Supported catalyst component, supported catalyst, their preparation, and addition polymerization process

Supporting catalyst components, supporting catalysts, preparation methods thereof, and addition polymerization methods

The present invention relates to a supported catalyst component including a support material and aluminoxane. A supported catalyst includes a support material, aluminoxane and a metallocene compound (metallocene), and a method for preparing such a supported catalyst The method of the medium component and the catalyst, and an addition polymerization method using the supported catalyst.

Homogeneous or unsupported aluminoxane metallocene catalysts are known to have high catalytic activity for olefin polymerization reactions. Under the polymerization conditions where the polymer forms solid particles, the homogeneous (soluble) catalyst forms polymer deposits on the reactor wall and agitator. The deposits must be removed frequently because the deposits will hinder the cooling of the reactor contents. Required effective heat exchange, and cause excessive wear of moving parts. The polymer produced by this soluble catalyst has a low bulk density, which limits the commercial use of the polymer and the method. To solve these problems, several supported aluminoxane metallocene catalysts have been proposed for particle formation polymerization methods.

U.S. Patent No. 5,057,475 describes a supported metallocene aluminoxane catalyst, wherein the aluminoxane can be a commercial aluminoxane or an aluminoxane generated on-site on a solid support, for example, by adding a trialkylaluminum compound to The hydrous support, for example, is formed by adding trimethylaluminum to hydrous silica. In the preferred method of US Patent No. 5,057,475, the metallocene component and the aluminoxane (pre-combined modifier compound) are combined in a suitable solvent in the first step. In a subsequent step, this solution is brought into contact with the support body. The solvent can then be removed, typically by applying a vacuum to remove the solvent. The solution can be heated to assist the removal of the solvent. In another method, undehydrated silica gel is added to the trialkyl aluminum solution to produce aluminoxane, which is deposited on the surface of silica gel particles. The solvent is then removed, and the residual solid is dried to a free-flowing powder. In a typical example, dried silica and aluminoxane are prepared into a slurry with toluene, filtered, washed with pentane and then dried. The metallocene compound is typically combined with aluminoxane in toluene or heptane, and this solution is then combined with the pre-treated silica. Finally, the toluene or heptane is removed under vacuum to recover the supported catalyst.

U.S. Patent No. 5,026,797 describes the use of aluminoxane in an aluminoxane solvent such as an aromatic hydrocarbon to treat porous water-insoluble inorganic oxide particle support, and then use an aromatic hydrocarbon solvent to clean the treated support until no more aluminum is detected in the supernatant. Oxane. In this way, it is said that the aluminum atomic weight of the aluminoxane bonded to the treated oxide support can be adjusted to the range of 2 to 10% by weight. The treated support body is then combined with the zirconium compound. The so-formed aluminoxane and zirconium compound-containing support material together with the additional aluminoxane are in solution for polymerization reaction.

US Patent No. 5,147,949 discloses a supported metallocene aluminoxane catalyst. Its preparation method is by adding a water-impregnated catalyst support body to a stirred solution of trialkyl aluminum, and adding a metallocene component to the reaction product.

US Patent 5,240,894 describes a method of producing a supported catalyst by forming a metallocene/aluminoxane reaction solution, adding a porous carrier, and evaporating the resulting slurry, thereby removing residual solvent from the carrier, and selectively prepolymerizing the catalyst. Medium and olefinic monomers. The use of pre-polymerized supported catalysts can only achieve good polymer bulk density.

US Patent No. 5,252,529 discloses that a solid catalyst for olefin polymerization includes a particulate carrier containing at least 1% by weight of water, an aluminoxane compound and a metallocene compound. In the preparation of this catalyst, the reaction product of the particulate carrier and the aluminoxane is separated from the diluent (toluene) by decantation or drying under reduced pressure.

European Patent Application 368,644 discloses a method for preparing a supported metallocene aluminoxane catalyst, in which undehydrated silica gel is added to the stirred solution of triethyl aluminum, and the metal to which trimethyl aluminum has been added is added to the reaction mixtureMaoSolution. After adding the metallocene treated with trimethylaluminum to the silica gel solid treated with triethylaluminum, the catalyst is dried into a free-flowing powder. The drying of the catalyst can be carried out by filtering or evaporating the solvent at a temperature of up to 85°C.

European Patent Application 323,716 discloses a method for preparing a supported metallocene aluminoxane catalyst by adding undehydrated silica gel to a stirred solution of trialkyl aluminum, adding the metallocene to the reaction mixture, and removing the solvent And dry the solid into a free-flowing powder. After the metallocene is added, the solvent and residual solids are removed and dried at a temperature of up to 85°C.

European Patent Application 523,416 describes a supported catalyst component for olefin polymerization, which is prepared from an inorganic support and a metallocene. The metallocene and the support are thoroughly mixed in the solvent. It is preferable to extract the catalyst components in a suitable solvent such as toluene to remove the unfixed metallocene. Aluminoxane can then be added as a co-catalyst.

European Patent Application 567,952 describes a supported polymerization catalyst, including the reaction product of a supported organoaluminum compound and a metallocene catalyst compound. The supported catalyst is prepared by combining trimethylaluminum and the previously dried support material in a lipid inert suspension medium, and adding water to it. This suspension can be used as it is or can be filtered, and the resulting solid can be resuspended in a lipid-inert suspension medium and then combined with the metallocene compound. When the reaction is completed, the supernatant liquid is separated and removed, and the remaining solid is washed one to five times with an inert suspension medium, such as toluene, n-decane, diesel or methylene chloride.

It is desirable to provide a supported catalyst component, which can prevent or substantially reduce the problem of reactor fouling in the gas phase polymerization or slurry polymerization method, including the reactor wall and the inside of the reactor. Problem with polymer deposits formed on the agitator. It is also preferred that the polymer product produced by the gas phase polymerization or slurry polymerization method is free-flowing, and preferably has a high bulk density.

In one aspect of the present invention, there is provided a supported catalyst component including a support material and an aluminoxane, and the composition contains 15 to 40% by weight of aluminum based on the total weight of the support material and the aluminoxane, and the support therein The amount of aluminum present in the catalyst component of the supported catalyst component uses 10 ml of toluene per gram of the supported catalyst component. The extractable amount in the toluene extraction at 90°C for 1 hour does not exceed 10%. The supported catalyst component is The following method is used to obtain A. Heating the aluminoxane-containing support material for a period of time under an inert atmosphere and at a temperature sufficient to fix the aluminoxane on the support material.

A second aspect provides a supported catalyst comprising: the supported catalyst component according to the present invention and a transition metal compound containing at least one ring system or acyclic system π-bonded anion ligand.

According to another aspect, a method for preparing a supported catalyst component is provided, including: A. Heating the aluminoxane-containing support material for a period of time under an inert atmosphere and at a temperature sufficient to fix the aluminoxane to the support material ; Therefore, in the heating step A, select conditions to form a supported catalyst component, which contains 15 to 40% by weight of aluminum based on the total weight of the support material and aluminoxane, and the aluminum present in the supported catalyst component, Using 10 ml of toluene per gram of the supported catalyst component, the extractable amount does not exceed 10% when the toluene is extracted at 90°C for 1 hour.

In another aspect, the present invention provides a method for preparing a supported catalyst, comprising: A. Heating a section of aluminoxane-containing support material under an inert atmosphere and at a temperature sufficient to fix the aluminoxane to the support material Time; and optionally followed by B. The aluminoxane-containing support body material is subjected to one or more washing steps to remove the aluminoxane that is not fixed on the support body material; therefore, in the heating step A and the selective washing step B The conditions are selected to form a supported catalyst component, which contains 15 to 40% by weight of aluminum based on the total weight of the support material and aluminoxane, and the aluminum present in the supported catalyst component, relative to each gram of the supported catalyst component. Use 10 ml of toluene as the catalyst component, and the extractable amount during 1 hour extraction at 90°C toluene does not exceed 10%; and before or after step A or step B, add a π bond containing at least one ring system or acyclic system A transition metal compound that forms an anionic ligand, but once the transition metal compound is added, the product thus obtained no longer accepts a temperature equal to or higher than the decomposition temperature of the transition metal compound.

In yet another aspect, an addition polymerization method is provided, in which one or more addition polymerizable monomers are contacted with the supported catalyst according to the present invention under addition polymerization conditions.

Detailed description of the invention

The elements or metals mentioned here belong to a certain group of periodic table of the elements published by CRC in 1989 and have the copyright. The reference to the family means the family in the periodic table that uses the IUPAC family numbering system. The term hydrocarbyl group is used herein to mean aliphatic group, cycloaliphatic group, aromatic group or any combination thereof. The term hydrocarbyloxy refers to a hydrocarbyl group with an oxygen bond between the hydrocarbyl group and the element to which the hydrocarbyl group is attached. The term "substituted cyclopentadienyl" used in the specification and patent application includes the ring-substituted or polynuclear derivative of the cyclopentadienyl moiety, where the substituent is a hydrocarbyl group, a hydrocarbyloxy group, a hydrocarbylamino group, a cyano group, A halogen atom, a silyl group, a germanium group, a siloxy group or a mixed group thereof, or two substituents are hydrocarbylene groups, and the substituent (or two substituents) contains at most 30 non-hydrogen atoms. The term "cyclopentadienyl" specifically includes indenyl, tetrahydroindenyl, fluorenyl and octahydrofluorenyl.

