BRPI0805303A2 - process for the polymerization of ethylene and optionally one or more (alpha) -olefins and process for the polymerization of one or more addition polymerizable monomers - Google Patents

Abstract

A catalyst composition comprising one or more metal complexes of a multifunctional Lewis base binder comprising a predominantly flat, substituted aromatic or aromatic group and polymerization processes employing the same, especially continuous solution polymerization of one or more 244> -olefins at high catalyst efficiencies are disclosed.

Description

"PROCESS FOR POLYMERIZATION OF ETHYLENE AND OPTIONALLY ONE OR MORE α-OLEFINES AND PROCESS FOR POLYMERIZATION OF ONE OR MORE POLYMERIZABLE MONOMERS BY ADDITION".

Background of the invention

Higher temperature solution processes for olefin polymerization are highly desirable due to the increased production, reduced energy required for adhesification and reduced contamination that higher temperatures allow. Although Ziegler-Natta decatalyst systems can be operated at commercially high temperatures, 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 increased molecular weight distributions, thus limiting their suitability for use in many applications. Conventional Ziegler-Natta cataslysers are typically composed of many types of catalytic species, each having different oxidation states and different co-ordinating coordination environments. Examples of such heterogeneous systems are known and include metal halides activated by an organometallic catalyst, such as titanium chloride supported on magnesium chloride, activated with triaalkyl aluminum. Because these systems contain more than one catalytic species, they have polymerization sites with different activities and varying capacities to incorporate comonomer into a polymeric chain. The consequence of such multisite chemistry is a product with poor control of the polymer chain architecture, leading to a heterogeneous composition. In addition, differences in individual catalyst sites produce polymers of high molecular weight in some sites and low molecular weight in others, resulting in a polymer with a broad molecular weight distribution. Due to these reasons, the mechanical and other properties of polymers are often less than desired.

More recently, catalyst compositions based on well-defined metal complexes, especially transition metal complexes such as Restricted Geometry Catalysts (CGCs), Metallocenes "and post-metallocenes have been shown to provide better monomer incorporation and narrow molecular weight distribution. However, These catalysts often have poor high temperature stability and suffer from poor efficiencies at elevated polymerization temperatures.In addition, the molecular weight of polymers formed from these catalysts often decreases dramatically with increasing temperatures, especially for polymers containing significant amounts of comonomer (lower density). of most olefin polymerization catalysts to incorporate higher α-olefin in an ethylene / α-olefin copolymer by decreasing the increasing polymerization temperature. However, the reactivity ratio r ± generally increases with increasing polymerization temperature. Reactivity ratios of catalysts can be

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

M '+ M1 K ") M' (D

M * + M2 K »> M * 2 (2)

M2 + M1 **> M * (3)

Mt2 + M2 K ») M2 * (4)

where Mi refers to a monomer molecule which is arbitrarily designated as "i" where i = 1,2; and M2 * refers to a growing polymeric chain to which i was most recently attached.

The kij values are the rate constants for the indicated reactions. For example, in the ethylene / propylene copolymerization, kn represents the rate at which an ethylene unit is inserted into an increasing polymer chain in which the previously inserted monomer unit was also ethylene. Reactivity ratios follow as: ri = kn / ki2 and r2 = k22 / k21 wherekn, ki2, k22 and k2i are the rate constants for the addition of ethylene (1) or propylene (2) to a catalyst site where the last polymerized monomer is an ethylene (kxx) or propylene (kxx).

Thus, an olefin olefin polymerization process 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 overall molecular poorness in the resulting polymers. Emadition, low molecular weight distribution (Mw / Mn <3.0) is desired in such a process. Ideally, such a process can be performed at high temperatures and still produces polymers having high molecular weight and relatively high deconomer incorporation. It is known in the art that polymer molecular weight is readily controlled using chain transfer agents such as hydrogen or organometallic compounds. Therefore, a high temperature polymerization process that is capable of high levels of comonomer incorporation and produces high molecular weight polymers having low molecular weight distributions is desired in the art. Such a process further including a chain transfer agent to produce lower or lower molecular weight polymers. Incorporation of long decade branches is additionally desired.

In US 20 05 / 0215737A1, a continuous solution olefin polymerization process is disclosed for preparing ethylene-butene and ethylene-propylene interpolymers and further ethylene conversions. Disadvantageously, the resulting polymers were primarily plastomeric having relatively low molecular weights. No chain transfer agent was employed, indicating that the molecular weight of the resulting polymer was relatively low and that catalyst efficiencies were also low, especially at higher shear temperatures.

In WO 99/45041, another continuous solution of olefin polymerization process is disclosed using bridged hafnocene complexes with noncoordinating anionic cocatalysts. Although the resulting polymers had significant comonomer amounts, catalyst efficiencies were relatively low and the polymer molecular weights, even in the absence of chain transfer agent, were lower than desired. In WO 03/102042, a high olefin solution polymerization process temperature is disclosed using indenoindolyl transition metal complexes to prepare polyolefins at temperatures above 130 ° C. In one example, ethylene and 1-hexenophen copolymerization was performed at 1800C resulting in the formation of a polymer having poor comonomer incorporation (density = 0.937 g / cm3) at relatively low catalyst efficiencies.

In USP 6,827,976, certain highly active polymerization catalysts comprising Group 3-6 or Lanthanide, preferably Group 4 metal complexes of bridged bi-aromatic ligands containing a divalent Lewis base chelating group are disclosed. The metal complexes were employed in combination with olefin polymerization activation cocatalysts including ethylene and α-olefin mixtures, including 1-octene, to obtain polymers containing high comonomer incorporation rates at higher temperatures. US2 004/0010103 has disclosed certain metal polyether aromatics derivatives. and its use as catalysts for olefin polymerizations. Typical olefin polymerizations using prior art compositions are disclosed in US2003229188, WOOO / 24793, Akimoto, et al., J. Mol. Cat. A: Chem.156 (1-2), 133-141 (2000), among other references. We have now found that certain metal complexes can be employed in a solution polymerization process to prepare relatively high molecular weight ethylene interpolymers containing relatively large amounts of comonomer incorporated into them at unusually high temperatures and high conversions of olefin. if certain con process conditions are observed.

Accordingly, a process is now provided for preparing olefin polymer products, especially high molecular weight polyolefins, with very high catalyst efficiency. In addition, we have found that these catalyst compositions retain their catalyst activity using relatively low molar ratios of conventional alumoxane cocatalysts. The use of reduced amounts of alumoxane catalysts (up to 90 percent or less than conventionally employed) allows the preparation of polymeric products having reduced metal content and consequently increased clarity, dielectric properties and other improved physical properties. Accordingly, the use of reduced amounts of alumoxane cocatalysts results in reduced polymer production costs.

Summary of the invention

In accordance with the present invention there is now provided a process for the polymerization of ethylene and optionally one or more C3-2o α-olefins under high temperature solution polymerization conditions with a catalyst composition comprising a transition metal complex and allowing high molecular weight copolymers containing high comonomer with right molecular weight distribution.

Despite the <table> <table> use of extremely high solution polymerization temperatures, the resulting interpolymers have relatively high molecular weights (correspondingly low melt ratios) and high levels of comonomer incorporation (low densities).

We have found that the above metal complexes can be activated with relatively low molar ratios (100 or less) of neutral Lewis acid activators such as alumoxanes and still be able to 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 ethylene interpolymers and one or more C3-20 α-olefins and is particularly advantageous for use under continuous solution polymerization conditions where a reaction mixture comprising metal complex, co-catalyst of Activation, optionally a chain transfer agent, and at least one C2-20 α-olefin is continuously added to a reactor operating under solution polymerization conditions, and polymeric product is continuously or semicontinuously removed from it. In one embodiment, the invention is used to prepare ethylene copolymers and at least one C 3-20 α-olefin, preferably ethylene and at least one C 6-20 α-olefin. In another embodiment, this invention may be used to prepare α- homopolymers. C3-20 olefin, or copolymers consisting essentially of two or more C3-20 α-olefins. In addition, the process may employ other catalyst compositions comprising more than one metal complex or compound and / or using or employing multiple reactors.

The key to achieving the above benefits is the use of solution polymerization conditions, temperatures of 170 0C or 1850C or even 190 ° C and up to 230 ° C or 240 ° C or even 250 ° C, high monomer conversions, which is hollow of ethylene-containing polymerizations, are at least 85 percent, and low cocatalyst concentrations, preferably molar alumoxane concentrations of less than 200: 1, preferably less than 100: 1, more preferably less than 50: 1 based on the transition metal notor. catalyst.

Detailed Description of the Invention

All references to the Periodic Table of Elements here shall refer to the published and copyrighted Periodic Table of Elements for CRC Press, Inc., 2003. Also, any references to a Group or Groups must be to the Group or Groups reflected in this Periodic Table of Elements using the IUPAC system to number groups. Unless otherwise noted, implied from context, or usually in the art, all parts and percentages 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 equivalent US aversion thereof is hereby incorporated by reference) especially in connection with 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 disclosed herein. For the avoidance of doubt, all compositions claimed herein by use of the term "comprising" may include any additive, adjuvant, or additional compound whether polymeric or otherwise, unless otherwise noted. In contrast, the term "consisting essentially of" excludes from the scope of any statement following any other component, step or procedure except those which are not essential for operability. The term "consisting of" excludes any component, step, or procedure not specifically defined or listed. The term "or", unless otherwise noted, applies to members listed individually as well as in any combination.

As used herein with respect to a chemical compound, unless otherwise specifically indicated, osingular includes all isomeric forms and vice versa (e.g. "hexane" includes all dehexane isomers individually or collectively). The terms "compound" and "complex" are used interchangeably herein to refer to organic, inorganic and organometallic compounds. The term "atom" refers to the smallest constituent of an ionic state-independent element, that is, whether or not it carries a partial charge or charge or is attached to another atom. The term "heteroatom" refers to an atom other than carbon or hydrogen. Preferred heteroatoms include: F, Cl, BR, Ν, O, Ρ, 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 cyclic, polycyclic or non-cyclic, saturated or unsaturated, branched or non-amino species. Examples include alkyl, cycloalkyl, alkenyl, alkadienyl, cycloalkenyl, cycloalcadienyl, aryl, and alkynyl groups. "Substituted hydrocarbyls" refers to a hydrocarbyl group that is substituted with one or more nonhydrocarbyl substituent groups. The terms "hetero-containing hydrocarbyl" or "heterohydrocarbyl" refer to univalent groups in which at least one atom other than hydrogen or carbon is present together with one or more carbon atoms and one or more hydrogen atoms. The term "heterocarbyl" refers to groups containing one or more carbon atoms and one or more heteroatoms, but not 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 donor bond. Thus, an alkyl group substituted with an alkyl-substituted heterocycloalkyl, heterocycloalkyl, heteroaryl, alkyl-substituted heteroaryl group, alkoxy, aryloxy, dihydrocarbilboryl, dihydrocarbylphosphine, dihydrocarbylamino, trihydrocarbylsilyl, hydrocarbylthio, or hydrocarbylthio is within the hydrocarbyl group. Examples of heteroalkyl groups include cyanomethyl, benzomethyl, (2-pyridyl) methyl, etrifluoromethyl groups.

As used herein the term "aromatic" refers to a conjugated, cyclic, polyatomic ring system containing (4δ + 2) π-electrons, where δ is an integer greater than or equal to 1. The term "fused" as used herein with A ring system containing two or more polyatomic cyclic rings means that for 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 that are fused together, covalently linked, or attached to a common group such as a methylene or ethylene parcel. Examples of aromatic rings include phenyl, naphthyl, anthracenyl, and biphenyl, among others.

"Substituted aryl" refers to an aryl group in which one or more hydrogen atoms attached to any carbonos are substituted by one or more functional groups such as alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, halogen, alkyl (e.g. CF3), hydroxy, amino, phosphido, alkoxy, amino, thio, nitro, and both saturated and unsaturated cyclic hydrocarbons that are fused to aromatic rings, covalently bonded or bonded to a group such as a methylene or ethylene moiety. The common bonding group may also be a carbonyl such as benzophenone, or oxygen as in diphenyl ether, or as in diphenylamine.

Embodiments of the invention provide a novel solution process for producing olefin polymers with a catalyst composition containing a homogeneous transition metal complex at high temperature, high catalyst efficiency and high monomer conversion, with the polymers being of sufficiently high molecular weight to further permit the presence of significant amounts of a chain transfer agent such as hydrogen to control the molecular weight of the polymers. Most desirably, the polymers produced are of high molecular weight (I2 <2.0) and may be of varying density (due to varying amounts of deconomer incorporation). Of particular interest is the ability to produce high molecular weight high monomer-containing ethylene interpolymers under these conditions of high conversion, high temperature, with very high catalyst efficiency. These polymers desirably have a narrow molecular weight distribution (Mw / Mn <3.0) and can provide high levels of long-term branches, preferably> 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 resins for wire and cable insulation.

The unique process conditions employed according to the invention can be summarized in an equation that takes into account the reaction temperature and ethylene conversion together with the properties of the resulting polymer 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, Ψ, which is greater than or equal to zero according to the following equation:

Ψ = β o + βχΤ + β2Χ + β3Ε + β4ρ + β5Ι2

where: T is the polymerization temperature in degrees Celsius, X is the conversion of ethylene in the reactor to mole percent, and E is the catalyst efficiency in g of metal-produced polymer in the metal complex fed to the unit time reactor, p the resulting density polymer in units of g / ml, I2 is the melt index of polymer in units of dg / minute, and the equation constants βο ~ β5 are dimensionless numbers having the values defined in the following table:

<table> table see original document page 12 </column> </row> <table>

Preferred polymerization conditions are stable, continuous solution solution polymerization conditions in which the above 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 dimensionless value of the resulting stoma is used 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, terpolymers, interpolymers, and so forth, containing 5 or more repeated units. 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 branches as a result of chain termination reactions / olefin formation in situ, and olefin reincorporation. formed insi tu. Consequently, copolymers may result from the polymerization of a single monomer under the correct operating conditions. The less predominant monomer in the resulting interpolymer or interpolymer is generally referred to by the term "comonomer". The length of the resulting long chain branches above is therefore longer than the carbon length resulting from the polymerization of any deliberately added comonomer, and in particular is longer than 6 carbons. The presence of long branching can also be detected by the increased shear sensitivity of the polymer, as disclosed in EP-A-608.369, and elsewhere, or determined by the Melt Index Ratio (MIR), a ratio of polymer melt viscosities measured under different loads. , especially I21 / I2. 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, ethylene copolymers with one or more C 3-20 olefins, ethylene copolymers with one or more C 6-20 olefins, and ethylene / propylene, ethylene / l- copolymers. butene, ethylene / 1-hexene, ethylene / 4-methyl-1-pentene, ethylene / styrene, ethylene / propylene / styrene, ethylene / 1-octene, polypropylene / isotactic 1-butene, polypropylene / isotactic 1-hexene, polypropylene / 1-octenoisotactic, ethylene, propylene terpolymers and a conjugated dienon, e.g., EPDM terpolymers, as well as propylene, butylene, or styrene homopolymers.

Polymerization conditions generally refer to temperature, pressure, monomer content (including comonomer concentration), catalyst concentration, cocatalyst concentration, monomer conversion, or other conditions that influence the resulting polymer properties. By operation according to the prescribed polymerization conditions of the invention high molecular weight polymers can be prepared by having relatively high comonomer incorporation with various catalyst activities. In particular, activities (based on polymer weight for transition metal weight) greater than 0.5 g / Mg, preferably greater than 0.55 g / Mg, and even greater than 0.6 g / Mg are possible.

The weighted average molecular weight (Mw) of the polymer is measured by gel permeation chromatography, a technique as described in USP 5,272,236. Alternatively, the melt index, I2, I10 or I21 / measured, for example according to ASTM D-1238 may be employed as a molecular weight indication. Generally, the 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 ensures a process comprising contacting one or more olefins in a high temperature solution polymerization process. The present invented process is particularly advantageous for use under polymerization conditions where a reaction mixture comprising metal complex, activation cocatalyst, ethylene, and optionally at least one C3-20 α-olefin monomer is continuously added to a reactor operating under solution polymerization conditions, optionally in additional presence of a chain transfer agent, and polymerized product is continuously or semi-continuously removed from it. This process may consist of:

1) Polymerize ethylene and optionally one or more C3-2 α-olefins using a transition metal complex and an activation cocatalyst, especially a neutral Lewis acid, more preferably an alumoxane, under continuous solution polymerization conditions at a temperature of 185 ° C. at 250 ° C, preferably 200 to 250 ° C, under conditions of high ethylene conversion (> 85 percent) which results in a polymer having a density between 0.885 and 0.950 g / cm3 and a low melt index (I2 <20). with a narrow molecular weight distribution (Mw / Mn <3.0) and a catalyst efficiency of greater than 0.5 polymer /

When a chain transfer agent is used, a sufficient amount is used such that a molecular weight reduction substance (> 30 percent) occurs compared to a comparative polymerization without the use of chain transfer agent. When the chain transfer agent is hydrogen, at least 0.015 mol percent (based on ethylene) is used, and a maximum of about 2 mol percent is used. In addition, this process can be used to produce polymers that contain significant amounts of long decade branches.

