WO1999003581A1 - Method for producing a supported catalyst - Google Patents

Method for producing a supported catalyst Download PDF

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Publication number
WO1999003581A1
WO1999003581A1 PCT/EP1998/004058 EP9804058W WO9903581A1 WO 1999003581 A1 WO1999003581 A1 WO 1999003581A1 EP 9804058 W EP9804058 W EP 9804058W WO 9903581 A1 WO9903581 A1 WO 9903581A1
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Prior art keywords
support material
supported catalysts
preparation
alkyl
supported
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PCT/EP1998/004058
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German (de)
French (fr)
Inventor
Rutger Anthony Van Santen
Hendrikus Cornelius Louis Abbenhuis
Simon Krijnen
Rob Willem Johan Maria Hanssen
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Solvay Deutschland Gmbh
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Priority to AU87311/98A priority Critical patent/AU8731198A/en
Publication of WO1999003581A1 publication Critical patent/WO1999003581A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1608—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes the ligands containing silicon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2282—Unsaturated compounds used as ligands
    • B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/19—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic hydroperoxides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
    • B01J2231/72—Epoxidation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/46—Titanium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/48—Zirconium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/49—Hafnium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/50—Complexes comprising metals of Group V (VA or VB) as the central metal
    • B01J2531/56—Vanadium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/50—Complexes comprising metals of Group V (VA or VB) as the central metal
    • B01J2531/57—Niobium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/50—Complexes comprising metals of Group V (VA or VB) as the central metal
    • B01J2531/58—Tantalum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
    • B01J2531/62—Chromium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
    • B01J2531/64—Molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
    • B01J2531/66—Tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/70—Complexes comprising metals of Group VII (VIIB) as the central metal
    • B01J2531/74—Rhenium

Definitions

  • the invention relates to a process for the preparation of a supported catalyst which contains silasesquioxane-metal complexes as catalytically active compounds, and to the use of these supported catalysts for the oxidation or epoxidation of unsaturated hydrocarbons or alcohols.
  • amorphous Ti0 2 -Si0 2 oxides can catalyze selective oxidations with organic hydroperoxides.
  • the object of the invention is to provide a heterogeneous catalyst based on silasesquioxane-metal complexes.
  • the catalyst should be characterized by a high level of economy. It should have a long service life, be thermally and air-stable and be easy to remove.
  • known crystalline or amorphous support materials based on SiO 2 with a pore diameter of 20 to 250 A, preferably 20 to 40 A, in particular 20 to 27 A, impregnated or impregnated with a silasesquioxane-metal complex solution.
  • silasesquioxane-metal complexes are understood to be the complexes which are obtained by reacting a metal compound with a silasesquioxane with defined denticity.
  • Halides, in particular chlorides, are used to prepare the complexes. or aryl compounds that do not contain a beta hydrogen atom, e.g. B. methyl, benzyl, neopentyl, xylyl, mesityl, neophile, adamantyl compounds, silyl, fluorenyl, idenyl, cyclopentadienyl compounds, the individual ligands by C 1 -C 4 - alkyl, C ⁇ -C ,, - alkylsilyl, alkoxy, aryl or arylsilyl groups can be substituted,
  • Oxides, imides, amides, alkoxides e.g. -OR, where R is hydrogen, -C jQ -alkyl, in particular methyl, ethyl, isopropyl, tert-butyl, aryl, in particular benzyl, phenyl, toluyl, naphthyl, xylyl, means
  • R is hydrogen, -C jQ -alkyl, in particular methyl, ethyl, isopropyl, tert-butyl, aryl, in particular benzyl, phenyl, toluyl, naphthyl, xylyl, means
  • their mixed compounds e.g. B.
  • SiMe 2 (CH 2 ) s CHACH 3 where A stands for OH, COOH, NH 2 , S0 3 -, COO "and s stands for 1 to 20, y stands for 2 and 3 and R 1 and R 3 can be functionalized by halogen or OH and
  • an organic solvent e.g. B. an alkylated aromatic hydrocarbon, preferably toluene, optionally in the presence of a basic compound, suspended with stirring at -80 ° C to 110 ° C.
  • an organic solvent e.g. B. an alkylated aromatic hydrocarbon, preferably toluene, optionally in the presence of a basic compound, suspended with stirring at -80 ° C to 110 ° C.
  • Pyridine is preferably used as the basic compound.
  • Metal compounds are understood to mean, in particular, compounds of titanium, zirconium, hafnium, chromium, tungsten, molybdenum, vanadium, niobium, tantalum, rhenium.
  • the by-products are separated by simple centrifugation.
  • M stands for the metals and Y for the above-mentioned radicals of the metal compound bonded to the metal, R 1 , B, n, m, q, r have the abovementioned meaning, R 2a is oxygen u 1 to 4 v 1 to 4 w 0 to 12, z. B. directly by adding acetonitrile and cleaned in a known manner, for. B. by recrystallization.
  • the metal complexes thus produced can, for. B. 4- or 6-fold coordinated metal complexes.
  • titanium complexes are prepared, wherein each titanium atom is 6-coordinate. This structural feature of the 6-fold coordination of all titanium atoms represents an important prerequisite for the hydrolysis resistance of the metal complexes and for their catalytic effectiveness.
  • silasesquioxane-titanium complexes e.g. B. [ 7 Si 7 0 12 ] -Ti ( ⁇ 5 -C 5 -H 5 ) used as a catalytic compound.