Surprisingly, it has been found that by using a supported catalyst in which aluminoxane is fixed to the support material, a polymer with good bulk density can be prepared in a particle form polymerization process, and reactor fouling is not substantially reduced or substantially reduce. According to the present invention, for ethylene-based polymers and copolymers, a good bulk density is at least 0.20 g/cm³, Preferably at least 0.25 g/cm³, And better at least 0.30 g/cm³The volume density. It is believed that the degree of reactor fouling is related to the amount of aluminoxane leached from the support body during the polymerization conditions, which may cause the active catalyst to exist in the homogeneous phase, and so dissolve in the diluent, which may produce very small particles under the conditions of particle formation. Polymer particles or poorly-shaped polymer particles may adhere to the metal parts or static parts of the reactor. It is also believed that the bulk density of the polymer is related to the way the aluminoxane is fixed to the support and the amount of unfixed aluminoxane on the support, that is, the amount of aluminum that can be extracted from the support by 90°C toluene. Fixing the aluminoxane on the support body according to the special treatment of the present invention can lead to substantially no aluminoxane percolation from the support body and substantially no soluble active catalyst species present in the polymer mixture under polymerization conditions. It is found that the supported catalyst can not only be used in slurry and gas phase polymerization methods to prepare in the traditional high-density polyethylene range (0.970 to 0.940 g/cm³) Ethylene polymers and copolymers, and can also be manufactured with a density lower than 0.940 g/cm³As low as 0.880g/cm³Or the following copolymers, while maintaining good bulk density properties and at the same time can prevent or substantially reduce reactor fouling.

The supported catalyst component of the present invention includes a support material and aluminoxane, wherein, roughly speaking, the aluminum present in the supported catalyst component uses 10 milliliters of toluene per gram of supported catalyst component, with a ratio of 90 The extractable amount of toluene for 1 hour at °C does not exceed 10%. Preferably, the amount of extractable aluminum does not exceed 9% of the aluminum present in the supported catalyst component, and most preferably does not exceed 8%. It is found that when the extractable amount is lower than this concentration, a supported catalyst based on these supported catalysts can be used to obtain a good polymer bulk density.

The toluene extraction test was performed as follows. One gram of supported catalyst component or supported catalyst with a known aluminum content is added to 10 ml of the product, and then the mixture is heated to 90°C under an inert atmosphere. The suspension was stirred thoroughly at this temperature for 1 hour. The suspension is then filtered and reduced pressure is applied to the auxiliary filtration step. The solid was washed twice with 3 to 5 milliliters of toluene per gram of solid. The solid was then dried at 120°C for 1 hour, and then the solid content was measured. The difference between the primary aluminum content and the aluminum content after benzene is divided by the primary aluminum content and multiplied by 100% to obtain extractable aluminum.

The aluminum content is determined by mixing 0.5 g of the supported catalyst component or the supported catalyst into a slurry in 10 ml of hexane. The slurry is treated with 10 to 15 milliliters of 6N sulfuric acid, followed by the addition of a known excess of EDTA. Then the excess amount of EDTA is back titrated with zinc chloride.

When the extractable aluminum concentration is 10%, the volume density of the polymer polymerized with the supported catalyst (component) described herein is extremely sensitive to small changes in the percentage of extractable aluminum. In view of the sensitivity of polymer bulk density and the margin of error in determining the percentage of extractable aluminum (estimated to be 1% absolute value), another test to distinguish between the supported catalyst composition and the supported catalyst according to the present invention is to use a supported catalyst The catalyst is used in 80% hydrocarbon diluent and 15 Pa (bar) to carry out the ethylene polymerization method and determine the degree of reactor binding and/or the bulk density of the produced ethylene polymer. The reactor generally does not foul, in other words, there is generally no polymer deposits on the reactor wall or the agitator and/or the bulk density is at least 0.20g/cm³, And preferably at least 0.25 g/cm³, Belongs to the supported catalyst component and characteristics of the catalyst of the present invention.

The support material suitable for the present invention preferably has a surface area (measured by the nitrogen pore measurement method using the BET method) from 10 to 1000 m²/g, preferably from 100 to 600 m²/g. The porosity of the support body is preferably between 0.1 to 5 cm³/g, preferably from 0.1 to 3 cm³/g, best from 0.2 to 2 cm³/g. The average particle size is not particularly limited, but is typically 1 to 200 μm.

Suitable support materials for the supported catalyst component of the present invention include porous resin-containing materials, such as styrene-divinylbenzene copolymer, and solid inorganic oxides, such as silica, alumina, magnesia, titania, and oxides. Thorium, and mixed oxides of silicon oxide and one or more group 2 or 13 metal oxides, such as silicon oxide-magnesia and silicon oxide-alumina mixed oxides. Silicon oxide, aluminum oxide and one or more mixed oxides of group 2 or 13 metal oxides are preferred support materials. A preferred example of the mixed oxide is silica-alumina. The best is silicon oxide. Silica can be in the form of particles, agglomerates, smoked or other shapes. Suitable silicon oxides include Davison Syloid 245 under the number SD 3216.30, Davison 948 and Davison 952 from Grace Davison (a branch of WR Grace) and Degussa AG under the number Aerosil 812 By.

Before use, if there is a required support material, it can be heated and/or chemically treated to reduce the water content or hydroxyl content of the support material. A typical pre-heat treatment is performed at a temperature of 30°C to 1000°C under atmospheric pressure or reduced pressure for a period of 10 minutes to 50 hours.

The supported catalyst composition includes aluminoxane composition. Alumoxane (also known as aluminoxane) is an oligomer or polymer aluminum oxide compound containing alternating chains of aluminum and oxygen atoms. Therefore, aluminum has a substituent, preferably an alkyl group. The true structure of aluminoxane is unknown, but it is generally believed that the formula (-Al(R)-O)_mRepresents ring system aluminoxane, and R₂Al-O(-Al(R)-O)_m-AlR₂Represents a linear compound, where R is C in each occurrence₁To C₁₀The hydrocarbyl group is preferably an alkyl group or a halide anion, and m is an integer from 1 to 50, preferably at least 4. Aluminoxane is typically the reaction product of water and aluminum alkoxide, which may contain halide anion groups or alkoxy anion groups in addition to alkyl groups. Several different aluminum alkyl compounds such as trimethyl aluminum and triisobutyl aluminum react with water to obtain so-called modified or mixed aluminoxanes. Preferred aluminoxanes are methyl aluminoxane and methyl aluminoxane modified with a small amount of other lower alkyl groups such as isobutyl. Aluminoxanes usually contain small to substantial amounts of starting aluminum alkane compound.

The preparation method of aluminoxane is not particularly limited to the present invention. When prepared by reacting water with aluminum alkyl, water can be combined with aluminum alkyl in various forms such as liquid, gas, or solid, for example, as crystal water. A special technique for preparing aluminoxane-type compounds by contacting an aluminum alkyl compound with an inorganic salt containing crystal water is disclosed in US Patent No. 4,542,199. In a particularly preferred embodiment, the alkyl aluminum compound is in contact with renewable water-containing substances such as hydrated alumina, silica or other substances. It is disclosed in European Patent No. 338,044.

The supported catalyst component of the present invention usually contains 15 to 40% by weight, preferably 20 to 40% by weight, more preferably 25 to 40% by weight of aluminum based on the total weight of the support body, the material and the aluminoxane. The aluminum content is preferably at least 15% by weight, preferably 20% by weight, and most preferably 25% by weight. The reason is that a relatively high amount of transition metal compound can be deposited on the support, so that a relatively high activity can be obtained. This improves the overall catalyst efficiency, especially when expressed on the basis of the support material.

The supported catalyst material can be stored or transported under inert conditions or can be used to produce the supported catalyst of the present invention.

According to another aspect, the present invention provides a supported catalyst including the supported catalyst according to the present invention and a transition metal compound, preferably containing at least one ring or acyclic π-bonded anionic ligand, preferably Cyclopentadienyl moiety or transition metal compound substituted with cyclopentadienyl moiety. Suitable complexes are derivatives of any transition metal containing a lanthanide element, but preferably a group 3, 4, 5 or lanthanide metal in the +2, +3 or +4 formal oxidation state. Preferred compounds include metal complexes containing 1 to 3 π-bonded anionic ligands, which can be ring or acyclic non-limiting π-bonded anionic ligands. Examples of such π-bonded anions are conjugated or non-conjugated ring system or acyclic dienyl, allyl, and aralkenyl. The term "π-bonded" means that the ligand system uses a π-bond to bond to the transition metal. Each atom in the non-limited π-bonding group is substituted with a group selected from halogen atoms, hydrocarbyl groups, halohydrocarbyl groups and hydrocarbyl substituted metalloid groups (where the metalloid is selected from the 14th group of the periodic table). The term hydrocarbyl includes C_1-20Straight-chain, branched and ring-based alkyl group, C_6-20Aromatic group, C_7-20Alkyl substituted aromatic group, and C_7-20An aryl group replaces an alkyl group. In addition, two or more groups can jointly form a fused ring system or a hydrogenated fused ring system. Suitable hydrocarbyl-substituted organometalloid groups include mono-, di- and tri-substituted organometalloid groups of Group 14 elements. Each hydrocarbon group contains 1 to 20 carbon atoms. Examples of suitable hydrocarbyl substituted organometalloid groups include trimethylsilyl, triethylsilyl, ethyldimethylsilyl, methyldiethylsilyl, triphenylgermanyl and trimethylgermanium alkyl.

Examples of suitable anionic non-limiting π-bonding groups include cyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl, tetrahydrofluorenyl, octahydrofluorenyl, fluorenedienyl, cyclohexadienyl, Dihydroanthryl, hexahydroanthryl and decahydroanthryl, and C_1-10Hydrocarbyl substituted derivatives. Preferred anionic non-limited π-bonding groups are cyclopentadienyl, pentamethylcyclopentadienyl, tetramethylcyclopentadienyl, indenyl, 2,3-dimethylindenyl, fluorenyl , 2-methyl indenyl and 2-methyl-4-phenyl indenyl.

The term metallocene compound is used herein to mean a transition metal compound containing a derivative of a cyclopentadienyl moiety. Metallocenes suitable for use in the present invention are bridged or unbridged mono-, di- and tricyclopentadienyl or substituted cyclopentadienyl transition metal compounds.

