WO2003035252A1 - Modification chimique de surfaces de particules par reticulation - Google Patents

Modification chimique de surfaces de particules par reticulation Download PDF

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WO2003035252A1
WO2003035252A1 PCT/EP2002/010693 EP0210693W WO03035252A1 WO 2003035252 A1 WO2003035252 A1 WO 2003035252A1 EP 0210693 W EP0210693 W EP 0210693W WO 03035252 A1 WO03035252 A1 WO 03035252A1
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bis
groups
particles
triethoxysilyl
hours
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PCT/EP2002/010693
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German (de)
English (en)
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Thomas Eberle
Katrin Köhler
Herbert Schumann
Birgit Corinna Wassermann
Katharina Lange
Ralf Widmaier
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Merck Patent Gmbh
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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
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65925—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually non-bridged

Definitions

  • the invention relates to a process for the production of new catalyst supports based on modified inorganic spherical and non-spherical oxides, a process for the production of supported metallocene or “single-site catalysts” in combination with a cocatalyst and their use in The invention further relates to the use of the starting materials required in the process, so-called spacers or linkers, which are used for the production of the supported metallocene.
  • the support of the catalyst can be carried out according to various methods, with particular attention to the order of the reaction of the components with one another (W. Kaminsky, H. Winkelbach, Topics in Catalysis 1999, 7, 61.):
  • the cocatalyst methyuminuminoxane can also be generated in situ by reacting trimethylaluminum with a water-containing support material (EP 170 059 (1986), US 4,912,075 (1990)).
  • the catalyst carrier prevents "reactor fouling" and prevents agglomeration of the catalytically active centers.
  • the carrier should disintegrate into small particles during the polymerization, which should be evenly distributed in the resulting polymer. This is very important for the further processing of the polymer, since larger carrier particles can a. optical properties such as B. affect the transparency when using polyolefins as films, while too small a particle size of the carrier causes unpleasant dust during transport and processing, such as. B by M. O. Kristen, (Topics in Catalysis 1999, 7, 89) and M. R. Ribeiro, et al. (Ind. Eng. Chem. Res. 1997, 36, 1224.).
  • the aggregation is usually achieved by spray drying (WO 97/48742), alternatively, Müllen et al. on the crosslinking of polystyrenes by means of the Diels-Alder reaction, a retro-Diels-Alder Reaction during the polymerization should enable fragmentation under certain conditions (PCT WO99 / 60035 (1999), DE 199 27 766.4 (1999) M. Koch, N. Nenov, A. Falcou, M. Klapper, K. Müllen).
  • the object of the present invention is therefore
  • the object of the invention is achieved by providing selectively fragmentable support materials for cocatalysts and catalysts for polymerization reactions, in which inorganic particles have hydroxyl or hydrolyzable groups on their surface. before they are cross-linked or cross-linked with silicon-containing spacer and / or linker molecules to form larger particle groups.
  • Interlinked inorganic particles consisting of oxide particles of one or more elements of groups 2, 13 and 14 of the periodic table, serve as the basis for these carrier materials.
  • they are oxides of silicon or aluminum.
  • polysiloxane particles are crosslinked as particles.
  • the object of the invention is also achieved by providing silicon-containing spacer molecules according to the general formula
  • Rii R 21 R 3 independently of one another OR, OH, F, Cl, Br, I, H, NH 2 , NHR, NRR ', SH, SR, PH 2 , PHR, PRR', with the proviso that one of the groups Ri - R 3 is hydrolyzable,
  • R 4 OR, O, NH, NHR, NRR ', S, SR, PH, PHR, PRR', R,
  • Alkyl with C ⁇ - C 20 cycloalkyl with C 5 - C 7 , aryl with C 6 - C 20 , alkenyl with C 2 - C ⁇ 0 ,
  • Aralkyl with C 7 - C 20 Alkylaryl with C 7 - C 20) linear or branched alkyl with Ci - C 20
  • Arylenealkylene with C 7 - C 20 , a, b, c 0, 1, 2 or 3 with the proviso that a + b + c 3, d 0 - 30 and e mean 0 or 1.
