KR100460362B1 - Method for producing catalyst support, Supported polyolefin catalyst and method for producing polyolefin - Google Patents

Abstract

The present invention is to dry the hydrophilic inorganic oxides or mixtures or mixed oxides of Group II to Group IV elements of the periodic table of the elements or Group IV elements of the transition group at 110 to 800 ℃, if necessary, The present invention relates to a method for preparing a catalyst support which is reacted with aluminoxane or aluminum alkyl and then simultaneously reacted with aluminoxane and a multifunctional organic crosslinker. In a further step, the catalyst support is contacted with a polyolefin catalyst to obtain a supported polyolefin catalyst which is used in particular for olefin polymerization.

Description

Process for preparing catalyst support, supported polyolefin catalyst and process for preparing polyolefin

The present invention relates to catalyst supports based on inorganic oxides, supported polyolefin catalysts produced during the use of these catalyst supports and their use in olefin polymerization.

Polypropylenes include, for example, polyolefins comprising metallocenes and activators or promoters such as methylaluminoxane (MAO) or perfluorotetraphenylborate as described in EP 530 647. It can be prepared by using a catalyst. However, using such a homogeneous catalyst for polymerization yields only powders of low bulk density. The particle morphology of this product can be improved to some extent by special pretreatment of the metallocene with the original promoter (EP 302 424). However, this method has the disadvantage of forming heavy deposits, especially in industrial reactors (EPA 563 917).

The use of methylaluminoxane, which is insoluble in aliphatic solvents as the support material, improves the activity somewhat, but it also produces finely divided products (see Polymer 1991, Vol. 32, 2671-2673), which is also uneconomical. to be.

The support of metallocenes on oxidative materials such as silicon oxide or aluminum oxide by pretreatment of partially dehydrated starting materials with cocatalysts is known from WO 91/09882, which is used for homopolymerization and copolymerization of ethylene. That's how it is. However, in this method, the particle size of the polymer particles is essentially measured by the particle size of the support material, so there is a limit to increasing the particle size compared to conventional catalysts supported on magnesium chloride. Further methods describe the use of MAO to modify the oxidative support followed by the application of metallocene (EPA No.0206794). However, this method limits particle size control by the properties of the support material.

EP 685 494 provides another support prepared by applying methylaluminoxane to a hydrophilic oxide, crosslinking MAO using a multifunctional organic crosslinker, and then applying an activated MAO / metallocene complex. Catalysts are described. A disadvantage of these supported catalysts is that the strength of the supported catalysts at relatively high polymerization conversion rates achieved in industrial installations is not sufficient to obtain dense granular polymer products. This reduces the bulk density and increases the proportion of particulates, which causes considerable problems in the art.

It is therefore an object of the present invention to produce a supported polyolefin catalyst that can be used for olefin polymerization and to develop a process that overcomes the above disadvantages even when the polymerization conversion is high.

Surprisingly, in the present invention, when a specific support material is used and the catalyst is subsequently fixed to the support, the use of these supported polyolefin catalysts to polymerize the olefins yields high polymerization conversion, high bulk density products, It has been found that the particle size and particle size distribution of the polymer can be set in the desired manner.

Therefore, the present invention

(A) drying a hydrophilic inorganic oxide or a mixture or mixed oxides of the group II to IV elements of the periodic table of the elements or the group IV elements of the transition group at 110 to 800 ° C.,

Optionally, (b) reacting the free hydroxyl group of the oxide with or without aluminoxane or aluminum alkyl, and

Provided is a method of preparing a catalyst support, comprising the step (c) of reacting an oxide simultaneously with an aluminoxane and a multifunctional organic crosslinker.

The hydrophilic hydroxyl containing oxide used usually contains water. They are preferably macroporous and finely divided, typically having an average particle size of 10 to 300 microns, preferably 30 to 100 microns. Support oxides are commercially available and preference is given to using aluminum oxide, silicon oxide, magnesium oxide, titanium oxide and zirconium oxide. In particular, it is preferable to use Grace Davison-type silicon dioxide. However, other suitable starting materials are finely divided oxides, which are described, for example, in DE-C 870 242 or EP-A 585 544 and hot hot water from gaseous metal chlorides or silicon compounds. It is prepared by the decomposition method.

The invention also provides a catalyst support prepared by the process of the invention. The catalyst support of the present invention is prepared from hydrophilic inorganic oxides in a multistage reaction.

