CA2205376A1 - Supported catalyst component, supported catalyst, their preparation, and addition polymerization process - Google Patents

Abstract

A supported catalyst component comprising a support material and an alumoxane, wherein the alumoxane is fixed onto the support, a supported catalyst comprising said supported catalyst component and a transition metal compound, a process for the preparation of the supported catalyst component and the supported catalyst, and a process for addition polymerization of addition polymerizable monomers using said supported catalyst.

Description

CA 0220~376 1997-0~-14

2 PCT/US95/14192 SUPPORTED CATALYST COMPONENT, SUPPORTED CATALYST, THEIR PREPARATION, AND ADDITION POLYMERIZATION PROCESS

The present invention relates to a supported catalyst component comprising a 5 support material and alumoxane, to a supported catalyst col.lpr i,i, lg a support material, alumoxane, and a metallocene compound, to a process for preparing such a supported catalyst component and catalyst, and to an addition polymerization process using such a supported catalyst.
Backqround of the Invention Homogeneous or non-supported alumoxane metallocene catalysts are known for their high catalytic activity in olefin polymerizations. Under polymerization conditions where polymer is formed as solid particles, these homogeneous (soluble) catalysts form deposits of polymer on reactor walls and stirrers, which deposits should be removed frequently as they prevent an efficient heat-exchange, necessary for cool ing the reactor contents, and cause excessive wear of the moving parts. The polymers produced by these soluble catalysts further have a low bulk density which limits the commercial utility of both the polymer and the process. In order to solve these problems, several supported alumoxane metallocene catalysts have been proposed for use in particle forming polymerization processes.
U.S. Patent 5,057,475 describes a supported metallocene alumoxane catalyst 20 wherein the alumoxane can be a commercial alumoxane, or an alumoxane generdted in situ on the solid support, for example, by the addition of a trialkylaluminum compound to a water-containing support, such as by addition of trimethylaluminum to a water containing silica. In the prerer,ed methods of U.S. Patent 5,057,475, the metallocene component and the alumoxane (which previously may have been combined with a modifier compound) are25 combined in a first step in a suitable solvent. In a subsequent step, this solution is contacted with the support. Then, the solvent can be removed, typically by applying a vacuum. The solution may be heated in order to aid in the removal of the solvent. In an alternative method, an undehydrated silica gel is added to a solution of trialkylaluminum to produce an alumoxane which is deposited onto the surface of the silica gel particles. Then, the solvent is removed and 30 the residual solids are dried to a free-flowing powder. In typical examples, dried silica is slurried with an alumoxane in toluene, filtered, washed with pentane, and then dried under vacuum. The metallocene compound is typically combined with an alumoxane in toluene or heptane, which solution subsequently is combined with the pretreated silica. Finally, the toluene or heptane is removed under vacuum to recover the supported catalyst.
U.S. Patent 5,026,797 describes treating a porous water-insoluble inorganic oxide particle support with an alumoxane in a solvent for the alumoxane, such as an aromatic hydrocarbon, followed by rinsing the treated support with an aromatic hydrocarbon solvent until no alumoxane is detected in the supernatant. Thus, it is said to be possible to adiust the CA 0220~376 1997-0~-14 amount of the aluminum atom of the alumoxane bonded onto the treated oxide support in the range of 2 to 10 percent by weight. Subsequently, the treated support is combined with a zirconium compound. The so-formed support material containing alumoxane and zirconium compound is used together with additional alumoxane in solution in a polymel i~d li 5 reaction.
U.S. Patent 5,147,949 discloses supported metallocene alumoxane catalysts prepared by adding a water-impregnated catalyst support to a stirred solution of an aluminum trialkyl, and adding to the reaction productthereof a metallocene component.
U.S. Patent 5,240,894 describes a method to produce a supported catalyst by 10 forming a metallocene/alumoxane reaction solution, adding a porous carrier, evaporating the resulting slurry so as to remove residual solvent from the carrier, and optionally prepolymerizing the catalyst with olefinic monomer. A good polymer bulk density is only obtained using a prepolymerized supported catalyst.
U.S. Patent 5,252,529 discloses solid catalysts for olefin polymerization comprising a particulate carrier containing at least one percent by weight of water, an alumoxane compound, and a metallocene compound. In the preparation of this catalyst, the reaction product of the particulate carrier and the alumoxane is separated from the diluent (toluene) by decantation or drying at reduced pressure.
European Patent Application No. 368,644 discloses a process for preparing a 20 supported metallocene alumoxane catalyst wherein an undehydrated silica gel is added to a stirred solution of triethylaluminum, to which reaction mixture is added a solution of a metallocene to which trimethylaluminum has been added. Following the addition of the trimethylaluminum treated metallocene to the triethylaluminum treated silica gel solids, the catalyst is dried to a free-flowing powder. Drying of the catalyst may be done by filtration or 25 evaporation of solvent at a temperature up to 85C.
European PatentApplication No.323,716 discloses a process for preparing a supported metallocene alumoxane catalyst by adding undehydrated silica gel to a stirred solution of an aluminum trialkyl, adding a metallocene to the reacted mixture, removing the solvent, and drying the solids to a free-flowing powder. After the metallocene has been 30 added, the solvent is removed and the residual solids are dried at a temperature of up to 85C.
European Patent Application No. 523,416 describes a supported catalyst component for olefin polymerization prepared from an inorganic support and a metallocene.
The metallocene and support are intensively mixed in a solvent. P~ ererdbly, the catalyst component thus obtained is extracted in a suitable solvent, such as toluene, to remove 35 metallocene which is not fixed. Subsequently, alumoxane can be added as a cocatalyst.
European Patent Application No. 567,952 describes a supported polymerization catalyst comprising the reaction product of a supported organoaluminum compound and a metallocene catalyst compound. This supported catalyst is prepared by combining CA 0220~376 1997-0~-14 trimethylaluminum with a previously dried support material in an aliphatic inert suspension medium, to which water is added. This suspension can be used as such or can be filtered and the solids thus obtained can be resuspended in an aliphatic inert suspension medium, and then combined with the metallocene compound. When the reaction is complete, the su~,e. "dldnt 5 solution is separated off and the solid which remains is washed once to five times with an inert suspending medium, such as toluene, n-decane, diesel oil or dichloromethane.
It would be desirable to provide a supported catalyst component, a supported catalyst, and a polymerization process that pr_ le. ~l~ or sul"ldnlially reduces the problem of reactor fouling, including formation of polymer deposits on reactor walls and on the agitator 10 in the reactor, especially in gas phase polymerization or slurry polymerization processes.
Further, it is preferred that polymer products produced by gas phase polymerization or slurry polymerization processes are in free-flowing form and, advantageously, have high bulk densities.
Summarv of the Invention In one aspect of the present invention, there is provided a supported catalyst component comprising a support material and an alumoxane, which component contains 15 to 40 weight percent of aluminum, based on the total weight of the support material and alumoxane, and wherein not more than 10 percent aluminum present in the supported catalyst component is extractable in a one-hour extraction with toluene of 90C using 10 mL toluene 20 per gram of supported catalyst component, said supported catalyst component being obtainable by A. heating a support material containing alumoxane under an inert atmosphere for a period and at a temperature sufficient to fix alumoxane to the support material.
In a second aspect, there is provided a supported catalyst comprising: the supported catalyst component according to the present invention and a transition metal compound containing at least one cyclic or noncyclic n-bonded anionic ligand group.
According to a further aspect, there is provided a process for preparing a supported catalyst component comprising:
A. heating a support material containing alumoxane under an inert atmosphere for a period and at a temperature sufficient to fix alumoxane to the support material;
thereby selecting the conditions in heating step A so as to form a supported catalyst component, which component contains 15 to 40 weight percent of aluminum, based 35 on the total weight of the support material and alumoxane, and wherein not more than 10 percent aluminum present in the supported catalyst component is extractable in a one-hour extraction with toluene of 90C using 10 mL toluene per gram of supported catalyst component.

-3-CA 0220~376 1997-0~-14 In another aspect, the invention provides a process for preparing a supported catalyst comprising:
A. heating a support materiai containing alumoxane under an inert atmosphere for a period and at a temperature sufficient to fix alumoxane to the support 5 material; and optionallyfollowed by B. subjecting the support material containing alumoxane to one or more wash steps to remove alumoxane not fixed to the support material;
thereby selecting the conditions in heating step A and optional washing step B so as to form a supported catalyst component, which component contains 15 to 40 weight percent 10 of aluminum, based on the total weight of the support material and alumoxane, and wherein not more than 10 percent aluminum present in the supported catalyst component isextractable in a one-hour extraction with toluene of 90C using 10 mL toluene per gram of supported catalyst component; and adding, before or after step A or step B, a l, dn,ilion metal compound containing 15 at least one cyclic or noncyclic n-bonded an ionic ligand group, with the proviso that once the transition metal compound has been added, the product thus obtained is not subjected to temperatures equal to or higherthan the decomposition temperature of the lrdn~ilion metal compound.
In yet a further aspect, there is provided an addition polymerization process 20 wherein one or more addition polymerizable monomers are contacted with a supported catalyst according to the present invention under addition polymerizable conditions.
Detailed Descri,otion of the Invention All references herein to elements or metals belonging to a certain 6roup refer to the Periodic Table of the Elements published and copyrighted by CRC Press, Inc., 1989. Also, 25 any reference to the Group or Groups shall be to the Group or Groups as reflected in this Periodic Table of the Elements using the IUPAC system for numbering groups. The term hydrocarbyl as employed herein means any aliphatic, cycloaliphatic, aromatic group or any combination thereof. The term hydrocarbyloxy means a hydrocarbyl group having an oxygen link between it and the element to which it is attached. Where in the specification and claims 30 the expression "substituted cyclopentadienyl" is used, this includes ring-substituted or polynuclear derivatives of the cyclopentadienyl moiety wherein said substituent is hydrocarbyl, hydrocarbyloxy, hydrocarbylamino, cyano, halo, silyl, germyl, siloxy or mixtures thereof or two such substituents are a hydrocarbylene group, said substituent (or two substituents together) having up to 30 non-hydrogen atoms. By the term "substituted cyclopentadienyl" is specifically 35 included indenyl, tetrahydroindenyl, fluorenyl, and octahydrofluorenyl groups.
Surprisingly, it has been found that polymers having good bulk density can be prepared in a particle forming polymerization process, without or with substantially reduced reactor fouling, by using a supported catalyst wherein the alumoxane is fixed to the support

-4-CA 0220~376 1997-0~-14 material. According to the present invention, good bulk densities, for ethylene based polymers and interpolymers, are bulk densities of at least 0.20 g/cm3, preferably of at least 0.25 g/cm3, and more preferably of at least 0.30 g/cm3. It is believed that the extent of reactor fouling is - related to the amount of alumoxane which leaches off the support during polymerization

