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  Catalyst compounds, catalyst systems thereof and their use in a polymerization processUSPTO Application #: 20060014632Title: Catalyst compounds, catalyst systems thereof and their use in a polymerization process Abstract: The present invention relates to a cyclic germanium bridged bulky ligand metallocene-type catalyst compound, a catalyst system thereof, and to its use in a process for polymerizing olefin(s) to produce enhanced processability polymers. (end of abstract) Agent: Exxonmobile Chemical Company - Baytown, TX, US Inventors: Donna J. Crowther, Phillip T. Matsunaga USPTO Applicaton #: 20060014632 - Class: 502117000 (USPTO) Related Patent Categories: Catalyst, Solid Sorbent, Or Support Therefor: Product Or Process Of Making, Catalyst Or Precursor Therefor, Plural Component System Comprising A - Group I To Iv Metal Hydride Or Organometallic Compound - And B - Group Iv To Viii Metal, Lanthanide Or Actinde Compound - (i.e., Alkali Metal, Ag, Au, Cu, Alkaline Earth Metal, Be, Mg, Zn, Cd, Hg, Sc, Y, Al, Ga, In, Tl, Ti, Zn, Hf, Ge, Sn Or Pb Hydride Or Organometallic Compound And Ti, Zr, Hf, Ge, Sn, Pb, V, Nb, Ta, As, Sb, Bi, Cr, Mo, W, Po, Mn, Tc, Re, Iron Group, Platinum Group, Atomic Number 57 To 71 Inclusive Or Atomic Number 89 Or Higher Compound), Component A Metal Is Group Ia, Iia Or Iiia And Component B Metal Is Group Ivb To Viib Or Viii (i.e., Alkali Metal, Alkaline Earth Metal, Be, Mg, Al, Ga, In Or Tl And Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Iron Group Or Platinum Group) (e.g., Ziegler Catalyst, Etc.), Component B Metal Is Other Than Titanium Or Vanadium The Patent Description & Claims data below is from USPTO Patent Application 20060014632. Brief Patent Description - Full Patent Description - Patent Application Claims
CROSS-REFERENCE TO RELATED APPLICATION [0001] The present application is a divisional of and claims priority to U.S. Ser. No. 09/451,805 filed Dec. 01, 1999, herein incorporated by reference. FIELD OF THE INVENTION [0002] The present invention relates to catalyst compounds, catalyst systems incorporating these compounds and to their use in a process for polymerizing olefin(s). More particularly the catalyst compounds are cyclic germanium bridged bulky ligand metallocene-type catalyst compounds and catalyst system thereof. The invention is also directed to the use of this catalyst system in the polymerization of olefin(s) to produce polymers that have a combination of properties that make them easier to process into various articles of manufacture. BACKGROUND OF THE INVENTION [0003] Processability is the ability to economically process and shape a polymer uniformly. Processability involves such elements as how easily the polymer flows, melt strength, and whether or not the extrudate is distortion free. Typical bulky ligand metallocene-type catalyzed polyethylenes (mPE) are somewhat more difficult to process than low density polyethylenes (LDPE) made in a high pressure polymerization process. Generally, mPE's require more motor power and produce higher extruder pressures to match the extrusion rate of LDPE's. This is typically evident where a polymer exhibits a low melt index ratio. Typical mPE's also have lower melt strength which, for example, adversely affects bubble stability during blown film extrusion, and they are prone to melt fracture at commercial shear rates. On the other hand, however, mPE's exhibit superior physical properties as compared to LDPE's. [0004] It is now common practice in the industry to add various levels of an LDPE to an mPE to increase melt strength, to increase shear sensitivity, i.e., to increase flow at commercial shear rates; and to reduce the tendency to melt fracture. However, these blends generally have poor mechanical properties as compared with neat mPE. [0005] Traditionally, metallocene catalysts produce polymers having a narrow molecular weight distribution. Narrow molecular weight distribution polymers tend to be more difficult to process. The broader the polymer molecular weight distribution the easier the polymer is to process. A technique to improve the processability of mPE's is to broaden the products' molecular weight distribution (MWD) by blending two or more mPE's with significantly different molecular weights, or by changing to a polymerization catalyst or mixture of catalysts that produce broad MWD polymers. [0006] In the art specific bulky ligand metallocene-type catalyst compound characteristics have been shown to produce polymers that are easier to process. For example, U.S. Pat. No. 5,281,679 discusses bulky ligand metallocene-type catalyst compounds where the bulky ligand is substituted with a substituent having a secondary or tertiary carbon atom for the producing of broader molecular weight distribution polymers. U.S. Pat. No. 5,470,811 describes the use of a mixture of bulky ligand metallocene-type catalysts for producing easy processing polymers. Also, U.S. Pat. No. 5,798,427 addresses the production of polymers having enhanced processability using a bulky ligand metallocene-type catalyst compound where the bulky ligands are specifically substituted indenyl ligands. [0007] A need exists in the industry for catalyst compounds and catalyst systems that in a polymerization process produce polymers having a combination of properties for use in various