BRPI0710993A2 - metal complex, catalyst composition and addition polymerization process - Google Patents

Abstract

METALLIC COMPLEX, CATALYST COMPOSITION AND POLYMERIZATION PROCESS BY ADDITION. Hafnium complexes of heterocyclic organic imidazol-2-yl ligands containing internal orthometallization and their use as components of olefinic polymerization catalyst compositions, especially supported catalyst compositions, are disclosed.

Description

"METAL COMPLEX, CATALYST COMPOSITION AND ADDITION DEPOLYMERIZATION PROCESS".

This invention relates to certain hafnium complexes, catalyst compositions comprising the same, and addition polymerization processes, especially olefin polymerization processes, using such hafnium complexes as a component of a coordinating polymerization catalyst composition, especially a supported catalyst composition.

Advances in polymerization and catalysis have resulted in the inability to produce many new polymers with improved physical and chemical properties useful in a wide variety of superior applications and products. As development of new catalysts the choice of polymerization type (in solution, semi-fluid paste, high pressure or gas phase) to produce a particular polymer has greatly expanded. Also, advances in polymerization technology have provided more efficient, very productive and economically improved processes. Recently, several new disclosures have been published regarding metal complexes based on nometal centered heteroaryl donor ligands. These include: USP 6,103,657, USP 6,320,005, USP 6,653,417, USP 6,637,660, USP 6,906,160, USP 6,919,407, USP 6,927,256, USP 6,953,764, US-A-2002/0142912 , US-A-2004/0220050, US-A-2004/0005984, EP-A-874,005, EP-A-791,609, WO 2000/020377, WO 2001/30860, WO2001 / 46201, WO 2002/24331, WO 2002 / 038628, WO2003 / 040195, WO 2004/94487, WO 2006/20624, and WO2006 / 3,6748.

Notwithstanding the technological advances in the polyolefin industry provided by this new class of catalysts, there are common problems as well as new challenges associated with process operability. For example, it is known that Group 4 metal complexes based on donor ligands having an orthometallized binder architecture, which generally have higher catalytic properties, require elevated temperatures to form. Since typical olefin polymerization processes employing supported metal complexes operate at moderate or low reaction temperatures (generally less than 100 ° C) in order to avoid dissolution or agglomeration of polymeric departments, the formation of the preferred metallized reaction product from a metal complex precursor replaced by trihydrocarbyl, occasionally and not entirely. Alternatively, it is believed that without wishing to be bound by such belief, the formation of orthometallized metal complexes in the presence of a support, especially a desilic support, of the foregoing precursors appears to be inhibited and unlikely to occur by depositing the precursor onto the preformed support. For these or other presently unknown reasons, it has now been found that improved supported catalysts are prepared by employing the present orthometallized metal complex and placing this support on a support, with or without the additional presence of a supported cocatalyst or cocatalyst.

Thus, it would be advantageous to provide a catalyst composition for the polymerization of olefin monomers employing specific metal ligand-based donor complexes that are capable of operation at high temperatures and efficiencies and having improved production efficiencies in the presence of a support material.

In addition, it would be advantageous to provide a gas phase or semi-slurry slurry polymerization process for preparing tactical polymers, especially isotactic homopolymers and polymers comprising propylene and / or a C4-20 and optionally ethylene, which is capable of producing polymers at increased efficiency using a catalyst composition. supported.

SUMMARY OF THE INVENTION According to the present invention there is provided a hafnium complex of a heterocyclic organic binder for use as a catalyst component of an addition polymerization catalyst composition, said complex corresponding to the formula:

<formula> formula see original document page 4 </formula> where each occurrence of X is independently an anionic ligand, or two groups X together form a diionic grouping, or a neutral diene, preferably each occurrence of X is an C12-20 hydrocarbyl / trihydrocarbyl silyl or trihydrocarbyl silyl hydrocarbyl group T is a cycloaliphatic or aromatic group containing one or more rings; each occurrence of R1 is independently hydrogen, halogen, or a monovalent polyatomic anionic ligand, or two or more R1 groups thus join together to form a polyvalent fused ring system; each occurrence of R2 is independently hydrogen, halogen, or a monovalent polyatomic anionic ligand, or two or more R2 groups together forming a polyvalent fused ring system; and R 4 is hydrogen, alkyl, aryl, aralkyl, trihydrocarbylsilyl, or methyl trihydrocarbyl silyl of 1 to 20 carbons. Preferred complexes according to the invention corresponding to formula (I) are those wherein T is a bivalent polycyclic fused ring aromatic group, R 4 is alkyl of C 1-4, and each occurrence of X is C 1-20 alkyl / cycloalkyl or aralkyl.

Additionally, according to the present invention there is provided a catalyst composition comprising one or more of the foregoing hafnium complexes of formula (I), and an activating cocatalyst capable of converting the metal complex into an active catalyst supported for addition polymerization. Additional components of such catalyst composition may include a liquid solvent or diluent, a tertiary component such as a secondary activator or variant, and / or one or more additives or adjuvants such as processing aids, sequestrants, chain transfer agents, and chain exchange agents. . Especially preferred catalyst compositions include an inert support such as an organic or inorganic particulate material.