In a first step (a), the oxide is dehydrated under a stream of nitrogen or under reduced pressure over a period of 1 to 24 hours at a temperature of from 110 to 800 ° C. The concentration of the free hydroxyl group set as a function of the selected drying temperature is then measured. The free hydroxyl group can be reacted completely or partially with the aluminoxane or aluminum alkyl in step (b).

In step (c), the dried oxide is reacted simultaneously with the at least one multifunctional organic crosslinker with the aluminoxane suspended in a suitable hydrocarbon solvent such as, for example, toluene, in a solvent-coated manner. The solvents for the aluminoxanes and crosslinkers should be miscible and the same solvents are preferably used. Particular preference is given to using toluene.

According to the invention, the aluminoxanes used are the straight chain aluminoxanes of formula (1) and / or the cyclic aluminoxanes of formula (2).

[Formula 1]

[Formula 2]

In Chemical Formulas 1 and 2,

R may be the same or different and each is a C ₁ -C ₆ -alkyl group,

n is an integer from 1 to 50.

Preferably, the radicals R are the same and are methyl, isobutyl, phenyl or benzyl. Aluminoxane can be manufactured by various methods by a well-known method. One possibility is for example to react aluminum alkyl with aluminum sulphate containing crystalline water (see EP-A 302424 to Hoechst). In the present invention, it is preferable to use commercially available methylaluminoxane (trade name: MAO, manufactured by Witco) dissolved in toluene.

In the preparation of the catalyst support, the molar ratio of aluminum (as aluminoxane) to the surface hydroxyl groups is 1 to 50, preferably 1 to 30, particularly preferably 5 to 20.

In order to prepare the solution required for step (c), the solvent used for the crosslinker is the same solvent used for the MAO solution. Due to the temperature dependence of the solubility of these crosslinkers in the solvent used, the desired concentration can be set by selecting the temperature of the solution in the desired manner. It is particularly advantageous to select a solvent whose boiling point is below the decomposition temperature of the solid produced in step (c). Preference is given to using aromatic solvents such as xylene, benzene or toluene. Toluene is particularly suitable.

Suitable multifunctional organic crosslinkers used according to the invention are any organic compound having at least one functional group capable of reacting with metal-carbon bonds. Preference is given to using bifunctional crosslinkers. Such bifunctional organic compounds can be, for example, aliphatic or aromatic diols, aldehydes, dicarboxylic acids, primary or secondary diamines, diepoxy compounds. In order to avoid reaction products that require coherent secondary reactions or further purification, preference is given to using aliphatic and aromatic diols, secondary amines or diepoxy compounds or mixtures thereof. Particular preference is given to using ethylene glycol, butanediol, bisphenol A and 1,4-butanediol diglycidyl ether. Trifunctional or higher crosslinkers that can be used are, for example, triethanolamine, glycerol, phloroglucinol or tetraethylenepentamine.

When using a multifunctional crosslinker, it is also possible to deactivate unreacted reactive groups in further reaction steps, for example with an alkylaluminum compound, preferably trimethylaluminum.

The molar ratio between the aluminum and the crosslinker used in step (c) as aluminoxane can vary within a wide range and is 1: 100, preferably 1:40, particularly preferably 10:25. This depends in particular on the type and pretreatment of the metal oxide, the type of aluminoxane used, the respective molar ratio of A1 (as aluminoxane) to the surface hydroxyl groups on the metal oxide and the type of crosslinker. In particular when using trifunctional or higher crosslinking agents capable of correspondingly forming a large number of crosslinks, a high molar ratio of A1 to the crosslinking agent is used.

The oxide suspended and dried in step (a) is preferably treated with an aluminoxane solution and at least one multifunctional organic crosslinker solution in the same solvent. If necessary, in step (b), the free hydroxyl group of the oxide may be reacted with up to equimolar amounts of aluminoxane or aluminum alkyl solution (eg trimethylaluminum) before the crosslinking reaction. It is preferable to use MAO for this purpose. It has been found to be particularly advantageous when all hydroxyl groups react. However, partial response of these groups also provides a positive effect.

