MXPA00000017A - Catalyst for the production of olefin polymers - Google Patents

Abstract

A catalyst precursor having the formula:AqMLn wherein each A has formula (I);M is a metal selected from the group consisting of Group 3 to 13 elements and Lanthanide series elements;each L is a monovalent, bivalent, or trivalent anion;X and Y are each heteroatoms;Cyclo is a cyclic moiety;each R1 is independently a group containing 1 to 50 atoms selected from the group consisting of hydrogen and Group 13 to 17 elements,and two or more adjacent R1 groups may be joined to form a cyclic moiety;each R2 is independently a group containing 1 to 50 atoms selected from the group consisting of hydrogen and Group 13 to 17 elements, and two or more adjacent R2 groups may be joined to form a cyclic moiety;Q is a bridging group;each m is independently an integer from 0 to 5;n is an integer from 1 to 4;q is 1 or 2;and when q is 2, the A groups are optionally connected by a bridging group Z is provided. The catalyst precursor may be made by reacting an organometal compound with a heteroatom-containing ligand. The catalyst precursor, when combined with an activating cocatalyst, is useful for the polymerization of olefins.

Description

CATALYST FOR THE PRODUCTION OF OLEFIN POLYMERS This application claims the benefit of the Request North American Serial No. 60 / 051,581, filed July 2, 1997, the presentation of which is incorporated herein by reference. The invention relates to a family of catalyst precursors containing novel heteroatoms useful for the polymerization of olefins such as, for example, ethylene, higher alpha olefins, dienes, and mixtures thereof. BACKGROUND OF THE INVENTION Several ethanocenes and other similar single site catalysts have been developed to prepare olefin polymers. Metalócenes are organometallic coordination complexes that contain one or several pi-linked portions (ie, cyclopentadienyl groups) in association with a metal atom. Catalyst compositions containing metallocenes and other similar single-site catalysts are very useful for the preparation of polyolefins, producing relatively homogeneous copolymers with excellent polymerization rates while permitting close matching of the final properties of the polymer as desired. Recently, a work has been published in relation to certain catalysts of a single site type containing nitrogen. PCT Application No. WO 96/23101 refers to di (imine) metal complexes which are transition metal complexes of bidentate ligands selected from the group consisting of: wherein said transition metal is selected from the group consisting of Ti, Zr, Se, V, Cr, a rare earth metal, Fe, Co, Ni, and Pd; R2 and R5 are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom attached to the iminonitrogen atom has at least two carbon atoms attached thereto; R3 and R4 are each, independently, hydrogen, hydrocarbyl, substituted hydrocarbyl, or R3 and R4, together, are hydrocarbylene or substituted hydrocarbylene to form a carbocyclic ring; R44 is hydrocarbyl or substituted hydrocarbyl, and R28 is hydrogen, hydrocarbyl or substituted hydrocarbyl, or R44 and R28 together form a ring; R 45 is hydrocarbyl or substituted hydrocarbyl, and R 29 is hydrogen, substituted hydrocarbyl or hydrocarbyl, or R 45 and R 29 together form a ring; each R30 is independently hydrogen, substituted hydrocarbyl or hydrocarbyl, or two of R30 together form a ring; each R31 is independently hydrogen, hydrocarbyl or substituted hydrocarbyl; R4S and R47 are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bonded to the iminonitrogen atom has at least two carbon atoms attached thereto; R48 and R49 are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl; R20 and R23 are independently hydrocarbyl or substituted hydrocarbyl; R21 and R22 are independently hydrogen, hydrocarbyl or substituted hydrocarbyl; and n is 2 or 3; and provided that said transition metal also has attached thereto a ligand that can be displaced or added to the olefin monomer being polymerized; and when the transition metal is Pd, said bidentate ligand is (V), (VII) or (VIII). Similarly, PCT Application No. WO 97/02298 relates to a process for the polymerization of an olefin, comprising contacting a polymerizable monomer consisting essentially of ethylene, a norbornene or a styrene, with a system of catalyst comprising the product of the solution mixture of a tricoordinated or zero-coordinate nickel (II) compound with zero valence having at least one labile ligand and all ligands are neutral, an acid of the formula HX (IV), and a first compound selected from the group qμe consisting of: ArlQn (III); R 8 R 1 N-CRR 5 (CR 6 R 7) m-NR 8 10 (V); (XXIII); (XXVII); (XXXVI); (XXXVII); where: X is an anion of non-coordination; Ar1 is an aromatic portion with free n valences, or diphenylmethyl; each Q is -NR2R43 or -CR9 = NR3; R43 is hydrogen or alkyl; n is 1 or 2; E is 2-thienyl or 2-furyl; each R2 is independently hydrogen, benzyl, substituted benzyl, phenyl or substituted phenyl; each R9 is independently hydrogen or hydrocarbyl; and each R3 is independently a monovalent aromatic moiety; m is 1, 2 or 3; each R 4, R 5, R 6 and R 7 is independently hydrogen, hydrocarbyl or substituted hydrocarbyl; each R8 is independently hydrocarbyl or substituted hydrocarbyl containing 2 or more carbon atoms; each R10 is independently hydrogen, hydrocarbyl or substituted hydrocarbyl; Ar2 is an aryl moiety; R12, R13 and R14 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group; R11 and R15 are each independently hydrocarbyl, substituted hydrocarbyl, or an inert functional group whose Es is about -0.4 or less; each Rld and R17 is independently hydrogen or acyl containing from 1 to 20 carbon atoms; Ar3 is an aryl moiety; R18 and R19 are each independently hydrogen or hydrocarbyl; Ar4 is an aryl moiety; Ar5 and Ar6 are each independently hydrocarbyl; Ar7 and Ar8 are each independently an aryl moiety; Ar9 and Ar10 are each independently an aryl portion or -C02R25, where R25 is alkyl containing from 1 to 20 carbon atoms; Ar11 - is an aryl portion; R41 is hydrogen or hydrocarbyl; R42 is hydrocarbyl or -C (O) -NR41-Ar11; R44 is aryl; R22 and R23 are each independently phenyl groups substituted by one or more alkoxy groups, each alkoxy group contains from 1 to 20 carbon atoms; and R24 is alkyl containing from 1 to 20 carbon atoms, or an aryl portion. PCT Application No. WO 96/33202 relates to a transition metal catalyst containing a pyridine or quinoline moiety and having the formula: where Y is O, S, each R is independently selected from hydrogen or Ci-alkyl, each R 'is independently selected from Ci to C6 alkyl, Ci to C6 aryl C6 to C6 alkoxy, halogen, or CF3, M is titanium, zirconium or hafnium , each X is independently selected from halogen, Ci to Ce alkyl, Ci to Ce alkoxy or R / -N, L is X, cyclopentadienyl, cyclopentadienyl substituted with Ci to Ce alkyl, indenyl, fluorenyl, or, "is from 0 to 4, and" n "is from 1 to 4. Similarly, Fuhrmann et al., Inorg. Chem. 3_5: 6742-6745 (1996) presents certain Group 4 metal compounds containing aminopyridinate, amine, amido ligands such as for example: where TMS is trimethylsilyl. An olefin polymerization catalyst composition is disclosed which has a good polymerization activity and good productivity. The catalyst composition comprises a heteroatom containing catalyst precursor having the formula: qMLn where each A has the formula: M is a metal selected within the group consisting of elements from Groups 3 to 13 and elements from the series of Lantánidos; each L is a monovalent, bivalent or trivalent anion; X and Y are each heteroatoms; Cycle is a cyclical portion; each R1 is independently a group containing from 1 to 50 selected atoms within the group consisting of hydrogen and elements of Groups 13 to 17 and two or more adjacent R1 groups may be linked to form a cyclic portion; each R2 is independently a group containing from 1 to 50 selected atoms within the group consisting of hydrogen and elements of Groups 13 to 17, and two or more adjacent R2 groups may be linked to form a cyclic portion; Q is a bridge group; each is independently an integer from 0 to 5; n is an integer from 1 to 4; q is 1 or 2; and when q is 2, groups A are optionally connected by a bridge group Z. The catalyst precursor can be conveniently prepared by the reaction of an organometal compound with a heteroatom-containing ligand of the formula: O well where X, Y, Q, Cycle, R1, R2, and m have the meanings stated above. COMPENDIUM OF THE INVENTION The invention offers a catalyst precursor of the formula: gMLn where each A has the formula: M is a metal selected within the group consisting of elements from Groups 3 to 13 and elements from the series of Lantánidos; each L is a monovalent, bivalent, or trivalent anion; X and Y are each heteroatoms; Cycle is a cyclical portion; each R1 is independently