2) Polymerize ethylene and one or more C3-20 α-olefins, preferably one or more CS-20 α-olefins, using a transition metal complex and a reactivating cocatalyst, especially a neutral Lewis acid, more preferably an alumoxane, under conditions. continuous solution polymerization in the presence of a chain transfer agent at a temperature of 170 to 250 ° C under conditions of high ethylene conversion (> 85 percent) which results in a polymer having a density of between 0.865 and 0.885 g / cm3 and a low melt index (I2 <20) with a narrow pesomolecular distribution (Mw / Mn <3.0) and a decatalyst efficiency greater than 0.5 gpoiomer / Mgmetai ·

A sufficient amount of decade transfer agent is preferably used such that a substantial reduction in molecular weight (> 30 percent) occurs compared to comparative polymerization without the use of chain transfer agent. When the chain transfer agent is hydrogen, at least 0.015 mol percent (based on monomer content) is used, and a maximum of about 2 mol percent is used. Accordingly, this process can be used to produce polymers containing significant amounts of long chain deletions, preferably through catalysts comprising zirconium-containing metal complexes.

3.) Polymerize one or more C3-2 α-olefins using a transition metal complex and a reactivating cocatalyst, especially a neutral Lewis acid, more preferably an alumoxane, under continuous solution polymerization conditions in the presence of a transfer agent. chain at a temperature of-170 to 250 ° C which results in a polymer with a low melt index (I2 <20) with a narrow weight-molecular distribution (Mw / Mn <3.0) and a decatalyst efficiency greater than 0.5 gpoiomer / pgmetai ·

Polymerize one or more C3.20 α-olefins using a homogeneous transition metal catalyst and catalyst activator under continuous solution polymerization conditions at a temperature of 170 to 2500 ° C resulting in a polymer with a low melt index (<2 ) with narrow molecular weight distribution (<3) and a catalyst efficiency greater than 0.5 million degpoiomer / Sfetai and using a decade-long transfer agent to control molecular weight.

A sufficient amount of decade transfer agent is preferably used such that a substantial (> 30 percent) molecular weight reduction occurs compared to comparative polymerization without the use of chain transfer agent. When the chain transfer agent is hydrogen, at least 0.01 mol percent (based on total α-olefin content) is used, and a maximum of about 2 mol percent is used. Accordingly, this process can be used to produce polymers containing significant amounts of long chain dimifications, preferably using catalysts comprising zirconium-containing metal complexes.

Suitable alumoxanes include polymeric or oligomeric alumoxanes, especially metallumoxane (MAO) or isobutylalumoxane (IBA) as well as Lewis acid modified alumoxanes, such as trihydrocarbylaluminum trihydrocarbylhydrogen or tri (hydrocarbyl) halogenated boron, each having from 1 to 10 halogenated hydrocarbyl or hydrocarbyl group. Examples include tri (isobutyl) aluminum-modified metalumoxane, tri (n-octyl) aluminum-modified metalumoxan, and tris (pentafluorophenyl) borane-modified alumoxanes. Such activation catalysts 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 activation cocatalysts include C1.30 hydrocarbyl substituted Group 13 compounds, especially tri (hydrocarbyl) aluminum (hydrocarbyl) boron compounds and halogenated derivatives (including perhalogenates) thereof, having from 1 to 30 carbons in each hydrocarbyl group or halogenated hydrocarbyl. Editon, di (hydrocarbyl) zinc halides, di (hydrocarbyl) aluminum, aluminum (hydrocarbyl) aluminum and di (hydrocarbyl) aluminum amides may be employed.

The Lewis acid activator is preferably used in cocatalyst: catalyst molar ratios of 1-200, preferably 1-150 and most preferably 1-100. Aluminoxane and Lewis acid modified alumoxane cocatalysts are preferably used in molar moieties of 20-200, preferably 30-150 and most preferably 40-100. Preferred cocatalysts are metallumoxane, modified (i-butyl) aluminum modified metallumoxane and tri (n-octyl) aluminum modified metallumoxane. Due to the ability to be activated at relatively low levels of alumoxane or alumoxane or Lewis acid modified alumina co-catalysts, present metal complexes Also preferred for use in other polymerization processes, such as the high pressure gas phase polyolefin process or pulp. In these processes, metal complexes may be supported on conventional supports and activated under many different conditions which are not available for complexes requiring non-coordinating anionic activators or large amounts of alumoxanes to achieve adequate activity.

Multiple reactor polymerization processes are suitably employed in the present invention. Examples include such systems as disclosed in USP 3,914,342, among others. Multiple reactors may 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. Both reactors may also contain at least two catalysts having different comonomer incorporation capacity and / or different molecular weight capacity. In one embodiment, a relatively high molecular weight product (Mw 100,000 to more than 1,000,000, more preferably 200,000 to 500,000) is formed while in the second reactor a relatively low molecular weight product (Mw 2,000 to 300,000) is formed. Both of these reactor products may have similar or different densities. The final product is a mixture of the two reactor effluents that are combined prior to devolatilization to result in a uniform mixture of the two polymeric products. In another embodiment, the molecular weight of the products of both reactors is approximately the same, but the densities vary to the extent that one reactor produces a polymer with a density in the range of 0.865-0.895, while the other reactor produces polymer with a different density in the range of 0.885- 0.950. Such dual decatalyst / dual reactor process allows the preparation of products with particular properties. In one configuration, the reactors are connected in series, that is, the effluent from the first reactor is charged to the second reactor and fresh monomer, solvent and hydrogen is optionally added to the second reactor. The conditions of the reactors are adjusted such that the weight ratio of the polymer produced in the first reactor to that produced in the second reactor is ideally in the range from 20: 80 to 80:20. In addition, the temperature of either the first reactor or the second reactor or both may be at the high temperature and high catalyst efficiency conditions which are disclosed herein, preferably the second reactor is operated at the highest temperature and efficiency.

In one embodiment, one of the reactors in the polymerization process, including the first of two reactors operating in series, contains a known Ziegler-Nataheterogeneous catalyst or a chrome catalyst. Examples of Ziegler-Nata catalysts include, but are not limited to, MgCl2-supported titanium-based catalysts, and additionally comprise aluminum compounds containing at least one aluminum-alkyl bond. Suitable Ziegler-Nata 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 invention to operate despite the presence of significant amounts of a Ziegler / Natta or chromium-based heterogeneous catalyst composition or the by-products resulting from the use thereof. Simple reactor multi-catalyst processes are also useful in present invention. In one embodiment, two or more catalysts are introduced into a single reactor under the high temperature conditions disclosed herein, with each catalyst inherently producing different polyolefin 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 a catalyst while a relatively low molecular weight product (Mw from 2,000 to 300,000) is formed. of the other catalyst. Both of these catalyst compositions may have similar or different comonomer incorporation capabilities. The resulting polymer will have the dependent properties of the two catalysts that are employed in the single reactor. Suitable combinations of polymer molecular weight, comonomer incorporation capacity, processes, and catalyst ratios for such products are disclosed in USP 6,924,342. Due to the unique compatibility of the present catalyst compositions with other olefin polymerization catalysts, including Ziegler / Nata catalysts, the second decatalyst composition may comprise a metal complex as disclosed herein, a metallocene or other metal complex containing π-linked binder group (including restricted geometry metal complexes) , or a complexometallic containing heteroatom polyvalent linker group, especially complexes based on pyridylamine or polyvinyl imidizolylamine.

Metal complexes suitable for use in accordance with the present invention correspond to the formula:

<formula> formula see original document page 20 </formula>

Where

R20 is an inertly substituted aliphatic, aromatic or aromatic group containing from 5 to 20 non-hydrogen containing atoms, or a polyvalent derivative thereof;

T3 is a hydrocarbylene or silane group having from 1 to 20 atoms not containing hydrogen, or an inertly substituted derivative thereof;

M3 is a Group 4 metal, preferably zirconium or hafnium, most preferably zirconium;

Rd independently at each occurrence is a monovalent grouping or two groups Rd together are a divalent hydrocarbylene or hydrocarbadiyl group; Elections and electron donor interactions are represented by lines and arrows respectively.

Preferably, such complexes correspond to the formula:

<formula> formula see original document page 21 </formula>

T3 is a divalent bridging group of 2 to 20 non-hydrogen containing atoms, preferably a substituted or unsubstituted C3-6 alkylene group; and

Ar 2 independently at each occurrence is an alkylene, aryl, alkoxy or amino substituted arylene group or arylene of 6 to 20 atoms not containing hydrogen and not containing substituents;

M3 is a Group 4 metal, preferably hafnium or zirconium, most preferably zirconium;

Rd independently at each occurrence is a monovalent grouping or two groups R0 together are a grouping hydrocarbylene or hydrocarbyl; Electron donor interactions are represented by porsetas.

More preferred examples of metal complexes of the above formula include the following compounds: <formula> formula see original document page 22 / formula>

Where :

M3 is Hf or Zr, preferably Zr;

Ar4 is C6-2 aryl or inertly substituted derivatives thereof, especially 3,5-di (isopropyl) phenyl, 3,5-di (isobutyl) phenyl, dibenzo-1H-pyrrol-1-yl, naphthyl, anthracen-5-yl 1,2,3,4,6,7,8,9-octahydroantracen-5-yl and T4 independently at each occurrence comprises a C 3-6 alkylene group / a C 3-6 cycloalkylene group, or an inert substituted derivative thereof;

R21 independently at each occurrence is hydrogen, halo, hydrocarbyl, trihydrocarbylsilyl, trihydrocarbylsilylhydrocarbyl, alkoxy or amino of up to 50 atoms not containing hydrogen; and

Rd, independently at each occurrence is halo or a hydrocarbyl or trihydrocarbyl group of up to 20 non-hydrogen containing atoms, or 2 Rd groups together are a divalent hydrocarbylene, hydrocarbadiyl or hydrocarbyl group.

Especially preferred metal complexes are composed of the formula:

<formula> formula see original document page 22 / formula>

where M3 is Hf or Zr, especially Zr;

Ar4 is 3,5-di (isopropyl) phenyl, 3,5-di (isobutyl) phenyl, dibenzo-1H-pyrrol-1-yl, or anthracen-5-yl. Independently at each occurrence is hydrogen, halo, hydrocarbyl, trihydrocarbylsilyl,

trihydrocarbylsilylhydrocarbyl, alkoxy or amino of atoms not containing hydrogen;

T 4 is propan-1,3-diyl or butan-1,4-diyl, cyclohexanediyl or cyclohexanedialkylenyl; and

Rd, independently at each occurrence is halo or a hydrocarbyl or trihydrocarbylsilyl group of up to 20 atoms not containing hydrogen, or 2 groups R0 together are a divalent hydrocarbyl, hydrocarbadiyl or hydrocarbylsilyl group.

The most highly preferred metal complexes according to the invention correspond to the formulas:

<formula> formula see original document page 23 / formula>

Where

Rd independently in each occurrence is chlorine, methyl or benzyl, and

Electron donor interactions between the ezirconium ether groups are represented by arrows. Specific examples of the previous metal complexes are the following compounds:

A) Bis ((2-oxoyl-3- (1,2,3,4,6,7,8,9-octahydroantracen-5-yl) -5- (methyl) phenyl) -2-phenoxy) propane-1 , 2-diylzirconium (N) dimethyl, bis ((2-oxoyl-3- (1,2,3,4,6,7,8,9octahidroantracen-5-yl) -5 - (methyl) phenyl) dichloride 2-phenoxy) propane-1,2-diylzirconium (IV),

bis ((2-oxoyl-3- (dibenzo-β-pyrrol-1-yl) -5- (methyl) phenyl) -2-phenoxy) propane-1,2-diylzirconium (IV) dimethyl,

bis ((2-oxoyl-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) -2-phenoxy) propane-1,2-diylzirconium dichloride,

bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-yl) -5- (methyl) phenyl) -2-phenoxy) propane-1,2-diylzirconium (IV) dimethyl,

bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-yl) -5- (methyl) phenyl) -2-phenoxy) propane-1,2-diylzirconium (IV) dichloride,

bis ((2-oxoyl-3- (1,2,3,4,6,7,8,9-octahydroantracen-5-yl) -5- (methyl) phenyl) -2-phenoxy) -trans-cyclohexane-2-one 1,2-dimethylenyl-1,2-diylzirconium (IV) dimethyl,

bis ((2-oxoyl-3- (1,2,3,4,6,7,8,9-octahydroantracen-5-yl) -5- (methyl) phenyl) -2-phenoxy) -transdichloride dichloride cyclohexane-1,2-dimethylenyl-1,2-diylzirconium (IV),

bis ((2-oxoxy-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) -2-phenoxy) -trans-cyclohexane-1,2-dimethylenyl-1,2-diylzirconium ( IV) dimethyl,

bis ((2-oxoyl-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) -2-phenoxy) -trans-cyclohexane-1,2-dimethylenyl-1,2-dichloride diylzirconium (IV),

bis ((2-oxoxy-3- (1,1-dimethylethyl) phen-1-yl) -5- (methyl) phenyl) -2-phenoxy) -trans-cyclohexane-1,2-dimethylenyl-1,2-one diylzirconium (IV) dimethyl,

bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-yl) -5- (methyl) phenyl) -2-phenoxy) -trans-cyclohexane-1,2-dimethylenyl-1 dichloride, 2-diylzirconium (IV),

bis ((2-oxoyl-3- (1,2,3,4,6,7,8,9-octahydroantracen-5-yl) -5- (methyl) phenyl) -2-phenoxy) -cis-cyclohexane-2-one 1,3-diylzirconium (IV) dimethyl,

bis ((2-oxoyl-3- (1,2,3,4,6,7,8,9-octahydroantracen-5-yl) -5- (methyl) phenyl) -2-phenoxy) -cis-cyclohexane dichloride 1,3-diylzirconium (IV),

bis ((2-oxoxy-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) -2-phenoxy) -cyclohexane-1,3-diylzirconium (N) dimethyl,

bis ((2-oxoyl-3- (dibenzo-1H-pyrrol-1-yl) -5 (methyl) phenyl) -2-phenoxy) -cyclohexane-1,3-diylzirconium dichloride,

bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-yl) -5- (methyl) phenyl) -2-phenoxy) -cyclohexane-1,3-diylzirconium (IV) dimethyl,

bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-yl) 5- (methyl) phenyl) -2-phenoxy) -cyclohexane-1,3-diylzirconium dichloride (IV) ,

bis ((2-oxoyl-3- (1,2,3,4,6,7,8,9-octahydroantracen-5-yl) -5- (methyl) phenyl) -2-phenoxy) -cis-cyclohexene-2-one 1,2-dimethylenyl-1,2-diylzirconium (IV) dimethyl,

bis ((2-oxoyl-3- (1,2,3,4,6,6,7,9-octahydroantracen-5-yl) -5- (methyl) phenyl) -2-phenoxy) -cis-cyclohexene dichloride 1,2-dimethylenyl-1,2-diylzirconium (IV),

bis ((2-oxoyl-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) -2-phenoxy) -cyclohexene-1,2-dimethylenyl-1,2-diylzirconium ( IV) dimethyl,

bis ((2-oxoyl-3- (dibenzo-1H-pyrrol-1-yl) -5 (methyl) phenyl) -2-phenoxy) -cyclohexene-1,2-dimethylenyl-1,2-diylzirconium dichloride (IV),

bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-yl) -5- (methyl) phenyl) -2-phenoxy) -cyclohexene-1,2-dimethylenyl-1,2- diylzirconium (IV) dimethyl,

bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-yl) -5 (methyl) phenyl) -2-phenoxy) -cyclohexene-1,2-dimethylenyl-1,2 dichloride -diylzirconium (IV),

bis ((2-oxoyl-3- (1,2,3,4,6,7,8,9-octahydroantracen-5-yl) -5- (methyl) phenyl) -2-phenoxy) butane-1,4 -diylzirconium (IV) dimethyl,

bis ((2-oxoyl-3- (1,2,3,4,6,7,7,9-octahydroantracen-5-yl) -5- (methyl) phenyl) -2-phenoxy) butane-1,4-dichloride -diylzirconium (IV),

bis ((2-oxoyl-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) -2-phenoxy) butane-1,4-diylzirconium (IV) dimethyl,

bis ((2-oxoyl-3- (dibenzo-1H-pyrrol-1-yl) -5 (methyl) phenyl) -2-phenoxy) butane-1,4-diylzirconium dichloride,

bis ((2-oxoxy-3- (1,1-dimethylethyl) phen-1-yl) -5- (methyl) phenyl) -2-phenoxy) butane-1,4-diylzirconium (IV) dimethyl,

bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-yl) -5 (methyl) phenyl) -2-phenoxy) butane-1,4-diylzirconium dichloride,

