MXPA96004380A - Catalyst for the production of olef polymers - Google Patents

Abstract

A catalyst precursor of the formula: see in fig. wherein: L is a cycloalkadienyl coordinating group, W, X, Y and Z are independently hydrogen, a hydrocarbyl group containing from 1 to 20 carbon atoms, or a silyl group, and can be connected to L through a bridge or connection group comprising at least two atoms of the VAT Group, with the condition of the negative charge selected from the group consisting of trialkyl groups of the IVA Group, aryl groups, heteroaromatic groups, ethylenically unsaturated hydrocarbon groups, acetylenically unsaturated hydrocarbon groups, ketone groups, and organometallic aromatic residues. When combined with a compound comprising a metal of groups IIIB to VIII or of the Lantanide series of the Periodic Table of elements and an activating cocatalyst, the catalyst precursor is useful for the polymerization of olefin

Description

-. "CATALYST FOR THE PRODUCTION OF OLEFIN POLYMERS" The invention relates to a novel family of conjugated allylcycloalcadienyl dianions useful as catalyst precursors for the production of olefin polymers, such as ethylene polymers, higher alpha-olefins, dienes and mixtures thereof.

BACKGROUND 10 Recently, single-site catalysts have been developed to prepare olefin polymers. Typically, single-site catalysts are metallocenes, organometallic coordination complexes that contain one or more residues of / 7-linked in association with a metal atom of Groups 11IB to VIII or of the - > N Lantanuro series of the Periodic Table of Elements. Catalyst compositions containing single-site catalysts are reported to be highly useful in the Preparation of polyolefins, producing homogeneous polymers at excellent polymerization rates and allowing the final properties of the polymer to be tightly adapted as desired. European Patent Applications Number 0 586 167 Al and No. 0 586 168 Al relate to polyolefin catalyst compositions comprising metallocene complexes of the formula M [XRn]? And p XRm wherein R is a hydrocarbyl optionally containing oxygen, silicon, phosphorus, nitrogen or boron atoms, X is an organic group containing a cyclopentadienyl core, M is a Group IVA metal, and is a univalent anionic coordinating group, and Z is a connection or bridge group. In accordance with these applications, at least one R group must contain a group "A- polymerizable, preferably containing at least three carbon atoms. The matalocene complexes Preferred are zirconium complexes wherein the polymerizable group is vinyl. The compounds such as they make themselves known. German Patent Application Number 3840772 A1 relates to metallocene catalyst components for use in the polymerization of olefins prepared by reacting a metallocene compound of zirconium, titanium or hafnium with a poly (meth-hydrogen-siloxane) in the presence of a hydrosilation catalyst. The compounds such as they make themselves known. A novel single-site olefin polymerization catalyst composition having good polymerization activity and productivity, which is prepared easily and economically, is disclosed herein. The catalyst composition comprises the reaction product of 1) a precursor of the conjugated allyl-cycloalcadienyl dianion catalyst, 2) a compound comprising a metal of Groups IIIB to VIII or of the Lantanide series, and 3) a cocatalyst. of activation.

SUMMARY OF THE INVENTION The invention provides a catalyst precursor of the formula: wherein: L is a cycloalkadienyl coordinating group; 10 W, X, Y and Z are independently hydrogen, a hydrocarbyl group containing from 1 to 20 carbon atoms, a silyl group, and can be connected to L through a connection or bridge group comprising at least minus two atoms of the VAT Group; with the condition of one of X, Y and Z is a negative charge stabilization group that is selected from the trial group of the IVA Group, aryl groups, heteroaromatic groups, groups S * of unsaturated ethylenic hydrocarbon, unsaturated acetylenic hydrocarbon groups, ketonic groups and aromatic organometallic residues. The invention also provides a catalyst composition comprising the reaction product of the aforementioned catalyst precursor, a compound comprising a metal of Groups IIIB to VIII or the Lantanuro series, and an activation co-catalyst.

- - * • *. The invention also provides a process for the production of an olefin polymer, comprising contacting an olefin monomer under polymerization conditions, with the catalyst composition. mentioned above, as well as with olefin polymers, such as • ethylene polymers produced by this process.

DETAILED DESCRIPTION OF THE INVENTION O The catalyst precursor is a dianion of conjugated allyl-cycloalcadienyl having the formula: In the above formula, L is a cycloalkadienyl coordinating group, such as cyclopentadienyl, indenyl or fluorenyl, which may be unsubstituted or substituted with one or more hydrocarbyl groups such as alkyl, aryl, alkylaryl, or arylalkyl, silyl groups and similar. Preferably, L is an unsubstituted or substituted cyclopentadienyl or indenyl coordinating group. / • "t * Except as stipulated in the following paragraph, W, X, Y and Z are independently hydrogen, a hydrocarbyl group containing 1 to 20 carbon atoms, or a silyl group. of W, X, Y and Z 5 can be connected to L through connection or bridge groups comprising two or more atoms of the VAT Group It is necessary that one of X, Y and Z be a negative charge stabilization group. Examples of the negatively charged stabilization groups are the Group-trialkyl groups of the IVA Group, aryl groups, heteroaromatic groups, ethylenically unsaturated hydrocarbon groups, acetylenically unsaturated hydrocarbon groups, ketone groups and aromatic organometallic residues. of the VAT Group have the formula (element of the VAT Group) (R3) where R is an alkyl group containing from 1 to about 20 carbon atoms such as silyl, stanyl, germyl or plumbyl. The aryl groups are phenyl, naphthyl, biphenyl, anthracenyl, and substituted phenyl groups such as tolyl, methoxyphenyl and ortho-t-butyl-phenyl. Examples of heteroaromatic groups are pyridyl, furyl, pyrryl and thienyl.

