum, triisobutyl aluminum
  • Trialkylaluminum compounds are generally preferred.
  • the preferred trialkylaluminum compounds comprise triethyl aluminum (TEA) , tri-n- propyl aluminum, triisobutyl aluminum (TIBA) , trihexyl alumi- num, diisobutyl aluminum hydride (DIBA-H) and diethyl alumi- num fluoride.
  • aluminoxanes (a2) , it is known that these are compounds containing Al-O-Al bonds, with a varying O/Al ratio, obtained by the reaction, under controlled condi- tions, of an aluminum alkyl, or aluminum alkyl halide, with water or other compounds containing pre-established quantities of available water, as, for example, in the case of the reaction of aluminum trimethyl with aluminum hexahydrate sulfate, copper pentahydrate sulfate or iron pentahydrate sul- fate.
  • Aluminoxanes preferably used for the formation of the polymerization catalyst of the present invention are cyclic and/or linear, oligo- or polymeric compounds, characterized by the presence of repetitive units having the following formula: Ris
  • Each aluminoxane molecule preferably contains from 4 to 70 repetitive units which may also not be the same, but contain dif- ferent R 15 groups.
  • organo-derivatives of aluminum (a3) are the compounds (al) to which a quantity of protonating substance has been added in a molar ratio ranging from 0.001:1 to 0.2:1 protonating sub- stance : aluminum derivative.
  • the protonating substance is usually selected from water, alcohol, acid and is preferably water. Methanol, ethanol, isopropyl alcohol, n-propyl alcohol, t-butanol, isobutyl alcohol, n-butyl alcohol, and alcohols with a higher molecular weight, however, can also be used.
  • a wide range of carboxylic acids can also be used as protonating substance. An example of these acids is stearic acid.
  • Typical examples of compounds having general formula (III) are AlEt 2 Cl (diethylchloroalumninum) , AlMe 2 Cl (dimethylaluminumchloride) , AlEtCl 2 (ethylaluminumdi- chloride) , Al(i-bu) 2 Cl (diisobutylaluminumchloride) ; typical examples of compounds having general formula (IV) are Al 2 Et 3 Cl 3 (ethylaluminumsesquichloride) , Al 2 Me 3 Cl 3 (methylalu- minumsesquichloride) .
  • the molar ratio between the complex having general formula (I) and aluminum ranges from 1:5 to 1:10000, preferably from 1:100 to 1:1000.
  • the cobalt complex having general formula (I) can be used in a molar ratio with respect to the 1, 3-butadiene ranging from 1/10 5 to 1/10 2 , preferably from l/2xl0 4 to l/l0 3 .
  • a molar ratio between ligand (L) and cobalt salt higher than the stoichiometric value preferably, when the cobalt is bivalent, from 2.1/1 to 4/1, even more preferably from 2.2 to 2.5.
  • the above polymerization is preferably effected in a polymerization medium comprising an inert hydrocarbon which is a solvent of butadiene and of the catalytic system.
  • Inert hy- drocarbons which can be used in the polymerization process comprise aliphatic hydrocarbons, olefins included, cycloaliphatic, aromatic hydrocarbons and relative mixtures. More specifically, suitable hydrocarbons are those selected within the group of C 4 to C 8 aliphatic hydrocarbons, olefins in- eluded, within the group of C 5 to C ⁇ 0 cycloaliphatic hydrocarbons, and relative mixtures.
  • Typical, non-limiting examples of the above hydrocarbons are butane, pentane, hexane, heptane, cyclopentane, cyclohexane, butenes.
  • the use of the above aliphatic and cycloaliphatic solvents is particularly advisable as it reduces problems relating to environmental impact. When operating with these solvents, it is possible to obtain a branched polybutadiene, i.e. having branchings, with a high 1,4-cis content.
  • the presence of the above branchings is an essential requisite for the use of the above polybuta- diene as modifying agent of high impact polystyrene.
  • the process of the present invention can also be carried out in the presence of aromatic solvents, particularly toluene, as such or mixed with aliphatic solvents. Branched polybutadiene with a high 1,4-cis content is also obtained in these aromatic solvents.
  • the concentration of 1, 3-butadiene in the polymerization medium can vary in relation to the particular solvent medium or diluent used.
  • concentration of 1, 3-butadiene preferably ranges from 15 to 35% by weight with respect to the total weight of the mixture.
  • the polymerization temperature of 1, 3-butadiene preferably ranges from -30°C to +60°C, the lower temperature limit being determined more by the freezing point of the reaction mixture rather than by the catalytic activity. More preferably, the polymerization process is carried out at a temperature ranging from -10°C to +40°C.
  • the process of the present invention can also be carried out (see the experimental part) in the absence of the usual molecular weight regulators well-known to experts in the field, for example butene-1.
  • the molecular weight control can be effected by varying the type of phos- phine and/or ratio between the aluminum compound, particularly MAO, and cobalt.
  • the polymerization reaction can be stopped by the addition of one or more polymerization terminators which deacti- vate the catalytic system, followed by the conventional solvent-removal (desolventizing) , washing and drying phases, which are normal operations in the production of polydienes.
  • the terminator used to deactivate the catalytic system is typically a protic compound, which includes, but is not lim- ited to, an alcohol, a carboxylic acid, an inorganic acid, and water or a combination thereof .
  • An antioxidant such as 2,6-di-ter-butyl-l,4-methylphenol can be added, before, after or with the addition of the terminator.
  • the quantity of antioxidant usually ranges from 0.2% to 1% by weight with respect to the polymer.
  • the polybutadiene can be recovered according to the standard techniques, preferably by means of the coagulation technique. Any possible residues of the solvent can be removed from the polymer by means of evaporation, which can be facilitated by high temperatures and vacuum application.
  • the process of the present invention allows polybutadiene to be produced with a reduced gel content, particularly macro gels, thus making it applicable in high impact polystyrene.