  • spacer molecules can be the following compounds:
  • the present invention furthermore relates to silicon-containing linker molecules according to the general formula
  • R 1 -R 3 , R 5 -R 7 independently of one another OR, OH, F, Cl, Br, I, H, NH 2 ,
  • R 4 and R 8 are linear or branched alkylene with C 1 -C 20
  • linker molecules include the compounds bis (triethoxysilyl) octane bis [(3-trimethoxysily) propyljamine
  • 1,2-bis (trimethylsiloxy) -1,3-dimethyldisiloxane can be used.
  • the present invention furthermore relates to a process for the preparation of the carrier material described above by using inorganic particles or polysiloxane particles with spacer molecules of the general formula (1) or selected from the group of compounds listed above, which can serve as spacer molecules, and / or linker molecules according to the general formula (2) or compounds selected from the group of the listed compounds, which can serve as linker molecules, in the presence of stoichiometric amounts of water.
  • inorganic particles or polysiloxane particles are reacted with the above-mentioned linker molecules in an anhydrous medium.
  • a selectively adjustable fragmentation of support materials for cocatalysts and catalysts can be achieved by crosslinking or forming inorganic particles, preferably with sizes in the nanometer or picometer range, using silicon-containing spacers or linkers to form larger particle groups. be cross-linked.
  • the previously chemically introduced connections between the particles are destroyed by the resulting polymer and the particle assemblies are thus broken up into individual particles.
  • spherical and non-spherical particles which carry hydrolyzable or hydroxy groups on their surface, such as, for example, B. oxides of silicon and aluminum or polysiloxane compounds, wherein the carrier can be porous or non-porous.
  • Inorganic oxides consisting of one or more elements from groups 2, 13 and 14 of the periodic table are preferably used.
  • the surface of the support varies between 1 and 1000 m 2 / g, the pore volume between 0 and 4 ml / g.
  • Ri, R 2 , R 3 independently of one another OR, OH, F, Cl, Br, I, H, NH 2 ,
  • R, R 'R "independently of one another linear or branched alkyl with C1 - C 20 ,
  • R 1 -R 3 , R 5 -R 7 independently of one another OR, OH, F, Cl, Br, I, H, NH 2)
  • linear or branched alkyl with C 1 -C 20 linear or branched carbon chains with 1 to 20 C atoms are to be understood.
  • Such are e.g. B. methyl, ethyl, i- and n-propyl groups and as further groups the branched and to understand unbranched isomers of butyl, pentyl, hexyl, heptyl, octyl, etc. to C 20 .
  • Cycloalkyl groups with C 5 _C 7 are to be understood as cyclopentyl, cyclohexyl or cycloheptyl groups.
  • Aryl groups with C 6 - C 20 can for example be phenyl or naphthyl, indenyl, and other condensed aromatic groups with up to 20 C atoms.
  • Compounds which have aromatic groups and are suitable as spacers or linkers are preferably those in which “aryl” assumes the meaning phenyl- or naphthyl-.
  • Alkenyl groups are linear or branched carbon chains with 2 to 10 carbon atoms, such as. B. vinyl, propenyl or the isomeric butenyl groups. This includes not only the monounsaturated but also polyunsaturated groups such as B. Pentadienyl.
  • Compounds of the general formulas (1) and (2) can be substituted by aralkyl groups with 7 to 20 C atoms, preferably with 8 to 12, particularly preferably with 8 to 10 C atoms.
  • substituents such as benzyl, ethylbenzene, propylbenzene groups or those which contain a condensed ring system.
  • the alkyl part of these groups can be linear or branched carbon chains.
  • alkylaryl groups with 7 to 20, preferably with 8 to 12, particularly preferably with 8 to 10, carbon atoms which are connected via their aromatic system to the spacer or linker molecule.
  • alkylaryl groups are, for example, 3-methylphenyl or 3-ethylphenyl.
  • linear or branched alkylene groups with C - t - C 20 are examples of linear or branched alkylene groups with C - t - C 20.
  • Cycloalkylene groups are groups with 5 to 7 ring carbon atoms such as cyclopentylene, cyclohexylene or cycloheptylene groups.