- - Examples of ethylenically unsaturated hydrocarbon groups are vinyl groups, substituted vinyl groups, alkenic groups, substituted alkenic groups, dienyl groups, and substituted dienyl groups. Examples of acetylenically unsaturated hydrocarbon groups are phenylalkynyl, trimethyl-silylalkynyl, propynyl, hexynyl and 3-3-dimethylbutynyl. Examples of ketonic groups are benzoyl and pivaloyl. Examples of aromatic organometallic residues are ferrocene, titanocene, chromocene and vanadocene. Preferred negative charge stabilization groups are aryl groups, particularly phenyl. The catalyst precursor may be in the form of a monomer, a dimer, an oligomer, or a polymer. In a preferred embodiment of the invention, the catalyst precursor is a cyano-cyclopentadienyl dianion of the formula: 2- including any isomers thereof. In another preferred embodiment of the invention, the catalyst precursor is a cinnamyl indenyl dianion of the formula: including any of the isomers thereof. The catalyst precursor can be produced by any synthetic method, and the method for producing the catalyst precursor is not critical to the invention. A useful method for producing the catalyst precursor is by contacting a salt containing cidoalcadienyl with a halogen compound containing allyl, and metallizing the resultant product with a metallating agent, preferably a lithium-lithium compound LI-β-phenyl -lithium or n-butyl-lithium. The contact can be carried out at atmospheric pressures and at temperatures within the range of about -78 ° C to room temperature, preferably within the range of .30 ° C to room temperature.

For example, when the preferred cyanamylcyclopentadienyl dianion catalyst precursor is produced, the sodium cyclopentadiene can be reacted with the cinnamyl chloride or cinnamyl bromide. The product, the cinnamoyl cyclopentadielo can then be metallized with an equivalent of n-butyl-lithium in an appropriate solvent to form the mono-anion, the cyclopentadienide of cinnamyl (as the mono-lithium salt). Examples of useful solvents are ethers such as tetrahydrofuran (THF), mono-, di-, tri- and tetra-glymes, and methyl tertiary butyl ether (MTBE), chelating amines such as ethylene diamine N, N, N ', N 1 -tetramethyl and amides such as hexamethyl phosphoramide. The mono-anion can then be converted to the cinnamyl cyclopentadienyl dianion through a second metallization with a second equivalent of n-butyl lithium in a solvent. Alternatively, the cinnamyl cyclopentadiene can be converted directly into the cyanamylcyclopentadienyl dianion catalyst precursor in a synthesis by sequentially adding the sodium cyclopentadiene, cinnamyl chloride or cinnamyl bromide and two equivalents of the alkyl lithium compound. The catalyst composition comprises the reaction product of the conjugated allyl-cycloalcadienyl dianion catalyst precursor, a compound comprising "-" a metal of Groups IIIB to VIII or the Lantanide series. (to which reference will also be made herein as the "metal compound"), and an activation cocatalyst. By forming the reaction product, the precursor of The catalyst (which may be in the form of a salt containing the conjugated allyl-cycloalcadienyl dianion and a metal cation of the metallization reagent), the metal compound, and the activating cocatalyst are * - '"- contact at temperature within the scale of about -78 ° C at room temperature, preferably within the range of about -30 ° C to room temperature, at atmospheric pressure. The preferred contact is carried out in the presence of an appropriate solvent, i.e. an ether such as THF or a hydrocarbon such as hexane or toluene. The catalyst precursor, the metal compound, and the activation cocatalyst can be contacted in any order; however, it is preferred that either the catalyst precursor and the metal compound are contacted first, followed by contact with the cocatalyst of. activation, or the catalyst precursor and the cocatalyst. Activation is first contacted followed by contacting the metal compound. When the catalyst precursor is put in In the first contact with the activating cocatalyst, it may be desirable to add an additional activating cocatalyst to the reaction product after the metal compound has been added in order to adjust the total ratio of the metal activating cocatalyst to the composition of the catalyst. The compound comprising a metal of the Groups IIIB to VIII or from the Latanuro depreciaria series is a compound containing a Group IVB metal. Of greater '', preference, the metal compound is a compound of zirconium Suitable zirconium compounds include zirconium halides, zirconium alkylhalides, zirconium alkyls, zirconium amides, zirconium diketonates, zirconium alkoxides, zirconium carboxylates and the like. The specific examples of the compounds of Zirconium include zirconium tetrachloride, cyclopentadienyl zirconium trichloride, pentamethylcyclopentadienyl zirconium trichloride, tetrabenzyl zirconium, tetrakis (diethylamino) zirconium, zirconium acetylacetonate, zirconium hexafluoroacetoacetonate, dichloride bis (acetylacetonate) zirconium, zirconium isoproxide, zirconium 2-ethylhexanoate, CIZr [CH (SiMe 3> 3, Me 3 SiCH 2] 2 ZrCl 2 (Et 20) 2, [PhCH 2] 2 ZrCl 2, (Me3CH2) 2ZrCl2 (Et20) 2, and [ZrCl2 (THF) (eta-C8H8)]. When the catalyst precursor has synthesized with a concentrated metallization reagent such as an alkyl lithium compound, it may be useful to contact the catalyst precursor with a transmetalization compound before the catalyst precursor is contacted with the metal compound. The transmetallization compound, which is preferably a halide or alkoxide of Group ILA, IIB, IIIA or IVA, removes the metal cation (from the metallization reagent) associated with the catalyst precursor and replaces the same with? ", A more reactive metal, this in turn facilitates the reaction of the catalyst precursor with the metal compound. Particularly preferred transmetalization compounds are the halides and alkoxides of silicon, aluminum and tin. The activating cocatalyst is capable of activate the catalyst composition. Preferably, the activating cocatalyst is one of the following: (a) cyclic oligomeric poly (hydrocarbylaluminum oxide) s containing 1 repeat units of the general formula - (A1 (R *) 0) -, where R * is hydrogen, a radical of Alkyl containing from 1 to about 12 carbon atoms, or an aryl radical such as a substituted or unsubstituted phenyl or naphthyl group; (b) ionic salts of the general formula [A +] [BR ** 4 ~], wherein A + is a Lewis or Bronsted cationic acid capable of extracting a alkyl, halogen, or hydrogen of the catalysts of - ? - * metallocene, B is boron and R ** is an aromatic hydrocarbon substituted preferably a perfluorophenyl radical; (c) boron alkyls of the general formula BR ** 3, wherein R ** is as defined above; or mixtures of same. If an ionic salt of the formula [A +] [BR ** 4 ~] or a boron alkyl is used as the activating cocatalyst, it may be desirable to contact the metal compound with an aluminum alkyl such as trimethylaluminum or triisobutylaluminium, in order to alkylate the metal compound before it is contacted with the catalyst precursor and the activation cocatalyst. Preferably, the activating cocatalyst is a branched or cyclic oligomeric poly (hydrocarbylaluminum oxide) or a boron alkyl. More preferably, the activating cocatalyst is an aluminoxane such as methylaluminoxane (MAO) or r ~ "modified methylaluminoxane (MMAO), or a boron alkyl. The alu-inoxanes are well known in the art and comprise oligomeric linear alkyl aluminoxanes represented by the formula: ^ - \ and oligomeric cyclic alkyl aluminoxanes of the formula: wherein s is from 1 to 40, preferably from 10 to 20; p is from 3 to 40, preferably from 3 to 20; and R *** is an alkyl group containing from 1 to 12 carbon atoms, give r c. preferably a methyl or aryl radical such as a substituted or unsubstituted phenyl or naphthyl radical. Aluminoxanes can be prepared in a variety of ways. In general, a mixture of linear and cyclic aluminoxanes is obtained in the preparation of the aluminoxanes, for example trimethylaluminium and water.