The solution is metered in continuously and simultaneously, and the crosslinker solution is heated / cooled as necessary. The temperature at which the solution is heated / cooled depends on the solubility of the crosslinker in the selected solvent and the desired crosslink density on the support surface. The rate at which two streams are metered in can be set with a metering pump and the range is from 0.1 to 1000 ml per minute, preferably from 0.5 to 250 ml per minute and particularly preferably from 1 to 50 ml per minute. It is preferable to carry out the reaction in such a manner that all the MAOs are reacted after the metered introduction of the solution in two solutions simultaneously. Under some circumstances, fluctuations in reaction conditions on an industrial scale may leave unreacted MAO in solution. Useful catalyst supports described in EP 685494 indicate that, based on the MAO used, the proportion of soluble A1 in the solvent used is less than 1.4 mol%. In this case, one or more washing steps can be performed to reduce the concentration below the desired limit.

After the metered introduction is terminated, the reaction mixture is further stirred for about 60 minutes and then the solvent is removed. The residue can be dried under reduced pressure, but it is also preferred to use it in a wet state.

The catalyst support produced by the process of the invention can be advantageously used for the preparation of supported polyolefin catalysts.

The present invention therefore also provides a supported polyolefin catalyst comprising the reaction product of the catalyst support (A) and the polyolefin catalyst or mixture (B) of a plurality of polyolefin catalysts according to the invention. Possible polyolefin catalysts are, for example, metallocenes, which can originally react certain metallocenes or metallocene mixtures. Possible metallocenes are, for example, unsubstituted or substituted cyclopentadienyl, indenyl and fluorenyl compounds without bridges of Group IVb, Vb or VIb metals of the Periodic Table of Elements [e.g., bis ( 1,2-dimethylcyclopentadienyl) zirconium dichloride (see EP-A 283739)], unsubstituted or substituted asymmetric with bridges of Group IVb, Group Vb or Group VIb metals of the Periodic Table of the Elements Or symmetrical cyclovalentadienyl, indenyl and fluorenyl compounds such as dimethylsilanediylbis (indenyl) zirconium dichloride (see EP-A 574597), dimethylsilanediylbis (2-methyl Indenyl) zirconium dichloride (see EP-A No. 485822), bis (trimethylsilyl) silanediylbis (2-methylindenyl) zirconium dichloride (see DE-A No. 19527047) or isopropylidene (Cyclopentadienyl) (fluorenyl) zirconium dichlori It is: (see EP-A-351 391 call).

Supported metallocene catalysts are prepared by suspending the catalyst support of the invention in an inert hydrocarbon, preferably toluene, and contacting it with metallocene. In this process, the metallocene is dissolved in, for example, an inert hydrocarbon. Inert solvents that can be used are, for example, aliphatic or aromatic hydrocarbons, preferably toluene. It is preferable to use the metallocene in an amount of 0.3 to 5% by mass based on the total mass of the supported catalyst. The mixing time is 5 minutes to 24 hours, preferably 1 to 6 hours. Mix at a temperature of -10 to + 80 ° C, in particular 20 to 70 ° C. It is preferable to reduce the drying step by applying metallocene after synthesizing the support. After the reaction is complete, the solvent is decanted off and removed under reduced pressure until free flowing solid remains.

The metallocene content of the supported catalyst is from 0.01 to 5% by weight, preferably from 0.1 to 3% by weight, based on the mass of the supported catalyst.

For example, Group IV-VIII transition metal salts, which are known as Ziegler / Natta catalysts and are described, for example, in European Patent Application No. 95110693, are transition groups of the Periodic Table of the Elements. Based polyolefin catalysts can also be used.

The present invention also provides a process for preparing polyolefins by polymerization or copolymerization of olefins, wherein the polymerization catalyst used is the supported polyolefin catalyst of the present invention, and also in the polymerization or copolymerization of olefins for producing polyolefins. Provided is the use of the supported polyolefin catalyst according to the invention.

The supported catalyst of the invention can be introduced into the polymerization mixture as a powder or as a suspension in an inert hydrocarbon such as pentane, hexane, cyclohexane or mineral oil.

The polymerization is carried out continuously or batchwise in a known manner by solution, suspension or gas phase processes at a temperature of -10 to +200 ° C, preferably +20 to +80 ° C.

The supported catalyst of the present invention is polymerization activity without further activator. However, it has been found to be particularly advantageous to use aluminum alkyls, preferably trimethylaluminum, triethylaluminum or triisobutylaluminum as scavengers and further activators. The amount used is 50 to 5000 mol, preferably 100 to 500 mol, per mol of the transition metal of the polyolefin catalyst based on aluminum.

