Title of Invention

HIGH TEMPERATURE SOLUTION POLYMERIZATION PROCESS

Abstract Abstract HIGH TEMPERATURE SOLUTION POLYMERIZATION PROCESS A catalyst composition comprising one or more metal complexes of a multifunctional Lewis base ligand comprising a bulky, planar, aromatic- or substituted aromatic-group and polymerization processes employing the same, especially continuous, solution polymerization of one or more a- olefins at high catalyst efficiencies are disclosed.
Full Text

HIGH TEMPERATURE SOLUTION POLYMERIZATION PROCESS
Cross Reference Statement
This application claims the benefit of U.S. Provisional Application 60/801,182, filed May 17,2006,
Background of the Invention
Higher temperature solution processes for olefin polymerization are highly desirable due to the increased throughput, decreased energy necessary for devolatization and decreased fouling that these higher temperatures afford. Although Ziegler-Natta catalyst systems can be run at high temperatures commercially, these catalysts suffer from poor efficiency and poor comonomer incorporation at elevated temperatures. In addition, polymers produced from Ziegler-Natta catalysts at elevated temperatures have broadened molecular weight distributions, thereby limiting their suitability for use in many applications. Conventional Ziegler-Natta catalysts are typically composed of many types of catalytic species, each having different metal oxidation states and different coordination environments with ligands. Examples of such heterogeneous systems are known and include metal halides activated by an organometallic co-catalyst, such as titanium chloride supported on magnesium chloride, activated with trialkyl aluminum. Because these systems contain more than one catalytic species, they possess polymerization sites with different activities and varying abilities to incorporate comonomer into a polymer chain. The consequence of such multi-site chemistry is a product with poor control of the polymer chain architecture, leading to a heterogeneous composition. Moreover, differences in the individual catalyst site produce polymers of high molecular weight at some sites and low molecular weight at others, resulting in a polymer with a broad molecular weight distribution. Due to these reasons, mechanical and other properties of the polymers are often less than desired.
More recently, catalyst compositions based on well defined metal complexes, especially transition metal complexes such as constrained geometry catalysts (CGCs), metallocenes and post-metallocenes have been shown to give products having better comonomer incorporation and narrow molecular weight distribution. However, these catalysts often have poor high temperature stability and suffer from poor efficiencies at elevated polymerization temperatures. Additionally, the molecular weight of the polymers formed from these catalysts often decreases dramatically with increasing temperature, especially for polymers containing significant amounts of comonomer (lower density). That is. the ability of most olefin polymerization catalysts to incorporate higher a-olefins in an ethylene/a-olefm copolymer decreases with increasing polymerization temperature. In other words, the reactivity ratio r, generally increases with increasing polymerization temperature.

Reactivity ratios of catalysts may be obtained by known methods, for example, the technique described in "Linear Method for Determining Monomer Reactivity Ratios in Copolymerizadon", M. Fineman and S. D. Ross, J. Poivmer Science. 5, 259 (1950) or "Copolymerization", F. R. Mayo and C. Walling, Chem. Rev.. 46, 191 (J 950). One widely used copolymerization model is based on the following equations:

where Mi refers to a monomer molecule which is arbitrarily designated as "i" where i=l, 2; and M2* refers to a growing polymer chain to which monomer i has most recently attached.
The values are the rate constants for the indicated reactions. For example, in ethylene/propylene copolymerization, 1 represents the rate at which an ethylene unit inserts into a growing polymer chain in which the previously inserted monomer unit was also ethylene. The reactivity ratios follow as: are the rate constants for ethylene (1) or propylene (2) addition to a catalyst site where the last polymerized monomer is an ethyleneor propylene .
Thus, an olefin polymerization process is sought in which polymers containing various amounts of comonomer content can be produced with high catalyst efficiency and high monomer conversions and very high reactor temperatures without suffering from poor overall molecular weight in the resulting polymers. In addition, low molecular weight distribution (MW/MN In US 2005/0215737 Al, a continuous, solution, olefin polymerization process is disclosed for preparing ethylene-butene and ethylene-propylene interpolymers at high ethylene conversions. Disadvantageously, the resulting polymers were primarily plastomers having relatively low molecular weights. No chain transfer agent was employed, indicating that molecular weight of the

resulting polymer was relatively low and catalyst efficiencies were also low, especially at higher reaction temperatures.
In WO 99/45041, another continuous solution olefin polymerization process is disclosed using bridged hafnocene complexes with noncoordinating anionic cocatalysts. Although the resulting polymers contained significant amounts of comonomer, catalyst efficiencies were relatively low and polymer molecular weights, even in the absence of chain transfer agent were less than desirable.
In WO 03/102042, a high temperature solution olefin polymerization process is disclosed using indenoindoiyl transition metal complexes to prepare polyolefins at temperatures at greater than about I30°C. In one example, the copolymerization of ethylene and 1-hexene was carried out at 180 "C resulting in formation of a polymer having poor comonomer incorporation (density = 0.937 g/cm) at relatively low catalyst efficiencies.
In USP 6,827,976, there are disclosed certain highly active polymerization catalysts comprising Group 3-6 or Lanthanide metal complexes, preferably Group 4 metal complexes, of bridged bi-aromatic Iigands containing a divalent Lewis base chelating group. The metal complexes were employed in combination with activating cocatalysts in the polymerization of olefins including mixtures of ethylene and a-olefins, including 1-octene, to obtain polymers containing high comonomer incorporation rates at elevated temperatures.
US2004/0010103 disclosed certain aromatic polyether derivatives of transition metals and their use as catalysts for olefin polymerizations. Typical olefin polymerizations using prior art compositions are disclosed in US2003229188, WOOO/24793, Akimoto, et a)., J. Mol. Cat. A: Chem. 156(1-2), 133-141 (2000), among other references.
We have now discovered that certain metal complexes may be empjoyed in a solution polymerization process to prepare relatively high molecular weight ethylene interpolymers containing relatively large quantities of comonomer incorporated therein at unusually high temperatures and high olefin conversions if certain process conditions are observed. Accordingly, there is rjow provided a process for the preparation of olefin polymer products, especially high molecular weight polyolefins, at very high catalyst efficiency. In addition, we have discovered that these catalyst compositions retain their high catalyst activity using relatively low molar ratios of conventional alumoxane cocatalysts. The use of reduced quantities of alumoxane cocatalysts (up to 90 percent or more less than conventionally employed) allows for the preparation of polymer products having reduced metal content and consequently increased clarity, improved dielectric and other physical properties. In addition, the use of reduced quantities of alumoxane cocatalysts results in reduction in polymer production costs.

Summary of the Invention
According to the present invention there is now provided a process for polymerization of ethylene and optionally one or more C3.20 a-olefms under solution polymerization conditions at high temperatures with a catalyst composition comprising a transition metal complex and affording high molecular weight, high comonomer containing copolymers with narrow molecular weight distribution.
Despite the use of extremely high, solution polymerization temperatures, the resulting interpolymers possess relatively high molecular weights (with correspondingly low melt indices) and high levels of comonomer incorporation (low densities). We have discovered that the foregoing metal complexes can be activated with relatively low molar ratios (100 or l6ss) of neutral, Lewis acid activators, such as alumoxanes, and still are capable of use under these high temperature, high conversion conditions with very high catalyst efficiencies.
The present invention results in a high temperature solution polymerization process for preparing interpolymers of ethylene and one or more C3.20 a-olefins, and is particularly advantageous for use under continuous solution polymerization conditions wherein a reaction mixture comprising metal complex, activating cocatalyst, optionally a chain transfer agent, and at least one C2.20 a-olefin is continuously added to a reactor operating under solution polymerization conditions, and polymer product is continuously or semi-continuously removed therefrom. In one embodiment the invention is used to prepare copolymers of ethylene and at least one €3.20 a-olefm, preferably ethylene and at least one C6.20 ct-olefm. In another embodiment, this invention can be used to prepare C3.20 a-olefin homopolymers, or copolymers consisting essentially of two or more C3.20 a-olefms. In addition, the process may employ the use of catalyst compositions comprising more than one metal complex or compound and/or using or employing multiple reactors.
The key to obtaining the foregoing benefits is the use of solution polymerization conditions, temperatures from 170 "C or 185 "C or even 190 "C and up to 230 "C, or 240'*C or even 250 °C, high monomer conversions, which in the case of ethylene containing polymerizations, are at least 85 percent, and low cocatalyst concentrations, preferably molar concentrations of alumoxanes that are less than 200:1, preferably less than 100:1, more preferably less than 50:1 based on transition metal content of the catalyst.
Detailed Description of the Invention
All references to the Periodic Table of the Elements herein shall refer to the Periodic Table of the Elements, published and copyrighted by CRC Press, Inc., 2003. Also, any references to a Group or Groups shall be to the Group or Groups reflected in this Periodic Table of the Elements using the lUPAC system for numbering groups. Unless stated to the contrary, implicit from the

context, or customary in the art, all parts and percents are based on weight. For purposes of United States patent practice, the contents of any patent, patent application, or publication referenced herein are hereby incorporated by reference in their entirety (or the equivalent US version thereof is so incorporated by reference) especially with respect to the disclosure of synthetic techniques, definitions (to the extent not inconsistent with any definitions provided herein) and general knowledge in the art.
The term "comprising" and derivatives thereof is not intended to exclude the presence of any additional component, step or procedure, whether or not the same is disclosed herein. In order to avoid any doubt, all compositions claimed herein through use of the term "comprising" may include any additional additive, adjuvant, or compound whether polymeric or otherwise, unless stated to the contrary. In contrast, the term, "consisting essentially of excludes from the scope of any succeeding recitation any other component, step or procedure, excepting those that are not essential to operability. The term "consisting of excludes any component, step or procedure not specifically delineated or listed. The term "or", unless stated otherwise, refers to the listed members individually as well as in any combination.
As used herein with respect to a chemical compound, unless specifically indicated otherwise, the singular includes all isomeric forms and vice versa (for example, "hexane", includes all isomers of hexane individually or collectively). The terms "compound" and "complex" are used interchangeably herein to refer to organic-, inorganic- and organometal compounds. The term, "atom" refers to the smallest constituent of an element regardless of ionic state, that is, whether or not the same bears a charge or partial charge or is bonded to another atom. The term "heteroatom" refers to an atom other than carbon or hydrogen. Preferred heteroatoms include: F, CI, Br, N, O, P, B, S, Si, Sb, Al, Sn, As, Se and Ge. The term "amorphous" refers to a polymer lacking a crystalline melting point as determined by differential scanning calorimetry (DSC) or equivalent technique.
The term, "hydrocarbyl" refers to univalent substituents containing only hydrogen and carbon atoms, including branched or unbranched, saturated or unsaturated, cyclic, polycyclic or noncyclic species. Examples include alkyl-, cycloalkyl-, alkenyl-, alkadienyl-, cycloalkenyl-, cycloalkadienyl-, aryl-, and alkynyl- groups. "Substituted hydrocarbyl" refers to a hydrocarbyl group that is substituted with one or more nonhydrocarbyl substituent groups. The terms, "heteroatom containing hydrocarbyl" or "heterohydrocarbyl" refer to univalent groups in which at least one atom other than hydrogen or carbon is present along with one or more carbon atom and one or more hydrogen atoms. The term "heterocarbyl" refers to groups containing one or more carbon atoms and one or more heteroatoms and no hydrogen atoms. The bond between the carbon atom and any heteroatom as well as the bonds between any two heteroatoms, may be a single or multiple covalent bond or a coordinating or other donative bond. Thus, an afkyl group substituted

with a heterocycloalkyi-, aryl- substituted heterocycloalkyl-, heteroaryl-, alkyl- substituted heteroaryl-, alkoxy-, aryloxy-, dihydrocarbylboryl-, dihydrocarbyjphosphino-, dihydrocarbylamino-, trihydrocarbylsilyl-, hydrocarbylthio-, or hydrocarbylseieno- group is within the scope of the term heteroalkyl. Examples of suitable heteroalkyl groups include cyanomethyl-, benzoylmethy!-, (2-pyridyl)methyl-, and trifluoromethyl- groups.
As used herein the term "aromatic" refers to a polyatotnic, cyclic, conjugated ring system containing (48+2) Ji-electrons, wherein 5 is an integer greater than or equal to 1. The term "fused" as used herein with respect to a ring system containing two or more polyatomic, cyclic rings means that with respect to at least two rings thereof, at least one pair of adjacent atoms is included in both rings. The term "aryl" refers to a monovalent aromatic substituent which may be a single aromatic ring or multiple aromatic rings which are fused together, linked covalently, or linked to a common group such as a methylene or ethylene moiety. Examples of aromatic ring(s) include phenyl, naphthyl, anthracenyl, and biphenyl, among others.
"Substituted aryl" refers to an aryl group in which one or more hydrogen atoms bound to any carbon is replaced by one or more functional groups such as alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, halogen, alkylhalos (for example, CF3), hydroxy, amino, phosphide, alkoxy, amino, thio, nitro, and both saturated and unsaturated cyclic hydrocarbons which are fused to the aromatic ring(s), linked covalently or linked to a common group such as a methylene or ethylene moiety. The common linking group may also be a carbonyl as in benzophenone or oxygen as in diphenylether or nitrogen in diphenyiamine.
Embodiments of the invention provide a new solution process for making olefm polymers with a homogeneous transition metal complex containing catalyst composition at high temperature, high catalyst efficiency and high monomer conversion wherein the produced polymers are of sufficiently high molecular weight so as to still allow for the presence of sighificant amounts of a chain transfer agent such as hydrogen to control molecular weight of the polymers. Highly desirably, the produced polymers are of high molecular weight (I2 3.0 long chain branches per 10,000 carbons, especially when zirconium containing metal complexes are employed. Such polymers are suitably employed where improved extrusion performance is desired, such as in wire and cable insulating resins.
The unique process conditions employed according to the invention can be summarized in an equation which takes into account the reaction temperature and ethylene conversion along with

the resulting polymer properties of density, melt index and molecular weight that are produced at these temperatures and conversions. These conditions produce a polymer that results in a value for the polymerization index, H*, that is greater than or equal to zero according to the following equation:
where; T is the polymerization temperature in degrees Celsius, X is the ethylene conversion in the reactor in mol percent, E is the catalyst efficiency in g polymer produced per g of metal in the metal complex fed to the reactor per unit time, P is the resulting polymer density in
units of g/ml, 2 is the melt index of the polymer in units of dg/minute, and the equation constants,

Preferred polymerization conditions are steady state, continuous, solution polymerization conditions in which the foregoing polymerization index is at least 0.05, more preferably at least 0.1. Although units are associated with the various parameters used in the calculation of the polymerization index, only the unit-less value of the resulting sum is employed as the index.
The term "polymer" as used herein refers to a macromolecular compound prepared by polymerizing one or more monomers. A polymer refers to homopolymers, copolymers, lerpolymers, interpolymers, and so on. containing 5 or more repeat units. Compounds containing less than 5 repeating units are referred to as oligomers. The term "Interpolymer" is used herein interchangeably with the term copolymer to refer to polymers incorporating in polymerized form at least two copolymerizable monomers, or incorporating long chain branching as a result of chain termination/olefin formation reactions in situ, and reincorporation of the In $itu formed olefin. Accordingly, copolymers may result from the polymerization of a single monomer, under the correct operating conditions. The least prevalent monomer in the resulting copolymer or interpolymer is generally referred to by the term "comonomer". The chain length of the resulting long chain branches referred to above, is consequently longer than the carbon length resulting from polymerization of any deliberately added comonomer, and in particular, longer than 6 carbons. The presence of long chain branching may also be determined by the increased shear sensitivity of the polymer, as disclosed in EP-A-608369, and elsewhere, and determined by Melt Index Ratio (MIR), a ratio of polymer melt viscosities measured under differing loads, especially Iji/Ij. Preferred polymers according to the invention have MIR values from 30 to 80.