Appropriate unbridged monocyclopentadienyl or mono(substituted cyclopentadienyl) transition metal derivatives are represented by the general formula CpMXn, where Cp is cyclopentadienyl or its derivatives; M has 2, 3 or 4 Formal oxidation state of Group 3, 4 or 5 transition metal; X represents an anionic ligand (non-cyclic aromatic π-bonded anionic ligand) at each occurrence, X contains up to 50 non-hydrogen atoms; and n is The number is one less than the formal oxidation state of M, but 1, 2 or 3, preferably 3. Examples of ligand X are hydrocarbyl, hydrocarbyloxy, hydride, halogen, silyl, germanyl, amide and siloxy or two X groups can form a hydrocarbylene group (including hydrocarbylene).

Suitable bridges to a cyclopentadienyl or a (substituted cyclopentadienyl) transition metal compound include the well-known constrained geometric complexes. These complexes and their preparation methods are disclosed in U.S. Application 545,403 (application date July 3, 1990, corresponding to EP-A-416,815), U.S. Patent No. 5,374,696 (corresponding to WO-93/19104), and U.S. Patent 5,055,438, 5,057,475, 5,096,867, 5,064,802 and 5,132,380.

More particularly preferably bridged monocyclopentadienyl or mono(substituted cyclopentadienyl) transition metal compounds correspond to formula I:<chemistry general="n"><img file="TW353083B_D0001.tif" /></chemistry>Wherein: M is a group 3 to 5 metal, especially a group 4 metal, especially titanium; Cp* is bonded to Z'and η⁵The bonding mode is bonded to the substituted cyclopentadienyl group of M or such group is substituted with 1 to 4 selected from hydrocarbyl, silyl, germanyl, halogen, hydrocarbyloxy, amine, and mixed groups Group substitution, the substituent contains up to 20 non-hydrogen atoms, or optionally 2 further substituents (except halogen atoms or amino groups) together to make Cp* have a condensed ring structure; Z'is a ring system or a ring system π bond A divalent moiety other than an anion ligand, Z'includes boron or elements of group 14 of the periodic table and selective nitrogen, phosphorus, sulfur or oxygen, this moiety contains up to 20 non-hydrogen atoms, and selective Cp* and Z' Together to form a condensed ring system; each occurrence of X is an anionic ligand containing up to 50 non-hydrogen atoms (except for the ring system π-bonded group); and n is determined to be 1 or 2 according to the valence of M .

In accordance with the foregoing description, M is preferably a group 4 metal, especially titanium; n is 1 or 2; and X is a monovalent ligand containing up to 30 non-hydrogen atoms, more preferably C_1-20Hydrocarbyl.

When n is a metal of groups 1 and 3 to 5 (preferably a group 4 metal) in the +3 formal oxidation state, X is preferably a stable ligand.

The term "stabilizing ligand" means that the ligand can stabilize the metal complex through the following structures: 1) nitrogen, phosphorus, and sulfur oxide chelating bonds, or 2) η3 bonds with resonant non-limited π electronic structure.

Examples of Group 1 stable ligands include silyl, hydrocarbyl, amide or phosphorus anion ligands which can be substituted with one or more aliphatic or aromatic ether, thioether, amine or phosphine functional groups, in particular, the amine or phosphine group is three Substitution, the ligand contains 3 to 30 non-hydrogen atoms. The most preferred group 1 stabilizing ligand is 2-dialkylaminobenzyl or 2-(dialkylaminomethyl)phenyl and the alkyl group contains 1 to 4 carbons.

Examples of Group 2 stable ligands include C with ethylenic unsaturation_3-10Hydrocarbyl groups, such as allyl, 1-methylallyl, 2-methylallyl, 1,1-dimethylallyl or 1,2,3-trimethylallyl.

A better metal coordination complex corresponds to formula II:<chemistry general="n"><img file="TW353083B_D0002.tif" /></chemistry>

Wherein R'at each occurrence is selected from hydrogen, hydrocarbyl, silyl, germanyl, cyano, halogen atom and combinations thereof and containing up to 20 non-hydrogen atoms, or two R'groups (cyano or halogen (Except atoms) together to form its bivalent derivative; X at each occurrence is selected from hydrogen anion, halogen atom, alkyl, aryl, silyl, germanyl, aryloxy, alkoxy, amide group , Siloxy group, and combinations thereof, and containing up to 20 non-hydrogen atoms; Y is a divalent anion ligand including nitrogen, phosphorus, oxygen or sulfur and containing up to 20 non-hydrogen atoms, Y via nitrogen, phosphorus, oxygen Or sulfur is bonded to Z and M, and optionally Y and Z together form a fused ring system; M is a group 4 metal, especially titanium; Z is SiR*₂, CR*₂, SiR*₂SiR*₂, CR*₂CR*₂, CR*=CR*, CR*₂SiR*₂, GeR*₂, BR*, or BR*₂; Wherein: R* is selected from hydrogen, hydrocarbon group, silyl group, halogenated alkyl group, halogenated aryl group at each occurrence and contains up to 20 non-hydrogen atoms and their mixed groups, or two or more R from Z * Group, or an R* group from Z combined with the ring to form a fused ring system; and n is 1 or 2.

More preferably, Y is -O-, -S-, -NR*-, PR*-. It is highly preferred that Y corresponds to the formula -N(R')- or -P(R')-, wherein R'is as described above, that is, an amide group or a phosphorous anion group.

The most highly preferred metal coordination complexes correspond to formula III:<chemistry general="n"><img file="TW353083B_D0003.tif" /></chemistry>Wherein: M is titanium; R'is selected from hydrogen, silyl group, hydrocarbyl group and combinations thereof at each occurrence and contains up to 20, preferably up to 10 carbon or silicon atoms, or two of the substituted cyclopentadienyl moieties R'groups are combined together; E is silicon or carbon; X is an anion, a halogen atom, an alkyl group, an aryl group, an aryloxy group or an alkoxy group in each occurrence and contains up to 10 carbons; m is 1 or 2; and n is 1 or 2.

Examples of the aforementioned most highly preferred metal coordination compounds include the following compounds, wherein R'of the amide group is methyl, ethyl, propyl, butyl, pentyl, hexyl (including isomers), protobornyl , Benzyl, phenyl or cyclododecyl (ER'₂)_mIt is dimethylsilane or 1,2-ethylidene; R'of the π-bonding group of the ring system is hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, proto Borneyl, benzyl or phenyl or two R'groups combine to form an indenyl, tetrahydroindenyl, fluorenyl or octahydrofluorenyl moiety; and X is chlorine, bromine, iodine, methyl, ethyl, Propyl, butyl, pentyl, hexyl, protobornyl, benzyl or phenyl.

Particularly highly preferred compounds include: (third-butyramido) (tetramethyl-η⁵-Cyclopentadienyl)-1,2-ethanediyltitanium dimethyl, (third-butyramido)(tetramethyl-η⁵-Cyclopentadienyl)-1,2-ethanediyltitanium dibenzyl, (third-butyramido)(tetramethyl-η⁵-Cyclopentadienyl) dimethylsilyl titanium dimethyl, (third-butyramido) (tetramethyl-η⁵-Cyclopentadienyl) dimethylsilyl titanium dibenzyl, (methylamido) (tetramethyl-η⁵-Cyclopentadienyl) dimethylsilyl titanium dimethyl, (formamido) (tetramethyl-η⁵-Cyclopentadienyl) dimethylsilyl titanium dibenzyl, (phenylamido) (tetramethyl-η⁵-Cyclopentadienyl) dimethylsilyl titanium dimethyl, (phenylamido) (tetramethyl-η⁵-Cyclopentadienyl) dimethylsilyl titanium dibenzyl, (benzyl amido) (tetramethyl-η⁵-Cyclopentadienyl) dimethylsilyl titanium dimethyl, (benzylamino) (tetramethyl-η⁵-Cyclopentadienyl) dimethylsilyl titanium dibenzyl, (third-butyramido) (η⁵-Cyclopentadienyl)-1,2-ethanediyltitanium dimethyl, (third-butyramido) (η⁵-Cyclopentadienyl)-1,2-ethanediyltitanium dibenzyl, (third-butyramido) (η⁵-Cyclopentadienyl) dimethylsilyl titanium dimethyl, (third-butyramido) (η⁵-Cyclopentadienyl) dimethyl silyl titanium dibenzyl, (methyl amido) (η5-cyclopentadienyl) dimethyl silyl titanium dimethyl, (the third-butyl amido )(η⁵-Cyclopentadienyl) dimethyl silyl titanium dibenzyl, (3rd-butyl amide group) indenyl dimethyl silyl titanium dimethyl group, (3rd-butyryl amino group) indenyl dimethyl group Base silyl titanium dibenzyl, (benzyl amido) indenyl dimethylsilyl titanium dibenzyl; and corresponding zirconium or hafnium coordination complexes.

The transition metal compound in which the transition metal is in the +2 formal oxidation state and its preparation method are disclosed in detail in WO 9500526 (corresponding to US application 241,523, application date May 12, 1994). Appropriate complexes include those containing one and only one ring system non-limited anion π-bonding group, and the complexes correspond to formula IV:<chemistry general="n"><img file="TW353083B_D0004.tif" /></chemistry>Wherein: M is titanium or zirconium in the +2 formal oxidation state; L is a base containing a ring system non-limiting anion of the π system through which the base is bonded to M and the group is also bonded to Z; Z is through σ bond is preferred. The part of the 14th group of the periodic table that is bonded to M also includes nitrogen, phosphorus, sulfur or oxygen, and this part contains up to 60 non-hydrogen atoms; and X* is neutral, conjugated or non-conjugated diene , Optionally substituted with one or more hydrocarbon groups, X contains up to 40 carbon atoms and forms a π complex with M.

Preferred transition metal compounds of formula IV include wherein Z, M and X* are as defined above; and L is C₅H₄Base bonded to Z and with η⁵The bonding mode is bonded to M or substituted with 1 to 4 substituents selected from the group consisting of hydrocarbon group, silyl group, germanyl group, halogen atom, cyano group and combinations thereof.⁵Bonding group, the substituent contains up to 20 non-hydrogen atoms, and optionally two substituents (except cyano group or halogen atom) together make L have a condensed ring structure.