B) Bis ((2-oxoyl-3- (1,2,3,4,6,7,8,9-octahydroantracen-5yl) -5- (methyl) phenyl) - (4-methyl-2-phenoxy) ) propane-1,2-diylzirconium (IV) dimethyl,

bis ((2-oxoyl-3- (1,2,3,4,6,7,8,9-octahydroantracen-5-yl) -5- (methyl) phenyl) - (4-methyl-2-phenoxy) dichloride ) propane-1,2-diylzirconium (IV),

bis ((2-oxoxy-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) - (4-methyl-2-phenoxy)) propane-1,2-diylzirconium (IV) dimethyl bis ((2-oxoyl-3- (dibenzo-1H-pyrrol-1-yl) -5 (methyl) phenyl) - (4-methyl-2-phenoxy)) propane-1,2-diylzirconium dichloride (IV ),

bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-yl) -5- (methyl) phenyl) - (4-methyl-2-phenoxy)) propane-1,2-diylzirconium (IV ) dimethyl,

bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-yl) -5 (methyl) phenyl) - (4-methyl-2-phenoxy)) propane-1,2-diylzirconium dichloride ( IV),

bis ((2-oxoyl-3- (1,2,3,4,6,7,8,9-octahydroantracen-5-yl) -5- (methyl) phenyl) - (4-methyl-2-phenoxy) ) -trans-cyclohexane-1,2-dimethylenyl-1,2-diylzirconium (IV) dimethyl,

bis ((2-oxoyl-3- (1,2,3,4,6,7,8,9octahidroantracen-5-yl) -5- (methyl) phenyl) - (4-methyl-2-phenoxy) dichloride ) -trans-cyclohexane-1,2-dimethylenyl-1,2-diylzirconium (IV),

bis ((2-oxoyl-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) - (4-methyl-2-phenoxy)) - trans-cyclohexane-1,2-dimethylenyl- 1,2-diylzirconium (IV) dimethyl, bis ((2-oxoyl-3- (dibenzo-1H-pyrrol-1-yl) -5 (methyl) phenyl) - (4-methyl-2-phenoxy)) dichloride) -trans-cyclohexane-1,2-dimethylenyl-1,2-diylzirconium (IV),

bis ((2-oxoxy-3- (1,1-dimethylethyl) phen-1-yl) -5- (methyl) phenyl) - (4-methyl-2-phenoxy)) - trans-cyclohexane-1,2-one dimethylenyl-1,2-diylzirconium (IV) dimethyl,

bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-yl) -5 (methyl) phenyl) - (4-methyl-2-phenoxy)) - trans-cyclohexane-1,2-dichloride -dimethylenyl-1,2-diylzirconium (IV),

bis ((2-oxoxy-3- (1,2,3,4,6,7,8,9-octahydroantracen-5-yl) -5- (methyl) phenyl) - (4-methyl-2-phenoxy) ) -cyclohexane-1,3-diylzirconium (IV) dimethyl,

bis ((2-oxoyl-3- (1,2,3,4,6,7,8,9-octahydroantracen-5-yl) -5- (methyl) phenyl) - (4-methyl-2-phenoxy) dichloride ) -cis-cyclohexane-1,3-diylzirconium (IV),

bis ((2-oxoyl-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) - (4-methyl-2-phenoxy)) cis-cyclohexane-1,3-diylzirconium ( IV) dimethyl,

bis ((2-oxoyl-3- (dibenzo-1H-pyrrol-1-yl) -5 (methyl) phenyl) - (4-methyl-2-phenoxy)) cis -cyclohexane-1,3-diylzirconium dichloride (IV),

bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-yl) -5 (methyl) phenyl) - (4-methyl-2-phenoxy)) cis-cyclohexane-1,3-one diylzirconium (IV) dimethyl,

bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-yl) 5- (methyl) phenyl) - (4-methyl-2-phenoxy)) - cis-cyclohexane-1,3 dichloride -diylzirconium (IV),

bis ((2-oxoyl-3- (1,2,3,4,6,7,8,9-octahydroantracen-5-yl) -5- (methyl) phenyl) - (4-methyl-2-phenoxy) ) -cis-cyclohexene-1,2-dimethylenyl-1,2-diylzirconium (IV) dimethyl,

bis ((2-oxoyl-3- (1,2,3,4,6,7,8,9-octahydroantracen-5-yl) -5- (methyl) phenyl) - (4-methyl-2-phenoxy) dichloride ) -cis-cyclohexene-1,2-dimethylenyl-1,2-diylzirconium (IV),

bis ((2-oxoxy-3- (dibenzo-β-pyrrol-1-yl) -5- (methyl) phenyl) (4-methyl-2-phenoxy)) cis-cyclohexene-1,2-dimethylenyl-1 (2) diylzirconium dimethyl, bis ((2-oxoyl-3- (dibenzo-1H-pyrrol-1-yl) -5 (methyl) phenyl) - (4-methyl-2-phenoxy)) cis dichloride -cyclohexene-1,2 -

dimethylenyl-1,2-diylzirconium (IV),

bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-yl) -5- (methyl) phenyl) - (4-methyl2-phenoxy)) cis-cyclohexene-1,2-one

dimethylenyl-1,2-diylzirconium (IV) dimethyl,

bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-yl) 5- (methyl) phenyl) - (4-methyl-2-phenoxy)) - cis-cyclohexene-1,2 dichloride -

dimethylenyl-1,2-diylzirconium (IV),

bis ((2-oxoyl-3- (1,2,3,4,6,7,8,9-octahydroantracen-5-yl) -5- (methyl) phenyl) - (4-methyl-2-phenoxy) ) butane-1,4-diylzirconium (IV) dimethyl,

bis ((2-oxoyl-3- (1,2,3,4,6,7,8,9octahidroantracen-5-yl) -5- (methyl) phenyl) - (4-methyl-2-phenoxy) dichloride ) butane-1,4-diylzirconium (IV),

bis ((2-oxoyl-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) - (4-methyl-2-phenoxy)) butane-1,4-diylzirconium (IV) dimethyl ,

bis ((2-oxoyl-3- (dibenzo-1H-pyrrol-1-yl) -5 (methyl) phenyl) - (4-methyl-2-phenoxy)) butane-1,4-diylzirconium dichloride (IV) ,

bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-yl) -5- (methyl) phenyl) - (4-methyl-2-phenoxy)) butane-1,4-diylzirconium (IV ) dimethyl,

bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-yl) 5- (methyl) phenyl) - (4-methyl-2-phenoxy)) butane-1,4-diylzirconium dichloride ( IV),

C) Bis ((2-oxoyl-3- (1,2,3,4,6,7,8,9-octahydroantracen-5yl) -5- (methyl) phenyl) - (5- (2-methyl) propane -2-yl) -2-

phenoxy) propane-1,2-diylzirconium (IV) dimethyl, bis ((2-oxoyl-3- (1,2,3,4,6,7, 8, 9

octahidroantracen-5-yl) -5- (methyl) phenyl) - (5- (2-methyl) propan-2-yl) propane-1,2-diylzirconium (IV),

bis ((2-oxoyl-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) - (5- (2-methyl) propan-2-yl) propane-1,2-diylzirconium (IV) dimethyl,

bis ((2-oxoyl-3- (dibenzo-β-pyrrol-1-yl) -5 (methyl) phenyl) - (5- (2-methyl) propan-2-yl) propane-1,2-dichloride diylzirconium (IV),

bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-yl) -5- (methyl) phenyl) - (5- (2-methyl) propan-2-yl) propane-1,2 -diylzirconium (IV) dimethyl,

bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-yl) -5- (methyl) phenyl) - (5- (2-methyl) propan-2-yl) propane-1 dichloride , 2-diylzirconium (IV),

bis ((2-oxoyl-3- (1,2,3,4,6,7,8,9-octahydroantracen-5-yl) -5- (methyl) phenyl) - (5- (2-methyl) propane -2-yl) -trans-cyclohexane-1,2-dimethylenyl-1,2-diylzirconium (IV) dimethyl, bis ((2-oxoyl-3- (1,2,3,4,6,7, 8,9-octahydroantracen-5-yl) -5- (methyl) phenyl) - (5- (2-methylthi) propane-2-yl) -1-cyclohexane-1,2-dimethylthenyl -1,2-diylzirconium (IV),

bis ((2-oxoyl-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) - (5- (2-methyl) propan-2-yl) -trans-cyclohexane-1, 2-dimethylenyl-1,2-diylzirconium (IV) dimethyl,

bis ((2-oxoyl-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) - (5- (2-methyl) propan-2-yl) -trans-cyclohexane-dichloride 1,2-dimethylenyl-1,2-diylzirconium (IV),

bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-yl) -5- (methyl) phenyl) - (5- (2-methyl) propan-2-yl) -trans -ethylhexane -1,2-dimethylenyl-1,2-diylzirconium (IV) dimethyl, bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-yl) -5- (methyl) phenyl) dichloride (5- (2-methyl) propan-2-yl) trans

cyclohexane-1,2-dimethylenyl-1,2-diylzirconium (IV), bis ((2-oxoyl-3- (1,2,3,4,6,7,8,9-octahydroantracen-5-yl) - 5- (methyl) phenyl) - (5- (2-methyl) propan-2-yl) -cyclohexane-1,3-diylzirconium (IV) dimethyl,

bis ((2-oxoyl-3- (1,2,3,4,6,7,8,9-octahydroantracen-5-yl) -5- (methyl) phenyl) - (5- (2-methyl) dichloride ) propane-2-yl) cis-cyclohexane-1,3'-diylzirconium (IV),

bis ((2-oxoyl-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) - (5- (2-methyl) propan-2-yl) -cyclohexane-1, 3-diylzirconium (IV) dimethyl,

bis ((2-oxoyl-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) - (5- (2-methyl) propan-2-yl) -cyclohexane-dichloride 1,3-diylzirconium (IV),

bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-yl) -5- (methyl) phenyl) - (5- (2-methyl) propan-2-yl) -cyclohexane-2-one 1,3-diylzirconium (IV) dimethyl,

bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-yl) -5 (methyl) phenyl) - (5- (2-methyl) propan-2-yl) -cyclohexane dichloride -1,3-diylzirconium (IV),

bis ((2-oxoyl-3- (1,2,3,4,6,7,8,9-octahydroantracen-5-yl) -5- (methyl) phenyl) - (5- (2-methyl) propane -2-yl) -cyclohexene-1,2-dimethylenyl-1,2-diylzirconium (IV) dimethyl

bis ((2-oxoyl-3- (1,2,3,4,6,7,8,9octetrahydroantracen-5-yl) -5- (methyl) phenyl) - (5- (2-methyl) propane dichloride -2-yl) -cis-cyclohexene-1,2-dimethylenyl-1,2-diylzirconium (IV),

bis ((2-oxoyl-3- (dibenzo-β-pyrrol-1-yl) -5- (methyl) phenyl) - (5- (2-methyl) propan-2-yl) -cyclohexene-1, 2-dimethylenyl-1,2-diylzirconium (IV) dimethyl,

bis ((2-oxoyl-3- (dibenzo-1H-pyrrol-1-yl) -5 (methyl) phenyl) - (5- (2-methyl) propan-2-yl) -cyclohexene-1 dichloride , 2-dimethylenyl-1,2-diylzirconium (IV),

bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-yl) -5- (methyl) phenyl) - (5- (2-methyl) propan-2-yl) -cis-cyclohexene-2-one 1,2-dimethylenyl-1,2-diylzirconium (IV) dimethyl,

bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-yl) -5 (methyl) phenyl) - (5- (2-methyl) propan-2-yl) -cyclohexene dichloride -1,2-dimethylenyl-1,2-diylzirconium (IV),

bis ((2-oxoyl-3- (1,2,3,4,6,7,8,9-octahydroantracen-5-yl) -5- (methyl) phenyl) - (5- (2-methyl) propane -2-yl) butane-1,4-diylzirconium (IV) dimethyl,

bis ((2-oxoyl-3- (1,2,3,4,6,7,8,9octetrahydroantracen-5-yl) -5- (methyl) phenyl) - (5- (2-methyl) propane dichloride (2-yl) butane-1,4-diylzirconium (IV),

bis ((2-oxoxy-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) - (5- (2-methyl) propan-2-yl) butane-1,4-diylzirconium (IV) dimethyl,

bis ((2-oxoyl-3- (dibenzo-1H-pyrrol-1-yl) -5 (methyl) phenyl) - (5- (2-methyl) propan-2-yl) butane-1,4-dichloride diylzirconium (IV),

bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-yl) -5- (methyl) phenyl) - (5- (2-methyl) propan-2-yl) butane-1,4 -diylzirconium (IV) dimethyl, and

bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-yl) -5- (methyl) phenyl) - (5- (2-methyl) propan-2-yl) butane-1 dichloride 4,4-diylzirconium (IV).

The foregoing metal complexes are conveniently prepared by standard binder metallization and exchange procedures involving a metal-transferring source and a neutral polyfunctional binder source. Accordingly, the complexes may also be prepared by a process of amide elimination and hydrocarbylation starting from the corresponding transition metal tetraamide and a hydrocarbylating agent, such as trimethyl aluminum. The techniques employed are the same as or analogous to those disclosed in USP 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 decatalyst composition by combination with a cocatalyst, preferably a cation-forming cocatalyst, especially a cationic compound containing a non-coordinating anion or neutral Lewis acid, preferably a neutral Lewis acid modified alumoxane or alumoxane. , or a combination thereof. Activation may occur prior to the addition of the decatalyst composition to the reactor with or without the presence of other components of the reaction mixture, or in situ by the separate addition of the metal complex and activation cocatalyst to the reactor.

Monomers

Suitable olefins for use herein include C2-30 aliphatic, cycloaliphatic and aromatic compounds containing one or more ethylenic unsaturation. Examples include aliphatic, cycloaliphatic, or aromatic diolefins. Preferred olefin monomers include, but are not limited to, ethylene, propylene, isobutylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and 1- dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 4,6-dimethyl-1-one heptene, vinylcyclohexane, 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, norbornadiene, ethylidenonorbornene, and mixtures thereof.

The novel processes described herein are well suited for the production of olefin polymers comprising aromatic monovinylidene monomers including styrene, o-methyl styrene, p-methyl styrene, t-butylstyrene, and mixtures thereof. In particular, interpolymers comprising ethylene and styrene may suitably be prepared by following the teachings herein.

Optionally, copolymers comprising ethylene, styrene and / or a C 3-20 alpha olefin optionally comprising a conjugated or unconjugated C 4-20 diene having improved properties over those presently known in the art may be prepared.