The polymerization or copolymerization is carried out on the olefins of the formula R ^a -CH = CH-R ^b . In this formula, R ^a and R ^b are the same or different and are each hydrogen or alkyl having 1 to 20 carbon atoms. However, R ^a and R ^b may form a ring together with the carbon atom which bonds them. For example, olefins such as ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, cyclopentene, norbornene or norbornadiene are polymerized or copolymerized. Preference is given to polymerizing or copolymerizing ethylene, propylene and butenes, particularly preferably ethylene and propylene.

If necessary, hydrogen is added as molecular weight regulator. The total pressure in the polymerization is usually 0.5 to 150 bar. Preference is given to carrying out the polymerization at a pressure in the range from 1 to 40 bar.

When the polymerization is carried out as suspension polymerization or solution polymerization, an inert solvent is used. For example, aliphatic or cycloaliphatic hydrocarbons such as pentane, hexane or cyclohexane can be used. Toluene can also be used. Preference is given to carrying out the polymerization with liquid monomers.

In the copolymerization of ethylene and propylene, preference is given to carrying out the polymerization in liquid propylene or hexane as a suspending medium. In polymerization in liquid propylene, ethylene has a partial pressure ratio P _C3 / P _C2 to the liquid phase, where P _C2 is the partial pressure of gaseous ethylene to the suspension and P _C3 is the partial pressure of gaseous propylene to the suspension. Preference is given to feeding in excess, in particular above 1.0. Upon copolymerization in hexane as a suspending medium, an ethylene / propylene gas mixture is fed with a propylene content of 1 to 50 mol%, preferably 5 to 30 mol%. The total pressure is kept constant during the polymerization by metering in the additional amount. The total pressure is 0.5 to 40 bar, preferably 1 to 20 bar. The polymerization time is 10 minutes to 6 hours, preferably 30 minutes to 2 hours.

Supported catalysts used in accordance with the present invention allow the preparation of homopolymers, copolymers or block copolymers. Using these, the particle size of the polymer can be adjusted in a desired manner as a function of the manufacturing conditions used for support. Thus, a particular advantage of the catalyst of the present invention is the fact that the particle size of the polymer can meet the respective conditions of the technique used.

In addition to being able to control the particle size and particle size distribution in the desired manner, the process of the present invention also has the advantage that polyolefins with high bulk density and low fine powder content can be obtained in granule form, especially at high polymerization conversion rates. .

The manufacturing techniques provide further advantages. The catalyst can in principle be produced in a suitable reaction in which no coherent by-products are formed by the "single-vessel process" and the solvent used can be recycled.

The following examples are intended to illustrate the invention.

Abbreviations used are shown in Table 1 below.

Example

Example 1

Preparation of Supported Catalyst A

15 g of silicon dioxide (Grace grade 955W) are dried in a drying tube at 200 ° C. for 4 hours under nitrogen backflow. OH content is 1.83 mmol / SiO ₂ g.

In a three-necked flask equipped with a stirrer and two dropping funnels, 3.3 g of the dried oxide was suspended in 60 ml of anhydrous toluene. In the first dropping funnel, 6.27 g (30.2 mmol of aluminum) solution of 30% methyl aluminoxane in toluene was mixed with 95 ml of toluene, and the second dropping funnel contained bisphenol A solution and oxygen-free toluene (total beepphenol content: bisphenol). A 275.8 mg; 1.208 mmol) 100 ml. With gentle stirring, 20 ml of MAO solution is initially introduced into the suspension and both solutions are added dropwise simultaneously. The stirring speed during this process is 200 rpm. The dropping rate is slowed down and the two solutions are chosen to be consumed at a suitable reduction in volume. The suspension is further stirred for 1 hour and then left to stand. A fine white solid precipitates out. The supernatant toluene is removed and the residue is again dissolved in toluene and washed at 70 ° C. for 15 minutes. The aluminum content of the wash solution is 0.08 mol% (based on the mol of aluminum used). After removing the supernatant wash, a solution containing 0.096 mmol of bis (trimethylsilyl) silanediylbis (2-methylindenyl) zirconium dichloride (prepared as described in German Patent Application No. 19527047) and 60 ml of toluene is added. . The suspension becomes dark orange and this color becomes darker during stirring. After 10 hours, when the stirrer is stopped, the clear supernatant no longer discolors. The solvent is removed at 50 ° C. under reduced pressure to give a red / orange finely divided solid.

Example 2

Polymerization with Supported Catalyst A

A 2 L stirred reactor (Buchi) was inactivated and then charged with 1.2 ml of 1 M triisobutylaluminum / hexane solution and 200 g of liquid propylene at room temperature and the mixture was stirred at 350 rpm for 3 minutes.