  • Arylene groups with 6 to 20 carbon atoms are to be understood as aromatic ring systems which are bound twice in the spacer or linker molecule, such as, for example, phenylene groups (-C 6 H 4 -).
  • radicals R 4 and in the linker molecules R 4 and R 8 can each be akylidene groups with 2 to 20 C atoms. These groups integrated twice in the molecule can be mono- or polyunsaturated, linear or branched. Examples of corresponding alkylidene groups are vinylidene or propylidene groups.
  • the molecules according to the general formulas (1) and (2) also comprise compounds with arylene alkylene groups of 7 to 20 carbon atoms.
  • These can be groups which can have a simple aromatic ring such as phenyl or a fused aromatic ring system, while the alkyl part of this group can be linear or branched.
  • a simple representative of such groups is e.g. B. an ethylene phenylene group.
  • Compounds according to the general formula (1) must have at least one of the groups R 1t R 2 or R 3 have a hydrolylatable radical in order to be suitable according to the invention as spacer molecules.
  • Suitable hydrolyzable groups are, for example, ether groups or halogen radicals, in particular CL.
  • suitable linker molecules at least one of the groups R 1, R 2 , R 3 and R 5 , R 6 or R 7 must be able to be hydrolyzed accordingly.
  • Compounds of the general formula (1) which can be used according to the invention as spacer molecules have, in particular, Fi or F 2 NH 2 or NRNH 2 groups.
  • Suitable reactive spacer groups according to the general formula (1) are e.g. B. the following connections:
  • N N-diethyl-3-aminopropyl trimethoxysilane, 5,6-Epoxyhexyltriethoxysilan, 3-isocyanatopropyltriethoxysilane, isooctyltrimethoxysilane, 3-lodopropyltrimethoxysilan, mercaptomethylmethyldiethoxysilane, methacryloxymethyltrimethoxysilane, n-Octadecylmethoxydichlorosilan, n-octyltrimethoxysilane, N-phenylaminopropyltrimethoxysilane, phenylmethyldiethoxysilane, n-propyltrimethoxysilane .
  • Aminoorganotrialkoxysilanes can preferably be used as spacers.
  • a silane is e.g. B.
  • Commercial 3-aminopropyltrimethoxysilane In the following, this compound is also designated with the abbreviation "N1").
  • the cocatalyst can be chemically or physically anchored to the support.
  • spacers are, for example, compounds such as 3-aminopropyltrimethoxysilane (abbreviation: N1) (example 8), 3- (2-aminoethylamino) propyltrimethoxysilane (abbreviation: N2) (example 9) and 3- [2- (2-aminoethylamino) ethylamino] propyltrimethoxysilane (Abbreviation: N3) (Example 10).
  • one or more reactive groups Ri - R 4 of these compounds react with the support (eg alkoxysilyl), while the functional groups Fi and F 2 with the cocatalyst (eg NH 2 , NHR, OH by chemisorption or NRR 'and OR react by physisorption).
  • the support eg alkoxysilyl
  • the functional groups Fi and F 2 with the cocatalyst eg NH 2 , NHR, OH by chemisorption or NRR 'and OR react by physisorption.
  • the crosslinking of the support is only made possible by adding water or by using water-containing inorganic supports.
  • linker molecules can be used with or without water.
  • the following compounds are suitable as linker molecules, for example
  • linker e.g. B. 1,8-bis (triethoxysilyl) octane (abbreviation C8) (example 3) and bis [(3-trimethoxysiiyl) propyl] amine (abbreviation C3NC3) (example 1) with at least one reactive end group each from RR 3 and R 5 -R 7 , which are connected by a chain, more intensive networking is achieved.
  • This chain can contain the functionalities F- and F 2 in order to connect the cocatalyst in addition to the crosslinking.
  • linkers are used which, for example, per molectile.
  • B. carry two silyl groups with hydrolyzable alkoxy functions, whereby a crosslinking of the particles can be achieved more specifically.
  • the carrier material can be “tailored” in a wide range (examples 2, 4, 5, 6, 7, 8 and 9).