Suitable unconjugated dienes include straight chain, branched chain or cyclic hydrocarbon dienes having from 6 to 15 carbon atoms. Examples of suitable unconjugated 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-1,4-hexadiene; 3,7-dimethyl-1,6-octadiene; 3,7-dimethyl-1,7-octadiene and mixed isomers of dihydromyricene and dihydroocinene; single-alicyclic dienes such as 1,3-cyclopentadiene; 1,4-cyclohexadiene; 1,5-cyclooctadiene and 1,5-cyclododecadiene, and bridged ring multi-ring alicyclic dienes such as tetrahydroindene, methylthetrahydroindene, dicyclopentadiene, bicyclo (2,2,1) -hepta-2,5-diene; alkenyl, alkylidene, cycloalkenyl and cycloalkylidene norbornenes, such as 5-methylene-2-norbornene (MNB); 5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene, 5- (4-cyclopentyl) -2-norbornene, 5-cyclohexylidene-2-norbornene, 5-vinyl-2-norbornene, and norbornadiene. Of the dienes typically used to prepare EPDMs, particularly preferred dienes are 1,4-hexadiene (HD), 5-ethylidene-2-norbornene (ENB), 5-vinylidene-2-norbornene (VNB), 5-methylene-2-norbornene ( MNB), and dicyclopentadiene (DCPD). The most especially preferred diene is 5-ethylidene-2-norbornene (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 activation cocatalysts include neutral Lewis acids, such as C1-30 hydrocarbyl / especially tri (hydrocarbyl) substituted compounds. alumini (hydrocarbyl) boron and halogenated derivatives (including perhalogenates) thereof having from 1 to 10 carbons in each halogenated hydrocarbyl or hydrocarbyl group, more particularly perfluorinated tri (aryl) boron compounds, and most especially tris (pentafluorophenyl) borane; compatible, non-coordinating, non-polymeric ions (including use of such compounds under oxidizing conditions), especially the use of ammonium, phosphonium, oxonium, carbonyl, silyl or sulphonium salts of compatible, non-coordinating anions of ferrocene or silver non-coordinating anions, compare tible; and combinations of the preceding cocatalysts and cation formation techniques. Previous activation-activation cocatalysts and activation techniques have been previously taught for 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 WO 99/42467.

Neutral Lewis acid combinations, especially the combination of a trialkyl aluminum compound having from 1 to 4 carbons in each alkyl group and a halogenated detri (hydrocarbyl) compound having from 1 to 20 carbons in each hydrocarbyl group, especiallyetris (pentafluorophenyl) borane, additional combinations Further mixtures of Lewis acid with an oligomeric or oligomeric alumoxane, and combinations of a single neutral Lewis acid, especially tetris (pentafluorophenyl) borane with a polymeric or oligomeric alumoxane may be used as the activation cocatalyst. Preferred molar ratios of complexometallic: 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 fingering a proton, and a compatible, non-coordinating anion A. As used herein, the term "non-decoordination" means an anion or substance which either does not coordinate with Group 4's metal-containing precursor complex and the catalytic derivative derived therefrom, or which is only poorly coordinated with such complexes and thus remains sufficiently prone to be displaced by a neutral Lewis base.A non-decoordinated anion specifically refers to an anion that when functioning as a charge balancing anion in a cationic metal complex does not transfer an anionic substitute or fragment thereof to the forming citadocation thus neutral complexes. "Compatible anions" are anions that have not degraded to aneutrality when the initially formed complex has decomposed and are noninterfering with the desired subsequent polymerization or other uses of the complex.

Preferred anions are those containing a single decoordination complex comprising a charge-bearing metal or metalloid core whose anion is capable of balancing the charge of the active catalyst species (metal ocation) that can be formed when the two are sufficiently prone to be displaced by olefinic, diolefin compounds. and acetylenically unsaturated or other neutral Lewis bases such as ethers or nitriles. Suitable metals include, but are not limited to, aluminum, gold and platinum. Suitable osmetaloids include, but are not limited to, boron, phosphorus, and silicon. Anion-containing compounds comprising coordination complexes containing a single metal or metalloid atom are, of course, well known, and many, particularly such as having a single boron atom in the anion portion, are commercially available.

Preferably such cocatalysts may be represented by the following general formula:

<formula> formula see original document page 35 </formula>

Where:

L * is a neutral Lewis base;

(L * - Η) + is a conjugated Bronsted acid of L *;

A9 "is a compatible, non-coordinating anion having a g- charge, and

g is an integer from 1 to 3.

More preferably A9 "corresponds to the formula: [M'Q4]"; where:

M 'is boron or aluminum in the formal oxidation state +3; and

Independently at each occurrence, hydride, dialkyl starch, halide, hydrocarbyl, hydrocarbyl, halo substituted hydrocarbyl, halo substituted hydrocarboxy, and halo substituted silyl hydrocarbyl radicals (including hydrocarbyl perhalogenated, perhalogenated hydrocarbyloxy and

perhalogenated silyl hydrocarbyl), said Q having up to 20 carbons with the exception that in no more than one occurrence Q is halide. Examples of suitable hydrocarbyloxide Q groups are disclosed in US-A-5,296,433.

In a more preferred embodiment, d is one, i.e., boron-comprising activation catalysts which are particularly useful in the preparation of catalysts of this invention may be represented by the following general formula:

<formula> formula see original document page 36 </formula>

Where:

L * is as defined above;

B is boron in a formal oxidation state of 3; and

Q is a hydrocarbyl, hydrocarbyloxy, hydrocarbylfluorinated, fluorinated hydrocarbyloxy, or silyl hydrocarbylfluorinated group of up to 20 non-hydrogen atoms, with the exception that on no more than one occasion Q is hydrocarbyl.

Preferred Lewis base salts are ammonium salts, more preferably trialkylammonium salts containing one or more C 12-40 alkyl groups. Most preferably, each occurrence is a fluorinated aryl group, especially a pentafluorophenyl group.

Illustrative but not limiting examples of deboro compounds that can be used as a reactivation cocatalyst in the preparation of the improved catalysts for this invention are tri-substituted ammonium salts such as: trimethylammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate tripropylammonium tetrakis (pentafluorophenyl), tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, tri (sec-butyl) ammonium tetrakis (pentafluorophenyl) borate, N-N-dimethylanilinium tetrakis (pentafluorofenyl) borate -dimethylanilinium n-butyltris (pentafluorophenyl),,, Ν-dimethylaniliniumbenzyltris (pentafluorophenyl) borate, N, N-dimethylanilinium borate tetrakis (4- (t-butyldimethylsilyl) -2,3,5,6-tetrafluorophenyl) Ν, Ν-dimethylanilinethiotetrakis (4-triisopropylsilyl) -2,3,5,6-tetrafluorophenyl), Ν, Ν-dimethylanilinopentafluorophenyl borate (pentafluorophenyl) borate, Ν-diethylanilinium tetr Acquisition (pentafluorophenyl), N-borate, N-dimethyl-2,4,6-trimethylanilino-tetrakis (pentafluorophenyl), dimethyloctadecylammonium tetrakis (pentafluorophenyl), methyldioctadecylamoniotetrachis borate (pentafluorophenylamines),

di (i-propyl) ammoniothetrakis (pentafluorophenyl) borate, methyltoctadecylammonium borate tetrakis (pentafluorophenyl), methyloctadodecylammonium borate tetrakis (pentafluorophenyl), dioctadecylammonium tetramophenofluorophenophenyltrisofenylphenate ), methyldioctadecylphosphoniotetrakis borate (pentafluophophenyl), and tri (2,6-dimethylphenyl) phosphonium boronate tetrakis (pentafluophophenyl); disubstituted oxonium salts such as:

diphenyloxonium tetrakis (pentafluophophenyl) borate, di (o-tolyl) oxonium tetrakis (pentafluophophenyl) borate, and di (octadecyl) oxoniotetrakis borate (pentafluophophenyl); disubstituted sulfonium salts such as:

di (o-tolyl) sulphoniotetrakis borate (pentafluophophenyl), and methyloctadedylsulfonium boronate tetrakis (pentafluophophenyl).

Preferred (L * - Η) + cations are demethyldioctadecylammonium cations, dimethyloctadecylammonium cations, and trialkyl-derived ammonium-derived cations containing one or more C1-18 alkyl groups. A particularly preferred example of the latter compound is based on a commercially available long chain amine. and is referred to as: debis- (hydrogenated tallowalkyl) methylammoniotetrakis (pentafluophophenyl) borate.

Another suitable ion-forming activation cocatalyst comprises a salt of an oxidantechionic agent and a compatible, non-coordinating anion represented by the formula:

(0xh +) g (A9 ") h

Where:

0xh + is a cationic oxidizing agent having a charge of h +;

h is an integer from 1 to 3; and

A9 "and g are as defined above.

Examples of cationic oxidizing agents include: ferrocene, hydrocarbyl substituted ferrocene, Ag + or PB + 2. Preferred configurations of A9 "are those previously defined with respect to Bronsted acid-containing activation cocatalysts, especially tetrakis borate (pentafluophophenyl).

Another suitable ion-forming activation cocatalyst comprises a compound which is a salt of a decarbium ion and a non-coordinating compatible anion represented by the formula:

<formula> formula see original document page 38 </formula>

Where:

[C] + is a C1-20 carbon dioxide ion; and

A "is a compatible, non-coordinating anion having a charge of -1. A preferred carbonium ion is detrityl cation, which is triphenylmethyl.

A further suitable ion-forming activation cocatalyst comprises a compound which is a silyl ion salt and a compatible, non-decoordinated anion, represented by the formula: (Q13Si) + A "

Where:

Q1 is C1-10 hydrocarbyl, and A 'is as defined above.

Preferred silyl salt activation cocatalysts are tetrakis pentafluorophenyl trimethylsilyl borate, tetrakis pentafluorophenyl triethylsilyl borate and ether substituted substitutes thereof. Desilyl salts have been generically disclosed previously in J. Chem. Sound. Chem. Comm., 1993, 383-384, as well as Lambert, J.B., et al., Organometallics

[Organometallic], 1994, 13, 2430-2443. The use of the above disilyl salts as activation cocatalysts for addition polymerization catalysts is disclosed in US-A-5,625,087.

Certain complexes of alcohols, mercaptans, silanols, and tris (pentafluorophenyl) borane approaches are also effective catalyst activators and may be used in accordance with the present invention. Such cocatalysts are disclosed in US-A-5,296,433.

A class of cocatalysts comprising non-decoordinated anions generically referred to as pending anions, further disclosed in US6,395,671, may suitably be employed to activate the metal complexes of the present invention for olefin polymerization. Generally, these scocatalysts (illustrated by those having deimidazolide, substituted imidazolide, imidazolinide, substituted imidazolinide, benzimidazolide, or substituted benzimidazolide anions) can be represented as follows:

<formula> formula see original document page 39 </formula> where:

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 (C14-20 alkyl) ammonium cation.

Q3, independently at each occurrence, is hydrogen or a halo, hydrocarbyl, halocarbyl, halohydrocarbyl, silylhydrocarbyl, or silyl group (including mono-, di- and tri (hydrocarbyl) silyl) of up to 30 non-hydrogen containing atoms, preferably C1-2 alkyl # and

Q 2 is tris (pentafluorophenyl) borane and other (pentafluorophenyl) human.

Examples of such catalyst activators include detrihydrocarbyl ammonium salts, especially demethyldi (C14-20 alkyl) ammonium salts of:

bis (tris (pentafluorophenyl) borane) imidazolide,

bis (tris (pentafluorophenyl) borane) -2-undecylimidazolide,

bis (tris (pentafluorophenyl) borane) -2-heptadecylimidazolide,

bis (tris (pentafluorophenyl) borane) 4,5-

bis (undecyl) imidazolide,

bis (tris (pentafluorophenyl) borane) -4,5-bis (heptadecyl) imidazolide,

bis (tris (pentafluorophenyl) borane) imidazolinide,

bis (tris (pentafluorophenyl) borane) -2-undecylimidazolinide,

bis (tris (pentafluorophenyl) borane) -2-heptadecylimidazolinide

bis (tris (pentafluorophenyl) borane) -4,5-

bis (undecyl) imidazolinide,

bis (tris (pentafluorophenyl) borane) -4,5-bis (heptadecyl) imidazolinide,

bis (tris (pentafluorophenyl) borane) -5,6-dimethylbenzimidazolide,

bis (tris (pentafluorophenyl) borane) -5,6-bis (undecyl) benzimidazolide,

bis (tris (pentafluorophenyl) human) imidazolide,

bis (tris (pentafluorophenyl) alumano) -2-undecylimidazolide, bis (tris (pentafluorophenyl) alumano) -2-heptadecylimidazolide,

bis (tris (pentafluorophenyl) human) -4,5-bis (undecyl) imidazolide, bis (tris (pentafluorophenyl) human) -4,5-bis (heptadecyl) imidazolide,

bis (tris (pentafluorophenyl) alumano) imidazolinide, bis (tris (pentafluorophenyl) alumano) -2-undecylimidazolinide,

bis (tris (pentafluorophenyl) human) -2-heptadecylimidazolinide,

bis (tris (pentafluorophenyl) human) -4,5-bis (undecyl) imidazolinide,

bis (tris (pentafluorophenyl) human) -4,5-bis (heptadecyl) imidazolinide,

bis (tris (pentafluorophenyl) human) -5,6-dimethylbenzimidazolide, and

bis (tris (pentafluorophenyl) human) -5,6-bis (undecyl) benzimidazolide.

Other activators include those described in PCT publication WO 98/07515 such as fluoroaluminate detris (2,2 ', 2 "-nonafluorobiphenyl). Reactivator combinations are also contemplated by the invention, for example alumoxanes and ionizing activators in combination, see for example EP- AO 573 120, PCT Publications WO 94/07928 and WO 95/14044 and U.S. Patent Nos. 5,153,157 and 5,453,410 WO 98/09996 describes activation compounds with perchlorates, periodates, and dihydrates, including their hydrates WO 99/18135 describes use of organoboroaluminum activators WO 03/10171 discloses catalyst activators which are Bronsted acid adducts with Lewis acids Other activators or methods for activating a catalyst compound are described in, for example, US Patents 5,849,852,5859,653, 5,869,723, EP-A-615981, and PCT publication WO98 / 32775.

As mentioned earlier, cocatalysts. Suitable activations for use herein include alumoxanospolymeric or oligomeric, especially metallumoxane (ΜΑΟ), triisobutyl aluminum modified metalumoxane (MMAO), or tri n-octylaluminium modified metallumoxane (OMAO); Lewis acid-modified alumoxanes, especially tri (hydrocarbyl) modified perhalogenated aluminum (hydrocarbyl) perhalogenated boron, having from 1 to 10 carbons in each hydrocarbyl or hydrocarbylhalogen group, and most especially tris (pentafluorophenyl) borane modified alumoxanes. Such cocatalysts were previously disclosed in USP's 6,214,760,6,160,146, 6,140,521, and 6,696,379.

All of the above catalyst activators as well as any other known activator for transition metal complex catalysts may be employed alone or in combination according to the present invention.

The catalyst / cocatalyst molar ratio 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 on its own as an activation cocatalyst, may be employed in a lower amount (<100: 1) than the predominant catalyst literature, which is generally 100 times the amount of metal complex on a molar basis, and more often than not. around 1000 times this quantity. Tris (pentafluorophenyl) borane when used as an activation cocatalyst is employed in a molar ratio for the metal complex from 0.5: 1 to 10: 1, more preferably from 1: 1 to 6: 1, most preferably from 1: 1 to 5. :1. Restorative activation cocatalysts are generally employed in amounts approximately equal to the metal complex.

Process

In general, polymerization may be carried out under conditions well known in the prior art for olefin solution polymerization reactions. Preferred polymerization temperatures are dependent on the deconomer content of the resulting polymer. For polymers with densities ranging from 0.865 to 0.885, preferred temperatures range from 170-250 ° C, more preferably 180-220 ° C. For polymers of densities ranging from 0.885 to 0.940, temperatures range from 190-250 ° C, more preferably 195-250 ° C. Preferred polymerization pressures are from 100 kPa to 300 MPa (atmospheric at 3000 atmospheres), more preferably from 1 MPa to 10 MPa.

In most polymerization reactions the decatalyst: polymerizable compound molar ratio employed is from 10'12: 1 to 10 "1: 1, more preferably from 10" 12: 1 to 10 "5: 1.

Highly desirably, the reaction is conducted under continuous solution polymerization conditions, that is, conditions where the monomer or monomers are continuously added to a reactor operating under solution polymerization conditions, and the 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, mixtures thereof; alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof; perfluorinated hydrocarbons such as perfluorinated C 4-10 alkanes, and the like. Small amounts of aromatic hydrocarbons such as toluene, ethylbenzene or xylene may also be included, but are not preferred. The mixtures of the above are also suitable. A preferred liquid diluent is a mixture of hydrogenated oligomeric aliphatic hydrocarbons having distillation, ASTM D86, 118 ° C IBP, distillationASTM D86, Dry Point 137 ° C, and Specific Gravity, 15.6 ° C, ASTM D 1250 of 0.72 sold commercially under ISOPAR® E commercially available from ExxonMobilCorporation.

