MXPA01002794A - Functionalized catalyst supports and supported catalyst systems - Google Patents

Abstract

The present invention relates to functionalized catalyst supports that are useful in the formation of supported polymerization catalysts, supported catalysts derived from such functionalized catalyst supports, methods for preparing such functionalized catalyst supports and supported catalysts, and polymerization processes utilizing such supported catalysts. The functionalized catalyst support comprises a particulated support material having chemically bonded thereto a plurality of aluminum-containing groups derived from a non-ionic Lewis acid, said aluminum-containing groups:containing at least one fluoro-substituted hydrocarbyl ligand containing from 1 to 20 carbons, said hydrocarbyl ligand being bonded to aluminum, and being bonded to said support material, optionally through a bridging moiety, said composition being capable of activating a Group 3-10 metal complex for the addition polymerization of one or more addition polymerizable monomers.

Description

NUCLEARIZED FU CATALYST SUPPORTS AND SUPPORTED CATALYST SYSTEMS DESCRIPTION OF THE INVENTION The present invention relates to functionalized catalyst supports that are useful in the formation of supported polymerization catalysts. The present invention also relates to supported catalysts which are obtained using said functionalized catalyst supports, said supported catalysts are particularly adapted for use in a polymerization process, wherein at least one polymerizable olefin monomer is contacted with the catalyst supported under polymerization conditions to form a polymer product. The present invention also relates to methods for making said functionalized catalyst supports and supported catalysts. The present invention also relates to polymerization processes using said supported catalysts. Previously it has been known in. the technique activates Ziegler-Natta polymerization catalysts particularly those catalysts comprising metal complexes of Group 3-10 containing ligand groups linked to p-delocalised, through the use of an activator. Generally in the absence of said activating compound, also referred to as a cocatalyst, little or no polymerization activity is observed. One class of suitable activators are aluminoxanes, or alkylaluminoxanes, which are generally believed to be oligomeric or polymeric alkylaluminoxy compounds, including cyclic oligomers. Generally said compounds contain, on average, about 1.5 or alkyl groups per aluminum atom, and are prepared through the reaction of trialkylaluminum compounds or mixtures of compounds with water (Reddy et al., Prog. Poly. Sci., 1995 , 20, 309-367). The resulting product is in fact a mixture of several substituted aluminum compounds including, in particular, trialkylammonium compounds (resulting from the incomplete reaction of the trialkylaluminum starting reagent or decomposition of the alumoxane). The amount of said free trialkylaluminum compound in the mixture generally ranges from 1 to 50% by weight of the total product. Examples of alumoxanes include methylalumoxane (MAO) made through the hydrolysis of trimethylaluminum as well as modified methylalumoxane (MMAO), made through the hydrolysis of a mixture of trimethylaluminum and triisobutylaluminum. Although such activators are normally soluble in hydrocarbons (homogeneous cocatalyst), supported versions can be prepared by fixing the alumoxane to a solid, particulate substrate. The silica having alumoxane, particularly methylalumoxane, chemically bound thereto, presumably through reaction to form a silicon / oxygen / aluminum bond, is also well known and commercially available.

Disadvantageously, said supported, heterogeneous cocatalyst does not demonstrate important cocatalytic efficiency, possibly due in part to the oligomeric nature and low Lewis acidity of the alumoxane. A different type of activator compound is a Bronsted acid salt capable of transferring a proton to form a cationic derivative or other catalytically active derivative of said Group 3-10 metal complex. Examples of said Bronsted acid salts are protonated ammonium, sulfonium or phosphonium salts, capable of transferring a hydrogen ion, as described in US-A-5, 198,401, US-A-5,198,401, US-A-5, 132,389, US-A-5,470,927, and US-A-5,153,157, as well as oxidation salts such as lead, silver, carbonium, ferrocenium, and silylium salts, described in US Pat. 5,350,723, 5,189,192 and 5,626,087. The supported or polyionic salt activators described in the U.S.A. 5,427,991 are prepared by chemically attaching a plurality of said salt anions to a core component. Disadvantageously, the activation of a neutral metal complex through a proton transfer mechanism inevitably produces a neutral byproduct, such as an amine, which can interfere with the subsequent activity of the catalyst. Other suitable activators for the above metal complexes include strong Lewis acids including (trispentafluorophenyl) borane and tris (perfluorophenyl) borane. The first composition has been previously described for the final use set forth above in EP-A-520,732 and elsewhere, while the latter composition is described in Marks, et al., J Am. Chem. Soc, 118-12451-12452 ( nineteen ninety six). Additional teachings of the above activators can be found in Chen, and others, J. Am. Chem. Soc. 1997, 119, 2582-2583, Jia et al., Organometallics, 1997, 16, 842-857, and Coles et al. J. Am. Soc 1997, 119, 8126-8126. All the above Lewis acid activators in practice are based on boron compounds substituted with perfluorophenyl. The use of said activator compounds in a supported catalyst system has been met with limited success, due to the difficulty in retaining the activator on the support surface. In the patent of E.U.A. 5,453,410, an alumoxane, particularly methylalumoxane, is described for use in combination with Group 4 metal complexes of restricted geometry, especially at a molar ratio of metal complex to alumoxane of 1/1 to 1/50. This combination beneficially results in improved polymerization efficiency. Similarly, in the US patents US-A-5,527,929, US-A-5,616,664, US-A-5,470,993, US-A-5,556,928, US-A-5,624,878, various combinations of metal complexes with a boron cocatalyst are described. trispentafluorophenyl, and optionally an alumoxane, for use as cocatalyst compositions for the olefin polymerization. Despite the satisfactory performance of the above catalyst activators under a variety of polymerization conditions, there remains a need for improved catalysts for use in the activation of various metal complexes under a variety of reaction conditions. In particular, it is desirable to remove boron contaminating compounds from said activating composition. Such boron-containing contaminating compounds result primarily from the exchange of ligand with alumoxane, and comprises triaikylboroboro compounds having from 1 to 4 carbons in each alkyl group, for example, trimethylboroboro, triisobutylboro, or triaiquilboro blended products. It could be desirable if they will be provided. compounds that can be used in solution, slurry, gas phase or high pressure polymerizations and under homogenous or heterogeneous process conditions having improved activation properties, lacking said triaiquilboron species. It is known that an exchange reaction between trialkylaluminum compounds and tris (perfluorophenyl) borane occurs under certain conditions. This phenomenon has been previously described in the patent of US Pat. No. 5,602,269. Tris (perfluorophenyl) aluminum is also a strong Lewis acid. However, it generally works poorly on its own as an activator compared to tris (perfluorophenyl) borane. Similarly, it has been further demonstrated that active catalysts resulting from the use of an aluminate anion based on tris (perfluorophenyl) aluminum for the activation of ansa-metallocenes and zirconium (IV) bicyclopentadienyl derivatives are generally of lower activity than those formed by the corresponding borane (Ewen, Stud .In Surf, Sci. Catal. 1994, 89, 405-410). The above tri (fluoroaryl) alumino compounds are considered to be moderately sensitive to shock and temperature and difficult to handle in the pure state. In order to avoid this problem, the compounds can be prepared as adducts with Lewis bases such as ethers. Disadvantageously, however, the presence of an ether detrimentally affects the ability to use the compounds as activators for metal complexes, whereas, the removal of the ether can result in the detonation of the compound. The patent of E.U.A. 5763547 discloses a slurry polymerization process using a supported catalyst formed by making a slurry of a silica / alumoxane support with a solution of a metal complex of Group IV monocyclopentadienyl in ISOPAR E, and subsequently in short contact with a Borano activator. WO 97/44371 describes a gas phase polymerization process using a supported catalyst formed by contacting a dry or calcined silica support (optionally pretreated with water) with triethylaluminum, forming a slurry of the support with toluene and contacting a borane solution, and subsequently contacted with a solution of a metal complex of Group IV monocyclopentadienyl in toluene. The representative polymer compositions described demonstrate an improved rheological performance, and an elevation in the comonomer distribution. WO 97/43323 discloses slurry polymerization processes using a supported catalyst formed by depositing a Group IV metal complex of monocyclopentadienyl and a perfluorophenyl borate on a dried and / or calcined silica support, which has been passivated with a compound of trialkylaluminium. Representative polymer compositions demonstrated an elevation in the comonomer distribution. EP 824112A1 discloses a supported composition, wherein a compound containing a MIA Group metal is direct (or through a separator) and covalently bound to a portion on the support, said compound can be of neutral or ionic construction, and forms a catalyst system with a transition metal compound, such as a metallocene. Although aluminum-containing compounds are widely described as suitable Group IIIA metal-containing compounds, no example describes their use; nor is there any teaching that recognizes any unexpected utility of species that contain aluminum. US Patent 5643847 describes a catalyst composition comprising a metal oxide support having a counter anion derived from a Lewis acid that does not have an easily hydrolysable ligand (such as a tri-perfluorophenylborane) covalently bound to the surface of the support directly through the oxygen atom of the metal oxide, wherein the anion is also ionically bound to a catalytically active transition metal compound. Although Lewis acids containing aluminum are widely described, there is no example describing their use; nor is there any teaching that recognizes any unexpected utility of the aluminum-containing species. It may be desirable if functionalized catalyst supports, more particularly, supported catalyst systems that are obtained from the activation of a metal complex using such functionalized catalyst supports, are to be used for olefin polymerizations that can be employed in slurry polymerizations. , solid phase, gas phase or high pressure. Accordingly, the present invention provides a functionalized catalyst support comprising a particulate support material that is chemically bonded thereto a plurality of aluminum-containing groups derived from a non-ionic Lewis acid, said aluminum-containing groups: containing less a fluoro-substituted hydrocarbyl ligand containing from 1 to 20 carbons, the hydrocarbyl ligand being bound to the aluminum, and being attached to the support material, optionally through a bridge portion, said composition being capable of activating a complex of Group metal 3-10 for addition polymerization of 1 or more polymerizable addition monomers.