For example, an aluminum alkyl can be treated with water in the form of a wet solvent. Alternatively, an aluminum alkyl such as trimethylaluminum, can be contacted with a hydrated salt, such as ferrous sulfate hydrate. The last method involves treating a diluted trimethylaluminum solution, for example, in toluene with a suspension of ferrous sulfate heptahydrate. It is also possible to form methylaluminoxanes by the reaction of a tetralkyl-dialuminoxane containing alkyl groups of 2 carbon atoms with a quantity of trimethylaluminum which is r * - ^ less than a stoichiometric excess. The synthesis of the methylaluminoxanes can also be achieved by the reaction of a trialkylaluminum compound or a trialkyldialuminoxane containing alkyl groups of 2 carbon atoms or higher with water to form a polyalkylaluminoxane, which is then reacted with trimethylaluminum. The additional modified methylaluminoxanes, which contain both methyl groups and higher alkyl groups, can be synthesized by The reaction of a polyalkylaluminoxane containing alkyl groups of 2 carbon atoms or higher with trimethylaluminum and then with water as discussed, for example, in U.S. Patent No. 5,041,584. The amounts of the catalyst precursor, The metal compound, and the activating cocatalyst which are usefully employed in the catalyst composition, can vary accordingly. In general, the ratio of the catalyst precursor to the metal compound may vary from about 1: 5 to about 5: 1, preferably from about 1: 3 to about 3: 1, and most preferably from about 1: 2 to about 2: 1. When the activating cocatalyst is a branched oligomeric poly (hydrocarbylaluminum oxide) In a cyclic manner, the molar ratio of aluminum atoms contained in the poly (hydrocarbylaluminum oxide) to the total metal atoms contained in the metal compound generally falls 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 from about 50: 1 to about 2,000: 1. When the activating co-catalyst is an ionic salt of the formula [A +] [BR ** 4-] or a boron alkyl of the formula B ** 3, the molar ratio of the boron atoms contained in the ionic salt or the boron alkyl to the total metal atoms contained in the metal compound usually falls within the range of about 0.5: 1 to about 10: 1 preferably within the range of about 1: 1 to about 5: 1. The catalyst composition may be supported or unsupported or may be spray dried with or without a filler or filler. In the case of a supported catalyst composition, the catalyst composition can be impregnated into or deposited on the surface of an inert substrate such as silicon dioxide, aluminum oxide, magnesium dichloride, polystyrene, polyethylene, polypropylene or polycarbonate, in such a manner that the catalyst composition is between 1 percent and 90 percent by weight of the total weight of the catalyst composition and support. The catalyst composition can be used for the polymerization of defines by any process of suspension, solution, slurry or gas phase, using known equipment and reaction conditions, and is not limited to any specific type of the reaction system. In general, the olefin polymerization temperatures range from about 0 ° C to about 200 ° C at atmospheric, subatmospheric or superatmospheric pressures. Thick slurry or solution polymerization processes can utilize subatmospheric or superatmospheric pressures and temperatures within the range of about 40 ° C to about 110 ° C. A useful liquid phase polymerization reaction system is described in U.S. Patent Number 3,324,095. The liquid phase reaction systems generally comprise a reactor vessel to which the olefin monomer and catalyst composition are added 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 is not reactive under the polymerization conditions employed. Although this inert liquid hydrocarbon does not need 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 liquid hydrocarbons suitable for this purpose are isopentane, hexane, cyclohexane, heptane, benzene, toluene, and the like. The reactive contact between the olefin monomer and the catalyst composition must be maintained by constant agitation or stirring. The reaction medium that contains The olefin polymer product and the unreacted olefin monomer are continuously removed from the reactor. The olefin polymer product is separated and the unreacted olefin monomer and the liquid reaction medium are recycled to the reactor. Preferably, gas phase polymerization is used, with superatmospheric pressures within the range of .0703 to 70.30 kilograms per square centimeter gage preferably from 3.52 to 28.12 kilograms per square centimeter, more preferably from 7.03 to 21.09 kilograms per square centimeter and temperatures within the range of 30 ° C to 130 ° C, preferably 65 ° C to 110 ° C. Agitated gas or fluidized bed phase reaction systems are particularly useful. In general, a conventional gas phase process is carried out fluidized bed by passing a stream containing one or more olefin monomers continuously through the fluidized bed reactor, under the reaction conditions and in the presence of the catalyst composition, at a rate sufficient to maintain a bed of solid particles in a suspended condition. A stream containing the unreacted monomer is continuously removed from the reactor, compressed, cooled and recycled to the reactor. The product is removed from the reactor and the replacement monomer is added to the recycle stream. As desired, for the temperature control of the system, any inert gas for the catalyst composition and the reagents may be present in the gas stream. In addition, a fluidization aid such as carbon black, silica, clay or talc can be used, as disclosed in US Patent Number 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 essentially in the absence of pollutants or poisons for the catalyst. The organometallic compounds can be used as scavengers for the poisons or contaminants in order to increase the activity of the catalyst. Examples of scavengers are metal alkyls, preferably aluminum alkyls, triisobutylaluminum. Conventional adjuvants may be included in the process, as long as they do not interfere with the operation of the catalyst composition to form the desired polyolefin. Hydrogen can be used as a chain transfer agent in the process, in amounts up to about 10 moles of hydrogen per mole of the total monomer feed. The olefin polymers that can be produced according to the invention include, but are not limited to ethylene homopolymers, linear or branched higher alpha-olefin homopolymers containing from 3 to about 20 carbon atoms, and ethylene interpolymers and these alpha Higher olefins, with densities ranging from about 0.86 to about 0.95. 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. The olefin polymers according to the 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, carbon atoms. 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 styrene and substituted styrenes, and polar vinyl monomers such as acrylonitrile, maleic acid esters, vinyl acetate, acrylate esters, methacrylate esters, vinyltrialkyl silanes and the like can be polymerized according to with the invention likewise. Specific defined polymers that can be produced according to the invention include, for example, polyethylene, polypropylene, ethylene / propylene rubbers (EPR), ethylene / propylene / diene terpolymers (EPDM), polybutadiene, polyisoprene and the like. The following examples further illustrate the invention.