The better transition metal compound+2 compound according to the present invention corresponds to formula V:<chemistry general="n"><img file="TW353083B_D0005.tif" /></chemistry>Among them: R'is selected from hydrogen, hydrocarbon group, silyl group, germanyl group, halogen atom, cyano group and combinations thereof at each occurrence, R'contains up to 20 non-hydrogen atoms, and optionally two R'groups (Where R'is not a hydrogen, a halogen atom or a cyano group) together to form a divalent derivative connected to the adjacent position of the cyclopentadienyl ring to form a condensed ring structure; X* contains up to 30 non-hydrogen Atomic neutral η4-bonded dienyl, which forms a π complex with M; Y is -O-, -S-, -NR*-, -PR*-; M is in +2 formal oxidation state Of titanium or zirconium; and Z* is SiR*₂, CR*₂, SiR*₂SiR*₂, CR*₂CR*₂, CR*=CR*,CR*₂SiR*₂, Or GeR*₂; Among them: R* is hydrogen or selected from hydrocarbon group, silyl group, halogenated alkyl group, halogenated aryl group and a combination thereof, R* contains up to 10 non-hydrogen atoms, and optionally two From Z* and R* groups (when R* is not hydrogen), or one R* group from Z* and one R* group from Y form a ring system.

Preferably, R* is hydrogen, hydrocarbyl group, silyl group, halogen atom and combinations thereof at each occurrence. R'contains up to 10 non-hydrogen atoms or two R'(when R'is not hydrogen or halogen atom) Together to form a divalent derivative; the best R'is hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl (including all isomers when appropriate), cyclopentyl, cyclohexyl, Probornyl, benzyl or phenyl or two R'groups (except hydrogen) are bonded together, so the entire C_R'_ group is indenyl, tetrahydroindenyl, fluorenyl, tetrahydrofluorenyl or octahydrofluorenyl .

It is also preferable that at least one of Ror R* is an electron donating part. The term "electron donation" means that the electron donating ability of this part is stronger than that of hydrogen. Therefore, it is highly preferred that Y is a nitrogen-containing or phosphorus-containing group corresponding to the formula -N(R")- or -P(R")-, where R" is C_1-10Hydrocarbyl.

Examples of appropriate X* bases include: homo-trans-η⁴-1,4-Diphenyl-1,3-butadiene; homo-trans-η⁴-3-methyl-1,3-pentadiene; all-trans-η⁴-1,4-Dibenzyl-1,3-butadiene; homo-trans-η⁴-2,4-hexadiene; homo-trans-η⁴-1,3-pentadiene; homo-trans-η⁴-1,4-Xylyl-1,3-butadiene; homo-trans-η⁴-1,4-II (trimethylsilyl)-1,3-butadiene; homo-cis-η⁴-1,4-Diphenyl-1,3-butadiene; homo-cis-η⁴-3-methyl-1,3-pentadiene; homo-cis-η⁴-1,4-Dibenzyl-1,3-butadiene; homo-cis-η⁴-2,4-hexadiene; homo-cis-η⁴-1,3-pentadiene; homo-cis-η⁴-1,4-Xylyl-1,3-butadiene; and homo-cis-η⁴-1,4-II (trimethylsilyl)-1,3-butadiene, the homo-cis dienyl group and metal form a π complex as defined herein.

The most highly preferred transition metal +2 compound is a compound of formula V amidosilane- or amidoalkanediyl-, where: -Z*-Y- is -(ER'₂)_m-N(R")-, and R'at each occurrence are selected from hydrogen, silyl group and combinations thereof, R'contains up to 10 carbon or silicon atoms, or two R'substituted for cyclopentadienyl Group (when R'is not hydrogen) together to form a divalent derivative connected to the adjacent position of the cyclopentadienyl ring; R" is C_1-10Hydrocarbyl; R'is hydrogen or C at each occurrence_1-10Hydrocarbyl; E is silicon or carbon at each occurrence; and m is 1 or 2.

Examples of metal complexes according to the present invention include the following compounds wherein R" is methyl, ethyl, propyl, butyl, pentyl, hexyl (including all the foregoing isomers when applicable), cyclododecyl , Protobornyl, benzyl or phenyl; (ER'₂)_mIt is dimethylsilane or ethanediyl; and the non-limiting π-bonding group of the ring system is cyclopentadienyl, tetramethylcyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl, tetrahydrofluorene Group or octahydrofluorenyl.

Appropriate two-cyclopentadienyl or substituted cyclopentadienyl transition metal compounds include bridging groups containing linked cyclopentadienyl groups and those that do not contain bridging groups.

Appropriate unbridged two-cyclopentadienyl or two (substituted cyclopentadienyl) transition metal derivatives can be of the general formula Cp₂MXn' means where Cp is a π-bonded cyclopentadienyl group or a π-bonded substituted cyclopentadienyl group, and M and X are defined as formula II, and n'is 1 or 2 or less than the formal oxidation state of M 2. Preferably n'is 2. Examples of unbridged two cyclopentadienyl transition metal derivatives are: two cyclopentadienyl zirconium dimethyl, two cyclopentadienyl zirconium dibenzyl, two (methylcyclopentadienyl) zirconium di Methyl, two (n-butylcyclopentadienyl) zirconium dimethyl, two (tertiary-butylcyclopentadienyl) zirconium dimethyl, two (pentamethylcyclopentadienyl) zirconium two Methyl, two (indenyl) zirconium dibenzyl, two (fluorenyl) zirconium dimethyl, two (pentamethylcyclopentadienyl) zirconium two [2-(N,N-dimethylamino) benzyl Base], and the corresponding titanium and hafnium derivatives.

The better bridging base is the corresponding formula (ER"₂) x where E is silicon or carbon, R" is hydrogen or selected from silyl group, hydrocarbyl group and combinations thereof at each occurrence, R" contains up to 30 carbon or silicon atoms, and x is 1 to 8. Preferably, each occurrence of R" is methyl, benzyl, tertiary butyl or phenyl.

Examples of bridging ligands containing two π-bonding groups are: (dimethylsilyl-two-cyclopentadienyl), (dimethylsilyl-two-methylcyclopentadienyl) , (Dimethylsilyl-two (ethylcyclopentadienyl), (dimethylsilyl-two-tertiary butylcyclopentadienyl), (dimethylsilyl-two-tetramethyl Cyclopentadienyl), (dimethylsilyl-two-indenyl), (dimethylsilyl-two-tetrahydroindenyl), (dimethylsilyl-two-fluorenyl), ( Dimethylsilyl-two-tetrahydrofluorenyl), (dimethylsilyl-two-2-methyl-4-phenylindenyl), (dimethylsilyl-two-2-methylindenyl) Group), (Dimethylsilyl-cyclopentadienylfluorenyl), (1,1,2,2-tetramethyl-1,2-disilyl-II-cyclopentadienyl), ( 1,2-II (cyclopentadienyl)ethane), and (isopropylidene-cyclopentadienyl-fluorenyl).

Examples of the aforementioned bridged two cyclopentadienyl or two (substituted cyclopentadienyl) complexes include compounds of formula VI:<chemistry general="n"><img file="TW353083B_D0006.tif" /></chemistry>

Wherein: M, X, E, R', m and n are defined as the complexes of formula III. The two substituents X together form a neutral π-bonded conjugated diene containing 4 to 30 non-hydrogen atoms and form a π complex with M. At this time, M is in the +2 formal oxidation state, preferably zirconium or hafnium.

The aforementioned metal complexes are particularly suitable for preparing polymers with three-dimensional molecular structures. Due to this ability, preferred complexes have Cs symmetry or have an optically active, stereo-rigid structure. Examples of the first type are compounds with different non-restricted P-bonding systems, such as a cyclopentadienyl group and a fluorenyl group. Similar systems based on Ti(IV) or Zr(IV) are disclosed in Ewen et al.,<u style="single">J. Am. Chem. Soc.</u>, Vol. 110, pp. 6255-6256 (1980) for the preparation of syndiotactic olefin polymers. Examples of optically active structural formulas include indenyl complexes. Similar systems based on Ti(IV) or Zr(IV) are disclosed in Wild et al., J.<u style="single">Organomet, Chem.</u>, Vol. 232, pp. 233-47, (1982) for the preparation of isotactic olefin polymers.

Examples of complex compounds of formula IV are: (dimethylsilyl-two-cyclopentadienyl) zirconium dimethyl, (dimethylsilyl-two-tetramethylcyclopentadienyl) zirconium dimethyl , (Dimethylsilyl-two-tertiary butylcyclopentadienyl) zirconium diphenyl, (dimethylsilyl-two-tetramethylcyclopentadienyl) zirconium dibenzyl, (two Methylsilyl-two-indenyl) zirconium two (2-dimethylaminobenzyl), (isopropylidene cyclopentadienyl-fluorenyl) zirconium dimethyl, [2,2'-biphenyl Two base two (3,4-dimethyl-1-cyclopentadienyl)] titanium dibenzyl, [6,6'-dimethyl-2,2-biphenyl two (3,4-di Methyl-1-cyclopentadienyl)] zirconium dimethyl, and corresponding titanium and hafnium complexes.

Suitable tricyclopentadienyl or substituted cyclopentadienyl transition metal compounds include those containing two bridged cyclopentadienyl groups and those not containing a bridging group.

Appropriate non-bridged tricyclopentadienyl transition metal derivatives can be of the general formula Cp₃MXn" means that Cp, M and X are defined as before and n" is 3 less than the formal oxidation state of M and is 0 or 1, preferably 1. Preferably, the ligand X is a hydrocarbyl group, a hydrocarbyloxy group, a hydrogen ion, a halogen atom, a silyl group, a germanyl group, a amide group and a siloxy group.

Preferably, the transition metal compound is a bridged-cyclopentadienyl group 4 transition metal compound or a bridged 2-cyclopentadienyl group 4 transition metal compound, more preferably a bridged-cyclopentadienyl transition metal compound, especially wherein the The metal is a compound of titanium.