  • spherical silica gel of the designation Monospher 250 (“M250”, monodisperse, particle diameter 250 nm) was used as an example and reacted with commercial silanes, the silica gel being able to be predried, for example at 150 ° C./10 3 mbar, but does not necessarily have to be thermally pretreated.
  • a common aprotic solvent such as. B. toluene, heptane, hexane or pentane
  • CHN analyzes and via the functionalization with aluminum after the reaction of the carrier with trimethylaluminum or triethyl aluminum determined by means of aluminum atomic absorption spectrometry.
  • the achievable loads of NH function on carriers vary between 0.05 to 3.4 mmol / g.
  • the modified silicas were examined in particular with the aid of scanning electron microscopy:
  • the addition of water when modifying the M250 support with the spacers according to a) results in strong crosslinking.
  • the balls can have grown together so strongly that the boundary of the balls is no longer visible (Fig. 1).
  • Figures 2-5 show the same degree of cross-linking of the particles. All carriers were produced under the same conditions: The carrier material M250 was placed in toluene or heptane and heated to boiling for twelve hours without the addition of water. For comparison, 6 was passed through the suspension of M250, 3-aminopropyltrimethoxysilane and bis (3-trimethoxysilylpropyl) amine and humid air for 6.5 hours. As expected, Figures 6 and 7 show stronger networking. However, the degree of crosslinking as described in Example 1 is not achieved.
  • the silanization of still free silanol groups that have not reacted with spacers or linkers can be followed by the subsequent reaction, in situ or in a separate reaction, with substances such as hexamethyldisilazane, trimethylchlorosilane, etc. This ensures that the Al-organic component only reacts with the functional groups in the spacer and or linker. Free silanol groups can still be present because e.g. less reactive silicon alkoxy groups were added to the reaction than there are free silanol groups on the silica gel.
  • a reaction can, however, also be made possible by adding amines which catalyze the condensation of silanols with alkoxysilanes.
  • Aminoorganylalkoxysilanes can therefore react autocatalytically with dry silica. The same was done, for example, by EF
  • Vansant P. Van der Voort, K. C. Vrancken (in: Characterization and chemical Modification ofthe Silica Surface, in Studies in Surface Science and Catalysis, Vol. 93, 1995, Elsevier, Amsterdam.).
  • the amount of water present determines the extent to which the surface modification and crosslinking takes place (exception: the bis [(3-trimethoxysilyl) propyl] amine containing a secondary amine group, which react autocatalytically Due to steric requirements for the amine group, the amount of water that may be present in the system also has a limited influence on the degree of surface modification).
  • the more water there is in the reaction system the stronger the cross-linking on the surface of a particle and the more pronounced the cross-linking through the space, whereby the silica particles are cross-linked with each other.
  • the amount of water that remains on the solid after drying must be taken into account.
  • the drying conditions The amount of water given is the minimum that can be used. In order to use higher amounts of water in modification reactions, the water must be distributed as evenly as possible in the entire solid by metered addition to the silica gel.
  • the amount of water in the examples below was always based on the number of silanol groups per gram of silica gel, which were given as 0.12 mmol OH / g for M250.
  • the molar ratios of B: A were 1: 3 to 1:19.
  • the best molar mixing ratio was found to be 1: 5: 15:15 for 3-aminopropyltrimethoxysilane and bis [(3-tri-methoxysilyl) propyl] amine based on the silanol: B: A: water.
  • the cocatalyst is usually first used and then the catalyst.
  • An Al-organic component is preferably used as the cocatalyst, usually methylaluminoxane.
  • any metallocene or "single site catalyst” can be used as the catalyst. It is conceivable to use bridged (ansa-) as well as unbridged metallocene complexes with (substituted) ⁇ ligands such as cyclopentadienyl, indenyl or fluorenyl ligands. There are symmetrical or asymmetrical complexes with metal central atoms from the 3rd to 8th group of the periodic table of the elements, such as. B. simple zirconium (biscyclopentadienyl) dichloride or compounds as described in DE-A-44 17 542, EP-A-530647 or EP-A-563917.
  • the polymerization is carried out in a known manner in solution, suspension or gas phase polymerization continuously or batchwise at a temperature of 0 ° C. to +200 ° C., preferably between +20 and +100 ° C.