  • the present invention also relates, as a new compound, to the cobalt complex having the formula:
  • CoCl 2 [P (ter-butyl) 3 ] 2 i.e. cobalt dichloride (tri-ter-butylphosphine) 2 .
  • All the complexes having general formula (I) were prepared following the experimental procedure described in literature which comprises the reaction between a cobalt salt and ligand L in the presence of a suitable solvent (see for example F.A. Cotton, O.D. Faut, D.M.L. Goodgame and R.H. Holm, J.A . Chem. Soc. , 83, 1780, 1961).
  • the desired quantity of CoCl 2 -6H 2 0 (-28 g equal to 0.12 moles) is first heated under vacuum by means of a water bath, in order to remove part of the molecules of crystallization water.
  • the mixture is kept at reflux temperature ( ⁇ 78°C) for about 2 h, until the reaction is complete. At this point, the thionyl chloride has been almost completely used up; the mixture is left to decant and the supernatant solution is removed by siphoning.
  • Tri-n-propylphosphine (3.70 g, 2.3lxl0 ⁇ 2 moles, 4.6 ml) is added under stirring to a solution of CoCl 2 (1.20 g, 9.22xl0 "3 moles) in ethanol (50 ml). The reaction is instantaneous, the solution becomes blue. After about 20 hours, the solution is dried under vacuum at room temperature.
  • a blue-coloured crystalline product is obtained, which is washed at a low temperature with pentane (2 x 20 ml) .
  • the crystalline residue is dried under vacuum.
  • the reaction is instantaneous and the formation of a pale blue precipitate is observed, whose quantity increases over a period of time.
  • the suspension is left under magnetic stirring for about 20 h.
  • a light suspension is formed, which is kept under stirring for about 20 h. It is subsequently dried under vacuum obtaining a pitchy dark blue-coloured residue.
  • Various washings are effected with pentane (3 x 20 ml) and with ethanol at a low temperature, in order to remove traces of excess phosphine and non-reacted CoCl 2 .
  • the residue is dried under vacuum at room temperature for a whole night.
  • the suspension is left under magnetic stirring for about 20 h, and is then filtered on a vacuum filter.
  • the nitrogen in order to eliminate any possible traces of humidity and oxygen, was purified by passage through three successive columns: the first filled with calcium chloride and potassium hydroxide, the second with BTS catalyst (based on copper oxides), the third filled with molecular sieves.
  • Cobaltdichloride hexahydrate product of Strem Chemical (98% purity) .
  • Tri-n-propylphosphine product of Strem Chemical (minimum pu- rity 95%) .
  • Tri-i-propylphosphine product of Strem Chemical (minimum purity 98%) .
  • Tri-t-butylphosphine product of Strem Chemical (minimum purity 99%) .
  • Tricyclohexylphosphine product of Strem Chemical (purity 97%) .
  • Triphenylphosphine product of Strem Chemical (purity 99%).
  • Methylaluminoxane (MAO) product of Witco, toluene solution at 10% by weight, used as such.
  • 1,3-butadiene product of Air Liquide (purity of over 99.5%), purified by passage through a steel column containing sodium hydroxide and molecular sieves . Polymerization of butadiene The 1, 3-butadiene, dried by passage through a steel column containing molecular sieves, was condensed directly in the reactor maintained under vacuum and cooled to a temperature of -30°C.
  • the polymerization tests were carried out according to the following experimental procedure: after charging the bu- tadiene into the reactor, the solvent was added, the whole mixture was brought to the desired polymerization temperature and finally the aluminum compound and cobalt compound were added in succession.
  • the polymerization reaction was terminated by pouring the contents of the test-tube into a beaker containing metha- nol acidulated with small quantities of hydrochloric acid; the coagulated polymer was washed several times with metha- nol, dried under vacuum at room temperature and recovered.
  • Analytic procedures NMR ANALYSIS
  • the X H and 13 C NMR spectra were registered with a Bruker AM 270 MHz spectrophotometer. The spectra were obtained in CDC1 3 at room temperature using tetramethylsilane as internal standard or in C 2 D 2 C1 4 at a high temperature (103°C; HMDS as internal standard) . The concentration of the polymeric solutions is about 10% by weight.
  • micro-structure of the polybutadienes obtained was determined on the basis of what is already known in litera- ture (see for example V.D. Mochel, J. Polym. Sci . , A-l 10, 1009, 1972; K.F. Elgert, G. Quack, B. Stutzel, Makromol . Chem. 175, 1955, 1974; D. Morero, A. Santambrogio, L. Porri, F. Ciampelli, Chim. Ind. (Milan) 41, 758, 1958) . G.P.C. ANALYSIS Operating conditions: Agilent 1100 pump
  • Calculation of average g branching index ratio between the radius of gyration of the branched macromolecule and that of the linear macromolecule, with the same molecular weight; the ratio is determined for each point of the integrated chromatogram, and the average on all the points is then calculated.
  • a polybutadiene is considered as being branched when g 0.90.
  • Viscosity values less than 100 cP are acceptable for the modification of polystyrene.
  • the insoluble % is determined by means of gravimetry, by weighing the residue on each filter and expressing it in percentage with respect to the initial weight .
  • CoCl 2 + MAO system both in toluene and in heptane produces a cis (about 95-98%) linear (g about 1) polymer, as demonstrated by examples b228 and b335; the polymerization effected in hexane being slower.
  • the PB structure which is obtained is essentially 1,4-cis (> 80%), see Table 1.
  • the use of the hindered phosphines of the present invention has the following advantages: ** high catalytic activities also in aliphatic hydrocarbon solvents, not used so far due to their limited activity (see examples b330, b292, b332 compared with b335) ;
  • the molecular weight (200 x 10 3 ⁇ M w ⁇ 420 x 10 3 ) can, in fact, be regulated by varying the type of phosphinic ligand, the Al/Co ratio and the type of solvent; ** production of polybutadiene with a low gel content