The present invention further provides a functionalized catalyzed support comprising the reaction product of: (a) a solid inorganic oxide support material, and (b) a mixture both derived from contacting a non-ionic Lewis acid with one or more trihydrocarbylaluminum oxides, dihydrocarbylaluminum hydrocarbyl, or dihydrocarbylaluminum (dihydrocarbyl) amide compounds having up to 20 carbons that are not hydrogen in each hydrocarbyl, hydrocarbyloxy or dihydrocarbylamide group, or a mixture thereof to form a non-ionic Lewis acid component. The present invention further provides a supported catalyst comprising the functionalized catalyst support according to any of the preceding claims and a metal complex of Group 3-10 containing a substituent that reacts with the functionalized catalyst support to thereby form a composition that is catalytically active for the polymerization of olefins. The present invention further provides a method for preparing a functionalized catalyst support comprising: a. mixing in a slurry a particulate support in a hydrocarbon or aromatic diluent; b. add a compound, Arfz-AI2Q16.Z ", in an amount sufficient to fully react with surface groups as defined by titration with Et3AI, to form a treated support, wherein: Arf is a fluorinated aromatic hydrocarbyl portion of 6 to 30 carbon atoms; z "is a number from 0 to 6, and Q1 regardless of each occurrence is selected from hydrocarbyl, hydrocarbyloxy or dihydrocarbylamido, from 1 to 20 atoms that are not hydrogen, C. washing the treated support with a hydrocarbon or aromatic solvent, and d optionally drying The present invention further provides a method for preparing a functionalized catalyst support comprising: a) mixing in a slurry a particulate support optionally calcined with an alkyl aluminum reagent provided in an amount sufficient to fully react with groups of surface as defined by the titration with Et3AI, to form a passivated support, b.Add 0.1 to 50 mmoles of Ar 3M to form a treated support, where M = aluminum or boron and Ar is a fluorinated aromatic hydrocarbyl portion of 6 to 30 carbons, c) washing the solvent treated with a hydrocarbon or aromatic solvent, drying under reduced pressure. The polymerization process comprises contacting one or more polymerizable addition monomers under gas or slurry phase polymerization conditions with a catalyst composition of the invention. These and other advantages are fully set forth in the following detailed description. of functionalized catalyst of the invention is a preferred embodiment that can be illustrated as a chemical structure of the following formula: So [Mem1 (K1k1) (Dd)] s wherein: So is a solid particulate support material, Me is aluminum , m1 is a number of 1-20, preferably 1 to 3, most preferably 1; K1 independently of each occurrence is a ligand group bound to Me having from 1 to 30 atoms which are not hydrogen, provided that in at least one occurrence K1 is a fluoro-substituted hydrocarbyl group of 1 to 20 carbons, preferably an aryl fluoro group -substituted from 6 to 20 carbons, preferably a perfluoroaryl group of 6 to 20 carbons, most preferably pentafluorophenyl; and optionally two or more K1 groups can be joined together thereby forming a bridging group by linking two or more Me atoms or forming a fused ring system; K1 is a number from 1 to 5 selected to provide charge neutrality to the complex; D is a bridge portion chemically bonded to So through the group, [Mem1 (K1k1) (Dd)] s, is bonded to the solid support in particles; d is a positive number from 0 to 5, preferably from 1 to 3, most preferably 1, and less than or equal to m, d equaling the average number of chemical bonds to the substrate per group, [Mem1 (K1k1) (Dd)]; s is a number greater than or equal to 2 and is equal to the number of groups [Mem1 (K1k1) (Dd)], attached to the substrate, So. Preferably, s is selected to provide a concentration of groups [Mem? (K1k1) (D) j; on the substrate 1 x 10"5 μmoles / gram at 2 mmole / gram, most preferably 0.1 μmole / gram at 500 μmole / g The functionalized catalyst supports of the invention are easily prepared by combining a particulate support material reactive functional groups on the surface thereof, with a non-ionic Lewis acid source of the aluminum-containing groups that is capable of reacting with the functional surface groups of the support, preferably under conditions to chemically bind the aluminum of the group [Mem. (K1k1) (Dd) j and the support through a linking group D, optionally followed by removing the by-products formed by the reaction Preferred supports and sources of aluminum groups are those capable of reacting through ligand exchange to release a volatile hydrocarbon or substituted hydrocarbon byproduct, which is easily removed from the reaction environment. s ligand groups, [Mem1 (K1k1) (D)], are nonionic Lewis acids of the formula [Mem1 (K1) (K1k1)], especially, tri (fluoroaryl) aluminum compounds, most preferably tris (pentafluorophenyl) aluminum, as well as mixtures or adducts of said tri (fluoroaryl) aluminum compounds with one or more trialkylaluminum, alkylaluminumoxy, fluoroarylaluminoxy, or tri (fluoroaryl) boron compounds containing from 1 to 20 carbons in each alkyl group and from 6 to 20 carbons in each fluoroaryl ligand group. Said reagents are capable of reacting with a reactive functionality of the support to covalently bind to it, thus generating the linking group D, in the process. Preferred reagents are those capable of binding to a hydroxyl, hydrocarbyloxy, hydrocarbylmetal or hydrocarbyl methaloid functionality of the substrate, preferably through a ligand exchange mechanism, thus generating a linking group containing oxy, metal or metalloid, D. It should be understood that the linking group D, may be a component of either the substrate or the non-ionic Lewis acid, used to generate the compositions herein, or constitute a remnant resulting from the reaction of said components. Preferably, D will be a source portion containing oxygen, most preferably the oxygen contributed by the hydroxyl group of an optionally but preferably dry silica support. Examples of the above mixtures or nonionic Lewis acid adducts for use in the preparation of the functionalized supports of the invention include compositions that - * - - correspond to the formula: [(-AIQ1-O) z (-AIArf-O-) z]) Arfz AI2Q16-Z ") wherein: Q1 independently of each occurrence is selected from hydrocarbyl, hydrocarbyloxy or dihydrocarbylamido of 1 to 20 atoms which are not hydrogen; Arf is a fluorinated aromatic hydrocarbyl portion of 6 to 30 carbon atoms; z is a number from 1 to 50, preferably from 1.5 to 40, most preferably from 2 to 30, and the portion (-AIQ1-O-) is a cyclic or linear oligomer with a repeating unit of 2-30; z 'is a number from 1 to 50, preferably from 1.5 to 40, most preferably from 2 to 30, and the portion (-AIArf-O-) is a cyclic or linear oligomer with a repeating unit of 2-30; yz "is a number from 0 to 6, and the portion (Arfz AI2Q16-Z) is either tri (fluoroarylaluminum), trialkylaluminum, a dialkylaluminum alkoxide, a dialkylaluminum (dialkylamide) or a tri (fluoroarylaluminum) adduct with an amount sub-stoichiometric to super-stoichiometric of a trialkyl aluminum The portions (Arfz •• AI2Q16-Z ••) can exist as discrete entities or dynamic exchange products, ie, said portions can be in the form of dimeric products and other products multiple concentrates in combination with metal complexes and other organometallic compounds, including those that result from partial or complete ligand exchange during the process used for their manufacture.This more complex mixture of complexes can result from a combination of the above compounds, which are Lewis acid adducts, with other compounds such as metallocenes or alumoxanes. r inconstant by nature, the concentration of them being dependent on time, temperature, concentration of solution and the presence of other species capable of stabilizing the compounds, thus avoiding or reducing the exchange of additional ligand. Preferably, z "is 1-5, most preferably 1-3 The above class of nonionic Lewis acids is also suitable for use in the present invention in the absence of aluminumoxy species.These compounds are therefore adducts corresponding to the formula: Ar? AI2Q16-z wherein Arf is as previously defined The preferred nonionic Lewis acids for use herein are those of the above formula, wherein: Q1 independently of each occurrence is selected from alkyl of 1 to 20 carbon atoms, Arf is a fluorinated aromatic hydrocarbyl portion of 6 to 30 carbon atoms, z is a number greater than 0 and less than 6, and the Arfz portion AI2Q16.z is an adduct of tri (fluoroarylaluminum) with a sub-stoichiometric to super-stoichiometric amount of a trialkyl aluminum having from 1 to 20 carbons in each alkyl group Examples of non-ionic aluminum Lewis acid reagents for use herein, is of reagents and resulting products are illustrated below: Arf3AI + Q13AI? Arf3AI2Q13 (Arf3AI • AIQ13) Arf3B + 2Q13AI? Arf3AI2Q13 + BQ13 (Arf3AI • AIQ13) Arf3AI + 2Q13AI? 3 ArfAIQ12? 2/3 Arf3AI2Q14 (Arf3AI • 2 AIQ13) Arf3AI + 5Q13AI? 3 ArfAI2Q15 (Arf3AI • AIQ13) Arf3AI + 10Q13AI? 3 ArfAI2Q15 + 5 Q13AI (Arf3AI • 10AlfAIQ15) 2Arf3B + 3Q13AI? 3Arf2AIQ1 + 2BQ13? Arf4AI2Q12 (Arf3AI • Y2 A / Q 3) 5Arf3B + 6Q13AI? 5BQ13 + Arf5AI2Q1 (Arf3AI- 1/5 A / Q13) The above mixtures of non-ionic Lewis acids and adducts can be easily prepared by combining the tri (fluoroaryl) aluminum compound and the trialkylaluminum compound. The reaction can be carried out in a solvent or diluent, or net. The intimate contact of the net reactants can be effectively achieved by drying a solution of the two reagents to form a solid mixture, and then optionally continuing said assembly, optionally at elevated temperature. Preferred tri (fluoroaryl) aluminum compounds are tris (perfluoroaryl) aluminum compounds, most preferably tri (pentafluorophenyl) aluminum. The latter compound can be readily prepared through ligand exchange of a tpfluoroarilboro compound and a trialkylaluminum compound, especially methyl aluminum. The above mixtures of nonionic Lewis acids and adducts can be easily prepared through the reaction of a fluoroarylborane, preferably tris (pentafluorophenyl) borane with more than a stoichiometric amount of one or more trihydrocarbylaluminum compounds, dihydrocarbylaluminum hydrocarbyl, or dihydrocarbylaluminum oxides (hydrocarbyl) amide having up to 20 non-hydrogen atoms in each hydrocarbyl, hydrocarbyloxy or dihydrocarbylamide group, or a mixture thereof with one or more aluminoxy compounds (such as an alumoxane) substantially in accordance with the conditions described in the US Pat. EU to 5,602,269. Generally the various reagents that form the improved activators of the invention, such as the trifluoroaryl boron compound and the trialkylaluminum compound are merely contacted in a hydrocarbon liquid at a temperature of 0 to 75CC for a period of 1 minute to 10 days. Preferably, said contact occurs for a period of one minute to one day, preferably at least 30 minutes to allow the exchange of ligand to occur to a sufficient degree to produce the advantages associated with the practice of the invention. Preferred nonionic Lewis acid reagents for use in accordance with the present invention are those wherein Arf is pentafluorophenyl, and Q 1 is alkyl of 1 to 4 carbon atoms. The most preferred nonionic Lewis acids used with the present invention are those in which Ar is pentafluorophenyl, and Q1 in each occurrence is methyl, isopropyl or isobutyl. Preferred support materials are finely particulate materials which remain as solids under conditions of preparation and use and which do not interfere with subsequent polymerizations or other uses of the composition of the invention. Suitable support materials especially include particulate metal oxides, silicon or germanium oxides, polymers and mixtures thereof. Examples include alumina, silica, aluminosilicates, clay and particulate polyolefins. Suitable average volume particle sizes of the support are from 1 to 1000 μM, preferably from 10 to 100 μM. The most desired supports are silica, which is completely dry, conveniently heating from 200 to 900CC for 10 minutes to 2 days. The silica can be treated before being used to further reduce the surface hydroxyl groups therein, or to introduce a more reactive functionality than the hydroxyl functionality available for the subsequent reaction with the Lewis acid. Suitable treatments include reaction with a tri (one to 10 carbon atoms) silylhalogenide, hexa (alkyl of 1 to 10 carbon atoms) disilazane, tri (at least one of 10 carbon atoms) aluminum , or similar reactive compounds, preferably by contacting the support and a hydrocarbon solution of the reactive compound. In a preferred embodiment, the silica is reacted with a tri (alkyl) aluminum, preferably a tri (alkyl) aluminum, of 1 to 10 carbon atoms, most preferably trimethylaluminum, triethylaluminum, triisopropylaluminum or triisobutylaluminum, to form a support modified. The amount of trialkyl aluminum is selected to quench 1-99% of the reactive species on the surface, most preferably 50-90% as determined by titration with Et3AI. Titration with Et3AI is defined as the maximum amount of aluminum that chemically reacts with the particulate solid support material and can not be removed by washing with an inert hydrocarbon or aromatic solvent. Then, this modified support is contacted with the above cocatalyst composition, or a solution thereof, in an amount sufficient to provide a functionalized catalyst support for the olefin polymerization according to the invention. In an alternative, the modified support can be contacted with a nonionic Lewis acid and, for example, a trihydrocarbylaluminum, dihydrocarbylaluminum hydrocarbyl or dihydrocarbylaluminum (dihydrocarbyl) amide oxide, to form the in situ cocatalyst reagent. Polymeric particulate supports can be used, although less preferred than inorganic oxide supports. Said polymeric particulate supports are preferably also functionalized to provide reactive groups of hydroxyl, carboxylic acid or sulfonic acid. The resulting substrate material formed by the reaction with non-ionic Lewis acid will accordingly carry the corresponding oxy, carboxy or sulfoxy linking group. D. Nonionic Lewis acid and particulate support material can be combined and any aliphatic, alicyclic or aromatic liquid diluent or solvent, or mixtures thereof, reacted. Preferred diluents or solvents are hydrocarbons of 4 to 10 carbon atoms and mixtures thereof, including hexane, heptane, cyclohexane and mixed fractions such as lsopar ™ E, available from Exxon Chemicals Inc. Preferred contact times are at least 1. hour, preferably at least 90 minutes, at a temperature of 0 to 75 ° C, preferably 20 to 50 ° C, and most preferably 25 to 25 ° C. Desirably, contact is also made prior to the addition of a metal complex catalyst, such as a metallocene, to the mixture or any component separately, in order to avoid the formation of additional derivatives and multiple metal exchange products having Reduced catalytic effectiveness. After contacting the support and Lewis acid, the reaction mixture can be purified to remove byproducts, especially any triaiquilboron compounds by any suitable technique. Alternatively, but less desirably, a metal complex catalyst of Group 3-10 can first be combined with the reaction mixture before removing the by-products.