  • the support material is suspended in toluene, a toluene-Al-organic component (usually MAO solution or trimethyl aluminum (TMA) and MAO or triethyl aluminum (TEA) and MAO) is added.
  • a toluene-Al-organic component usually MAO solution or trimethyl aluminum (TMA) and MAO or triethyl aluminum (TEA) and MAO
  • Modified silica can also be modified with TEA, TMA, etc. in aliphatic solvents such as heptane, hexane or pentane.
  • the suspension is then heated to boiling for twelve hours. It is then filtered and washed thoroughly to leave only strongly adhering cocatalyst on the support.
  • the aluminum loads achieved are between 0.9 and 6.01 mmol Al / g and can be determined by means of aluminum atomic absorption spectrometry.
  • the polymerization can be carried out in a pressure autoclave.
  • the supported cocatalyst is added after the reaction a transition metal complex, here zirconocene dichloride, polymerized or copolymerized with an olefin.
  • the investigations carried out showed that by using heterogeneous cocatalysts produced according to the invention in combination with zirconocene dichloride, polymers with changed melting points, molar masses, molar mass distributions and intrinsic viscosities can be obtained.
  • the polymer produced in Example 20 has a melting point of about 137 ° C and is therefore in the range of highly linear polyethene.
  • Metallocene catalysts in homogeneous reaction systems generally have a dispersion index of molecular weight distribution of 2.
  • the intrinsic viscosity was determined to be 7.07 dl / g.
  • the polymer is obtained as a fine-grained, non-dusting product after the polymerization.
  • the cocatalyst (Example 19) and for comparison the homogeneous cocatalyst MAO were used in a three-hour polymerization.
  • the polymerization activity of the heterogeneous cocatalyst after three hours is significantly higher than the activity of the homogeneous cocatalyst MAO.
  • All glassware is evacuated, heated under vacuum and cooled before use. Then it is gassed with nitrogen. The glass equipment is only opened under nitrogen counterflow.
  • Nitrogen content was determined using elemental analysis on a Perkin-Elmer Series II CHN / O Analyzer 2400.
  • Aluminum content determinations are carried out using aluminum atomic absorption spectrometry (AAS) on a Perkin-Elmer 2380 atomic absorption spectrometer using flame AAS.
  • AAS aluminum atomic absorption spectrometry
  • the scanning electron micrographs are taken on a Hitachi S4000 FESEM (Field Emission Scanning Electron Microscope). The samples are sputtered with a 6 nm gold layer, for which they are handled briefly (1 - 2 min) in air.
  • Nitrogen content 0.41% or 0.29 mmol N / g silica.
  • Nitrogen content 0.92% or 0.66 mmol N / g silica.
  • Nitrogen content 0.67% or 0.48 mmol N / g silica. Carbon content: 4.25% C.
  • Nitrogen content 0.47% or 0.34 mmol N / g silica.
  • the suspension is filtered and the filter cake is washed with four times 50 ml of dry hexane and dried in an oil vacuum for 5 hours. A colorless powder is obtained.
  • Nitrogen content 2.81% N or 2.01 mmol N / g silica.
  • Nitrogen content 3.43% N or 2.45 mmol N / g silica.
  • the nitrogen content was 2.74% N or 1.96 N / g silica.
  • Aminoethyl) aminopropyltrimethoxysilane are slowly added dropwise to the suspension.
  • the reaction mixture is heated to boiling for 2 hours, stirred at room temperature for 10 hours and then the azeotrope of methanol / toluene is distilled off.
  • the suspension is filtered and the filter cake is washed three times with 50 ml of dry toluene and four times with 30 ml of dry pentane and dried in an oil vacuum for 5 hours. A colorless powder is obtained.
  • Nitrogen content 3.72% N or 2.66 mmol N / g silica.
  • 59 g of spherical, monodisperse silica with a surface area of 12 m 2 / g and an OH content of 0.12 mmol / g predried at 150 ° C. for 6 hours under an oil vacuum, are in 80 ml of dry toluene and 40 ml of dry heptane suspended and very slowly added 1.2 ml of double distilled water. 0.0708 mol of 3 [2-aminoethyl (2-aminoethyl)] aminopropyltrimethoxysilane are slowly added dropwise to the suspension. The reaction mixture is stirred at 85 ° C.