The use of molecular weight control agents or chain transfer agents in the present process is desired. Examples of such pesomolecular control agents include hydrogen, trialkyl aluminum compounds, or other known chain transfer agents. A particular benefit of using the present invention is the ability (depending on the dyeing conditions) to produce ethylene / α-olefin interpolymers of narrow molecular weight distribution. Preferred polymers have Mw / Mn less than 2.5, more preferably less than 2.3. Such narrow molecular weight distribution polymer products are highly desirable because of the improved tensile strength properties as well as reduced levels of extractables.

Without limiting in any way the scope of the invention, a means for carrying 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 dilute and polymer dissolved. Catalyst together with cocatalyst and optionally chain transfer agent are continuously or intermittently introduced into the reactor phasel or any recycled portion thereof. The reactor temperature can be controlled by adjusting solvent / monomer ratio, catalyst addition rate, as well as using coils, cooling or heating liners or both. The polymerization rate is controlled by the catalyst addition rate. Pressure is controlled by 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 molecular weight of the polymeric product is optionally controlled by controlling other polymerization variables such as temperature, demonomer concentration, or by the above-mentioned chain transfer agent. Upon leaving the reactor, the effluent is contacted with a catalyst neutralizing agent such as water, steam or an alcohol. The polymeric solution is optionally heated, and the polymeric product is recovered by flashing off the gaseous monomers as well as reduced solvent or residual diluent and, if necessary, leading to further devolatilization in equipment such as a devolatilizing extruder. In a continuous process, the average residence time of the catalyst and noreator polymer is generally from 5 minutes to 8 hours, preferably from 10 minutes to 6 hours.

Alternatively, the above polymerization may be performed in a continuous Iop reactor with or without a monomer, comonomer, catalyst or catalyst gradient established between different regions thereof, optionally accompanied by separate addition of decatalysts and / or chain transfer agent, and operating under adiabatic conditions. or non-adiabatic solution polymerization or combinations of previous reactor conditions. Examples of suitable Ioop reactors and a variety of operating conditions suitable for use with them 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 metal oxides, demetaloid oxides, or mixtures thereof (interchangeably referred to herein as an inorganic oxide) of large surface areas, particulates, solids. Examples include: talc, silica, alumina, magnesia, titania, zirconia, Sn2O3, aluminosilicates, borosilicates, clays, and mixtures thereof. Suitable supports preferably have a surface area as determined by nitrogen porosimetry using the B.E.T. from 10 to 1000 m2 / g, and preferably from 100 to 600 m2 / g. The average particle size is typically from 0.1 to 500 μιη, preferably from 1 to 200 μιη, more preferably from 10 to 100 μm.

In one embodiment of the invention the present decatalyst composition and optional support may be spray dried or otherwise recovered in solid, particulate form to provide a composition which is readily transported and handled. Suitable methods for spray drying a liquid-containing paste are well known in the art and usefully employed herein. Preferred techniques for spray drying decatalyst 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, oxidizing addition elements, and polymerization aids are continuously supplied to the deaeration zone and continuously removed polymeric product. Within the scope of the terms "continuously" and "continuously" as used in this context are those processes in which there are intermittent additions of reagents and removal of products at regular or irregular intervals, such that over time the overall process is substantially continuous.

Catalyst compositions may advantageously be employed in a high pressure polymerization process in solution, paste, or gas phase. 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. Such a process using an extremely fine silica or similar dispersing agent to produce such a homogeneous catalyst dispersion where either the metal or ococatalyst complex is only poorly soluble is disclosed in US-A-5,783,512. A high pressure process is usually performed at temperatures of 100 ° C to 4000 ° C and pressures above 50 MPa (500 bar). A process in pastatipically uses an inert hydrocarbon diluent at temperatures of 0 ° C 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 of 30 ° C are preferred. preferably from 60 ° C to 115 ° C, preferably up to 100 ° C. Pressures typically range from 100 kPa (atmospheric) to 3.4 MPa (500 psi). Supported catalyst compositions may be prepared by depositing or chemically bonding the required components into an inert organic or inorganic particulate solid, as previously disclosed. In one embodiment, a heterogeneous catalyst is prepared by co-precipitating the complexometallic and reaction product of an inorganic inert compound and an active hydrogen-containing activator, especially the reaction product of a detri (C1-4 alkyl) aluminum compound and an ammonium salt. of a hydroxyaryltris borate (pentafluorophenyl) such as a (4-hydroxy-3,5-dibutylphenyl tertiary) borate deamonium salt) tris (pentafluorophenyl). When prepared in a heterogeneous or supported form, the catalyst composition may be employed in a gaseous polymerization or gas phase. As a practical limitation, slurry polymerization occurs in liquid diluents in which the polymeric product is substantially insoluble. Preferably, the slurry polymerization diluent is one or more hydrocarbons of less than 5 carbon atoms. If desired, saturated hydrocarbons such as ethane, propane or butane may be used in whole or in part as the diluent. Preferably for use in gas phase polymerization processes, the support material and catalyst resulting have an average particle diameter of 20 to 200μπι, more preferably. preferably from 30 μιτι to 150 μιτι, and most preferably from 50 μιτι to 100 μπι. Preferably for use in slurry polymerization processes, the support has an average particle diameter d 1 μπι to 200 μτη, more preferably from 5 μπι to 100 μπι, and most preferably from 10 μπι to 80 μπι.

Suitable gas phase polymerization processes for use herein are substantially similar to known processes used commercially on a large scale to produce polypropylene, ethylene / α-olefin copolymers, and other olefin polymers. The employed gas phase process may be, for example, of the type employing a mechanically stirred bed or a fluidized gas bed as the polymerization reaction zone. Preferred is the process where the polymerization reaction is performed in a vertical cylindrical polymerization reactor containing a fluidized bed of supported or suspended polymer particles above a perforated plate or deflating grid by a fluidizing gas flow.

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 reaction bed reaction. Hot gases emerge from the top of the reactor, usually via a tranquilization zone, also known as the velocity reduction zone, having a larger diameter than the fluidized bed and where fine particles entrained in the gas stream have an opportunity to gravitate back to the bed.

It may also be advantageous to use a cyclone to remove ultrafine 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 exchanges to extract the gas from the heat of polymerization.

A preferred method for bed cooling, 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 a condensing mode operation. The volatile liquid employed herein may be, for example, a volatile inert liquid, for example, a saturated hydrocarbon having 3 to 8, preferably 4 to 6 carbon atoms. If the monomer or the monomer itself is a volatile liquid, or may be condensed to provide such liquid, it may be suitably fed to the bed to provide an evaporative cooling effect. The volatile liquid evaporates into the hot fluidized bed to form gas that 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. Recycling gas is cooled in the heat exchanger and if the temperature at which the gas is cooled is below the dew point, liquid will precipitate from the gas. This liquid is desirably continuously recycled to the fluidized bed. It is possible to recycle the precipitated liquid to the bed with liquid droplets charged 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 for recycling the liquid to the bed is to separate the liquid from the recycle gas stream and reinject this liquid directly into the bed, preferably using a method that generates fine droplets of the liquid within the bed. This process type 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 the catalyst composition according to the invention. Catalyst composition may be subjected to a prepolymerization step, for example by polymerizing a small amount of olefin monomer into a liquid diluent, to provide a catalyst compound 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 in the fluidised particulate catalyst composition, supported catalyst composition or prepolymerized decatalyst composition within the bed. The polymerization reaction is accomplished by using a bed of preformed polymer particles which are preferably similar to or equal to those of the polymer being produced, and conditioning the bed by drying with inert gas or nitrogen before introducing the catalyst composition, monomers and any other gases that you wish to have in the recycle gas stream, such as a diluent gas, hydrogen chain transfer agent, or an inert condensable gas when operating in the gas phase condensation mode. The polymer produced is continuously discharged continuously or 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 reagents to the reactor shedding zone and the removal of products from the reactor shedding zone, thus providing a macroscale stable state environment in the reactor zone. reactor reaction. The products are readily recovered by exposure to reduced pressure and optionally elevated temperatures (devolatilization) according to known techniques.

Typically, the fluidized bed of the fasegasosa process is operated at temperatures above 50 ° C, preferably from 60 ° C to 110 ° C, more preferably from 700 ° C to 100 ° C. Examples of gaseous phase processes which are adaptable for use in the process of this invention are disclosed in U.S. Patent Nos. 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 Settings

The following configurations are provided for specific disclosure purposes for the appended claims. A process for the polymerization of ethylene optionally one or more α-olefins under continuous solution polymerization conditions to prepare high molecular weight polymer, said process comprising conducting polymerization in the presence of a catalyst composition comprising a transition metal complex and a cocatalyst activation conditions that result in a value for the polymerization index, Ψ, that is greater than or equal to zero as determined by the following equation:

Ψ = β0 + βλΤ + β2Χ + β3Ε + β4ρ + β5Ι2

where: T is the polymerization temperature in degrees Celsius, X is the conversion of ethylene in the reactor to mole percent, and E is the catalyst efficiency in g of metal-produced polymer in the metal complex fed to the unit time reactor, p the resulting density of the polymer in units of g / ml, I2 is the polymer melt index in units of dg / minute, and the constants of the equation βο-ββ are dimensionless numbers having the values given in the following table:

<table> table see original document page 51 </column> </row> <table>

2. The configuration process 1 wherein the resulting polymer has a molecular weight distribution, Mw / Mn, of less than 3.0.

The process of configuration 1 wherein the decatalyst composition further comprises a chain transfer agent.

4. The process of configuration 3 wherein the amount of chain transfer agent present in the reactor is sufficient to decrease the Mw of the resulting polymer by at least 30 percent compared to the resulting molecular weight of the polymer prepared in the absence of a chain transfer agent.

5. The process of configuration 3 wherein the chain transfer agent is hydrogen, present in an amount of 0.015 to 2.0 moles percent (based on monomer content).

6. The configuration process 1 wherein the conversion of ethylene is at least 85 mol percent.

The process of any of the 1-6 configurations wherein ethylene and one or more C 3-20 α-olefins are polymerized.

8. The process of configuration 7 wherein ethylene and one or more C6.20 α-olefins are copolymerized.

9. The process of configuration 1 was conducted at a temperature of 1850 ° C to 2500 ° C in the presence of a chain transfer agent to prepare a polymer having a density between 0.885 and 0.950 g / cm3, a melt index, I2, <2.0, a distribution of molecular weight Mw / Mn <3.0, and a catalyst efficiency greater than -0.5 gpoiomer / Mgmetal ·

10. The process of configuration 9 wherein the chain transfer agent is present in an amount such that the reduction in Mw of the resulting polymer is> 30 percent compared to the Mw of the resulting polymer produced in the absence of decade transfer agent.

11. The process of configuration 10 wherein the chain transfer agent is hydrogen present in the reactor in an amount of 0.015 to 2 mol percent based on ethylene.

12. The process of any of the embodiments 9-11 wherein ethylene and one or more C 3-20 α-olefins are polymerized.

13. The process of configuration 12 wherein ethylene and one or more C 3-2 α-olefins are copolymerized.

14. The process of configuration 1 conducted at a temperature of 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 / cm3, a melt index, I2, <2.0, a distribution molecular weight Mw / Mn <3.0, and a catalyst efficiency greater than 0.5imer / M-Smetal ·

15. The process of embodiment 14 wherein the chain transfer agent is present in an amount that the reduction in Mw of the resulting polymer is> 30 percent compared to the Mw of the resulting polymer prepared in the absence of chain transfer agent.

16. The process of configuration 15 wherein the chain transfer agent is hydrogen present in the reactor in an amount of 0.015 to 2 mol percent based on ethylene.

17. The process of any of the configurations 14-16 wherein ethylene and one or more C 3-20 α-olefins are polymerized.

18. The process of configuration 17 wherein ethylene and one or more C6-2 α-olefins are copolymerized.

19. The process of configuration 1 is conducted at a temperature of 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 / cm3, melt index, I2, from 0.01 to 100, a molecular weight distribution Mw / Mn <3.0, and a catalyst efficiency greater than 0.5 gPolymer / Mgmetai / and where the reactivating cocatalyst is oligomeric modified alumoxane or polymeric alumoxane present in an amount to provide a molar reason, Al: metal complex, from 20-200.

20. The process of configuration 19 wherein the oligomeric or polymeric modified alumoxane or alumoxane is present in an amount to provide an Al: metal complex molar ratio of 30-150.21. The process of the configuration 20 wherein the oligomeric or polymeric modified alumoxane or alumoxane is present in an amount to provide an Al: metal complex molar ratio of 40-80.

The process of any of configurations 19-21 wherein the oligomeric or polymeric modified alumoxane or modified alumoxane is selected from the group consisting of methmialumoxane, isobutylalumoxane; and Lewis acid modified alumoxanes.

23. The process of embodiment 22 wherein the Lewis acid-modified alumoxane is modified methylalumoxane with trialkylaluminum, trioperhydrogenated aluminum (trihydrocarbyl), or perhalogenated tri (hydrocarbyl) boron.

24. The process of embodiment 23 wherein the Lewis acid-modified alumoxan is modified methylalumoxane with triisobutyl aluminum, modified methyl-al-octyl aluminum modified methyl, or comtris (pentafluorophenyl) boron modified methylalumoxane.

25. The process of any of configurations 19-24 wherein the chain transfer agent is present in such an amount that the reduction in Mw of the resulting polymer is> 30 percent compared to the Mw of the resulting polymer prepared in the absence of chain transfer agent. .

26. The process of configuration 25 wherein the chain transfer agent is hydrogen present in the reactor in an amount of 0.015 to 2 mol percent based on ethylene.

The process of any of the 1-6 configurations conducted in a single reactor and the decatalyst composition comprises at least two metal complexes or metal compounds.

28. The process of any of the 1-6 configurations conducted in at least one reactor of two or more series or parallel connected reactors.

29. The process of embodiment 28 wherein the decatalyst composition comprises at least two metal complexes.

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

<formula> formula see original document page 55 </formula>

Where :

R20 is an inertly substituted aliphatic, aromatic or aromatic group containing from 5 to 20 non-hydrogen containing atoms, or a polyvalent derivative thereof;

T3 is a hydrocarbylene or silane group having from 1 to 20 derivatives or one non-hydrogen-containing atoms, inertly substituted thereof;

M3 is a Group 4 metal, preferably zirconium or hafnium;

Rd independently at each occurrence is a monovalent grouping or two groups Rd together are a divalent hydrocarbylene or hydrocarbadiyl group; Elections and electron donor interactions are represented by lines and arrows respectively.

31. The process of configuration 30 wherein the complexometallic corresponds to the formula:

<formula> formula see original document page 55 </formula>

wherein: T3 is a divalent bridging group of 2 to 20 non-hydrogen containing atoms, preferably a substituted or unsubstituted C 3-6 alkylene group; and

Ar 2 independently at each occurrence is an alkylene, aryl, alkoxy or amino substituted arylene group or arylene of 6 to 20 atoms not containing hydrogen and not containing substituents;

M3 is a Group 4 metal, preferably hafnium or zirconium;

Rd independently at each occurrence is a monovalent grouping or two groups R0 together are a grouping hydrocarbylene or hydrocarbyl; Electron donor interactions are represented by porsetas.

32. The process of configuration 31 where the complexometallic corresponds to the formula:

<formula> formula see original document page 56 </formula>

where M3 is Hf or Zr;

Ar4 is C6-2 aryl or inertly substituted derivatives thereof, especially 3,5-di (isopropyl) phenyl, 3,5-di (isobutyl) phenyl, dibenzo-1H-pyrrol-1-yl, naphthyl, anthracen-5-yl 1,2,3,4,6,7,8,9-octahydroantracen-5-yl and T4 independently at each occurrence comprises a C 3-6 alkylene group, a C 3-6 cycloalkylene group, or an inert substituted derivative thereof;

R21 independently at each occurrence is hydrogen, halo, hydrocarbyl, trihydrocarbylsilyl, trihydrocarbylsilylhydrocarbyl, alkoxy or amino of up to 50 atoms not containing hydrogen; and

R 2 independently at each occurrence is halo or a hydrocarbyl or trihydrocarbyl group of up to 20 non-hydrogen containing atoms, or 2 R 0 groups together are a divalent hydrocarbylene, hydrocarbadiyl or hydrocarbyl group.