110 mg of the supported catalyst A prepared in Example 1 was washed with additional 300 g of propylene in the reactor, the stirring speed was increased to 700 rpm, the mixture was heated to a polymerization temperature of 70 ° C. for 15 minutes, and this temperature was kept constant. Keep it. After 2 hours the reaction is terminated by flashing propylene. 220 g of polypropylene having an average particle diameter (d ₅₀ ) measured by sieve analysis of 315 mu m and a fine powder content (less than 100 mu m) of 1.5% by weight are obtained. Activity is 2 kg / g supported catalyst. The polymer particles are granular (M _W = 385,000 g / mol; polydispersity 2.5: T _m = 147 ° C.) and no deposits remain on the reactor walls.

Example 3

Preparation of Supported Catalyst B

Supported catalyst B is prepared in a similar manner to the supported catalyst preparation method of Example 1. 2.97 g of the dried oxide is suspended in 60 ml of anhydrous toluene. In the first dropping funnel, 11.3 g (54.4 mmol of aluminum) solution of 30% methyl aluminoxane in toluene was mixed with 190 ml of toluene, and the second dropping funnel contained bisphenol A solution and toluene (total bisphenol A: 558.85 mg; 2.448 mmol) 200 ml. With gentle stirring, initially 50 ml of the MAO solution is added to the suspension, and then both solutions are slowly added dropwise at the same time. After the reaction is complete, the mixture is stirred for 1 hour and then washed twice with toluene. After removing the supernatant, a solution comprising 0.133 mmol of dimethylsilanediylbis (2-methylindenyl) zirconium dichloride (manufactured by Boulder Scientific Company) and 80 ml of toluene is added. After 10 hours the stirrer is stopped. After removing the supernatant, the solid is washed twice more with toluene and then dried at 50 ° C. under reduced pressure.

Example 4

Polymerization Using Supported Catalyst B

The polymerization is carried out in a similar manner as in Example 2, except that 67 mg of supported catalyst B and 1.2 ml of 1 M TIBAL / hexane solution are used. 114 g of polypropylene having an average particle diameter (d ₅₀ ) of 500 μm and a fine powder content (less than 100 μm) of 0.8 wt%, determined by sieve analysis, are obtained. Yield is 1.7 kg / g supported catalyst. The polymer particles are granular (M _W = 307,000 g / mol; polydispersity 2.3; T _m = 147 ° C.).

Example 5

Polymerization Using Supported Catalyst B

The 20 L capacity stirred reactor was deactivated and then charged with 14 ml of 1 M triisobutylaluminum / hexane solution and 6500 g of liquid propylene at room temperature and the mixture was stirred at 300 rpm for 5 minutes.

335 mg of the supported catalyst B prepared in Example 3 was washed further with 500 g of propylene in the reactor, the stirring speed was increased to 400 rpm, and the mixture was heated to a polymerization temperature of 70 ° C. over 20 minutes, followed by Keep the temperature constant. After 2 hours, the excess monomer is flashed to terminate the reaction. 856 g of polypropylene having an average particle diameter (d ₅₀ ) measured by a sieve analysis of 500 µm and a fine powder content (less than 100 µm) of 0.35% by weight are obtained. Activity is 2.14 kg / g supported catalyst. The polymer particles are granular and have glass flowability (M _W = 316,000 g / mol; polydispersity 2.4; T _m = 147 ° C.) and no deposits remain on the reactor walls.

Example 6

Polymerization Using Supported Catalyst B

The 20 L capacity stirred reactor was inactivated and then charged with 3 ml of 1 M triisobutylaluminum / hexane solution and 6500 g of liquid propylene at room temperature and the mixture was stirred at 300 rpm for 5 minutes.

408 mg of the supported catalyst B prepared in Example 3 was washed further with 500 g of propylene in the reactor, the stirring speed was increased to 400 rpm, and the mixture was heated to a polymerization temperature of 70 ° C. over 20 minutes, and then the temperature was Keep it constant. After 2 hours the reaction is terminated by flashing excess monomer. 1023 g of polypropylene having an average particle diameter (d ₅₀ ) measured by sieve analysis of 500 µm and a fine powder content (less than 100 µm) of 0.2% by weight are obtained. Activity is 2.5 kg / g supported catalyst. The polymer particles are granular and free flowing (M _W = 301,000 g / mol; polydispersity 2.5: T _m = 147 ° C.) and no deposits remain on the reactor walls.