The process described herein may be employed to prepare any olefin polymer, especially ethylene homopolymers, copolymers of ethylene with one or more C3.20 olefins, copolymers of ethylene with one or more Ce-ao olefins, and ethylene/propylene, ethylene/l-butene, ethylene/1-hexene, ethylene/4-methyl-l-pentene, ethylene/styrene, ethylene/propylene/styrene, and ethylene/1-octene copolymers, isotactic polypropylene/1-butene, isotactic polypropylene/1-hexene, jsotactic polypropylene/1-octene, terpolymers of ethylene, propylene and a non-conjugated diene, for example, EPDM terpolymers, as well as homopolymers of propylene, butylene, or styrene.
Polymerization conditions generally refer to temperature, pressure, monomer content (including comonomer concentration), catalyst concentration, cocatalyst concentration, monomer conversion, or other conditions that influence the properties of the resulting polymer. By operation according to the prescribed polymerization conditions of the invention high molecular weight polymers may be prepared having relatively high comonomer incorporation with high catalyst activities. In particular, activities (based on weight of polymer to weight of transition metal) greater than 0.5 g/}ig, preferably greater than 0.55 g/ig, and even greater than 0.6 g/{ig are possible.
Polymer weight-average molecular weight (Mw) is measured by gel permeation chromatography, one technique of which as described in US? 5,272,236, Alternatively, melt index, I2, lio or lai, measured for example according to ASTM D-1238 may be employed as an indication of molecular weight. Generally, melt index is inversely related to the molecular weight of the polymer. The higher the molecular weight, the lower the melt index, although the relationship is not necessarily linear.
One embodiment of this invention entails a process which comprises contacting one or more olefins in a high temperature solution polymerization process. The present invented process is particularly advantageous for use under polymerization conditions wherein a reaction mixture comprising metal complex, activating cocatalyst, ethylene, and optionally at least one C3.20 a-olefin comonomer is continuously added to a reactor operating under solution polymerization conditions, optionally in the additional presence of a chain transfer agent, and polymerized product is continuously or semi-continuously removed therefrom. This process can consist of:
i) Polymerizing ethylene and optionally one or more C3.20 a-olefms using a transition metal complex and an activating cocatalyst, especially a neutral Lewis acid, more preferably an alumoxane, under continuous, solution polymerization conditions at a temperature from 185 to 250 °C, preferably from 200 to 250 X, under high ethylene conversion conditions (>85 percent) which results in a polymer with a density between 0.885 and 0.950 g/cm' and a loW melt index (l2 than 0.5 gpolyr«r/fAgi»in|.



addition, this process can be used to produce polymers which contain significant amounts of long chain branches, preferably using catalysts comprising zirconium containing metal complexes.
Suitable alumoxanes include polymeric or oligomeric alumoxanes, especially methalumoxane (MAO) or isobutylalumoxane (DBA) as well as Lewis acid modified alumoxanes, such as trihydrocarbylaluminum-, halogenated tri(hydrocarbyl)aluminum- or halogenated tri(hydrocarbyl)boron- modified alumoxanes, having from 1 to 10 carbons in each hydrocarbyl or halogenated hydrocarbyl group. Examples include, tri(isobutyl)aluminum modified methalumoxane tri(n-octyl)aluminum modified methalumoxane, and tris(pentafIuorophenyl)borane modified alumoxanes. Such activatingcocatalysts are previously disclosed in USP's 6,214,760, 6,160,146, 6,140,521, and 6,696,379, and elsewhere.
Additional suitable neutral Lewis acid activating cocatalysts include C1.30 hydrocarbyl substituted Group 13 compounds, especially tri(hydrocarbyl)aluminum- or tri(hydrocarbyl)boron compounds and halogenated (including perhalogenated) derivatives thereof, having from 1 to 30 carbons in each hydrocarbyl or halogenated hydrocarbyl group. In addition, di(hydrocarbyl)zinc, di(hydrocarbyl)aluminum halides. di(hydrocarbyl)aluminum alkoxides'and di(hydrocarbyl)-aluminum amides may be employed.
The Lewis acid activator is preferably utilized in molar ratios cocatalyst:catalyst from 1-200, preferably from 1-150 and most preferably from 1-iOO. Alumoxane and Lewis acid modified alumoxane cocatalysts are preferably utilized in molar ratios Alxatalyst from 20-200, preferably from 30-150 and most preferably from 40-100. Preferred cocatalysts are methalumoxane, tri(i-butyl)laluminum modified methalumoxane and tri(n-octyl)aluminum modified methalumoxane.
Because of the ability to be activated at relatively low levels of alumoxane or Lewis acid modified alumoxane cocatalysts, the present metal complexes are also preferred for use in other polymerization processes, such as gas phase, high pressure, or slurry polyolefin process. In these processes, the metal complexes may be supported on conventional supports and activated under many different conditions that are not available to complexes which require non-coordinating anionic activators or large amounts of alumoxanes to achieve suitable activity.
Multiple reactor polymerization processes are suitably employed in the present invention. Examples include such systems as are disclosed in USP 3,914,342, among others. The multiple reactors can be operated in series or in parallel, with at least one catalyst composition according to the present invention employed in at least one of the reactors. One or both reactors may also contain at least two catalysts which have different comonomer incorporation capability and/or different molecular weight capability. In one embodiment, a relatively high molecular weight product (M„ from 100,000 to over 1,000,000, more preferably 200,000 to 500,000) is formed while in the second reactor a product of a relatively low molecular weight (M* 2,000 to 300,000) is

formed. Both of these reactor products can have similar or different densu.ies. The final product is a mixture of the two reactor effluents which are combined prior to devolatilization to result in a uniform mixing of the two polymer products. In another embodiment, the molecular weight of the products from both reactors is nearly the same but the densities vary to the extent that one of the reactors produces a polymer with density in the range of 0.865-0.895, while the other reactor produces polymer with density in the range of 0.885-0.950. Such a dual reactor/dual catalyst process allows for the preparation of products with tailored properties. In one embodiment, the reactors are connected in series, that is, the effluent from the first reactor i& charged to the second reactor and firesh monomer, solvent and hydrogen is optionally added to the second reactor. Reactor In one embodiment, one of the reactors in the polymerization process, including the first of two reactors operating in series, contains a heterogeneous Ziegler-Natta catalyst or chrome catalyst known in the art. Examples of Ziegler-Natta catalysts include, but are not limited to, titanium-based catalysts supported on MgClj, and additionally comprise compounds of aluminum containing at least one aiuminum-alkyi bond. Suitable Ziegler-Natta catalysts and their preparation include, but are not limited to, those disclosed in USP's 4,612,300,4,330,646, and 5,869,575. A unique advantage of the present invention is the ability of the present catalysts to operate despite the presence of significant quantities of a Ziegler/Natta or chrome based heterogeneous catalyst composition or the byproducts resulting from the use thereof.
Single reactor, multiple catalyst processes are also useful in the present invention. In one embodiment, two or more catalysts are introduced into a single reactor at the high temperature conditions that are herein disclosed, wherein each catalyst inherently produces different polyoiefin copolymers. In one embodiment, a relatively high molecular weight product (Mw from 100,000 to over 1,000,000, more preferably 200,000 to 500,000) is formed from one catalyst while a product of a relatively low molecular weight (Mw 2,000 to 300,000) is formed from the other catalyst. Both of these catalyst compositions can have similar or different comonomer incorporation ability. The resulting polymer will have properties dependant on the ratio of the two catalysts that are employed in the single reactor. Suitable combinations of polymer molecular weight, comonomer incorporation ability, processes and ratios of catalysts, for such products aire disclosed in USP 6,924,342. Due to the unique compatibility of the present catalyst compositions with other olefin polymerization catalysts, including Ziegler/Natta catalysts, the second catejlyst composition may

comprise a meta] complex as herein disclosed, a metallocene or other n-botided ligand group containing metal complex (including constrained geometry metal complexes), or a polyvalent heteroatom ligwid group containing metal complex, especially polyvalent pyridylamine or imidizolylamine based complexes.
METAL COMPLEXES
Suitable metal complexes for use according to the present invention correspond to the formula:
R** is an aliphatic, aromatic or inertly substituted aromatic group containing from 5 to 20 atoms not counting hydrogen, or a polyvalent derivative thereof;
T"* is a hydrocarbylene or silane group having from 1 to 20 atoms riot counting hydrogen, or an inertly substituted derivative thereof;
M is a Group 4 metal, preferably zirconium or hafnium, most preferably zirconium;
R° independently each occurrence is a monovalent ligand group or two R'* groups together are a divalent hydrocarbylene or hydrocarbadiyi group; and
bonds and electron donative interactions are represented by lines and arrows respectively.
Preferably, such complexes correspond to the formula:

T' is a divalent bridging group of from 2 to 20 atoms not counting hydrogen, preferably a substituted or unsubstituted, C3.6 alkylene group; and
Ar independently each occurrence is an arylene or an alkyl-, aryl-, alkoxy- or amino-substituted arylene group of from 6 to 20 atoms not counting hydrogen and not counting the substituents;
M is a Group 4 metal, preferably hafnium or zirconium, most preferably zirconium;

R" independently each occurrence is a monovalent ligand group or two R* groups together are a divalent hydrocarbylene or hydrocarbadiyl group; and
electron donative interactions are represented by arrows.
More preferred examples of metal complexes of foregoing formula include the following

M is Hf or Zr, preferably Zr;
Ar' is C6.20 aryl or inertly substituted derivatives thereof, especially 3,5-di(isopropyl)phenyl, 3,5-di T* independently each occurrence comprises a C3.6 alkylene groups a C3.S cycloalkylene group, or an inertly substituted derivative thereof;
R' independently each occurrence is hydrogen, halo, hydrocarbyl, trihydrocarbylsilyl, trihydrocarbylsilylhydrocarbyl, alkoxy or amino of up to 50 atoms not counting hydrogen; and
R, independently each occurrence is halo or a hydrocarbyl or trihydrocarbylsilyl group of up to 20 atoms not counting hydrogen, or 2 R° groups together are a divaleSnt hydrocarbylene, hydrocarbadiyl or trihydrocarbylsilyl groups.


R' independently each occurrence is hydrogen, halo, hydrocarbyl, trihydrocarbylsilyl, trihydrocarbylsilylhydrocarbyl, alkoxy or amino of up to 50 atoms not counting hydrogen;
T* is propan-l,3-diyl or butan-l,4-diyl, cyclohexanediyl or cyclohexanedialkylenyl; and
R°, independently each occurrence is halo or a hydrocarbyl or trihydrocarbylsilyl group of up to 20 atoms not counting hydrogen, or 2 R" groups together are a divalent hydrocarbylene, hydrocarbadiyi or trihydrocarbylsilyl groups.
Most highly preferred metal complexes according to the invention correspond to the

wherein
R° independently each occurrence is chloro, methyl or benzyl, and electron donative interactions between the ether groups and zirconium are represented by arrows.
Specific examples of the foregoing metal complexes are the following compounds:

A) bis((2-oxoyl-3-Cl,2,3,4,6,7,8,9-octahydroanthracen-5-yI)-5-(methy[)pheny0-2-phenoxy)propane-
1,2-diylzirconiuni (IV) dimethyl,
bis((2-OKoyl-3-( 1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)propane-1,2-
diylzirconium (IV) dichloride,
bis((2-oxoyl-3-(dibenzo-lH-pyrrole-l-yI)-5-(methyl)phenyl)-2-phenoxy)propane-l,2-diylzirconium
(IV) dimethyl,
bis((2-oxoyl-3-(dibenzo-lH-pyrrole-l-yl)-5-(methyl)phenyl)-2-plienoxy)propane-l,2-diylzirconium
(IV) dichloride,
bis((2-oxoyl-3-( 1,1 -dimethylethyl)piien-1 -y l)-5-(methyl)phenyl)-2-phenoxy)propane-1,2-
diylzirconium (IV) dimethyl,
bis((2-oxoy]-3-( 1,1 -dimethylethy!)phen-! -yI)-5-(methyl)phenyl)-2-phenoxy)propane-1,2-
diylzirconium (IV) dichloride,
bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-trans-
cyclohexane-l,2-dimethylenyl-l',2-diyl2irconium (IV) dimethyl,
bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-trans-
cycIohexane-l,2-dimethylenyl-l,2-diylzirconJum (IV) dichloride,
bis((2-oxoyl-3-(dibenzo-1 H-pyrrole- l-yl)-5-(methyl)phenyl)-2-phenoxy)-trans-cyclohexane-1,2-
dimethylenyl-l,2-diylzirconitim (IV) dimethyl,
bis((2-oxoyl-3-(dibenzo-lH-pyrrole-l-yl)-5-(methyI)phenyl)-2-phenoxy)-trans-cyclohexane-l,2-
dimethylenyH,2-diylzirconium (IV) dichloride,
bis((2-oxoyl-3-( 1,1 -dimethylethyl)phen-1 -yI)-5-(methy l)phenyI)-2-phenoxy)-trans-cyclohexane-1,2-
dimethylenyl-l,2-diylzirconium (IV) dimethyl,
bis((2-oxoyI-3-(l,l-dimethylethyl)phen-l-yO-5-(nnethyl)phenyI)-2-phenoxy)-trans-cyclohexane-l,2-
dimethylenyl-1,2-diylzirconium (IV) dichloride,
bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-Qctahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-cis-cyclohexane-1,3-diylzirconium (IV) dimethyl, bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)2-phenoxy)-cis-
cycIoh6xane-l,3-diylzirconium(FV) dichloride,
bis((2-oxoy l-3-(dibenzo-1 H-pynrole-1 -yl)-5-(methyl)phenyI)-2-phenoxy)-cis-cycIohexane-1,3-diylzirconium (IV) dimethyl,
bis((2-oxoyl-3-(dibenzo- IH-pyrrole-1 -yl)-5-(methyl)phenyl)-2-phenoxy)-cis-cyclohexane-1,3-diylzirconium (IV) dichloride, bis((2-oxoyl-3-( 1,1 -dimethylethyOphen-1 -yl)-5-(methyI)phenyI)-2-phenoxy)-cis-cyclohexane-1,3-

diylzirconium (IV) dimethyl.
bis((2-oxoyl-3-(l, ] -dimethylethy I)phen-1 -yI)-5-(methyI)phenyI)-2-phenoxy)-cis-cyclohexane-1,3-diylzirconium (IV) dichloride,
bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyI)phenyI)-2-phenoxy)-cis-
cycIohexene-l,2-dimethylenyl-l,2-diyl2irconium (IV) dimethyl,
bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-cis-
cyclohexene-l,2-dimethylenyl-l,2-diylzirconium (IV) dichloride,
bis((2-oxoyl-3-(dibenzo-IH-pyrroIe-l-yI)-5-(methyl)phenyI)-2-phenoxy)-cis-cycIohex6ne-l,2-
dimethylenyl-l,2-diylzirconium (IV) dimethyl,
bis((2-oxoyl-3-(dibenzo-1 H-pyrrole-1 -yI)-5-(methyl)phenyl)-2-phenoxy)-cis-cyclohexene-1,2-
dimethylenyl-l,2-diylzirconium (IV) dichloride,
bis((2-oxoyl-3-( 1,1 -dimethylethy l)phen-1 -y l)-5-(methyl)phenyl)-2-phenoxy)-cis-cyclohexene-1,2-
dimethylenyl-l,2-diylzirconium (IV) dimethyl,
bis((2-oxoyl-3-( 1,1 -dimethylethyl)phen-1 -yl)-5-(methyJ)phenyl)-2-phenoxy)-cis-cyclohexene-1,2-
dimethylenyl-l,2-diyl2irconium (IV) dichloride,
bis((2-oxoyI-3-( 1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)pheny!)*2-phenoxy)butane-1,4-diylzirconium (IV) dimethyl,
bis((2-oxoyl-3-( 1,2,3,4,6,7,8,9-octahydroanthracen-5-yI)-5-(methyl)phenyi)-2-phenoxy)butane-1,4-diylzirconium (FV) dichloride,
bis((2-oxoyl-3-(dibenzo-1 H-pyrrole-1 -yl)-5-(methyl)phenyl)-2-phenoxy)butane-1,4-diylzirconium (IV) dimethyl,
bis((2-oxoyl-3-(dibenzo-1 H-pyrrole-1 -yl)-5-(methyl)phenyI)-2-phenoxy)butane-l ,4-diylzJrconium (FV) dichloride,
bis((2-oxoyl-3-( 1, l-dimethylethyl)phen-l -yl)-5-(raethyl)phenyl)-2-phenoxy)butane-1,4-diylzirconium (IV) dimethyl,
bis((2-oxoyl-3-(l,l-dimethylethyl)ph6n-l-yl)-5-(methyl)phenyl)-2-phenoxy)butane-l ,4-diylzirconium (IV) dichloride,
B) bis((2-oxoyl-3-( 1,2,3,4,6,7,8,9-octahydroanthracen-5-y!)-5-(methyl)phenyl)-(4-methyl-2-
phenoxy))propane-l,2-diylzirconium (IV) dimethyl, bis((2-oxoy|.3-(I,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-methyl-2-