EXAMPLES Glossary The activity is measured in kilograms of polyethylene / millimoles of Zr.hr.ethylene at a pressure of 7.03 kilograms per square centimeter. 12 is the melt index (dg / minute), which is measured using Method D-1238 Condition E of the American Society for the Testing of Materials at a temperature of 190 ° C. 121 is the flow rate (dg / minute), which is measured using Method D-1238 Condition F of the American Society for the Testing of Materials. MFR is the Fusion Flow Ratio, 121/12. MMAO is a solution of methylaluminoxane modified in heptane, about 1.9 molar in aluminum, which can be obtained commercially from Akzo Chemicals, Inc. '(type 3). BBF is the Butyl Branching Frequency, the number of butyl branches per 1000 carbon atoms of the main chain. Mw is the Average Molecular Weight in Weight, as determined by gel permeation chromatography using crosslinked polystyrene columns, and a pore size sequence: 1 column of less than 1000 angstrom units, 3 columns of 5 x 10 ^ angstrom units mixed a 1, 2, 4-trichlorobenzene solvent at 140 ° C with refractive index detection. PDI is the Polydispersity Index, equivalent to the Molecular Weight Distribution (Mw / Mn).

/ "- Examples 1 to 10 The catalyst compositions comprising the reaction products of the cyanomyl-cyclopentadienyl dianion, the modified methylaluminoxane, and various zirconium compounds were prepared and used to copolymerize ethylene and 1-hexene in the following manner. Isolation Preparation of the Ilan-10 Cyclopentadienyl Cyan Dianion A solution of cinnamyl bromide (102 mmol) in 95 milliliters of water was cooled to 0 ° C.