Suitable techniques for removing by-products from the reaction mixture include degassing, optionally at reduced pressures, distillation, solvent exchange, solvent extraction, extraction with a volatile agent, and combinations of the above techniques, all of which are conducted in accordance with conventional procedures, preferably, the amount of residual by-product is less than 10% by weight, preferably less than 1.0% by weight, most preferably less than 0.1% by weight, based on the weight of the functionalized catalyst support. The highly preferred compounds according to the invention are those which comprise less than one portion of tri (alkyl) aluminum per portion of tri (fluoroaryl) aluminum. The most highly desired adducts are those corresponding to the formula, Arf4AI2Q12 and Arf5AI2Q1. Said compositions possess extremely high catalyst activation properties. The support material and the cocatalyst derived from non-ionic Lewis acid are preferably contacted to chemically bind a plurality of functional groups to the surface of the support. The reaction is also preferably conducted before the formation of the active polymerization catalyst through the addition of a metal complex. Metal complexes suitable for use in combination with the above functionalized catalyst supports include any complex of a metal of groups 3-10 of the Periodic Table of the Elements capable of being activated to polymerize addition polymerizable compounds, especially olefins through the activators of the present. Suitable complexes include Group 3, 4 derivatives, or lanthanide metals containing from 1 to 3 neutral or p-anionic ligand groups, which may be p-linked anionic, cyclic, or non-cyclic, delocalized ligand groups. Examples of said anionic ligand groups attached to p are cyclic or non-cyclic, conjugated or non-conjugated dienyl groups, allyl groups, boratabenzene groups, and arene groups. By the term "linked to p" is meant that the ligand group is attached to the transition metal by sharing electrons from a partially delocalized p-bond.