phenoxy))propane-l ,2-diyIzirconium (IV) dichloride,
bis((2-oxoyl-3-(dibenzo-1 H-pyrrole-1 -yI)-5-(methyi)pheny!)-(4-methyl-2-phenoxy))propane- \ ,2-
diylzirconium (IV) dimethyl,
bis((2-oxoyl-3-(dibenzo-1 H-pyrrole-1 -yI)-5-(methyI)phenyl)-(4-methyl-2-phenoxy))propane-1,2-
diylzirconium (IV) dichloride,
bis((2-oxoyl-3-( 1,1 -dimethylethyOphen-1 -yl)-5-(methyl)phenyl)-(4-methyK2-phenoxy))propane-1,2-
diylzirconium (IV) dimethyl,
bis((2-oxoyl-3-( 1,1 -di methylethyl)phen-1 -yl)-5-(methyI)phenyl)-(4-methyl-2-phenoxy))propane-1,2-
diylzirconium (IV) dichloride,
bis((2-oxoyl-3-(I,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methy0phenyI)-(4-methyl-2-phenoxy))-
trans-cyclohexane-l,2-dimethylenyl-l,2-diyl2irconium (IV) dimethyl,
bis((2-oxoyl-3-( 1,2,3,4,6,7,8,9-octahydroanthracen-5-yI)-5-(methyI)phenyl)-(4-methyI-2-phenoxy))-
trans-cyclohexane-1,2-dimethylenyl-1,2-diylzirconium (IV) dichloride,
bis((2-oxoyl-3-(dibenzo-1 H-pyrrole-1 -yI)-5-(methyI)phenyI)-(4-methyl-2-phenoxy))-trans-
cyclohexane-l,2-dimethylenyi-l,2-diyl2irconium (IV) dimethyl,
bis((2-oxoyl-3-(dibenzo-1 H-pyrrole-1 -yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-trans-
cycIohexane-I,2-dimethylenyI-l,2-diyIzirconium (IV) dichloride,
bis((2-oxoyl-3-( 1,1 -dimethylethyOphen-1 -yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-trans-
cyclohexane-l,2-dimethy!enyI-l,2-diylzirconium (IV) dimethyl,
bis((2-oxoyl-3-( 1,1 -dimethylethyOphen-1 -yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-trans-
cyclohexane-l,2-dimethylenyl-l,2-diylzirconium (IV) dichloride,
bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-methyl-2-pbenoxy))-
cis-cyclohexane-l,3-diylzirconium(rV) dimethyl,
bis((2-oxoyI-3-(1.2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-methyI-2-phenoxy))-
cis-cycIohexane-I,3-diylzirconium (IV) dichloride,
bi s((2-oxoyl-3-(dibenzo-1 H-pyrrole-1 -yl)-5-(methy l)pheny 0-(4-methyI-2-phenoxy))-c is-
cyclohexane-1,3-diylzirconium (IV) dimethyl.
bis((2-oxoyl-3-(dibenzo-lH-pyrrole-l-yl)-5-(methy0pheny0-(4-methyl-2-phenoxy))-cis-
cyclohexane-l,3-diylzlrconium (TV) dichloride,
bis((2-oxoyl-3-( 1,1 -dimethylethyOphen- l-yI)-5-(methyl)phenyI)-(4-methyl-2phenoxy))-cis-
cycIohexane-l,3-diylzirconium (TV) dimethyl,
bis((2-oxoyI-3-( 1,1 -dimethylethyOphen- I-yl)-5-(methy0phenyi)-(4-methyl-2-phenoxy))-cis-

cyclohexane-l,3-diyIzirconium (IV) dichloride,
bis((2-oxoyl-3-(U2,3,4,6,7,8.9-octahydroanthracen-5-yl)-5-(methyl)phenyI)-(4-methyl-2-phenoxy))-cis-cyclohexene-l,2-dimethyIenyI-I,2-diyl2irconium (IV) dimethyl,
bis((2-oxoyl-3-(I,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyI)phenyI)-(4-methyI-2-phenoxy))-cis-cyclohexene-1,2-dimethylenyl-l ,2-diylzirconium (IV) dichloride, bis((2-oxoyl-3-(dibenzo-1 H-pyrrole-1 -yl)-5-(methyI)phenyl)-(4-methyl-2-phenoxy))-cis-cyclohexene-1.2-dimethylenyl-l,2-diylzirconium (IV) dimethyl, bis((2-oxoyl-3-(dibenzo-lH-pyrrole-l-yl)-5-(methyl)phenyl)-(4-methyI-2-phenoxy))-cJs-cyclohexene-1,2-dimethyIenyI- 1,2-diylzirconium (IV) dichloride,
bis((2-oxoyl-3-(I.I-dimethyIethyl)phen-I-yl)-5-(methyI)phenyI)-(4-methyI-2-phenoxy))-cis-cycIohexene-l,2-dimethylenyl-1,2-diylzirconium (IV) dimethyl,
bis((2-oxoyl-3-( 1,1 -dimethylethyOphen-1 -yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-cis-cyclohexene-1,2-dimethylenyl-l,2-diylzirconium (IV) dichloride,
bis((2-oxoyl-3-(1.2,3,4,6.7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyI)-(4-methyl-2-phenoxy))butane-l,4-diylzirconium (IV) dimethyl,
bis((2-oxoyI-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))butane-l ,4-diylzirconium (IV) dichloride,
bis((2-oxoyl-3-(dibenzo-1 H-pyrroIe-1 -yl)-5-(methyl)pheny l)-(4-methyl-2-phenoxy))butane-1,4-diylzirconium (IV) dimethyl,
bis((2-oxoyl-3-(dibenzo-1 H-pyrrole-1 -y!)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))butane-1,4-diylzirconium (IV) dichloride,
bis((2-oxoyl-3-( 1,1 -dimethylethyOphen-1 -yl)-5-(methyl)phenyl)-(4-methyl-!2-phenoxy))butane-1,4-diylzirconium (rV) dimethyl,
bis((2-oxoyl-3-(l, 1 -dimethylethyOphen- l-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))butane-l ,4-diylzirconium (IV) dichloride,
C) bis((2-oxoyI-3-( 1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyI)-(5-(2-methyl)propane-2-yl)-2-phenoxy)propane-l ,2-diylzirconium (IV) dimethyl, bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(5-(2-methyl)propane-
2-yl)propane-1,2-diylzirconium (IV) dichloride,
bis((2-oxoyl-3-(dibenzo-1 H-pyrrole-1 -yl)-5-(methyl)pheny0-(5-(2-methyl)propane-2-yl)propane-
1,2-diylzirconium (IV) dimethyl,
bis((2-oxoyl-3-(dibenzo- IH-pyrrole-1 -yl)-5-(methyl)phenyl)-(5-(2-methyI)propane-2-yl)propane-

1,2-diylzirconium (IV) dichloride,
bis((2-oxoyl-3-(i, l-dtmethylethyl)phen-1 -yI)-5-(methyI)phenyI)-(5-(2-metliyI)propane-2-
yOpropane-l ,2-diylzirconium (IV) dimethyl,
bis((2-ox oyl-3-( 1,1 -dimethylethyl)phen-1 -y l)-5-(methyl)phenyI)-(5-(2-methyI)propane-2-yOpropane-1,2-diylzirconium (IV) dichloride,
bis((2-oxoyI-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)pheny0-(5-(2-methyI)propane-2-yl)-trans-cyclohexane-1,2-dimethyIenyl-l ,2-diylzirconium (IV) dimethyl, bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyI)-(5-(2-methyl)propane-2-yl)-trans-cyclohexane-l ,2-dimethylenyI-l ,2-diylz:irconium (IV) dichloride, bis((2-oxoyl-3-(dibenzo-1 H-pyrrole-1 -yl)-5-(niethyl)phenyl)-(5-(2-methyl)propane-2-yl)-trans-cyclohexane-1,2-dimethylenyI- 1,2-diyIzirconium (IV) dimethyl,
bis((2-oxoyI-3-(dibenzo-lH-pyrrole-l-yI)-5-(methyI)phenyi)-(5-(2-methyl)propane-2-yI)-trans-cyclohexane-l,2-dimethylenyl-l,2-diylzirconium (IV) dichloride,
bis((2-oxoyl-3-( 1,1 -dimethylethyl)phen-1 -yl)-5-(methyl)phenyl)-(5-(2-methy l)propane-2-yl)-trans-cyclohexane-l,2-dimethylenyl-l,2-dlylzirconium (IV) dimethyl,
bis((2-oxoyl-3-(l»l-dimethylethyl)phen-l-yl)-5-(methyl)phenyl)-(5-(2-methyl)propane-2-yl)-trans-cyclohexane-l,2-dimethylenyI-1,2-diylzirconium (IV) dichloride,
bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-y!)-5-(methyl)pheny!)-(5-(2-methyl)propane-
2-yl)-cis-cyclohexane-l,3-diyl2irconium (IV) dimethyl,
bis((2-oxoyI-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)(5-(2-methyl)propane-
2-yI)-cis-cycIohexane-r,3-diyl2irconium (IV) dichloride,
bis((2-oxoyl-3-(dibenzo-l H-pyrrole-1 -yI)-5-(methyI)phBnyI)-(5-(2-methyl)propane-2-yI)-cis-
cyclohexane-I,3-diylzirconium (IV)dimethyl,
bis((2-oxoyI-3-(dibenzo-1H-pyrroIe-l-yl)-5-(methyl)phenyl>-(5-(2-metbyl)propane-2-yl)-cis-
cyclohexane-l,3-diylzirconium (IV) dichloride,
bis((2-oxoyl-3-(l,l-dimethylethyl)phen-l-yl)-5-(methyl)phenyl)-(5-(2-methyl)propane-2-yl)-cis-
cyclohexane-1,3-diyIzirconium (IV) dimethyl,
bis((2-oxoyl-3-( 1,1 -dimethy]ethyl)phen-1 -yl)-5-(methyl)phenyl)-(5-(2-methyI)propane-2-yl)-cis-
cyclohexane-l,3-diylzirconium (TV) dichloride,
bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)T(5-(2-methyl)propane-2-yl)-cis-cyclohexene-l ,2-dimethylenyl-1,2-diylzirconium (IV) dimethyl.

bis((2-o>coyl-3-(l,2.3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyI)-C5-(2-methyI)propane-
2-yl)-cis-cyclohexene-l ,2-dimethylenyl-l ,2-diylzirconium (IV) dichloride,
bis((2-oxoyl-3-(dibenzo-lH-pyn-ole-l-yl)-5-(melhyI)phenyl)-(5-(2-methyl)propane-2-yl)-cis-
cyclohexene-l ,2-dimethyIenyl-1.2-diylzirconium (IV) dimethyl,
bis((2-oxoyl-3-(dibenzo-lH-pyrroIe-l-yl)-5-(methyl)phenyl)-(5-(2-methyl)propane-2-yl)-cis-
cyclohexene-1,2-dimethylenyl-1.2-diylzirconium (IV) dichloride,
bis((2-oxoyl-3-( 1, l-dimethylethyl)phen-1 -yl)-5-(methyl)phenyl)-(5-(2-methy l)propane-2-yl)-cis-
cyclohexene-l,2-dimethylenyl-l,2-diylzirconium (IV) dimethyl,
bis((2-oxoyl-3-( 1,1 -dimethylethyl)phen-1 -yl)-5-(methyI)phenyI)-(5-(2-methyI)propane-2-y l)-cis-
cyclohexene-l,2-dimethylenyl-l,2-diylzircQnium (IV) dichloride,
bis((2-oxoyl-3-(I,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(5-(2-methyl)propane-2-yl)butane-l,4-diylzirconium (IV) dimethyl,
bis((2-oxoyl-3-(l,2.3,4,6,7,8,9-octahydroanthracen-5-yI)-5-(methyl)phenyl)-(5-(2-methyl)propane-2-yl)butane-l ,4-diylzirconium (IV) dichloride,
bis((2-oxoyl-3-(dibenzo-1 H-pyrrole-1 -yl)-5-(methyl)phenyl)-(5-(2-methyl)propane-2-yl)butane-1,4-diylzirconium (IV) dimethyl,
bis((2-oxoyl-3-(dibenzo-lH-pyrrole-l-yl)-5-(methyl)phenyl)-(5-(2-methyl)propane-2-yl)butane-l,4-diylzirconium (IV) dichloride,
bis((2-oxoyl-3-(l, 1 -dimethylethyl)phen-1 -yI)-5-(methyl)phenyl)-(5-(2-methyl)propane-2-yl)butane-1,4-diylzirconium (IV) dimethyl, and
bis((2-oxoyI-3-( I, I -dimethylethyl)phen- l-yI)-5-(methyl)phenyl)-(5-(2-methyl)propane-2-y0butane-1,4-diylzirconium (IV) dichloride.
The foregoing metal complexes are conveniently prepared by standard metallation and ligand exchange procedures involving a source of the transition metal and a neutral polyfiinctional Hgand source. In addition, the complexes may also be prepared by means of an amide elimination and hydrocarbylatlon process starting from the corresponding transition metal tetraamide and a hydrocarbylating agent, such as trimethylaluminum. The techniques employed are the same as or analogous to those disclosed in USFs 6,320,005, 6,103,657, WO 02/38628. WO 03/40195, US-A-2004/0220050, and elsewhere.
The metal complex is activated to form the active catalyst composition by combination with a cocatalyst, preferably a cation forming cocatalyst, especially a cationic compound containing a non-coordination anion or a neutral Lewis acid, preferably an alumoxane or neutral Lewis acid modified alumoxane, or a combination thereof. The activation may occur prior to addition of the catalyst composition to the reactor with or without the presence of other components of the reaction

mixture, or in situ through separate addition of the metal complex and activating cocatalyst to the reactor.
MONOMERS
Suitable olefins for use herein include C2-30 aliphatic-, cycloaliphatic- and aromatic-compounds containing one or more ethylenic unsaturations. Examples include aliphatic-, cycloaliphatic- and aromatic olefins or diolefins. Preferred olefin monomers include, but are not limited to, ethylene, propylene, isobutylene, 1-butene, 1-pentene, I-hexene, 1-heptene, 1-octene, 1-nonene, I-decene, and 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 3-methyl-I-butene, 3-methyl-l-pentene,4-methyI-1-pentene, 4,6-dimethyl-I-heptene, vinylcyclo-hexane, styrene, cyclopentene, cyclohexene, cyclooctene, 1,3-butadiene, 1,3-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,7-octadiene, 1,9-decadiene, 4-vinylcyclohexene, dicyclopentadiene, norbomadiene, ethylidenenorbomene, and mixtures thereof.
The novel processes described herein are well suited for the production of olefin polymers comprising monovinylidene aromatic monomers including styrene, o-methyl styrene, p-methyl styrene, t-butylstyrene, and mixtures thereof. In particular, interpolymers comprising ethylene and styrene can be advantageously prepared by following the teachings herein. Optionally, copolymers comprising ethylene, styrene and/or a C3.20 alpha olefin, optionally comprising a conjugated or non-conjugated C4.20 diene, having improved properties over those presently known in the art can be prepared.
Suitable non-conjugated dienes include straight chain-, branched dbain- or cyclic-hydrocarbon dienes having from 6 to 15 carbon atoms. Examples of suitable non-conjugated dienes include, but are not limited to, straight chain acyclic dienes, such as 1,4-hexadiene, 1,6-octadiene, 1,7-octadiene, 1,9-decadiene, branched chain acyclic dienes, such as 5-methyl-l,4-hexadiene; 3,7-dimethyl-U6-octadiene; 3,7-dimethyl-l,7-octadieneand mixed isomers of dihydromyricene and dihydroocinene, single ring aiicyclic dienes, such as 1,3-cyclopentadiene; 1,4-cyclohexadiene; 1,5-cyclooctadiene and l,S-cyclododecadiene, and multi-ring alicycUc fused and bridged ring dienes, such as tetrahydroindene, methyl tetrahydroindene, dicyclopentadiene, bicyclo-(2,2,l)-hepta-2, 5-dlene; aikenyl, alkylidene, cycloalkenyl and cycloalkylidene norbomenes, such as 5-methylene-2-norbomene (MNB); 5-propenyl-2-norbomene,5-isopropylidene-2-norbomene, 5-(4-cyclopentenyl)-2-norbornene, 5-cyclohexylidene-2-norbomene, 5-vinyl-2-norbomene, and norbomadiene. Of the dienes typically used to prepare EPDMs, the particularly preferred dienes are 1,4-hexadiene (HD), 5-ethylidene-2-norbomene (ENB), 5-vinylidene-2-norbomene (VNB), 5-m6thylene-2-norbomene (MNB), and dicyclopentadiene (DCPD). The especially preferred dienes are 5-ethylidene-2-norbomene (ENB) and 1,4-hexadiene (HD).