  • Amorphous support materials based on SiO 2 are to be understood as support material in the sense of the invention, which can be produced in a known manner by a sol-gel process and which are characterized by high porosity and uniform pore distribution.
  • Support material in the sense of the invention are also zeolitic support materials which are mesoporous and have a pore diameter of 20 to 100 A, e.g. B. MCM-41.
  • the carrier material is pure SiO 2 .
  • the carrier material in addition to Si0 2 also contains aluminum in oxidic form, for. B. 0.1 wt .-% aluminum or more.
  • carrier materials are used which have the following parameters.
  • the aluminum content of the support material is also important.
  • the Si / Al atomic ratio of MCM-41 can vary between 12 and 100, preferably 12 and 200.
  • the carrier material in the sense of the invention can have an aluminum content (in oxidic form) of at most 15% by weight, preferably from 0.2 to 5% by weight.
  • the carrier material is silylated before or after impregnation with the active component.
  • the support material is silylated before or after impregnation with the silasesquioxane-metal complex in order to adjust the hydrophobicity of the support material.
  • the silylation of the carrier material is carried out in a manner known per se by the silylating agent, for. B. dichlorodiphenylsilane or dichlorodimethylsilane is brought into contact with the carrier material.
  • the silylation is preferably carried out by refluxing.
  • organic solvents known per se are suitable as solvents for the impregnation or silylation.
  • Solvents in which the silasesquioxane-metal complexes used are soluble are particularly suitable for the impregnation.
  • Hexane, methylene dichloride or toluene are preferably used.
  • the silylation is preferably carried out in the presence of hexane. If appropriate, the supported catalyst can be dried after impregnation or silylation.
  • the supported catalyst produced according to the invention is characterized by a high level of economy. No leaching effect occurred in the observed test period.
  • the catalyst is thermally stable, air-stable and has a high abrasion resistance. It is easily separable from the reaction mixtures, e.g. B. by simple filtration. It was found that the catalyst had at least three reaction cycles, e.g. B. withstands an epoxidation of alkenes.
  • the supported catalyst produced according to the invention can be used both in powder form and as a lumpy shaped body.
  • the invention furthermore relates to the supported catalysts obtainable by the process according to the invention.
  • They comprise crystalline or amorphous support material based on SiO 2 with a pore diameter of 20 to 250 A, preferably 20 to 40 A, and silasesquioxane-metal complexes of the general formula II as a catalytically active compound.
  • the complexes of formula II are explained above.
  • the catalytically active compound (one can use a compound of the formula II, but if desired also more than one compound of the formula II) is then soaked or impregnated in the support material. Since the catalytically active compound is thus embedded in the pore system of the support material with mesopores, no leaching occurs.
  • a particularly preferred supported catalyst has a content of 0.2 to 15% by weight of aluminum, in particular 0.2 to 5% by weight of aluminum.
  • Aluminum-containing supported catalysts e.g. B. with more than 0.5 wt .-% aluminum are preferably silylated.
  • Supported catalysts with a content of aluminum in the support material of from 0.2% by weight are particularly advantageously silylated.
  • Preferred silylating agents are described above. In this way, supported catalysts with adjusted hydrophobicity of the support material can be obtained.
  • the supported catalysts prepared according to the invention are suitable for the oxidation or epoxidation of unsaturated hydrocarbons, preferably of alkenes or alcohols, in particular in the presence of tert.
  • unsaturated hydrocarbons preferably of alkenes or alcohols
  • tert preferably of alkenes or alcohols
  • TBHP butyl hydroperoxide
  • the catalyst is filtered off, washed three times with 20 ml of hexane each time and dried at 80 ° C. for 24 hours.
  • composition 1.2 mg Ti / g carrier Example 2;
  • 0.5 g of a supported catalyst impregnated according to Example 1 with an Si / Al ratio of 42 (atomic ratio) are refluxed for 72 hours with a solution of 70 ml of hexane and 2.5 g of dichlorodiphenylsilane.
  • the catalyst is filtered off, washed three times with 20 ml of hexane and acetone and dried at 80 ° C for 24 hours.
  • composition 1.2 mg Ti / g carrier
  • An amorphous carrier material based on Si0 2 which was produced by a sol-gel process, with a BET surface area of 759 m 2 / g, a total pore volume of 0.51 cm 3 / g and an aluminum oxide content of 2.7 wt .-% is impregnated as in Example 1 and silylated as in Example 2.
  • composition 1.2 mg Ti / g carrier

Abstract

The invention relates to a method for producing supported catalysts by impregnating or imbibing SiO2-based crystalline or amorphous support material with a pore diameter of 20 to 250 Å with silasesquioxane metal complexes. Said supported catalysts are suitable for oxidising or epoxidising unsaturated hydrocarbons or alcohols.

Description

Verfahren zur Herstellung eines Trägerkatalysators Process for the preparation of a supported catalyst
Beschreibungdescription
Die Erfindung betrifft ein Verfahren zur Herstellung eines Trägerkatalysators, der Silasesquioxan-Metallkomplexe als katalytisch aktive Verbindungen enthält, sowie die Verwendung dieser Trägerkatalysatoren zur Oxidation oder Epoxidation von ungesättigten Kohlenwasserstoffen oder Alkoholen.The invention relates to a process for the preparation of a supported catalyst which contains silasesquioxane-metal complexes as catalytically active compounds, and to the use of these supported catalysts for the oxidation or epoxidation of unsaturated hydrocarbons or alcohols.