a group containing from 1 to 50 selected atoms within the group consisting of hydrogen and elements of Groups 13 to 17 and two or more adjacent R1 groups may be linked to form a cyclic portion; each R2 is independently a group containing from 1 to 50 selected atoms within the group consisting of hydrogen and elements of Groups 13 to 17, and two or more adjacent R2 groups may be linked to form a cyclic portion; Q is a bridge group; each m is independently an integer from 0 to 5; n is an integer from 1 to 4; q is 1 or 2; and when q is 2, groups A are optionally connected by a bridge group Z; together with a catalyst composition comprising this catalyst precursor and an activating cocatalyst, as well as a process for the polymerization of olefins, using this catalyst composition. The invention also provides a catalyst precursor comprising the reaction product of an organometal compound and heteroatom-containing ligand having a formula selected from the group consisting of: O well where X and Y are each heteroatoms; Cycle is a cyclical portion; each R1 is a group containing from 1 to 50 selected atoms within the group consisting of hydrogen and elements of Groups 13 to 17 and two or more adjacent R1 groups may be linked to form a cyclic portion; each R2 is a group containing from 1 to 50 selected atoms within the group consisting of hydrogen and elements from Groups 13 to 17, and two or more adjacent R2 groups may be linked to form a cyclic portion; Q is a bridge group; and each m is independently an integer from 0 to 5; as well as a catalyst composition comprising this catalyst precursor and an activation cocatalyst, and a process for the polymerization of olefins using this catalyst composition. DETAILED DESCRIPTION OF THE INVENTION The catalyst precursor may have the formula: AgMLn In the above formula, each A has the formula: M is a metal selected from the group consisting of elements of Groups 3 to 13 and elements of the Lanthanide series, preferably an element of Group 4, more preferably zirconium. Each L is a monovalent, bivalent, or trivalent anion, preferably selected independently within the group consisting of halogens; hydrogen; alkyl, aryl, alkenyl, alkylaryl, arylalkyl, hydrocarboxy radicals having from 1 to 50 carbon atoms; amides; phosphides; sulfides; silylalkyl; diketoates; and carboxylates. More preferably, each L is selected from the group consisting of halides, alkyl radicals, and arylalkyl radicals. More preferably, each L is selected from the group consisting of arylalkyl radicals such as benzyl. Each L may contain one or more heteroatoms. X and Y are each heteroatoms and are preferably selected independently within the group consisting of N, O, S, and P. Most preferably, X and Y are each independently selected from the group consisting of N and P. More preferably, X and Y are both nitrogen. And it is contained in a heterocyclic ring containing from 2 to 7 carbon atoms, preferably from 3 to 6 carbon atoms, more preferably 5 carbon atoms. The heterocyclic ring may contain additional heteroatoms (ie, in addition to Y). Cycle is a cyclical portion. Preferably, Cycle is a carbocyclic ring containing from 3 to 7 carbon atoms. More preferably, Cycle is an aryl group. Each R1 is independently a group containing from 1 to 50 carbon atoms selected from the group consisting of hydrogen and elements from Groups 13 to 17 and two or more adjacent R1 groups may be linked to form a cyclic portion such as a aliphatic ring or an aromatic ring. Preferably, R1 is alkyl. More preferably, R1 is isopropyl. Optionally, a group R1 may be linked to Q. It is preferred that at least R1 be ortho relative to X. Each R2 is independently a group containing from 1 to 50 selected atoms within the group consisting of hydrogen and elements of the groups 13 to 17, and two or more adjacent R2 groups may be linked to form a cyclic portion such as an aliphatic or aromatic ring. Preferably, R2 is hydrogen or aryl. More preferably R2 is hydrogen. When R2 is an aryl group and Y is N, a quinoline group can be formed. Optionally, a group R2 can be linked on Q. Q is a bridge group. Preferably Q contains one or more elements of Groups 13, 14, 15, or 16. More preferably, Q contains one or more elements of Group 14. Especially Q is a substituted carbon. Each is independently an integer from 0 to 5, preferably 2, and n is an integer from 1 to 4, preferably 3. The letter q is 1 or 2, and when q is 2, groups A are optionally connected by a bridge group Z. When present, Z preferably contains one or more elements of Group IIIA, Group IVA, Group VA, or Group VIA. More preferably, Z contains one or more elements of the VAT Group. In one embodiment of the present invention, the catalyst precursor has the formula: where Ra and Rb are each independently selected from the group consisting of alkyl, aryl, heterocyclic groups, and hydrogen. Rc and Rd are each independently selected from the group consisting of alkyl, aryl, and hydrogen; and each L has the meaning stated above. In another embodiment of the invention, the catalyst precursor has the formula; where Ra, Rb / C / d and L have the meanings stated above. In a further embodiment of the invention, the catalyst precursor has the formula: where Ra, Rb Rc / Rd and L have the meanings stated above. In a particularly preferred embodiment of the invention, the catalyst precursor has the formula: where Ra, Rb / RC / Rd and L have the meanings stated above. In a particularly preferred embodiment of the invention, the catalyst precursor has the formula: Compound 1 In another particularly preferred embodiment of the invention, the catalyst precursor has the formula: Compound 2 In a particularly preferred additional embodiment of the invention, the catalyst precursor has the formula: Compound 3 Another preferred catalyst precursor is: Compound 4 The catalyst precursor can be prepared by any method. The method of making the catalyst precursor is not a critical factor for the invention. However, a useful method for preparing the catalyst precursor is by reacting an organometal compound or a metal halide with a heteroatom-containing ligand having a formula selected from the group consisting of: or 2 m Rm When X, Y, Q, Cycle / R1 R2 and m have the meanings stated above, the catalyst precursor is preferably prepared by the reaction of an organometal compound with the heteroatom-containing ligand. In one embodiment of the invention, the catalyst precursor comprises the reaction product of an organometal compound and a heteroatom-containing ligand having a formula selected from the group consisting of: O well where X, Y, Qf Cycle, R1 R2 and m have the meanings stated above. The metal of the organometal compound can be selected within the elements of Groups 3 to 13 and elements of the Lanthanide series. Preferably, the metal is an element of Group 4. More preferably, the metal is zirconium. The organometal compound, for example, can be a metal hydrocarbyl, such as for example metal alkyl, metal aryl, or metal arylalkyl. Silylalkyls, metal amides, or metal phosphides can also be used. Preferably, the organometal compound is a zirconium hydrocarbyl. More preferably, the organometal compound is an arylalkyl of zirconium. Especially, the organometal compound is a tetrabenzylzirconium. Examples of useful organometal compounds are tetramethylzirconium, tetraethylzirconium, tetrakis (trimethylsilylmethyl) zirconium, tetrakis (dimethylamino) zirconium, dichlorodibenzylzirconium, chlorotribenzylzirconium, trichlorobenzylzirconium, bis (dimethylamino) bis (benzyl) zirconium, and tetrabenzylzirconium. Tetramethyltinitanium, tetraethyltitanium, tetrakis (trimethylsilylmethyl) titanium, tetrakis (dimethylamino) titanium, dichlorobenzyltitanium, chlorotribencyltitanium, trichlorobenzylthitanium, bis (dimethylamino) bis (benzyl) titanium, and tetrabenzyl titanium. Tetramethylhafnium, tetraethylhafnium, tetrakis (dimethylamino) hafnium, dichlorodibenzylhafnium, chlorotribenzylhafnium, trichlorobenzylhafnium, bis (dimethylamino) bis (benzyl) hafnium, and tetrabenzylhafnium. Tetrakis (tertbutyl) lanthanates; lithium hexamethantanes; tetrakis (allyl) lanthanates; and tris (bis (trimethylsilyl) methyl) lanthanides. Since organometal compounds containing lanthanides and some transition metals are often difficult to prepare, it is preferred to prepare the catalyst precursors containing these in a two-step process by first reacting the heteroatom containing ligand with a lithium alkyl to prepare a lithium amide, and then reacting with a lanthanide or a halide of transition metal in order to generate the amide complex. The ligand that contains heteroatom has the formula: O well 2 Rm Ocfo XH Y I where X, Y, Q, Cycle, R5?, R and m have the meanings stated above. Preferably, the heteroatom-containing ligand has the formula: More preferably, the heteroatom-containing