Other compounds that can be used to prepare the catalyst composition according to the present invention, especially containing other Group 4 metal compounds, are of course self-evident to those in the industry.

Roughly speaking, the molar ratio of the supported catalyst (derived from the aluminoxane component) to the transition metal atom is 1 to 5000, preferably 25 to 1000 and most preferably 50 to 500. If the ratio is too low, the activity of the supported catalyst is insufficient, and if the ratio is too high, the cost of using a large amount of aluminoxane is quite high, so the catalyst becomes uneconomical.

The content of the transition metal compound in the supported catalyst of the present invention is not particularly limited, but is typically in the range of 0.1 to 1000 micromoles of the transition metal compound per gram of the support material. Preferably, the supported catalyst contains 1 to 250 micromoles of transition metal compound per gram of support material. It is found that increasing the aluminum loading on the support body results in a catalyst with a lower aluminum loading but approximately the same aluminum/transition metal ratio when expressed on a transition metal basis, and a catalyst with a higher efficiency. When these higher aluminum-loaded support components are expressed in terms of aluminum or support materials, they can also provide a supported catalyst with higher efficiency.

The supported catalyst of the present invention can be used as it is or can be used in a pre-polymerized form by subjecting olefins to polymerization conditions in the presence of the supported catalyst.

The supported catalyst component of the present invention is obtained by heating the aluminoxane-containing aluminoxane material for a period of time under an inert atmosphere and at a temperature sufficient to fix the aluminoxane to the aluminoxane material.

Aluminoxane-containing support material can be obtained by combining aluminoxane and support material in a diluent. Based on the total weight of the support material and water, the support material contains 0 to not more than 20% by weight of water, preferably 0 to Not more than 6 wt% water. The substantially water-free support can achieve good results in terms of the catalytic properties of the supported catalyst. In addition, it has been found that a support material containing a relatively small amount of water can be used in this method without any problems. When the water-containing support material is combined with the same amount of aluminoxane under the same conditions, a supported catalyst component can be obtained in this method, which has a slightly higher aluminum content than the support material without water. It is believed that the water reacts with the residual amount of aluminum alkyl present in the aluminoxane to convert the aluminum alkyl into additional aluminoxane. Another advantage is that in this way, less aluminum alkyl is lost to waste or recycle streams. It is desirable to use aluminoxane in a dissolved form.

In addition, the aluminoxane-containing support material can be obtained in the following manner by combining 5 to 30% by weight of water in a diluent, preferably 6 to 20% by weight of water (based on the total weight of the support material and water) Support body material and formula R"_n*AlX"_3-n*Compounds, where R" is a hydrocarbyl group at each occurrence, X" is a halogen atom or a hydrocarbyloxy group, and n* is an integer from 1 to 3. Preferably n* is 3. When the aluminoxane passes through the formula R" in situ_n*AlX"_3-n*When the compound is prepared by reacting with water, R"_n*AlX"_3-n*The molar ratio to water is typically 10:1 to 1:1, preferably 5:1 to 1:1.

Support body material is added to aluminoxane or formula R"_n*AlX""_3-n*, preferably dissolved in a solvent, the best hydrocarbon solvent; or aluminoxane or formula R"_n*AlX"_3-n*The solution is added to the support material. The support material can be used in a dry form or mixed with a hydrocarbon diluent into a slurry for use. Both aliphatic and aromatic hydrocarbons can be used. Suitable aliphatic hydrocarbons include, for example, pentane, isopentane, hexane, heptane, octane, isooctane, nonane, isononane, decane, cyclohexane, methylcyclohexane and two or more A combination of thinners. Suitable examples of aromatic diluents are benzene, toluene, xylene and other alkyl or halogen atom substituted aromatic compounds. The best diluent is aromatic hydrocarbons, especially toluene. The appropriate concentration of the solid support in the hydrocarbon medium is 0.1 to 15, preferably 0.5 to 10, more preferably 1 to 7% by weight. There are no special restrictions on the contact time and temperature. The preferred temperature is 0°C to 60°C, more preferably 10°C to 40°C. The contact time is 15 minutes to 40 hours, preferably 1 hour to 20 hours.

Before the heating step of the aluminoxane-containing support body material, the diluent or solvent is removed to obtain a free-flowing powder. The preferred method is to apply a technique that can only remove the liquid and leave the aluminum compound on the solid, such as damp heat, reduced pressure, evaporation or a combination of these techniques.

The heating step A is followed by the selective washing step B in a manner that a large proportion (more than 90% by weight) of the aluminoxane remaining on the supported catalyst component is fixed. In the heating step, the aluminoxane is fixed to the support material, and in the selective washing step, the unfixed aluminoxane is removed to a substantial extent to provide the supported catalyst component of the present invention. The upper limit of the temperature of the heat treatment is preferably lower than the temperature at which the support material starts to adhere and form agglomerates that are difficult to re-disperse, but lower than the decomposition temperature of the aluminoxane. When the metallocene compound (detailed later) is added before the heat treatment, the heating temperature must be lower than the decomposition temperature of the metallocene compound. The aluminoxane-containing support material in a free-flowing or powder form is preferably at least 75°C, preferably at least 85°C, more preferably at least 100°C up to 250°C, more preferably at most 200°C, heat treatment for 15 minutes to 72 hours, more At most 24 hours. More preferably, the heat treatment is performed at a temperature of 160°C to 200°C for 30 minutes to 4 hours. Good results can be obtained by heating at 100°C for 8 hours and at 175°C for 2 hours. Through preliminary experiments, industry players will be able to define which heat treatment conditions can obtain the desired results. It is found that the longer the heat treatment time, the greater the amount of the aluminoxane fixed to the support material. The heat treatment is performed under reduced pressure or under an inert atmosphere such as nitrogen, but is preferably performed under reduced pressure. Depending on the conditions of the heating step, the aluminoxane can be fixed to the support material to a high degree where the washing step can be eliminated.

In the selective washing step B, the number of washing times and the solvent used are unfixed aluminoxane, and the amount removed is sufficient to obtain the supported catalyst component of the present invention. The washing conditions must be such that the aluminoxane is soluble in the washing solvent. The aluminoxane-containing support body material that has been subjected to the heat treatment is preferably subjected to 1 to 5 washing steps using an aromatic hydrocarbon solvent at a temperature of 0°C to 110°C. More preferably, the temperature is 20°C to 100°C. Preferred examples of aromatic solvents include toluene, benzene and xylenes. More preferably, the aromatic hydrocarbon solvent is toluene. At the end of the washing treatment, the aluminoxane dissolved in the solvent can also be removed by a technology such as filtration or decantation to remove the solvent. Preferably, the washing solvent is removed to obtain a free-flowing powder of supported catalyst components.

The washing step is preferably carried out under the condition of refluxing the washing solvent. Carrying out the washing step under reflux conditions can control the particle size distribution properties. It is better to obtain a distribution similar to the starting support material. It has also been found that a supported catalyst with higher polymerization activity can be obtained. Typically, after the heating step, the supported catalyst component is mixed with the aromatic hydrocarbon to form a slurry, and the slurry is refluxed or heated at the boiling point of the aromatic hydrocarbon. The slurry is maintained under reflux conditions for 5 minutes to 72 hours. The agglomerated particles formed during the heating step will de-agglomerate or decompose during the washing step under reflux conditions. The concentration of the supported catalyst component in the aromatic hydrocarbon is not particularly limited, but is typically in the range of 1 to 500 g/l hydrocarbon, preferably 10 to 250 g/l. Preferred examples of aromatic hydrocarbons include toluene, benzene and xylene. More preferably, the aromatic hydrocarbon solvent is toluene. Agitation may be applied during the reflux step.

After the aforementioned washing and refluxing steps, the supported catalyst component of the present invention is preferably subjected to a dispersion treatment and then combined with the supported catalyst component and the transition metal compound. It is found that the catalyst activity of the final supported catalyst can be improved. Generally, hydrocarbons are used as the dispersion medium such as aliphatic, cycloaliphatic or aromatic hydrocarbons. Suitable examples are aliphatic hydrocarbons of 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms, or mixtures thereof. The temperature is not particularly limited, but it is conveniently in the range of 0°C to 50°C. The time is at least 5 minutes to as long as 72 hours. There is no special limit on the upper limit, but it can be determined by practical considerations.

The transition metal compound is preferably added after the heating step, and more preferably after the heating step and the selective washing and dispersion step. If the transition metal compound is added before any of these steps, care must be taken not to subject the transition metal to high temperature which may cause its decomposition or deactivation. Preferably, the transition metal compound is added after washing, so as to prevent the transition metal from being washed away by the support material together with the aluminoxane.

The transition metal is in contact with the aluminoxane-containing material, preferably in contact with the supported catalyst component of the present invention in a diluent, preferably under conditions where the transition metal compound is soluble. Suitable diluents include aliphatic and aromatic hydrocarbons, preferably aliphatic hydrocarbons such as hexane. The metallocene is preferably added to the support body material slurry, and preferably the support body material is dissolved in the support body material to prepare the same diluent for the slurry. Generally speaking, the aluminoxane-containing material is mixed into a slurry with a diluent at a ratio of 1 to 20, preferably 2 to 10% by weight. There are no special restrictions on the contact time and temperature. The preferred temperature is 10°C to 60°C, more preferably 20°C to 45°C. The contact time is from 5 minutes to 100 hours, preferably from 0.5 hour to 3 hours. The diluent is typically removed after the metallocene is added. This can be achieved by any suitable technique, such as applying heat and/or applying reduced pressure, evaporation, filtration or decantation, or any combination thereof. If heat is applied, the temperature should not exceed the decomposition temperature of concentration.

Preferably, the olefin accepts polymerization conditions in the presence of a supported catalyst to provide a pre-polymerized supported catalyst.