Example 7

Preparation of Supported Catalyst C

12 g of silicon dioxide (Grace grade 955W) are dried in a drying tube at 120 ° C. over 4 hours under nitrogen backflow. OH content is 2.26 mmol / SiO ₂ g.

In a three-necked flask equipped with a stirrer and two dropping funnels, 2.97 g of dried oxide was suspended in 60 ml of anhydrous toluene. In the first dropping funnel, 8.45 g (40.69 mmol of aluminum) solution of methylaluminoxane at 30% concentration in toluene was mixed with 100 ml of toluene, and the second dropping funnel contained bisphenol A solution and oxygen-free toluene (total bisphenol A content: bisphenol A). 459 mg; 2.01 mmol) 180 ml are charged. With gentle stirring, initially 20 ml of MAO solution is introduced into the suspension, and then both solutions are added dropwise at the same time. The stirring speed during this process is 200 rpm. The dropping rate is lowered and the two solutions are chosen to be consumed at a suitable reduction in volume. The suspension is then stirred for an additional hour and then left to stand. A fine white solid precipitates out. The supernatant toluene is removed and the residue is again dissolved in toluene and washed at 70 ° C. for 15 minutes. The aluminum content of the wash solution is 0.09 mol% (based on the mol of aluminum used). After removing the supernatant, a solution containing 0.102 mmol of dimethylsilanediylbis (2-methylindenyl) zirconium dichloride (Boulder Scientific Company) and 60 ml of toluene is added. The suspension turns orange and this color grows darker during the stirring process. The mixture is stirred at 70 ° C. for 5 hours, the clear supernatant is removed and the solid is washed again with toluene at 70 ° C. Subsequently, the residue is dried at 50 ° C. under reduced pressure to give a red / orange fine solid.

Example 8

Polymerization Using Supported Catalyst C

However, the polymerization is carried out in a similar manner to Example 2, except that 68 mg of supported catalyst C and 0.8 ml of 1 M TIBAL / hexane solution are used.

80 g of polypropylene having an average particle diameter (d ₅₀ ) measured by sieve analysis of 400 mu m and a fine powder content (less than 100 mu m) of 0.8 wt% is obtained. Yield is 1.17 kg / g supported catalyst. The polymer particles are granular (M _W = 316,000 g / mol; polydispersity 2.3, T _m = 146 ° C .; bulk density 0.31 g / cm 3).

Example 9

Polymerization Using Supported Catalyst C

The polymerization is carried out in a similar manner to Example 2, except that 98 mg of supported catalyst B and 2 ml of 1 M TIBAL / hexane solution are used. However, unlike the previous examples, only half of the TIBAL solution was initially charged with 200 g of polypropylene, the other half was added directly to the supported catalyst in the catalyst feeder, and with the TIBAL solution before metering into the reactor. The residence time of the remaining catalyst is 5 minutes.

110 g of polypropylene having an average particle diameter (d ₅₀ ) measured by sieve analysis of 400 mu m and a fine powder content (less than 100 mu m) of 0.51% by weight is obtained. Yield is 1.12 kg / g supported catalyst. The polymer particles are granular (bulk density 0.33 g / cm 3; M _W = 339,000 g / mol; polydispersity 2.4; T _m = 147 ° C.).

Example 10

Polymerization Using Supported Catalyst C

The polymerization was carried out in a similar manner as in Example 5 except that 508 mg of supported catalyst C and 7.5 ml of 1 M TIBAL / hexane solution were used in a 20 L reactor. 910 g of polypropylene having an average particle diameter (d ₅₀ ) of 400 μm and a fine powder content (less than 100 μm) measured by sieve analysis of 0.15% by weight are obtained. Activity is 1.8 kg / g supported catalyst. The polymer particles are granular and free flowing, with no deposits remaining on the reactor walls.