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention se rapporte à un procédé de préparation de polybutadiène ramifié à forte teneur en unités 1,4-sis par polymérisation de 1,3-butadiène, en présence d'un ou de plusieurs solvants et d'un système catalytique qui comprend un complexe de cobalt, préformé ou formé in situ, représenté par la formule générale (I) Cox+Ln, dans laquelle x est égal à 1, 2 ou 3, et de préférence égal à 2 ; n est compris entre 1 et 3; L est sélectionné parmi un ou plusieurs ligands de Co. Ce procédé est caractérisé par le fait que le ligand L est sélectionné parmi des dérivés phosphoreux représentés par la formule générale (Ia) P[-(O) mR1] [-(O) mR2] [-(O) mR3], dans laquelle m est égal à 0 ou 1, de préférence égal à 0; R1, R2, qui sont identiques ou différents, sont sélectionnés parmi des radicaux aliphatiques et cycloalkyle, R3 est sélectionné parmi l'hydrogène et des radicaux monofonctionnels aliphatiques et cycloalkyle, le composé représenté par la formule (Ia) possédant une valeur d'encombrement stérique thêta (υ) supérieure à 145°, de préférence supérieure à 150°.
PCT/EP2002/008450 2001-08-24 2002-07-25 Complexes de cobalt utiles pour la polymerisation de 1,3-butadiene WO2003018649A1 (fr)