5 conditions, which may lead to active catalyst being present in the homogeneous phase, thus disso!ved in the di!uent, which under particle forming condi.ions may give very smaii poiymer parlicles or polymer particles of poor morphology that may adhere to metal parts or static parts in the reactor. Further, it is believed that the bulk density of a polymer is related to the manner in which alumoxane is fixed to the support and to the amount of non-fixed alumoxane on the 10 support, that is, the amount of aluminum that can be extracted from the support by toluene of 90C. The fixation of the alumoxane on the support according to the specific treatment of the present invention results in substantially no alumoxane being leached off of the support under polymerization conditions and substantially no soluble active catalyst species being present in the polymerization mixture. It has been found that the present supported catalysts can be used 15 not only to prepare ethylene polymers and copolymers in the traditional high density polyethylene density range (0.970 to 0.940 g/cm3) in slurry and gas phase polymerization processes, but also copolymers having densilies lower than 0.940 g/cm3 down to 0.880 g/cm3 or lower while reta ining good bulk density properties and while preventing or substantially decreasing reactorfouling.
The supported catalyst component of the present invention comprises a support material and an alumoxane wherein in general not more than 10 percent aluminum present in the supported catalyst component is exllacldble in a one-hour extraction with toluene of 90C
using 10 mL toluene per gram of supported catalyst component. P-ereral)ly, not more than 9 percent aluminum present in the supported catalyst component is extractable, and most 25 preferably not more than 8 percent. It has been found that when the amount of extractables is below these levels, a good polymer bulk density is obtained with supported catalysts based on these supported catalyst components.
The toluene extraction test is carried out as follows. 1 g of supported catalystcomponentorsupportedcatalyst,withaknownaluminumcontent,isaddedto10mLtoluene 30 and the mixture is then heated to 90C under an inert atmosphere. The suspension is stirred well at this temperature for 1 hour. Then, the suspension is filtered applying reduced pressure to assist in the filtration step. The solids are washed twice with 3 to 5 mL toluene of 90C per gram of solids. The solids are then dried at 1 20C for 1 hour, and subsequently the aluminum content of the solids is measured. The difference between the initial aluminum content and 35 the aluminum content after the extraction divided by the initial aluminum content and multiplied by 100 percent, gives the amount of extractable aluminum.
The aluminum content is determined by slurrying 0.5 g of supported catalyst componentorsupportedcatalystin10mLhexane. Theslurryistreatedwith10to15mL6N

CA 0220~376 l997-0~-l4 WO 96/16092 PCI~/US95tl4192 sulfuric acid, followed by addition of a known excess of EDTA. The excess amount of EDTA is then back-titrated with zinc chloride.
At a ievel of 10 percent extractables, the polymer bulk density obtained by polymerization using supported catalysts (components) described herein is quite sensitive with 5 respect to small changes in the percentage of aluminum extractables. In view of the sensitivity of the polymer bulk density and the error margin in the determination of the pe. cen Ldge aluminum extractables (which is estimated to be 1 percent absolute), an alternative test to distinguish the supported catalyst component and supported catalyst according to the present invention is to use a supported catalyst in an ethylene polymerization process in a hydrocarbon 10 diluent at 80C and 15 bar and determine the extent of reactor fouling and/or the bulk density of the ethylene polymer produced. The suL~ldnlial absence of reactor fouling, that is, substantially no polymer deposits on reactor walls or agitator, and/or bulk densities of at least 0.20 g/cm3, and preferably of at least 0.25 g/cm3, are characteristic of the inventive supported catalyst components and catalysts.
Support materials suitable for the present invention preferably have a surface area as determined by nitrogen porosimetry using the B.E.T. method from 10 to 1000 m2/g, and preferdbly from 100 to 600 m2/g. The porosity of the support advantageously is between 0.1 and 5 cm3/g, preferably from 0.1 to 3 cm3/g, most preferably from 0.2 to 2 cm3/g. The average particle size is not critical but typically from 1 to 200 I m.
Suitable support materials for the supported catalyst component of the present invention include porous resinous materials, for example, copolymers of styrene-divinylbenzene, and solid inorganic oxides, such as silica, alumina, magnesium oxide, titanium oxide, thorium oxide, as well as mixed oxides of silica and one or more Group 2 or 13 metal oxides, such as silica-magnesia and silica-alumina mixed oxides. Silica, alumina, and mixed 25 oxides of silica and one or more Group 2 or 13 metal oxides are preferred support materials.
Preferred examples of such mixed oxides are the silica-aluminas. Most preferred is silica. The silica may be in granular, agglomerated, fumed or otherform. Suitable silicas include those that are available from Grace Davison (division of W.R. Grace & Co.) under the designations SD
3216.30, Davison Syloid 245, Davison 948 and Davison 952, and from Degussa AG under the 30 designation Aerosil 812.
Prior to its use, if desired, the support material may be subjected to a heat treatment and/or chemical treatment to reduce the water content or the hydroxyl content of the support material. Typical thermal pretreatments are carried out at a temperature from 30C to 1 000C for a duration of 10 minutes to 50 hours in an inert atmosphere or under 35 reduced pressure.
The supported catalyst component further comprises an alumoxane component.
An alumoxane (also referred to as aluminoxane) is an oligomeric or polymeric aluminum oxy compound containing chains of alternating aluminum and oxygen atoms, wherebythe

-6-, CA 0220~376 l997-0~-l4 WO 96/16092 PCTrUS95/14192 aluminum carries a substituent, pl efel dbly an alkyl group. The exact structure of alumoxane is not known, but is generally believed to be rep~esented by the following general formulae (-AI(R)-O)m, for a cyclic alumoxane, and R2Al-o(-Al(R)-o)m-AlR2l for a linear compound, wherein - R independently each occurrence is a C1 to C10 hydrocarbyl, preferably alkyl, or halide and m is 5 an integer ranging from 1 to 50, p~ efel dbly at least 4. Al umoxanes are typically the reaction products of water and an aluminum alkyl, which in addition to an alkyl group may contain halide or alkoxide groups. Reacting several different aluminum alkyl compounds, such as, for example, trimethylaluminum and tri-isobutyl aluminum, with water yields so-called modified or mixed alumoxanes. P~ efe~ ~ ~d alumoxanes are methylalumoxane and methylalumoxane 10 modified with minor amounts of other lower alkyl groups such as isobutyl. Alumoxanes generally contain minor to substantial amounts of starting aluminum alkyl compound.
The way in which the alumoxane is prepared is not critica I for the present invention. When prepared by the reaction between water and aluminum alkyl, the water may be combined with the aluminum alkyl in various forms, such as liquid, vapor, or solid, for 15 example, in the form of water of crystallization. Particular techniques for the preparation of alumoxane-type compounds by contacting an aluminum alkyl compound with an inorganic salt containing water of crystallization are disclosed in U.S. Patent 4,542,199. In a particular p, efel . ed embodiment, an aluminum alkyl compound is contacted with a regeneratable water-containing substance such as hydrated alumina, silica or other substance. This is disclosed in 20 European PatentApplication No. 338,044.
The supported catalyst component of the present invention generally contains 15 to 40 weight percent, preferably from 20 to 40 weight percent, and more preferdbly from 25 to 40 weight percent of aluminum, based on the total weight of the support material and alumoxane. Amounts of aluminum of at least 15 weight percent, preferdbly at least 20 weight 25 percent, and most preferably at least 25 weight percent are advantageous because these enable the deposit of relatively high amounts of transition metal compound on the support and thereby enable a relatively high activity to be obtained. This improves the overall catalyst efficiency, especially when expressed on the basis of the support material.
The supported catalyst component as such or slurried in a diluent can be stored or 30 shipped under inert conditions, or can be used to generate the supported catalyst of the present invention.
According to a further aspect, the present invention provides a supported catalyst comprising the supported catalyst component according to the present invention and a transition metal compound, preferably a transition metal compound containing at least one 35 cyclic or non-cyclic n-bonded anionic ligand group, preferably a cyclopentadienyl or substituted cyclopentadienyl moiety. Suitable complexes are derivatives of any transition metal including Lanthanides, but preferably of 6roup 3, 4, 5, or Lanthanide metals which are in the + 2, + 3, or +4 formal oxidation state. P~ efer,ed compounds include metal complexes containing from 1

-7-CA 0220~376 1997-0~-14 to 3 n-bonded anionic ligand groups, which may be cyclic or non-yclic delocalized n-bonded anionic ligand groups. Exemplary of such n-bonded anionic ligand groups are conjugated or nonconjugated, cyclic or non-yclic dienyl groups, allyl groups, and arene groups. By the term "n-bonded " is meant that the ligand group is bonded to the transition metal by means of a n 5 bond. Each atom in the delocalized n-bonded group may independently be substituted with a radical selected from halogen, hydrocarbyl, halohydrocarbyl, and hydrocarbyl-substituted metalloid radicals wherein the metalloid is selected from Group 14 of the Periodic Table of the Elements. Included within the term hydrocarbyl are preferably C1 20 straight, branched and cyclic alkyl radicals, C6 20 aromatic radicals, C7 20 alkyl-substituted aromatic radicals, and C7 20 10 aryl-substituted alkyl radicals. In addition two or more such radicals may together form a fused ring system or a hydrogenated fused ring system. Suitable hy.l~ .carbyl-substituted organometalloid radicals include mono-, di- and trisubstituted organometalloid radicals of Group 14 elements wherein each of the hydrocarbyl groups contains from 1 to 20 carbon atoms. Examples of suitable hydrocarbyl-substituted organometalloid radicals include 15 trimethylsilyl, triethylsilyl, ethyldimethylsilyl, methyldiethylsilyl, triphenylgermyl, and trimethylgermyl groups.
Examples of suitable anionic, delocalized n-bonded groups include yclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl, tetrahydrofluorenyl, octahydrofluorenyl, pentadienyl, yclohexadienyl, dihydroanthracenyl, hexahydroanthracenyl, 20 and decahydroanthracenyl groups, as well as C1-10 hydrocarbyl-substituted derivatives thereof.
Preferred anionic delocalized n-bonded groups are yclopentadienyl, pentamethylcyclopentadienyl, tetramethylyclopentadienyl, indenyl, 2,3-dimethylindenyl, fluorenyl, 2-methylindenyl and 2-methyl-4-phenylindenyl.
The term metallocene compound as used herein refers to transition metal 25 compounds containing a derivative of a cyclopentadienyl moiety. Suitable metallocenes for use in the present invention are the bridged or unbridged mono-, bis-, and triyclopentadienyl or substituted yclopentadienyl transition metal compounds.
Suitable unbridged monocyclopentadienyl or mono(substituted yclopentadienyl) transition metal derivatives are represented by the general formula CpMXn 30 wherein Cp is cyclopentadienyl or a derivative thereof; M is a Group 3, 4, or 5 transition metal having a formal oxidation state of 2, 3 or 4; X independently each occurrence represents an anionic ligand group (otherthan a cyclic, aromatic n-bonded anionic ligand group), said X
having up to 50 non-hydrogen atoms; and n, a number equal to one less than the formal oxidation state of M, is 1, 2 or 3, preferably 3. Exemplary of such ligand groups X are 35 hydrocarbyl, hydrocarbyloxy, hydride, halo, silyl, germyl, amide, and siloxy or two X groups together mayform a hydrocarbylene (including hydrocarbylidene).
Suitable bridged monocyclopentadienyl or mono(substituted yclopentadienyl) transition metal compounds include the well-known constrained geometry complexes.