33. The configuration process 32 where M3 is Zr.

34. The configuration process 33 wherein the complexometallic is selected from the group consisting of:

A) Bis ((2-oxoyl-3- (1,2,3,4,6,7,8,9-octahydroantracen-5-yl) -5- (methyl) phenyl) -2-phenoxy) propane-1 , 2-diylzirconium (N) dimethyl,

bis ((2-oxoyl-3- (1,2,3,4,6,7,8,9octahidroantracen-5-yl) -5- (methyl) phenyl) -2-phenoxy) propane-1,2-dichloride -diylzirconium (IV),

bis ((2-oxoyl-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) -2-phenoxy) propane-1,2-diylzirconium (IV) dimethyl,

bis ((2-oxoyl-3- (dibenzo-β-pyrrol-1-yl) -5- (methyl) phenyl) -2-phenoxy) propane-1,2-diylzirconium dichloride,

bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-yl) -5- (methyl) phenyl) -2-phenoxy) propane-1,2-diylzirconium (IV) dimethyl,

bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-yl) -5- (methyl) phenyl) -2-phenoxy) propane-1,2-diylzirconium (IV) dichloride,

bis ((2-oxoyl-3- (1,2,3,4,6,7,8,9-octahydroantracen-5-yl) -5- (methyl) phenyl) -2-phenoxy) -trans-cyclohexane-2-one 1,2-dimethylenyl-1,2-diylzirconium (IV) dimethyl,

bis ((2-oxoyl-3- (1,2,3,4,6,7,8,9-octahydroantracen-5-yl) -5- (methyl) phenyl) -2-phenoxy) -transdichloride dichloride cyclohexane-1,2-dimethylenyl-1,2-diylzirconium (IV),

bis ((2-oxoyl-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) -2-phenoxy) -trans-cyclohexane-1,2-dimethylenyl-1,2-diylzirconium ( IV) dimethyl,

bis ((2-oxoyl-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) -2-phenoxy) -trans-cyclohexane-1,2-dimethylenyl-1,2-dichloride diylzirconium (IV),

bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-yl) -5- (methyl) phenyl) -2-phenoxy) -trans-cyclohexane-1,2-dimethylenyl-1,2- (IV) dimethyl dimethyl, bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-yl) -5 (methyl) phenyl) -2-phenoxy) -trans-cyclohexane-1,2-dichloride -dimethylenyl-1,2-diylzirconium (IV) 7

bis ((2-oxoyl-3- (1,2,3,4,6,7,8,9-octahydroantracen-5-yl) -5- (methyl) phenyl) -2-phenoxy) -cyclohexane-2-one 1,3-diylzirconium (IV) dimethyl,

bis ((2-oxoyl-3- (1,2,3,4,6,7,8,9-octahydroantracen-5-yl) -5- (methyl) phenyl) -2-phenoxy) -cis-cyclohexane dichloride 1,3-diylzirconium (IV),

bis ((2-oxoyl-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) -2-phenoxy) -cyclohexane-1,3-diylzirconium (N) dimethyl,

bis ((2-oxoyl-3- (dibenzo-β-pyrrol-1-yl) -5 (methyl) phenyl) -2-phenoxy) -cyclohexane-1,3-diylzirconium dichloride,

bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-yl) -5- (methyl) phenyl) -2-phenoxy) -cyclohexane-1,3-diylzirconium (IV) dimethyl,

bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-yl) 5- (methyl) phenyl) -2-phenoxy) -cyclohexane-1,3-diylzirconium dichloride (IV) ,

bis ((2-oxoyl-3- (1,2,3,4,6,7,8,9-octahydroantracen-5-yl) -5- (methyl) phenyl) -2-phenoxy) -cis-cyclohexene-2-one 1,2-dimethylenyl-1,2-diylzirconium (IV) dimethyl,

bis ((2-oxoyl-3- (1,2,3,4,6,7,8,9-octahydroantracen-5-yl) -5- (methyl) phenyl) -2-phenoxy) -cis-cyclohexene dichloride 1,2-dimethylenyl-1,2-diylzirconium (IV),

bis ((2-oxoxy-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) -2-phenoxy) -cyclohexene-1,2-dimethylenyl-1,2-diylzirconium ( IV) dimethyl,

bis ((2-oxoyl-3- (dibenzo-1H-pyrrol-1-yl) -5 (methyl) phenyl) -2-phenoxy) -cyclohexene-1,2-dimethylenyl-1,2-diylzirconium dichloride (IV),

bis ((2-oxoxy-3- (1,1-dimethylethyl) phenyl-1-yl) -5- (methyl) phenyl) -2-phenoxy) -cyclohexene-1,2-dimethylenyl-1,2-yl diylzirconium (IV) dimethyl,

bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-yl) -5 (methyl) phenyl) -2-phenoxy) -cyclohexene-1,2-dimethylenyl-1,2 dichloride -diylzirconium (IV),

bis ((2-oxoxy-3- (1,2,3,4,6,7,8,9-octahydroantracen-5-yl) -5- (methyl) phenyl) -2-phenoxy) butane-1,4 -diylzirconium (IV) dimethyl,

bis ((2-oxoyl-3- (1,2,3,4,6,7,8,9-octahydroantracen-5-yl) -5- (methyl) phenyl) -2-phenoxy) butane-1,4-dichloride -diylzirconium (IV),

bis ((2-oxoyl-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) -2-phenoxy) butane-1,4-diylzirconium (IV) dimethyl,

bis ((2-oxoyl-3- (dibenzo-1H-pyrrol-1-yl) -5 (methyl) phenyl) -2-phenoxy) butane-1,4-diylzirconium dichloride,

bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-yl) -5- (methyl) phenyl) -2-phenoxy) butane-1,4-diylzirconium (IV) dimethyl,

bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-yl) -5 (methyl) phenyl) -2-phenoxy) butane-1,4-diylzirconium dichloride,

B) Bis ((2-oxoyl-3- (1,2,3,4,6,7,8,9-octahydroantracen-5yl) -5- (methyl) phenyl) - (4-methyl-2-phenoxy) ) propane-1,2-diylzirconium (IV) dimethyl,

bis ((2-oxoyl-3- (1,2,3,4,6,7,8,9-octahydroantracen-5-yl) -5- (methyl) phenyl) - (4-methyl-2-phenoxy) dichloride ) propane-1,2-diylzirconium (IV),

bis ((2-oxoyl-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) - (4-methyl-2-phenoxy)) propane-1,2-diylzirconium (IV) dimethyl ,

bis ((2-oxoyl-3- (dibenzo-1H-pyrrol-1-yl) -5 (methyl) phenyl) - (4-methyl-2-phenoxy)) propane-1,2-diylzirconium dichloride (IV) ,

bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-yl) -5- (methyl) phenyl) - (4-methyl-2-phenoxy)) propane-1,2-diylzirconium (IV ) dimethyl,

bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-yl) -5 (methyl) phenyl) - (4-methyl-2-phenoxy)) propane-1,2-diylzirconium dichloride ( IV),

bis ((2-oxoyl-3- (1,2,3,4,6,7,8,9-octahydroantracen-5-yl) -5- (methyl) phenyl) - (4-methyl-2-phenoxy) ) -trans-cyclohexane-1,2-dimethylenyl-1,2-diylzirconium (IV) dimethyl,

bis ((2-oxoyl-3- (1,2,3,4,6,7,8,9-octahydroantracen-5-yl) -5- (methyl) phenyl) - (4-methyl-2-phenoxy) dichloride ) -trans-cyclohexane-1,2-dimethylenyl-1,2-diylzirconium (IV),

bis ((2-oxoxy-3- (dibenzo-β-pyrrol-1-yl) -5- (methyl) phenyl) - (4-methyl-2-phenoxy)) - trans-cyclohexane-1,2-dimethylenyl- 1,2-diylzirconium (IV) dimethyl,

bis ((2-oxoyl-3- (dibenzo-1H-pyrrol-1-yl) -5 (methyl) phenyl) - (4-methyl-2-phenoxy)) - trans-cyclohexane-1,2-dimethylenyl dichloride -1,2-diylzirconium (IV),

bis ((2-oxoxy-3- (1,1-dimethylethyl) phen-1-yl) -5- (methyl) phenyl) - (4-methyl-2-phenoxy)) - trans-cyclohexane-1,2-one dimethylenyl-1,2-diylzirconium (IV) dimethyl,

bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-yl) -5 (methyl) phenyl) - (4-methyl-2-phenoxy)) - trans-cyclohexane-1,2-dichloride -dimethylenyl-1,2-diylzirconium (IV),

bis ((2-oxoxy-3- (1,2,3,4,6,7,8,9-octahydroantracen-5-yl) -5- (methyl) phenyl) - (4-methyl-2-phenoxy) ) -cyclohexane-1,3-diylzirconium (IV) dimethyl,

bis ((2-oxoyl-3- (1,2,3,4,6,7,8,9-octahydroantracen-5-yl) -5- (methyl) phenyl) - (4-methyl-2-phenoxy) dichloride ) -cis-cyclohexane-1,3-diylzirconium (IV),

bis ((2-oxoyl-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) - (4-methyl-2-phenoxy)) cis-cyclohexane-1,3-diylzirconium ( IV) dimethyl,

bis ((2-oxoyl-3- (dibenzo-1H-pyrrol-1-yl) -5 (methyl) phenyl) - (4-methyl-2-phenoxy)) cis -cyclohexane-1,3-diylzirconium dichloride (IV),

bis ((2-oxoyl-3- (1,1-dimethyl) phenyl-1-yl) -5 (methyl) phenyl) - (4-methyl-2-phenoxy)) cis-cyclohexane-1,3 diylzirconium (IV) dimethyl,

bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-yl) 5- (methyl) phenyl) - (4-methyl-2-phenoxy)) - cis-cyclohexane-1,3 dichloride -diylzirconium (IV),

bis ((2-oxoyl-3- (1,2,3,4,6,7,8,9-octahydroantracen-5-yl) -5- (methyl) phenyl) - (4-methyl-2-phenoxy) ) -cis-cyclohexene-1,2-dimethylenyl-1,2-diylzirconium (IV) dimethyl,

bis ((2-oxoyl-3- (1,2,3,4,6,7,8,9-octahydroantracen-5-yl) -5- (methyl) phenyl) - (4-methyl-2-phenoxy) dichloride ) -cis-cyclohexene-1,2-dimethylenyl-1,2-diylzirconium (IV),

bis ((2-oxoyl-3- (dibenzo-β-pyrrol-1-yl) -5- (methyl) phenyl) (4-methyl-2-phenoxy)) cis-cyclohexene-1,2-dimethylenyl-1 , 2 diylzirconium (IV) dimethyl,

bis ((2-oxoyl-3- (dibenzo-1H-pyrrol-1-yl) -5 (methyl) phenyl) - (4-methyl-2-phenoxy)) -is-cyclohexene-1,2-dimethylenyl dichloride -1,2-diylzirconium (IV),

bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-yl) -5- (methyl) phenyl) - (4-methyl2-phenoxy)) cis-cyclohexene-1,2-dimethylenyl 1,2-diylzirconium (IV) dimethyl,

bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-yl) -5- (methyl) phenyl) - (4-methyl-2-phenoxy)) cis-cyclohexene-1 dichloride, 2-dimethylenyl-1,2-diylzirconium (IV),

bis ((2-oxoyl-3- (1,2,3,4,6,7,8,9-octahydroantracen-5-yl) -5- (methyl) phenyl) - (4-methyl-2-phenoxy) ) butane-1,4-diylzirconium (IV) dimethyl,

bis ((2-oxoyl-3- (1,2,3,4,6,7,8,9octahidroantracen-5-yl) -5- (methyl) phenyl) - (4-methyl-2-phenoxy) dichloride ) butane-1,4-diylzirconium (IV),

bis ((2-oxoyl-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) - (4-methyl-2-phenoxy)) butane-1,4-diylzirconium (IV) dimethyl ,

bis ((2-oxoyl-3- (dibenzo-1H-pyrrol-1-yl) -5 (methyl) phenyl) - (4-methyl-2-phenoxy)) butane-1,4-diylzirconium dichloride (IV) ,

bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-yl) -5- (methyl) phenyl) - (4-methyl-2-phenoxy)) butane-1,4-diylzirconium (IV ) dimethyl,

bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-yl) -5- (methyl) phenyl) - (4-methyl-2-phenoxy)) butane-1,4-diylzirconium dichloride (IV),

C) Bis ((2-oxoyl-3- (1,2,3,4,6,7,8,9-octahydroantracen-5yl) -5- (methyl) phenyl) - (5- (2-methyl) propane -2-yl) -2-phenoxy) propane-1,2-diylzirconium (IV) dimethyl,

bis ((2-oxoyl-3- (1,2,3,4,6,7,8,9octahidroantracen-5-yl) -5- (methyl) phenyl) - (5- (2-methyl) propane dichloride) -2-yl) propane-1,2-diylzirconium (IV), bis ((2-oxoxy-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) - (5- (2 (methyl) propane-2-yl) propane-1,2-diylzirconium (IV) dimethyl,

bis ((2-oxoyl-3- (dibenzo-β-pyrrol-1-yl) -5 (methyl) phenyl) - (5- (2-methyl) propan-2-yl) propane-1,2-dichloride diylzirconium (IV),

bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-yl) -5- (methyl) phenyl) - (5- (2-methyl) propan-2-yl) propane-1,2 -diylzirconium (IV) dimethyl,

bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-yl) -5- (methyl) phenyl) - (5- (2-methyl) propan-2-yl) propane-1 dichloride , 2-diylzirconium (IV),

bis ((2-oxoyl-3- (1,2,3,4,6,7,8,9-octahydroantracen-5-yl) -5- (methyl) phenyl) - (5- (2-methyl) propane -2-yl) -trans-cyclohexane-1,2-dimethylenyl-1,2-diylzirconium (IV) dimethyl, bis ((2-oxoyl-3- (1,2,3,4,6,7, 8,9-octahydroantracen-5-yl) -5- (methyl) phenyl) - (5- (2-methyl) propan-2-yl) -trans-cyclohexane-1,2-dimethylenyl-1,2-diylzirconium ( IV),

bis ((2-oxoyl-3- (dibenzo-β-pyrrol-1-yl) -5- (methyl) phenyl) - (5- (2-methyl) propan-2-yl) -trans-cyclohexane-1, 2-dimethylenyl-1,2-diylzirconium (IV) dimethyl,

bis ((2-oxoyl-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) - (5- (2-methyl) propan-2-yl) -trans-cyclohexane-dichloride 1,2-dimethylenyl-1,2-diylzirconium (IV),

bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-yl) -5- (methyl) phenyl) - (5- (2-methyl) propan-2-yl) -trans-cyclohexan-2-one 1,2-dimethylenyl-1,2-diylzirconium (IV) dimethyl bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-yl) -5- (methyl) phenyl) - ( 5- (2-methyl) propan-2-yl) -trans-cyclohexane-1,2-dimethylenyl-1,2-diylzirconium (IV),

bis ((2-oxoyl-3- (1,2,3,4,6,7,8,9-octahydroantracen-5-yl) -5- (methyl) phenyl) - (5- (2-methyl) propane -2-yl) -cyclohexane-1,3-diylzirconium (IV) dimethyl,

bis ((2-oxoyl-3- (1,2,3,4,6,7,8,9-octahydroantracen-5-yl) -5- (methyl) phenyl) - (5- (2-methyl) dichloride ) propane-2-yl) cis-cyclohexane-1,3'-diylzirconium (IV),

bis ((2-oxoyl-3- (dibenzo-β-pyrrol-1-yl) -5- (methyl) phenyl) - (5- (2-methyl) propan-2-yl) -cis-cyclohexane-1, 3-diylzirconium (IV) dimethyl,

bis ((2-oxoyl-3- (dibenzo-1H-pyrrol-1-yl) -5 (methyl) phenyl) - (5- (2-methyl) propan-2-yl) -cyclohexane-1 dichloride , 3-diylzirconium (IV),

bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-yl) -5- (methyl) phenyl) - (5- (2-methyl) propan-2-yl) -cyclohexane-2-one 1,3-diylzirconium (IV) dimethyl,

bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-yl) -5 (methyl) phenyl) - (5- (2-methyl) propan-2-yl) -cyclohexane dichloride -1,3-diylzirconium (IV),

bis ((2-oxoyl-3- (1,2,3,4,6,7,8,9-octahydroantracen-5-yl) -5- (methyl) phenyl) - (5- (2-methyl) propane -2-yl) -cyclohexene-1,2-dimethylenyl-1,2-diylzirconium (IV) dimethyl

bis ((2-oxoyl-3- (1,2,3,4,6,7,8,9octetrahydroantracen-5-yl) -5- (methyl) phenyl) - (5- (2-methyl) propane dichloride -2-yl) -cis-cyclohexene-1,2-dimethylenyl-1,2-diylzirconium (IV),

bis ((2-oxoyl-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) - (5- (2-methyl) propan-2-yl) -cyclohexene-1, 2-dimethylenyl-1,2-diylzirconium (IV) dimethyl,

bis ((2-oxoyl-3- (dibenzo-1H-pyrrol-1-yl) -5 (methyl) phenyl) - (5- (2-methyl) propan-2-yl) -cyclohexene-1 dichloride , 2-dimethylenyl-1,2-diylzirconium (IV),

bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-yl) -5- (methyl) phenyl) - (5- (2-methyl) propan-2-yl) -cyclohexene-2-one 1,2-dimethylenyl-1,2-diylzirconium (IV) dimethyl,

bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-yl) -5 (methyl) phenyl) - (5- (2-methyl) propan-2-yl) -cyclohexene dichloride -1,2-dimethylenyl-1,2-diylzirconium (IV),

bis ((2-oxoyl-3- (1,2,3,4,6,7,8,9-octahydroantracen-5-yl) -5- (methyl) phenyl) - (5- (2-methyl) propane -2-yl) butane-1,4-diylzirconium (IV) dimethyl,

bis ((2-oxoyl-3- (1,2,3,4,6,7,8,9octetrahydroantracen-5-yl) -5- (methyl) phenyl) - (5- (2-methyl) propane dichloride -2-yl) butan-1,4-diylzirconium (IV), bis ((2-oxoyl-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) - (5- (2 (methyl) propane-2-yl) butane-1,4-diylzirconium (IV) dimethyl,

bis ((2-oxoyl-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) - (5- (2-methyl) propan-2-yl) butane-1,4-dichloride -diylzirconium (IV),

bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-yl) -5- (methyl) phenyl) - (5- (2-methyl) propan-2-yl) butane-1,4 -diylzirconium (IV) dimethyl, and

bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-yl) -5- (methyl) phenyl) - (5- (2-methyl) propan-2-yl) butane-1 dichloride , 4-diylzirconium (IV).