Example 11

Preparation of Supported Catalyst D

In a three-necked flask equipped with a stirrer and two dropping funnels, 3.0 g of oxide (as in Example 7) dried at 120 ° C. are suspended in 60 ml of anhydrous toluene. In the first dropping funnel, 11.3 g (54.4 mmol of aluminum) solution of methylaluminoxane in 30% concentration in toluene was mixed with 210 ml of toluene, and the second dropping funnel contained bisphenol A solution and oxygen-free toluene (total bisphenol content: bisphenol A 559 mg). 2.44 mmol) 220 ml. Initially, 20 ml of the MAO solution is introduced into the suspension with gentle stirring, and both solutions are added dropwise simultaneously. The stirring speed during this process is 200 rpm. The dropping rate is slowed down and the two solutions are chosen to be consumed at a suitable reduction in volume. The suspension is stirred for an additional hour and then left to stand. A fine white solid precipitates out. The supernatant toluene is removed and the residue is again dissolved in 180 ml of toluene and washed at 70 ° C. for 15 minutes. The aluminum content of the wash solution is 0.6 mol% (based on the mol of aluminum used). After removing the supernatant, a solution containing 0.136 mmol of dimethylsilanediylbis (2-methylindenyl) zirconium dichlorine (Boulder Scientific Company) and 80 ml of toluene is added. The suspension turns orange and this color grows darker during the stirring process. The mixture is stirred at 70 ° C. for 8 hours, the clear supernatant is removed and the solid is washed again with toluene at 70 ° C. Subsequently, drying the residue at 50 ° C. under reduced pressure gives a red / orange finely divided solid.

Example 12

Polymerization Using Supported Catalyst D

The polymerization is carried out in a similar manner as in Example 2, except that 66 mg of supported catalyst D and 1.2 ml of 1 M TIBAL / hexane solution are used.

164 g of polypropylene are obtained in the state that the average particle diameter (d ₅₀ ) measured by the sieve analysis is 400 m and no fine powder (less than 100 m). Yield is 2.48 kg / g supported catalyst. The polymer particles are granular (M _W = 312,000 g / mol; polydispersity 2.4: T _m = 147 ° C .; bulk density 0.31 g / cm 3).

Example 13

Polymerization Using Supported Catalyst D

The polymerization was carried out in a similar manner as in Example 2, except that 66 mg of supported catalyst D and 0.8 ml of 1 M TIBAL / hexane solution were used.

206 g of polypropylene are obtained in the state that the average particle diameter (d ₅₀ ) measured by the sieve analysis is 500 µm and there is no fine powder (less than 100 µm). Yield is 3.12 kg / g supported catalyst. The polymer particles are granular and glass flowable (M _W = 301,000 g / mol; polydispersity 2.3; T _m = 148 ° C.) and no deposits remain on the reactor walls.

Example 14

Polymerization Using Supported Catalyst D

The polymerization is carried out in a similar manner as in Example 2, except that 69 mg of supported catalyst D and 0.6 ml of 1 M TIBAL / hexane solution are used.

220 g of polypropylene is obtained in the state that the average particle diameter (d ₅₀ ) measured by the sieve analysis is 500 µm and there is no fine powder (less than 100 µm). Yield is 3.18 kg / g supported catalyst. The polymer particles are granular and glass flowable (M _W = 294,000 g / mol; polydispersity 2.4; T _m = 148 ° C.) and no deposits remain on the reactor walls.

Example 15

Preparation of Supported Catalyst E

Supported catalyst E is prepared in a similar manner to the preparation of the supported catalyst of Example 1. 3.2 g of the dried oxide is suspended in 80 ml of anhydrous toluene. In the first dropping funnel, 12.16 g (58.5 mmol of aluminum) solution of methylaluminoxane in 30% concentration in toluene was mixed with 190 ml of toluene, and the second dropping funnel contained bisphenol A solution and toluene (total bisphenol A: 601.5 mg; 2.63 mmol) 200 ml. Initially 50 ml of the MAO solution is introduced into the suspension with gentle stirring, and then both solutions are added dropwise simultaneously. After the reaction is complete, the mixture is stirred for 1 hour and then washed twice with toluene. The supernatant was removed and a solution containing 0.155 mmol of dimethylsilanediylbis (indenyl) zirconium dichloride (Witco) and 80 ml of toluene was added. After 6 hours the stirrer is stopped. After removing the supernatant, the solid is washed again with toluene and then dried at 50 ° C. under reduced pressure.

Example 16

Polymerization Using Supported Catalyst E

The polymerization was carried out in a similar manner as in Example 2, except that 51 mg of supported catalyst E and 0.4 ml of 1 M TIBAL / hexane solution were used. The polymerization time is 1 hour.