-8-CA 0220~376 1997-0~-14 WO 96/16092 PCT/US95/1'1192 Examples of such complexes and methods for their preparation are disclosed in U.S. Application Serial No. 545,403, filed July 3, 1990 (corresponding to EP-A-416,815), U.S. Patent 5,374,696 (corresponding to WO-93/19104), as well as U.S. Patents 5,055,438, 5,057,475, 5,096,867, - 5,064,802 and 5,132,380.
More particularly, pr~r~r. ed bridged monocyclopentadienyl or mono(substituted cyclopentadienyl) transition metal compounds correspond to the formula l:

Cp* M

(X)n wherein:
M is a metal of Group 3 to 5, especially a Group 4 metal, particularly titanium;Cp* is a substituted cyclopentadienyl group bound to Z' and, in an rlS bonding mode, to M or such a group is further substituted with from one to four substituents selected from hydrocarbyl, silyl, germyl, halo, hydrocarbyloxy, amino, and mixtures thereof, said substituent having up to 20 non-hydrogen atoms, or optionally, two such further substituents (except halo or amino) together cause Cp* to have a fused ring structure;
Z' is a divalent moiety other than a cyclic or non-cyclic n-bonded anionic ligand, said Z' comprising boron, or a member of Group 14 of the Periodic Table of the Elements, and optionally nitrogen, phosphorus, sulfur or oxygen, said moiety having up to 20 non-hydrogen atoms, and optionally Cp* and Z' togetherform a fused ring system;
X independently each occurrence is an anionic ligand group (other than a cyclic n-bonded group) having up to 50 non-hydrogen atoms; and n is 1 or 2 depending on the valence of M.
In consonance with the previous explanation, M is prererdbly a Group 4 metal, especially titanium; n is 1 or 2; and X is a monovalent ligand group of up to 30 non-hydrogen atoms, more preferably, C1-20 hydrocarbyl.
When n is 1 and the Group 3 to 5 metal (preferably the Group 4 metal) is in the +3 formal oxidation state, X is preferably a stabilizing ligand.
By the term "stabilizing ligand" is meant that the ligand group stabilizes the metal complex through either:
1) a nitrogen, phosphorus, oxygen or sulfur chelating bond, or 2) an rl3 bond with a resonant, delocalized n-electronic structure.
Examples of stabilizing ligands of group 1 include silyl, hydrocarbyl, amido or phosphido ligands substituted with one or more aliphatic or aromatic ether, thioether, amine CA 0220~376 1997-0~-14 or phosphine functional groups, especially such amine or phosphine groups that are tertiary substituted, said stabilizing ligand having from 3 to 30 non-hydrogen atoms. Most pref~r, ed group 1 stabilizing ligands are 2-dialkylaminobenzyl or 2-(dialkylaminomethyl)phenyl groups containing from 1 to 4 carbons in the alkyl groups.
Examples of stabilizing ligands of group 2 include C3 10 hydrocarbyl groups containing ethylenic unsaturation, such as allyl, 1-methylallyl, 2-methylallyl, 1,1-dimethylallyl, or 1,2,3-trimethylallyl groups.
More preferably still, such metal coordination complexes cur, ~" ond to the formula ll:
R ' z ~ Y
R~<O I M/ II
'f R ~ ~X)n R~

wherein R' each occurrence is independently selected from hydrogen, hydrocarbyl, silyl, germyl, cyano, halo and combinations thereof having up to 20 non-hydrogen atoms, or two R' groups (except cyano or halo) together form a divalent derivative thereof;
X each occurrence independently is selected from hydride, halo, alkyl, aryl, silyl, 20 germyl, aryloxy, alkoxy, amide, siloxy, and combinations thereof having up to 20 non-hydrogen atoms;
Y is a divalent anionic ligand group comprising nitrogen, phosphorus, oxygen or sulfur and having up to 20 non-hydrogen atoms, said Y being bonded to Z and M through said nitrogen, phosphorus, oxygen or sulfur, and optionally Y and Z together form a fused ring 25 system;
M is a Group 4 metal, especiallytitanium;
Z is SiR*2, CR*2, SiR*2SiR*2, CR*2CR*2, CR* = CR*, CR*ZsiR*2~ GeR*2, BR*, or BR*2;
wherein:
R* each occurrence is independently selected from hydrogen, hydrocarbyl, silyl, 30 halogenated alkyl, halogenated aryl groups having up to 20 non-hydrogen atoms, and mixtures thereof, or two or more R* groups from Z, or an R* group from Z together with Y
form a fused ring system; and n is 1 or 2.
Further more preferably, Y is-O-, -S-, -NR*-, -PR*-. Highly preferably, Y is a 3 nitrogen or phosphorus containing group corresponding to the formula -N(R')- or -P(R')-, wherein R' is as previously described, that is, an amido or phosphido group.

CA 0220~376 1997-0~-14 Most highly prefer. ed metal coordination complexes correspond to the formula 111:
R~ (ER 2)m~N R~

S R~/ M III

R~ (X)n R

wherein:
M istitanium;
R' each occurrence is independently selected from hydrogen, silyl, hydrocarbyl andcombinationsthereofhavingupto20,prererdblyuptolOcarbonorsiliconatoms,ortwo R' groups of the substituted cyclopentadienyl moiety are joined together;
E is silicon or carbon;
X independently each occurrence is hydride, halo, alkyl, aryl, aryloxy or alkoxy of up to 10 carbons;
m is 1 or 2; and nis1 or2.
Examples of the above most highly prer~r.ed metal coordination compounds 20 include compounds wherein the R' on the amido group is methyl, ethyl, propyl, butyl, pentyl, hexyl (including isomers), norbornyl, benzyl, phenyl or cyclododecyl; (ER'z)m is dimethyl silane or 1 ,2-ethylene; R' on the cyclic n-bound group independently each occurrence is hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, norbornyl, benzyl or phenyl or two R' groups are joined forming an indenyl, tetrahydroindenyl, fluorenyl or octahydrofluorenyl moiety; and X is5 chloro, bromo, iodo, methyl, ethyl, propyl, butyl, pentyl, hexyl, norbornyl, benzyl or pheny l.
Specific highly prerer-ed compounds include: (tert-butylamido)(tetramethyl-rl5-cyclopentadienyl)-1,2-ethanediyltitanium dimethyl, (tert-butylamido)(tetramethyl-rl5-cyclopentadienyl)-1,2-ethanediyltitanium dibenzyl, (tert-butylamido)(tetramethyl-rl5-cyclopentadienyl)dimethylsilanetitanium dimethyl, (tert-butylamido)(tetramethyl-30 rl5-cyclopentadienyl)dimethylsilanetitanium dibenzyl, (methylamido)(tetramethyl-rl5-cyclopentadienyl)dimethylsilanetitanium dimethyl, (methylamido)(tetramethyl-rl5-cyclopenta-dienyl)dimethylsilanetitanium dibenzyl, (phenylamido)(tetramethyl-rl5-cyclopenta-dienyl)dimethylsilanetitanium dimethyl, (phenylamido)(tetramethyl-rl5-cyclopenta-dienyl)dimethylsilanetitanium dibenzyl, (benzylamido)(tetramethyl-rl5-cyclopenta-35 dienyl)dimethylsilanetitanium dimethyl, (benzylamido)(tetramethyl-rl5-cyclopenta-dienyl)dimethylsilanetitanium dibenzyl, (tert-butylamido)(rl5-cyclopentadienyl)-1,2-ethanediyltitanium dimethyl, (tert-butylamido)(r~5-cyclopentadienyl)-CA 0220~376 lgg7-o~-l4 WO 96tl6092 PCT/US9S/14192 1,2-ethanediyltitanium dibenzyl, (tert-butylamido)(~5-cyclopentadienyl)-dimethylsilanetitanium dimethyl, (tert-butylamido)(rl5-cyclopentadienyl)dimethyl-silanetitanium dibenzyl, (methylamido)(rl5-cyclopentadienyl)dimethylsilanetitanium dimethyl, (t-butylamido)(rl5-cyclopentadienyl)dimethylsilanetitanium dibenzyl, (t-5 butylamido)indenyldimethylsilanetitanium dimethyl, (t-butylamido)indenyldimethylsilane-titanium dibenzyl, (benzylamido)indenyldimethylsilanetitanium dibenzyl; and the cor.e".onding zirconium orhafnium coordination complexes.
Transition metal compounds wherein the l,ansilion metal is in the + 2 formal oxidation state and processes for their preparation are disclosed in detail in WO 9500526 which 10 corresponds to U.S. Application Serial No. 241,523, filed May 12,1994. Suitable complexes include those containing one, and only one, cyclic, delocalized, anionic, n-bonded group, said complexes corresponding to the formula lV:
z IV
L M--X*
wherein:
M is titanium or zirconium in the + 2 formal oxidation state;
L is a group containing a cyclic, delocalized, anionic, n-system through which the group is bound to M, and which group is also bound to Z;
Z is a moiety bound to M via a a-bond, comprising boron, or a member of Group 14 of the Periodic Table of the Elements, and also comprising nitrogen, phosphorus, sulfur or oxygen, said moiety having up to 60 non-hydrogen atoms; and X* is a neutral, conjugated or non-conjugated diene, optionally substituted withone or more hydrocarbyl groups, said X having up to 40 carbon atoms and forming a n-complex with M.
Preferred transition metal compounds of formula IV include those wherein Z, M
and X* are as previously defined; and L is a C5H4 group bound to Z and bound in an rl5 bonding mode to M or is such an rl5 bound group substituted with from one to four substituents independently selected from hydrocarbyl, silyl, germyl, halo, cyano, and combinations thereof, said substituent having up to 20 non-hydrogen atoms, and optionally, two such substituents (except cyano or halo) together cause L to have a fused ring structure.
More preferred transition metal + 2 compounds according to the present invention correspond to the formula V:
R' Z~
R ~,~ M V
R~ X*
R