THF An equi olar amount of sodium cyclopentadiene (2.0 M in THF) was added slowly to the cooled solution under an argon atmosphere. After the addition, the reaction to the cyclopentadiene of cinnamyl was completed according to the GC analysis. The reaction mixture was concentrated to a residue in vacuo, yielding a brownish oil. The cinnamyl cyclopentadiene residue (102 mmol) was then placed under an argon atmosphere, diluted with 100 milliliters of ether and stirred. The mixture was then vacuum filtered in an oven-dried double end frit (to remove the sodium bromide) and the solids were washed with ether. The filtrate was placed under an argon atmosphere and cooled to -78 ° C. To the solution 0.6 equivalent of n-butyl lithium (3.089 M in hexanes, 19.4 milliliters, 60 mmol) was added. The mixture was stirred overnight. The solid monoanion product was filtered under vacuum using a dry double-ended frit and washed with dry ether. The solids were dried under vacuum and stored in a dry box. A solution of the resultant lithium cinnamoyl cyclopentadienide in THF was placed under an argon atmosphere. Thereto was added 3 equivalents of methyl lithium (in ether) at room temperature. The resulting solution was stirred for two hours at room temperature and then concentrated to a residue under an intense vacuum. To the residue was added dry ether, and the result was filtered to yield the dianion as the di-lithium salt. Preparation of the Catalyst Compositions A series of catalyst compositions were then produced by reacting the cyanomyl cyclopentadiene dianion (such as the dilithium salt) prepared above with zirconium tetrachloride, cyclopentadienyl zirconium trichloride (CpZrCl3), or pentamethylcyclopentadienyl zirconium trichloride ( Cp * ZrCl3), and MMAO, as follows.

Equimolar amounts of the cyclopentadienide of dilithium cinnamyl and zirconium compound were charged to a flask in a dry box. To this mixture with stirring about 1 milliliter of ether was added, either cooled or at room temperature, as indicated in Table 1. The resulting mixture was concentrated as a residue under vacuum. In the case of Examples 6 and 10, the flask was first removed from the box, cooled in a low temperature bath (-78 ° C) and treated with stirring with 10 milliliters of ether. The mixture was then allowed to warm slowly to room temperature overnight and then concentrated to a residue in vacuo. For each Example, the resulting dianion / zirconium complex was then dissolved in dry toluene. In Examples 4, 5, 9 and 10, 500 equivalents of MMAO were loaded into a small glass bottle dried in the oven under stirring, and the toluene solution of the dianion / zirconium complex was added thereto. In Examples 1, 2, 3, 7 and 8, 10 milliliters of toluene were first charged into the small vial before the introduction of MMAO. In Example 6, the dianion / zirconium complex was charged to the small bottle, 10 milliliters of toluene were added with stirring and then 500 equivalents of MMAO were added to the small bottle. The catalyst compositions having molar ratios of MMAO / zirconium of 1000 were formed in each case. Polymerization Polymerizations were carried out using these catalyst compositions in the slurry phase in a one liter capacity stainless steel autoclave equipped with a mechanical stirrer. The reactions were carried out at 75 ° C under a pressure of 5.94 kilograms per absolute square centimeter of ethylene, with 43 milliliters of 1-hexene and 600 milliliters of a hexane solvent that was also present in the reactor. The reaction times were each 30 minutes. The results are shown in Table 1.

Examples 11 to 16 Additional catalyst compositions comprising the reaction products of cinnamyl cyclopentadienyl dianion, modified methylaluminoxane, and various zirconium compounds were prepared and used to copolymerize ethylene and 1-hexene as described above in Examples 1 to 10. The results are shown in Table 2.

Examples 17 to 24 Additional catalyst compositions comprising cinnamyl cyclopentadienyl dianion reaction products, the modified methylaluminoxane, and various zirconium compounds were prepared and used to copolymerize ethylene and 1-hexene in the following manner. Preparation of the Catalyst Compositions. For each of Examples 17 to 24, the dianion of cinnamyl cyclopentadienyl (0.0452 millimole) prepared in Examples 1 to 10 was combined with 1.5 milliliters of MMAO at room temperature and stirred for four days. Approximately 5 micromoles of the resulting dianion / MMAO complex was added to a small oven-dried flask containing approximately 5 micromoles of the zirconium compound shown in Table 3 (except in the case of Examples 22 and 23, where they were only used about 2.5 micromoles of the zirconium compound). In the case of Examples 17, 18, 20, 21 and 22, toluene was also added to the small bottle. The resulting mixture was stirred for 20 to 55 minutes to form the catalyst composition. Polymerization For each of Examples 17 to 24, the catalyst composition was introduced into the autoclave reactor with 2 additional millimoles of MMAO (except in the case of Examples 22 and 23, where 1 millimole and 0.33 millimole were additionally used, respectively). Referring to Table 3 below, the polymerizations using these catalyst compositions were carried out as in Examples 1 to 10.