ligand is a pyridine / imine ligand of the formula: wherein each R 'is a hydrocarbon group containing 1 to 20 carbon atoms and two or more adjacent R' groups may be linked to form an aliphatic or aromatic ring; each R "is a hydrocarbon group containing from 1 to 20 carbon atoms and two or more adjacent R" groups can be attached to form an aliphatic or aromatic ring; and R3 is a hydrogen, a hydrocarbon group containing 1 to 20 carbon atoms optionally substituted with one or more heteroatoms, or a heteroatom optionally substituted with a hydrocarbon group. For example, Compound 1 can be prepared by the reaction of a substituted pyridine / imine ligand with a zirconium aryl such as for example tetrabenzylzirconium: This reaction is preferably carried out in a suitable solvent such as toluene or benzene at a temperature within a range of -50 to 50 ° C and under a pressure that is within a vacuum range at 1000 psi. Alternatively and preferably, the catalyst precursor can be made by reacting the heteroatom-containing ligand with a metal halide and then reacting the product thereof with a Grignard reagent, such as for example organomagnesium halide. For example, the same catalyst precursor, Compound 1, can be prepared by reacting a substituted pyridine / imine ligand with a zirconium halide such as zirconium tetrachloride, and then reacting the product with PhCH2MgCl. Another preferred catalyst precursor, Compound 2, can be prepared by the reaction of a substituted pyridine / amine ligand with a zirconium aryl such as for example tetrabenzylzirconium: hPhCH3 This reaction is preferably carried out in a suitable solvent such as, for example, toluene or benzene at a temperature within a range of -50 to 50 ° C and within a vacuum pressure range at 1000 psi. Another preferred catalyst precursor, Compound 3, can be prepared by the reaction of Compound 2 with acetone: As another example, Compound 4 can be made in a multi-step process by reacting a substituted pyridine / amine ligand sequentially with methyllithium, chlorotri ethylsilane, zirconium tetrachloride, and benzylmagnesium chloride in accordance with the following: ZrCl4 toluene This reaction is preferably carried out in a suitable solvent such as, for example, toluene or benzene at a temperature which is within a range of -50 to 50 ° C and within a range of vacuum pressure at 1000 psi. The catalyst precursor can be isolated by conventional methods. The catalyst composition comprises the catalyst precursor and an activation cocatalyst. The activating cocatalyst can activate the catalyst precursor. Preferably, the activating cocatalyst is one of the following: (a) branched or cyclic oligomeric poly (hydrocarbylaluminum oxide (s)) containing recurring units of the general formula (A1 (R *) 0) -, where R * is hydrogen, an alkyl radical containing from 1 to about 12 carbon atoms, or an aryl radical such as, for example, a substituted or unsubstituted phenyl or naphthyl group; (b) ionic salts of the general formula [A +] [BR ** 4 ~], where A + is a Lewis acid or Bronsted cationic capable of abstracting an alger, halogen or hydrogen from the metallocene catalysts, B is boron , and R ** is a substituted aromatic hydrocarbon, preferably a perfluorophenyl radical; (c) boron alkyls of the general formula BR ** 3, where R ** is in accordance with that defined above; or mixtures thereof. The activating cocatalyst can also be an organoaluminum compound, such as, for example, triisobutylaluminum or diethylaluminum chloride. Preferably, the activating cocatalyst is an oligomeric branched or cyclic poly (hydrocarbylaluminum oxide) or a boron alkenyl. More preferably, the activating cocatalyst is an aluminoxane such as for example methylaluminoxane (MAO) or modified methylaluminoxane (MMAO), or a boron alkyl. Aluminoxanes are well known in the art and comprise oligomeric linear alkyl aluminoxanes represented by the formula: and oligomeric cyclic alkyl aluminoxanes of the formula: where s is 1-40, preferably 10-20; p is 3-40, preferably 3-20; and R *** is an alkyl group containing from 1 to 12 carbon atoms, preferably methyl. Aluminoxanes can be prepared in several ways. Generally, a mixture of linear and cyclic aluminoxanes is obtained in the preparation of aluminoxanes from, for example, trimethylaluminum and water. For example, an aluminum alkyl can be treated with water in the form of a wet solvent. Alternatively, an aluminum alkeyl such as for example trimethylaluminum can be contacted with a hydrated salt such as for example ferrous sulfate hydrate. The latter method comprises the treatment of a dilute solution of trimethylaluminum, for example, in toluene with a suspension of ferrous sulfate heptahydrate. It is also possible to form the methylaluminoxanes by reacting a tetraalkyldialuminoxane containing C2 or higher alkyl groups with an amount of trimethylaluminum which is less than a stoichiometric excess. The synthesis of methylaluminoxanes can also be achieved by the reaction of a trialkylaluminum compound or a tetraalkyldialuminoxane containing C 2 or higher alkenyl groups with water to form a polyalipyl aluminoxane, which then reacts with trimethylaluminum. Additional modified methylaluminoxanes containing both higher methyl groups and alkyl groups, i.e. isobutyl groups, can be synthesized by reaction of a polyalkyl aluminoxane containing C2 or higher alkyl groups with trimethylaluminium, and then with water as presented , for example, in U.S. Patent No. 5,041,584. When the activating cocatalyst is a cyclic or branched oligomeric poly (hydrocarbylaluminum oxide), the molar ratio between the aluminum atoms contained in the poly (hydrocarbylaluminum oxide) and the total metal atoms contained in the catalyst precursor is generally found within the range of about 2: 1 to about 100,000: 1, preferably within the range of about 10: 1 to about 10,000: 1, and especially preferably within the range of about 50: 1 to about 2,000: 1. When the activating cocatalyst is an ionic salt of the formula [A +] [BR ** 4 ~] or a boron alkyl of the formula BR ** 3, the molar ratio between the boron atoms contained in the ionic salt or the boron alkyl and the total metal atoms contained in the catalyst precursor is generally within a range of about 0.5: 1 to about 10: 1, preferably within a range of about 1: 1 to about 5: 1. The catalyst precursor, the activating cocatalyst or the entire catalyst composition can be impregnated in an inert, solid support, in liquid form such as, for example, solution, dispersion, or pure liquid, spray-dried, in the form of a prepolymer, or formed in situ during the polymerization. Particularly preferred among these is a catalyst composition which is spray dried in accordance with that described in European Patent Application No. 0 668 295 Al or in liquid form in accordance with that described in US Pat. No. 5,317,036. In the case of a supported catalyst composition, the catalyst composition may be impregnated or deposited on the surface of an inert substrate, such as, for example, silica, carbon black, polyethylene, crosslinked porous polycarbonate polystyrene, cross-linked porous polypropylene, alumina , toria, zirconia, or magnesium halide (e.g., magnesium dichloride), such that the catalyst composition is between 0.1 and 90% by weight of the total weight of the catalyst composition and the support. The catalyst composition can be used for the polymerization of olefins by any gas phase process, paste, solution, or suspension, employing known reaction conditions and type, and is not limited by any specific type of reaction system. Generally, the range of olefin polymerization temperatures is between about 0 ° C and about 200 ° C at atmospheric, subatmospheric or superatmospheric pressures. Polymerization processes in paste or solution can employ subatmospheric or superatmospheric pressures and temperatures within a range of about 40 ° C to about 110 ° C. A useful liquid phase polymerization reaction system is described in U.S. Patent No. 3,324,095. Liquid phase reaction systems generally comprise in a reactor vessel to which are added olefin monomers and catalyst composition, and which contains a liquid reaction medium for dissolving or suspending the polyolefin. The liquid reaction medium may consist of bulk liquid monomer or an inert liquid hydrocarbon which does not react under the polymerization conditions employed. Although said inert liquid hydrocarbon does not have to function as a solvent for the catalyst composition or the polymer obtained by the process, it usually serves as a solvent for the monomers used in the polymerization. Among the inert liquefied hydrocarbons suitable for this purpose are isopentane, hexane, cyclohexane, heptane, benzene, toluene, and the like. The reaction contact between the olefin monomer and the catalyst composition must be maintained by