  • the nitrogen content was 3.5% N or 2.606 mmol N / g silica.
  • Example 12 M250 (PDMS) 5 25.8 g spherical, monodisperse silica with a surface area of 12 m 2 / g and an OH content of 0.12 mmol / g, predried at 150 ° C. for 6 hours under an oil vacuum, were suspended in 100 ml of dry toluene and 0.58 mmol of polydimethylsiloxane were added dropwise. After heating under reflux for 15 h (foaming strongly), the suspension was filtered and the filter cake was washed with 50 ml of dry hexane. It was then dried in an oil pump vacuum. A colorless powder is obtained. 5 The carbon content was 2.42% C. Preparation of the cocatalyst
  • a suspension of 14 g of the carrier from Example 1 in 80 ml of dry toluene is mixed with 95 ml of a 10% toluene solution of methylaluminoxane and heated to boiling for 12 hours. It is then filtered, washed four times with 60 ml of dry hexane and then dried in an oil vacuum for 12 hours. A colorless powder is obtained.
  • Aluminum content 1.55 mmol Al / g (determined by atomic absorption spectrometry).
  • a suspension of 17 g of the carrier from Example 2 in 90 ml of dry toluene is mixed with 95 ml of a 10% toluene solution of methylaluminoxane and heated to boiling for 12 hours. It is then filtered, washed with 40/20/30/50 ml of dry toluene and twice 30 ml of dry hexane and then dried in an oil vacuum for 5 hours. A colorless, dusting powder is obtained.
  • a suspension of 21.4 g of the carrier from Example 3 in 100 ml of dry toluene is mixed with 67 ml of a 10% toluene solution of methylaluminoxane and heated to boiling for 12 hours. It is then filtered, washed with 30 and 50 ml of dry toluene and twice with 30 and 40 ml of dry hexane and then dried in an oil vacuum for 5 hours. A colorless powder is obtained.
  • Example 16 M250 (C8) N1 7MAO A suspension of 21.1 g of the carrier from Example 5 in 100 ml of dry toluene is mixed with 65 ml of a 10% toluene solution of methylaluminoxane and heated to boiling for 12 hours. It is then filtered, washed with four times 40 ml of dry toluene and three times with 40 ml of dry hexane and then dried in an oil vacuum for 5 hours.
  • a colorless powder is obtained.
  • Example 17 M250 (C3NC3) N3 / TEA
  • a suspension of 28.2 g of the carrier from Example 7 in 130 ml of dry toluene is mixed with 0.183 mol of triethylaluminum and heated to boiling for 62 hours. It is then filtered, washed with 70 and twice 40 ml of dry hexane and then dried in an oil vacuum for 5 hours. A colorless powder is obtained.
  • Example 18 M250 (C3NC3) N3 / MAO
  • a suspension of 18.7 g of the carrier from Example 7 in 130 ml of dry toluene is mixed with 100 ml of a 10% toluene solution of methylaluminoxane and heated to boiling for 62 hours. The mixture is then filtered, washed with 50 and four times 40 ml of dry toluene and twice 40 ml of dry hexane and then dried in an oil vacuum for 5 hours. A colorless powder is obtained.
  • Example 19 M250 (C3NC3) N3 / TEA / MA0
  • a suspension of 21.1 g of the modified carrier from Example 17 is suspended with 200 ml of a 10% toluene solution of methyialuminoxane and heated to boiling for 60 hours. It is then filtered hot, with five times 50 ml of hot, dry toluene and Washed twice 50 ml dry hexane and then dried in an oil vacuum for 5 hours. A colorless powder is obtained.
  • Example 20 M250 (C3NC3) N1 / MAO
  • a suspension of 12.8 g of the carrier from Example 6 in 100 ml of dry toluene was mixed with 50 ml of a 10% toluene solution of MAO and heated to boiling for 12 h. The mixture was then filtered hot, washed with four times 40 ml of hot, dry hexane and then dried in an oil vacuum for 5 hours. A colorless powder was obtained.