In a highly preferred embodiment, the preparation of the supported catalyst includes: heating the silicon oxide containing methylaluminoxane material at a temperature of 75°C to 250°C under an inert atmosphere, preferably under reduced pressure; The product of the heating step is washed with toluene for one or more times; therefore, the conditions of the heating step and the washing step are selected to form a supported catalyst component, wherein the amount of aluminum present in the supported catalyst component is 1 gram Supported catalyst components/10ml of toluene, extracted with toluene at 90°C for 1 hour, the extractable amount does not exceed 9%; and after the heating step and the selective washing step, add a bridged cyclopentadienyl group or one ( Substituted cyclopentadienyl) group 4 transition metal compound or bridged two cyclopentadienyl group or transition metal compound of group two (substituted cyclopentadienyl) group 4 transition metal compound, but once the transition metal compound is added, this is the case The resulting product can no longer be placed at a temperature equal to or higher than its decomposition temperature.

Preferably, the supported catalyst prepared in this way contains 20 to 40% by weight of aluminum based on the total weight of the support material and the aluminoxane. Preferably, the molar ratio of the aluminum atom to the transition metal atom of the supported catalyst thus generated is 25 to 1,000. Preferably, the supported catalyst thus produced contains 0.1 to 1000 micromolar transition metal compound per gram support body material.

The supported catalyst thus obtained can be used as it is without separation or purification, but it is preferably recovered first in the form of free-flowing particles. The separated catalyst can be stored in an inert atmosphere for a long time, for example, 1 to several months. Before use, the supported catalyst can easily be reconstituted into a slurry in the diluent, preferably hydrocarbon. The supported catalyst does not require additional activators or auxiliary catalysts.

In another aspect, the present invention provides an addition polymerization method in which one or more addition polymerizable monomers are contacted with the supported catalyst according to the present invention under addition polymerization conditions.

Suitable addition polymerizable monomers include ethylenically unsaturated monomers, acetylenic compounds, conjugated or non-conjugated dienes, polyenes and carbon monoxide. Preferred monomers include olefins, such as α-olefins containing 2 to 20, preferably 2 to 12, and more preferably 2 to 8 carbon atoms, and combinations of two or more α-olefins. Particularly suitable α-olefins include, for example, ethylene, propylene, 1-butene, 1-pentene, 4-methylpentene-1,1-hexene, 1-heptene, 1-octene, 1-nonene , 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene or a combination thereof. Preferably, the α-olefin is ethylene, propylene, 1-butene, 4-methyl-1-pentene-1,1-hexene, 1-octene, and ethylene and/or propylene and one or more of these Combinations of other α-olefins. Other preferred monomers include styrene, halogen or alkyl substituted styrenes, vinyl chloride, acrylonitrile, methyl acrylate, methyl methacrylate, tetrafluoroethylene, methacrylonitrile, vinylidene chloride, vinyl ring Ene, 1,4-hexadiene, and 1,7-octadiene. Appropriate addition polymerizable monomers also include mixtures of any of the aforementioned monomers.

The supported catalyst can be generated on-site in the polymerization mixture by introducing the supported catalyst component of the present invention and the appropriate metallocene component into the mixture. The supported catalyst component and the supported catalyst of the present invention are preferably used in high pressure, solution, slurry or gas phase polymerization methods. The high pressure method is usually carried out at a temperature of 100°C to 400°C and a pressure higher than 500 Pa. The slurry process typically uses an inert hydrocarbon diluent and 0°C to just below the temperature at which the resulting polymer is substantially soluble in the inert polymerization medium. The preferred temperature is 20°C to 115°C, preferably 60°C to 105°C. The solution method is carried out at the temperature at which the resulting polymer is soluble in an inert solvent to 275°C. Generally, the solubility of a polymer depends on its density. For density 0.86 g/cm³For ethylene copolymers, solution polymerization can be achieved at temperatures as low as 60°C. The preferred solution polymer temperature is 75°C to 260°C, more preferably 80°C to 170°C. As for the inert solvent, hydrocarbons are typically used, and aliphatic hydrocarbons are preferably used. The solution method and the slurry method are usually carried out under a pressure of 1 to 100 Pa. Typical operating conditions for gas phase polymerization are 20°C to 100°C, more preferably 40°C to 80°C. In the gas phase method, the pressure is typically from below atmospheric pressure to 100 Pa. Typical gas phase polymerization methods are disclosed in U.S. Patent Nos. 4,588,790, 4,543,399, 5,352,749, 5,405,922 and U.S. Application 122,582 (application date September 17, 1993 corresponds to WO 9507942).

Preferably used in a gas phase polymerization method, the support has an intermediate particle diameter from 20 to 200 μm, more preferably from 30 μm to 150 μm, most preferably from 35 μm to 100 μm. Preferably used in a slurry polymerization method, the diameter of the intermediate particles of the support is 1 to 200 μm, more preferably 5 to 100 μm, and most preferably 20 μm to 80 μm. Preferably, the support for solution or high-pressure polymerization methods has an intermediate particle diameter of 1 to 40 μm, more preferably 2 μm to 30 μm, and most preferably 3 μm to 20 μm.

When the supported catalyst of the present invention is used in a slurry method or a gas phase method, it can not only produce high density polyethylene with a density in the typical range of 0.970 to 0.940g/cm³At the same time, surprisingly, copolymers with a substantially lower density can also be produced. Density below 0.940 g/cm³, Especially below 0.930 g/cm³As low as 0.880 g/cm³Copolymers below or below can be manufactured while maintaining good bulk density properties and can prevent or substantially remove reactor fouling. The invention can produce ethylene polymers and copolymers with a weight average molecular weight of up to 1,000,000 or even higher.

In the polymerization method of the present invention, an impurity scavenger can be used to protect the supported catalyst from being poisoned by catalyst poisons such as water, oxygen and polar compounds. These scavengers are usually used in amounts based on the amount of impurities, and are typically added to the monomer and diluent feed or to the reactor. Typical scavengers include trialkyl aluminum or boron compounds and aluminoxanes.

In this polymerization method, molecular weight control agents such as hydrogen or other chain transfer agents can be used.

The present invention has been described, and the following examples are provided for further exemplification but by no means limit its scope. Unless stated to the contrary, all scores and percentages are expressed on a weight basis.

The following support materials are used in the examples: granular silica obtained from Grace GmbH under the number SD 3216.30; spherical agglomerated silica obtained from Grace Davison (branch of WR Grace) under the number SD 3216.30; spherical agglomerated silica having a surface area of 250 m²/g and pore volume 1.4 cm³/g Unless otherwise indicated, the silica used has been heated in a vacuum at 250°C for 3 hours to obtain a final water content of approximately 0 (measured by a differential scanning card meter). If hydrated silica is used, it should be used without pre-heating as supplied.

Aluminoxane is used as 10 wt% methyl aluminoxane (MAO) in toluene solution, obtained from Witco GmbH. The metallocene is 0.0714M (third-butyramido) (tetramethyl-η⁵-Cyclopentadienyl) (dimethyl) silane titanium dimethyl (hereinafter referred to as MCpTi) in ISOPAR^TM E (trade name of Exxon Chemical Company) is used for the solution.

The bulk density of the produced polymer is determined in accordance with ASTM 1895. The aluminum content of the support material is treated with sulfuric acid, followed by adding EDTA and measuring with zinc chloride back titration.

Unless otherwise indicated, all experiments were performed under a nitrogen atmosphere.

<u style="single">Example 1</u>

11.1 g of silica SD 3216.30 was fed into the 1000 flask. Add 300 g of MAO solution and stir the mixture for 16 hours. The solvent was then removed under reduced pressure at 20°C to obtain 38 g of free-flowing powder with an aluminum content of 31.6%. The sample is divided into 4 equal parts of 9 grams. Each part was heated at unequal temperatures under reduced pressure for 2 hours. After the treatment, the aluminum content of each sample was measured, and then each was adjusted into a slurry in toluene (100 mL), and the mixture was stirred for 1 hour, filtered, and then the support body was washed with 2 portions of 50 mL of fresh toluene and vacuum dried at 120°C for 1 hour. The results of aluminum analysis are summarized below.

<tables><img file="TW353083B_D0007.tif" /></tables>

Repeat the previous procedure but use 12.1g of silica and 327g of MAO solution to obtain 42g of free-flowing powder with 31.3% aluminum content. The sample was divided into 4 equal parts, each as described above, and then subjected to the same washing procedure, but using 90°C toluene. The results are summarized in Table II.

<tables><img file="TW353083B_D0008.tif" /></tables>

These examples show that for the same time of heat treatment, an increase in the heat treatment temperature can lead to a larger amount of aluminoxane immobilized on the silicon oxide. Toluene washing at 90°C is compared with toluene washing at room temperature. For the same treatment time, the percentage of unfixed aluminum removed will increase.

<u style="single">Example 2</u>

6.2 g of silica SD 3216.30 was fed into a 250 mL flask. 168 g of MAO solution was added and the mixture was stirred for 16 hours. After this period of time, toluene was removed under reduced pressure at 20°C, and then the solid was vacuum dried at 20°C for 16 hours to obtain a free-flowing powder. The solid weight is 22.1 g and the aluminum content is 26.8%.

<u style="single">Example 3</u>

Repeat the procedure of Example 2, but use 3g silica and 56.6g MAO solution to obtain 7.6g free-flowing powder with 26.1% aluminum content. 5.2 g of the support body was slurried in toluene (50 mL) at 20°C and the mixture was stirred for 1 hour. The mixture was filtered and the support body was washed with two 20 mL portions of fresh toluene, and then vacuum dried at 20°C for 1 hour. The weight is 3.0 g and the aluminum content is 18.2%.

<u style="single">Example 4</u>

Repeat the procedure of Example 2 but use 3g silica and 75.6g MAO solution to obtain a free-flowing powder. The powder was then vacuum heated at 100°C for 2 hours. The weight is 8.4g and the aluminum content is 29.0%. 4.4 g of this support was slurried in toluene (50 mL) at 20°C and the mixture was stirred for 1 hour. The mixture was filtered and the support body was washed with two 20 mL portions of fresh toluene, and then vacuum dried at 20°C for 1 hour. The weight is 2.2 g and the aluminum content is 17.3%.