constant stirring. The reaction medium containing the olefin polymer product and the unreacted olefin monomer is continuously removed from the reactor. The olefin polymer product is separated and the unreacted olefin monomer and the liquid reaction medium are recycled in a reactor. Preferably, a gas phase polymerization is employed with superatmospheric pressures within a range of 1 to 1000 psi, preferably 50 to 400 psi, more preferably 100 to 300 psi, and temperatures within a range of 30 to 130 ° C, preferably 65 to 110 ° C. Reaction systems in fluidized or stirred bed gas phase are especially useful. Generally, a fluidized bed process, in conventional gas phase, is carried out by passing a stream containing one or more olefin monomers continuously through a fluidized bed reactor under the reaction conditions and in the presence of a catalyst composition at a sufficient rate to maintain a bed of solid particles in a suspended condition. A stream containing unreacted monomers is withdrawn from the reactor continuously, compressed, cooled, optionally condensed either fully or partially in accordance with that presented in US Pat. Nos. 4,528,790 and 5,462,999, and recycled to the reactor. The product is removed from the reactor and compensating monomer is added to the recycle stream. As desired for the control of system temperature, any inert gas for the catalyst composition and reagents may also be present in the gas stream. In addition, a fluidization aid such as carbon black, silica, clay or talc may be employed, as presented in US Patent No. 4,994,534. The polymerization can be carried out in a single reactor or in two or more reactors in series, and is carried out substantially in the absence of catalyst poisons. Organometallic compounds can be used as poisons removal agents to implement the catalyst activity. Examples of removal agents are metal alloys, preferably aluminum alkyls, more preferably triisobutylaluminum. Conventional adjuvants may be included in the process, provided they do not interfere with the operation of the catalyst composition in the formation of the desired polyolefin. Hydrogen either a metal or a non-metallic hydride, such as for example a silyl hydride can be used as a chain transfer agent in the process. Hydrogen can be used in amounts of up to about 10 moles of hydrogen per mole of the total monomer feed. Olefin copolymers which can be produced according to the present invention include, without being limited thereto, ethylene homopolymers, linear or branched higher alpha-olefin homopolymers containing from 3 to 20 carbon atoms as well as higher ethylene and alpha olefin interpolymers of this type, with densities that range from about 0.86 to about 0.96. Suitable higher alpha-olefins include, for example, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, and 3, 5, 5-trimethyl-1-hexene. Olefin polymers according to the present invention may also be based on or contain conjugated or non-conjugated dienes, such as linear, branched or cyclic hydrocarbon dienes having from about 4 to about 20, preferably from 4 to 12, atoms. carbon. Preferred dienes include 1,4-pentadiene, 1,5-hexadiene, 5-vinyl-2-norbornene, 1,7-octadiene, vinyl cyclohexene, dicyclopentadiene, butadiene, isobutylene, isoprene, ethylidene norbornene and the like. Aromatic compounds having vinyl unsaturation such as for example styrene and substituted styrenes, and polar vinyl monomers, such as for example acrylonitrile, maleic acid esters, vinyl acetate, acrylate esters, methacrylate esters, vinyl trialkylsilanes and the like can be polymerized in accordance with the invention. Specific olefin polymers that can be prepared according to the present invention include, for example, polyethylene, polypropylene, ethylene / propylene rubbers (EPR's), ethylene / propylene / diene terpolymers (EPDM's), polybutadiene, polyisoprene, and the like. The following examples further illustrate the invention. EXAMPLES Glossary The activity is measured in g of polyethylene / mmol of metal • hour * 100 psi of ethylene. 12 is the melt index (dg / min), measured using ASTM D-1238, Condition E at a temperature of 190 ° C-121 is the flow index (dg / min), measured using ASTM D-1238-Condition F MFR is the Fusion Flow Ratio, 121/12. BBF is Butyl Branching Frequency, number of butyl branches per 1000 carbon atoms of the main chain based on infrared measurement techniques. Mn is the Average Molecular Weight Number, in accordance with that determined by gel permeation chromatography, using cross-linked polystyrene columns; Pore size sequence: 1 column of less than 1000 Á, 3 columns of x 107 Mixed A; 1,2-trichlorobenzene solvent at a temperature of 140 ° C with refractive index detection.

PDI is the Polydispersity Index, equivalent to Distribution of Molecular Weights (Mw / Mn). EXAMPLE 1 Preparation of the 2-acetylpyridine ligand [2,6-diisopropylphenylimin] Into a 50 mL round bottom flask equipped with a stir bar and a septum were charged 11.0 mmol of 2,6-diisopropylaniline and 9.5 mmol of 2-acetylpyridine. With vigorous stirring, 0.5 mmol of 2-acetylpyridine-HC1 was added. The reaction vessel was placed under a strong nitrogen purge and was vented to a trap. The reaction was heated to a temperature of 160 ° C for 2 hours. The reaction vessel was cooled to room temperature. 10 mL of hexane was added and stirred vigorously, allowing it to settle overnight. The mixture was filtered and the filtrate was washed in vacuo to obtain the yellow solid product with a melting point of 68-70 ° C. EXAMPLE 2 Preparation of [2-pyridyl (Me) (PhCH2) C (N-2,6-diisopropylphenyl)] Zr (PhCH2) 3 In a dark box darkened in a dark room, 0.5 mmol (0.14g) of the ligand was charged. Example 1 in a 50 L round bottomed flask dried in an oven equipped with a stir bar and containing 0.5 mmol (0.23 g) of tetrabenzylzirconium. With vigorous stirring, 7.5 mL of benzene-dß was added to prepare a 0.067M solution. The reaction vessel was immediately covered with a film and the solution was stirred in the dry box overnight. EXAMPLE 3 Preparation of [2-pyridyl (Me) (PhCH2) C (N-2,6-diisopropylphenyl)] Zr (PhCH2) 3 In a dry box, 50 mmole (11.65 g) of ZrCl4 was loaded into a Schlenk flask of 300 mL equipped with a stir bar. Into a 100 mL Schlenk flask equipped with a stir bar, 50 mmol (14.02 g) of the ligand of Example 1 was charged. To each flask was added 100 mL of dry toluene. Both bottles were sealed with a septum and allowed to shake. Once the ligand was dissolved, the solution was slowly transferred through a syringe into a ZrCl4 paste with vigorous stirring. The pale yellow mixture was stirred overnight in the dry box. While the ligand / ZrCl4 mixture was being stirred, the preparation of a Grignard solution began. Two hundred moles (200 mL) of benzylmagnesium chloride (1.0M solution in diethyl ether) were loaded through a syringe into a Schlenk 500 mL bottle dried in an oven equipped with a stir bar and sealed with a septum. The ether was washed under high vacuum (0.2 Torr). The container was taken to the dry box where 100 L of dry toluene was added to the residue. The residue was dissolved and removed from the dry box, placed in a high vacuum manifold, and washed again. This method was repeated three additional times, until the residue was no longer a reddish viscous liquid but a whitish powder. When the powder stage was reached, 100 mL of dry toluene was added and the solids dissolved. The container was removed from the dry box and placed under an argon atmosphere. After stirring overnight, the ligand / ZrCl4 mixture exhibited a light yellow color. The container was removed from the dry box and placed under argon next to the container containing the Grignard solution. The ligand / ZrCl4 solution was covered with a film and cooled to a temperature of -78 ° C. In the dark room, the Grignard solution was slowly transferred through a double-ended cannula into the ligand / ZrCl4 solution. The reaction mixture turned bright red when the addition was completed. The reaction was slowly warmed to room temperature. After stirring for a few hours, the container was returned to the dry box and filtered through a frit of medium porosity. Toluene was added to the filtrate with the object to shake the volume to 500 mL. The filtrate was transferred to an amber bottle. A subsample of 1.0 mL was removed and placed in a stopped 10 mL vial. The subsample was washed in vacuum and the mass of the residue was used to determine the molarity of the solution at 0.089M. The preparation of 1 liter of a 0.02M solution was achieved using 224.7 mL of catalyst solution and diluting to 1000 mL with dry toluene. EXAMPLE 4 A series of ethylene / hexene copolymers were prepared in a laboratory scale pulp reactor, employing a catalyst composition comprising the catalyst precursor of Example 2 with modified methylaluminoxane, MMAO (7.0 