It is understood that the present invention is operable in the absence of any component that has not been specifically disclosed and may be combined with any other suitable reaction or process in a suitable multistage polymerization system. The following examples are provided to further illustrate the invention and should not be construed as limiting. Unless otherwise noted, all parts and percentages are expressed by weight.

Examples 1-10

Preparation of the metal complex

The synthetic procedures of US-A-2004/0010103 have been substantially repeated to prepare the Al-AlO metal complexes <formula> formula see original document page 65 </formula> <formula> formula see original document page 66 </formula>

Polymerization - batch reactor

An agitated one-gallon (3.79 L) reactor is charged with about two liters of alkanesmixed solvent (Isopar® E) and varying amounts of 1-octene. The reactor is heated to the desired temperature and charged with hydrogen in the indicated amount followed by enough ethylene to bring the total pressure to 450 psig (3.1 MPa). The catalyst composition is prepared in a greenhouse under an inert atmosphere by combining together catalyst, cocatalyst (in a mixture of 1.2 equivalents borate of (tallow bishydrogen) methylammonium tetrakis (pentafluorophenyl) and 10 equivalents of modified methoxobutyl aluminum methoxane containing a molar ratio of about 1/3 butyl / methyl groups (MMAO) with solvent added to provide a total volume of about 17 ml The activated catalyst mixture is injected into the reactor for approximately 4 minutes.

Reactor temperature and pressure are kept constant by continuously feeding ethylene during polymerization and cooling the reactor as required. After 10 minutes the ethylene is cut and the hot solution transferred to a nitrogen purged resin crucible. An additive solution containing a phosphorus stabilizer and phenolic antioxidant (Irgaphos 168 and Irganox 1010 in toluene at a weight ratio of 2: 1) is added to provide a total additive concentration of about 0.1 percent in the polymer. The polymer is recovered by intense drying in a vacuum oven. After drying the samples are weighed to determine catalyst efficiency. Between polymerizations the reactor is intensively washed with hot mixed hexanes. The results are contained in Table 1. <table> table see original document page 68 </column> </row> <table> Polymerization - continuous solution reactor

Continuous solution polymerizations are performed in a computer controlled autoclave reactor equipped with an internal stirrer. Purified mixed alkane solvent (Isopar® E available from ExxonMobili Inc.), Ethylene, 1-octene, and hydrogen are supplied to a 3.8 l reactor equipped with a temperature control jacket and an inert thermocouple. The solvent fed to the reactor is measured by a flow controller. A variable speed diaphragm pump controls the solvent flow rate and pressure to the reactor. At pump discharge, a side stream is drawn to provide flush flows to the catalyst and cocatalyst injection lines and the stirrer agitator. These flows are measured by Micro-Motion flowmeters and controlled by control valves or manual adjustment of needle valves. Remaining solvent is combined with 1-octene, ethylene, ehydrogen and fed to the reactor. A mass flow controller is used to supply hydrogen to the reactor as needed. The temperature of the solvent / monomer solution is controlled by the use of a heat exchanger before entering the reactor. This deep current flows from the reactor. Catalyst component solutions are measured using pumps and mass flow meters and are combined with the catalyst flush solvent and introduced at the bottom of the reactor. The reactor is operated liquid liquid at 3.45 MPa (500 psig) with vigorous agitation. Product is removed through the outlet lines at the top of the reactor. All reactor output lines have vapor traces and are isolated. Polymerization is interrupted by adding a small amount of water to the outlet line together with any stabilizers or other additives and passing the mixture through a static mixer. The product stream is then heated through a heat exchanger prior to devolatilization. The polymeric product is recovered by extrusion using a water-cooled extruder and pelletizer. Details and process results are contained in Tables 2 and 3. <table> table see original document page 71 </column> </row> <table> Table 3 represent polymerizations that were performed using low alumoxane levels as the only high temperature activation cocatalyst. <table> table see original document page 73 </column> </row> <table>

Claims (34)