CA 0220~376 1997-0~-14 wherein:
R' each occurrence is independently selected from hydrogen, hydrocarbyl, silyl, germyl, halo, cyano, and combinations thereof, said R' having up to 20 non-hydrogen atoms, - and optionally, two R' groups (where R' is not hydrogen, halo or cyano) together form a 5 divalent derivative thereof connected to adjacent positions of the cycloper,lddienyi ring to form a fused ring structure;
X* is a neutral rlAbonded diene group having up to 30 non-hydrogen atoms, which forms a n-complex with M;
Y is-O-,-S-,-NR*-, -PR*-;
M is titanium or zirconium in the + 2 formal oxidation state; and Z* is SiR*z, CR*z, SiR*2SiR*2, CR*2CR*z, CR*=CR*, CR*2SiR*2, or GeR*2; wherein:
R* each occurrence is independently hydrogen, or a member selected from hydrocarbyl, silyl, halogenated alkyl, halogenated aryl, and combinations thereof, said R*
having up to 10 non-hydrogen atoms, and optionally, two R* groups from Z* (when R* is not 15 hydrogen), or an R* group from Z* and an R* group from Y form a ring system.
P~ eferdbly, R' independently each occurrence is hydrogen, hydrocarbyl, silyl, halo and combinations thereof said R' having up to 10 non-hydrogen atoms, or two R' groups (when R' is not hydrogen or halo) together form a divalent derivative thereof; most prererdbly, R' is hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, (including where appropriate all isomers), 20 cy~lopenlyl, cyclohexyl, norbornyl, benzyl, or phenyl ortwo R' groups (except hydrogen) are linked together, the entire CsR'4 group thereby being, for example, an indenyl, tetrahydroindenyl, fluorenyl, tetrahydrofluorenyl, or octahydrofluorenyl group.
Further preferdbly, at least one of R' or R* is an electron donating moiety. By the term "electron donating" is meant that the moiety is more electron donating than hydrogen.
25 Thus, highly preferably Y is a nitrogen or phosphorus containing group corresponding to the formula -N(R")- or-P(R")-, wherein R" is C1 10 hydrocarbyl.
Examples of suitable X* groups include: s-trans-rl4-1,4-diphenyl-1,3-butadiene; s-trans-rl4-3-methyl-1 ,3-pentadiene; s-trans-rl4-1 ,4-dibenzyl-1 ,3-butadiene; s-trans-rl4-2,4 hexadiene; s-trans-rl4-1,3-pentadiene; s-trans-rl4-1,4-ditolyl-1,3-butadiene; s-trans-rl4-1,4-30 bis(trimethylsilyl)-1,3-butadiene; s-cis-rl4-1,4-diphenyl-1,3-butadiene; s-cis-rl4-3-methyl-1,3-pentadiene; s-cis-rl4-1,4-dibenzyl-1,3-butadiene; s-cis-rl4-2,4-hexadiene; s-cis-rl4-1,3-pentadiene; s-cis-rl4-1,4-ditolyl-1,3-butadiene; and s-cis-rl4-1,4-bis(trimethylsilyl)-1,3-butadiene, said s-cis diene group forming a n-complex as defined herein with the metal.
Most highly preferred transition metal +Z compounds are amidosilane- or 35 amidoalkanediyl- compounds of formula V wherein:
-Z*-Y- is -(ER"'2)m-N(R )-, and R' each occurrence is independently selected from hydrogen, silyl, hydrocarbyl and combinations thereof, said R' having up to 10 carbon or silicon atoms, or two such R' groups on the substituted cyclopentadienyl group (when R' is not CA 0220~376 1997-0~-14 hydrogen) together form a diva lent derivative thereof connected to adjacent positions of the cy~lopehlddienyl ring;
R" is C1-10 hydrocarbyl;
R"' is independently each occurrence hydrogen or Cl 10 hydrocarbyl;
E is independently each occurrence silicon or carbon; and mis1 or2.
Examples of the metal complexes according to the present invention include compounds wherein R" is methyl, ethyl, propyl, butyl, pentyl, hexyl (including all isomers of the foregoing where applicable), cyclododecyl, norbornyl, benzyl, or phenyl; (ER"'2)m is 10 dimethylsilane, or ethanediyl; and the cyclic delocalized n-bonded group is cyclopentadienyl, tetramethylcyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl, tetrahydrofluorenyl or octahydrofluorenyl.
Suitable bis-cyclopentadienyl or substituted cyclopentadienyl trdn~ on metal compounds include those containing a bridging group linking the cyclopentadienyl groups and 15 those without such bridging groups.
Suitable unbridged bis-cyclopentadienyl or bis(substituted cyclopentadienyl) transition metal derivatives are represented by the general formula Cp2MXn~ wherein Cp is a n-bound cyclopentadienyl group or a n-bound substituted cyclopentadienyl group, and M and X are as defined with respect to formula ll, and n' is 1 or 2 and is two less than the formal 20 oxidation state of M. Preferably n' is 2. Exemplary of the unbridged biscyclopentadienyl l-dn~ilion metal derivatives are: biscyclopentadienyl zirconium dimethyl, biscyclopentadienyl zirconium dibenzyl, bis(methylcyclopentadienyl) zirconium dimethyl, bis(n-butyl cyclopentadienyl) zirconium dimethyl, bis(t-butylcyclopentadienyl) zirconium dimethyl, bis(pentamethylcyclopentadienyl) zirconium dimethyl, bis(indenyl) zirconium dibenzyl, 25 bis(fluorenyl) zirconium dimethyl, bis(pentamethylcyclopentadienyl) zirconium bis[2-(N,N-dimethylamino)benzyl], and corresponding titanium and hafnium derivatives.
P, e fer, ed bridging groups are those correspond ing to the form ula (ER"2)X
wherein E is silicon or carbon, Rn independently each occurrence is hydrogen or a group selected from silyl, hydrocarbyi and combinations thereof, said R having up to 30 carbon or 30 silicon atoms, and x is 1 to 8. Preferably R" independently each occurrence is methyl, benzyl, tert-butyl, or phenyl.
Exemplary bridged ligands containing two n-bonded groups are: (dimethylsilyl-bis-cyclopentadienyl), (dimethylsilyl-bis-methylcyclopentadienyl), (dimethylsilyl-bis-ethylcyclopentadienyl, (dimethylsilyl-bis-t-butylcyclopentadienyl), (dimethylsilyl-bis-35 tetramethylcyclopentadienyl), (dimethylsilyl-bis-indenyl), (dimethylsilyl-bis-tetrahydroindenyl), (dimethylsilyl-bis-fluorenyl), (dimethylsilyl-bis-tetrahydrofluorenyl), (dimethylsilyl-bis-2-methyl-4-phenylindenyl), (dimethylsilyl-bis-2-methylindenyl), (dimethylsilyl-cyclopentadienyl--CA 0220~376 l997-0~-l4 fluorenyl), (1,1,2,2-tetramethyl-1,2-disilyl-bis-cyclopentadienyl), (1,2-bis(cyclopentadienyl)ethane, and (isopropylidene-cyclopentadienyl-fluorenyl).
Examples of the foregoing bridged biscyclopentadienyl or bis(substituted - cy.lopenlddienyl) complexes are compounds corresponding to the formula Vl:

(R~2E< ~

~ /M-Xn 15 R~R' VI

wherein:

M, X, E, R', m, and n are as defined for the complexes of formula lll. Two of the substituents X together may form a neutral n-bonded conjugated diene having from 4 to 30 non-hydrogen atoms forming a n-complex with M, whereupon M, preferably being zirconium or hafnium, is in the +2 formal oxidation state.

The foregoing metal complexes are especially suited for the preparation of polymershavingstereoregularmolecularstructure. Insuchcapacity,itisprer~.,edthatthe complex possess Cs symmetry or possess a chiral, stereorigid structure. Examples of the first type are compounds possessing different delocalized p-bonded systems, such as one cyclopentadienyl group and one fluorenyl group. Similar systems based on Ti(lV) or Zr(lV) were disclosed for preparation of syndiotactic olefin polymers in Ewen et al., J. Am. Chem. Soc., Vol.110, pp.6255-6256 (1980). Examples of chiral structures include bis-indenyl complexes.

Similar systems based on Ti(lV) or Zr(lV) were disclosed for preparation of isotactic olefin polymers in Wild et al., J. Orqanomet. Chem., Vol. 232, pp. 233-47, (1982).

Exemplary complexes of formula lV are: (dimethylsilyl-bis-cyclopentadienyl) zirconium dimethyl, (dimethylsilyl-bis-tetramethylcyclopentadienyl) zirconium dimethyl, (dimethylsilyl-bis-t-butylcyclopentadienyl) zirconium diphenyl, (dimethylsilyl-bis-tetramethylcyclopentadienyl) zirconium dibenzyl, (dimethylsilyl-bis-indenyl) zirconium bis(2-dimethylaminobenzyl), (isopropylidene-cyclopentadienyl-fluorenyl) zirconium dimethyl, CA 0220~376 1997-0~-14 [Z,2'-biphenyldiylbis(3,4-dimethyl-1-cyclopentadienyl)] titanium dibenzyl, [6,6-dimethyl-2,2'biphenyl-bis(3,4dimethyl-1-cyclopentadienyl)] zirconium dimethyl, and corresponding titanium and hafnium complexes.
Suitable tricyclopentadienyl or substituted cyclopentadienyl l. ansilion metal 5 compounds include those containing a bridging group linking two cyclopentadienyl groups and those without such bridging groups.
Suitable unbridged tricyclopenlddienyl transition metal derivatives are represenled by general formula Cp3MXn - wherein Cp, M and X are as previously defined and n" is three less than the formal oxidation state of M and is 0 or 1, prere- dbly 1. Preferred ligand 10 groups X are hydrocarbyl, hydrocarbyloxy, hydride, halo, silyl, germyl, amido, and siloxy.
P~ ererdbly, the transition metal compound is a bridged monocyclopentadienyl Group 4 transition metal compound or a bridged biscyclopentadienyl Group 4 transition metal compound, more preferably a bridged monocyclopentadienyl transition metal compound, especially such a compound wherein the metal is titanium.
Other compounds which are useful in the preparation of catalyst compositions according to this invention, especially compounds containing other Group 4 metals, will, of course, be apparent to those skilled in the art.
Generally, the aluminum atom (from the alumoxane component) to transition metal atom mole ratio in the supported catalyst is from 1 to 5000, preferably from 25 to 1000 20 and most preferably from 50 to 500. At too low ratios, the supported catalyst will not be very active, whereas at too high ratios, the catalyst becomes less economic due to the relatively high cost associated with the use of large quantities of alumoxane.
The quantity of transition metal compound in the supported catalyst of the present invention is not critical, but typically ranges from 0.1 to 1000 micromoles of transition 25 metal compound per gram of support material. Preferably, the supported catalyst contains from 1 to 250 micromoles of transition metal compound per gram of support material. It has been found that increased aluminum loadings on the support result in catalysts having higher efficiencies, when expressed on a transition metal basis, compared to catalysts having lower aluminum loadings but about the same aluminum/t.dnsilion metal ratio. These higher 30 aluminum loaded support components also provide supported catalysts having higher efficiencies, when ex~,re,~ed based on aluminum or support material.
The supported catalyst of the present invention can be used as such or in prepolymerized form obtained by subjecting an olefin, in the presence of the supported catalyst, to polymerization conditions.
The supported catalyst component of the invention is obtainable by heating a support material containing alumoxane under an inert atmosphere for a period and at a temperature sufficient to fix al umoxane to the support material.