wt% Al in heptane, commercially available from Akzo Chemicals Inc.). In each case, the catalyst composition was prepared by combining a solution of the catalyst precursor of Example 2 in benzene with a solution of MMAO in the presence of 0.1 mL of l-hexene. The conditions of the reaction and the results appear in Table 1 below. TABLE 1 Example Hexeno Proportion T, ° C c2 Activity BBF mL molar psi MMAO / Zr 4a 43 1000 65 ° C 85 115K 7.16 4b 43 1000 75 ° C 85 80.6K 10.34 4c 43 1000 85 ° C 85 49.1K 9.71 4d 43 1000 65 ° C 170 101K 2.41 4e 43 1000 92.9K 170 92.9K 4.95 4f 43 1000 85 ° C 170 61.8K 2.37 4g 21.5 1000 75 ° C 85 8.1K 3.16 4h 43 1000 75 ° C 85 80.6K 10.34 4i 86 1000 75 ° C 85 95.6K 17.99 4j 43 2000 65 ° C 85 210K 7.30 4k 43 1000 65 ° C 85 115K 7.16 41 43 500 65 ° C 85 4.6K 9.22 EXAMPLE 5 A series of ethylene / hexene copolymers were prepared in a pulp reactor, on a laboratory scale, using catalyst compositions comprising several catalyst precursors according to the invention with MMAO catalyst. In each case, the catalyst composition was prepared by contacting the ligand illustrated below in Table 2 with tetrabenzylzirconium, dissolving the resulting material in toluene and then contacting with a solution of MMAO (7.0 wt% Al in heptane, commercially available from Akzo Chemicals, Inc.) in the presence of 0.1 mL of l-hexene. The polymerization reactions were carried out at a temperature of 65 ° C, 85 psi of ethylene, 1.0 micromole of Zr and a molar ratio of MMAO / Zr of 1000. The ligands and the results appear in Table 2 below. TABLE 2 Example activity 121 BBF 5a 25647 9.83 10.51 5b 24,941 0.897 4.37 5c 5.647 5d 2.353 5e 23.294 0.511 9.23 5f 68.235 too 6.85 or slow for measurement 5g 10.118 5.86 5h 39,059 1.04 12.49 5i 22,824 5.39 13.64 5j 15,765 5.96 5k 40,941 2.42 13.36 51 183,059 too much 8.68 or slow for measurement 5m 4706 5n 941 Example Ligand EXAMPLE 6 A series of ethylene / hexene copolymers were prepared in a pulp reactor, on a laboratory scale, using catalyst compositions blended according to the invention with MMAO cocatalyst. In each case, the catalyst composition was prepared by contacting mixtures of the ligands illustrated below in Table 3 with tetrabenzylzirconium, dissolving the resulting material in toluene, and then contacting a solution of MMAO (7.0% in weight of Al in heptane, commercially available from Akzo Chemicals, Inc.), in the presence of 0.1 mL of l-hexene. The polymerization reaction conditions were 65 ° C, 85 psi ethylene, 1.0 micromole Zr, and a MMAO / Zr molar ratio of 1000. The ligands and results are shown in Table 3 below. TABLE 3 Example Ligands Activity BBF EXAMPLE 7 An ethylene / hexene copolymer was prepared in a pulp reactor, on a laboratory scale, using a mixed catalyst composition comprising the catalyst precursor of Example 2, biscyclopentadienylzirconium dichloride, and MMAO. The polymerization reaction conditions were 65 ° C, 85 psi ethylene, 1.0 micromole Zr, and a MMAO / Zr molar ratio of 1000. The activity of the catalyst composition was 20,706. A polyethylene copolymer having a 121 of 1.74 was prepared. EXAMPLE 8 The catalyst precursor of Example 3 in combination with MMAO was employed as the catalyst composition for polymerizing an ethylene / 1-hexene copolymer (density 0.917, 1.0 melt index) in a gas phase, fluidized bed reactor, on a pilot scale. The reactor nominally had a 1-foot diameter and was operated at a bed height of 8 feet and a surface gas velocity of approximately 1.8 feet / sec. The total pressure of the reactor was 350 psig. A seeded bed was charged to the reactor and dried until <5 ppm of water. The reactor was placed under pressure at 200 psig of ethylene. The molar ratio between 1-hexene / ethylene and hydrogen / ethylene was set at 0.048 and 0.041. The temperature of the bed was adjusted to 70 ° C. The composition of the catalyst was used in liquid form. The catalyst composition was prepared by mixing the catalyst precursor of Example 3 in toluene with MMAO (2.8% by weight of Al, commercially available from Akzo Chemicals, Inc.). A further dilution of the catalyst composition was carried out by the addition of isopentane to the mixture. The catalyst composition was sprayed into the reactor with the help of 5.0-7.0 pound / hour of nitrogen gas and a current of 1950 pound / hour of recycle gas. The reactor static was clearly absent during the experiment. The expanded section, recycling line and distributor plate i were free of staining. The average particle size (APS) was kept constant and could be controlled by varying the nitrogen vehicle flow and the density of the resin. EXAMPLE 9 Preparation of [1- (2-pyridyl) N-l-methylethyl] [l-N-2,6-diisopropylphenyl] amine In a dry box, 22.45 mmoles (6.34 g) of 2-acetylpyridine (2,6-diisopropylphenylimine) were charged to a 250 mL round bottom flask eguided with a stir bar and a septum. The bottle was sealed, removed from the dry box and placed under a nitrogen purge. Dry toluene (50 mL) was added and stirred to dissolve the ligand. The vessel was cooled to 0 ° C in a wet ice bath. Trimethylaluminum (Aldrich, 2. OM in toluene) was added dropwise in ten minutes. The temperature of the reaction was not allowed to exceed 10 ° C. When the addition of trimethylaluminum was complete, the mixture was allowed to warm slowly to room temperature and then placed in an oil bath and heated to a temperature of 40 ° C for 25 minutes. The container was removed from the oil bath and placed in an ice bath. A dropping funnel containing 100 mL of 5% KOH was fixed on the bottle. The caustic soda was charged to the reaction dropwise over a period of 1 hour. The mixture was transferred to a separatory funnel. The aqueous layer was removed. The separation layer was washed with 100 mL of water and then with 100 mL of brine. The red-brown product was dried in Na 2 SO 4, washed in vacuum and placed under high vacuum overnight. 80 mL of a red-brown liquid was transferred to a 200 mL Schlenk flask equipped with a stir bar. A distillation head with a dry ice condenser was fixed on the bottle. The mixture was distilled in vacuo to give approximately 70 g of a dark yellow viscous liquid product. EXAMPLE 10 A series of catalyst precursors in accordance with the present invention were prepared using the ligand of the Example 9 and various metal compounds. Each catalyst precursor was prepared by first combining the ligand in ether with methyllithium and then contacting the resulting product with the metal compound shown in FIG.

Table 4 below. The resulting catalyst precursors were combined with a cocatalyst and used for the homopolymerization in ethylene paste in a laboratory scale reactor in the manner described in Example 4. The results appear in Table 4. TABLE 4 - Example Metal compound cocatalyst, PE g 9a ZrCl4 MMAO 0.484 9b Cr (THF) 3Cl3 MMAO 0.239 9c V (THF) 3C13 MMAO 0.158 9d SmCl3 MMAO 0.797 9e YC13 MMAO 0.935 9f TaCl5 MMAO 0.195 9g NbCl5 MMAO 0.185 9h SmCl3 TIBA (lOOeq) 0.024 91 YC13 TIBA (lOOeq) 0.053 9j ZrCl4 TIBA (lOOeq) 0.024 9k V (THF) 3C13 TIBA (lOOeq) 0.022 91 Cr (THF) 3Cl3 TIBA (lOOeq) 0.037 9m NbCl5 TIBA (lOOeq) 0.032 9n TaCl5 TIBA (lOOeq) 0.024 9th V (THF) 3C13 DEAC (lOOeq) 0.090 9p Cr (THF) 3C13 IBAO (lOOeq) 0.134 EXAMPLE 11 Tribenzyl preparation of [1- (2-pyridyl) Nl-methylethyl] [1-N-2,6-diisopropylphenylamido] zirconium In a dark room and in a dark dry box, they were charged . 0 mmol (1.45 g) of the ligand prepared in Example 10 to a 100 mL Schlenk tube equipped with a stir bar. The ligand was dissolved in 5 mL of toluene. To a second vessel equipped with a stir bar was charged 5.5 mmoles (2.5 g) of tetrabenzylzirconium and 10 L of toluene. The ligand solution was transferred into the tetrabenzylzirconium solution. The container was covered with a film and allowed to stir at room temperature in the dry box. After 6 hours at room temperature, 80 mL of dry hexane was added to the reaction solution and stirred overnight. The reaction mixture was filtered through a medium porosity frit with a collection of approximately 2 g of pale yellow solids. EXAMPLE 12 Preparation of Dibenzyl [[1- (2-pyridyl) Nl-methylethyl] [1-N-2,6-diisopropylphenylamido]] [2-methyl-1-phenyl-2-propoxy] zirconium To a GC bottle sealed, purged, cooled, oven dried 0.10 mL of dry acetone was charged. The GC bottle was sealed in a shell jar and taken to the dry box. In a dark room and a dark dry box, 2.0 mmoles were loaded (1.3g) of the material prepared in Example 11 and 9 mL of toluene in a 100 mL Schlenk flask equipped with a stir bar. To a second GC flask was charged 2.0 mmol (146 uL) of acetone and 1.0 mL of toluene. The acetone / toluene solution was transferred dropwise through a syringe into the stirred tribenzyl solution of [1- (2-pyridyl) N-l-methylethyl] [l-N-2,6-diisopropylphenylamido] zirconium. The container was covered with a film and was stirred at room