Example 25 A catalyst composition comprising the dianion reaction product of 1-cinnamyldendenyl, modified methylaluminoxane and ZrCl was prepared and used to copolymerize ethylene and 1-hexene in the following manner. Preparation of 1-Cinamylindenyl Dianion A 98 percent solution of indene (364 mmol) in 300 milliliters of THF was cooled to -78 ° C under an argon atmosphere. An equi olar amount of n-butyl lithium was added to the solution. The resulting mixture was allowed to warm to room temperature. It was then loaded in an equimolar amount of 95 percent cinnamyl chloride (58.45 grams) in 100 milliliters of THF at -30 ° C. The mixture was then allowed to warm to room temperature and reacted for one hour to form cinnamyl indene. The cinnamyl indene was concentrated to a residue in an intense vacuum and then washed and concentrated twice with 100 milliliters of hexane. The residue was washed a third time with 100 milliliters of hot hexane and filtered while still hot. The filtered material was again concentrated to a residue under vacuum. The cinnamyl indene filtrate melted at a temperature of 55 ° C to 69 ° C. The recovery yield was 62 percent. A solution of cinnamyl indene (224 mmol) in 300 milliliters of ether was placed under an argon atmosphere, and cooled to 0 ° C. To the solution 0.89 equivalent (200 millimoles) of n-butyllithium was added after which the solution was allowed to warm to room temperature. Hexane was added to the mixture and concentrated almost to a residue. More hexane was added to the mixture and allowed to stir overnight. The product, the cinnamyl indenide of the solid lithium was then filtered, washed and dried under vacuum. The recovery yield was 44 grams. To generate the dianion, a solution of lithium cinnamyl indenide (11 mmol) in 50.0 milliliters of THF was placed under an argon atmosphere and cooled to 0 ° C. 1.0 equivalent of butyl lithium was fed thereto, followed by stirring at room temperature for one hour.

Preparation of the Catalyst Composition The dianion solution was then transferred by a double ended needle with a solution containing 2.0 equivalents of zirconium tetrachloride (5.0 grams, 21.4 millimoles) in 50 milliliters of THF at -30 ° C and stirred for three days. The reaction mixture was concentrated to a residue in vacuo and combined with 500 equivalents of MMAO in a small glass bottle dried in the oven, with stirring. Polymerization The copolymerization of ethylene and 1-hexene using the catalyst composition containing 1-cinnamyldendenyl dianion was carried out as in Examples 1 to 10 above. The activity of the catalyst was 6,700. A copolymer having a butyl branching frequency of 11.9, a 12 of 0.513 and a melt flow ratio of 26.3 was obtained.

Examples 26 to 29 Additional catalyst compositions comprising the reaction products of cinnamyl cyclopentadienyl dianion, boron compounds, modified methylaluminoxane and various zirconium compounds were prepared and used to copolymerize 1-hexene in the following manner. Preparation of the Catalyst Compositions In each of Examples 26 to 29, a solution of cinnamyl cyclopentadienide of dilithium as prepared in Examples 1 to 10 above (0.28 millimole) in THF was placed under an argon atmosphere and cooled to 0 ° C. An equimolar amount of the boron compound was added to the solution as indicated in Table 4. The resulting mixture was stirred for 30 minutes at 0 ° C. before heating to room temperature. It was then charged to a solution of the zirconium compounds as shown in Table 4 in THF, at room temperature. The mixture was stirred overnight and then concentrated to a residue under vacuum. For each of Examples 26 to 29, the resulting dianion / boron / zirconium complex was then dissolved in dry toluene. In Example 28, 500 equivalents of MMAO were charged to a small glass bottle dried in the oven, under stirring, and a solution of toluene from the dianion / boron / zirconium complex was added thereto. In Examples 26 and 27, 10 milliliters of toluene was first charged to the small vial before the introduction of MMAO. In Example 29, the dianion / boron / zirconium complex was charged to the small vial, 10 milliliters of toluene were added under stirring then 500 equivalents of MMAO were added to the small vial. Polymerization With reference to Table 4 presented below, polymerizations were carried out using these catalyst compositions as in Examples 1 to 10 above.

Example 30 A catalyst composition comprising the reaction product of the cymelan-cyclopentadienium dianion transmetalated first with chlorotrimethyl silane, ZrCl 4 and the modified methylaluminoxane was prepared and used to copolymerize ethylene and 1-hexene in the following manner. A cyclopentadiene solution of dilithium cinnamyl as prepared in the above Examples 1 to 10 (1.09 mmol) in about 1 milliliter of THF was placed under an argon atmosphere. 2.5 equivalents of chlorotrimethylsilane were charged thereto followed by stirring for 1 hour. The mixture was concentrated to a residue in vacuo. The residue was washed with toluene twice and filtered under vacuum to remove the lithium chloride.

The filtrate was then charged in an equimolar amount of zirconium tetrachloride at room temperature and stirred. The mixture was concentrated to a residue in vacuo and combined with 500 equivalents of MMAO in a small glass bottle dried in the oven, with stirring. Polymerization The copolymerization of ethylene and 1-hexene using this catalyst composition as in Examples 1 to 10. The activity of the catalyst was 7.211. A copolymer having a 12 of 0.176 was obtained, and 121 of 3.35 and a melt flow ratio of 22.05.