<u style="single">Example 5</u>

Repeat the procedure of Example 2 but use 3g silica and 56.6g MAO solution to obtain a free-flowing powder. The powder was heated under vacuum at 150°C for 2 hours. The resulting weight is 7.2 g and the aluminum content is 26.6%.

<u style="single">Example 6</u>

Repeat the procedure of Example 2 but use a 1000 mL flask, 12.1 g silica and 327 g MAO solution to obtain a free-flowing powder. Then 9.5 g of powder was heated at 175°C under vacuum for 2 hours. The measured aluminum content is 30.7%. 2.7 g of the support body was slurried in hexane (40 mL) at 20°C and the mixture was stirred for 4 hours. The mixture was filtered and the support body was washed with two 30 mL portions of fresh hexane, and then vacuum dried at 20°C for 1 hour. The weight is 2.4g and the aluminum content is 30.4%.

<u style="single">Example 7</u>

Follow the procedure of Example 2. The powder was then vacuum heated at 150°C for 2 hours. The weight is 7.25g and the aluminum content is 26.6%. 3 g of the obtained support was slurried in toluene (40 mL) at 20°C and the mixture was stirred for 1 hour. The mixture was filtered, and the support was washed with two 10 mL portions of fresh toluene, and then vacuum dried at 20°C for 1 hour. The weight is 2.4g and the aluminum content is 24.1%.

<u style="single">Example 8</u>

Repeat the procedure of Example 2 but use 3g silica and 75.5g MAO solution to obtain a free-flowing powder. The powder was heated under vacuum at 150°C for 2 hours. The weight is 8.4g and the aluminum content is 29.8%. 5g of the support was slurried in toluene (40 mL) at 20°C and the mixture was stirred for 1 hour. The mixture was filtered and the support body was washed with two 20 mL portions of fresh toluene, and then vacuum dried at 20°C for 1 hour. The weight is 4.5g and the aluminum content is 28.9%.

<u style="single">Example 9</u>

Repeat the procedure of Example 2 but use a 1000 mL flask, 9.1 g silica and 246 g MAO solution to obtain a free-flowing powder. The powder was then vacuum heated at 150°C for 2 hours. The weight is 29.0g and the aluminum content is 29.6%. The support body was adjusted to a slurry in toluene (300 mL) at 20°C and the mixture was stirred for 1 hour. The mixture was filtered and the support body was washed with two 100 mL portions of fresh toluene, and then vacuum dried at 20°C for 1 hour. The weight is 24.3g and the aluminum content is 28.5%.

<u style="single">Example 10</u>

Repeat the procedure of Example 2 using 5g silica and 101g MAO solution to obtain a free-flowing powder. The powder was heated under vacuum at 175°C for 2 hours. The aluminum content of this material is 28.8%. The powder (12.8 g) was slurried again in toluene (130 mL), and the mixture was heated to 90° C. and stirred for 1 hour. The mixture was filtered and the resulting solid was washed with two 50 mL portions of fresh toluene at 90°C. The support body was then vacuum dried at 120°C for 1 hour. The 10.4g support body obtained has an aluminum content of 26.3%.

<u style="single">Example 11</u>

Repeat the procedure of Example 2 using 10g silica and 76g MAO solution to obtain a free-flowing powder. This powder was heated under vacuum at 175°C for 2 hours. The aluminum content of this material is 17.2%. The powder (15.6g) was slurried again in toluene (150mL) and the mixture was heated to 90°C and stirred for 1 hour. The mixture was filtered and the resulting solid was washed with two 50 mL portions of 90°C fresh toluene. The support body was then vacuum dried at 120°C for 1 hour. The obtained 13.0g support body has an aluminum content of 16.3%.

<u style="single">Example 12</u>

Repeat the procedure of Example 2, but use 5g silica SD 3216.30 (water content 2.8%) and 101g MAO solution to obtain a free-flowing powder. The powder was heated under vacuum at 175°C for 2 hours. The aluminum content of this material is 29.4%. The powder (13g) was again slurried in toluene (130mL), and the mixture was heated to 90°C and stirred for 1 hour. The mixture was filtered and the resulting solid was washed with two 50 mL portions of fresh toluene at 90°C. The support body was then vacuum dried at 120°C for 1 hour. The obtained 11.5g support body has an aluminum content of 29.0%.

<u style="single">Example 13</u>

Repeat the procedure of Example 2 but use a 1000 mL flask, 9 g SYLOPOL 2212 and 243 g MAO solution to obtain a free-flowing powder. The powder was heated under vacuum at 150°C for 2 hours. The weight is 29.3g and the aluminum content is 29.8%. The support was again slurried in toluene (300 mL) at 20°C, and the mixture was stirred for 1 hour. The mixture was filtered and the support body was washed with two 100 mL portions of fresh toluene, and then vacuum dried at 120°C for 1 hour. The weight is 25.9g and the aluminum content is 29.3%.

<u style="single">Example 14</u>

Repeat the procedure of Example 2 but use a 1000 mL flask, 9.1 g silica and 246 g MAO solution to obtain a free-flowing powder. The powder was heated under vacuum at 175°C for 2 hours. The weight is 30.8g and the aluminum content is 30.0%. The support was again slurried in toluene (300 mL) at 20°C, and the mixture was stirred for 1 hour. The mixture was filtered and the support body was washed with two 100 mL portions of fresh toluene, and then vacuum dried at 20°C for 1 hour. The weight is 27.1 g and the aluminum content is 29.0%.

<u style="single">Example 15</u>

Repeat the procedure of Example 2 but use 5.1 g silica and 101 g MAO solution to obtain a free-flowing powder. 6.8g of powder was heated at 100°C under vacuum for 2 hours. Then the support was adjusted to a slurry in toluene (100 mL) at 90° C. and the mixture was stirred for 1 hour. The mixture was filtered and the support body was washed with two 50 mL portions of fresh toluene (90°C), and then vacuum dried at 100°C for 1 hour. The weight is 3.4g and the aluminum content is 16.6%.

<u style="single">Example 16</u>

Repeat the procedure of Example 2 but use 5.1 g silica and 101 g MAO solution to obtain a free-flowing powder. 6.8 g of powder was slurried again in toluene (100 mL) at 90°C and the mixture was stirred for 1 hour. The mixture was filtered and the support body was washed with two 50 mL portions of fresh toluene (90°C), and then vacuum dried at 100°C for 1 hour. The weight is 3.0 g and the aluminum content is 13.4%.

<u style="single">Example 17</u>

Repeat the procedure of Example 2, but use 5g silica SD 3216.30 containing 2.8% water, and 101g MAO solution to obtain a free-flowing powder. The powder was slurried again at 90°C in toluene (100 mL) and the mixture was stirred for 1 hour. The mixture was filtered and the support body was washed with two 50 mL portions of fresh toluene (90°C), and then vacuum dried at 20°C for 1 hour. The weight is 2.9g and the aluminum content is 16.4%.

<u style="single">Example 18</u>

Repeat the procedure of Example 2, but use 5g silica SD 3216.30 containing 2.8% water, and 101g MAO solution to obtain a free-flowing powder. The powder was heated at 100°C for 2 hours. 6g of this powder was slurried again in toluene (100 mL) at 90°C and the mixture was stirred for 1 hour. The mixture was filtered and the support body was washed with two 50 mL portions of fresh toluene (90°C), and then vacuum dried at 20°C for 1 hour. The weight is 3.8g and the aluminum content is 22.2%.

<u style="single">Example 19</u>

<u style="single">Preparation of supported catalyst</u>

The supported catalyst components prepared from Examples 2 to 18 were prepared according to the following procedure.

Typically, 1 g of the support body component is slurried in 20 mL of hexane and the mixture is stirred for 30 minutes. A portion of MCpTi solution (0.0714M) was fully added to obtain the transition metal loading shown in Table III. The mixture was stirred for 30 minutes and then moved to the polymerization reactor.

<u style="single">Polymerization</u>

The 10-liter pressure steam reactor is fed with 6 liters of anhydrous hexane, the comonomer (if required), hydrogen (if required) and the contents are heated to 80°C (unless otherwise indicated). Add ethylene to increase the pressure to the desired level. The amount of supported catalyst indicated in Table III was added to it via a pressurized adding cylinder. Ethylene is continuously supplied to the reactor as needed. After the required polymerization time, block the ethylene pipeline and pour the contents of the reactor into the sample container. The hexane was decanted from the polymer and the polymer was dried overnight, and then weighed to measure the yield.

In the 22nd round, the temperature was 70°C, and 100mL 1-octene comonomer was added to the reactor to obtain an ethylene/1-octene copolymer with a density of 0.9266 g/cm³. In the 23rd round, the temperature was 50°C and 200mL 1-octene comonomer was added to the reactor to obtain ethylene/1-octene comonomer with a density of 0.9230 g/cm³。

The specific polymerization conditions and results are summarized in Table III. The data in this table shows that high-density polymers can be prepared from supported catalyst components prepared using a combination of unequal heating and/or washing treatments. The highest efficiency can be obtained from supported catalyst components and catalysts containing more than 20% aluminum by weight. Excellent efficiency can be obtained from supported catalyst components dispersed in toluene at 90°C. The bulk density of the supported catalyst component that has not been subjected to heat treatment at a sufficiently high temperature or has undergone sufficient time or has not been sufficiently washed (rounds 1 to 3).

<tables><img file="TW353083B_D0009.tif" /></tables><tables><img file="TW353083B_D0010.tif" /></tables>

<u style="single">Example 20</u>

The procedure of Example 2 was repeated, but using 6.2 g of silica SD 3216.30 and 68 g of MAO solution to obtain 22.1 g of free-flowing powder with an aluminum content of 27.8%. 11 g of this support was slurried in toluene (75 mL) and 440 micromolar MCpTi (6.16 mL 0.0714M in hexane solution) was added. The mixture was stirred for 1 hour, then the solvent and residue were removed under reduced pressure and heated at 150°C for 2 hours. The 11 g of free-flowing powder thus obtained has an aluminum content of 28.2%. The materials were slurried in toluene (100 mL) and the mixture was stirred for 1 hour, filtered and the solid was washed with two 50 mL portions of fresh toluene, and then vacuum dried at 100°C for 1 hour. The weight is 9g, the aluminum content is 24.8%, and the Ti content is 40 micromoles/g.