end-use applications. SUMMARY OF THE INVENTION [0008] This invention relates to a catalyst compound, a catalysts system thereof and to their use in a polymerization process. The catalyst compound is a cyclic bridge, preferably a cyclic germanium bridged bulky ligand metallocene-type compound. In one embodiment, this cyclic germanium bridged bulky ligand metallocene-type catalyst compound is activated or combined with an activator to form a catalyst system. In another embodiment, the invention is directed to a polymerization process utilizing this catalyst system. The preferred polymerization processes are a gas phase or a slurry phase process, most preferably a gas phase process, especially where the catalyst system is supported. [0009] In one preferred embodiment, the invention provides for a process for polymerizing ethylene alone or in combination with one or more other olefin(s) in the presence of a catalyst system of a cyclic germanium bridged bulky ligand metallocene-type catalyst compound, preferably a cyclic germanium bridged bulky ligand metallocene-type catalyst compound and an activator. DETAILED DESCRIPTION OF THE INVENTION Introduction [0010] The invention relates to a catalyst compound, a catalyst system thereof and to it use in a polymerization process for producing polymers having a balance of properties needed for processing the polymers into various end-use applications, such as film. It has been surprisingly discovered that using a cyclic germanium bridged bulky ligand metallocene-type catalyst of the invention, particularly in a slurry or gas phase polymerization process, polymers having a high Melt Index Ratio (MIR) and high Melt Strength (MS) are produced. It was previously found that cyclic bridged bulky ligand metallocene-type catalyst system produce polymers having a high MIR, however, the melt strength needed improvement. For example, U.S. patent application Ser. No. 09/306,142 filed May 6, 1999 illustrates a cyclic silicon bridged bulky ligand metallocene-type catalyst system for producing polymers having a high MIR, which is fully incorporated herein by reference. Also, U.S. patent application Ser. No. 09/222,973 filed Dec. 30, 1998 discusses a germanium bridged bulky ligand metallocene-type catalyst system in a polymerization process for producing polymers having better melt strength, which is fully incorporated herein by reference. It is highly unusual in the art that a combination of catalyst compound structures provide the benefits to a particular polymer product that each bring separately. Thus, it was surprising and totally unexpected that the cyclic germanium bridged bulky ligand metallocene-type catalyst compounds would produce in a polymerization process a polymer having both a high MIR and MS. Cyclic Ge Bridged Bulky Ligand Metallocene-Type Catalyst Compounds [0011] Generally, bulky ligand metallocene-type catalyst compounds include half and full sandwich compounds having one or more bulky ligands bonded to at least one metal atom. Typical bulky ligand metallocene-type compounds are generally described as containing one or more bulky ligand(s) and one or more leaving group(s) bonded to at least one metal atom. In one preferred embodiment, at least one bulky ligand is .eta.-bonded to a metal atom, most preferably .eta..sup.5-bonded to the metal atom. [0012] For purposes of this patent specification and appended claims a cyclic germanium bridge is one in which the germanium element(s) serves as the bridging element(s) between at least two bulky ligands and "cyclic" refers to the atoms forming a ring or ring system containing the germanium element(s). [0013] The bulky ligands are generally represented by one or more open, acyclic, or fused ring(s) or ring system(s) or a combination thereof. These bulky ligands, preferably ring(s) or ring system(s) are typically composed of atoms selected from Groups 13 to 16 atoms of the Periodic Table of Elements, preferably the atoms are selected from the group consisting of carbon, nitrogen, oxygen, silicon, sulfur, phosphorous, boron and aluminum or a combination thereof. Most preferably the ring(s) or ring system(s) are composed of carbon atoms such as but not limited to those cyclopentadienyl ligands or cyclopentadienyl-type ligand structures or other similar functioning ligand structure such as a pentadiene, a cyclooctatetraendiyl or an imide ligand. The metal atom is preferably selected from Groups 3 through 15 and the lanthanide or actinide series of the Periodic Table of Elements. Preferably the metal is a transition metal from Groups 4 through 12, more preferably 4, 5 and 6, and most preferably the metal is from Group 4. [0014] In one embodiment, cyclic germanium bridged bulky ligand metallocene-type catalyst compounds are represented by the formula: L.sup.A(AGe)L.sup.BMQ.sub.n (I) where M is a metal atom from the Periodic Table of the Elements and may be a Group 3 to 12 metal or from the lanthanide or actinide series of the Periodic Table of Elements, preferably M is a Group 4, 5 or 6 transition metal, more preferably M is a Group 4 transition metal, even more preferably M is zirconium, hafnium or titanium. The bulky ligands, L.sup.A and L.sup.B, are open, acyclic, or fused ring(s) or ring system(s) such as unsubstituted or substituted, cyclopentadienyl ligands or cyclopentadienyl-type ligands, heteroatom substituted and/or heteroatom containing cyclopentadienyl-type ligands. Non-limiting examples of bulky ligands include cyclopentadienyl ligands, indenyl ligands, benzindenyl ligands, fluorenyl ligands, octahydrofluorenyl ligands, cyclooctatetraendiyl ligands, azenyl ligands, azulene ligands, pentalene ligands, phosphoyl ligands, pyrrolyl ligands, pyrozolyl ligands, carbazolyl ligands, borabenzene ligands and the like, including hydrogenated versions thereof, for example tetrahydroindenyl ligands. In one embodiment, L.sup.A and L.sup.B may be any other ligand structure capable of .eta.