Each atom in the group aplocally independently ap can be substituted with a radical selected from the group consisting of hydrogen, halogen, hydrocarbyl, halohydrocarbyl, hydrocarbyl substituted radicals, wherein the metalloid is selected from group 14 of the Periodic Table of the Elements, and said hydrocarbyl or substituted hydrocarbyl metalloid radicals further substituted with a portion containing a heterogeneous atom of Group 15 or 16. Included within the term "hydrocarbyl" are alkyl radicals of 1 to 20 carbon atoms, straight, branched and cyclics, aromatic radicals, of 6 to 20 carbon atoms, alkyl-substituted aromatic radicals of 7 to 20 carbon atoms, and aryl-substituted alkyl radicals of 7 to 20 carbon atoms.

In addition, two or more of these radicals together can form a fused ring system, including partially or fully hydrolyzed ring systems, or can form a metallocycle with the metal. Suitable hydrocarbyl-substituted organometaloid radicals include mono, di and tp organometaloid radicals -substituted from the elements of group 14, wherein each of the hydrocarbyl groups contains from 1 to 20 carbon atoms. Examples of suitable hydrocarbyl-substituted organometalloid radicals include trimethylsilyl, triethylsilyl, ethyldi-methylisilyl, n; ^ mdiethylsilyl, triphenylgermyl and trimethylgermyl. Examples of portions containing a heterogeneous atom of group 15 or 16 include amine, phosphine, ether or thioether portions or their divalent derivatives, for example, amide, phosphide, ether or thioether groups bound to the transition metal or lanthanide metal, and attached to the hydrocarbyl group or to the group containing hydrocarbyl-substituted metalloid. Examples of suitable delocalised, anionic attached groups include cyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl, tetrahydrofluorenyl, octahydrofluorenyl, pentadienyl, cyclohexadienyl, dihydroanthracenyl, hexahydroanthracenyl, decahydroanthracenyl, and boratabenzene groups, as well as their hydrocarbyl-substituted derivatives of 1 to 10 carbon atoms. carbon or substituted hydrocarbyl-substituted silyl of 1 to 10 carbon atoms. Preferred anionic, delocalized p-linked groups are cyclopentadienyl, pentamethylcyclopentadienyl, tetramethylcyclopentadienyl, tetramethylsilyl-pentadienyl, indenyl, 2,3-dimethylindenyl, fluorenyl, 2-methylindenyl, 2-methyl-4-phenylindenyl, tetrahydrofluorenyl, octahydrofluorenyl, and tetrahydroindenyl. Suitable metal complexes include mine derivatives of group 10 corresponding to the formula: N ^ - ^ CT-CT M * X'2A * where N N is Ar * -N N-Ar * (N M * is Ni (ll) or Pd (ll); X 'is halogen, hydrocarbyl or hydrocarbyloxy; Ar * is an aryl group, especially a 2,6-diisopropylphenyl or aniline group; CT-CT is 1, 2-ethanediyl, 2,3-butanediyl, or form a fused ring system, wherein the two T groups together are a 1,8-naphthanediyl group; and A "is the anionic component of the above separate charge activators Similar complexes of the above are also described by M. Broockhart, et al., in J. Am. Chem. Soc, 118, 267-268 (1996) and J. Am. Chem. Soc, 117, 6414-6415 (1995), as being polymerization catalysts active especially for the polymerization of α-olefins, either alone or in combination with polar comonomers such as vinyl chloride, alkyl acrylates and alkyl methacrylates.

Boratabenzenes are anionic ligands that are boron-containing analogs for benzene. They are previously known in the art and have been described by G. Herberich, et al., In Organometallics, 1995, 14, 1, 471-480. The preferred boratabenzenes correspond to the formula: wherein R "is selected from the group consisting of hydrocarbyl, silyl, or germyl, R" having up to 20 non-hydrogen atoms. In complexes involving divalent derivatives of said groups attached to delocalized p, one atom thereof is bound through a covalent bond or a divalent group covalently bonded to another atom of the complex, thereby forming a bridge system. Very preferred are the metal complexes corresponding to the formula: L | MXmX nX p, or a dimer thereof, wherein: L is an attached, delocalized, anionic group that is attached to M, containing up to 50 atoms that are not are hydrogen, optionally two L groups can be linked together through one or more substituents, thus forming a bridged structure, and further optionally one L can be linked to X through one or more L substituents; M is a metal of Group 4 of the Periodic Table of the Elements in the formal oxidation state +2, +3, or +4; X is a divalent, optional substituent of up to 50 non-hydrogen atoms that together with L form a metallocycle with M; X 'is an optional neutral Lewis base having up to 20 non-hydrogen atoms; X "in each occurrence is an anionic, monovalent moiety having up to 40 non-hydrogen atoms, optionally, two X groups" may be covalently linked together forming a divalent dianionic moiety having both valencies attached to M, or forming a neutral, conjugated diene or unconjugated that is linked by pa M (where M is in the oxidation state +2), or optionally one or more groups X "and one or more X 'groups may be linked together thus forming a portion that is both covalently linked to M and coordinated thereto via a base functionality Lewis; I is 1 or 2; m is 0 or 1; n is a number from 0 to 3; p is an integer from 0 to 3; and the sum, l + m + p, is equal to the formal oxidation state of M. Said preferred complexes include those which already contain - »is one or two groups L. The last complexes include those that contain a bridge group joining the two groups L. The preferred bridge groups are those corresponding to the formula (Er * 2) x, where E is silicon or carbon, R * independently of each occurrence is hydrogen or a selected group of silyl, hydrocarbyl, hydrocarbyloxy, and combinations thereof, R * having up to 30 carbon or silicon atoms, and X is from 1 to 8. Preferably, R * independently of each occurrence is methyl, benzyl, tert-butyl or phenyl. Examples of the above compounds containing bis (L) are compounds corresponding to the formula: wherein: M is titanium, zirconium or hafnium, preferably zirconium or hafnium, in the formal oxidation state +2 or +4; R3 in each occurrence independently is selected from the group consisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halogen, and mixtures thereof, R3 having up to 20 non-hydrogen atoms, or adjacent R3 groups together form a divalent derivative (i.e., a hydrocarbyldiyl, siladiyl or germadillo group) thus forming a fused ring system, and X "independently of each occurrence is an anionic ligand group of up to 40 non-hydrogen atoms, or two X groups" together form a divalent anionic ligand group of up to 40 non-hydrogen atoms or together they are a conjugated diene having from 4 to 30 non-hydrogen atoms forming a complex of p with M, wherein M is in the formal oxidation state +2, and R *, E and x are as previously defined. The above metal complexes are especially suitable for the preparation of polymers having a stereoregular molecular structure. In said capacity, it is preferred that the complex possess C2 symmetry or possess a stereorigid, chiral structure. Examples of the first type are compounds possessing different systems attached to delocalized p, such as a cyclopentadienyl group and a fluorenyl group. Similar systems based on Ti (IV) or Zr (IV) were described for the preparation of syndiotactic olefin polymers by Ewen, et al., J. Am. Chem. Soc. 110, 6255-6256 (1980). Examples of chiral structures include bis-indenyl complexes. Similar systems based on Ti (IV) or Zr (IV) were described for the preparation of isotactic olefin polymers by Wild et al., J. Organomet. Chem. 232, 233-47, (1992). Illustrative bridge ligands contain two groups ^^ * ¡^ attached to p and are: (dimethylsilyl-bis-cyclopentadienyl), (dimethylsilyl-bis-methylcyclopentadienyl), (dimethylsilyl-bis-ethylcyclopentadienyl, (dimethylsilyl-bis-t-butylcyclopentadienyl), (dimethylsilyl-bis-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-fluorenyl), (1,1,2,2-tetramethyl-1,2-disilyl-bis-cyclopentadienyl), (1,2-bis (cyclopentadienyl) ethane and (isopropylinden-cyclopentadienyl-fluorenyl) The preferred "X" groups are selected from hydride, hydrocarbyl, silyl, germyl, halohydrocarbyl, halosilyl, silyl id rocarbyl and aminohydrocarbyl groups, or two X groups "together form a divalent diene derivative conjugated or together form a conjugated, ap-linked, neutral diene.The highly preferred groups X are hydrocarbyl groups of 1 to 20 carbon atoms.An additional class of metal complexes used in the present invention corresponds to the formula: L | MXmX ' nX "p, or a dimer thereof, wherein: L is a bonded, de-localized, anionic group that is attached to M, containing up to 50 non-hydrogen atoms, M is a metal of group 4 of the Periodic Table of the Elements in the formal oxidation state +2, +3, or +4; X is a divalent, optional substituent of up to 50 non-hydrogen atoms that together with L form a metallocycle with M; X 'is an optional neutral Lewis base ligand having up to 20 non-hydrogen atoms; X "in each occurrence is an anionic, monovalent moiety having up to 20 non-hydrogen atoms, optionally, two X groups" may be covalently linked together forming a divalent anionic moiety having both valencies attached to M, or forming a conjugated diene 5 at 30 carbon atoms, neutral, and optionally further X 'and X "may be linked together thereby forming a portion that is both covalently linked to M and coordinated thereto via a Lewis base functionality; I is 1 or 2; m is 1; n is a number from 0 to 3, p is an integer from 1 to 2, and the sum, l + m + p, is equal to the formal oxidation state of M. Divalent X substituents, preferred from Preferred include groups containing up to 30 non-hydrogen atoms comprising at least one atom which is oxygen, sulfur, boron or a member of group 14 of the Periodic Table of the Elements, directly attached to the group attached to, de-localized or, and a different atom, selected from the group consisting of nitrogen, phosphorus, oxygen or sulfur that is covalently bound to M.