COCATALYSTS
Suitable cocatalysts include those compounds previously known in the art for use with Group 4 metal olefin polymerization complexes. Examples of suitable activating cocatalysts include neutral Lewis acids, such as C1.30 hydrocarbyl substituted Group 13 compounds, especially tri(hydrocarbyOaIuminum- or tri(hydTOcarbyl)boron compounds and halogenated (including perhalogenated) derivatives thereof, having from I to 10 carbons in each hydrocarbyl or halogenated hydrocarbyl group, more especially perfluorinated tri(aryl)boron compounds, and most especially tris(pentafluorophenyl)borane; nonpolymeric, compatible, noncoordinating, ion forming compounds (including the use of such compounds under oxidizing conditions), especially the use of anrmionium-, phosphonium-, oxonium-, carbonium-, silylium- or sulfonium- salts of compatible, noncoordinating anions, or ferrocenium-, lead- or silver salts of compatible, noncoordinating anions; and combinations of the foregoing cation forming cocatalysts and techniques. The foregoing activating cocatalysts and activating techniques have been previously taught with respect to different metal complexes for olefin polymerizations in the following references: EP-A-277,003, US-A-5,153.157, US-A-5,064,802.US-A-5,321.106, US-A-5,721,185, US-A-5,350,723, US-A-5,425.872, US-A-5,625,087, US-A-5,883,204, US-A-5,919.983, US-A-5.783,512, WO 99/15534, and W099/42467.
Combinations of neutral Lewis acids, especially the combination of a trialkyi aluminum compound having from 1 to 4 carbons in each alkyl group and a halogenated tri(hydrocarbyl)boron compound having'from 1 to 20 carbons in each hydrocarbyl group, especially tris(pentafluorophenyl)borane, further combinations of such neutral Lewis acid mixtures with a polymeric or oligomeric alumoxane, and combinations of a single neutral Lewis acid, especially tris(pentafluorophenyl)borane with a polymeric or oligomeric alumoxane may be used as activating cocatalysts. Preferred molar ratios of metal complex:tris(pentafluorophenyl-borane:alumoxane are from 1:1:1 to 1:5:20, more preferably from 1:1:1.5 to 1:5:10.
Suitable cation forming compounds useful as cocatalysts in one embodiment of the present invention comprise a cation which is a Bronsted acid capable of donating a proton, and a compatible, noncoordinating anion. A". As used herein, the term "noncoordinating" means an anion or substance which either does not coordinate to the Group 4 metal containing precursor complex and the catalytic derivative derived there from, or which is only weakly coordinated to such complexes thereby remaining sufficiently labile to be displaced by a neutral Lewis base. A noncoordinating anion specifically refers to an anion which when functioning as a charge balancing anion in a cationic metal complex does not transfer an anionic substituent or fragment thereof to said cation thereby forming neutral complexes. "Compatible anions" are anions which are not

degraded to neutrality when the initially formed complex decomposes and are noninterfering with desired subsequent polymerization or other uses of the complex.
Preferred anions are those containing a single coordination complex comprising a charge-bearing metal or metalloid core which anion is capable of balancing thechiarge of the active catalyst species (the metal cation) which may be formed when the two components are combined. Also, said anion should be sufficiently labile to be displaced by olefinic, diolefmic and acetylenically unsaturated compounds or other neutral Lewis bases such as ethers or nttriles. Suitable metals include, but are not limited to, aluminum, gold and platinum. Suitable metalloids include, but are not limited to, boron, phosphoms, and silicon. Compounds containing anions which comprise coordination complexes containing a single metal or metalloid atom are, of course, well known and many, particularly such compounds containing a single boron atom in the eimon portion, are available commercially.
Preferably such cocatalysts may be represented by the following general formula:
wherein:
L* is a neutral Lewis base;
(L*-H)"'" is a conjugate Bronsted acid of L*;
A" is a noncoordinating, compatible anion having a charge of g-, nd
g is an integer firom 1 to 3.
More preferably A' corresponds to the formula: [M'Q4]'; wherein:
M' is boron or aluminum in the +3 formal oxidation state; and
Q independently each occurrence is selected from hydride, dialkylamido, halide, hydrocarbyl, hydrocarbyloxide, halosubstituted-hydrocarbyl, balosubstituted hydrocarbyloxy, and halo- substituted silylhydrocarbyl radicals (including perhalogenated hydrocarbyl- perhalogenated hydrocarbyloxy- and perhalogenated silylhydrocarbyl radicals), said Q having up to 20 carbons with the proviso that in not more than one occurrence is Q haiide. Examples of suitable hydrocarbyloxide Q groups are disclosed in US-A-5,296,433.
In a more preferred embodiment, d is one, that is, the counter ion has a single negative charge and is A". Activating cocatalysts comprising boron which are particularly useful in the preparation of catalysts of this invention may be represented by the following general formula:
(L*-H)*(BQ4)-; wherein;
L* iis as previously defined;
B is boron in a formal oxidation state of 3; and

Q is a hydrocarbyl-, hydrocarbyloxy-, fiuorinated hydrocarbyl-, fiuorinated hydrocarbyloxy-, or fiuorinated silylhydrocarbyl- group of up to 20 nonhydrogen atoms, with the proviso that in not more than one occasion is Q hydrocarbyl.
Preferred Lewis base salts are ammonium salts, more preferably trialkylammonium salts containing one or more C12.40 slkyl groups. Most preferably, Q is each occurrence a fiuorinated aryl group, especially, a pentafluorophenyl group.
Illustrative, but not limiting, examples of boron compounds which may be used as an activating cocatalyst in the preparation of the improved catalysts of this invention are tri-substituted ammonium salts such as:
trimethylammonium tetrakis(pentafluorophenyl) borate, triethylammonium tetrakis(pentafluorophenyl) borate, tripropy I ammonium tetrakisCpentafluorophenyl) borate, tri(n-buty!)ammonium tetrakis(pentafluorophenyl) borate, tri(sec-butyl)ammonium tetrakis(pentafluorophenyl) borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl) borate, N,N-dimethylaniUnium n-butyltris(pentafluorophenyl) borate, N,N-dimethylanilinium benzyltris(pentafluorophenyl) borate,
N,N-dimethyIaniliniumtetrakis(4-(t-butyldimethylsilyl)-2, 3, 5, 6-tetrafluorophenyl) borate, N,N-dimethyIanilinium tetrakis(4-(triisopropylsilyI)-2, 3,5,6-tetrafluorophenyl) borate, N,N-dimethylanilinium pentafluorophenoxytris(pentafluorophenyl) borate, N,N-diethylanilinium tetrakis(pentafluorophenyl) borate, N,N-dimethyl-2,4,6-trimethylaniliniumtetrakis(pentafIuorophenyl) borate, dimethyloctadecylammonium tetrakis(pentafluoropheny]) borate, methyldioctadecylammonium tetrakis(pentafluorophenyl) borate, dialkyl ammonium salts such as:
di-(i-propyI)ammonium tetrakis(pentafluorophenyl) borate, methyloctadecylammonium tetrakisCpentafluorophenyl) borate, methyloctadodecylammonium tetrakis(pentafluorophenyl) borate, and dioctadecylammonium tetrakisCpentafluorophenyl) borate; tri-substituted phosphonium salts such as:
triphenylphosphonium tetrakisCpentafluorophenyl) borate, methyldioctadecylphosphonium tetrakisCpentafluorophenyl) borate, and triC2,6-dimethylphenyl)phosphonium tetrakisCpentafluorophenyl) borate;
di-substituted oxonium salts such as:

diphenyloxonium tetrakis(pentafluorophenyl) borate, di(o-tolyl)oxonium tetrakis(pentafluorophenyl) borate, and di(octadecyl)oxonium tetrakis(pentafluorophenyI) borate; di-substituted sulfonium salts such as:
di(o-toIyi)sulfonium tetrakis(pentafluorophenyl) borate, and methylcotadecylsulfonium tetrakis(pentafluorophenyl) borate.
Preferred (L*-H)* cations are methyldioctadecylammonium cations, dimethyloctadecylammonium cations, and ammonium cations derived from mixtures of trialkyi amines containing one or 2 C|4.ig alkyl groups. A particularly preferred example of the latter compound is based on a commercially available long chain amine and is referred to as: bis-(hydrogenated tallowalkyl)methylammonium tetrakis(pentafluorophenyI)borate.
Another suitable ion forming, activating cocatalyst comprises a salt of a cationic oxidizing agent and a noncoordinating, compatible anion represented by the formula:
wherein:
Ox' is a cationic oxidizing agent having a charge of h+;
h is an integer from 1 to 3; and
A®' and g are as previously defined.
Examples of cationic oxidizing agents include: ferrocenium, hydrocarbyl-substituted ferrocenium, Ag*' or Pb". Preferred embodiments of A' are those anions previously defined with respect to the Bronsted acid containing activating cocatalysts, especially tetrakis(pentafluorophenyI)borate.
Another suitable ion forming, activating cocatalyst comprises a compound which is a salt of a carbenium ion and a noncoordinating, compatible anion represented by the formula:
wherein:
[C]"*" is a C|.2o carbenium ion; and
A" is a noncoordinating, compatible anion having a charge of -1. A preferred carbenium ion is the trityl cation, that is triphenylmethylium.
A further suitable ion forming, activating cocatalyst comprises a compound which is a salt of a silylium ion and a noncoordinating, compatible anion represented by the formula:
wherein:
Q' is CMO hydrocarbyl, and A' is as previously defined.

Preferred silylium salt activating cocatalysts are trimethylsilylium tetrakispentafluorophenylborate, triethylsilylium tetrakispentafluorophenylborate and ether substituted adducts thereof. Silylium salts have been previously generically disclosed in J. Chem Soc. Chem. Comm.. 1993, 383-384, as well as Lambert. J. B., et al., Oreanometallics. 1994, 13, 2430-2443. The use of the above silylium salts as activating cocatalysts for addition polymerization catalysts is disclosed in US-A-5,625,087.
Certain complexes of alcohols, mercaptans, silanols, and oximes with tris(pentafluorophenyl)borane are also effective catalyst activators and may be used according to the present invention. Such cocatalysts are disclosed in US-A-5,296,433.
A class of cocatalysts comprising non-coordinating anions generically referred to as expanded anions, further disclosed in US Patent 6,395,671, may be suitably employed to activate the metal complexes of the present invention for olefin polymerization. Generally, these cocatalysts (illustrated by those having imidazolide, substituted imidazolide, imidazolinide, substituted imidazolinide, benzimidazolide, or substituted benzimidazolide anions) may be depicted as follows:

wherein:
A'* is a cation, especially a proton containing cation, and preferably is a trihydrocarbyl ammonium cation containing one or two C10.40 alkyl groups, especially a methyldi (Ci4.2oalkyl)animonium cation,
Q, independently each occurrence, is hydrogen or a halo, hydrocarbyl, halocarbyl, halohydrocarbyl. silylhydrocarbyl. or silyl, (including mono-, di- and tri(hydrocarbyl)silyl) group of up to 30 atoms not counting hydrogen, preferably C1.20 alkyl, and
Q is tris(pentafluorophenyl)borane or tris(pentafluorophenyl)alumane).
Examples of these catalyst activators include trihydrocarbylammonium- salts, especially, methyldi(Ci4.2oalkyl)anunonium- salts of:
bis(tris(pentafluorophenyl)borane)imida2olide, bis(tris(pentafluorophenyl)borane)-2-undecylimidazolide, bis(tris(pentafluorophenyl)borane)-2-heptadecylimidazolide, bis(tris(pentafluorophenyl)borane)-4,5-bis(undecyl)imidazolide, bis(tris(pentafluorophenyI)borane)-4,5-bis(heptadecyl)imidazoIide,

bis(tris(pentafluorophenyl)borane)imidazoUnide,
bis(tris(pentafIuorophenyl)borane)-2-undecyliniidazolinide,
bis(tris(pentafluorophenyl)borane)-2-heptadecyIinnidazolinide,
bis(tris(pentaf]uorophenyl)borane)-4,5-bis(undecyI)imidazolinide,
bis(trig(pentafIuorophenyl)borane)-4,5-bis(heptadecyI)imidazoiinide,
bis(tris(pentafluorophenyl)borane)-5,6-dimethylbenzimidazolide,
bis(tris(pentafluorophenyl)borane)-5,6-bis(undecyI)benzimidazolide,
bis(tris(peniafIuoropheny l)alumane)i midazol ide, bis(tris(pentafluorophenyI)aIumane)-2-undecylimida2oIide, bis(tris(pentafluorophenyl)alumane)-2-heptadecylimidazolide, bis(tris(pentafluorophenyl)alumane)-4,5-bis(undecyl)imidazonde, bis(tris(pentafluorophenyl)alumane)-4,5-bis(heptadecyl)imidazolide. bis(tris(pentafluorophenyl)alumane)imidazolinide, bis(tris(pentafluorophenyl)alumane)-2-undecyHmidazolinide, bisCtris(pentafluorophenyl)alumane)-2-heptadecylimidazolinide, bis(tris(pentafluorophenyl)alumane),5-bisCundecyl)imidazolinide, bis(tris(pentafluorophenyl)alumane)-4,5-bis(heptadecyl)imidazoHnide, bis(tris(pentafluorophenyl)alumane)-5,6-dimethylbenzimidazolide, and bis(tris(pentafluorophenyl)alumane)-5,6-bis(undecy0benzimidazolide.
Other activators include those described in PCT publication WO 98/07515 such as tris (2, 2', 2"-nonaf!uorobiphenyl)fluoroaluminate. Combinations of activators are also contemplated by the invention, for example, alumoxanes and ionizing activators in combinations, see for example, EP-A-0 573120, PCT publications WO 94/07928 and WO 95/14044 and US Patents 5.153.157 and 5,453,410. WO 98/09996 describes activating catalyst compounds with perchlorates. periodates and iodates, including their hydrates. WO 99/18135 describes the use of organoboroaluminum activators. WO 03/10171 discloses catalyst activators that are adducts of Bronsted acids with Lewis acids. Other activators or methods for activating a catalyst compound are described in for example. US Patents 5,849,852, 5.859, 653,5,869,723, EP-A-615981, and PCT publication WO 98/32775.
As previously mentioned, suitable activating cocatalysts for use herein include polymeric or oligomeric alumoxanes, especially methalumoxane (MAO), triisobutyl aluminum modified methalumoxane (MMAO), or tri n-ootylaluminum modified methalumoxane (OMAO); Lewis acid modified alumoxanes, especially perhalogenated tri(hydrocarbyl)aluminum- or perhalogenated tri(hydrocarbyl)boron modified alumoxanes, having from I to 10 carbons in each hydrocarbyl or halogenated hydrocarbyl group, and most especially tris(pentafluorophenyI)borane modified

alumoxanes. Such cocatalysts are previously disclosed in USP's 6,214,760, 6, J60,146, 6,140,521, and 6,696,379.
AH of the foregoing catalyst activators as well as any other know activator for transition metal complex catalysts may be employed alone or in combination according to the present invention.
The molar ratio of catalyst/cocatalyst employed preferably ranges from 1:10,000 to 100:1, more preferably from 1:5000 to 10:1, most preferably from 1:1000 to 1:1. Alumoxane. when used by itself as an activating cocatalyst, may be employed in lower quantity ( PROCESS
In general, the polymerization may be accomplished at conditions well known in the prior art for olefin solution polymerization reactions. Preferred polymerization temperatures are dependent upon the comonomer content of the resulting polymer. For polymers of densities ranging from 0.865 to 0.885, the preferred temperatures range from 170-250'C, more preferably from 180-220°C. For polymers of densities ranging from 0.885 to 0.940, the preferred temperatures range from 190-250°C, more preferably from J 95-250 "C. Preferred polymerization pressures are from atmospheric to 3000 atmospheres (100 kPa to 300 MPa), more preferably from 1 MPa to 10 MPa. In most polymerization reactions the molar ratio of catalyst:polymerizable compound employed is from 10"':1 to 10"':1, more preferably from lO"':! to 10"':1. Highly desirably, the reaction is conducted under continuous, solution polymerization conditions, that is, conditions wherein the monomer or monomers are continuously added to a reactor operating under solution polymerization conditions, and polymerized product is continuously or semi-continuously, removed and recovered.
Desirably, the polymerization mixture comprises an aliphatic or alicyclic liquid diluent. Examples of such aliphatic or alicyclic liquid diluents include straight and branched-chain hydrocarbons such as isobutane, butane, pentane, hexane, heptane, octane, and mixtures thereof; alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcyclo-heptane, and mixtures thereof; and perfluorinated hydrocarbons such as perfluorinated C4.10 alkanes, and the like. Small quantities of aromatic hydrocarbons such as toluene, ethylbenzene or xylene may be included as well, but are not preferred. Mixtures of the foregoing are also suitable. A

preferred liquid diluent is an hydrogenated oligomeric aliphatic hydrocarbon mixture having a distillation, ASTM D 86, IBP of 118 °C, distillation, ASTM D 86, Dry Point of 137 °C, and Specific Gravity, 15.6 "C, ASTM D 1250 of 0.72 sold commercially under the trade designation Isopar™ E, available from ExxonMobil Corporation.
The use of molecular weight control agents or chain transfer agents in the present process is desired. Examples of such molecular weight control agents include hydrogen, trialkyl aluminum compounds, or other known chain transfer agents. A particular benefit of the use of the present invention is the ability (depending on reaction conditions) to produce narrow molecular weight distribution ethylene/ a-olefm interpolymers. Preferred polymers have Mw/Mn of less than 2.5, more preferably less than 2.3. Such narrow molecular weight distribudon polymer products are highly desirable due to improved tensile strength properties as well as reduced levels of extractables.
Without limiting in any way the scope of the invention, one means for C£inying out the present polymerization process is as follows. In a stirred-tank reactor, the monomers to be polymerized are introduced continuously together with any solvent or diluent. The reactor contains a liquid phase composed substantially of monomers together with any solvent or diluent and dissolved polymer. Catalyst along with cocatalyst and optional chain transfer agent are continuously or intermittently introduced in the reactor liquid phase or any recycled portion thereof. The reactor temperature may be controlled by adjusting the solvent/mononfter ratio, the catalyst addition rate, as well as by use of cooling or heating coils, jackets or both. The polymerization rate is controlled by the rate of catalyst addition. Pressure is controlled by the monomer flow rate and partial pressures of volatile components. The ethylene content of the polymer product is determined by the ratio of ethylene to comonomer in the reactor, which is controlled by manipulating the respective feed rates of these components to the reactor. The polymer product molecular weight is controlled, optionally, by controlling other polymerization variables such as the temperature, monomer concentration, or by the previously mentioned chain transfer agent. Upon exiting the reactor, the effluent is contacted with a catalyst kill agent such as water, steam or an alcohol. The polymer solution is optionally heated, and the polymer product is recovered by flashing off gaseous monomers as well as residual solvent or diluent at reduced pressure, and, if necessary, conducting further devolatilization in equipment such as a devolatilizing extruder. In a continuous process, the mean residence time of the catalyst and polymer in the reactor generally is from 5 minutes to 8 hours, and preferably from 10 minutes to 6 hours.
Alternatively, the foregoing polymerization may be carried out in a continuous loop reactor with or without a monomer, comonomer, catalyst or cocatalyst gradient established between differing regions thereof, optionally accompanied by separated addition of catalysts and/or chain