Es ist bekannt, kristallines Titansilikalit (EP 100 119) als Katalysator zur selektiven Oxidation mit H202-Lösungen zu verwenden .It is known to use crystalline titanium silicalite (EP 100 119) as a catalyst for the selective oxidation with H 2 0 2 solutions.
Es ist ebenfalls bekannt, daß amorphe Ti02-Si02-Oxide selektive Oxidationen mit organischen Hydroperoxiden katalysieren können.It is also known that amorphous Ti0 2 -Si0 2 oxides can catalyze selective oxidations with organic hydroperoxides.
Die Wirkung von Silasesquioxan-Titankomplexen als homogener Katalysator ist ebenfalls bekannt.The effect of silasesquioxane-titanium complexes as a homogeneous catalyst is also known.
Die Aufgabe der Erfindung besteht darin, einen heterogenen Katalysator auf der Basis von Silasesquioxan-Metallkomplexen bereitzustellen.The object of the invention is to provide a heterogeneous catalyst based on silasesquioxane-metal complexes.
Der Katalysator soll sich durch eine hohe Wirtschaftlichkeit auszeichnen. Er soll eine hohe Lebensdauer aufweisen, thermisch und luftstabil sein sowie leicht abtrennbar sein.The catalyst should be characterized by a high level of economy. It should have a long service life, be thermally and air-stable and be easy to remove.
Erfindungsgemäß werden an sich bekannte kristalline oder amorphe Trägermaterialien auf der Basis von Si02, mit einem Porendurchmesser von 20 bis 250 A, vorzugsweise 20 bis 40 A, insbesondere 20 bis 27 A mit einer Silasesquioxan- Metallkomplex-Lösung imprägniert bzw. getränkt.According to the invention, known crystalline or amorphous support materials based on SiO 2 , with a pore diameter of 20 to 250 A, preferably 20 to 40 A, in particular 20 to 27 A, impregnated or impregnated with a silasesquioxane-metal complex solution.
Als Silasesquioxan-Metallkomplexe im Sinne der Erfindung werden die Komplexe verstanden, die durch Umsetzung einer Metallverbindung mit einem Silasesquioxan mit definierter Zähnigkeit erhalten werden.For the purposes of the invention, silasesquioxane-metal complexes are understood to be the complexes which are obtained by reacting a metal compound with a silasesquioxane with defined denticity.
Zur Herstellung der Komplexe werden Halogenide, insbesondere Chloride,
Figure imgf000004_0001
oder Aryl-Verbindungen, die kein Betawasserstoffatom enthalten, z. B. Methyl-, Benzyl-, Neopentyl-, Xylyl-, Mesityl-, Neophil-, Adamantyl-Verbindungen, Silyl-, Fluorenyl-, Idenyl-, Cyclopentadienyl-Verbindun- gen, wobei die einzelnen Liganden durch C1-C4-alkyl- , C^-C,,- alkylsilyl, alkoxy- , aryl- oder arylsilyl-Gruppen substituiert sein können,Halides, in particular chlorides, are used to prepare the complexes.
Figure imgf000004_0001
or aryl compounds that do not contain a beta hydrogen atom, e.g. B. methyl, benzyl, neopentyl, xylyl, mesityl, neophile, adamantyl compounds, silyl, fluorenyl, idenyl, cyclopentadienyl compounds, the individual ligands by C 1 -C 4 - alkyl, C ^ -C ,, - alkylsilyl, alkoxy, aryl or arylsilyl groups can be substituted,
Oxide, Imide, Amide, Alkoxide (z. B. -OR, wobei R Wasserstoff, -CjQ-alkyl, insbesondere methyl, ethyl, isopropyl, tert.-butyl, aryl, insbesondere benzyl, phenyl, toluyl, naph- thyl, xylyl, bedeutet) oder deren Mischverbindungen, z. B. Oxohalogenide, Aryl- oder Alkylhalogenide, Halogenamide oder Alkylalkoxide der Metalle der 4. bis 7. Nebengruppe des PSE und mindestens ein Silasesquioxan der allgemeinen Formel IOxides, imides, amides, alkoxides (e.g. -OR, where R is hydrogen, -C jQ -alkyl, in particular methyl, ethyl, isopropyl, tert-butyl, aryl, in particular benzyl, phenyl, toluyl, naphthyl, xylyl, means) or their mixed compounds, e.g. B. oxohalides, aryl or alkyl halides, halamides or alkyl alkoxides of the metals of the 4th to 7th subgroup of the PSE and at least one silasesquioxane of the general formula I.