<u style="single">Example 21</u>

Repeat the procedure of Example 6, but use 12.1 g silica SD 3216.30, and 327 g MAO solution to obtain a free-flowing powder. 9.1g of this powder was heated in vacuum at 150°C for 2 hours to obtain a material with an aluminum content of 30.7%. 3.5 g powder was slurried in toluene (35 mL) and 140 micromolar MCpTi (1.96 mL 0.0714M solution in hexane) was added and the mixture was stirred for 1 hour. The mixture was filtered and the support body was washed with 6 portions of 50 mL fresh toluene (the washing was colorless at this time), and then vacuum dried at 20°C for 1 hour. The weight is 22.0g and the Ti content is 30 micromoles/g.

<u style="single">Example 22</u>

Repeat the procedure of Example 2, but use 3.0 g of silica SD 3216.30 and MAO solution to obtain 10.5 g of free-flowing powder. 4.85g powder was slurried in toluene (50mL) and the mixture was stirred for 1 hour. The mixture was filtered and the support body was freshly washed with two 20 mL portions, and then heated under vacuum at 150°C for 2 hours. The weight is 2.1 g and the aluminum content is 14.9%. Add MCpTi according to the procedure of Example 19.

<u style="single">Example 23</u>

A 250 mL flask was charged with 3.3 g of silica SD 3216.30. Toluene (80 mL) was added to the slurry followed by 130 micromolar MCpTi (1.82 mL 0.0714M solution in hexane) and the mixture was stirred for 2 hours. 101 g of MAO solution was added and the mixture was stirred for 16 hours. At this time, the solvent was removed under reduced pressure at 20°C to obtain a free-flowing powder.

After the summary aggregation procedure of Example 19, the specific conditions described in Table IV were used to obtain the results indicated in the same table.

The data in this table shows that when the metallocene is added before the heat treatment at 150°C, a low-activity catalyst is obtained (Example 20). When the metallocene was added after the heating step but before the washing step, a reasonable bulk density was obtained (Example 21). When the washing step was performed before the heating step, a good bulk density was obtained (Example 22). When the metallocene was first added to the silicon oxide, it resulted in deactivation of the catalyst (Example 23).

<tables><img file="TW353083B_D0011.tif" /></tables>

<u style="single">Example 24</u>

Repeat the procedure of Example 1, but after removing the solvent from the MAO/silica mixture under reduced pressure at 20°C, part of the obtained powder was subjected to 2 hours of heating treatment and selective washing treatment, as summarized in Table V. After these treatments, on the one hand, the supported catalyst components are extracted with 90°C toluene to determine the extractable percentage of aluminum, and on the other hand, it is used in the polymerization reaction. All washing and extraction steps are performed with 1g support/10mL toluene, stirred for 1 hour, then filtered and washed twice with 5mL toluene/g first support. The supported catalyst was roughly prepared according to the procedure described in Example 19. The entire polymerization reaction was carried out at 80°C and a total pressure of 15 Pa for 1 hour. The results are shown in Table VI. The example shows that an excellent bulk density can be obtained when the extractable aluminum percentage is much lower than 10%.

In the first round, heat treatment at 175°C was performed alone without any washing treatment, and a polymer with good bulk density could be produced.

<tables><img file="TW353083B_D0012.tif" /></tables>

<tables><img file="TW353083B_D0013.tif" /></tables>

<u style="single">Example 25</u>

Repeat the procedure of Example 2 but use 5g silica and 101g MAO solution to obtain a free-flowing powder. The powder was heated at 100°C under vacuum to obtain 12.5 g of material. The support was then adjusted to a slurry in toluene (125 mL) at 90°C, and the mixture was stirred for 1 hour. The mixture was filtered and the support body was washed with two 50 mL portions of fresh toluene (90°C), and then vacuum dried at 100°C for 1 hour. The weight is 11.1 g and the aluminum content is measured to be 26.1% by weight. According to the procedure of Example 19 and using the numbers in Table VII at a total pressure of 15 Pa, the polymerization experiment was carried out at 80°C for 1 hour. The results are shown in Table VII.

<tables><img file="TW353083B_D0014.tif" /></tables>

<u style="single">Example 26</u>

Repeat the procedure of Example 5 of US Patent No. 5,240,894 to form the supported catalyst composition as follows. 0.58 micromolar MCpTi (8.1 mL, 0.0714M solution) was added to 35 mL of toluene. 75mL of 10wt% MAO was added to the toluene solution and the mixture was stirred for 15 minutes. Silica (5g, SD 3216.30 pre-treated at 250°C for 3 hours) was added and the mixture was stirred for 20 minutes. The mixture was heated under vacuum at 65°C for 75 minutes and the dried solid was washed with 2×70 mL of pentane, filtered and dried under high vacuum to obtain a yellow solid (8 g) with an aluminum content of 18.1% by weight. Toluene extraction at 90° C. followed by drying to obtain a yellow solid with an aluminum content of 16.2% by weight. The extractable aluminum percentage is 10.5%. Some MCpTi was lost during washing, also during hot toluene extraction, as the supernatant was yellow. A supported catalyst not treated with hot toluene (round 1) and a supported catalyst treated with hot toluene (round 2) were used. Follow the outline procedure of Example 19 for the aggregation experiment. The results are shown in Table VIII.

The results showed that the volume density of the catalyst (containing 10.5% extractable Al) without toluene treatment was poor. Hot toluene extraction via a supported catalyst can greatly improve the bulk density (round 2).

<tables><img file="TW353083B_D0015.tif" /></tables>

<u style="single">Example 27</u>

Put 508g of 10% MAO solution in toluene into a 1000mL flask, and add 25g of silica SYLOPOL 2212 with 3.5% water content under continuous stirring. The mixture was stirred for another 2 hours, and then the solvent was removed under reduced pressure at 20°C to obtain a free-flowing powder. The powder was then vacuum heated at 175°C for 2 hours. The powder was again slurried in toluene (700 mL), and the mixture was heated and refluxed for 1 hour. The mixture was filtered and the support body was washed with two 200 mL portions of 100°C fresh toluene. The support body was then vacuum dried at 120°C for 1 hour. A 63.9g support body with an aluminum content of 26.4% is obtained. The support sample was slurried in toluene and stirred for 1 hour, and then the particle size distribution was measured on the Malvern mill X instrument. It indicates that d(v,0.5) is about 12 microns. According to this procedure, supported catalyst compositions with slightly different aluminum loads were prepared.

The quantitative support component is adjusted into a slurry in hexane and the mixture is stirred for 16 hours, and then the MCpTi component (1st to 3rd) or (third-butyramido) (tetramethyl-η) is added.⁵-Cyclopentadienyl) (dimethyl) silane titanium η⁴-1,3-pentadiene (hereinafter referred to as MCpTi(II) in round 4). Then MCpTi or MCpTi(II) was added in the quantity indicated in Table IX (in ISOPAR^TM E). The supported catalyst thus prepared was subjected to a slurry polymerization reaction at 80° C. as outlined in Example 19. Other conditions and results are described in Table IX. The results show that the use of long-term dispersion before adding the transition metal compound leads to increased catalyst activity (Compare Table III).

<tables><img file="TW353083B_D0016.tif" /></tables>

<u style="single">Example 28</u>

3 Feed the 1-octene indicated in Table X into the elevated pressure steam reactor, and then add enough Isopar to obtain a total volume of 1500 mL^TM E number. Add 300 mL of hydrogen and heat the contents of the reactor to the desired temperature. Then add enough ethylene to adjust the system pressure to 30 Pa. A supported catalyst is added to initiate polymerization and ethylene is continuously supplied to the reactor as needed. After the required polymerization time, block the ethylene pipeline and pour the contents of the reactor into the sample container. The polymer was dried overnight and then weighed to determine the catalyst efficiency. The results are described in Table X, in which the molecular weight distribution (Mw/Mn) is the melt index I_ derived from gel permeation chromatography measured according to ASTM D-1238-65T (at 190° C. and 2.16 kg load).

The following supported catalysts are used for the polymerization reaction. A support body containing 23.8% aluminum/dehydrated SD 3216.30 silica was prepared in a manner similar to Example 10. In the 1st to 3rd rounds, 0.075g is supported by Isopar^TMMake a slurry and stir for a few minutes. A quantitative MCpTi solution (0.0714M) was added, the amount of which was sufficient to obtain a titanium loading of 2045 ol/g. The mixture was stirred for several minutes and then moved to the polymerization reactor. In the 4th to 6th rounds, a 0.3g support body and the same titanium load were used.

<tables><img file="TW353083B_D0017.tif" /></tables>

When used in a solution polymerization method, the supported catalyst shows good efficiency and produces a polymer with a narrow molecular weight distribution.

<u style="single">Example 29</u>

This example describes continuous polymerization rounds. These rounds used the supported catalyst prepared according to the procedure of Example 27. The support body contains 25% by weight of aluminum. In each round, the MCpTi load was 40 μmol/g.

Isopentane, ethylene, 1-octene, hydrogen and supported catalyst are continuously fed to a 10 liter jacketed and continuously stirred reaction tank, and the formed slurry product is continuously removed. The total pressure of each polymerization round is 15 Pa. The withdrawn slurry is fed to the flash tank, the diluent is removed, and the dry free-flowing polymer powder is collected. Table XI summarizes the conditions and properties of the products obtained. Melt indicator system is abbreviated as I according to ASTM D-1238-65T (190°C and load 21.6kg)₂₁)Measurement. The butene content of the polymer is measured by infrared spectroscopy. The results indicate that high bulk density polymer powder can be produced in a wide density range while still retaining the particle form.

<tables><img file="TW353083B_D0018.tif" /></tables>