transfer agent, and operating under adiabatic or non-adiabatic solution polymerization conditions or combinations of the foregoing reactor conditions. Examples of suitable loop reactors and a variety of suitable operating conditions for use therewith are found in USP's 5,977,251, 6, 319,989 and 6,683,149.
Supports may be employed in the present invention, especially in slurry or gas-phase polymerizations. Suitable supports include solid, particulated, high surface area, metal oxides, metalloid oxides, or mixtures thereof (interchangeably referred to herein as an inorganic oxide). Examples include: talc, silica, alumina, magnesia, titania, zirconia, Sn203, alumlnosilicates, borosilicates, clays, and mixtures thereof. Suitable supports preferably have a surface area as determined by nitrogen porosimetry using the B.E.T. method from 10 to 1000 m/g, and preferably from 100 to 600 m/g. The average particle size typically is from 0.1 to 500 |jun, preferably from I to 200 Jim, more preferably 10 to 100 \un.
In one embodiment of the invention the present catalyst composition and optional support may be spray dried or otherwise recovered in solid, particulated form to provide a composition that is readily transported and handled. Suitable methods for spray drying a liquid-containing slurry are well known in the art and usefully employed herein. Preferred techniques for spray drying catalyst compositions for use herein are described in US-A's-5,648,310 and 5,672,669.
The polymerization is desirably carried out as a continuous polymerization, preferably a continuous, solution polymerization, in which catalyst components, monomers, and optionally solvent, adjuvants, scavengers, and polymerization aids are continuously supplied to the reaction zone and polymer product continuously removed there from. Within the scope of the terms "continuous" and "continuously" as used in this context are those processes in which there are intermittent additions of reactants and removal of products at small regular or irregular intervals, so that, over time, the overall processis substantially continuous.
The catalyst compositions can be advantageously employed in a high pressure, solution, slurry, or gas phase polymerization process. For a solution polymerization process it is desirable to employ homogeneous dispersions of the catalyst components in a liquid diluent in which the polymer is soluble under the polymerization conditions employed. One such process utilizing an extremely fine silica or similar dispersing agent to produce such a homogeneous catalyst dispersion where either the metal complex or the cocatalyst is only poorly soluble is disclosed in US-A-5, 783,512. A high pressure process is usually carried out at temperatures from 100 "C to 400 "C and at pressures above 500 bar (50 MPa). A slurry process typically uses an inert hydrocarbon diluent and temperatures of from 0 "C up to a temperature just below the temperature at which the resulting polymer becomes substantially soluble in the inert polymerization medium. Preferred temperatures

in a slurry polymerization are from 30 "C, preferably from 60 "C up to M5 "C, preferably up to 100 "C. Pressures typically range from atmospheric (100 kPa) to 500 psi (3.4 MPa).
Supported catalyst compositions may be prepared by depositing or chemically bonding the requisite components on an inert inorganic or organic particulated solid, as previously disclosed. In one embodiment, a heterogeneous catalyst is prepared by co-precipitating the metal complex and the reaction product of an inert inorganic compound and an active hydrogen containing activator, especially the reaction product of a tri (Cjalkyl) aluminum compound and an ammonium salt of a hydroxyaryltris(pentafIuorophenyl)borate, such as an ammonium salt of (4-hydroxy-3,5-ditertiarybutylphenyl)tris(pentafluorophenyl)borate. When prepared in heterogeneous or supported form, the catalyst composition may be employed in a slurry or a gas phase polymerization. As a practical limitation, slurry polymerization takes place in liquid diluents in which the polymer product is substantially insoluble. Preferably, the diluent for slurry polymerization is one or more hydrocarbons with less than 5 carbon atoms. If desired, saturated hydrocarbons such as ethane, propane or butane may be used in whole or part as the diluent.
Preferably for use in gas phase polymerization processes, the support material and resulting catalyst has a median particle diameter from 20 to 200 jim, more preferably from 30 jim to ! 50 Jim, and most preferably from 50 |xm to 100 |iim. Preferably for use in slurry polymerization processes, the support has a median particle diameter from 1 |xm to 200 fim, more preferably from 5 fj.m to 100 Jim, and most preferably from 10 jim to 80 |i,m.
Suitable gas phase polymerization process for use herein are substantially similar to known processes used commercially on a large scale for the manufacture of polypropylene, ethylene/ a-olefin copolymers, and other olefin polymers. The gas phase process employed can be, for example, of the type which employs a mechanically stirred bed or a gas fluidized bet! as the polymerization reaction zone. Preferred is the process wherein the polymerization reaction is carried out in a vertical cylindrical polymerization reactor containing a fluidized bed of polymer particles supported or suspended above a perforated plate or fluidization grid, by a flow of fluidization gas.
The gas employed to fluidize the bed comprises the monomer or monomers to be polymerized, and also serves as a heat exchange medium to remove the heat of reaction from the bed. The hot gases emerge from the top of the reactor, normally via a tranquilization zone, also known as a velocity reduction zone, having a wider diameter than the fluidized bed and wherein fine particles entrained in the gas stream have an opportunity to gravitate back into the bed. It can also be advantageous to use a cyclone to remove ultra-fine particles from the hot gas stream. The gas is then normally recycled to the bed by means of a blower or compressor and one or more heat exchangers to strip the gas of the heat of polymerization.

A preferred method of cooling of the bed, in addition to the cooling provided by the cooled recycle gas, is to feed a volatile liquid to the bed to provide an evaporative cooling effect, often referred to as operation in the condensing mode. The volatile liquid employed in this case can be, for example, a volatile inert liquid, for example, a saturated hydrocarbon having 3 to 8, preferably 4 to 6, carbon atoms. In the case that the monomer or comonomer itself is a volatile liquid, or can be condensed to provide such a liquid, this can siiitably be fed to the bed to provide an evaporative cooling effect. The volatile liquid evaporates in the hot fluidized bed to form gas which mixes with the fluidizing gas. If the volatile liquid comprises a monomer or comonomer, it will undergo some polymerization in the bed. The evaporated liquid then emerges from the reactor as part of the hot recycle gas, and enters the compression/heat exchange part of the recycle loop. The recycle gas is cooled in the heat exchanger and, if the temperature to which the gas is cooled is below the dew point, liquid will precipitate from the gas. This liquid is desirably recycled continuously to the fluidized bed. It is possible to recycle the precipitated liquid to the bed as liquid droplets carried in the recycle gas stream. This type of process is described, for example in EP-89691; U.S. 4,543,399; WO-94/25495 and U.S. 5,352,749. A particularly preferred method of recycling the liquid to the bed is to separate the liquid from the recycle gas stream and to reinject this liquid directly into the bed, preferably using a method which generates fine droplets of the liquid within the bed. This type of process is described in WO-94/28032.
The polymerization reaction occurring in the gas fluidized bed is catalyzed by the continuous or semi-continuous addition of catalyst composition according to the invention. The catalyst composition may be subjected to a prepolymerization step, for example, by polymerizing a small quantity of olefin monomer in a liquid inert diluent, to provide a catalyst composite comprising supported catalyst particles embedded in olefin polymer particles as well.
The polymer is produced directly in the fluidized bed by polymerization of the monomer or mixture of monomers on the fluidized particles of catalyst composition, supported catalyst composition or prepolymerized catalyst composition within the bed. Start-tip of the polymerization reaction is achieved using a bed of preformed polymer particles, which are preferably similar to or the same as the polymer to be produced, and conditioning the bed by drying with inert gas or nitrogen prior to introducing the catalyst composition, the monomers and any other gases which it is desired to have in the recycle gas stream, such as a diluent gas, hydrogen chain transfer agent, or an inert condensable gas when operating in gas phase condensing mode. The produced polymer is discharged continuously or semi-continuously from the fluidized bed as desired.
The gas phase processes most suitable for the practice of this invention are continuous processes which provide for the continuous supply of reactants to the reaction zone of the reactor and the removal of products from the reaction zone of the reactor, thereby providing a steady-state

environment on the macro scale in the reaction zone of the reactor. Products are readily recovered by exposure to reduced pressure and optionally elevated temperatures (devolatilization) according to known techniques. Typically, the fluidized bed of the gas phase process is operated at temperatures greater than 50 °C, preferably from 60 "C to 110 °C, more preferably from 70 "C to 110 °C. Examples of gas phase processes which are adaptable for use in the process of this invention are disclosed in US Patents: 4,588,790; 4,543, 399; 5,352,749; 5,436,304; 5,405,922; 5,462,999; 5,461,123; 5,453.471; 5,032,562; 5,028,670; 5,473,028; 5,106,804; 5,556,238; 5,541,270; 5,608,019; and 5,616,661.
SPECIFIC EMBODIMENTS
The following embodiments are provided for purposes of specific disclosure for the appended claims.
1. A process for polymerization of ethylene and optionally one or more a-olefins
under continuous, solution polymerization conditions to prepare a high molecular weight polymer, said process comprising conducting the polymerization in the presence of a catalyst composition comprising a transition metal complex and an activating cocatalyst under conditions that result in a value for the polymerization index, , that is greater than or equal to zero,as determined by the following equation:
» where, T is the polymerization temperature in degrees Celsius, X is the ethylene
conversion in the reactor in mol percent, E is the catalyst efficiency in g polymer produced per g of metal In the metal complex fed to the reactor per unit time, P is the resulting polymer density in units of g/ml, A is the melt index of the polymer in units of dg/minute, and the equation constants,

3 2. The process of embodiment 1 wherein the resulting polymbr has a molecular weight
distribution, Mw/Mn, less than 3,0.
3. The process of embodiment 1 wherein the catalyst composition additionally
f
comprises a chain transfer agent.

4 The process of embodiment 3 wherein the quantity of chain transfer agent present
in the reactor is sufficient to decrease the Mw of the resulting polymer at least 30 percent compared to the molecular weight of the resulting polymer prepared in the absence of a chain transfer agent.
5. The process of embodiment 3 wherein the chain transfer agent is hydrogen, present in an amount from 0.015 to 2.0 mol percent (based on monomer content).
6. The process of embodiment 1 wherein the ethylene conversion is at least 85 mol percent.
7. The process of any one of embodiments I -6 wherein ethylene and one or more C3.20 a-olefms are copolymerized.
8. The process of embodiment 7 wherein ethylene and one or more C6.20 a-olefms are copolymerized.
9. The process of embodiment 1 conducted at a temperature from 185 to 250 "C in the presence of a chain transfer agent to prepare a polymer having a density between 0.885 and 0.950 g/cm', a melt index, I2, 10. The process of embodiment 9 wherein the chain transfer agent is present in a quantity such that the decrease in Mw of the resulting polymer is >30 percent compared to the Mw of the resulting polymer made in the absence of chain transfer agent.
.11. The process of embodiment 10 wherein the chain transfer agent is hydrogen present in the reactor in an amount of from 0.015 to 2 mol percent based on ethylene.
12. The process of any one of embodiments 9-11 wherein ethylene and one or more C3.20 a-olefins are copolymerized.
13. The process of embodiment 12 wherein ethylene and one or more Ce-a a-olefms are copolymerized.
14. The process of embodiment 1 conducted at a temperature from 170 to 250 "C in the presence of a chain transfer agent to prepeu-e a polymer having a density between 0.885 and 0.950 g/cm a melt index, I2, 15. The process of embodiment 14 wherein the chain transfer agent is present in a quantity such that the decrease in Mw of the resulting polymer is >30 percent compared to the Mw of the resulting polymer made in the absence of chain transfer agent.
16. The process of embodiment 15 wherein the chain transfer agent is hydrogen present in the reactor in an amount of from 0.015 to 2 mol percent based on ethyleiae.
17. The process of any one of embodiments 14-16 wherein ethylene and one or more C3.20 a-olefms are copolymerized.

18. The process of embodiment 17 wherein ethylene and one or more C6.20 a-olefins are
copolymerized.
19. The process of embodiment 1 conducted at a temperature from 130 to 250 °C and
an ethylene conversion of at least 80 mol percent, in the presence of a chain transfer agent to
prepare a polymer having a density between 0.865 and 0.950 g/cm', a melt index, T2, from 0.01 to
100, a molecular weight distribution Mw/Mn and wherein the activating cocatalyst is oligomeric or polymeric alumoxane or
modified alumoxane present in an amount to provide a molar ratio, Al: metal complex, fronti 20-200.
20. The process of embodiment 19 wherein the oligomeric or polymeric alumoxane or modified alumoxane is present in an amount to provide a molar ratio, Alrndetal complex, from 30-150.
21. The process of embodiment 20 wherein the oligomeric or polymeric alumoxane or modified alumoxane is present in an amount to provide a molar ratio, Ahmetal complex, from 40-80.
22. The process of any one of embodiments 19-21 wherein th6 oligomeric or polymeric alumoxane or modified alumoxane is selected from the group consisting of methylalumoxane, isobutylalumoxahe; and Lewis acid modified alumoxanes.
23. The process of embodiment 22 wherein the Lewis acid modified alumoxane is trialkyi aluminum-, perhalogenated tri(hydrocarbyl)aIuminum-, or perhalogenated tri(hydrocarbyI)boron modified methylalumoxane.
24. The process of embodiment 23 wherein the Lewis acid modified alumoxane is triisobutyl aluminum- modified methylalumoxane, tri-n-octyl aluminum- modified methylalumoxane, or tris(pentafluorophenyl)boron- modified methylalumoxane.
25. The process of any one of embodiments 19-24 wherein the chain transfer agent is present in a quantity such that the decrease in Mw of the resulting polymer is >30 percent compared to the Mw of the resulting polymer made in the absence of chain transfer agent.
26. The process of embodiment 25 wherein the chain transfer agent is hydrogen present in the reactor in an amount of from 0.015 to 2 mol percent based on ethylene.
27. The process of any one of embodiments 1-6 conducted in a single reactor and the catalyst composition comprises at least two metal complexes or metal compounds.
28. The process of any one of embodiments 1-6 conducted in at least one reactor of two or more reactors connected in series or in parallel.
29. The process of embodiment 28 wherein the catalyst composition comprises at least two metal complexes.

30. A process for polymerization of one or more addition polymerizable monomers to
prepare a high molecular weight polymer, said process comprising conducting the polymerization in
the presence of a catalyst composition comprising a transition metal complex and an activating
cocatalyst wherein the metal complex corresponds to the formula:

R is an aliphatic, aromatic or inertly substituted aromatic group containing from 5 to 20 atoms not counting hydrogen, or a polyvalent derivative thereof;
T is a hydrocarbylene or silane group having from 1 to 20 atoms not counting hydrogen, or an inertly substituted derivative thereof;
M' is a Group 4 metal, preferably zirconium or hafnium;
R' independently each occurrence is a monovalent ligand group or two R' groups together are a divalent hydrocarbylene or hydrocarbadiyi group; and
bonds and electron donative interactions are represented by lines and arrows respectively.
31. The process of embodiment 30 wherein the metal complex correspond to the
formula:
T' is a divalent bridging group of from 2 to 20 atoms not counting hydrogen, preferably a substituted or unsubstituted, Cj.6 alkylene group; and
Ar' independently each occurrence is an arylene or an alkyl-, aryl-, alkoxy- or amino-substituted arylene group of from 6 to 20 atoms not counting hydrogen and not counting the substituents;
M is a Group 4 metal, preferably hafnium or zirconium;
R' independently each occurrence is a monovalent ligand group or two R" groups together are a divalent hydrocarbylene or hydrocarbadiyi group; and electron donative interactions are represented by arrows.