{(RiSi01<s)n(R2Si01>5)m[(H)p(B)q(0)r]}{(R i Si0 1 <s ) n (R 2 Si0 1> 5 ) m [(H) p (B) q (0) r ]}
in derin the
R1 C5-C10-cycloalkyl, insbesondere cyclopentyl, cyclohexyl, cycloheptyl, norbornyl, adamantyl R2 OH B H, OH, Halogen, alkoxy oder SiR3 y, wobei R3 C^-C^-alkyl, insbesondere methyl, aryl, insbesondere phenyl, oder SiMe2(CH2)sCH = CH2, SiMe2 (CH2) SCH2CH2A,R 1 C 5 -C 10 cycloalkyl, in particular cyclopentyl, cyclohexyl, cycloheptyl, norbornyl, adamantyl R 2 OH BH, OH, halogen, alkoxy or SiR 3 y , where R 3 is C ^ -C ^ alkyl, in particular methyl, aryl , in particular phenyl, or SiMe 2 (CH 2 ) s CH = CH 2 , SiMe 2 (CH 2 ) S CH 2 CH 2 A,
SiMe2(CH2)sCHACH3, wobei A für OH, COOH, NH2, S03-, COO" und s für 1 bis 20 steht, sein kann, y für 2 und 3 steht und R1 und R3 durch Halogen oder OH funktionalisiert sein können undSiMe 2 (CH 2 ) s CHACH 3 , where A stands for OH, COOH, NH 2 , S0 3 -, COO "and s stands for 1 to 20, y stands for 2 and 3 and R 1 and R 3 can be functionalized by halogen or OH and
n 6 und 7 m 0 und 1 p 0 bis 4 q 0 bis 2 r 0 bis 2n 6 and 7 m 0 and 1 p 0 to 4 q 0 to 2 r 0 to 2
bedeuten,mean,
in einem organischen Lösungsmittel, z. B. einen alkylierten aromatischen Kohlenwasserstoff, vorzugsweise Toluol, gegebenenfalls in Gegenwart einer basischen Verbindung, unter Rühren bei -80 °C bis 110 °C suspendiert. Das Herstellungsverfahren ist in den deutschen Patentanmeldungen 197 15 786.6 und 197 48 835.8 beschrieben.in an organic solvent, e.g. B. an alkylated aromatic hydrocarbon, preferably toluene, optionally in the presence of a basic compound, suspended with stirring at -80 ° C to 110 ° C. The manufacturing process is described in German patent applications 197 15 786.6 and 197 48 835.8.
Als basische Verbindung wird vorzugsweise Pyridin verwendet .Pyridine is preferably used as the basic compound.
Als Metallverbindungen werden insbesondere Verbindungen von Titan, Zirkon, Hafnium, Chrom, Wolfram, Molybdän, Vanadium, Niob, Tantal, Rhenium verstanden.Metal compounds are understood to mean, in particular, compounds of titanium, zirconium, hafnium, chromium, tungsten, molybdenum, vanadium, niobium, tantalum, rhenium.
Die Nebenprodukte werden durch einfaches Zentrifugieren abgetrennt .The by-products are separated by simple centrifugation.
Aus der überstehenden Lösung werden die Silansesquioxan- Metallkomplexe der allgemeinen Formel IIThe silane sesquioxane metal complexes of the general formula II
{ (RiSi01<5)n(R2aSi0lι5)n[ (B)q(0)r] }U(M)V(Y)W {(R i Si0 1 <5 ) n (R 2a Si0 lι5 ) n [(B) q (0) r ]} U (M) V (Y) W
in derin the
M für die Metalle und Y für die an das Metall gebundenen obengenannten Reste der MetallVerbindung steht, R1, B, n, m, q, r die obengenannte Bedeutung haben, R2a Sauerstoff u 1 bis 4 v 1 bis 4 w 0 bis 12 bedeuten, z. B. durch Zugabe von Acetonitril direkt gefällt und in bekannter Weise gereinigt, z. B. durch Umkristallisation.M stands for the metals and Y for the above-mentioned radicals of the metal compound bonded to the metal, R 1 , B, n, m, q, r have the abovementioned meaning, R 2a is oxygen u 1 to 4 v 1 to 4 w 0 to 12, z. B. directly by adding acetonitrile and cleaned in a known manner, for. B. by recrystallization.
Die so hergestellten Metallkomplexe können z. B. 4- oder 6-fach koordinierte Metallkomplexe sein. So können nach dem obengenannten Verfahren z. B. Titankomplexe hergestellt werden, worin jedes Titanatom 6-fach koordiniert ist. Dieses Strukturmerkmal der 6-fachen Koordination aller Titanatome stellt eine wichtige Voraussetzung für die Hydrolysebeständigkeit der Metallkomplexe und für deren katalytische Wirksamkeit dar.The metal complexes thus produced can, for. B. 4- or 6-fold coordinated metal complexes. Thus, for. B. Titanium complexes are prepared, wherein each titanium atom is 6-coordinate. This structural feature of the 6-fold coordination of all titanium atoms represents an important prerequisite for the hydrolysis resistance of the metal complexes and for their catalytic effectiveness.
In einer Ausführungsform werden Silasesquioxan-Titan- komplexe, z. B. [
Figure imgf000006_0001
7 Si7012] -Ti (η5-C5-H5) als katalytische Verbindung verwendet.In one embodiment, silasesquioxane-titanium complexes, e.g. B. [
Figure imgf000006_0001
7 Si 7 0 12 ] -Ti (η 5 -C 5 -H 5 ) used as a catalytic compound.
Als Trägermaterial im Sinne der Erfindung sind amorphe Trägermaterialien auf Basis von Si02 zu verstehen, die in bekannter Weise nach einem Sol-Gel-Verfahren hergestellt werden können und die sich durch hohe Porosität und gleichmäßige Porenverteilung auszeichnen.Amorphous support materials based on SiO 2 are to be understood as support material in the sense of the invention, which can be produced in a known manner by a sol-gel process and which are characterized by high porosity and uniform pore distribution.