temperature overnight in the dry box. The reaction solution was washed in vacuo until a sticky orange residue was obtained. Dry hexane (20 mL) was added, and the residue was stirred vigorously, then washed again in vacuo until a yellow-orange glass was obtained. Hexane was added again and vigorously stirred. The container was placed in a freezer (-24 ° C) for approximately 2 hours. The mixture was filtered through a frit of medium porosity. Pale yellow solids (0.8g) were collected. EXAMPLE 13 Hexane (600 mL), triisobutylaluminum (100 μmol of a solution to 1. OM in toluene) and l-hexene (43 ml, dry alumina) were charged to a 1 liter pulp reactor. The complex of Example 11 (2.46 μmol) and trityl (tetraperfluorophenyl) borate (2.33 μmol) were weighed in an oven-dried glass bottle. Toluene (1.0 ml) was added and the mixture was stirred for 5 minutes which resulted in a yellow solution. Triisobutylaluminum (10 μmol of a 1.0M solution in toluene) was added to the solution to form a reaction solution. An aliquot of the reaction solution (0.20 ml, 0.5 μmol Zr) was charged to the reactor 4 minutes after the addition of triisobutylaluminum and the reaction was initiated. The reactor was activated at a temperature of 75 ° C and under an ethylene pressure of 85 psia for 30 minutes. The polyethylene resin produced had a weight of 76.5 g. The calculated activity was 360000 g / mmol Zr / 100 psi ethylene / hour. The molecular weight of the resin was too high to obtain 121 or 12. EXAMPLE 14 Hexane (600 mL), triisobutylaluminum (100 μmol of a solution 1. OM in toluene) and l-hexene (43 ml, dried alumina) were charged. to a 1 liter pasta reactor. Trityl (tetraperfluorophenyl) borate (1.89 μmol, Akzo) was added to an oven-dried glass bottle. Toluene (1.0 ml) was added, which resulted in the dark yellow solution. The complex described in Example 12, (2.0 μmol, 0.025 ml of a solution of 80 μmol / ml in deuterated benzene) was added to the dark yellow solution which resulted in a pale yellow solution immediately. After 5 minutes of stirring, triisobutylaluminum (10 μmol of a 1.0M solution in toluene) was added to the solution to prepare a reaction solution. An aliquot of the reaction solution (0.25 ml, 0.5 μmol Zr) was charged to the reactor 2 minutes after the addition of triisobutylaluminum the reaction started. The reactor was operated at a temperature of 75 ° C and under a pressure of 85 psia of ethylene for 30 minutes. The product had a weight of 16.8 g. The activity was 79059 g / mmol Zr / 100 psi ethylene / hour. The resin was treated with approximately 1000 ppm of antioxidant (4 parts of Irgafos® 168, one part of Irganox® 1076) and 3 g were loaded in a Tinius Olsen extrusion plastometer. The resin was extruded through the plastometer under the weight of the plunger (100 g). Therefore data 12 could not be obtained, but rapid extrusion indicates a low molecular weight product. A 3 mil plate of the treated resin was prepared which was analyzed on an FTIR providing a buty branching frequency of 8.04 / 1000 CH2. EXAMPLE 15 In each of Examples 15a-15f, in a dark dry box and in a dark room, 0.100 mmol of [1- (2-pyridyl) Nl-methylethyl] [lN-2,6-diisopropylphenylamide tribenzyl was dissolved. ] zirconium in 1.0 L of benzene-dß in a 10 mL Schlenk bottle. To a second vessel was charged 0.100 mmol of the desired reagent described in Table 5 and 0.5 mL of benzene-d6. The second solution was transferred to the first solution drop by drop. The container was sealed, covered with a movie and was agitated during the night. The resulting solutions were analyzed by lH-nmr to determine the conversion of tribencyl of [1- (2-pyridyl) N-methylethyl] [lN-2,6-diisopropylphenylamido] zirconium to the products described in Table 5. A preparation was prepared series of ethylene / hexene copolymers in a pulp reactor, on a laboratory scale, using products described in Table 5 with MMAO (7.0 wt% Al in heptane, commercially available from Akzo Chemicals, Inc.). In each case, the catalyst composition was prepared by combining a benzene solution of the product described in Table 5 with a solution of MMAO in the presence of 0.1 mL of l-hexene. The reaction conditions were 85 ° C, 85 psi of ethylene, 0.5 micromol of zirconium complex, 43 mL of l-hexene and 1000 equivalents of MMAO by zirconium. The results appear in Table 5. TABLE 5 Example Reactive product conversion Benzaldehyde -100% 5c Piperidine -83Í Morpholine -94í Phenol -90% 15f Acetylacetone -100Í Example activity 121 BBF 15a 87.059 too 12.97 slow for measurement 15b 101.647 0.235 10.48 15c 96.941 0.141 6.71 15d 148.235 0.292 20.48 15e 189.176 too much 10.19 slow for measurement 15f 141.176 0.095 10.66 EXAMPLE 16 Preparation of tribencyl of [1- (2-pyridyl) N- ethenyl (2,6-diisopropylphenylamido) zirconium In a dry box, 10 mmoles (2.80 g) of 2-acetylpyridine (2,6-diisopropylphenylimine) were charged to a 100 mL Schlenk bottle eguided with a stir bar and sealed with a The flask was removed from the dry box and placed under an argon atmosphere, 20 mL of tetrahydrofuran was added to the ligand and stirred until dissolved, the solution was cooled to -70 ° C and 10 moles were added dropwise. 7.1 L) of methyllithium (Aldrich, 1.4M solution in ether) The light red-orange mixture was slowly warmed to room temperature The mixture thickened as it was heated, an additional 20 mL of THF was added. At room temperature for 4 hours, the mixture was again cooled to -70 ° C and 10 mmol (1.27 mL) of chlorotrimethylsilane (Aldrich) was added dropwise to the ligand / methyllithium mixture. The red-orange mixture was slowly warmed to room temperature and stirred overnight. The reaction mixture was washed in vacuo to obtain a pale yellow, powder-like residue, which was taken to the dry box. The resulting ligand was dissolved in 20 mL of toluene. In a second vial, a paste of 10 mmol (2.33 g) of zirconium chloride (IV) was formed in 10 mL of toluene. The ligand solution was added to the ZrCl4 paste with vigorous stirring. The yellow paste was stirred overnight in a dry box.

The paste was removed from the dry box, washed in vacuo, and 20 L of toluene was added to the residue. In a second flask of Schlenk of 100 mL, 30 mmoles of benzylmagnesium chloride (30 mL) were charged (Aldrich, 1.0 M in solution in ether). The solution was washed in vacuo and the solvent replaced with toluene. Repeat washing three times resulted in the production of a powdery whitish residue that was dissolved in 20 mL of toluene. In a dark laboratory and under a hood, the benzylmagnesium chloride solution was transferred by cannula to the cooled paste (-70 ° C) of the ligand / ZrCl4. The vessel was covered with a film and allowed to warm slowly to room temperature with stirring overnight. The reaction mixture was taken to the dry box and filtered through a frit of medium porosity. The solids were washed with toluene and then discarded. The filtrate was transferred in an amber bottle. EXAMPLE 17 A series of ethylene / hexene copolymers were prepared in a laboratory scale pulp reactor using a catalyst composition comprising the catalyst precursor of Example 17 with MMAO (7.0 wt% Al in heptane, commercially available from Akzo Chemicals, Inc.). In each case, the catalyst composition was prepared by combining a solution of the catalyst precursor of Example 17 in benzene with the MMAO solution in the presence of 0.1 mL of 1-hexene. The conditions of the reaction and the results appear in Table 6, below. TABLE 6 Example CßmL T, C C2 psi gPE Activity 12 MFR 17a 43 65 85 27.7 28,000 .512 44.21 17b 86 65: 170 42.4 30.235 NF NF 17c 43 75 85 12.1 26,118 .577 27.56 17d 86 75: 170 32.6 17,765 .09 34.52 17e 43 85 85 9.7 14,588 1,138 31.38 17f 86 85: L70 25.3 14,118,208 29.13 Example Mn POI BBF 17a 24,120 4,707 12.26 17b - - 15.06 17c 13,944 5,896 14.46 17d 51,382 3,779 12.09 17e 31,332 3,367 9.13 17f 45,632 3,524 11.23 EXAMPLE 18 Preparation of N-tetrahydrofurfuryl [N-2,6-diisopropylphenyl] amine 2,6-diisopropylaniline (50 mmol) was charged, 8.86 g Aldrich, 90%) to a Schlenk bottle, cooled, oven dried, equipped with a stir bar and septum. The flask was placed under a nitrogen purge and 20 mL of dry tetrahydrofuran was added. The flask was cooled to a temperature of 0 ° C and added dropwise via a n-butyllithium syringe (50 mmol, 17.8 L, Aldrich, 2.81M solution in hexane). The mixture was heated slowly to room temperature. Tetrahydrofurfuryl chloride (50 mmol, 5.4 mL, Aldrich, 98%) was added through a syringe and the mixture was heated to a temperature of 50 ° C overnight. The reaction solution was cooled to room temperature and hydrolyzed. The aqueous layer was extracted 3 times with ether. The organic parts were combined and washed in vacuo. The residue was distilled in vacuo using a short distillation column. The distilled product (140-144 ° C, 0.25 torr, 4 grams) was a light yellow liquid.