110 g of polypropylene having an average particle diameter (d ₅₀ ) measured by sieve analysis of 400 µm and a fine powder content (less than 100 µm) of 0.7% by weight is obtained. The yield is 2.16 kg / g supported catalyst. The polymer particles are granular and glass flowable (M _W = 40,000 g / mol; polydispersity 2.3, T _m = 136 ° C.) and no deposits remain on the reactor walls.

Example 17

Preparation of Supported Catalyst F

In a three-necked flask equipped with a stirrer and two dropping funnels, 3.47 g of the dried oxide as in Example 1 was suspended in 80 ml of anhydrous toluene. In the first dropping funnel, 13.28 g (63.5 mmol of aluminum) solution of 30% methylaluminoxane in toluene was mixed with 187 ml of toluene, and the second dropping funnel contained a saturated solution of bisphenol A and oxygen-free toluene (total bisphenol content: bisphenol A 655 mg; 2.87 mmol) 201 ml is charged. Then both solutions are added dropwise at the same time. The stirring speed during this process is 200 rpm. The dropping rate is slowed down and the two solutions are chosen to be consumed at a suitable reduction in volume. Subsequently, the suspension is stirred for an additional hour and then left to stand. A fine white solid precipitates out. The supernatant toluene is removed and the residue is again dissolved in toluene and washed at 70 ° C. for 15 minutes. After removal of the supernatant, a solution comprising 0.196 mmol of bis (trimethylsilyl) silanediylbis (2-methylindenyl) zirconium dichloride (prepared as described in German Patent Application No. 195 27 047) and 60 ml of toluene Add. The suspension turns orange and this color grows darker during the stirring process. After 8 hours, when the stirrer is stopped, the clear supernatant no longer discolors. Removal of the solvent at 50 ° C. under reduced pressure gives a red / orange finely divided solid.

Example 18

Polymerization Using Supported Catalyst F

The 2 L stirred reactor (Bühley) was inactivated and then charged with 1.2 ml of 1 M triisobutylaluminum / hexane solution and 200 g of liquid propylene at room temperature and the mixture was stirred at 350 rpm for 3 minutes.

101 mg of the supported catalyst F prepared in Example 17 was washed with additional 300 g of propylene in the reactor, the stirring speed was increased to 700 rpm, the mixture was heated to a polymerization temperature of 70 ° C. for 15 minutes, and the temperature was kept constant. Let's do it. After 2 hours propylene is flashed to terminate the reaction. 260 g of polypropylene having an average particle diameter (d ₅₀ ) of 315 mu m and a fine powder content (less than 100 mu m) measured by sieve analysis of 4% by weight are obtained. Activity is 2.6 kg / g supported catalyst. The polymer particles are granular (M _W = 380,000 g / mol; polydispersity 2.4; T _m = 147 ° C.) and no deposits remain on the reactor walls.

The catalyst supported according to the process of the present invention can provide homopolymers, copolymers or block copolymers while controlling the particle size and particle size distribution in a desired manner, in particular granulating polyolefins having high bulk density and low fine content In the form of high polymerization conversions.

Claims (10)

(A) drying a hydrophilic inorganic oxide or a mixture or mixed oxides of the group II to IV elements of the periodic table of the elements or the group IV elements of the transition group at 110 to 800 ° C., Optionally, (b) reacting the free hydroxyl group of the oxide with or without aluminoxane or aluminum alkyl, and And (c) reacting the oxide simultaneously with the aluminoxane and the multifunctional organic crosslinker. The process of claim 1 wherein aluminum oxide, silicon oxide, magnesium oxide, titanium oxide, zirconium oxide, or mixtures or mixed oxides thereof are used in step (a). The process of claim 1 or 2, wherein the bifunctional crosslinker is used in step (c). 4. The process of claim 3 wherein the bifunctional crosslinker used in step (c) is a diol, diamine, diepoxy compound or mixtures thereof. A supported polyolefin catalyst comprising the reaction product of a catalyst support prepared according to the method of claim 1 with at least one polyolefin catalyst. A supported polyolefin catalyst comprising the reaction product of a catalyst support prepared according to the method of claim 1 with at least one metallocene. A process for producing polyolefins by polymerizing or copolymerizing olefins, wherein the polymerization catalyst used is a supported polyolefin catalyst according to claim 5. 8. The process of claim 7, wherein aluminum alkyl is further used for the polymerization. A process for producing polyolefins by polymerizing or copolymerizing olefins, wherein the polymerization catalyst used is a supported polyolefin catalyst according to claim 6. 10. The process of claim 9, wherein aluminum alkyl is further used for the polymerization.