A process for the polymerization of ethylene and optionally one or more α-olefins under continuous solution polymerization conditions to prepare high molecular weight polymer which comprises conducting polymerization in the presence of a catalyst composition comprising a transition metal complex. and an activation cocatalyst under conditions that result in a value for the polymerization index, Ψ, which is greater than or equal to zero as determined by the following equation: Ψ = β0 + βιΤ + β2Χ + β3Ε + β4ρ + β5Ι2where: T is the polymerization temperature in degrees Celsius, X is the conversion of ethylene in the reactor to mol percent, and is the efficiency of the catalyst in g of polymer produced by g of metal in the metal complex fed to the unit time reactor, p the resulting density of polymer in units of g / ml, i2 is the polymer melt index in units of dg / minute, and the constants of the equation 5 are dimensionless numbers having the values defined in the following listing: Constant equation Valueβο ......................- 13796, 073; βι ...... ................ 111,445393; β2 .................... 137,437524; β3 .. .................... 62.5876298; β4 .................. -18931, 8878; eβ5 ...................... -108,320017. Process according to Claim 1, characterized in that the resulting polymer has a molecular weight distribution, Mw / Mn, of less than 3.0. Process according to Claim 1, characterized in that the catalyst composition further comprises a decade transfer agent. Process according to Claim 3, characterized in that the amount of chain transfer agent present in the reactor is sufficient to decrease the Mw of the resulting polymer by at least percent compared to the molecular weight of the resulting polymer prepared in the absence of an agent. chain transfer. Process according to Claim 3, characterized in that the transfer agent is hydrogen, present in an amount of from 0.015 to 2.0 moles percent (based on the monomer content). Process according to Claim 1, characterized in that the ethylene conversion is less than 85 mole percent. Process according to any one of claims 1-6, characterized in that ethylene and one or more C 3-2 α-olefins are copolymerized. Process according to Claim 7, characterized in that ethylene and one or more α-olefins Ce-20 are copolymerized. Process according to Claim 1, characterized in that it is conducted at a temperature of 1850 ° C 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 / cm3, a melt index. , I2, <2.0, a molecular weight distribution Mw / Mn <3.0, and a catalyst efficiency greater than 0.5Spol immer / MOmetal · Process according to claim 9, characterized in that the transfer agent is present in an amount such that the reduction in Mw of the resulting polymer is> 30 percent compared to the Mw of the resulting polymer produced in the absence of transfer agent. chain Process according to Claim 10, characterized in that the transfer agent is hydrogen present in the reactor in an amount of 0.015 to 2 mol percent based on ethylene. Process according to any one of claims 9-11, characterized in that ethylene and one or more C 3-20 α-olefins are copolymerized. Process according to Claim 12, characterized in that ethylene and one or more C 3-20 α-olefins are copolymerized. Process according to Claim 1, characterized in that it is conducted at a temperature of 170 to 2500 ° C in the presence of a chain transfer agent to prepare a polymer having a density between 0.885 and 0.950 g / cm3, a melt index. , I2, <2.0, a molecular weight distribution Mw / Mn <3.0, and a catalyst efficiency greater than 0.5gpolymer / MiSmetal · Process according to claim 14, characterized in that the transfer agent is present in an amount such that the reduction in Mw of the resulting polymer is> 30 percent compared to the Mw of the resulting polymer prepared in the absence of detergent. chain transfer. Process according to Claim 15, characterized in that the transfer agent is hydrogen present in the reactor in an amount of 0.015 to 2 mol percent based on ethylene. Process according to any one of claims 14-16, characterized in that ethylene and one or more C 3-20 α-olefins are copolymerized. Process according to Claim 17, characterized in that ethylene and one or more C6.20 α-olefins are copolymerized. Process according to Claim 1, characterized in that it is conducted at a temperature of 130 to 250 ° C and an ethylene conversion of at least 80 mole percent in the presence of a chain transfer agent to prepare a polymer having a density. between 0.865 and 0.950 g / cm3, a melt index, I2, of 0.01 to 100, a molecular weight distribution Mw / Mn <3.0, and a catalyst efficiency greater than 0.5 gpoiomer / Mgmetai, and where the cocatalyst The activation is oligomeric or polymeric modified alumoxane or alumoxane present in an amount to provide a molar moiety, Al: metal complex, of 20-200. Process according to Claim 19, characterized in that the oligomeric or polymeric alumoxane or alumoxanomodified is present in an amount to provide an Al: complexometallic molar ratio of 30-150. Process according to Claim 20, characterized in that the oligomeric or polymeric alumoxane or alumoxanomodified is present in an amount to provide an Al: complexometallic molar ratio of 40-80. Process according to any of claims 19-21, characterized in that the oligomeric or polymeric modified alumoxane or alumoxane is selected from the group consisting of methylalumoxane, isobutylalumoxane; and Lewis modified acid alumoxanes. Process according to Claim 22, characterized in that the Lewis acid modified alumoxane is triaalkylaluminum modified methylalumoxane, perhalogenated tri (hydrocarbyl), or perhalogenated tri (hydrocarbyl) boron. Process according to Claim 23, characterized in that the Lewis acid modified alumoxane is tri-n-octyl aluminum modified methylalumoxane, tri-n-octyl aluminum modified methylalumoxane, or comtris (pentafluorophenyl) boron modified methylalumoxane. Process according to any one of claims 19-24, characterized in that the chain transfer agent is present in such an amount that the reduction in Mw of the resulting polymer is> 30 percent compared to the Mw of the resulting polymer prepared in the absence of one. chain transfer agent agent. Process according to Claim 25, characterized in that the transfer agent is hydrogen present in the reactor in an amount of 0.015 to 2 mol percent based on ethylene. Process according to any one of claims 1-6, characterized in that it is conducted in a single reactor and the decatalyst composition comprises at least two metal complexes or metal compounds. Process according to any one of claims 1-6, characterized in that it is conducted in at least one reactor of two or more reactors connected in series or in parallel. Process according to Claim 28, characterized in that the catalyst composition comprises at least two metal complexes. A process for the polymerization of one or more addition-polymerizable monomers to prepare a high molecular weight polymer, which comprises conducting polymerization in the presence of a catalyst composition comprising a transition metal complex and an activation cocatalyst where the metal complex corresponds. to: <formula> formula see original document page 78 </formula> where: R20 is an inertly substituted aliphatic, aromatic or aromatic group containing from 5 to 20 non-hydrogen containing atoms or a polyvalent derivative thereof, T3 is a hydrocarbylene group or silane having from 1 to 20 atoms not containing hydrogen, or an inertly substituted derivative thereof M3 is a Group 4 metal; Rd independently at each occurrence is a monovalent grouper or two groups R0 together are a divalent hydrocarbylene or hydrocarbadiyl group; Elections and electron donor interactions are represented by lines and arrows respectively. Process according to Claim 30, characterized in that the metal complex corresponds to the formula: where: T3 is a divalent bridging group of 2 to 20 atoms not counting hydrogen; Ar2 independently at each occurrence is an alkylene, aryl, alkoxy or amino substituted arylene group or arylene of 6 to 20 atoms not containing hydrogen and not containing substituents; M3 is a Group 4 metal; Rd independently at each occurrence is a monovalent grouper or two groups R 0 together are a group-hydrocarbylene or hydrocarbyl; Electron donor interactions are represented by porsetas. Process according to Claim 31, characterized in that the metal complex corresponds to the formula: wherein M3 is Hf or Zr, preferably Zr; Ar4 is C6-2 aryl or inertly substituted derivatives; T4 independently at each occurrence comprises a group. C 3-6 alkylene, a C 3-6 cycloalkylene group, or an inert substituted derivative thereof R 21 independently at each occurrence is hydrogen, halo, hydrocarbyl, trihydrocarbylsilyl, trihydrocarbylsilylhydrocarbyl, alkoxy or amino of up to 50 atoms not containing hydrogen; and R d, independently at each occurrence is halo or a hydrocarbyl or trihydrocarbyl group of up to 20 non-hydrogen containing atoms, or 2 R d groups together are a divalent hydrocarbylene, hydrocarbadiyl or hydrocarbyl group. Process according to Claim 32, characterized in that M3 is Zr. Process according to Claim 33, characterized in that the selected metal complex of the group consisting of: A) bis ((2-Oxoxy-3- (1,2,3,4,6,7,8, 9-octahydroantracen-5-yl) -5- (methyl) enyl) -2-phenoxy) propane-1,2-diylzirconium (N) dimethyl bis ((2-oxoyl-3- (1,2,3) dichloride 4,6,6,7,8,9octahidroantracen-5-yl) -5- (methyl) phenyl) -2-phenoxy) propane-1,2-diylzirconium (IV), bis ((2-oxoyl-3- ( dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) -2-phenoxy) propane-1,2-diylzirconium (IV) dimethyl bis ((2-oxoyl-3- (dibenzoyl) 1H-pyrrol-1-yl) -5- (methyl) phenyl) -2-phenoxy) propane-1,2-diylzirconium (IV), bis ((2-Oxoxy-3- (1,1-dimethylethyl) phenyl) 1-yl) -5- (methyl) phenyl) -2-phenoxy) propane-1,2-diylzirconium (IV) dimethyl bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-dichloride -yl) -5 (methyl) phenyl) -2-phenoxy) propane-1,2-diylzirconium (IV), bis ((2-oxoyl-3- (1,2,3,4,6,7,8, 9-octahydroantracen-5-yl) -5- (methyl) phenyl) -2-phenoxy) -trans-cyclohexane-1,2-dimethylenyl-1,2-diylzirconium (IV) dimethyl, bile dichloride s (((2-oxoyl-3- (1,2,3,4,6,6,7,8,9octahidroantracen-5-yl) -5- (methyl) phenyl) -2-phenoxy) -trans-cyclohexane-1, 2-dimethylenyl-1,2-diylzirconium (IV), bis ((2-oxoyl-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) -2-phenoxy) -transmethyl cyclohexane-1,2-dimethylenyl-1,2-diylzirconium (IV) dimethyl bis ((2-oxoyl-3- (dibenzo-1H-pyrrol-1-yl) -5 (methyl) phenyl) -2- phenoxy) -trans-cyclohexane-1,2-dimethylenyl-1,2-diylzirconium (IV), bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-yl) -5- (methyl) phenyl) -2-phenoxy) -trans-cyclohexane-1,2-dimethylenyl-1,2-diylzirconium (IV) dimethyl, bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-dichloride) yl) -5 (methyl) phenyl) -2-phenoxy) -trans-cyclohexane-1,2-dimethylenyl-1,2-diylzirconium (IV), bis ((2-oxoyl-3- (1,2,3, 4,6,7,8,9-octahydroantracen-5-yl) -5- (methyl) phenyl) -2-phenoxy) -cyclohexane-1,3-diylzirconium (IV) dimethyl, bis (( 2-oxoyl-3- (1,2,3,4,6,7,8,9octahidroantracen-5-yl) -5- (methyl) phenyl) -2-phenoxy) -cyclohexane-1,3-diylzirconium (IV) bis ((2-oxoyl-3- (dibenzo-1H-pyrrol-1-yl) - 5- (methyl) phenyl) -2-phenoxy) -cyclohexane-1,3-diylzirconium (N) dimethyl, bis ((2-oxoyl-3- (dibenzo-1H-pyrrol-1-yl) dichloride ) -5- (methyl) phenyl) -2-phenoxy) -cyclohexane-1,3-diylzirconium (IV), bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-yl) -5- (methyl) phenyl) -2-phenoxy) -cyclohexane-1,3-diylzirconium (IV) dimethyl, bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1) dichloride -yl) -5- (methyl) phenyl) -2-phenoxy) -cyclohexane-1,3-diylzirconium (IV), bis ((2-OXO-1-3- (1,2,3,4,6, 7,8,9-octahydroantracen-5-yl) -5- (methyl) phenyl) -2-phenoxy) -cyclohexene-1,2-dimethylenyl-1,2-diylzirconium (IV) dimethyl, bis dichloride ((2-oxoyl-3- (1,2,3,4,6,7,8,9octahidroantracen-5-yl) -5- (methyl) phenyl) -2-phenoxy) -cyclohexene-1,2 -dimethylenyl-1,2-diylzirconium (IV), bis ((2-oxoyl-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) -2-phenoxy) -cyclohexene -1,2-dimethylenyl-1,2-diylzirconium (IV) dimethyl bis ((2-oxoyl-3- (dibenzo-1H-pyrrol-1-yl) -5 (methyl) phenyl) -2-phenoxy dichloride ) -cis-cyclohexene-1,2-dimethylenyl-1,2-diylzirconium (IV), bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-yl) -5- (methyl) phenyl) -2-phenoxy) -cyclohexene-1,2-dimethylenyl-1,2- (IV) dimethyl dimethyl, bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-yl) -5 (methyl) phenyl) -2-phenoxy) -cyclohexene-1,2-dichloride -dimethylenyl-1,2-diylzirconium (IV), bis ((2-oxoyl-3- (1,2,3,4,6,7,8,9-octahydroantracen-5-yl) -5- (methyl ) phenyl) -2-phenoxy) butane-1,4-diylzirconium (IV) dimethyl bis ((2-oxoyl-3- (1,2,3,4,6,7,8,9,9octahidroantracen-5-dichloride yl) -5- (methyl) phenyl) -2-phenoxy) butane-1,4-diylzirconium (IV), bis ((2-oxoyl-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) -2-phenoxy) butane-1,4-diylzirconium (IV) dimethyl bis ((2-oxoyl-3- (dibenzo-1H-pyrrol-1-yl) -5 (methyl) dichloride) phenyl) -2-phenoxy) butan-1,4-diylzirconium (IV), bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-yl) -5- (methyl) phenyl) - 2-phenoxy) butane-1,4-diylzirconium (IV) dimethyl bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-yl) -5 (methyl) phenyl) -2- phenoxy) butane-1,4-diylzirconium (IV), B) bis ((2-oxoyl-3- (1,2,3,4,6,7,8,9-o ctahidroantracen-5yl) -5- (methyl) phenyl) - (4-methyl-2-phenoxy)) propane-1,2-diylzirconium (IV) dimethyl bis ((2-oxoyl-3- (1,2) dichloride 3,4,6,7,8,9-octahydroantracen-5-yl) -5- (methyl) phenyl) - (4-methyl-2-phenoxy)) propane-1,2-diylzirconium (IV), bis ((2-oxoyl-3- (dibenzo-β-pyrrol-1-yl) -5- (methyl) phenyl) - (4-methyl-2-phenoxy)) propane-1,2-diylzirconium (IV) dimethyl, bis ((2-oxoyl-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) - (4-methyl-2-phenoxy)) propane-1,2-diylzirconium dichloride (IV ), bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-yl) -5- (methyl) phenyl) - (4-methyl-2-phenoxy)) propane-1,2-diylzirconium (IV) dimethyl, bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-yl) -5- (methyl) phenyl) - (4-methyl-2-phenoxy)) propane dichloride 1,2-diylzirconium (IV), bis ((2-oxoyl-3- (1,2,3,4,6,7,8,9-octahydroantracen-5-yl) -5- (methyl) phenyl) - (4-methyl-2-phenoxy)) - trans-cyclohexane-1,2-dimethylenyl-1,2-diylzirconium (IV) dimethyl bis ((2-oxoyl-3- (1,2,3 4,6,7,8,9-octahydroantracen-5-yl) -5- (methyl) phenyl) - (4-methyl-2-phenoxy)) trans-cyclohexane-1,2-dimethyl Nyl-1,2-diylzirconium (IV), bis ((2-Oxoxy-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) - (4-methyl-2-phenoxy)) -trans-cyclohexane-1,2-dimethylenyl-1,2-diylzirconium (IV) dimethyl bis ((2-oxoyl-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) dichloride) phenyl) - (4-methyl-2-phenoxy)) - trans-cyclohexane-1,2-dimethylenyl-1,2-diylzirconium (IV), bis ((2-oxoyl-3- (1,1-dimethylethyl) phen) -1-yl) -5- (methyl) phenyl) - (4-methyl-2-phenoxy)) -trans-cyclohexane-1,2-dimethylenyl-1,2-diylzirconium (IV) dimethyl, bis (( 2-oxoyl-3- (1,1-dimethylethyl) phen-1-yl) -5- (methyl) phenyl) - (4-methyl-2-phenoxy)) trans-cyclohexane-1,2-dimethylenyl-1 , 2-diylzirconium (IV), bis ((2-oxoyl-3- (1,2,3,4,6,7,8,9-octahydroantracen-5-yl) -5- (methyl) phenyl) - (4-methyl-2-phenoxy)) - cis-cyclohexane-1,3-diylzirconium (IV) dimethyl, bis ((2-oxoyl-3- (1,2,3,4,6, 7, 8 9octahidroantracen-5-yl) -5- (methyl) phenyl) - (4-methyl-2-phenoxy)) cis-cyclohexane-1,3-diylzirconium (IV), bis ((2-oxoyl-3- ( dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) - (4-methyl-2-phenoxy)) cis-cyclohexane-1,3 diylzirconium (IV) dimethyl, bis ((2-oxoyl-3- (dibenzo-1H-pyrrol-1-yl) -5 (methyl) phenyl) - (4-methyl-2-phenoxy)) - cis-cyciohexane dichloride -1,3-diylzirconium (IV), bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-yl) -5 (methyl) phenyl) - (4-methyl-2-phenoxy) ) -cis-cyclohexane-1,3-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), bis ((2-oxoyl-3- (1,2,3,4,6,7,8,9-octahidroantracen -5-yl) - 5- (methyl) phenyl) - (4-methyl-2-phenoxy)) - cis-cyclohexene-1,2-dimethylenyl-1,2-diylzirconium (IV) dimethyl, bis ( (2-oxoyl-3- (1,2,3,4,6,6,8,9octahidroantracen-5-yl) -5- (methyl) phenyl) - (4-methyl-2-phenoxy)) -cis cyclohexene-1,2-dimethylenyl-1,2-diylzirconium (IV), bis ((2-oxoyl-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) (4-methylmethyl) 2-phenoxy)) - cis-cyclohexene-1,2-dimethylenyl-1,2-diylzirconium (IV) dimethyl bis ((2-oxoyl-3- (dibenzo-1H-pyrrol-1-yl) -5) dichloride (methyl) phenyl) - (4-methyl-2-phenoxy)) - cis-cyclohexene-1,2-dimethylenyl-1,2-diyl (IV) zirconium, bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-yl) -5- (methyl) phenyl) - (4-methyl2-phenoxy)) - cis-cyclohexene-1 (2) dimethylenyl-1,2-diylzirconium (IV) dimethyl bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-yl) -5- (methyl) phenyl) - (4) dichloride (methyl-2-phenoxy)) - cis-cyclohexene-1,2-dimethylenyl-1,2-diylzirconium (IV), bis ((2-oxoyl-3 - (1,2,3,4,6,7, 8,9-octahydroantracen-5-yl) -5- (methyl) phenyl) - (4-methyl-2-phenoxy)) butane-1,4-diylzirconium (IV) dimethyl bis ((2-oxoyl dichloride -3- (1,2,3,4,6,6,8,9octahidroantracen-5-yl) -5- (methyl) phenyl) - (4-methyl-2-phenoxy)) butane-1,4-diylzirconium (IV) bis ((2-oxoyl-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) - (4-methyl-2-phenoxy)) butane-1,4-diylzirconium (IV) Dimethyl, bis ((2-oxoyl-3- (dibenzo-1H-pyrrol-1-yl) -5 (methyl) phenyl) - (4-methyl-2-phenoxy)) butane-1,4-dichloride (IV) -diylzirconium, bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-yl) -5- (methyl) phenyl) - (4-methyl-2-phenoxy)) butane-1 (4-diylzirconium) dimethyl, bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-yl) -5- (methyl) phenyl) - (4-methyl-2) dichloride (phenoxy)) butane-1,4-diylzirconium (IV), C) bis ((2-oxoyl-3- (1,2,3,4,6,7,8,9-octahydroantracen-5yl) -5- (methyl) phenyl) - (5- (2-methyl) propan-2-yl) -2-phenoxy) propane-1,2-diylzirconium (IV) dimethyl bis ((2-oxoyl-3- (1 2,3,4,6,6,7,9,9octahidroantracen-5-yl) -5- (methyl) phenyl) - (5- (2-methyl) propan-2-yl) propane-1,2-diylzirconium ( IV), bis ((2-oxoyl-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) - (5- (2-methyl) propan-2-yl) propane-1, 2-Diylzirconium (IV) dimethyl, bis ((2-oxoyl-3- (dibenzo-β-pyrrol-1-yl) -5- (methyl) phenyl) - (5- (2-methyl) propane-2) dichloride (yl) propane-1,2-diylzirconium (IV), bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-yl) -5- (methyl) phenyl) - (5- (2 (methyl) propane-2-yl) propane-1,2-diylzirconium (IV) dimethyl bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-yl) -5- ( methyl) phenyl) - (5- (2-methyl) propan-2-yl) propane-1,2-diylzirconium (IV), bis ((2-oxoyl-3- (1,2,3,4,6, 7,8,9-octahidroantracen-5-yl) -5- (methyl) phenyl) - (5- (2-methyl) propan-2-yl) -trans-cyclohexane-1,2-dimethylenyl-1,2 -diylzirconium (IV) di methyl, bis ((2-oxoyl-3- (1,2,3,4,6,6,7,9-octahydroantracen-5-yl) -5- (methyl) phenyl) dichloride - (5- (2 (methyl) propane-2-yl) -trans-cyclohexane-1,2-dimethylenyl-1,2-diylzirconium (IV), bis ((2-OXO-1-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) - (5- (2-methyl) propan-2-yl) -trans-cyclohexane-1,2-dimethylenyl-1,2-diylzirconium (IV) dimethyl, bis ((2) dichloride -oxoyl-3- (dibenzo-1H-pyrrol-1-yl) -5 (methyl) phenyl) - (5- (2-methyl) propan-2-yl) -trans-cyclohexane-1,2-dimethylenyl-1 , (2-Diylzirconium (IV), bis ((2-Oxoxy-3- (1,1-dimethylethyl) phen-1-yl) -5- (methyl) phenyl) - (5- (2-methyl) propane-2 bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-yl) -5-methyl (-1-yl) -trans-cyclohexane-1,2-dimethylenyl-1,2-diylzirconium (IV) dimethyl dichloride ) phenyl) - (5- (2-methyl) propan-2-yl) -trans-cyclohexane-1,2-dimethylenyl-1,2-diylzirconium (IV), bis ((2-oxoyl-3 - (1, 2,3,4,6,7,8,9-octahydroantracen-5-yl) -5- (methyl) phenyl) - (5- (2-methyl) propan-2-yl) -cis-cyclohexane-1 1,3-diylzirconium (IV) dimethyl, bis ((2-oxoyl-3- (1,2,3,4, 6,7,8,9octahidroantracen dichloride -5-yl) -5- (methyl) phenyl) - (5- (2-methyl) propan-2-yl) -cyclohexane-1 ', 3-diylzirconium (IV), bis ((2-OXO-1-3) (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) - (5- (2-methyl) propan-2-yl) -cyclohexane-1,3-diylzirconium (IV) dimethyl dichloride bis ((2-oxoyl-3- (dibenzo-1H-pyrrol-1-yl) -5 (methyl) phenyl) - (5- (2-methyl) propan-2-yl) -cis-cyclohexane-1 (3-diylzirconium), bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-yl) -5- (methyl) phenyl) - (5- (2-methyl) propane-2 -yl) -cyclohexane-1,3-diylzirconium (IV) dimethyl, bis ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-yl) -5 · (methyl) phenyl dichloride ) - (5- (2-methyl) propan-2-yl) -cyclohexane-1,3-diylzirconium (IV), bis ((2-oxoyl-3- (1,2,3,4,6 7,8,9-octahydroantracen-5-yl) -5- (methyl) phenyl) - (5- (2-methyl) propan-2-yl) -cyclohexene-1,2-dimethylenyl-1, 2-diylzirconium (IV) dimethyl, bis ((2-oxoyl-3- (1,2,3,4,6,7,8,9-octahydroantracen-5-yl) -5- (methyl) phenyl) dichloride - (5- (2-methyl) propan-2-yl) -cyclohexene-1,2-dimethylenyl-1,2-diylzirconium (IV), bis ((2-Oxoxy-3- (dibenzo-1H-pyrrol -1-yl) -5- (methyl) phenyl) - (5- (2-methyl) propan-2-yl) -cyclohexene-1,2-dimethylenyl-1,2-diylzirconium (IV) dimethyl dichloride bis ((2-oxoyl-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) - (5- (2-methyl) propan-2-yl) -cis-cyclohexene-- 1,2-dimethylenyl-1,2-diylzirconium (IV), bis ((2-oxoxy-3- (1,1-dimethylethyl) phen-1-yl) -5- (methyl) phenyl) - (5- ( 2-methyl) propan-2-yl) -cis-cyclohexene-1,2-dimethylenyl-1,2-diylzirconium (IV) dimethyl bis ((2-oxoyl-3- (1,1-dimethylethyl) dichloride fen-1-yl) -5- (methyl) phenyl) - (5- (2-methyl) propan-2-yl) -cyclohexene-1,2-dimethylenyl-1,2-diylzirconium (IV), bis ((2-oxoyl-3 - (1,2,3,4,6,7,8,9-octahydroantracen-5-yl) -5- (methyl) phenyl) - (5- (2-methyl) propane-2-yl) butane-1,4-diylzirconium (IV) dimethyl bis ((2-oxoyl-3- (1,2,3,4,6,7,8,9-octahydroantracen-5-dichloride (5-yl) -5- (methyl) phenyl) - (5- (2-methyl) propan-2-yl) butane-1,4-diylzirconium (IV), bis ((2-Oxoxy-3- (dibenzo-1H) pyrrol-1-yl) -5- (methyl) phenyl) - (5- (2-methyl) propan-2-yl) butan-1,4-diylzirconium (IV) dimethyl, bis ((2-oxoyl) dichloride 3- (dibenzo-1H-pi rrol-1-yl) -5- (methyl) phenyl) - (5- (2-methyl) propan-2-yl) butan-1,4-diylzirconium (IV), bis ((2-oxoyl-3- ( 1,1-dimethylethyl) phen-1-yl) -5- (methyl) phenyl) - (5- (2-methyl) propan-2-yl) butane-1,4-diylzirconium (IV) dimethyl, bis edichloride ((2-oxoyl-3- (1,1-dimethylethyl) phen-1-yl) -5- (methyl) phenyl) - (5- (2-methyl) propan-2-yl) butane-1,4-one diylzirconium (IV).