  • the aluminum content was 2.84 mmol Al / g (AAS).
  • a suspension of 18.2 g of the carrier from Example 11 in 100 ml of dry toluene was mixed with 120 ml of a 10% toluene solution of methylaluminoxane and heated to boiling for 20 hours. The mixture was then filtered, washed twice with 40 ml of dry toluene and twice with 50 ml of dry hexane and then dried in an oil vacuum. A colorless, dusting powder was obtained.
  • the aluminum content was 3.32 mmol Al / g (AAS).
  • a suspension of 9.7 g of the carrier from Example 12 in 80 ml of dry toluene was mixed with 70 ml of a 10% toluene solution of methylaluminoxane and heated to boiling for 18 hours. It was then filtered, washed three times with 35 ml of dry toluene and twice 40 ml of dry hexane and then dried in an oil vacuum. A colorless powder was obtained.
  • the aluminum content was 2.66 mmol Al / g (AAS). polymerizations
  • the catalytic activities of the heterogeneous cocatalysts shown are investigated under constant conditions in a 500 ml glass autoclave.
  • Triisobutyl aluminum is used as scavenger.
  • Pre-activated systems are used for the polymerization: the cocatalyst and catalyst are stirred in a little solvent for 10 minutes and then added to the reactor. Ethen is then pressed on.
  • the pressure and temperature are kept constant throughout the polymerization. After an hour of reaction, the polymerization is terminated by releasing the pressure and adding ethanol. For working up, the polymer suspension in toluene is stirred for several hours with dilute hydrochloric acid and then filtered, washed until neutral and dried to constant weight.

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Abstract

L'invention concerne un procédé permettant de produire de nouveaux supports de catalyseurs à base d'oxydes sphériques et non sphériques inorganiques modifiés, un procédé permettant de produire des catalyseurs métallocène ou </= à site unique >/= supportés, en combinaison avec un cocatalyseur, ainsi que leurs utilisation dans le cadre de la polymérisation de l'oléfine. L'invention concerne par ailleurs l'utilisation des éduits requis pour mettre ledit procédé en oeuvre, des séparateurs ou des lieurs, utilisés pour produire le métallocène supporté.
PCT/EP2002/010693 2001-10-20 2002-09-24 Modification chimique de surfaces de particules par reticulation WO2003035252A1 (fr)

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WO2004089961A1 (fr) * 2003-04-07 2004-10-21 Consortium für elektrochemische Industrie GmbH Particules fonctionnalisees organosilyle et leur production
JP2006241084A (ja) * 2005-03-03 2006-09-14 Tokyo Univ Of Science 表面改質剤、細胞親和性材料、細胞親和性材料の製造方法並びに、骨様移植物及び骨様移植物の製造方法。

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US4912075A (en) * 1987-12-17 1990-03-27 Exxon Chemical Patents Inc. Method for preparing a supported metallocene-alumoxane catalyst for gas phase polymerization
EP0893467A2 (fr) * 1997-07-21 1999-01-27 Dow Corning Corporation Epaissisement d'un solvant au moyen d'un latex de silicone stabilisé au moyen d'un silicone polyether

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US4912075A (en) * 1987-12-17 1990-03-27 Exxon Chemical Patents Inc. Method for preparing a supported metallocene-alumoxane catalyst for gas phase polymerization
EP0893467A2 (fr) * 1997-07-21 1999-01-27 Dow Corning Corporation Epaissisement d'un solvant au moyen d'un latex de silicone stabilisé au moyen d'un silicone polyether

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004089961A1 (fr) * 2003-04-07 2004-10-21 Consortium für elektrochemische Industrie GmbH Particules fonctionnalisees organosilyle et leur production
US7816009B2 (en) 2003-04-07 2010-10-19 Wacker Chemie Ag Organosilyl functionalized particles and the production thereof
JP2006241084A (ja) * 2005-03-03 2006-09-14 Tokyo Univ Of Science 表面改質剤、細胞親和性材料、細胞親和性材料の製造方法並びに、骨様移植物及び骨様移植物の製造方法。

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