CA 0220~376 1997-0~-14 The support material containing alumoxane can be obtained by combining in a diluent an alumoxane with a support material containing from 0 to not more than 20 weight percent of water, preferably from 0 to not more than 6 weight percent of water, based on the - total weight of support material and water. Support materials containing substantially no 5 water give good results with respect to catalytic properties of the SU,upOI led catalyst. In addition, it has been found that support materials containing relatively small amounts of water can be used without problem in the present process. The water containing support materials, when combined under identical conditions with the same amount of alumoxane, gives, in the present process, a supported catalyst component having a slightly higher aluminum content 10 than the sub~ldntially water-free support material. It is believed that the water reacts with the residual amounts of aluminum alkyl present in the alumoxane to convert the aluminum alkyl to extra alumoxane. An additional advantage is that, in this way, less aluminum alkyl will be lost to waste or recycle streams. The alumoxane desirably is used in a dissolved form.
Alternatively, the support material containing alumoxane may be obtained by combining in a diluent a support material containing from 5 to 30 weight percent water, pl ererdbly from 6 to 20 weight percent water, based on the total weight of support material and water, with a compound of the formula R"n*AlX"3 n* wherein R" independently each occurrence is a hydrocarbyl radical, X" is halogen or hydrocarbyloxy, and n* is an integer from 1 to 3. Preferably, n* is 3. When the alumoxane is prepared in situ by reacting the compound of 20 theformulaR"n*AlXN3n*withwater,themoleratioofR"n*AIX"3n*towateristypically10:1 to 1 :1, preferably from 5: 1 to 1 :1.
The support material is added to the alumoxane or compound of the formula R"n*AIXN3 n*, preferably dissolved in a solvent, most prererdbly a hyd~ ~,cdrLon solvent, or the solution of alumoxane or compound of the formula R"n*AlX"3 n* is added to the support 25 material. The support material can be used as such in dry form or slurried in a hydrocarbon diluent. Both aliphatic and aromatic hydrocarbons can be used. Suitable aliphatic hydrocarbons include, for example, pentane, isopentane, hexane, heptane, octane, iso-octane, nonane, isononane, decane, cyclohexane, methylcyclohexane and combinations of two or more of such diluents. Suitable examples of aromatic diluents are benzene, toluene, xylene, 30 and other alkyl or halogen substituted aromatic compounds. Most preferably, the diluent is an aromatic hydrocarbon, especially toluene. Suitable concentrations of solid support in the hydrocarbon medium range from 0.1 to 15, preferably from 0.5 to 10, more preferably from 1 to 7 weight percent. The contact time and temperature are not critical. Preferably, the temperature is from 0C to 60C, more preferably from 1 0C to 40C. The contact time is from 35 15 minutes to 40 hours, preferably from 1 hour to 20 hours.
Before subjecting the support material containing alumoxane to the heating step, the diluent or solvent is removed to obtain a free-flowing powder. This is preferably done by applying a technique which only removes the liquid and leaves the aluminum compounds CA 0220~376 1997-0~-14 on the solid, such as by applying heat, reduced pressure, evaporation, or combinations of such techniques.
The heating step A followed by the optional washing step B is conducted in such a way that a very large proportion (more than 90 percent by weight) of the alumoxane which 5 remains on the supported catalyst component is fixed. In the heating step, the alumoxane is fixed to the support material, whereas in the optional washing step, the alumoxane which is not fixed is removed to a substantial degree to provide the supported catalyst component of the present invention. The upper lempe~ d lure for the heat treatment is preferably below the temperature at which the support material begins to agglomerate and form lumps which are 10 difficult to redisperse, and below the alumoxane decomposition temperature. When the metallocene compound is added beforethe heattreatment, aswill be explained herein, the heating temperature should be below the decomposition temperature of the metallocene compound. The support material containing alumoxane in free-flowing or powder form, is preferably subjected to a heat treatment at a temperature from at least 75C, pref~rdbly at 15 least 85C, more preferably at least 1 00C, up to 250C, more preferably up to 200C for a period from 15 minutes to 72 hours, preferably up to 24 hours. More prererdbly, the heat treatment is carried out at a temperature from 1 60C to 200C for a period from 30 minutes to 4 hours.
Good results have been obtained while heating for 8 hours at 1 00C as well as while heating for 2 hours at 1 75C. By means of preliminary experiments, a person skilled in the art will be able 20 to define the heat treatment conditions that will provide the desired result. It is noted that the longer the heat treatment takes, the higher the amount of al umoxane fixed to the support material will be. The heat treatment is carried out at reduced pressure or under an inert atmosphere, such as nitrogen gas, but pl eferdbly at reduced pressure. Depending on the conditions in the heating step, the alumoxane may be fixed to the support material to such a 25 high degree that a wash step may be omitted.
In the optional wash step B, the number of washes and the solvent used are such that amounts of non-fixed alumoxane are removed sufficient to give the supported catalyst component of the invention. The washing conditions should be such that non-fixedalumoxane is soluble in the wash solvent. The support material containing alumoxane, already 30 subjected to a heat treatment, is preferably subjected to one to five wash steps using an aromatic hydrocarbon solvent at a temperature from 0C to 1 1 ODC. More preferably, the temperature is from 20C to 1 00C. Preferred examples of aromatic solvents include toluene, benzene and xylenes. More preferdbly, the aromatic hydrocarbon solvent is toluene. At the end of the wash treatment, the solvent is removed by a technique that also removes the 35 alumoxane dissolved in the solvent, such as by filtration or decdnld lion. Preferably, the wash solvent is removed to provide a free-flowing powder of the supported catalyst component.
The wash step advantageously can be carried out under conditions of refluxing the wash solvent. The wash step under refluxing conditions allows control of the particle size CA 0220~376 1997-0~-14 distribution properties, preferably to give a distribution similar to that of the starting support material, and has also been found to give a supported catalyst having increased polymerization activity. Typically, the supported catalyst component, after the heating step, is slurried in an aromatic hydrocarbon, and the slurry is refluxed or heated at the boiling point of the aromatic 5 hydrocarbon. The slurry is kept at these refluxing conditions for 5 minutes up to 72 hours. Any agglomerated particles that may have been formed during the heating step will bedeagglomerated or dispersed during the wash step at reflux condition. The longer the refluxing conditions are maintained, the better dispersion is obtained. The concenl.dlion of supported catalyst component in the aromatic hyd~ Gcdrbon is not critical, but is typically in the 10 range of 1 to 500 g per liter hydrocarbon, preferdbly from 10 to 250 g per liter. P~ ert r, ed examples of aromatic hydrocarbons include toluene, benzene and xylenes. More preferably, the aromatic hydrocarbon solvent is toluene. During the reflux step, agitation can be applied.
The supported catalyst component of the present invention, after the wash or reflux stps described above, is preferably subjected to a dispersion treatment before combining 15 the supported catalyst component with the transition metal compound. This has been found to increase the catalytic activity of the final supported catalyst. In general, a hydrGcd, Lon is used as a dispersing medium, such as aliphatic, cycloaliphatic or aromatic hydrocarbons.
Suitable examples are aliphatic hydr~cd-l ons of 6 to 20 carbon atoms, preferably of 6 to 10 carbon atoms or mixtures thereof. The temperature is not critical but is conveniently in the 20 range from 0C to 50C. The duration is generally at least 5 minutes to up to 72 hours. The upper limit is not critical but determined by practical considerations.
The transition metal compound is preferably added after the heating step, and more preferably after both the heating step and the optional washing and dispersion steps. If the ll dnsi lion metal compound is added before either of these steps, care shou Id be taken no 25 to submit the transition metal to too high temperatures which may cause decomposition or inactivation thereof. Advantageously, the l~dnsilion metal compound is added after the washing step in order to avoid that the transition metal is washed off the support material togetherwith alumoxane.
The transition metal is contacted with the support material containing 30 alumoxane, and preferably with the supported catalyst component of the present invention, in a diluent, preferably under such conditions that the transition metal compound is soluble.
Suitable di!uents include aliphatic and aromatic hydrocarbons, preferably an aliphatic hydrocarbon such as, for example, hexane. The metallocene is preferably added to a slurry of the support material, advantageously dissolved in the same diluent in which the support 35 material is slurried. Generally, the support material containing alumoxane is slurried in the diluent at concentrations from 1 to 20, preferably from 2 to 10 weight percent. The contact time and temperature are not critical. Preferably, the temperature is from 1 0C to 60C, more preferdblyfrom20Cto45C. Thecontacttimeisfrom5minutesto100hours,preferablyfrom CA 0220~376 1997-0~-14 WO 96/16092 ~ PCT/US95/14192 0.5 hour to 3 hours. Typically, the diluent is removed after adding the metallocene. This can be done by any suitable technique, such as applying heat and/or reduced pressure, evaporation, filtration or decanldLion~ or any combination thereof. If heat is applied, the temperature should not exceed the decomposition temperature of the metallocene.
It can be advantageous to subject an olefin in the presence of the supported catalyst to polymerization conditions to provide a prepolymerized supporled catalyst.
In a highly prerer, ed embodiment, the process for preparing a supported catalyst comprises:
heating at a temperature from 75C to 250C under an inert atmosphere, 10 preferably under reduced pressure, a silica support material containing methylalumoxane;
optionally followed by subjecting the product of the heating step to one or morewash steps using toluene;
thereby selecting the conditions in the heating step and washing step so as to form a supported catalyst component wherein not more than 9 percent aluminum present in 15 the supported catalyst component is extractable in a one-hour extraction with toluene of 90C
using 1 g of supported catalyst component per 10 mL toluene; and adding, after the heating step and optional washing step, a transition metal compound selected from a bridged monocyclopentadienyl or monotsubstituted cyclopentadienyl) Group 4 l- an~ on metal compounds or bridged biscyclopentadienyl or 20 bis(substituted cyclopentadienyl) Group 4 transition metal compounds, with the proviso that once the transition metal compound has been added, the product thus obtained is not subjected to temperatures equal to or higher than its decomposition temperature.Preferably, the supported catalyst so prepared contains 20 to 40 weight percent of aluminum, based on the total weight of the support material and alumoxane.
25 Advantageously, the aluminum atom to transition metal atom mole ratio in the supported catalyst thus formed is from 25 to 1000. Preferably, the supported catalyst so formed contains from 0.1 to 1000 micromoles of transition metal compound per gram of support material.
The supported catalyst thus obtained may be employed as such, without isolation or purification, but is preferably first recovered in the form of free-flowing particles. The 30 isolated catalyst can be stored under inert atmosphere for an extended period of time, for example for one to several months. Prior to its use, the supported catalyst can be easily reslurried in a diluent, preferably a hydrocarbon. The present supported catalyst does not require additional activators or cocatalysts.
In a further aspect, the present invention provides an addition polymerization 35 process wherein one or more addition polymerizable monomers are contacted with the supported catalyst according to the invention, under addition polymerization conditions.
Suitable addition polymerizable monomers include ethylenically unsaturated monomers, acetylenic compounds, conjugated or non-conjugated dienes, polyenes, and CA 0220~376 1997-0~-14 carbon monoxide. P~ere"ed monomers include olefins, for example, alpha-olefins having from 2 to 20, prererdbly from 2 to 12, more prerel ably from 2 to 8 carbon atoms and combinations of two or more of such alpha-olefins. Particularly suitable alpha-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 - combinations thereof. P~ ~ r~, dbly, the alpha-olefins are ethylene, propene,1-butene, 4-methyl-pentene-1,1-hexene,1-octene, and combinations of ethylene and/or propene with one or more of such other alpha-olefins. Other prer~r,~d monomers include styrene, halo- or alkyl substituted styrenes, vinyl chloride, acrylonitrile, methyl acrylate, methyl methacrylate, 10 tetrafluoroethylene, methacrylonitrile, vinylidene chloride, vinylcyclobutene,1,4-hexadiene, and 1,7-octadiene. Suitable addition polymerizable monomers also include any mixtures of the above-mentioned monomers.
The supported catalyst can be formed in situ in the polymerization mixture by introducing into said mixture both a supported catalyst component of the present invention as 15 well as a suitable metallocene component. The supported catalyst component and the supported catalyst of the present invention can be advantageously employed in a high pressure, solution, slurry or gas phase polymerization process. A high pressure process is usually carried out at temperatures from 100C to 400C and at pressures above 500 bar. A slurry process typically uses an inert hydrocarbon diluent and temperatures of from 0C up to a 20 temperature j ust below the temperature at which the resulting polymer becomes substantially soluble in the inert polymerization medium. P~ ~ferled temperatures are from 20C to 115C, preferdbly from 60C to 105C. The solution process is carried out at temperatures from the temperature at which the resulting polymer is soluble in an inert solvent up to 275C.
6enerally, solubility of the polymer depends on its density. For ethylene copolymers having 25 densities of 0.86 g/cm3, solution polymerization may be achieved at temperatures as low as 60C. P~ ererdbly, solution polymerization temperatures range from 75C to 260C, more preferdbly from 80C to 170C. As inert soivents, typically hydrocarbons and -prererdbly aliphatic hydrocarbons are used. The solution and slurry processes are usually carried out at pressures between 1 to 100 bar. Typical operating conditions for gas phase polymerizations are 30 from 20C to 100C, more preferably from 40C to 80C. In gas phase processes, the pressure is typicallyfrom subatmosphericto 100 bar. Typical gas phase polymerization processes are disclosed in U.S. Patents 4,588,790, 4,543,399, 5,352,749, 5,405,922, and U.S. Applicatioin Serial No. 122,582,filed September 17,1993 (corresponding toWO 9507942).
Preferably, for use in gas phase polymerization processes, the support has a 35 median particle diameter from 20 to 200 i~m, more preferably from 30 ~um to 150 ilm, and most preferablyfrom35~umto100~um. P~efeldblyforuseinslurrypolymerizationprocesses,thesupport has a median particle diameterfrom 1 to 200 iJm, more preferably from 5 i m to 100 m, and most preferably from 20 i m to 80 i m. Preferably, for use in solution or high pressure CA 0220~376 1997-0~-14 polymerization processes, the support has a median particle diameter from 1 to 40,um, more preferably from 2 ,um to 30 ,um, and most preferably from 3 ~Im to 20 ,um.
The supported catalysts of the present invention, when used in a slurry process or gas phase process, not only are able to produce ethylene copolymers of densities typical for high density polyethylene, in the range of 0.970 to 0.940 g/cm3, but su"uri~ingly~ also enable the production of copolymers having substantially lower densities. Copolymers of densities lower than 0.940 g/cm3 and especially lower than 0.930 g/cm3 down to 0.880 g/cm3 or lower can be made while retaining good bulk density properties and while preventing orsubstantially eliminating reactor fouling. The present invention is capable of producing 10 ethylene polymers and copolymers having weight average molecular weights of up to 1,000,000 and even higher.
In the polymerization process of the present invention, impurity scavengers may be used which serve to protect the supported catalyst from catalyst poisons such as water, oxygen, and polar compounds. These scavengers can generally be used in amounts depending 15 on the amounts of impurities and are typically added to the feed of monomers and diluent or to the reactor. Typical scavengers include trialkyl aluminum or boron compounds and alumoxanes.
In the present polymerization process, also, molecular weight control agents canbe used, such as hydrogen or other chain transfer agents.
Having described the invention, the following examples are provided as further illustration thereof and are not to be construed as limiting. Unless stated to the contrary, all parts and percentages are ex,~,ressed on a weight basis.
Examples In the examples, the following support materials were used: granular silica available from Grace GmbH under the designation SD 3216.30; a spherical agglomerated silica available as SYLOPOL 2212 from Grace Davison (division of W.R. Grace & Co.) having a surface area of 250 m2/g and a pore volume of 1.4 cm3/g. Unless indicated otherwise, the silicas used have been heated at 250C for 3 hours under vacuum to give a final water content of substantially 0 as determined by di rrerenlial scanning calorimetry. Where a silica is used 30 containing water, it was used as supplied, without heat pretreatment.
Alumoxane was used as a 10 weight percent solution of methylalumoxane (MAO) in toluene available from Witco GmbH. Metal locene was used as a 0.0714M solution of {(tert-butylamido) (tetramethyl-rlS-cyclopentadienyl) (dimethyl) silane}titanium dimethyl (hereinafter MCpTi) in ISOPARTU E (trademark of Exxon Chemical Company).
The bulk density of the polymers produced was determined according to ASTM
1895. The aluminum content on the support material was determined by treatment with sulfuric acid, followed by EDTA addition and back titration with zinc chloride.