A preferred class of said Group 4 metal coordination complexes used in accordance with the present invention corresponds to the formula: R3 RJ wherein: M is titanium or zirconium in the formal oxidation state +2 or +4; R3 in each occurrence independently is selected from the group consisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halogen and combinations thereof, R3 having up to 20 non-hydrogen atoms, or adjacent R3 groups together form a divalent derivative (i.e. a hydrocarbyldiyl, siladiyl or germadiyl group), thus forming a fused ring system, each X "is a halogen, hydrocarbyl, hydrocarbyloxy or silyl group, said group having up to 20 non-hydrogen atoms, or two X groups" together form a conjugated diene of 5 to 30 carbon atoms; And it is -O-, -S-, -NR * -, -PR * -; and Z is SiR * 2, CR * 2l SiR * 2SiR * 2, CR * 2CR * 2, CR * = CR *, CR * 2SR2, or GeR * 2, where: R * is as previously defined.

Illustrative Group 4 metal complexes that can be employed in the practice of the present invention include: cyclopentadienyl trimethyl cyclopentadienyl titanium, cyclopentadienyl triethyl titanium, cyclopentadienyl trisopropyl titanium, cyclopentadienyl triphenyl titanium, Cyclopentadienyl Tribenzyl Titanium, Cyclopentadienyl 2,4-Pentadienyl Titanium, Cyclopentadienyl Titanium Dimethyl Methoxide, Cyclopentadienyl Titanium Dimethyl Chloride, Pentamethylcyclopentadienyl Trimethyl Titanium, Trimethyl Indenyl Titanium, Indenyl Triethyl Titanium, Triphenyl Indenyl Titanium, Titanium triphenyl, indenyl triphenyl, tetrahydroindenyl tribenzyl titanium, pentamethylcyclopentadienyl trisopropyl titanium, pentamethylcyclopentadienyl tribenzyl titanium, pentamethylcyclopentadienyl dimethyl methoxide, pentamethylcyclopentadienyl titanium dimethyl chloride, (? 5-2,4-dimethyl-1, 3-) trimethylenitrile titanium pentadienyl), trimethyl octahydrofluorenyl titanium, trimethyl tetrahydroindenyl titanium, trimethyl tetrahydrofluorenyl titanium, trimethyl (1, 1-dimethyl-2, 3,4,9,10-? -1, 4,5,6,7 titanium), 8-hexahydronaphthalenyl), trimethyl (1, 1, 2) titanium , 3-tetramethyl-2,3,4,9, 10 -? - 1, 4,5,6,7,8-hexahydronaphthalenyl), titanium dichloride of (tert-butylamido) (tetramethyl-? 5-cyclopentadienyl) ) dimethylsilane, dimethyl (tert-butylamido) titanium (tetramethyl) -5-cyclopentadienyl) dimethylsilane, dimethyl (tert-butylamido) titanium (tetramethyl-? 5-cyclopentadienyl) 1,2-ethanediyl, dimethyl titanium from (ter) -butylamido) (tetramethyl-? 6-indenyl) dimethylsilane, titanium (III) 2- (dimethylamino) benzyl (tert-butylamido) (tetramethyl-? 5-cyclopentadienyl) dimethylsilane; Titanium (III) allyl (tert-butylamido) (tetramethyl-? 5-cyclopentadienyl) dimethylsilane, Titanium (II) 1,4-diphenyl-1,3-butadienyl (tert-butylamido) (tetramethyl-? 5-cyclopentadienyl) Dimethylsilane, Titanium (II) 1,4-diphenyl-1,3-butadienyl (tert-butylamido) (2-methylindenyl) d -methylsilane, Titanium (IV) 1,3-butadienyl (tert-butylamido) (2) -methyldenyl) dimethylsilane, titanium (II) 1,4-diphenyl-1,3-butadienyl (tert-butylamido) (2,3-methylindenyl) dimethylsilane, titanium (IV) 1,3-butadienyl (tert-butylamido) (2,3-methylindenyl) dimethylsilane, Titanium (II) 1, 3-pentadienyl (tert-butylamido) (2,3-methylindenyl) dimethylsilane, Titanium (II) 1,3-pentadienyl (tert-butylamido) (2-methylindenyl) dimethylsilane, titanium (IV) dimethyl (tert-butylamido) (2-methylindenyl) dimethylsilane, Titanium (II) 1, 4-d if enyl-1,3-butadienyl of (tert-butylamido) (2-methyl-4-phenylindenyl) dimethylsilane, Titanium (II) 1,4-dibenzyl-1,3-butadienyl (tert-butylamido) (tetramethyl-? 5-cyclopentadienyl) dimethylsilane, titanium (II) 2,4-hexadienylic (tert-butylamido) (tetramethyl-? 5-cyclopentadienyl) dimethylsilane, titanium (II) 3-methyl- 1, 3-pentadienyl of (tert-butylamido) (tetramethyl-? 5-cyclopentadienyl) dimethylsilane, dimethyl (tert-butylamido) titanium (2,4-dimethyl-1,3-pentadien-2-yl) dimethylsilane, Dimethyl ((tert-butylamido) titanium (1,1-dimethyl-2,3,4,9,10 -? - 1,4,5,6,7,8-hexahydronaphthalen-4-yl) dimethylsilane, dimethyl titanium (tert-butylamido) (1, 1, 2,3-tetramethyl-2,3,4,9, 10 -? - 1,4,5,6,7,8-hexahydronaphthalen-4-yl) dimethylsilane, Titanium 1 , 3-pentadienyl of (tert-butylamido) (tetramethylcyclopentadienyl) dimethylsilane, Titanium 1,3-pentadienyl of (tert-butylamido) (3- (N-pyrrolidinyl) inden-1-yl) dimethylsilane, Titanium 1, 3- pentadienyl of (ter-butilami) do) (2-methyl-s-indacen-1-yl) dimethylsilane, and Titanium 1, 4-d if in i-1, 3-butadienyl of (tert-but-lamido) (3,4-c? clopenta (/) phenanthren-2-? l) dimethylsilane. Bis (L) -containing complexes including bridge complexes suitable for use in the present invention include-biscyclopentadienyl dimethyl titanium, biscyclopentadienyl diethyl titanium, biscyclopentadienyl diisopropyl titanium, biscyclopentadienyl diphenyl titanium, biscyclopentadienyl dibenzyl zirconium, titanium 2,4 Biscyclopentadienyl Peptide, Biscyclopentadienyl Titanium Methoxide, Biscyclopentadienyl Titanium Methyl, Biscyclopentamethyl Cyclopentadienyl Dimethyl Titanium, Bisindenyl Dimethyl Titanium, Indenyl Fluorenyl Diethyl Titanium, Titanium Methyl (2- (Dimethyl Ammonium) Benzyl Titanium), Bisindenyl Titanium, Methyltrimethylsilyl Titanium bisindenyl, titanium methyltrimethylsilyl bistetrahydroindenyl, bispentamethylcyclopentadienyltitaniumdiisopropy, bispentamethylcyclopentadienyl benzylic titanium, bispentamethylcyclopentadienyl titanium methoxide, Methyl bispentamethylcyclopentadienyl chloride, dimethylsilyl-bis-cyclopentadienyl zirconium, 2,4-pentadienyl titanium (dimethylsilyl-bis-pentamethylcyclopentadienyl), zirconium dichloride (dimethylsilyl-bis-t-butylcyclopentadienyl), titanium (III) 2- (dimethylamino) benzyl of (methylene-bis-pentamethylcyclopentadienyl), zirconium dichloride (dimethylsilyl-bis-indenyl), dimethyl (2-dimethylsilyl-bis-2-methylindenyl) zirconium, dimethylsilyl-bis-2-methyl 4-phenylindenyl), Zirconium 1, -dif in 1- (1,3-dimethylsilyl-bis-2-methylindenyl) -l, 3-butadienyl), zirconium (ii) 1,4-d-dimethyl-1,3-butadienyl (dimethylsilyl) bis-2-methyl-4-phenylindenyl), zirconium (II) 1,4-d ifeni I-1,3-butadienyl (dimethylsilyl-bis-tetrahydroindenyl), zirconium dichloride (dimethylsilyl-bis-fluorophenyl), zirconium di (trimethylsilyl) of (dimethylsilyl-bis-tetrahydrofluorenyl), dibenzyl (isopropylidene) zirconium (cyclopentadiene) enyl) (fluorenyl), and dimethyl (dimethylsilylpentamethylcyclopentadienyl-fluorenyl) zirconium. Suitable polymerizable monomers include ethylenically unsaturated monomers, acetylenic compounds, conjugated or non-conjugated dienes, and polyenes. Preferred monomers include olefins, for example, alpha-olefins having from 2 to 20,000, preferably from 2 to 20, and most preferably from 2 to 8 carbon atoms, and combinations of 2 or more of these 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, as well as oligomeric or polymeric long-chain vinyl-terminated reaction products, formed during polymerization, and alpha-olefins of 10 to 30 carbon atoms specifically added to the reaction mixture in order to produce relatively long chain branches in the resulting polymers. Preferably, 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 other alpha-olefins. Other preferred monomers include styrene, halo or alkyl-substituted styrenes, tetrafluoroethylene, vinylcyclobutene, 1,4-hexadiene, dicyclopentadiene, ethylidene norbornene, and 1,7-octadiene. Mixtures of the aforementioned monomers can also be used. In general, polymerization can be achieved at conditions well known in the prior art for Ziegler-Natta or Kaminsky-Slinn type polymerization reactions conducted under slurry or gas phase polymerization conditions. The preferred polymerization temperatures are 0-250 ° C. The preferred polymerization pressures are atmospheric at 3000 atmospheres. Molecular weight control agents can be used in combination with the cocatalysts herein. Examples of such molecular weight control agents include hydrogen, silanes or other known chain transfer agents.