Trägermaterial im Sinne der Erfindung sind auch zeo- lithische Trägermaterialien, die mesoporös sind und einen Porendurchmesser von 20 bis 100 A haben, z. B. MCM-41.Support material in the sense of the invention are also zeolitic support materials which are mesoporous and have a pore diameter of 20 to 100 A, e.g. B. MCM-41.
Gemäß einer anderen Ausführungsform ist das Trägermaterial reines Si02. Gemäß einer weiteren Ausführungsform enthält das Trägermaterial neben Si02 auch Aluminium in oxidischer Form, z. B. 0,1 Gew.-% Aluminium oder mehr.According to another embodiment, the carrier material is pure SiO 2 . According to a further embodiment, the carrier material in addition to Si0 2 also contains aluminum in oxidic form, for. B. 0.1 wt .-% aluminum or more.
In einer bevorzugten Ausführungsform werden Trägermaterialien verwendet, die folgende Parameter aufweisen.In a preferred embodiment, carrier materials are used which have the following parameters.
Figure imgf000007_0002
Figure imgf000007_0002
Es wurde gefunden, daß neben dem Porendurchmesser des Trägermaterials auch der Aluminiumgehalt des Trägermaterials bedeutsam ist.It was found that in addition to the pore diameter of the support material, the aluminum content of the support material is also important.
Das Si/Al-Atom-Verhältnis von MCM-41 kann zwischen 12 und oo, vorzugsweise 12 und 200 variieren.The Si / Al atomic ratio of MCM-41 can vary between 12 and 100, preferably 12 and 200.
Das Trägermaterial im Sinne der Erfindung kann einen Aluminiumgehalt (in oxidischer Form) von maximal 15 Gew.-%, vorzugsweise von 0,2 bis 5 Gew.-% aufweisen.The carrier material in the sense of the invention can have an aluminum content (in oxidic form) of at most 15% by weight, preferably from 0.2 to 5% by weight.
In Abhängigkeit vom Aluminiumgehalt des Trägermaterials erfolgt vor oder nach der Imprägnierung mit der Aktivkomponente eine Silylierung des Trägermaterials.Depending on the aluminum content of the carrier material, the carrier material is silylated before or after impregnation with the active component.
Es hat sich als günstig erwiesen, Trägermaterial ab einem Aluminiumgehalt von ca. 0,5 Gew.-%, vorzugsweise 0,2 Gew.-%, zu silylieren.It has proven advantageous to silylate carrier material with an aluminum content of approximately 0.5% by weight, preferably 0.2% by weight.
Als Silylierungsmittel werden vorzugsweise Verbindungen der allgemeinen Formel IIICompounds of the general formula III are preferably used as silylating agents
Figure imgf000007_0001
in der
Figure imgf000007_0001
in the
X Halogen oder OR5 X halogen or OR 5
R4, R5 aryl, vorzugsweise phenyl, C^- bis C10-alkyl, Cx bisR 4 , R 5 aryl, preferably phenyl, C ^ - to C 10 -alkyl, C x bis
C10-cycloalkyl, vorzugsweise methyl, wobei die einzelnen Substituenten gleichfalls durch aryl oder C^C-Lg-alkyl substituiert sein können, und n = 0 bis 4 bedeuten, verwendet.C 10 -cycloalkyl, preferably methyl, where the individual substituents may be also substituted by aryl or C ^ C- Lg alkyl, and n = 0 to 4 denote used.
Erfindungsgemäß wird bei einem Aluminiumgehalt von 0,2 bis 15 Gew.-% Aluminium das Trägermaterial vor oder nach der Imprägnierung mit dem Silasesquioxan-Metallkomplex silyliert, um die Hydrophobie des Trägermaterials einzustellen. Die Silylierung des Trägermaterials erfolgt in an sich bekannter Weise, indem das Silylierungsmittel, z. B. Dichlordiphenylsi- lan oder Dichlordimethylsilan mit dem Trägermaterial in Kontakt gebracht wird.According to the invention, with an aluminum content of 0.2 to 15% by weight of aluminum, the support material is silylated before or after impregnation with the silasesquioxane-metal complex in order to adjust the hydrophobicity of the support material. The silylation of the carrier material is carried out in a manner known per se by the silylating agent, for. B. dichlorodiphenylsilane or dichlorodimethylsilane is brought into contact with the carrier material.
Vorzugsweise erfolgt die Silylierung durch Kochen am Rückfluß.The silylation is preferably carried out by refluxing.
Als Lösungsmittel für die Imprägnierung oder Silylierung sind die an sich bekannten organischen Lösungsmittel geeignet .The organic solvents known per se are suitable as solvents for the impregnation or silylation.
Insbesondere sind für die Imprägnierung Lösungsmittel geeignet, in denen die verwendeten Silasesquioxan-Metallkomplexe löslich sind.Solvents in which the silasesquioxane-metal complexes used are soluble are particularly suitable for the impregnation.
Vorzugsweise werden Hexan, Methylendichlorid oder Toluol verwendet.Hexane, methylene dichloride or toluene are preferably used.
Die Silylierung erfolgt vorzugsweise in Gegenwart von Hexan. Gegebenenfalls kann der Trägerkatalysator nach der Imprägnierung oder der Silylierung getrocknet werden.The silylation is preferably carried out in the presence of hexane. If appropriate, the supported catalyst can be dried after impregnation or silylation.