=
CA 0220~376 1997-0~-14 All experiments were pe, ro""ed under a nitrogen atmosphere, unless indicated otherwise.
Example 1 - A 1000 mL flask was charged with 11.1 g of silica SD 3216.30. 300 9 of MAO
5 solution was added and the mixture stirred for 16 hours. Then the solvent was removed under reduced pressure at 20C to yield 38 9 of a free-flowing powder having an aluminum content of 31.6 percent. The sample was split into four equal portions of 9 9 and each was heated at a dirfere"l temperature for Z hours under reduced pressure. After this treatment, the aluminum content of each sample was measured and then each was slurried in toluene (100 mL) and the 10 mixture stirred for 1 hour, filtered, and then the supports washed with two 50 mL portions of fresh toluene and dried under vacuum at 1 20C for 1 hour. The results of the aluminum analyses are summarized below.
Table I - Heat Treatment / Room Temperature Toluene Wash T[C [AllAfterHeating [AllAfterWashing ] (wt% ) (wt% ) 125 30.7 20.3 150 30.0 25.7 175 30.8 30.3 200 31.1 31.4 The above procedure was repeated but with 12.1 9 silica, and 327 9 MAO solution to yield 42 9 of free-flowing powder having an aluminum content of 31.3 percent. This sample was split into four equal portions and each was heated as described above, and then subjected to the same wash procedure exceptthat toluene of 90C was used. The results are summarized in Table ll.
Table ll - Heat Treatment / 90C Toluene Wash T [C ] [Al] After Heating (wt%) (wt%) 125 31.0 16.4 150 30.7 23.8 175 30.7 29.3 200 31.0 29.1 These examples show that, for heat treatments of the duration, an increase in the heat treatment temperature resu Its in more alumoxane becom ing fixed to the si lica. The 90C
toluene wash results in an increased percentage of non-fixed aluminum being removed, 35 compared to the room temperature tol uene wash for wash treatments of the same duration.

=
CA 0220~376 l997-0~-l4 Example 2 A 250 mL flask was charged with 6.2 g of silica SD 3216.30. 168 g of MAO solution was added and the mixture stirred for 16 hours. Afterthis time, the toluene was removed under reduced pressure at 20C, and then the solids were dried under vacuum for 16 hours at 5 20C to yield a free-flowing powder. The weight of the solid was 22.1 g and the aluminum content was 26.8 percent.
Example 3 The procedure of Example 2 was repeated using 3 g silica and 56.6 g of MAO
solution to give 7.6 9 of a free-flowing powder having an aluminum content of 26.1 percent.
10 5.2 9 of this support was slurried in toluene (50 mL) at 20C and the mixture stirred for 1 hour.
The mixture was filtered and the support washed with two 20 mL portions of fresh toluene and then dried under vacuum at 20C for 1 hour. The weight was 3.0 g and the aluminum content was 18.2 percent.
Example 4 The procedure of Example 2 was repeated using 3 9 of silica and 75.6 9 of MAO
solution to give a free-flowing powder. This powder was then heated at 1 00C for two hours under vacuum. The weight was 8.4 9 and the aluminum content was 29.0 percent. 4.4 9 of this support was slurried in toluene (50 mL) at 20C and the mixture stirred for 1 hour. The mixture was filtered and the support washed with two 20 mL portions of fresh toluene and then dried under vacuum at 20C for 1 hour. The weight was 2.2 9 and the aluminum content was 17.3 percent.
Example 5 The procedure of Example 2 was repeated using 3 9 silica and 56.6 9 MAO
solution to give a free-flowing powder. The powder was heated for two hours at 1 50C under vacuum. The weight obtained was 7.2 9 and the aluminum content 26.6 percent.
Example 6 The procedure of Example 2 was repeated using a 1000 mLflask, 12.1 9 of silica, and 327 g of MAO solution to yield a free-flowing powder. 9.5 9 of this powder was then heated at 175C fortwo hours under vacuum. The aluminum content was measured as 30-7 percent. 2.7 g of this support was slurried in hexane (40 mL) at 20C and the mixture stirred for 4 hours. The m ixture was filtered and the support washed with two 30 mL portions of fresh hexane and then dried under vacuum at 20C for 1 hour. The weight was 2.4 g and the aluminum content was 30.4 percent.
Example 7 The procedure of Example 2 was followed. This powder was then heated at 1 50C
for two hours under vacuum. The weight was 7.25 9 and the aluminum content was 26.6 percent. 3 g of the support obtained was slurried in toluene (40 mL) at 20C and the mixture stirred for 1 hour. The mixture was filtered and the support washed with two 10 mL portions of CA 0220~376 1997-0~-14 fresh toluene and then dried under vacuum at 20C for 1 hour. The weight was 2.4 9 and the aluminum content was 24.1 percent.
Example 8 The procedure of Example 2 was repeated using 3 g of silica and 75.5 9 of MAO
5 solution to yield a free-flowing powder. This powder was heated at 150C for two hours under vacuum. The weight was 8.4 g and the aluminum content was 29.8 percent. 5 9 of this support was slurried in toiuene (40 mL) at 20C and the mixture stirred for 1 hour. The mixture was filtered and the support washed with two 20 mL portions of fresh toluene and then dried under vacuum at 20C for 1 hour. The weight was 4.5 9 and the aluminum content was 10 28-9 percent.
Example 9 The procedure of Example 2 was repeated using a 1000 m L flask, 9.1 g silica and246 g MAO solution to give a free-flowing powder. This powder was then heated at 150C for two hours under vacuum. The weight was 29.0 g and the aluminum content was 29.6 percent.
15 This support was slurried in toluene (300 mL) at 20C and the mixture stirred for 1 hour. The mixture was filtered and the support washed with two 100 mL portions of fresh toluene and then dried under vacuum at 20C for 1 hour. The weight was 24.3 g and the aluminum con lent was 28.5 percent.
Example 10 The procedure of Example 2 was repeated using 5 g silica and 101 g MAO solution to yield a free-flowing powder. The powder was heated at 175C for two hours under vacuum.
The aluminum content of this materia I was 28.8 percent. The powder (12.8 9) was reslurried in toluene (130 mL) and the mixture heated to 90C and stirred for 1 hour. The mixture was filtered and the resulting solid washed with two 50 mL portions of fresh toluene at 90C. The support was then dried under vacuum at 120C for 1 hour. 10.4 g of support was obtained having an aluminum content of 26.3 percent.
Example 11 The procedure of Example 2 was repeated using 10 9 silica and 76 9 MAO solution to give a free-flowing powder. This powder was heated at 175C for two hours under vacuum.
The aluminum content of this material was 17.2 percent. The powder (15.6 9) was reslurried in toluene (150 mL) and the mixture heated to 90C and stirred for 1 hour. The mixture was filtered and the resulting solid washed with two 50 mL portions of fresh toluene at 90C. The support was then dried under vacuum at 120C for 1 hour. 13.0 9 of support was obtained having an aluminum content of 16.3 percent.
35 Example 12 The procedure of Example 2 was repeated using 5 9 silica SD 3216.30 having a water content of 2.8 percent, and 101 9 of MAO solution to give a free-flowing powder. This powder was heated at 175C for two hours under vacuum. The aluminum content of this CA 0220~376 1997-0~-14 WO 96/16092 PCT/US9!;/14192 material was 29.4 percent. The powder (13 g) was reslurried in toluene (130 mL) and the mixture heated to 90C and stirred for 1 hour. The mixture was filtered and the resulting solid washed with two 50 mL portions of fresh toluene at 90C. The support was then dried under vacuum at 120C for 1 hour. 11.5 9 of support was obtained having an aluminum content of 5 29.0 percent.
Example 13 The procedure of Example 2 was repeated using a 1000 m L flask, 9 g of SYLOPOL
2212 and 243 g MAO solution to give a free-flowing powder. This powder was heated at 150C
for two hours under vacuum. The weight was 29.3 9 and the aluminum content was 29.8 10 percent. This support was slurried in toluene (300 mL) at 20C and the mixture stirred for 1 hour. ThemixturewasfilteredandthesupportwashedwithtwolOOmLportionsoffresh toluene and then dried under vacuum at 120C for 1 hour. The weight was 25.9 g and the aluminum content was 29.3 percent.
Example 14 Theprocedureof Example2wasrepeated usinga 1000mLflask,9.1 gsilicaand 246 9 MAO solution to give a free-flowing powder. This powder was heated at 175C for two hours under vacuum. The weight was 30.8 9 and the aluminum content was 30.0 percent. This support was slurried in toluene (300 mL) at 20C and the m ixture stirred for 1 hour. The mixture was filtered and the support washed with two 100 mL portions of fresh toluene and then dried 20 under vacuum at 120C for 1 hour. The weight was 27.1 g and the aluminum content was 29.0 percent.
Example 15 The procedure of Example 2 was repeated using 5.1 9 silica and 101 g MAO
solution to give a free-flowing powder. 6.8 g of this powder was heated at 100C for two hours 25 under vacuum. The support was then slurried in toluene (100 mL) at 90C and the mixture stirred for 1 hour. The mixture was filtered and the support washed with two 50 mL portions of fresh toluene (90C) and then dried under vacuum at 100C for 1 hour. The weight was 3.4 g and the aluminum content was 16.6 percent.
Example 16 The procedure of Example 2 was repeated using 5.1 g silica and 101 g MAO
solution to give a free-flowing powder. 6.8 g of this powder was slurried in toluene (100 mL) at 90C and the mixture stirred for 1 hour. The mixture was filtered and the support washed with two 50 mL portions of fresh toluene (90C) and then dried under vacuum at 100C for 1 hour.
Theweightwas3.0gandthealuminumcontentwas13.4percent.
35 Example 17 The procedure of Example 2 was repeated using 5 g of silica SD 3216.30 containing Z.8 percent of water, and 101 g MAO solution to give a free-flowing powder. 6 g of this powder was slurried in toluene (100 mL) at 90C and the mixture stirred for 1 hour. The CA 0220~376 l997-0~-l4 mixture was filtered and the support washed with two 50 mL portions of fresh toluene (90C) and then dried under vacuum at 20C for 1 hour. The weight was 2.9 9 and the aluminum content was 16.4 percent.
Example 18 The procedure of Example 2 was repeated using 5 9 of silica SD 3216.30 - containing 2.8 percent of water, and 101 g MAO solution to give a free-flowing powder. This powder was heated at 1 00C for 2 hours. 6 9 of this powder was slurried in toluene (100 mL) at 90C and the mixture stirred for 1 hour. The mixture was filtered and the support washed with two 50 mL portions of fresh toluene (~0C) and then dried under vacuum at 20C for 1 hour.
10 The weight was 3.8 9 and the aluminum content was 22.2 percent.
Example 19 Preparation of suPported catalYsts Supported catalysts were prepared from the supported catalyst components prepared in Examples 2 to 18 according to the following procedure.
Typically, 1 g of support component was slurried in 20 mL hexane and the mixturestirred for 30 minutes. An aliquot of MCpTi solution (0.0714M) was added sufficient to give a transition metal loading as shown in Table lll. This mixture was stirred for 30 minutes and then t. dn,~r, ed to a polymerization reactor.
Polvmerization A 10 L autoclave reactor was charged with 6 L anhydrous hexane, co-monomer if required, hydrogen gas if required, and the conle,.lswere heated to 80C, unless otherwise stated. Ethylene was added to raise the pressure to the desired level. The amount of the supported catalyst indicated in Table lll was added through a pressurized addition cylinder.
Ethylene was supplied to the reactor continuously on demand. After the desired 25 poiymerization time, the ethylene I ine was blocked and the reactor conter.l, were dumped into a sample container. The hexane was decanted from the polymer and the polymer dried overnight and then weighed to determine the yield.
In run 22, the temperature was 70C, and 100 mL of 1 -octene comonomer was added to the reactor to give an ethylene/1-octene copolymer of density 0.9266 g/cm3. In run 30 23, the temperature was 50C, and 200 mL of 1 -octene comonomer was added to the reactor to give an ethylene/1-octene copolymer of density 0.9230 g/cm3.
The specific polymerization conditions and results are summarized in Table lll.
The data in this table show that high bulk density polymers can be prepared from supported catalyst components prepared with various combinations of heat and/or wash treatments. The 35 highest efficiencies result from supported catalyst components and catalysts containing more than 20 percent Al by weight. Superior efficiencies are obtained from supported catalyst components subjected to dispersion in 90C toluene. Poor bulk densities (runs 1 to 3) result from supported catalyst components which have either not been heat-treated at a sufficientiy high temperature or for a sufficiently long time, or have not been sufficiently washed.