The gas phase processes for the polymerization of olefins of 2 to 6 carbon atoms, especially the homopolymerization and copolymerization of ethylene and propylene, and the copolymerization of ethylene with alpha-olefins of 3 to 6 carbon atoms, such as, example, 1-butene, 1-hexene, 4-methyl-1-pentene, are well known in the art. These processes are commercially used on a large scale for the manufacture of high density polyethylene (HDPE), medium density polyethylene (MDPE), linear low density polyethylene (LLDPE) and polypropylene, especially isotactic polypropylene. The gas phase process employed can be, for example, of the type employing a mechanically agitated bed or a fluidized gas bed as the polymerization reaction zone. The process is preferred in which the polymerization reaction is carried out in a vertical cylindrical polymerization reactor containing a fluidized bed of polymer particles supported above a perforated plate, the fluidization grid, through a flow of fluidizing gas. The gas used to fluidize the bed comprises the monomer or monomers that will be polymerized and also serves as a means of heat exchange to remove heat from the bed reaction. The hot gases that emerge from the upper part of the reactor, usually through a zone of tranquility, also known as a zone of speed reduction, having a diameter wider than the fluidized bed, where ÉlñlriikMÍHaMMHM- fine particles enter the gas stream, have the opportunity to gravitate in the bed. It is also advantageous to use a cyclone to remove ultrafine particles from the hot gas stream. The gas is then typically recirculated to the bed through a blower or compressor and one or more heat exchangers to separate the gas from the polymerization heat. A preferred method of cooling the bed, in addition to the cooling provided by the cooled recirculation gas, is feeding a volatile liquid to the bed to provide an evaporative cooling effect. The volatile liquid used in this case can be, for example, a volatile inert liquid, for example, a saturated hydrocarbon having from 3 to 8, preferably from 4 to 6 carbon atoms. In the case where the monomer or comonomer itself is a volatile liquid, or can be condensed to provide such a liquid, it can be conveniently fed into the bed to provide an evaporative cooling effect. Examples of olefin monomers which can be cooled in this manner are olefins containing from 3 to 8, preferably from 3 to 6 carbon atoms. The volatile liquid evaporates in the hot fluidized bed to form gas, which is mixed with the fluidizing gas. If the volatile liquid is a monomer or comonomer, it will experience some polymerization in the bed. The evaporated liquid then emerges from the reactor as part of the hot recirculation gas, and enters the compression / thermal exchanger part of the recirculation cycle. The recirculation gas is cooled in the term exchanger and, if the temperature at which the cooled gas is below the dew point, the liquid will precipitate from the gas. This liquid is desirably recirculated continuously to the fluidized bed. It is possible to recirculate the precipitated liquid to the bed as liquid droplets carried in the recirculation gas stream, as described, for example, in EP-A-89691, US-A-4543399, WO 94/25495 and US-A- 5352749, which are incorporated herein by reference. A particularly preferred method for recirculating the liquid to the bed is to separate the liquid from the recirculation gas stream and reinject this liquid directly into the bed, preferably using a method that generates fine droplets of the liquid within the bed. This type of process is described in WO 94/28032, the teachings of which are incorporated herein by reference. The polymerization reaction that occurs in the gas fluidized bed is catalysed through the addition of a catalyst, in a continuous or semicontinuous manner. The catalyst can also be subjected to a prepolymerization step, for example, by polymerizing a small amount of olefin monomer in a liquid inert diluent, to provide a mixed catalyst material comprising catalyst particles embedded in olefin polymer particles. The polymer is produced directly in the fluidized bed through catalysed (co) polymerization of the monomer (s) on the fluidized particles of the catalyst, supported catalyst or prepolymer within the bed. The start of the polymerization reaction is achieved using a bed of preformed polymer particles, which, preferably, are similar to the objective polyolefin, and conditioning the bed by drying with inert gas or nitrogen before introducing the catalyst, the monomer (s) ) and any other gas that is desired to have in the recirculation gas stream, such as a diluent gas, hydrogen chain transfer agent, or an inert condensable gas when operating in a gas phase condensation mode. The produced polymer is discharged continuously or discontinuously from the fluidized bed as desired, optionally exposed to a catalyst annihilator and optionally pelletized. It is possible to prepare and use, according to previously known techniques, supported catalysts for use in slurry polymerization. In general, said catalysts are prepared by the same techniques as are used to make supported catalysts used in gas phase polymerizations. The slurry polymerization conditions generally encompass polymerization of an olefin of 2 to 20 carbon atoms, diolefin, cycloolefin, or a mixture thereof in an aliphatic solvent at a temperature below that at which the polymer is readily soluble in. presence of a supported catalyst. Particularly suitable slurry phase processes for polymerization of olefins of 2 to 6 carbon atoms, especially the homopolymerization and copolymeation of ethylene and propylene, and the copolymerization of ethylene with alpha-olefins of 3 to 8 carbon atoms, such as, for example, 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene are well known in the art. These processes are commercially used on a large scale for the manufacture of high density polyethylene (HDPE), medium density polyethylene (MDPE), linear low density polyethylene (LLDPE) and polypropylene, especially isotactic polypropylene. It should be understood that the present invention can operate in the absence of any component that has not been specifically described. The following examples are provided in order to further illustrate the invention and are not constructed as limiting. Unless otherwise indicated, all parts and percentages are expressed on a weight basis. When the term "room temperature" is established, it refers to a temperature of 20 to 25 ° C, the term "during the night" refers to a time of 12 to 18 hours, and the term "mixed or mixed alkanes" refers to to the aliphatic solvent, lsopar ™ E, available from Exxon Chemicals Inc.

EXAMPLES Tris (perfluorophenyl) borane was obtained as a Boulder solid Scientific Inc., and was used without further purification. The modified metalumoxane (MMAO-3A) in heptane was purchased from Akzo-Nobel. MAO and trimethylaluminum (TMA) both in toluene were purchased from Aldrich Chemical Co. Tris (perfluorophenyl) aluminum (FAAL) in toluene was prepared through an exchange reaction between tris (perfluorophenyl) borane and trimethylaluminum. The silica, Davison ™ 948, was purchased from Grace-Davison Incorporated. All solvents were purified using the technique described by Pangborn et al., Organometallics, 1996, 15, 1518-1520. All the compounds and solutions were handled under an inert atmosphere (drying box).