Example 31 A catalyst composition comprising the reaction product of the first transmetalated cinnamyl cyclopentadienyl dianion with trimethyltin chloride, ZrCl 4 and modified methylaluminoxane was prepared and used to copolymerize ethylene and 1-hexene in the following manner. A solution of cyclopentadienido cinnamyl dilithium as prepared in the previous Examples 1 to 10 (0.2 millimole) in 5.0 milliliters of THF was placed under an argon atmosphere and cooled to -78 ° C. To this was charged 1.0 equivalent of trimethyltin chloride and the resulting mixture was allowed to warm to room temperature. The mixture was concentrated to a residue in vacuo. To form the catalyst composition, the resulting product was then charged to an equimolar amount of zirconium tetrachloride at room temperature and stirred overnight. It was concentrated to a residue in vacuo and combined with 500 equivalents of MMAO in a small glass bottle dried in the oven, with stirring. Polymerization The copolymerization of ethylene and 1-hexene was carried out using this catalyst composition as examples 1 to 10. The activity of the catalyst was 20,888. A copolymer was obtained which obtained a 12 of 0.294, a 121 of 5.2, and a melt flow ratio of 17.6.

Example 32 A catalyst composition comprising the reaction product of the first transmetally cyanamyl cyclopentadienyl dianion with trimethylaluminum, ZrCl 4 and modified methylaluminoxane was prepared and used to copolymerize ethylene and 1-hexene in the following manner: A cyclopentadiene solution of cinnamyl dilithium as were prepared in Examples 1 to 10 above (0.124 millimole) in 5.0 milliliters of THF was placed under an argon atmosphere and cooled to -30 ° C. 2.0 equivalents of trimethylaluminum were charged to it.

Then it was warmed to room temperature and stirred for four hours. The mixture was concentrated to a residue under an intense vacuum. The resulting product was then charged in 2 equivalents of zirconium tetrachloride at room temperature, and stirred for three days. It was concentrated to a residue under vacuum and combined with 500 equivalents of MMAO in a small glass bottle dried in the oven, with stirring. Polymerization The copolymerization of ethylene and 1-hexene using this catalyst composition as in Examples 1 to 10. The activity of the catalyst was 12,205. A copolymer having 12 of 0.166 was obtained, and a 121 of 3.08, and a melt flow ratio of 18.5, and a BBF of 9.39.

EXAMPLE 33 A catalyst composition comprising the reaction product of cyanamyl cyclopentadienyl dianion transmetalated first with magnesium bromide, ZrCl 4 and modified methylaluminoxane was prepared and used to copolymerize ethylene and 1-hexene in the following manner. An equimolar mixture (0.22 millimole) of cyclopentadienido of cinnamyl dilithium as prepared in Examples 1 to 10 above and magnesium bromide was stirred at room temperature in a dry box. To the solids was added about 1 milliliter of cooled THF-d8 (-30 ° C). The solution was stirred for two hours. The catalyst composition was prepared by first charging the resulting product in an equimolar solution in zirconium tetrabromide in about 1 milliliter of THF-d8, at room temperature. The mixture was stirred overnight. The solvent layer was concentrated to a residue under vacuum. To the residue was added 10 milliliters of toluene under stirring, followed by 500 equivalents of MMAO. Polymerization The copolymerization of ethylene and 1-hexene was carried out using this catalyst composition as in Examples 1 to 10. The activity of the catalyst was from FIG. 1 Example Ether, ° C Compound Zr Molar ratio of Dianion / Zr 1 THF, RT ZrCl 2.0 2 THF, -30 ° ZrCl4 1.0 3 THF, RT ZrCl4 1.0 4 THF, -30 ° ZrCl4 0.5 5 THF, -30 ° ZrCl4 0.5 6 Et20, -78 ° CpZrCl3 1.0 7 THF, RT CpZrCl3 1.0 8 THF, RT Cp * ZrCl3 1.0 9 THF, -30 ° Cp * ZrCl3 1.0 10 Et20, -78 ° Cp * ZrCl3 1.0 TABLE 1 (continued) Example Activity BBF MW / PDI 1 38.325 13.9 208K / 3.955 2 67.577 10.4 187K / 3,264 3 20,013 10.3 242K / 2.91 4 13,998 10.9 5 15,402 8.8 6 34,067 13.0 143K / 3.78 7 63.823 10.5 165K / 3.44 8 55.114 6.6 374K / 4.97 9 44, 690 5.3 338K / 4.49 10 61.025 3.6 317k / 3.31 TABLE 2 Example Compound Activity 12 121 MFR of Zr 11 ZrCl 20,013 .085 2.29 27.05 12l ZrCl 67,577 .26 8.04 30.91 132 CpZrCl3 27,420,179 3.62 20.23 14 CpZrCl3 63, 823.331 11.82 35.71 153 ZrCl 38,325,189 7.99 42.23 16 Cp * ZrCl3 55, 014 < .l .559 NA 1 dianion contact and the zirconium compound at -30 ° C. 2 the molar ratio of dianion / Zr was 2. 3 the molar ratio of dianion / Zr was 0.5 TABLE 3 Example Micromole Compound of the Molar Ratio of Zr Compound of Total Zr of Al / Zr 17 ZrC14 5 500 18 (PhCH2) 4Zr 5 500 19 Z (NEt2) 4 5 500 20 CpZrC13 5 500 21 Cp * ZrCl 5 500 22 Cp * ZrCl3 2.5 500 23 Cp * ZrCl3 2.5 200 241 ZrCl4 5 500 TABLE 3 (continued) Example Activity BBF Mw / PDI 17 9,320 8.5 174K / 2,998 18 3,447 19 3,396 20 25,530 7.2 132K / 3,307 21 25,059 22 61,421 6.3 240K / 3,090 23 8,208 241 31, 616 12.4 1 was digested using 20 equivalents of MMAO.