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Z^' ~ ~ ^' -- N ~ ~ ~ cn CA 0220~376 1997-0~-14 Example 20 The procedure of Example 2 was repeated using 6.2 9 of silica SD 3216.30, and 68g MAO solution to give 22.1 9 of free-flowing powder having an aluminum conlenl of 27.8 percent. 11 9 of this support was slurried in toluene (75 mL) and 440 micromoles of MCpTi (6.16 m L of a 0.0714M solution in hexane) was added. The m ixture was stirred 1 hour and then the solvent was removed under reduced pressure and the residue heated at 150C for two hours.
This yielded 11 9 of a free-flowing powder having an aluminum content 28.2 percent. The material was slurried in toluene (100 mL) and the mixture stirred for 1 hour, filtered, and the solids washed with two 50 mL portions of fresh toluene and then dried under vacuum at 100C
for 1 hour. The weight was 9 9, the aluminum content was 24.8 percent, and the Ti content was 40 micromoles/g.
Example 21 The procedure of Example 6 was repeated using 12.1 9 of silica SD 3216.30, and 327 9 MAO solution to give a free-flowing powder. 9.1 9 of this powder was heated at 150C
under vacuum for 2 hours to yield a material with an aluminum content of 30.7 percent. 3.5 9 of this powder was slurried in toluene (35 mL) and 140 micromoles of MCpTi (1.96 mL of a 0.0714M solution in hexane) added and the mixture stirred for 1 hour. The mixture was filtered and the support washed with six 50 mL portions of fresh toluene (at which point the washings were colorless) and then dried under vacuum at 20C for 1 hour. The weight was 22.0 9 and the 20 Ti content30 micromoles/g.
Example 22 The procedure of Example 2 was repeated using 3.0 9 of si lica SD 3216.30, and 82 g MAO solution to give 10.5 9 of free-flowing powder. 4.85 9 of this powder was slurried in toluene (50 mL) and the mixture stirred for one hour. The mixture was filtered and the support 25 washed with two 20 mL portions of fresh tol uene and then heated under vacuum at 150C for 2 hours. The weight was 2.1 9 and the aluminum content was 14.9 percent. MCpTi was added according to the procedure of Example 19.
Example 23 A 250 mL flask was charged with 3.3 9 of silica SD 3216.30. Toluene (80 mL) was 30 addedtotheslurryfollowedby130micromolesofMCpTi(1.82mLofaO.0714Msolutionin hexane) and the mixture stirred for two hours. 101 9 of MAO solution was added and the m ixture stirred for 16 hours. After this time, the solvent was removed under red uced pressure, at 20C, to yield a free-flowing powder.
Following the general polymerization procedure of Example 19, using the specific35 conditions mentioned in Table IV, the results indicated in the same table were obtained.
The data in this table show that a low activity catalyst results when the metallocene is added before a heat treatment of 150C (Example 20). A reasonable bulk density is obtained when the metallocene is added after the heat step, but prior to wash step CA 0220~376 1997-0~-14 Wo 96/16092 PCT/US95114192 (Example 21). A good bulk density results when the wash step is performed prior to the heating step (Example 22). An inactive catalyst results when the metallocene is first added to the silica (Example 23).

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CA 0220~376 1997-0~-14 Example 24 The procedure of Example 1 was repeated except that after removing the solvent from the MAO/silica mixture under reduced pressure at 20C, portions of the resulting powder were subjected to two hour heat tredl")en l~ and optional wash treatments as summarized in 5 Table V. After these treatments, the supported catalyst components were, on the one hand, extracted with 90C toluene to establish the percenldge aluminum extractables, and, on the other hand, used in polymerization reactions. All wash and extraction steps were pe, ror."ed with 1 g support per 10 m L toluene, stirred for one hourl then filtered and washed with 2 times 5 mL toluene per gram initial support. The supported catalysts were prepared according to the 10 general procedure described in Example 19. All polymerizationswere perr~.r",ed at 15 bar total pressure at 80C for one hour. The results are given in Table Vl. The examples show that at extractable aluminum percentages well below 10 percent, excellent bulk densities are obtained. = ==
The 1 75C heat treatment alone in run 1, without any wash treatment, enabled 15 polymers of good bulk density to be made.
Table V Extraction Test Heat 20C Alin t AlAfter Extracted Bulk RunTreatment Toluene CatalysExtraction Al Density Temp. [C] Wash SUPPort [o/] [%] [g/cm3]

1 175 no 29.8 27.9 6.4 0.35 2 175 yes 28.3 27.9 5.0 0.34 3 165 no 30.5 27.6 10 0.12 4 165 yes 29.3 27.6 5.8 0.31 125 no 30.1 20.9 33 0.06 6 75 yes 16.6 15.9 4.2 0.34 U~
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U_ CA 0220~376 1997-0~-14 Example 25 The procedure of Example 2 was repeated using 5 g silica and 101 9 MAO solution to give a free-flowing powder. The powder was heated at 100C for eight hours under vacuum to yield 12.5 9 of material. The support was then slurried in toluene (125 mL) at 90C and the 5 mixture stirred for one hour. The mixture was filtered and the support washed with two 50 mL
portions of fresh toluene (90C) and then dried under vacuum at 100C for one hour. The weight was 11.1 grams and the aluminum content was measured as 26.1 percent by weight.
A~curding to the procedures of Example 19 and using the amounts in Table Vll, a polymerization experiment was per ru, -, led at 15 bar total pressure,80C, for one hour. The 10 results are included in Table Vll.
Table Vll Polymerization Run Tj2 [Ti~4 Yield7 E(Ti)s E(SiO2)9 E(Al)-o Bulk [llmol/ Al/Ti3 ( mol) ( ) [gPE/g[gPE/gSiO2 [gPE/gAI/ Dens.

9] 11 9 Ti/hr] /hr] hr] (g/cm3) 242 20 365 381,002 1,662 2,797 0.33 Footnotes are the same as in Table lll Example 26 The procedure of Example 5 from U.S. Patent 5,240,894 was essenlidlly repeated to form a supported catalyst component as follows. 0.58 ~umoles of MCpTi (8.1 mL of a 0.0714M
solution) was added to 35 mL toluene. To this was added 75 mL of 10 weight percent MAO in toluene and the mixture stirred for 15 minutes. Silica (5 9, SD 3216.30, pretreated at 250C for three hours) was added and the mixture stirred 20 minutes. The mixture was heated at 65C
under vacuum for 75 minutes and the dried solid washed with 2x70 mL pentane, filtered and dried under high vacuum to give a yellow solid (8 9) having an aluminum content of 18.1 percent by weight. A toluene extraction at 90C followed by drying gave a yellow solid with an aluminum content of 16.2 percent by weight. The extractable aluminum percentage is

10.5 percent. Upon washing, some MCpTi was lost and also upon the hot toluene extraction, as 30 indicated by the yellow color of the supernatant. Polymerization experiments following the general procedure of Example 19 were performed with a supported catalyst that was not treated with hot toluene (run 1) and with one that was treated with hot toluene (run 2). The results are given in Table Vlll.
The results show that the non-toluene-treated catalyst (having 10.5 percent 35 extractable Al) gives a poor bulk density. Subjecting the obtained supported catalyst to a hot toluene extraction greatly improves the bulk density (run 2).