EXAMPLE 19 Tribenzyl preparation of [N-tetrahydrofurfuryl] [N-2,6-diisopropylphenylated] zirconium Tetrabenzylzirconium (0.200 mmol, 0.091 g) was charged to a 7 mL amber bottle equipped with a stir bar and a screw cap. Dry benzene-dß (2 mL) was added and stirred until dissolved. The ligand prepared in Example 18 (0.200 mmol, 0.052 g), and dry benzene-d (1.0 mL) were charged to a second vial. The solution of N-tetrahydrofurfuryl] [N-2,6-diisopropylphenylimin] was transferred into the stirred tetrabenzylzirconium solution. The bottle was capped and the reaction solution was allowed to stir overnight. EXAMPLE 20 A series of ethylene / hexene copolymers were prepared in a pulp reactor, on a laboratory scale, using a catalyst composition comprising the catalyst precursor of Example 19 with MMAO (7.0 wt% Al in heptane , commercially available from Akzo Chemicals, Inc.). In each case, the catalyst composition was prepared by combining a solution of the catalyst precursor in benzene with the MMAO solution in the presence of 0.1 mL of 1-hexene. The polymerization reactions were performed at an ethylene pressure of 85 psi, 0.5 micromol of Zr, and a molar ratio of MMAO / Zr of 1000. The reaction conditions and results are shown in Table 7 below. TABLE 7 Example CemL T, C C2 psi Activity 12 BBF 20a 43 65 85 35,765 NF 9.82 20b 43 75 85 20,235 114 9.77 20c 43 85 85 13,176

Claims (1)

1. CLAIMS A catalyst precursor that has the formula: qMLn where each A has the formula: M is a metal selected from the group consisting of the elements of Groups 3 to 13 and elements of the Lanthanide series; each L is a monovalent, bivalent or trivalent anion; X and Y are each heteroatoms; cycle is a cyclical portion; each R1 is independently a group containing from 1 to 50 selected atoms within the group consisting of hydrogen and elements of Groups 13 to 17 and two or more adjacent R1 groups may be linked to form a cyclic portion; each R2 is independently a group that contains 1 to 50 selected atoms within the group consisting of hydrogen and elements of Groups 13 to 17, and two or more adjacent R2 groups may be linked to form a cyclic portion; Q is a bridge group; each m is independently an integer from 0 to 5; n is an integer from 1 to 4; q is 1 or 2; and when q is 2, groups A are optionally connected to a bridge group Z. The catalyst precursor of claim 1, having the formula: where Ra and Rb are each independently selected from the group consisting of alkyl, aryl, heterocyclic groups, and hydrogen and Ra and b may optionally be connected to form a ring; Rc and Rd are each independently selected from the group consisting of alkyl, aryl, and hydrogen; and each L is a monovalent, bivalent or trivalent anion. The catalyst precursor according to claim 1, having the formula: wherein Ra and R are each independently selected from the group consisting of alkyl, aryl, heterocyclic groups, and hydrogen, and Ra and Rb may be optionally connected to form a ring; Rc and Rd are each independently selected from the group consisting of alkyl, aryl, and hydrogen; and each L is a monovalent, bivalent or trivalent anion. The catalyst precursor according to claim 1, having the formula: wherein Ra and Rb are each independently selected from the group consisting of alkyl, aryl, heterocyclic groups, and hydrogen and Ra and Rb may optionally be connected to form a ring; Rc and R are each selected independently from the group consisting of alkyl, aryl, and hydrogen; and each L is a monovalent, bivalent or trivalent anion. A catalyst precursor having the formula: A catalyst precursor having the formula: A catalyst precursor having the formula: The catalyst precursor of claim 1, having the formula: wherein Ra and Rb are each independently selected from the group consisting of alkyl, aryl, heterocyclic groups, and hydrogen and Ra and Rb may optionally be connected to form a ring; Rc and R are each independently selected from the group consisting of alkyl, aryl, and hydrogen; and each L is a monovalent, bivalent or trivalent anion. A catalyst composition comprising: a) a catalyst precursor having the formula AgMLn where each A has the formula: M is a metal selected from the group consisting of elements from Groups 3 to 13 and elements of the Lanthanide series; each L is a monovalent, bivalent or trivalent anion; X and Y are each heteroatoms; cycle is a cyclical portion; each R1 is independently a group containing from 1 to 50 selected atoms within the group consisting of hydrogen and elements of Groups 13 to 17 and two or more adjacent R1 groups may be linked to form a cyclic portion; each R2 is independently a group containing from 1 to 50 selected atoms within the group consisting of hydrogen and elements of Groups 13 to 17, and two or more adjacent R2 groups may be linked to form a cyclic portion; Q is a bridge group; each m is independently an integer from 0 to 5; n is an integer from 1 to 4; q is 1 or 2; and when q is 2, the groups A are optionally connected by means of a bridge group Z; and b) an activation cocatalyst. . The catalyst composition according to claim 9, wherein the catalyst precursor has the formula: where Ra and Rb are independently selected from each other within the group consisting of alkyl, aryl, heterocyclic groups, and hydrogen and Ra and Rb may optionally be connected to form a ring; Rc and R are each independently selected from the group consisting of alkyl, aryl, and hydrogen; and each L is a monovalent, bivalent or trivalent anion. The catalyst composition according to claim 9, wherein the catalyst precursor has the formula: where Ra and Rb are each independently selected from the group consisting of alkyl, aryl, heterocyclic groups, and hydrogen and Ra and b may optionally be connected to form a ring; Rc and Rd are each independently selected from the group consisting of alkyl, aryl, and hydrogen; and each L is a monovalent, bivalent or trivalent anion. The catalyst composition according to claim 9, wherein the catalyst precursor has the formula: where Ra and Rb are each independently selected from the group consisting of alkyl, aryl, heterocyclic groups, and hydrogen and Ra and Rb can optionally be connected to form a ring; Rc and Rd are each independently selected from the group consisting of alkyl, aryl, and hydrogen; and each L is a monovalent, bivalent or trivalent anion. . The catalyst composition according to claim 9, wherein the catalyst precursor has the formula: The catalyst composition according to claim 9, wherein the catalyst precursor has the formula: The catalyst composition according to claim 9, wherein the catalyst precursor has the formula: The catalyst composition according to claim 9, wherein the catalyst precursor has the formula: wherein Ra and Rb are each independently selected from the group consisting of alkyl, aryl, heterocyclic groups, and hydrogen and Ra and Rb may optionally be connected to form a ring; Rc and Rd are each independently selected from the group consisting of alkyl, aryl, and hydrogen; and each L is a monovalent, bivalent or trivalent anion. 17. The catalyst composition according to claim 9 in liquid form. 18. The catalyst composition according to claim 9 supported on an inert support. 19. A process for the polymerization of olefins, comprising contacting an olefin under polymerization conditions with a catalyst composition comprising: a) a catalyst precursor having the formula wherein each A has the formula: M is a metal selected from the group consisting of elements from Groups 3 to 13 and elements of the Lanthanide series; each L is a monovalent, bivalent or trivalent anion; X and Y are each heteroatoms; cycle is a cyclical portion; each R1 is independently a group containing from 1 to 50 selected atoms within the group consisting of hydrogen and elements of Groups 13 to 17 and two or more adjacent R1 groups may be linked to form a cyclic portion; each R2 is independently a group containing from 1 to 50 selected atoms within the group consisting of hydrogen and elements of Groups 13 to 17, and two or more adjacent R2 groups may be linked to form a cyclic portion; Q is a bridge group; each m is independently an integer from 0 to 5; n is an integer from 1 to 4; q is 1 or 2; and when q is 2, groups A are optionally connected through a bridge group Z; and b) an activation cocatalyst. The process of claim 19, wherein the catalyst precursor has the formula: wherein Ra and Rb are independently selected from the group consisting of alkyl, aryl, heterocyclic groups, and hydrogen and Ra and Rb can optionally be connected to form a ring; Rc and Rd are each independently selected from the group consisting of alkyl, aryl, and hydrogen; and each L is a monovalent, bivalent or trivalent anion. The process according to claim 19, wherein the catalyst precursor has the formula: where Ra and Rb are independently selected from the group consisting of alkyl, aryl, heterocyclic groups, and hydrogen and Ra and Rb may optionally be connected to form a ring; Rc and Rd are each independently selected from the group consisting of alkyl, aryl, and hydrogen; and each L is a monovalent, bivalent or trivalent anion. 22. The process according to claim 19, wherein the catalyst precursor has the formula: where Ra and Rb are independently selected from the group consisting of alkyl, aryl, heterocyclic groups, and hydrogen and Ra and Rb may optionally be connected to form a ring; Rc and Rd are each independently selected from the group consisting of alkyl, aryl, and hydrogen; and each L is a monovalent, bivalent or trivalent anion. 