Der erfindungsgemäß hergestellte Trägerkatalysator zeichnet sich durch eine hohe Wirtschaftlichkeit aus. Im beobachteten Versuchszeitraum trat kein Leaching-Effekt auf. Der Katalysator ist thermisch stabil, luftstabil und weist eine hohe Abriebfestigkeit auf. Er ist leicht aus den Reaktionsgemischen abtrennbar, z. B. durch einfaches Filtrieren. Es wurde gefunden, daß der Katalysator ohne Aktivitätsverlust mindestens drei Reaktionszyclen z. B. einer Epoxidierung von Alkenen standhält.The supported catalyst produced according to the invention is characterized by a high level of economy. No leaching effect occurred in the observed test period. The catalyst is thermally stable, air-stable and has a high abrasion resistance. It is easily separable from the reaction mixtures, e.g. B. by simple filtration. It was found that the catalyst had at least three reaction cycles, e.g. B. withstands an epoxidation of alkenes.
Der erfindungsgemäß hergestellte Trägerkatalysator kann sowohl in Pulverform als auch als stückiger Formkörper verwendet werden.The supported catalyst produced according to the invention can be used both in powder form and as a lumpy shaped body.
Ein weiterer Gegenstand der Erfindung sind die nach dem erfindungsgemäßen Verfahren erhältlichen Trägerkatalysatoren. Sie umfassen kristallines oder amorphes Trägermaterial auf Basis von Si02 mit einem Porendurchmesser von 20 bis 250 A, vorzugsweise 20 bis 40 A, und Silasesquioxan-Metallkomplexe der allgemeinen Formel II als katalytisch aktive Verbindung. Die Komplexe der Formel II sind weiter oben erläutert. Die katalytisch aktive Verbindung (man kann eine Verbindung der Formel II einsetzen, gewünsc tenfalls aber auch mehrere Verbindungen der Formel II) ist dann im Trägermaterial getränkt oder imprägniert enthalten. Da die katalytisch aktive Verbindung somit im Porensystem des Trägermaterials mit Mesoporen eingelagert ist, tritt kein Leaching auf.The invention furthermore relates to the supported catalysts obtainable by the process according to the invention. They comprise crystalline or amorphous support material based on SiO 2 with a pore diameter of 20 to 250 A, preferably 20 to 40 A, and silasesquioxane-metal complexes of the general formula II as a catalytically active compound. The complexes of formula II are explained above. The catalytically active compound (one can use a compound of the formula II, but if desired also more than one compound of the formula II) is then soaked or impregnated in the support material. Since the catalytically active compound is thus embedded in the pore system of the support material with mesopores, no leaching occurs.
Bevorzugte Ausführungsformen des Trägermaterials und der Sesquisiloxan-Metallkomplexe sind weiter oben beschrieben. Ein besonders bevorzugter Trägerkatalysator weist einen Gehalt von 0,2 bis 15 Gew.-% Aluminium, insbesondere 0,2 bis 5 Gew.-% Aluminium, auf. Aluminiumhaltige Trägerkatalysatoren, z. B. mit mehr als 0,5 Gew.-% Aluminium sind vorzugsweise silyliert. Besonders vorteilhaft liegen Trägerkatalysatoren mit einem Gehalt von Aluminium im Trägermaterial ab 0 , 2 Gew.-% silyliert vor. Bevorzugte Silylierungsmittel sind weiter oben beschrieben. Auf diese Weise sind Trägerkatalysatoren mit eingestellter Hydrophobie des Trägermaterials erhältlich.Preferred embodiments of the carrier material and the sesquisiloxane metal complexes are described above. A particularly preferred supported catalyst has a content of 0.2 to 15% by weight of aluminum, in particular 0.2 to 5% by weight of aluminum. Aluminum-containing supported catalysts, e.g. B. with more than 0.5 wt .-% aluminum are preferably silylated. Supported catalysts with a content of aluminum in the support material of from 0.2% by weight are particularly advantageously silylated. Preferred silylating agents are described above. In this way, supported catalysts with adjusted hydrophobicity of the support material can be obtained.
Die erfindungsgemäß hergestellten Trägerkatalysatoren sind geeignet die Oxidation oder die Epoxidation von ungesättigten Kohlenwasserstoffen, vorzugsweise von Alkenen oder Alkoholen, insbesondere in Gegenwart von tert. Butylhydroper- oxid (TBHP) , zu katalysieren.The supported catalysts prepared according to the invention are suitable for the oxidation or epoxidation of unsaturated hydrocarbons, preferably of alkenes or alcohols, in particular in the presence of tert. To catalyze butyl hydroperoxide (TBHP).
Die nachfolgenden Beispiele sollen die Erfindung erläutern, jedoch nicht einschränken.The following examples are intended to illustrate the invention but not to limit it.
BeispieleExamples
Beispiel 1:Example 1:
Imprägnierung des TrägerkatalysatorsImpregnation of the supported catalyst
50 ml einer 10"3-molaren Lösung von [ (c-C6Hι:L) 7Si7012] -Ti (η5- C5H5) in Hexan werden langsam in eine Suspension von 2 g MCM- 41 und 50 ml Hexan eingebracht und 24 Stunden gerührt.50 ml of a 10 " 3 molar solution of [(cC 6 H ι: L ) 7 Si 7 0 12 ] -Ti (η 5 - C 5 H 5 ) in hexane are slowly added to a suspension of 2 g of MCM-41 and 50 ml of hexane were introduced and stirred for 24 hours.