CA 0220~376 1997-0~-14 Table Vlll Run Al Time YieldBulk Dens.
" No. (%) (min) (g) (g/cm3) 1 18.1 60 175 0.10 2 1 6.2 60 50 0.30 Example 27 A 1000 mL flask was charged with 508 9 of 10 percent MAO solution in toluene and 25 9 of silica SYLOPOL 2212 having a water content of 3.5 percent was added while continuously stirring. The mixture was stirred for a further two hours and then the solvent was removed under reduced pressure at 20C to yield a free-flowing powder. This powder was then heated at 1 75C for two hours under vacuum. The powder was reslurried in toluene (700 mL) and the mixture was heated and refluxed for one hour. The mixture was filtered and the supportwashedwithtwo200mLportionsoffreshtolueneat100C. Thesupportwasthen dried under vacuum at 1 20C for 1 hour. 63.9 9 of support was obtained having an aluminum content of 26.4 percent. A sample of the support was slurried in toluene, agitated for one hour, and then the particle size distribution was measured on a Malvern Ma~ler~i~er X
instrument. This indicated d(v, 0.5) to be approximately 12 microns. According to this procedure further supported catalyst components were prepared having slightly dirrere"l aluminum loadings.
A weighed amount of the support components was slurried in hexane and the mixture stirred for 16 hours before addition of the MCpTi component (runs 1 to 3) or ~(tert-butylamido)(tetramethyl-rlS-cyclopentadienyl) (dimethyl) silane} titanium rl4-1 ,3-pentadiene (hereinafter MCpTi(ll) in run 4). Subsequently, MCpTi or MCpTi(ll) was added (in ISOPART" E) in the amounts as indicated in Table IX. The supported catalysts thus prepared were subjected to slurry polymerization as generally described in Example 19 at 80C. The other conditions and results are mentioned in Table IX. These results show that using an extended dispersion period before the transition metal compound is added results in increased catalytic activity (compare with Table lll).

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CA 0220~376 1997-0~-14 Example 28 A 3 L autoclave reactor was charged with an amount of 1-octene as indicated in Table X followed by an amount of Isopar"' E sufficient to give a total volume of 1500 mL. 300 mL of hydrogen gas was added and the reactor cunte~ were heated to the desired 5 temperature. Ethylene was then added sufficient to bring the pressure of the system to 30 bar.
A supported catalyst was added to initiate the polymerization and ethylene was supplied to the reactor continuously on demand. After the desired polymerization time, the ethylene line was blocked and the reactor con Len l~ were dumped into a sample container. The polymer was dried overnight and then weighed to determine catalyst efficiencies. The results are described 10 in Table X, wherein the molecular weight distribution (MwlMn) is derived from gel permeation chromatoyldphy~ and the melt index 12 is determined according to ASRM D-1238-65T (at 190C
and 2.16 kg load).
The following supported catalysts were used in the polymerizations. A support containing 23.8 percent aluminum on dehydrated SD 3216.30 silica was prepared in a manner similar to Example 10. In runs 1 to 3, 0.075 9 of support was slurried in Isopar"', and stirred for a few minutes. An aliquot of MCpTi solution (0.0714M) was added, sufficientto give a titanium loading of 20 ,umoles/g. This mixture was stirred for a few minutes and then l. dn~r~r, ed to the polymerization reactor. In runs 4 to 6, 0.3 9 of support was used and the same titanium loading.
Table X

Run 1-octene Time Yield Average Effi j 12 Density No. [ml] [min] [gram] [ocjP [gPE/gTi] [m/in] [g/cm3] MWlMn 1 302 20 69 81 960,334 0.25 0.882 2.18 2 382 20 55 80 765,484 0.25 0.873 2.09 3 456 17 35 80 487,126 0.41 0.870 2.09 4 455 20 244 133 848,990 1.30 0.877 2.44 455 20 217 143 755,045 0.47 0.882 2.88 6 457 20 200 152 695,894 0.33 0.880 2.99 When used in a solution polymerization process, the supported catalysts show good efficiencies and make narrow molecular weight distribution polymers.
Example 29 In the present example, continuous polymerization runs are described. These runs were performed using a supported catalyst prepared according to a procedure similar to CA 0220~376 lgg7-0~-l4 that of Example 27. The support contained 25 weight percent of aluminum. In all runs, the loading of MCpTi was 40 ymoles/g.
Isopentane, ethylene,1-butene, hydrogen and supported catalyst were continuously fed into a 10 L jacketed, contin uously stirred tank reactor and the sl urry product 5 formed was removed continuously. The total pressure in all polymerization runs was 15 bar.
The slurry withdrawn was fed to a flash tank to remove the diluent and the dry, free-flowing polymer powder was collected. Table Xl summarizes the condilions and the properties of the products made. The melt index values were measured a.cc r.Ji"g to ASTM D-1238-65T (at 190C
and a load of 21.6 kg, abbreviated as 121)- The butene content of the polymerwas determined 10 byin~ld-edspe~l~oscopy. Theresultsindicatethathighbulkdensitypolymerpowderscanbe produced over a wide density range, with particle morphology being retained.

Table Xl Isopen Ethyl Butene Hydro 1216 Polymer Run tane ene Flow gen T(C) [g/;0 Density Butene B.D.
No. Flow Flow Flow .[g/cm3] Content g/cm3 [g/h] [g/h] [g/h] ll/h] mln][wt %]
2500 1600 195 0.54 601.28 0.9305 1.94 0.34 2 2500 1000 80 0.30 600.38 0.9136 5.58 0.34 3 2500 800 80 0.30 550.28 0.9190 6.34 0.38 4 2500 1150 125 0.30 550.18 0.9112 8.54 0.39 2500 850 100 0.30 550.21 0.9050 10.18 0.37 6 2500 675 100 0.30 550.45 0.9035 11.64 0.38 7 2500 550 160 0.50 351.40 0.8958 14.60 0.23

Claims (30)

WHAT IS CLAIMED IS:

1. A supported catalyst component comprising a support material and an alumoxane, which component contains 15 to 40 weight percent of aluminum, based on the total weight of the support material and alumoxane, and wherein not more than 10 percent aluminum present in the supported catalyst component is extractable in a one-hour extraction with toluene of 90°C using 10 mL toluene per gram of supported catalyst component, said supported catalyst component being obtainable by A. heating a support material containing alumoxane under an inert atmosphere for a period and at a temperature sufficient to fix alumoxane to the support material.

2. The supported catalyst component of Claim 1 wherein heating step A is followed by B. subjecting the support material containing alumoxane to one or more wash steps to remove alumoxane not fixed to the support material.

3. The supported catalyst component of Claim 2 wherein the wash step is carried out under conditions of refluxing the wash solvent by slurrying the supported catalyst component in an aromatic hydrocarbon and heating the slurry at the boiling point of the aromatic hydrocarbon.

4. The supported catalyst component according to any of the Claims 1 to 3 wherein not more than 9 percent aluminum present in the supported catalyst component is extractable.

5. The supported catalyst component according to any of the Claims 1 to 4 wherein the support material is silica.

6. The supported catalyst component according to any of the Claims 1 to 5 wherein the alumoxane is methylalumoxane.

7. The supported catalyst component according to any of the Claims 1 to 6 which contains 20 to 40 weight percent of aluminum, based on the total weight of the support material and alumoxane.

8. A supported catalyst comprising:
a supported catalyst component according to any of the Claims 1 to 7; and a transition metal compound.

9. The supported catalyst of Claim 8 wherein the transition metal compound is a bridged monocyclopentadienyl Group 4 transition metal compound or a bridgedbiscyclopentadienyl Group 4 transition metal compound.

10. The supported catalyst according to Claim 8 or 9 wherein the aluminum atom to transition metal atom mole ratio is from 1 to 5000.

11. The supported catalyst according to any of the Claims 8 to 10 which contains from 0.1 to 1000 micromoles of transition metal compound per gram of support material.

12. The supported catalyst according to any of the Claims 8 to 11 in prepolymerized form obtained by subjecting an olefin in the presence of the supported catalyst to polymerization conditions.

13. A process for preparing a supported catalyst component comprising:
A. heating a support material containing alumoxane under an inert atmosphere for a period and at a temperature sufficient to fix alumoxane to the support material;
thereby selecting the conditions in heating step A so as to form a supported catalyst component, which component contains 15 to 40 weight percent of aluminum, based on the total weight of the support material and alumoxane, and wherein not more than 10 percent aluminum present in the supported catalyst component is extractable in a one-hour extraction with toluene of 90°C using 10 mL toluene per gram of supported catalyst component.

14. The process of Claim 13 wherein heating step A is followed by B. subjecting the support material containing alumoxane to one or more wash steps to remove alumoxane not fixed to the support material.

15. The process of Claim 14 wherein the wash step is carried out under conditions of refluxing the wash solvent by slurrying the supported catalyst component in an aromatic hydrocarbon and heating the slurry at the boiling point of the aromatic hydrocarbon.

16. The process according to any of the Claims 13 to 15 wherein the heat treatment is carried out at a temperature from 75°C to 250°C.

17. The process according to any of the Claims 14 to 16 wherein the wash solvent is an aromatic hydrocarbon solvent.

18. The process according to Claim 17 wherein the aromatic hydrocarbon solvent is toluene.

19. The process according to any of the Claims 13 to 18 wherein the heat treatment is carried out under reduced pressure.

20. The process according to any of the Claims 13 to 19 wherein the support material is silica.

21. The process according to any of the Claims 13 to 20 wherein the alumoxaneis methylalumoxane.

22. A process for preparing a supported catalyst comprising:
preparing a supported catalyst component according to any of the Claims 13 to 21; and adding, before or after heating step A or optional washing step B, a transition metal compound, with the proviso that once the transition metal compound has been added, the product thus obtained is not subjected to temperatures equal to or higher than the decomposition temperature of the transition metal compound.

23. The process of Claim 22 wherein the transition metal compound is added after the heating step.

24. The process according to Claim 23 wherein the transition metal compound is added after the optional washing step.

25. The process according to any of the Claims 22 to 24 wherein the transition metal compound is a bridged monocyclopentadienyl or mono(substituted cyclopentadienyl) Group 4 transition metal compound or a bridged biscyclopentadienyl or bis(substituted cyclopentadienyl) Group 4 transition metal compound.

26. The process according to any of the Claims 22 to 25 wherein the aluminum atom to transition metal atom mole ratio in the supported catalyst is from 1 to 5000.

27. The process according to any of the Claims 22 to 26 wherein the supported catalyst contains from 0.1 to 1000 micromoles of transition metal compound per gram of support material.

28. The process according to any of the Claims 22 to 27 further comprising subjecting an olefin in the presence of the supported catalyst to polymerization conditions to provide a prepolymerized supported catalyst.

29. An addition polymerization process wherein one or more addition polymerizable monomers are contacted with a supported catalyst according to any of the Claims 8 to 12 or obtainable according to any of the Claims 22 to 28 under addition polymerization conditions.

30. The addition polymerization process according to Claim 29 carried out under slurry or gas phase polymerization conditions.