23. The process according to claim 19, wherein the catalyst precursor has the formula: The process according to claim 19, wherein the catalyst precursor has the formula: The process according to claim 19, wherein the catalyst precursor has the formula: . The process according to claim 19, wherein the catalyst precursor has the formula: wherein Ra and Rb are each independently selected from the group consisting of alkyl, aryl, heterocyclic groups, and hydrogen and Ra and Rb may optionally be connected to form a ring; R- and Rd are each independently selected from the group consisting of alkyl, aryl, and hydrogen; and each L is a monovalent, bivalent or trivalent anion. The process according to claim 19, wherein the catalyst composition is in liquid form. The process according to claim 19, wherein the catalyst composition is supported on an inert support. The process according to claim 19 carried out in the gas phase. A catalyst precursor comprising the reaction product of an organometal compound and a heteroatom-containing ligand having a formula selected from the group consisting of: O well where X and Y are each heteroatoms; cycle is a cyclical position; each R1 is a group containing from 1 to 50 selected atoms within the group consisting of hydrogen and elements of Groups 13 to 17 and two or more adjacent R1 groups may be linked to form a cyclic portion; each R2 is a group containing from 1 to 50 selected atoms within the group consisting of hydrogen and elements from Groups 13 to 17, and two or more adjacent R2 groups may be linked to form a cyclic portion; Q is a bridge group; and each ia is independently an integer from 0 to 5. 31. The catalyst precursor according to claim 30, wherein the organometal compound is a zirconium hydrocarbyl and the heteroatom containing ligand has the formula: where Cycle is a cyclical position; each R1 is a group containing from 1 to 50 selected atoms within the group consisting of hydrogen and elements of Groups 13 to 17 and two or more adjacent R1 groups may be linked to form a cyclic portion; each R2 is a group containing from 1 to 50 selected atoms within the group consisting of hydrogen and elements from Groups 13 to 17, and two or more adjacent R2 groups may be linked to form a cyclic portion; Q is a bridge group; and each m is independently an integer from 0 to 5. 32. The catalyst precursor according to claim 30, wherein the organometal compound is a zirconium hydrocarbyl and the heteroatom-containing ligand is a pyridine / imine ligand. the formula: where each R 'is a hydrocarbon group containing from 1 to 20 carbon atoms and two or more adjacent R' groups can be joined to form an aliphatic or aromatic ring; each R "is a hydrocarbon group containing from 1 to 20 carbon atoms and two or more adjacent R" groups can be linked to form an aliphatic or aromatic ring;R3 is a hydrogen, a hydrocarbon group containing from 1 to 20 carbon atoms optionally substituted with one or more heteroatoms, or a heteroatom optionally substituted with a hydrocarbon group; and each m is independently an integer from 0 to 5. A catalyst composition comprising: a) a catalyst precursor which is the product of the reaction of an organometal compound and a heteroatom-containing ligand, having a selected formula within the group consisting of: where X and Y are each heteroatoms; cycle is a cyclical portion; each R1 is a group containing from 1 to 50 selected atoms within the group consisting of hydrogen and elements of Groups 13 to 17 and two or more adjacent R1 groups may be linked to form a cyclic portion; each R2 is a group containing from 1 to 50 selected atoms within the group consisting of hydrogen and elements from Groups 13 to 17, and two or more adjacent R2 groups may be linked to form a cyclic portion; Q is a bridge group; and each is independently an integer from 0 to 5; and b) an activation cocatalyst. . The catalyst composition according to claim 33, wherein the catalyst precursor comprises the product of the reaction of a zirconium hydrocarbyl and a heteroatom-containing ligand of the formula: where Cycle is a cyclic portion; each R1 is a group containing from 1 to 50 selected atoms within the group consisting of hydrogen and elements of Groups 13 to 17 and two or more adjacent R1 groups may be linked to form a cyclic portion; each R2 is a group containing from 1 to 50 selected atoms within the group consisting of hydrogen and elements of Groups 13 to 17, and two or more adjacent R2 groups may be linked to form a cyclic portion; Q is a bridge group; and each m is independently an integer from 0 to 5. The catalyst composition of claim 33, wherein the catalyst precursor comprises the product of the reaction of a zirconium hydrocarbyl and a pyridine / imine ligand of the formula: wherein each R 'is a hydrocarbon group containing 1 to 20 carbon atoms and two or more adjacent R' groups may be linked to form an aliphatic or aromatic ring; each R "is a hydrocarbon group containing from 1 to 20 carbon atoms and two or more adjacent R" groups can be attached to form an aliphatic or aromatic ring; R3 is a hydrogen, a hydrocarbon group containing from 1 to 20 carbon atoms optionally substituted with one or more heteroatoms, or a heteroatom optionally substituted with a hydrocarbon group; and each m is independently an integer from 0 to 5. The catalyst composition according to claim 33, in liquid form. The catalyst composition according to claim 33, supported on an inert support. A process for the polymerization of olefins, comprising contacting an olefin under polymerization conditions with a catalyst composition comprising: a) a catalyst precursor which is the product of the reaction of an organometal compound and a ligand containing heteroatoms, which has a formula selected from within the group consisting of: where X and Y are each heteroatoms; cycle is a cyclical portion; each R1 is a group containing from 1 to 50 selected atoms within the group consisting of hydrogen and elements of Groups 13 to 17 and two or more adjacent R1 groups may be linked to form a cyclic portion; each R2 is a group containing from 1 to 50 selected atoms within the group consisting of hydrogen and elements from Groups 13 to 17, and two or more adjacent R2 groups may be linked to form a cyclic portion; Q is a bridge group; and each m is independently an integer from 0 to 5; and b) an activation cocatalyst. The process according to claim 98, wherein the catalyst precursor comprises the product of the reaction of a zirconium hydrocarbyl and a heteroatom-containing ligand having the formula: where Cycle is a cyclic portion; each R1 is a group containing from 1 to 50 selected atoms within the group consisting of hydrogen and elements of Groups 13 to 17 and two or more adjacent R1 groups may be linked to form a cyclic portion; each R2 is a group containing from 1 to 50 selected atoms within the group consisting of hydrogen and elements from Groups 13 to 17, and two or more adjacent R2 groups may be linked to form a cyclic portion; Q is a bridge group; and each m is independently an integer from 0 to 5. The process according to claim 38, wherein the catalyst precursor comprises the product of the reaction of a zirconium hydrocarbyl and pyridine / imine ligand of the formula: wherein each R 'is a hydrocarbon group containing 1 to 20 carbon atoms and two or more adjacent R' groups may be linked to form an aliphatic or aromatic ring; each R "is a hydrocarbon group containing from 1 to 20 carbon atoms and two or more adjacent R" groups can be attached to form an aliphatic or aromatic ring; R3 is a hydrogen, a hydrocarbon group containing from 1 to 20 carbon atoms optionally substituted with one or more heteroatoms, or a heteroatom optionally substituted with a hydrocarbon group; and each m is independently an integer from 0 to 5. 41. The process according to claim 38, wherein the catalyst composition is in liquid form. 42. The process according to claim 38, wherein the catalyst composition is supported on an inert support. 43. The process according to claim 38 carried out in the gas phase. SUMMARY OF THE INVENTION A catalyst precursor is offered having the formula: qMLn where each A has the formula: M is a metal selected from the group consisting of elements of Groups 3 to 13 and elements of the lanthanide series; each L is a monovalent, bivalent, or trivalent anion; X and Y are each heteroatoms; cycle is a cyclical portion; each R1 is a group containing from 1 to 50 selected atoms within the group consisting of hydrogen and elements of Groups 13 to 17, and two or more adjacent R1 groups may be linked to form a cyclic portion; each R2 is a group containing from 1 to 50 atoms selected from the group consisting of hydrogen and elements from Groups 13 to 17, and 2 or more adjacent R2 groups may be linked to form a cyclic portion; Q is a bridge group; each m is independently an integer from 0 to 5; n is an integer from 1 to 4 that is 1 or 2; and when q is 2, the groups A are optionally connected by a bridge group Z. The catalyst precursor can be made by the reaction of an organometal compound with a heteroatom containing ligand. The catalyst precursor, when combined with an activating cocatalyst, is useful for the polymerization of olefins.