-bonding to M, preferably .eta..sup.3-bonding to M, and most preferably .eta..sup.5-bonding to M. In another embodiment, L.sup.A and L.sup.B may comprise one or more heteroatoms, for example, nitrogen, silicon, boron, germanium, sulfur and phosphorous, in combination with carbon atoms to form an open, acyclic, or preferably a fused, ring or ring system, for example, a heterocyclopentadienyl ancillary ligand. Other L.sup.A and L.sup.B bulky ligands include but are not limited to bulky amides, phosphides, alkoxides, aryloxides, imides, carbolides, borollides, porphyrins, phthalocyanines, corrins and other polyazomacrocycles. Independently, each L.sup.A and L.sup.B may be the same or different type of bulky ligand that is bonded to M. [0015] Independently, each L.sup.A and L.sup.B may be unsubstituted or substituted with a combination of substituent groups R. Non-limiting examples of substituent groups R include one or more from the group selected from hydrogen, or linear, branched alkyl radicals, or alkenyl radicals, alkynyl radicals, cycloalkyl radicals or aryl radicals, acyl radicals, aroyl radicals, alkoxy radicals, aryloxy radicals, alkylthio radicals, dialkylamino radicals, alkoxycarbonyl radicals, aryloxycarbonyl radicals, carbomoyl radicals, alky- or dialkyl-carbamoyl radicals, acyloxy radicals, acylamino radicals, aroylamino radicals, straight, branched or cyclic, alkylene radicals, or combination thereof. Non-limiting examples of alkyl substituents R include methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, benzyl or phenyl groups and the like, including all their isomers, for example tertiary butyl, isopropyl, and the like. Other hydrocarbyl radicals include fluoromethyl, fluoroethyl, difluoroethyl, iodopropyl, bromohexyl, chlorobenzyl and hydrocarbyl substituted organometalloid radicals including trimethylsilyl, trimethylgermyl, methyldiethylsilyl and the like; and halocarbyl-substituted organometalloid radicals including tris(trifluoromethyl)-silyl, methyl-bis(difluoromethyl)silyl, bromomethyldimethylgermyl and the like; and disubstitiuted boron radicals including dimethylboron for example; and disubstituted pnictogen radicals including dimethylamine, dimethylphosphine, diphenylamine, methylphenylphosphine, chalcogen radicals including methoxy, ethoxy, propoxy, phenoxy, methylsulfide and ethylsulfide. Non-hydrogen substituents R include the atoms carbon, silicon, boron, aluminum, nitrogen, phosphorous, oxygen, tin, sulfur, germanium and the like, including olefins such as but not limited to olefinically unsaturated substituents including vinyl-terminated ligands, for example but-3-enyl, prop-2-enyl, hex-5-enyl and the like. Also, at least two R groups, preferably two adjacent R groups, are joined to form a ring structure having from 3 to 30 atoms selected from carbon, nitrogen, oxygen, phosphorous, silicon, germanium, aluminum, boron or a combination thereof. Also, a substituent group R such as 1-butanyl may form a carbon sigma bond to the metal M. [0016] Other ligands may be bonded to the metal M, such as at least one leaving group Q. For the purposes of this patent specification and appended claims the term "leaving group" is any ligand that can be abstracted from a bulky ligand metallocene-type catalyst compound to form a bulky ligand metallocene-type catalyst cation capable of polymerizing one or more olefin(s). In one embodiment, Q is a monoanionic labile ligand having a sigma-bond to M. Depending on the oxidation state of the metal, the value for n is 0, 1 or 2 such that formula (I) above represents a neutral bulky ligand metallocene-type catalyst compound. Non-limiting examples of Q ligands include weak bases such as amines, phosphines, ethers, carboxylates, dienes, hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides or halogens and the like or a combination thereof. In another embodiment, two or more Q's form a part of a fused ring or ring system. Other examples of Q ligands include those substituents for R as described above and including cyclobutyl, cyclohexyl, heptyl, tolyl, trifluromethyl, tetramethylene, pentamethylene, methylidene, methoxy, ethoxy, propoxy, phenoxy, bis(N-methylanilide), dimethylamide, dimethylphosphide radicals and the like. [0017] A is cyclic ring or ring system that includes the Ge atom and preferably contains 3 or greater non-hydrogen atoms, preferably greater than 4 carbon atoms, to form a ring or ring system about the Ge atom. The atoms forming the ring or ring system of A may be substituted with substituents as defined above for R. Non-limiting examples of cyclic bridging groups A include cyclo-tri or tetra-alkylene germyl, for example, cyclotrimethylenegermyl group or cyclotetramethylenegermyl group. Continue reading... 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