TABLE 4 Example Compounds Activity 12 121 MFR of B and Zr 26 BPh3, ZrC14 18,704 < .l .899 NA 27 BEt3, ZrC14 9,921 NA NA NA 28 BEt3, ZrCl41 53.289 .152 3.35 22.05 29 Ph2BBr1, 14,337 .202 3.75 18.54 ZrBr41 iQ.d micromoles.

Claims (17)

1. - - CLAIMS: A catalyst precursor of the formula; wherein: L is a cycloalkadienyl coordinating group; W, X, Y and Z are independently hydrogen, a hydrocarbyl group containing 1 to 20 carbon atoms, or a silyl group, and can be connected to L through a connection or bridge group comprising at least two atoms of the VAT Group; with the proviso that one of X, Y and Z is a negative charge stabilizing group selected from the group consisting of trialkyl groups of the IVA Group, aryl groups, heteroaromatic groups, ethylenically unsaturated hydrocarbon groups, hydrocarbon groups acetylenically unsaturated, ketonic groups and aromatic organometallic residues.
2. 2. A catalyst precursor of the formula:
3. 3. A catalyst precursor of the formula:
4. 4. A catalyst composition comprising the reaction product of: 1) a catalyst precursor of the formula: wherein L is a cycloalkadienyl coordinating group; W, X, Y and Z are independently hydrogen, a hydrocarbyl group containing from 1 to 20 atoms of 12 - carbon, or a silyl group, and can be connected to L through a bridge or connection group comprising at least two atoms of the VAT Group: with the proviso that one of X, Y and Z is a stabilization group of negative charge which is selected from the group consisting of trialkyl groups of the IVA Group, aryl groups, heteroaromatic groups, ethylenically unsaturated hydrocarbon groups, hydrocarbon, acetylenically unsaturated groups, ketonic groups and aromatic organometallic residues; 2) a compound comprising a metal of Groups I I IB to VIII or the Lantanide series; and 3) an activation cocatalyst.
5. 5. The catalyst composition according to claim 4, wherein the catalyst precursor is:
6. 6. The catalyst composition according to claim 4, wherein the catalyst precursor is: -
7. 7. The catalyst composition according to claim 4, wherein the compound comprising a metal of Groups IIIB to VIII or the Lantanide series is a zirconium compound.
8. The catalyst composition according to claim 4, wherein the activating co-catalyst is selected from the group consisting of methylaluminoxane, modified methylaluminoxane, boron alkyls, and mixtures thereof.
9. 9. A process for preparing an olefin polymer, comprising contacting at least one olefin monomer under polymerization conditions, with a catalyst composition comprising the reaction product of: 1) a catalyst precursor of the formula: wherein: L is a cycloalkadienyl coordinating group; W, X, Y and Z are independently hydrogen, a hydrocarbyl group containing 1 to 20 carbon atoms or a silyl group, and can be connected to L through a bridge or connection group comprising at least two atoms of the VAT Group; with the proviso that one of X, Y and Z is a negative charge stabilizing group selected from the group consisting of trialkyl groups of the IVA Group, aryl groups, heteroaromatic groups, ethylenically unsaturated hydrocarbon groups,. acetylenically unsaturated hydrocarbon groups, ketone groups, and aromatic organometallic residues; 2) a compound comprising a metal of the Groups IIIB to VIII or a series of Latanuro; and 3) an activation co-catalyst.
10. 10. The process according to claim 9, wherein the catalyst precursor has the formula: 2-
11. 11. The process according to claim 9, wherein the catalyst precursor has the formula:
12. 12. The process according to claim 9, wherein the compound comprising a metal of Groups IIIB to VIII or of the Lantanide series is a zirconium compound.
13. 13. The process according to claim 9, wherein the activating cocatalyst is selected from the group consisting of methylaluminoxane, modified methylaluminoxane, boron alkyls and mixtures thereof.
14. 14. The process according to claim 9, which is carried out in the gas phase.
15. 15. The process according to claim 9, wherein the olefin monomer is selected from the group consisting of ethylene, higher alpha-defines, dienes, and mixtures thereof.
16. 16. An olefin polymer produced by the process of claim 9.
17. 17. An ethylene polymer produced by the process of claim 9. - SUMMARY OF THE INVENTION A catalyst precursor of the formula wherein: L is a cycloalkadienyl coordinating group; W, X, Y and Z are independently hydrogen, a hydrocarbyl group containing from 1 to 20 carbon atoms, or a silyl group, and can be connected to L through a bridge or connection group comprising at least minus two atoms of the VAT Group; with the proviso that one of X, Y and Z is a negative charge stabilizing group selected from the group consisting of trialkyl groups of the IVA Group, aryl groups, heteroaromatic groups, ethylenically unsaturated hydrocarbon groups, groups of acetylenically unsaturated hydrocarbons, ketone groups, and aromatic organometallic residues. When combined with a compound comprising a metal of Groups IIIB to VIII or of the Lantanide series of the Periodic Table of elements and an activating cocatalyst, the catalyst precursor is useful for the polymerization of defines.