Der Katalysator wird abfiltriert, dreimal mit je 20 ml Hexan gewaschen und 24 Stunden bei 80 °C getrocknet.The catalyst is filtered off, washed three times with 20 ml of hexane each time and dried at 80 ° C. for 24 hours.
Zusammensetzung: 1,2 mg Ti/g Träger Beispiel 2;Composition: 1.2 mg Ti / g carrier Example 2;
Silylierung des TrägerkatalysatorsSilylation of the supported catalyst
0,5 g eines gemäß Beispiel 1 imprägnierten Trägerkatalysators mit einem Si/Al-Verhältnis von 42 (Atomverhältnis) werden mit einer Lösung von 70 ml Hexan und 2,5 g Dichlordiphenylsilan 72 Stunden am Rückfluß gekocht. Der Katalysator wird abfiltriert, je dreimal mit je 20 ml Hexan und Aceton gewaschen und bei 80 °C 24 Stunden getrocknet.0.5 g of a supported catalyst impregnated according to Example 1 with an Si / Al ratio of 42 (atomic ratio) are refluxed for 72 hours with a solution of 70 ml of hexane and 2.5 g of dichlorodiphenylsilane. The catalyst is filtered off, washed three times with 20 ml of hexane and acetone and dried at 80 ° C for 24 hours.
Zusammensetzung: 1,2 mg Ti/g TrägerComposition: 1.2 mg Ti / g carrier
Beispiel 3;Example 3;
Silylierung des TrägerkatalysatorsSilylation of the supported catalyst
Ein amorphes Trägermaterial auf Basis von Si02, das nach einem Sol-Gel-Verfahren hergestellt wurde, mit einer BET- Oberfläche von 759 m2/g, einem Gesamtporenvolumen von 0,51 cm3/g und einem Aluminiumoxidgehalt von 2,7 Gew.-% wird analog Beispiel 1 imprägniert und analog Beispiel 2 silyliert.An amorphous carrier material based on Si0 2 , which was produced by a sol-gel process, with a BET surface area of 759 m 2 / g, a total pore volume of 0.51 cm 3 / g and an aluminum oxide content of 2.7 wt .-% is impregnated as in Example 1 and silylated as in Example 2.
Zusammensetzung: 1,2 mg Ti/g TrägerComposition: 1.2 mg Ti / g carrier
Beispiele 4 - 6;Examples 4-6;
Epoxidation von CyclooctenEpoxidation of cyclooctene
1,6 mmol Cycloocten und 1,6 mmol tert . Butylhydroperoxid werden in 1 ml Hexan gemischt. In Gegenwart von 60 mg Ti- Katalysator erfolgt die Umsetzung bei 50 °C.1.6 mmol cyclooctene and 1.6 mmol tert. Butyl hydroperoxide are mixed in 1 ml hexane. The reaction is carried out at 50 ° C. in the presence of 60 mg of Ti catalyst.
Ergebnisse siehe Tabelle 1 Tabelle 1See Table 1 for results Table 1
Figure imgf000012_0001
Figure imgf000012_0001

Claims

Patentansprüche claims
1. Verfahren zur Herstellung von Trägerkatalysatoren, ie Silasesquioxan-Metall-Komplexe der allgemeinen Formel II1. Process for the preparation of supported catalysts, ie silasesquioxane-metal complexes of the general formula II
{RiSi0lι5)n(R*Si01)5)m[ (B)q(0)r] }U(M)V(Y)W {R i Si0 lι5 ) n (R * Si0 1) 5 ) m [(B) q (0) r ]} U (M) V (Y) W
in derin the
R1 C5-C10-cycloalkyl-, norbornyl, adamantylR 1 is C 5 -C 10 cycloalkyl, norbornyl, adamantyl
R2a SauerstoffR 2a oxygen
B SiR3 y, wobei R3 , C1-C4-alkyl, aryl sein kann, H, OH, Halogen, alkoxy,B SiR 3 y , where R 3 , C 1 -C 4 alkyl, aryl, H, OH, halogen, alkoxy,
SiMe2(CH2)s CH = CH2, SiMe2 (CH2) SCH2CH2A, SiMe2 (CH2 ) SCHACH3 , wobei A für OH, COOH, NH,, S03 ~, COO~, und s für 1 bis 20 steht, y für 2 und 3 steht undSiMe 2 (CH 2 ) s CH = CH 2 , SiMe 2 (CH 2 ) S CH 2 CH 2 A, SiMe 2 (CH 2 ) S CHACH 3 , where A is OH, COOH, NH ,, S0 3 ~ , COO ~ , and s stands for 1 to 20, y stands for 2 and 3 and
R1 und R3 durch Halogen oder OH funktionalisiert sein können,R 1 and R 3 can be functionalized by halogen or OH,
M Metalle der 4. bis 7. Nebengruppe des PSEM metals of the 4th to 7th subgroup of the PSE
Y C1-C20-alkyl- oder aryl-Gruppen, die kein Betawasserstoffatom enthalten, z. B. methyl, benzyl, neopentyl , xylyl, mesityl, neophil, adamantyl, silyl, fluorenyl, indenyl-, cyclopentadienyl, wobei die einzelnen Substituenten durch C1-C4-alkyl- , C1-C4- alkylsilyl, alkoxy-, aryl- oder arylsilyl-Gruppen substituiert sein können, oxo, i ido, Halogen, OR wobei R Wasserstoff, C^C^-al- kyl, insbesondere methyl, ethyl, isopropyl, tert. butyl, aryl, insbesondere benzyl, phenyl, toluyl, naphthyl, xylyl , bedeuten wobei Y gleich oder verschieden sein kannYC 1 -C 20 alkyl or aryl groups which do not contain a beta hydrogen atom, e.g. B. methyl, benzyl, neopentyl, xylyl, mesityl, neophile, adamantyl, silyl, fluorenyl, indenyl, cyclopentadienyl, the individual substituents by C 1 -C 4 alkyl, C 1 -C 4 alkylsilyl, alkoxy, Aryl or arylsilyl groups can be substituted, oxo, i ido, halogen, OR where R is hydrogen, C ^ C ^ alkyl, especially methyl, ethyl, isopropyl, tert. butyl, aryl, especially benzyl, phenyl, toluyl, naphthyl, xylyl, where Y can be the same or different