Comparative Example 1 Tris (pentafluorophenyl) boron (5.775 g, 11.3 mmol) was dissolved in 100 ml of toluene. A solution of MMAO-3A in heptane (11.6 ml of a 7.1% by weight aluminum solution, Akzo) was added and the mixture was stirred on a mechanical stirrer for 15 minutes. The volatiles were removed in vacuo to give a pale yellow glass. 200 ml of toluene was added to dissolve the material and the resulting solution was added to 2 g of the Davison ™ 948 silica which was dehydrated at 250 ° C for 3 hours in air. The mixture was stirred for 3 days. The slurry was collected in a frit funnel and the resulting solid was washed with 50 ml of toluene and dried in vacuo. Yield = 2.9 g; [Al] = 8.2% by weight. 1 g of the treated support was combined in a slurry in 10 ml of hexane, 0.2 ml of a 0.2 M solution of titanium, (N-1,1-dimethylethyl) dimethyl (1- (1,2,3,4 , 5-eta) -2,3,4,5-tetramethyl-2,4-cyclopentadien-1-yl) silanaminate)) (2-) N) - (? 4-1, 3-pentadiene) (C5Me SiMe2NtBu) Ti (? -1, 3-pentadiene) in mixed alkanes, and the mixture was stirred for 30 minutes resulting in the formation of a green solid phase and a colorless supernatant. The solid was collected on a frit funnel, washed with 30 ml of hexane and dried in vacuo.

Gas Phase Polymerization Continuous gas phase polymerization was performed in a 6-liter gas phase reactor having a fluidization zone with a diameter of 5.08 cm and a length of 30.48 cm and a zone of velocity reduction with a diameter of 20.32 cm and a length of 20.32 cm, through a transition section having tapered walls. Typical operating conditions varied from 40 to 100 ° C, from 0.7 to 2.4 MPa, from total pressure, and up to 8 hours of reaction time. The monomer, comonomer and other gases introduced at the bottom of the reactor were passed through a plate of gas distributors. The gas flow was 2 to 8 times the minimum particle fluidization rate [Fluidization Engineering, 2o. Ed., D. Kunii and O. Levenspiel, 1991, Butterworth-Heinemann]. Most of the suspended solids were uncoupled in the zone of speed reduction. The gases left the top of the velocity reduction zone and passed through a dust filter to remove any fine particles. The gases were then passed through a gas booster pump. The polymer was allowed to accumulate in the reactor during the course of the reaction. The total pressure of the system was kept constant during the reaction by regulating the monomer flow in the reactor. The polymer was removed from the reactor to a recovery vessel by opening a series of valves located at the bottom of the fluidization zone, thereby discharging the polymer into a recovery vessel maintained at a lower pressure than in the reactor. The monomer pressures, Comonomer and other gases reported refer to partial pressures. The catalyst prepared above, 0.05 g, was charged to a catalyst injector in an inert atmosphere glove box. The injector was removed from the glovebox and inserted into the upper part of the reactor. The catalyst was added to the semi-intermittent gas phase reactor, which was under an ethylene (monomer) pressure of 0.65 MPa, a pressure of 1-butene (comonomer) of 14 kPa, a hydrogen pressure of 4 kPa and a nitrogen pressure of 0.28 MPa. The polymerization temperature through the operation was 70 ° C. The polymer was allowed to accumulate for 30 minutes. The total pressure of the system was kept constant during the reaction by regulating the monomer flow in the reactor. The dry free-flowing copolymer, ethylene / 1-butene powder yield was 64.7 grams. An additional comparative catalyst prepared without the use of B (C6F5) 3 (only a silica support treated with MMAO) yielded 2.7 g of powder under identical polymerization conditions.

EXAMPLE 1 3 g of the Davison 948 silica was combined in a slurry in 30 ml of toluene, which was dehydrated by heating in air for 3 hours at 250 ° C. 4.5 ml of a 1 M solution of triethylaluminum was added and the mixture was stirred for 15 minutes. The solid was collected in a frit funnel, washed with 20 ml of toluene followed by 20 ml of hexane. The solid was recombined in slurry in 30 ml of toluene. In a separate vessel, a solution of tris (pentafluorophenyl) borane (0.768 g, 1.5 mmol) in 30 ml of toluene was treated with 1.5 ml of a 1 M solution of triethylaluminum in hexane. The mixture was stirred for 10 minutes and then added to the slurry of the treated silica. The mixture was stirred for 5 hours, collected in a frit funnel, washed with two 30 ml portions of toluene followed by 30 ml of hexane and then dried in vacuo. A 2 g sample was combined in a slurry in 20 ml of hexane and 0.5 ml of a 0.2 M solution of (C5Me SiMe2N'Bu) Ti (α 4-1, 3-pentadiene) in lsopar ™ E were added. The mixture was stirred 2 hours, filtered on a frit funnel, and the green solid was washed with 2% 20 ml of hexane and then dried under vacuum.

Slurry phase polymerization A stirred 4 liter reactor was charged with 2.8 liters of hexane and then heated to 70 ° C. 0.5 g of TEA / silica was introduced to the reactor and scavenger. Then ethylene was added to the reactor in an amount sufficient to reach a total pressure of 1.2 MPa. An aliquot of 0.4 g of the catalyst prepared as described above was then added to initiate the polymerization. The reactor pressure was kept essentially constant by continuously feeding ethylene on demand during the polymerization reaction. The temperature was kept substantially constant using the reactor as required. After 60 minutes, the ethylene feed was stopped and the contents of the reactor were transferred to a sample tray. After drying, 160 g of a free-flowing polyethylene powder with a bulk density of 0.40 g / cm 3 was obtained.

Gas Phase Polymerization The polymerization conditions of Comparative Example 1 were substantially repeated using 0.325 g of the above supported catalyst. The yield of the free flowing, dry ethylene / 1-butene copolymer powder was 112.5 grams.

Example 2 To 15.04 g of the Davison ™ 948 silica (heated with air at 250 ° C for 4 hours) were combined in slurry in 90 ml of hexane, and an excess (2.0 mmoles / g, 30 ml of a solution of 1.0 M in hexanes) of triethylaluminum. The mixture was stirred for 12 hours. The solids were collected in a frit funnel, washed 3 times with 50 ml portions of hexanes, and dried in vacuo. To 2.00 g of this material was added 50 ml of a 0.023 M solution of AI (C6F5) 3 in toluene. The mixture was stirred on a mechanical stirrer for 15 hours. The slurry was evacuated to dryness. The solids were then recombined in a slurry in toluene, collected in a frit funnel, washed twice with 30 ml of toluene, and dried in vacuo. To 1.73 g of this material mixed in slurry in 15 ml of hexane was added 410 μL of a 0.202 M solution of mixed alkanes of (C5Me4S¡Me2N'Bu) T1 (β -1, 3-pentadiene). The mixture was stirred for 1 hour, then the solids were collected in a frit funnel, washed twice with hexane and dried in vacuo.

Gas phase polymerization The polymerization conditions of Example 1 were substantially repeated using 0.075 g of the above supported catalyst. The yield of the free flowing, ethylene / 1-butene copolymer powder was 43 grams.

Example 3 Solutions (10 mmol each) of B (6F5) 3 and AIMe3 in toluene were added to 2.0 g of the Davison ™ 948 silica which had been dried at 250 ° C for 2 hours. The slurry was stirred for 2 days. At that time, the solids were collected in a frit funnel, washed twice with toluene and dried under vacuum. The solids were recombined in a slurry in 15 ml of mixed hexanes, and 0.5 ml of a 0.202 M solution of (t-butylamide) dimethyl- (tetramethylcyclopentadienyl) silantitanium 1,3-pentadiene was added. in mixed alkanes for a nominal load of 50 μmoles / g. The silica quickly became a dark green color leaving a pale yellow filtrate. The slurry was stirred for 1 hour on a mechanical stirrer, then the solids were collected in a frit funnel, washed with hexane and dried in vacuo. The solids were analyzed for 29.3 μmoles / g Ti and 0.96 mmoles / g Al. The boron levels were below the limit of detection (<50 μg / g).

Slurry Phase Polymerization The slurry phase polymerization in Example 1 was substantially repeated using an aliquot of 0.379 grams of the catalyst prepared as described above. After 30 minutes, the yield of the free reduced polyethylene was 109 grams.

Gas phase polymerization The polymerization conditions of Example 1 were substantially repeated using 0.065 g of the supported catalyst above. The yield of free flowing dry ethylene / 1-butene copolymer powder was 51 grams.