32. The process of embodiment 31 wherein the metal complex corresponds to the

Ar"* is €5,20 aryl or inertly substituted derivatives thereof, especially 3,5-di(isopropyl)phenyl, 3,5-di(isobutyl)phenyl, dibenzo-lH-pyrrole-l-yl, naphthyl, anthracen-5-yl, 1,2,3,4,6,7,8,9-octahydroanthracen-5-yl and
T* independently each occurrence comprises a C3.6 alkylene group, a C3.6 cycloalkylene group, or an inertly substituted derivative thereof;
R' independently each occurrence is hydrogen, halo, hydrocarbyl, trihydrocarbylsilyl, trihydrocarbylsilylhydrocarbyl, alkoxy or amino of up to 50 atoms not counting hydrogen; and
BP, independently each occurrence is halo or a hydrocarbyl or trihydrocarbylsilyl group of up to 20 atoms not counting hydrogen, or 2 R° groups together are a divalent hydrocarbylene, hydrocarbadiyl or trihydrocarbylsilyl groups.
33. The process of embodiment 32 wherein M' is Zr.
34. The process of embodiment 33 wherein the metal complex is selected from the
group consisting of:
A) bis((2-oxoyl-3-( 1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)propane-
1,2-diylzirconium (IV) dimethyl,
bis((2-oxoyl-3-( 1,2,3,4,6,7,8,9-octahydroanthracen-5-y I)-5-(methyl)pheny l)-2-phenoxy)propane-1,2-
diylzirconium (IV) dichloride,
bis((2-oxoyl-3-(dibenzo-lH-pyiToIe-l-yl)-5-(methyl)phenyl)-2-phenoxy)propane-l,2-diyIzirconium
(IV) dimethyl,
bis((2-oxoyl-3-(dibenzo-lH-pyrrole-l-yl)-5-(methyl)phenyl)-2-phenoxy)propane-l,2-diylzirconium
(IV) dichloride,
bis((2-oxoyl-3-( 1,1 -dimethylethyOphen-1 -yl)-5-(methyl)phenyI)-2-phenoxy)propane-1,2-
diylzirconium (IV) dimethyl.

bis((2-oxoyI-3-(l,l-dimethylethyl)phen-l-yl)-5-(niethyl)phenyl)-2-phenoxy)propane-1.2-diylzirconium (IV) dichloride,
bis((2-oxoyl-3-(l,2,3.4,6.7,8,9-octahydroanthracen-5-yI)-5-(methyl)phenyl)-2-phenoxy)-trans-
cyclohexane-l,2-dimethylenyI-l,2-diyl2irconium (IV) dimethyl,
bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-trans-
cyclohexane-l,2-dimethylenyl-I,2-diylzirconmm (IV) dichloride,
bis((2-oxoyl-3-(dibenzo-1 H-pyrrole-1 -yl)-5-(methyl)phenyl)-2-phenoxy)-trans--cyclohexane-1,2-
dimethylenyl-l,2-diylzirconium (IV) dimethyl,
bis((2-oxoyl-3-(dibenzo-lH-pyrroIe-l-yI)-5-(methy!)phenyI)-2-phenoxy)-trans-cycIohexane-l,2-
dimethylenyl-l,2-diylzirconium (IV) dichloride,
bis((2-oxoyl-3-( 1,1 -dimethylethyl)phen-l -yl)-5-(methyl)phenyl)-2-pheiioxy)-trans-cyclohexane-1,2-
dimethylenyl-1,2-diyIzirconium (TV) dimethyl,
bis((2-oxoyl-3-( 1,1 -dimethylethy l)phen-1 -yI)-5-(methyl)pheny l)-2-phenoxy)-trans-cyclohexane-1,2-
dimethyIenyl-l,2-diylzirconium (IV) dichloride,
bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyI)-2-phenoxy)-cis-
cyclohexane-1,3-diylzirconiviin (IV) dimethyl,
bis((2-oxoyl-3-( 1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-cis-
cyclohexane-l,3-diylzirconium (IV) dichloride,
bis((2-oxoyl-3-(dibenzo-lH-pyrrole-l-yl)-5-(methyl)phenyl)-2-phenoxy)-cis-cyclohexane-l,3-
diylzirconium (IV) dimethyl,
bis((2-oxoyl-3-(dibenzo-1 H-pyrroJe-1 -yl)-5-(methyJ)phenyI)-2-phenoxy)-cis-cyclohexane-1,3-
diylzirconium (IV) dichloride,
bis((2-oxoyl-3-( 1,1 -diTnethylethyl)phen-1 -yl)-5-(methyI)phenyI)-2-phenoxy)-cis-cyclohexane-1,3-
diylzirconium (IV) dimethyl,
bis((2-oxoyl-3-( 1,1 -dimethylethyOphen-1 -yl)-5-(methyl)phenyl)-2-phenoxy)-cis-cyclohaxane-1,3-
diylzirconium (IV) dichloride,
bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-cis-cycIohexene-l,2-dimethylenyl-I,2-diylzirconium (IV) dimethyl,
bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)r2-phenoxy)-cis-cyclohexene-l,2-dimethylenyl-l,2-diylzirconium (IV) dichloride,
bis((2-oxoyl-3-(dibenzo-1 H-pyrrole-1 -yI)-5-(methy!)phenyI)-2-phenoxy)-cis-cyclohexene-1,2-dimethylenyl-I,2-diylzirconium (IV) dimethvl.

bis((2-oxoyl-3-(dibenzo-1 H-pyrroIe-1 -yl)-5-(methyl)phenyl)-2-phenoxy)-cis-cycIohexene-1,2-
dimethylenyI-l,2-diyIzirconium (IV) dichioride,
bis((2-oxoyl-3-(l,l-dimethylethyl)phen-l-yl)-5-(methyl)phenyl)-2-phenoxy)-cis-cyclohexene-l,2-
dimethylenyl-l,2-diylzirconium (IV) dimethyl,
bis((2-oxoyl-3-( 1,1 -dimethylethyOphen-1 -yl)-5-(methyl)phenyl)-2-phenoxy)-cis-cycIohexene-1,2-
dtmethyIenyl-l,2-diylzirconium (IV) dichioride,
bis((2-oxoyl-3-( 1,2,3,4,6,7,8,9-octahydroanthracen-5-yI)-5-(methyl)phenyl)-2-phenoxy)butane-1.4-
diylzirconium (IV) dimethyl,
bJs((2-oxoyI-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(niethyl)phenyl)-2-phenoxy)butane-l,4-
diylzirconium (TV) dichioride,
bis((2-oxoyl-3-(dibenzo-lH-pyrrole-l-yl)-5-(methyI)phenyl)-2-phenoxy)butane-l,4-diylzirconium
(rV) dimethyl,
bis((2-oxoyl-3-(dibenzo-lH-pyrrole-l-yl)-5-(methyl)phenyl)-2-phenoxy)butane-l,4-diylzirconium
(IV) dichioride,
bis((2-oxoyl-3-( 1,1 -dimethylethyOphen-1 -yI)-5-(methyl)phenyI)-2-phenoxy)butane-1,4-
diylzirconium (IV) dimethyl,
bis((2-oxoyl-3-( 1,1 -dimethylethyOphen-1 -y0-5-(methyl)pheny0-2-phenoxy)butane-1,4-
diylzirconium (IV) dichioride,
B) bis((2-oxoyl-3-( 1,2.3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-methyl-2-
phenoxy))propane-l,2-diyIzirconium (IV) dimethyl,
bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methy0phenyl)-(4-methyl-2-
phenoxy))propane-l,2-diylzirconium (IV) dichioride,
bis((2-oxoyl-3-(dibenzo-1 H-pyrroIe-1 -yl)-5-(methyI)phenyl)-(4-methyl-2-phenoxy))propane-1,2-
diylzirconium (IV) dimethyl,
bis((2-oxoyl-3-(dibenzo-1 H-pyrrole-1 -yl)-5-(methy0phenyl)-(4-methyl-2-phenoxy))propane-1,2-
diylzirconium (IV) dichioride,
bis((2-oxoyl-3-( 1,1 -dimethylethyOphen-1 -y l)-5-(methyl)phenyl)-(4-methy l-2-phenoxy))propane-1,2-
diylzirconium (IV) dimethyl,
bis((2-oxoyI-3-( 1,1-dimethylethyOphen-1 -yI)-5-(methyI)phenyl)-(4-methyl-2-phenoxy))propane-1,2-
diylzirconium (IV) dichioride,
bis((2-oxoyl-3-(1.2,3,4,6,7.8,9-octahydroanthracen-5-y0-5-(methyl)pheny0-(4-methyI-2-phenoxy))-trans-cyclohexane-l,2-dimethylenyl-l ,2-diylzirconium (IV) dimethyl.

bis((2-oxoyl-3-(1.2,3.4,6,7,8,9-octahydroanthracen-5-yl)-5-(niethyl)phenyl)-(4-niethyl-2-phenoxy))-
trans-cyclohexane-l,2-dimethylenyl-l,2-diylzirconium (IV) dichloride,
bis((2-oxoyl-3-(dibenzo-1 H-pyrrole-1 -y l)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-trans-
cyclohexane-l,2-dimethylenyl-l,2-diylzirconium (IV) dimethyl,
bis((2-oxoyl-3-(dibenzo-lH-pyrroIe-I-yl)-5-(methyl)phenyI)-(4-methyl-2-phenoxy))-trans-
cyclohexane-1,2-dimethyIenyl-l,2-diylzirconium (IV) dichloride,
b)S((2-oxoyl-3-( ], 1 -dimethylethyl)phen-l -yl)-5-(methyl)phenyl)-(4-methyN2-phenoxy))-trans-
cyclohexane- 1,2-dimethyIenyl-1,2-diylzirconium (IV) dimethyl,
bis((2-oxoyl-3-( 1,1 -dimethylethyl)phen-1 -yl)-5-(methyI)phenyl)-(4-methyl-2-phenoxy))-trans-
cyclohexane-l,2-dimethylenyl-l,2-diylzirconium (IV) dichloride,
bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-methyI-2-phenoxy))-
cis-cyclohexane-1,3-diylzirconium (IV) dimethyl,
bis((2-oxoyl-3-(1.2,3,4,6,7,8,9-octahydroanthracen-5-yI)-5-(methyl)phenyI)-(4-methy]-2-phenoxy))-
cis-cyclohexane-1,3-diyl2irconium (IV) dichloride,
bis((2-oxoyl-3-(dibenzo-lH-pyrrole-l-y!)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-cis-
cyclohexane-1,3-diylzirconium (IV) dimethyl,
bis((2-oxoyl-3-(dibenzo-1 H-pyrrole-1 -yl)-5-(methyI)phenyl)-(4-methyl-2-phenoxy))-cis-
cycIohexane-l,3-diylzirconium (TV) dichloride,
bis((2-oxoy l-3-( 1,1 -dimethylethy])phen- l-yl)-5-(methyl)phenyl)-(4-methyl-2-pheiioxy))-cis-
cyclohexane-l,3-diylzirconium (IV) dimethyl,
bis((2-oxoyl-3-( 1,1 -dimethylethyl)phen-1 -yl)-5-(methyl)phenyl)-(4-methyl=-2-phenoxy))-cis-
cyclohexane-1,3-diylzirconium (IV) dichloride,
bis((2-oxoyI-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-cis-cyclohexene-l,2-dimethylenyl-l ,2-diylzirconium (IV) dimethyl,
bts((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yI)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-cis-cyclohexene-l,2-dimethylenyl-I,2-diyIzirconium (IV) dichloride, bis((2-oxoyl-3-(dibenzo-lH-pyrrole-l-yI)-5-(methyl)phenyl)-(4-methyl-2-|ihenoxy))-cis-
cyclohexene-l,2-dimethylenyl-!,2-diyIzirconium (JV) dimethyl, bis((2-oxoyl-3-(dibenzo-lH-pyrrole-l-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-cis-
cyclohexene-l,2-dimethylenyl-I,2-diylzirconium (IV) dichloride,
bis((2-oxoyl-3-( 1,1 -dimethylethyl)phen-1 -yl)-5-(methy!)phenyl)-(4-m6thyl-2-phenoxy))-cis-
cyclohexene- 1,2-dimethylenyl- 1,2-diylzirconium (IV) dimethyl.

bis((2-oxoyl-3-( 1,1 -dimethylethyl)phen-1 -yl)-5-(methyl)phenyI)-(4-methyl-2-phenoxy))-cis-cyclohexene-I,2-dimethy]enyl-l,2-diylzirconium (IV) dichloride,
bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyI)phenyl)-(4-methyl-2-
phenoxy))butane-l,4-diyizirconium (IV) dimethyl,
bis((2-oxoyl-3-( 1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(nnethyl)phenyl)-(4-methyl-2-
pbenoxy))butane-l,4-diylzirconium (IV) dichloride,
bis((2-oxoyl-3-(dibenzo-lH-pyiTole-l -yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))butane-! ,4-
diylzirconium (IV) dimethyl,
bis((2-oxoy l-3-(dibenzo-1 H-pyrroIe-1 -y !)-5-(methyI)pheny!)-(4-methyl-2-phenoxy))butane-1,4-
diylzirconium (IV) dichloride,
bis((2-oxoy l-3-( 1,1 -dimethylethyl)phen-1 -yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))butane-1,4-
diylzirconium (TV) dimethyl,
bis((2-oxoy l-3-( 1,1 -dimethylethyl)phen-1 -yI)-5-(methyI)phenyl)-(4-methyl-2-phenoxy))butane-1,4-
diylzirconium (IV) dichloride,
C) bis((2-oxoyl-3-( 1,2.3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(inethyl)phenyl)-(5-(2-methyl)propane-2-yl)-2-phenoxy)propane-l ,2-diylzircoi\ium (IV) dimethyl, bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyI)phenyl)-(5-(2-methyI)propane-2-yl)propane-l,2-diylzirconium (IV) dichloride,
bis((2-oxoyl-3-(dibenzo-lH-pyrrole-l-yl)-5-(methyl)phenyl)-(5-(2-metbyl)propane-2-yl)propane-1,2-diylzirconium (IV) dimethyl,
bis((2-oxoyl-3-(dibenzo-1 H-pyrrole-l -yl)-5-(methyl)phenyl)-(5-(2-methyl)propane-2-yl)propane-1,2-diylzirconium (IV) dichloride,
bis((2-oxoyl-3-(l,l-dimethylethyl)phen-l-yl)-5-(methyl)phenyI)-(5-(2-methyl)propane-2-yI)propane-l,2-diylzirconium (TV) dimethyl,
bis((2-oxoyl-3-(l,l-dimethylethyl)phen-l-yl)-5-(methyl)phenylH5-(2-methyl)propane-2-yI)propane-l,2-diylzirconium (IV) dichloride,
bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(5-(2-methyl>propane-
2-yl)-trans-cyclohexane-l,2-dimethylenyl-l,2-diylzirconium (IV) dimethyl, bis((2-oxoyl-3-(1,2.3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(5-(2~methyI)propane-
2-yI)-trans-cycIohexane-1,2-dimethylenyl-t,2-diylzircQnium (IV) dichloride, bis((2-oxoy|-3-(dibenzo-lH-pyrrole-l-yl)-5-(methyl)phenyl)-(5-(2-methyl)propane-2-yl)-trans-cyclohexane-I,2-dimethylenyl-],2-diylzirconium (IV) dimethyl,

bis((2-oxoyl-3-(dibenzo-lH-pyrrole-I-yl)-5-Cinethyl)phenyI)-(5-(2-methyl)propane-2-yI)-trans-
cyclohexane-l,2-dimethylenyl-l,2-diylzirconium (IV) dichloride,
bis((2-oxoyl-3-( 1,1 -dimethylethyl)phen-1 -yl)-5-(niethyl)phenyl)-(5-(2-methy l)propane-2-y l)-trans-
cyclohexane-1,2-di methylenyl-1,2-diyIzirconium (JV) dimethyl,
bis((2-oxoyI-3-(l,l-dimethylethyI)phen-l-yI)-5-(methyI)phenyl)-(5-(2-inethyI)propane-2-yl)-trans-
cyclohexane-l,2-dimethylenyl-l,2-diylzirconium (IV) dichloride,
bis((2-oxoyI-3-(l,2,3.4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(5-(2-methyl)propane-
2-yI)-cis-cyclohexane-l,3-diylzirconium (IV) dimethyl,
bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(5-(2-methyl)propane-
2-yl)-cis-cyclohexane-l,3-diylzirconiuni (IV) dichloride,
bis((2-oxoyl-3-(dibenzo-lH-pyrrole-l-yl)-5-(methyl)phenyl)-(5-(2-methyl)propane-2-yl)-cis-
cyclohexane-l,3-diylzirconium (IV) dimethyl,
bis((2-oxoyl-3-(dibenzo-1 H-pyrrole-1 -y!)-5-(methy0phenyI)-(5-(2-methyl)propane-2-y I)-cis-
cyclohexane-l,3-diylzirconium (IV) dichloride,
bis((2-oxoyl-3-( 1,1 -dimethylethyOphen-1 -yl)-5-(methyl)phenyl)-(5-(2-methy0propane-2-y 0-cis-
cyclohexane-l,3-diylzirconium (IV) dimethyl,
bis((2-oxoyl-3-( 1,1 -dimethylethyOphen-1 -yl)-5-(methyl)phenyl)-(5-(2-methyl)propane-2-yl)-cis-
cyclohexane-l,3-diylzirconium (FV) dichloride,
bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-C5-(2-methyl)propane-2-yl)-cis-cyclohexene-l ,2-dimethylenyl-1,2-diyIzirconium (IV) dimethyl,
bis((2-oxoyI-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyI)phenyI)-(5-(2-methyI)propane-2-yl)-cis-cyclohexene-1,2-dimethylenyl-1,2-diylzirconium (IV) dichloride, bis((2-oxoyl-3-(dibenzo-1 H-pyrrole-1 -yl)-5-(methyl)phenyl)-(5-(2-methyl)propane-2-yI)-cis-cyclohexene-l,2-dimethylenyl-l,2-diylzirconium (IV) dimethyl,
bjs((2-oxoyl-3-(dibenzo-1 H-pyrrole-1 -yl)-5-(methy!)pheny!)-(5-(2-methyl)propane-2-yl)-cis-cyclohexene-l,2-dimethylenyl-l,2-diyIzirconium (IV) dichloride,
bis((2-oxoyl-3-(l,l-dimethylethyl)phen-l-yl)-5-(methyl)phenyI)-(5-(2-methyl)propane-2-yl)-cis-cycIohexene-l,2-dimethylenyl-l,2-diylzirconium (IV) dimethyl,
bis((2-oxoyl-3-(l,l-dimethylethyl)phen-l-yl)-5-(methyl)phenyl)-(5-(2-methyl)propane-2-yl)-cis-cycIohexene-I,2-dimethy!enyI-I,2-diyIzirconium (IV) dichloride,
bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyI)-(5-(2-methyI)propane-2-yl)butane-l,4-diyIzirconium (IV) dimethyl.

bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yI)-5-(methyl)phenyl)-(5-(2-methyI)propane-
2-yl)butane-l,4-diylzirconiumi (IV) dichloride,
bi s((2-oxoyI-3-(dibenzo-1 H-pyrrolcT 1 -yl)-5-(methyl)phenyl)-(5-(2-niethyl)propane-2-yl)butane-1,4-
diylzirconium (IV) dimethyl,
bis((2-oxoyl-3-(dibenzo-lH-pyrrole-l-yl)-5-(methyl)phenyl)-(5-(2-methyl)propane-2-yl)butane-l,4-
diylzirconium (IV) dichloride,
bis((2-oxoyl-3-( 1,1 -dimethylethyl)phen-1 -yI)-5-(methyl)phenyl)-(5-(2-methyl)propane-2-yl)butane-
I,4-diylzircoiiium (IV) dimethyl, and
bis((2-oxoyl-3-(l,l-diniethylethyl)phen-l-yI)-5-(methyl)phenyl)-(5-(2-methyl)propane-2-yl)butane-
1,4-diylzirconium (IV) dichloride.
It is understood that the present invention is operable in the absence of any component which has not been specifically disclosed and may be combined with any other suitable reaction or process in a multistep polymerization system design. The following examples are provided in order to further illustrate the invention and are not to be construed as limiting. Unless stated to the contrary, all parts and percentages are expressed on a weight basis.
EXAMPLES 1-10 Preparation of Metal Complex
The synthetic procedures of US-A-2004/0010103 were substantially repeated to prepare metal complexes Al-AlO.