und n 6 und 7 m 0 und 1 q 0 bis 2 r 0 bis 2 u 1 bis 4 v 1 bis 4 w 0 bis 12 bedeuten als katalytische Verbindung enthalten, dadurch gekennzeichnet, daß kristallines oder amorphes Trägermaterial auf der Basis von Si02 mit einem Porendurchmesser von 20 bis 250 Ä mit der katalytischen Verbindung imprägniert oder getränkt wird.and n 6 and 7 m 0 and 1 q 0 to 2 r 0 to 2 u 1 to 4 v 1 to 4 w 0 to 12 contain as a catalytic compound, characterized in that crystalline or amorphous support material based on Si0 2 with a pore diameter of 20 to 250 Å with the impregnated or impregnated catalytic compound.
2. Verfahren zur Herstellung von Trägerkatalysatoren nach Anspruch 1, dadurch gekennzeichnet, daß das Trägermaterial einen Porendurchmesser von 20 bis 40 A hat.2. A process for the preparation of supported catalysts according to claim 1, characterized in that the support material has a pore diameter of 20 to 40 A.
3. Verfahren zur Herstellung von Trägerkatalysatoren nach Anspruch 1 und 2, dadurch gekennzeichnet, daß das Trägermaterial 0,2 bis 15 Gew.-% Aluminium enthält.3. A process for the preparation of supported catalysts according to claim 1 and 2, characterized in that the support material contains 0.2 to 15 wt .-% aluminum.
4. Verfahren zur Herstellung von Trägerkatalysatoren nach Anspruch 1 bis 3, dadurch gekennzeichnet, daß das Trägermaterial vor oder nach der Imprägnierung mit der katalytischen Verbindung mit einem Silylierungsmittel behandelt wird.4. A process for the preparation of supported catalysts according to claim 1 to 3, characterized in that the support material is treated with a silylating agent before or after the impregnation with the catalytic compound.
5. Verfahren zur Herstellung von Trägerkatalysatoren nach Anspruch 1 bis 4, dadurch gekennzeichnet, daß als Silylierungsmittel Dichlordiphenylsilan oder Dichlordimethylsilan verwendet wird.5. A process for the preparation of supported catalysts according to claim 1 to 4, characterized in that dichlorodiphenylsilane or dichlorodimethylsilane is used as the silylating agent.
6. Verwendung der Trägerkatalysatoren gemäß Anspruch 1 bis 5 zur Oxidation oder Epoxidation von ungesättigten Kohlenwasserstoffen oder Alkoholen.6. Use of the supported catalysts according to claim 1 to 5 for the oxidation or epoxidation of unsaturated hydrocarbons or alcohols.
7. Verwendung der Trägerkatalysatoren gemäß Anspruch 1 bis 6 zur Epoxidierung von Alkenen. 7. Use of the supported catalysts according to claims 1 to 6 for the epoxidation of alkenes.
8. Trägerkatalysator, umfassend kristallines oder amorphes Trägermaterial auf Basis von Si02 mit einem Porendurchmesser von 20 bis 250 A und einen oder mehrere Silasesquioxan-Metallkomplexe der allgemeinen Formel II als katalytisch aktive Verbindung.8. supported catalyst comprising crystalline or amorphous support material based on Si0 2 with a pore diameter of 20 to 250 A and one or more silasesquioxane-metal complexes of the general formula II as a catalytically active compound.
9. Trägerkatalysator nach Anspruch 8, gekennzeichnet durch einen Porendurchmesser von 20 bis 40 A.9. supported catalyst according to claim 8, characterized by a pore diameter of 20 to 40 A.
10. Trägerkatalysator nach Anspruch 8 oder 9, gekennzeichnet durch einen Gehalt von 0,2 bis 15 Gew.-% Aluminium im Trägermaterial .10. supported catalyst according to claim 8 or 9, characterized by a content of 0.2 to 15 wt .-% aluminum in the support material.
11. Trägerkatalysator nach Anspruch 10 mit einem Aluminiumgehalt von mindestens 0,5 Gew.-%, dadurch gekennzeichnet, daß er silyliert ist. 11. A supported catalyst according to claim 10 with an aluminum content of at least 0.5 wt .-%, characterized in that it is silylated.
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