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ITMI2001A001813 2001-08-24
IT2001MI001813A ITMI20011813A1 (it) 2001-08-24 2001-08-24 Complessi di cobalto utili nella polimerizzazione del 1,3-butadiene

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1557433A1 (fr) * 2004-01-22 2005-07-27 Polimeri Europa S.p.A. Procédé pour la préparation de polybutadiène ayant un degré de ramification bas
CN1293108C (zh) * 2004-04-12 2007-01-03 上海应用技术学院 一步合成含苯甲撑结构的超支化聚合物的方法
CN103450374A (zh) * 2013-07-30 2013-12-18 浙江大学 双组分钴系催化剂及其在1,3-丁二烯溶液聚合或悬浮聚合中的应用
WO2015068094A1 (fr) 2013-11-05 2015-05-14 Versalis S.P.A. Polybutadiènes diblocs stéréo-réguliers comprenant une structure 1,4-cis/ une structure 1,2 syndiotactique obtenue par polymérisation stéréospécifique
WO2015068095A1 (fr) 2013-11-05 2015-05-14 Versalis S.P.A. Polybutadiènes diblocs stéréo-réguliers comprenant une structure 1,4-cis/ une structure 1,2 syndiotactique obtenus par polymérisation stéréospécifique
IT201700085384A1 (it) * 2017-07-26 2019-01-26 Versalis Spa Procedimento per la preparazione di polibutadiene 1,2 sindiotattico in presenza di un sistema catalitico comprendente un complesso di cobalto con un legante fosfinico
RU2772250C2 (ru) * 2017-07-26 2022-05-18 ВЕРСАЛИС С.п.А. Способ получения 1,2-синдиотактического полибутадиена в присутствии каталитической системы, содержащей кобальтовый комплекс, включающий фосфиновый лиганд
IT202000028823A1 (it) 2020-11-27 2022-05-27 Consiglio Nazionale Ricerche Copolimeri dienici a stereoblocchi e relativo processo di preparazione.

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US4324939A (en) * 1980-01-10 1982-04-13 Chemische Werke Huels, Ag Process for preparing reaction products of conjugated diolefins and aromatic hydrocarbons
US5879805A (en) * 1997-09-09 1999-03-09 Union Carbide Chemicals & Plastics Technology Corporation Gas phase polymerization of vinylpolybutadiene

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US4324939A (en) * 1980-01-10 1982-04-13 Chemische Werke Huels, Ag Process for preparing reaction products of conjugated diolefins and aromatic hydrocarbons
US5879805A (en) * 1997-09-09 1999-03-09 Union Carbide Chemicals & Plastics Technology Corporation Gas phase polymerization of vinylpolybutadiene

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COTTON F A ET AL: "MAGNETIC INVESTIGATIONS OF SPIN-FREE COBALTOUS COMPLEXES. VI.1 COMPLEXES CONTAINING PHOSPHINES AND THE POSITION OF PHOSPHINESIN THE SPECTROCHEMICAL SERIES", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, AMERICAN CHEMICAL SOCIETY, WASHINGTON, DC, US, vol. 83, 1961, pages 1780 - 1785, XP001053774, ISSN: 0002-7863 *

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1557433A1 (fr) * 2004-01-22 2005-07-27 Polimeri Europa S.p.A. Procédé pour la préparation de polybutadiène ayant un degré de ramification bas
US7030195B2 (en) 2004-01-22 2006-04-18 Polimeri Europa S.P.A. Process for the preparation of polybutadiene with a low branching degree
CN100436494C (zh) * 2004-01-22 2008-11-26 波利玛利欧洲股份公司 制备具有低支化度的聚丁二烯的方法
CN1293108C (zh) * 2004-04-12 2007-01-03 上海应用技术学院 一步合成含苯甲撑结构的超支化聚合物的方法
CN103450374A (zh) * 2013-07-30 2013-12-18 浙江大学 双组分钴系催化剂及其在1,3-丁二烯溶液聚合或悬浮聚合中的应用
WO2015068094A1 (fr) 2013-11-05 2015-05-14 Versalis S.P.A. Polybutadiènes diblocs stéréo-réguliers comprenant une structure 1,4-cis/ une structure 1,2 syndiotactique obtenue par polymérisation stéréospécifique
WO2015068095A1 (fr) 2013-11-05 2015-05-14 Versalis S.P.A. Polybutadiènes diblocs stéréo-réguliers comprenant une structure 1,4-cis/ une structure 1,2 syndiotactique obtenus par polymérisation stéréospécifique
IT201700085384A1 (it) * 2017-07-26 2019-01-26 Versalis Spa Procedimento per la preparazione di polibutadiene 1,2 sindiotattico in presenza di un sistema catalitico comprendente un complesso di cobalto con un legante fosfinico
WO2019021195A1 (fr) * 2017-07-26 2019-01-31 Versalis S.P.A. Procédé de préparation de 1,2-polybutadiène syndiotactique en présence d'un système catalytique comprenant un complexe de cobalt avec un ligand phosphine
RU2772250C2 (ru) * 2017-07-26 2022-05-18 ВЕРСАЛИС С.п.А. Способ получения 1,2-синдиотактического полибутадиена в присутствии каталитической системы, содержащей кобальтовый комплекс, включающий фосфиновый лиганд
IT202000028823A1 (it) 2020-11-27 2022-05-27 Consiglio Nazionale Ricerche Copolimeri dienici a stereoblocchi e relativo processo di preparazione.
WO2022112387A1 (fr) 2020-11-27 2022-06-02 Km Technologies Gmbh Copolymères de diènes à stéréoblocs et leur procédé de préparation

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