CH3
CH3


A3: bis((2-oxoyl-3-(3,5-di-(l ,1 -dimethyl-ethyl) phen- ] -y])-5-(methyl)phenyl)-2- phenoxy)-propane-1,3-diyl zirconium (IV) dimethyl

A4: bis((2-oxoyl- 3-(dibenzo-1 H-pyrro!e-1 -yl)- 5-(msthyl)pheny!)-2-phenoxy)-propane-1,3-diyl zirconium (TV) dimethyl



CH3 CH3
on

A5: bis((2-oxoyl-3-(dibenzo-lH-pyrrole- l-yl)-5-(mBthyl)phenyI)-2-phenoxy)-cis-cyclohexane-1,3-diyl zirconium (IV) dimethyl

A6:bis((2-oxoyl-3-(dibenzo-lH-pyrrole-l-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-cis-cyclohexene-l,2-dimethylenyl zirconium (EV) dinthyl







A7: bis((2-oxioyl-3-(diben2D-lH-pyirole-l-}d)-5-(inBthyI)phertyi)-(4-iiEth2-phBnoxy))- trans-cycJohexane- l,2-dinneth54enyl zirconium (IV) dimethyl

A8: bis((2-oxoyJ-3-(diben20- IH-pyrrole- l-yI)-5-(thyI)phenyI)-2-phenoxy)-butane-l,4-diyl zirconium (IV) dimethyl


H-iC

t-Bu

t-Bu

.t-Bu t-Bu

t-Bu

t-Bu



\9: bis((2-oxoyl-3-(diben2D-1 H-pyrro!e-1 -yO-5-(methyOphenyI)-(4-(2-niethyOpropane-2-yl)-2-phenoxy)propane-1,3-diyl zirconium (IV) dimethyl

Al 0: bis((2-oxoyl-3-(3,5-bB-(l, 1 -dimethytetfiyl) phenyI)-(5-nfithyI)phenyl)(4-( 1,1 -dimethylethyl)--2-phenoxy)-propane- 1,3-diyl zirconium (TV) dimethyl

Polymerization - Batch Reactor
, A stirred, one gallon (3.79 L) autoclave reactor is charged with about two liters of mixed ilkanes solvent (Isopar™ E) and varying amounts of 1-octene. The reactor is heated to the desired temperature and charged with hydrogen in the indicated quantity followed by sufficient ethylene to bring the total pressure to 450 psig (3.1 MPa). The catalyst composition is prepared in a drybox under inert atmosphere by combining together catalyst, cocatalyst (a mixture of 1.2 equivalents of bis-hydrogenated tallowalkyl)med7ylammonium tetrakis(pentafIuorophenyl)borate and 10 equivalents of triisobutylaluminum modified methalumoxane containing a molar ratio of i-butyl/methyl groups of about 1/3 (MMAO) with additional solvent to give a total volume of about J 7 mL. The activated catalyst mixture Is injected into the reactor over approximately 4 minutes.
The reactor temperature and pressure are maintained constant by continually feeding ethylene during the polymerization and cooling the reactor as required. After 10 minutes the ethylene is shut off and the hot solution transferred into a nitrogen purged resin kettle. An additive solution containing a phosphorus stabilizer and phenolic antioxidant (Irgaphos 168 and Irganox 1010 in toluene in a 2:1 weight ratio) is added to provide a total additive concentration of about 0.1 percent in the polymer. The polymer is recovered by thorough drying in a vacuum oven. After drying the samples are weighed to determine catalyst efficiency. Between polymerizations the reactor is thoroughly rinsed with hot mixed hexanes. Results are contained in Table 1.


Polymerization — Continuous Solution Reactor
Continuous solution polymerizations are carried out in a computer controlled autoclave
reactor equipped with an internal stirrer. Purified mixed alkanes solvent (Isopar™ E available from
ExxonMobil, Inc.). ethylene, 1-octene, and hydrogen are supplied to a 3.8 L reactor equipped with a
jacket for temperature control and an internal thermocouple. The solvent feed to the reactor is
measured by a mass-flow controller. A variable speed diaphragm pump cqntrols the solvent flow
rate and pressure to the reactor. At the discharge of the pump, a side stream is taken to provide
flush flows for the catalyst and cocatalyst injection lines and the reactor agitator. These flows are
measured by Micro-Motion mass flow meters and controlled by control valves or by the manual
adjustment of needle valves. The remaining solvent is combined with 1-octene, ethylene, and
hydrogen and fed to the reactor. A mass flow controller is used to deliver hydrogen to the reactor as
needed. The temperature of the solvent/monomer solution is controlled by use of a heat exchanger
before entering the reactor. This stream enters the bottom of the reactor. The catalyst component
solutions are metered using pumps and mass flow meters and are combined with the catalyst flush
solvent and introduced into the bottom of the reactor. The reactor is run li(]uid-full at 500 psig
(3.45 MPa) with vigorous stirring. Product is removed through exit lines ajc the top of the reactor.
All exit lines from the reactor are steam traced and insulated. Polymerization is stopped by the
addition of a small amount of water into the exit line along with any stabilizersor other additives
and passing the mixture through a static mixer. The product stream is then heated by passing
through a heat exchanger before devolatilization. The polymer product is recovered by extrusion
using a devolatilizing extruder and water cooled pelletizer. Process details and results are contained
in Tables 2 and 3. >.




CLAIMS:
1. A process for polymerization of ethylene and optionally one or more a-olefins
under continuous, solution polymerization conditions to prepare a high molecular weight polymer,
said process comprising conducting the polymerization in the presence of a catalyst composition
comprising a transition metal complex and an activating cocatalyst under conditions that result in a
value for the polymerization index, *P , that is greater than or equal to zero as determined by the
following equation:

where, T is the polymerization temperature in degrees Celsius, X is the ethylene conversion in the reactor in mol percent, E is the catalyst efficiency in g polymer produced per g of metal in the metal complex fed to the reactor per unit time, P is the resulting polymer density in
units of g/ml, ^2 is the melt index of the polymer in units of dg/minute, and the equation constants,

2. The process of claim I wherein the resulting polymer has a molecular weight distribution, Mw/Mn, less than 3.0.
3. The process of claim 1 wherein the catalyst composition additionally comprises a chain transfer agent.
4 The process of claim 3 wherein the quantity of chain transfer agent present in the
reactor is sufficient to decrease the Mw of the resulting polymer at least 30 percent compared to the molecular weight of the resulting polymer prepared in the absence of a chain transfer agent.
5. The process of claim 3 wherein the chain transfer agent is hydrogen, present in an amount from 0.015 to 2.0 mol percent (based on ethylene).
6. The process of claim I wherein the ethylene conversion is at least 85 mol percent.
7. The process of any one of claims 1-6 wherein ethylene and one or more C3.20 ct-
olefms are copolymerized.
8. The process of claim 7 wherein ethylene and one or more Ce-ao a-olefins are
copolymerized.
9. The process of claim I conducted at a temperature from 185 to 250 "C in the
presence of a chain transfer agent to prepare a polymer having a density between 0.885 and 0.950

g/cm^, a melt index, I2, 10. The process of claim 9 wherein the chain transfer agent is present in a quantity such that the decrease in Mw of the resulting polymer is >30 percent compared to the Mw of the resulting polymer made in the absence of chain transfer agent.
11. The process of claim 10 wherein the chain transfer agent is hydrogen present in the reactor in an amount of from 0.015 to 2 mol percent based on monomer content.
12. The process of any one of claims 9-11 wherein ethylene aiid one or more Cj.ia a-olefms are copolymerized.
13. The process of claim 12 wherein ethylene and one or more C6-20 a-olefms are copolymerized.
14. The process of claim 1 conducted at a temperature from 170 to 250 °C in the presence of a chain transfer agent to prepare a polymer having a density between 0.885 and 0.950 g/cm^, a melt index, l2, 15. The process of claim 14 wherein the chain transfer agent is present in a quantity such that the decrease in Mw of the resulting polymer is >30 percent compared to the Mw of the resulting polymer made in the absence of chain transfer agent,
16. The process of claim 15 wherein the chain transfer agent is hydrogen present in the reactor in an amount of from 0.015 to 2 mol percent based on ethylene.
17. The process of any one of claims 14-16 wherein ethylene and one or more C3.3D a-oleJins are copolymerized.
18. The process of claim 17 wherein ethylene and one or more C^o a-olefins are copolymerized.
19. • The process of claim 1 conducted at a temperature from 130 to 250 °C and an
ethylene conversion of at least 80 mol percent, in the presence of a chain transfer agent to prepare a
polymer having a density between 0.865 and 0.950 g/cm', a melt index, I2, from 0.01 to 100, a
molecular weight distribution Mw/Mn gpoiymei/fJ-gmeiai, and wherein the activating cocatalyst is oligomeric or polymeric alumoxane or
modified alumoxane present in an amount to provide a molar ratio, Alrmetal complex, from 20-200.
20. The process of claim 19 wherein the oligomeric or polymeric alumoxane or
modified alumoxane is present in an amount to provide a molar ratio, Ahmetal complex, from
30-150.

21. The process of claim 20 wherein rhe oligomeric or polymeric alumoxane or modified alumoxane is present in an amount lo provide a molar ratio, AI:metal complex, from 40-80.
22. The process of any one of claims 19-21 wherein the oligomeric or polymeric alumoxane or modified alumoxane is selected from the group consisting of methylalumoxane, isobutylalumoxane; and Lewis acid modified alumoxanes.
23. The process of claim 22 wherein the Lewis acid modified alumoxane is trialkyl aluminum-, perhalogenated tri(hydrocarbyl)aluminum-, or perhalogenated tri(hydrocarbyl)boron modified methylalumoxane.
24. The process of claim 23 wherein the Lewis acid modified alumoxane is triisobutyl aluminum- modified methylalumoxane, tri-n-octyl aluminum- modified methylalumoxane, or tris(pentafluorophenyl)boron- modified methylalumoxane.
25. The process of any one of claims 19-24 wherein the chain transfer agent is present in a quantity such that the decrease in Mw of the resulting polymer is >30 percent compared to the Mw of the resulting polymer made in the absence of chain transfer agent.
26. The process of claim 25 wherein the chain transfer agent is hydrogen present in the reactor in an amount of from 0.015 to 2 mol percent based on ethylene.
27. The process of any one of claims 1-6 conducted in a single reactor and tw catalyst composition comprises at least two metal complexes.
28. The process of any one of claims 1 -6. conducted in at least one reactor of two or more reactors connected in series or in parallel.
29. The process of claim 28 wherein the catalyst composition comprises at least two metal complexes or metal compounds.
30. A process for polymerization of one or more addition polymerizable monomers to prepare a high molecular weight polymer, said process comprising conducting the polymerization in the presence of a catalyst composition comprising a transition metal complex and an activating cocatalyst wherein the metal complex corresponds to the formula:

R^° is an aliphatic, aromatic or inertly substituted aromatic group containing from 5 to 20 atoms not counting.hydrogen, or a polyvalent derivative thereof;

T is a hydrocarbylene or silane group having from 1 to 20 atoms not counting hydrogen, or an inertly substituted derivative thereof;
M' is a Group 4 metal;
R** independently each occurrence is a monovalent ligand group of two R° groups together are a divalent hydrocarbylene or hydrocarbadiyl group; and
bonds and electron donative interactions are represented by lines and arrows respectively.
31. The process of claim 30 wherein the metal complex correspond to the formula:

wherein:
T^ is a divalent bridging group of from 2 to 20 atoms not counting hydrogen;
Ar^ independently each occurrence is an arylene or an alkyl-, aryl-, alkoxy- or amino-substituted arylene group of from 6 to 20 atoms not counting hydrogen and not counting the sulfstituents;
M^ is a Group 4 metal;
R° independently each occurrence is a monovalent ligand group or two R° groups together are a divalent hydrocarbylene or hydrocarbadiyl group; and
electron donative interactions are represented by arrows.
32. The process of claim 31 wherein the metal complex corresponds to the formula:

where M' is Hf or Zr;
Ar* is C6.20 aryl or inertly substituted derivatives thereof;
T* independently each occurrence comprises a C3.6 alkylene group, a C3.6 cycloalkylene group, or an inertly substituted derivative thereof;

R^' independently each occurrence is hydrogen, halo, hydrocarbyl' trihydrocarbylsilyl, trihydrocarbylsilylhydrocarbyl, alkoxy or amino of up to 50 atoms not counting hydrogen; and
R°, independently each occurrence is halo or a hydrocarbyl or trihydrocarbylsilyl group of up to 20 atoms not counting hydrogen, or 2 R*^ groups together are a divalent hydrocarbylene, hydrocarbadiyl or trihydrocarbylsilyl groups.
33. The process of claim 32 wherein M^ is Zr.
34, The process of claim 33 wherein the metal complex is selected from the group
consisting of:
A) bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)propane-1,2-diylzirconium (IV) dimethyl,
bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)propane-l,2-diylzirconium (IV) dichloride,
bis((2-oxoyl-3-(dibenzo-lH-pyrrole-l-y!)-5-(methyI)phenyl)-2-phenoxy)propane-l,2-diyIzirconium (IV) dimethyl,
bis((2-oxoyl-3-(dibenzo-lH-pyrrole-l-yI)-5-(methyl)phenyl)-2-phenoxy)propane-l,2-diylzirconium (IV) dichloride,
bis((2-oxoyl-3-(1,l-dimethylethyI)phen-l-yl)-5-(methyl)phenyI)-2-phenoxy)propane-l,2-diylzirconium (FV) dimethyl,
bis((2-oxoyl-3-(l,l-dimethylethyl)phen-l-yl)-5-(methyl)phenyl)-2-phenoxy)propane-l,2-diylzirconium (FV) dichloride,
bis((2-oxoyl-3-( 1,2,3,4,6,7,8,9-octahydroanthracen-5-y l)-5-(methyl)phenyl)-2-phenoxy)-trans-cyclohexane-l ,2-dimethylenyl-l,2-diyIzirconium (FV) dimethyl,
bis((2-oxoyl-3-(l,2,3,4,6,7,8.9-octahydroanthracen-5-yI)-5-(methyl)phenyl)-2-phenoxy>trans-cyclohexane-1,2-dimethylenyl-1,2-diylzirconium (IV) dichloride, bis((2-oxoyl-3-(dibenzo-lH-pyrrole-l-yl)-5-(methyl)phenyl)-2-phenoxy)-trans-cycIohexane-I,2-
dimethylenyI-l,2-diylzirconium (IV) dimethyl, bis((2.oxoyl-3-(dibenzo-lH-pyrrole-l-yI)-5-(methyl)phenyl)-2-phenoxy)-tfans-cyclohexane-l,2-
dimethylenyl-],2-diylzirconium (IV) dichloride, bis((2-oxoyI-3-(l,l-dimethylethyl)phen-l-yl)-5-(methyl)phenyl)-2-phenoxy)-trans-cyclohexane-l,2-
dimethylenyl-l,2-diylzirconium (IV) dimethyl,
bis((2-oxoyl-3-(] ,1 -dimethylethyl)phen-l -yl)-5-(methyl)phenyl)-2-phenoxy)-trans-cyclohexane-l ,2-
dimethylenyl-l,2-diylzirconium (IV) dichloride.

bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl')-2-phenoxy)-cis-cyclohexane-1,3-diylzirconium (IV) dimethyl,
bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yI)-5-(nnethyl)phenyl)-2-phenoxy)-cis-cyclohexane-1,3-diylzirconium (IV) dichloride,
bis((2-oxoyl-3-(dibenzo- IH-pyrrole-1 -yI)-5-(methyl)phenyl)-2-phenoxy)-c|s-cyclohexane- ] ,3-diylzirconium (TV) dimethyl,
bis((2-oxoyl-3-(dibenzo-1 H-pyrrole-1 -yl)-5-(methyl)phenyl)-2-phenoxy)-cis-cyclohexane-1,3-diylzirconium (IV) dichloride,
bis((2-oxoyl-3-(l, l-dimethylethyl)phen-1 -yl)-5-(methyl)phenyl)-2-phenoxy)-cis-cyclohexane-l ,3-diylzirconium (rV) dimethyl,
bis((2-oxoyl-3-(l,l-dimethylethyl)phen-l-yl)-5-(methyl)phenyl)-2-phenoxy)-cis-cyclohexane-I,3-diylzirconium (IV) dichloride,
bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-cis-
cycIdhexene-l,2-dimethyIenyl-l,2-diylzirconium (IV) dimethyl,
bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-cis-
cyclohexene-l,2-dimethylenyl-l,2-diylzirconium (IV) dichloride,
bis((2-oxoyl-3-(dibenzo-1 H-pyrrole-1 -yl)-5-(methyl)phenyl)-2-phenoxy)-cis-cyclohexene-1,2-
dimethylenyl-l,2-diylzirconium (IV) dimethyl,
bis((2-oxoyl-3-(dibenzo-lH-pyrrole-l-yl)-5-(methyl)phenyl)-2-phenoxy)-c|s-cyclohexene-l,2-
dimethylenyl-l,2-diylzirconium (IV) dichloride,
bis((2-oxoyl-3-(l ,l-dimethylethyl)phen-1 -yl)-5-(methyl)phenyl)-2-phenoxy)-cis-cyclohexene-1,2-
dimethylenyl-l,2-diylzirconium (IV) dimethyl,
bis((2-oxoyl-3-(l, l-dimethylethyl)phen-l -yl)-5-(methy))phenyl)-2-phenoxy)-cis-cyclohexene-i,2-
dimethylenyl-l,2-diylzirconium (IV) dichloride,
bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)butane-l,4-diylzirconium (IV) dimethyl,
bis((2-oxoyl-3-( 1.2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyI)-2-phenoxy)butane-1,4-diylzirconium (IV) dichloride, bis((2-oxoyl-3-(dibenzo-1 H-pyrrole-1 -yI)-5-(methyl)phenyl)-2-phenoxy)biitane-1,4-diylzirconium
(IV) dimethyl, bis((2-oxoyl-3-(dibenzo-lH-pyrrole-l-yl)-5-(methyl)phenyl)-2-phenoxy)butane-I,4-diylzirconium
(IV) dichloride,
bis((2-oxoyl-3-( 1,1 -dimethylethyl)phen-1 -yl)-5-CmethyI)phenyl)-2-phenoxy)butane-1,4-

diylzirconium (IV) dimethyl,
bis((2-oxoyI-3-(l,l-dimethyIethyI)phen-l-yl)-5-(methyl)phenyl)-2-phenoxy)butane-I,4-diylzirconium (IV) dichloride,
B) bis((2-oxoyl-3-( 1,2,3,4,6,7,8,9-octahydroanthracen-5-yI)-5-(methyl)phenyl)-(4-methyl-2-
phenoxy))propane-l ,2-diylzirconivjm (IV) dimethyl,
bis((2-oxoyI-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yI)-5-(methyl)phenyl)-(4-methyl-2-
phenoxy))propane-l,2-diylzirconium (IV) dichloride,
bis((2-oxoyI-3-(dibenzo-IH-pyrroIe-l-yI)-5-(inethyl)phenyI)-(4-methyI-2-phenoxy))propane-l,2-
diylzirconium (IV) dimethyl,
bis((2-oxoyl-3-(dibenzo-1 H-pyrrole-1 -yl)-5-(methy])phenyl)-(4-methyl-2-phenoxy))propane-1,2-
diylzirconium (IV) dichloride,
bis((2-oxoyl-3-( 1,1 -dimethylethyl)phen-1 -yl)-5-(niethyl)phenyI)-(4-methy lr2-phenoxy))propane-1,2-
diylzirconium (IV) dimethyl,
bis((2-oxoyl-3-(l,l-dimethyIethyl)phen-l-yl)-5-(methyl)phenyl)-(4-methyl-2-pheiioxy))propane-l,2-
diylzirconium (IV) dichloride,
bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyI)phenyl)-(4-methyl-2-phenoxy))-
trans-cyclohexane-l ,2-dimethylenyl-l ,2-diylzirconium (IV) dimethyl,
bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyI)phenyl)-(4-methyl-2-phenoxy))-
trans-cyclohexane-l ,2-dimethylenyl-l ,2-diyIzirconium (IV) dichloride,
bis((2-oxoyl-3-(dibenzo-IH-pyrrole-I-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-trans-
cyclohexane-1,2-dimethylenyl-l,2-diylzirconium (IV) dimethyl,
bis((2-oxoyl-3-(dibenzo-1 H-pyrrole-1 -yI)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-trans-
cyclohexane-1,2-dimethylenyl-l ,2-diylzirconium (IV) dichloride,
bis((2-oxoyI-3-( 1,1 -dimethylethyl)phen-1 -yI)-5-(methyI)phenyl)-(4-methyl'2-phenoxy))-trans-
cyclohexane-1,2-dimethylenyl-1,2-diylzirconium (IV) dimethyl,
bis((2-oxoyl-3-(l,l-dimethylethyl)phen-l-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-trans-
cyclohexane-l,2-dimethyIenyl-l,2-diylzirconium (IV) dichloride,
bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-
cis-cyclohexane-l,3-diylzirconium(IV) dimethyl, bis((2-oxoyl-3-(l,2,3.4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyI)-(4-methyl-2-phenoxy))-
cis-cyclohexane-1,3-diylzirconium (IV) dichloride, bis((2-oxoyl-3-(dibenzo-lH-pyrrole-l-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-cis-

cycIohexane-l,3-diyIzirconium (rV) dimethyl,
bis((2-oxoyl-3-(dibenzo-1 H-pyrrole-1 -yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-cis-
cyclohexane-l,3-diylzirconium (IV) dichloride,
bis((2-oxoyl-3-(l, 1 -dimethylethyOphen-1 -yl)-5-(methyI)phenyl)-(4-methyl-2-phenoxy))-cis-
cyclohexane-l,3-diylzirconium (IV) dimethyl,
bis((2-oxoyl-3-(1,1 -di methylethyl)phen-1 -yl)-5-(methy!)phenyl)-(4-methyl-2-phenoxy))-cis-
cycIohexane-l,3-diylzirconium (IV) dichloride,
bis((2-oxoyl-3-(l,2,3,4,6,7.8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-cis-cyclohexene-l,2-dimethylenyl-l,2-diylzirconium (IV) dimethyl,
bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-methyI-2-phenoxy))-cis-cyclohexene-1,2-dimethyIenyI-l ,2-diylzirconium (IV) dichloride, bis((2-oxoyl-3-(dibenzo-1 H-pyrrole-1 -yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-cis-cyclohexene-l,2-dimethylenyl-l,2-diylzirconium (IV) dimethyl,
bis((2-oxoyl-3-(dibenzo-lH-pyrrole-l-yl)-5-(methyl)phenyl)-(4-methyl-2-'pihenoxy))-cis-cyclohexene-l,2-dimethylenyl-l,2-diyl2irconium (IV) dichloride,
bis((2-oxoyl-3-(l,l-dimethylethyl)phen-l-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-cis-cyclohexene-!,2-dimethylenyl-l,2-diylzirconium (IV) dimethyl,
bis((2-oxoyl-3-( I, I -dimethylethyOphen-1 -yl)-5-(methy0phenyI)-(4-methyl-2-phenoxy))-cis-cyclohexene-l,2-dimethylenyl-l,2-diylzirconium (IV) dichloride,
bis((2-cxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yO-5-(methyl)phenyl)-(4-methyl-2-
phenoxy))butane-l,4-diylzirconium (IV) dimethyl,
bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyI)phenyl)-(4-methyl-2-
phenoxy))butane-l,4-diylzirconium (IV) dichloride,
bis((2-oxoyl-3-(dibenzo-1 H-pyrrole-1 -yl)-5-(methyl)pbenyl)-(4-methyl-2-phenoxy))butane-1,4-
diylzirconium (IV) dimethyl,
bis((2-oxoyl-3-(dibenzo-1 H-pyrrole-l -yl)-5-(methyl)phenyl)-(4-methyI-2-phenoxy))butane-1,4-
diylzirconium (IV) dichloride,
bis((2-oxoyI-3-(l, 1 -di methylethyOphen-1 -yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))butane-1,4-
diylzirconium (IV) dimethyl, bis((2-oxoyl-3-(l,l-dimethylethy0phen-l-yI)-5-(methy0phenyl)-(4-methyl-2-phenoxy))butane-l,4-
diylzirconium (IV) dichloride,
C) bis((2-oxoyI-3-( 1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(5-(2-

melhyl)propane-2-y!)-2-phenoxy)propane-1,2-diyIzirconium (IV) dimethyl,
bis((2-oxoyl-3-(I,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyI)phenyI)-(5-(2-methyI)propane-
2-yl)propane-l,2-diy I zirconium (W) diciiloride,
bis((2-oxoyl-3-(dibenzo-lH-pyrrole-l-yl)-5-(methyl)phenyl)-(5-(2-methyl)propane-2-yI)propane-
1,2-diylzirconium (IV) dimethyl,
bis((2-oxoyl-3-(dibenzo-1 H-pyrrole-1 -yO-5-(methyl)phenyI)-(5-(2-methyI)propane-2-yI)propane-
1,2-diylzirconium (IV) dichloride,
bi s((2-oxoyl-3-( 1,1 -dimethylethyl)phen-1 -y 1 )-5-(methyl)phenyl)-(5-(2-methyl)propane-2-
yI)propane-I,2-diyIzirconium (IV) dimethyl,
bis((2-oxoyl-3-( 1,1 -dimethylethyl)phen-1 -yl )-5-(methyl)phenyI)-(5-(2-methyl)propane-2-
yl)propane-l,2-diyIzirconium (IV) dichloride,
bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyI)-(5-(2-methyl)propane-
2-yl)-trans-cyclohexane-1,2-dimethylenyl-1,2-diylzirconium (IV) dimethyl,
bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(5-(2-methyl)propane-
2-yl)-trans-cyclohexane-1,2-dimethylenyl-1,2-diylzirconium (IV) dichloride,
bis((2-oxoy l-3-(dibenzo-1 H-pyrrole-1 -yl)-5-(methyl)phenyl)-(5-(2-methyl)propane-2-yl)-trans-
cyclohexane-l,2-dimethylenyl-l,2-diylzirconium (IV) dimethyl,
bis((2-oxoyl-3-(dibenzo-1 H-pyrrole-1 -yl)-5-(methyl)phenyl)-(5-(2-methyl)propane-2-yl)-trans-
cyclohexane-1,2-dimethylenyl-l ,2-diylzirconium (IV) dichloride,
bis((2-oxoyl-3-( 1,1 -dimethylethyOphen-1 -yI)-5-(methyl)phenyl)-(5-(2-methyl)propane-2-yI)-trans-
cyclohexane-I,2-dimethylenyl-I,2-diylzirconium (IV) dimethyl,
bis((2-oxoyl-3-( 1,1 -di methylethyOphen-1 -yl)-5-(methyl)phenyl)-(5-(2-methyl)propane-2-y l)-trans-
cyclohexane-l,2-dimethylenyM ,2-diylzirconium (IV) dichloride,
bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyi)phenyl)-(5-(2-methyl)propane-2-yl)-cis-cycIohexane-l,3-diylzirconium (IV) dimethyl,
bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyi)-(5-(2-methyl)propane-2-yl)-cis-cyclohexane-l,3-diylzirconium (IV) dichloride, bis((2-oxoyl-3-(dibenzo-IH-pyrrole-l-yl)-5-(methyI)phenyl)-(5-(2-methyl)propane-2-yl)-cis-
cycIohexane-1,3-diylzirconium (TV) dimethyl,
bis((2-oxoyl-3-(dibenzo-1 H-pyrrole-1-yl)-5-(methyl)phenyl)-(5-(2-methyl)propane-2-yl)-cis-
cyclohexane-l,3-diylzirconium (IV) dichloride, bis((2-oxoyI-3-(l,J-dimethylethyl)phen-I-yl)-5-(methyl)phenyl)-(5-(2-methyl)propane-2-yl)-cis-

cyclohexane-1,3-diylzirconiuin (IV) dimethyl,
bis((2-oxoyl-3-(l,l-dimethylethy\)phen-l-y\)-5-(methyl)phenyl)-(5-(2-methyl)propane-2-yl)-cis-cycIohexane-l,3-diylzirconium (IV) dichloride,
bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyJ)pheny])-(5-(2-methyl)propane-
2-yl)-cis-cyclohexene-],2-dimethy)enyl-l ,2-diylzirconium (IV) dimethyl,
bis((2-oxoyl-3-(l,2,3.4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyI)-(5-(2-methyl)propane-
2-yl)-cis-cyclohe3cene-l,2-dimethylenyl-l,2-diyIzirconium (IV) dichloride,
bis((2-oxoyl-3-(dibenzo-1 H-pyrrole-1 -yl)-5-(methyI)phenyl)-(5-(2-methyl)propane-2-yl)-cis-
cyclohexene-I,2-dimethylenyl-I,2-diylzirconiuni (IV) dimethyl,
bi s((2-oxoy l-3-(dibenzo-1 H-py rrole-1 -yl)-5-(methyl)pheny l)-(5-(2-methy l)i>ropane-2-yl)-cis-
cyclohexene-l,2-dimethylenyl-l,2-diylzircontum (IV) dichloride,
bis((2-oxoyl-3-( 1,1 -dimethylethyl)phen-1 -yl)-5-(methyl)phenyl)-(5-(2-methyl)propane-2-y0-cis-
cyclohexene-l,2-dimethylenyl-l,2-diylzirconium (IV) dimethyl,
bis((2-oxoyl-3-(l,l-dimethylethyl)phen-l-yl)-5-(methyl)phenyl)-(5-(2-methyi)propane-2-yl)-cis-
cyclohexene-l,2-djmethylenyl-l,2-diylzirconium (IV) dichloride,
bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(5-(2-methyl)propane-
2-yI)butane-l,4-diylzirconium (IV) dimethyl,
bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(5-(2-methyl)propane-
2-yl)butane-l,4-diyIzirconium (IV) dichloride,
bis((2-oxoyl-3-(dibenzo-1 H-pyrrole-1 -yl)-5-(methyl)phenyl)-(5-(2-methyl)propane-2-yl)butane-1,4-
diylzirconium (IV) dimethyl,
bis((2-oxoyl-3~(dibenzo-lH-pyiTole-l-yl)-5-(methyl)phenyI)-(5-(2-methyl)propane-2-yl)butane-l,4-
diylzirconium (IV) dichloride,
bis((2-oxoyI-3-( 1,1 -dimethylethyl)phen- l-yl)-5-(methy l)phenyI)-(5-(2-methyl)propane-2-yi)butane-
1,4-diylzirconium (IV) dimethyl, and
bis((2-oxoyl-3-( 1,1 -dimethylethyl)phen-l -yl)-5-(methyl)phenyJH5-(2-methyJ)propane-2-yI)butane-
1,4-diyIzirconium (IV) dichloride.


Documents:

http://ipindiaonline.gov.in/patentsearch/GrantedSearch/viewdoc.aspx?id=2aOP4PypOB6AB5PBIM6vYA==&loc=egcICQiyoj82NGgGrC5ChA==


Patent Number 279876
Indian Patent Application Number 6939/CHENP/2008
PG Journal Number 05/2017
Publication Date 03-Feb-2017
Grant Date 31-Jan-2017
Date of Filing 17-Dec-2008
Name of Patentee Dow Global Technologies LLC
Applicant Address 2040 Dow Center, Midland, Michigan 48674
Inventors:
# Inventor's Name Inventor's Address
1 KONZE, WAYDE, V., 3423 CHAMBERS CIRCLE, MISSOURI CITY, TEXAS 77459
2 VANDERLENDE, DANIEL, D. 5003 KINGSLAND COURT, SUGAR LAND, TEXAS 77479
PCT International Classification Number C08F2/04
PCT International Application Number PCT/US07/09845
PCT International Filing date 2007-04-24
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 60/801,182 2006-05-17 U.S.A.