Example 4 To 1.95 mmole of tris (pentafluorophenyl) borane (B (C6F5) 3) in 40 ml of toluene was added 3.91 mmole of AIMe3 in toluene to form (C6F5) 3Me3AI2 in situ. The product was identified through comparison with known chemical shifts in 19F. { 1 HOUR} NMR. The solution was added to 0.5 g of Davison ™ 948 silica dried with air at 250 ° C. The slurry was stirred for 1 day. At that time, the solids were collected in a frit funnel, washed twice with 10 ml of toluene, and dried in vacuo. The solids were recombined in a slurry in 10 ml of pentane, and 0.25 ml of a 0.202 M solution of (t-butylamido) dimethyl- (tetramethylcyclopentadienyl) silantitanium 1,3-pentadiene in mixed alkanes was added. The silica quickly became dark green leaving a red-brown filtrate. The slurry was stirred for 1 hour on a mechanical stirrer, then the solids were collected in a frit funnel, washed with 2 x 10 ml of pentane, and dried in vacuo.

Gas phase polymerization The polymerization conditions of Example 1 were substantially repeated using 0.05 g of the above supported catalyst. The dry powder free ethylene / 1-butene copolymer powder yield was 15.5 grams.

Example 5 To 1.95 g of the Davison ™ 948 silica dried by heating in air at 250 ° C was added 45 ml of a 0.067 M solution of AI (C6F5) 3. The slurry was stirred for 12 hours. At that time, the solids were collected in a frit funnel, washed 1 time with 20 ml of toluene and twice with 20 ml of hexane, and dried in vacuo. An aliquot of 0.5 ml of the prewash solution was mixed with 0.25 ml of C6D6 and the 19F spectrum was recorded. { 1 HOUR} NMR: the only major resonances recorded were due to AI (C6F5) 3 and C6F5H, formed with a byproduct of reaction AI (C6F5) 3 with silica-hydroxy lo groups. d-124.0 (C6F5AI), -140.2 (C6F5H), -152.0 (C6F5AI), -155.2 (C6F5H), -161.8 (C6F5AI), -163.6 (C6F5H) ppm. The ratio of unreacted AI (C6F5) 3 to pentafluorobenzene was about 0.75: 1. The above solids were combined in a slurry in 20 ml of hexane, and 0.50 ml of a 0.202 M solution of (t-butylamido) dimethyl- (tetramethylcyclopentadienyl) silantitanium 1,3-pentadiene in mixed alkanes was added. The silica quickly became dark green, leaving a colorless filtrate. After 2 minutes, a second 0.50 ml portion of the 0.202 M solution of (t-butylamido) d, methyl- (tetramethylcyclopentadienyl) silantitanium 1,3-pentadiene was added. The slurry was stirred for 10 minutes, during which the supernatant again became colorless. The solids were collected in a frit funnel, washed with 2 x 10 ml of pentane, and dried in vacuo.

Gas phase polymerization The polymerization conditions of Example 1 were repeated "JJ-> -1" * - substantially using 0.075 g of the above catalyst, yielding 57 g of the ethylene / 1-butene copolymer as a fine, free flowing powder.

Claims (18)

1. - A functionalized catalyst support comprising a particulate support material having chemically bound thereto a plurality of non-ionic aluminum containing Lewis acid groups containing at least one fluoro-substituted hydrocarbyl ligand containing from 1 to 20 carbons attached to aluminum, the functionalized catalyst support being capable of activating a Group 3-10 metal complex for the addition polymerization of one or more polymerizable addition monomers.

2. A functionalized catalyst support according to claim 1, having the chemical structure of the following formula: So [Mem1 (K1k1) (Dd)] s where: So is a solid particulate support material, Me is aluminum, m1 is a number of 1-20; K1 independently of each occurrence is a ligand group bound to Me having from 1 to 30 atoms which are not hydrogen, provided that in at least one occurrence K1 is a fluoro-substituted hydrocarbyl group of 1 to 20 carbons, and optionally two or more K1 groups can be joined together thus forming a bridge group by linking two or more Me atoms or forming a fused ring system; k1 is a number from 1 to 5 selected to provide charge neutrality to the complex; D is a bridge portion chemically bonded to So through which the group is attached to the solid support in particles; d is a positive number from 0 to 5, and less than or equal to m, d equaling the average number of chemical bonds to the substrate per group, [Mem1 (K1k1) (Dd)]; s is a number greater than or equal to 2 and is equal to the number of groups [Mem1 (K1k1) (Dd)], attached to the substrate, So. 3.- A functionalized catalyst support according to claim 2, wherein the support is silica, the fluoro-substituted hydrocarbyl group is a fluoroaryl group, and s is selected to provide a concentration of groups [Mem (K1k1) (Dd)] in the substrate from 1 x 10 ~ 5 μmoles / gram to 2 mmoles / gram. 4. A functionalized catalyst support according to claim 2, wherein K1 is pentafluorophenyl and k1 is equal to 2. 5. A functionalized catalyst support comprising the reaction product of: (a) a support material of solid inorganic oxide, and (b) a mixture at once derived from the contact of an acid - - * - • - - - - - - - Nonionic Lewis selected from the compounds trifluoroarylboron and trifluoroarylaluminum with one or more trihydrocarbylaluminum compounds, dihydrocarbylaluminum hydrocarbyl, or dihydrocarbylaluminum (dihydrocarbyl) amido having up to 20 non-hydrogen atoms in each hydrocarbyl, hydrocarbyloxy or dihydrocarbylamido group, or a mixture thereof to form a functionalized Lewis acid catalyst support. 6. A supported catalyst comprising the functionalized catalyst support according to any of the preceding claims, and a metal complex of Group 3-10 containing a substituent that reacts with the functionalized catalyst support to thereby form a composition that is catalytically active for the polymerization of olefins. 7. A supported catalyst according to claim 6, wherein the metal complex of Group 3-10 contains at least one apion linked anionic ligand, which is a cyclic or non-cyclic dienyl group, conjugated or non-conjugated , an aryl group, an allyl group, or a substituted derivative thereof. 8. A supported catalyst according to claim 7, wherein the anionic ligand group attached to p is a cyclopentadienyl group or a derivative thereof. 9. A method for preparing a functionalized catalyst support according to claim 1, comprising: a. mixing in a slurry a particulate support containing reactive groups on its surface in hydrocarbon diluent; b. add a compound of the formula Arfz-AI2Q16_Z, in an amount sufficient to fully react with reactive surface groups of the support as defined by the titration with Et3AI, to form a treated support, wherein: Arf is a fluorinated aromatic hydrocarbyl portion of 6 at 30 carbon atoms; z "is a number from 0 to 6, and Q1 regardless of each occurrence is selected from hydrocarbyl, hydrocarbyloxy or dihydrocarbylamido, from 1 to 20 atoms that are not hydrogen, C. washing the treated support with a hydrocarbon or aromatic solvent, and d optionally drying the resulting catalyst support 10. A method according to claim 9, wherein the support has been dried by heating at a temperature of 200 to 600 ° C for a time of 10 minutes to 2 days, treated with a compound of the formula Q13AI, wherein Q1 is independently selected from hydrocarbyl, hydrocarbyloxy or dihydrocarbylamido, from 1 to 20 atoms that are not hydrogen, and the amount of Q13AI is selected to quench 1-99% of any reactive species in the surface, as determined by titration with Et3AI 11. A method according to claim 10, wherein the amount of Q13AI is selected to quench 50-90% of any reactive species in the supe rficie, as determined by the titration with Et3AI. 12. A method according to claim 9, wherein the catalyst support is an inorganic oxide that has been pre-treated with a compound of the formula Q 3AI in an amount of 0.1 to 1.5 mmol A1 / gram of support, wherein Q 'is as defined in claim 10. 1

3. A method according to claims 9-12, wherein the support is calcined. 1

4. A method according to any of claims 9-12 wherein the particulate solid support material is silica. 1

5. A method for preparing a supported catalyst composition, comprising the step of adding to the functionalized catalyst support of any of claims 1-5, a metal complex of Group 3-10 containing a substituent that reacts with the support of functionalized catalyst to thereby form a composition that is catalytically active for the polymerization of olefins. 1

6. A polymerization process comprising contacting one or more polymerizable addition monomers under gas phase or slurry polymerization conditions with a catalyst composition according to any of claims 6-8. 1

7. A process according to claim 16, wherein the propylene is polymerized to form polypropylene. 1

8. A process according to claim 16, wherein the ethylene is polymerized, optionally with one or more α-olefin and / or a, O-diene monomers, to form an ethylene polymer. _M M ^^^