Further, the present invention provides an addition polymerization process, especially an olefin polymerization process, in which one or more addition polymerizable monomers are polymerized in the presence of the above catalyst composition, including preferred and most preferred embodiments thereof, to form a high polymer. molecular weight. Preferred polymerization processes are slurry or gas phase polymerizations, most preferably processes in which polymerization or copolymerization of ethylene, propylene, mixtures of ethylene and propylene, or mixtures of ethylene and / or propylene with one or more C4-20 diolefins or olefins are polymerized. Desirably, the processes are capable of operating at high catalyst efficiencies to prepare polymers having desirable physical properties.

Most desirably, the present invention provides a process in which one or more addition-polymerizable monomers are polymerized by addition, especially under semifluid slurry or gas phase polymerization conditions in the presence of the above catalyst composition to form a high molecular weight tactical polymer, especially a polymer that is isotactic or very isotactic, improved operational efficiency.

The metal complexes and catalysts of the invention may be used alone or in combination with other metal complexes or catalyst compositions and the polymerization process may be used in series or in common parallel or more other polymerization processes. Additional polymerization catalyst compositions suitable for use in combination with the metal complexes of the present invention include Ziegler-Natta-type transition metal polymerization catalysts as well as π-bonded transition metal compounds such as metallocene-type catalysts, or other transition metal complexes including other donor binder complexes.

The metal complexes of the invention are preferred for use as supported polymeric polymerization catalyst components, particularly for use in a gas phase polymerization process, because they have improved reaction kinetics, particularly longer reaction life, reduced heat release, and increased time. to achieve maximum temperature (TMT) activity. This combination of properties makes metal complexes ideally suited for use in supported catalyst compositions where rapid and intense heat generation can lead to fragmentation of supported catalyst particles and / or agglomeration of polymeric particles, or polymer coating over reactor surfaces. In addition, increased TMT is indicative of longer average total catalyst life leading to improved product morphology. Ideally, average catalyst life is greater than approximately the average reactor monomer residence time and shorter about 5 demonomer residence times in the catalyst. reactor. Most preferably the catalyst life is approximately 2-3 times the average monomer residence time in the reactor. This allows the polymeric particles to more accurately reproduce the catalyst particle morphology, with reduced particle agglomeration and fines generation due to particle scattering or decomposition.

In addition, complexes where X is n-alkyl, aralkyl or other hydrocarbyl silyl hydrocarbyl of 4 to 20 carbon atoms are capable of use with aliphatic hydrocarbon solvents to transport them in the reactor.

In addition, such complexes can be synthesized at extremely high impurity and consequently high activity due to the almost complete removal of metal salts, especially by-products of magnesium salts synthesis, by grinding or washing with aliphatic or cycloaliphatic hydrocarbons.

Catalyst compositions comprising the present metal complexes Olefinic polymerizations can be employed to prepare polymers and polymers for use in injection molding applications as well as for use in fiber preparation, especially by extrusion or meltblown spinning processes. In addition, the polymers are usefully employed in multi-layer and laminate adhesive formulations or pellets.

Detailed Description of the Invention

Here, all reference to the Periodic Table of Elements will refer to the Periodic Table of Elements, published and copyrighted by CRC Press, Inc., 2003. Unless otherwise stated, evident from the context, or conventional in the art, all parts and percentages are based on weight. Likewise, any reference to Group or Groups will be to the Group or groups reflected in this Periodic Table of Elements using the IUPAC system to number groups.

The term "comprising" and derivatives thereof are not intended to exclude the presence of any additional component, step or procedure, whether disclosed or not. For the avoidance of doubt, all compositions claimed herein by use of the term "comprising" may include any additive, adjuvant, or compound whether polymeric or different, unless otherwise stated. By contrast, "consisting essentially of" excludes from the scope of any subsequent recitation any other component, step or procedure, except those which are not essential to operability or novelty. The term "consisting of" excludes any component, step or procedure not related or specifically described. The term "or", unless stated otherwise, refers to the individually listed members as well as any combination.

The term "hetero" or "heteroatom" refers to a carbon-different atom, especially Si, Β, Ν, P, S, or O. "Heteroaryl", "heteroalkyl", "hetero cycloalkyl" and "heteroaralkyl" "refers to aryl, alkyl, cycloalkyl or aralkyl groups respectively, in which at least one carbon atom is substituted by a heteroatom. "Inertly substituted" refers to substituents on a binder that neither destroys the operability of the invention nor the identity of the binder. For example, an alkoxy group is not a substituted alkyl group. Preferred inert substituents are halogen, di (C 1-6 hydrocarbyl) amino, C 2-6 hydrocarbylamino, C 1-6 halocarbyl, and tri (C 1-6 hydrocarbyl) silyl. When used herein, the term "polymer" includes both homopolymers that is, polymers prepared from a single reactive component, such as copolymers, that is, polymers prepared by reacting at least two polymer-forming reactive monomeric compounds. The term "crystalline" refers to a polymer that exhibits an X-ray diffraction pattern at 25 ° C and has a first order crystalline or transition melting point (Tm) of the differential-calorimetry heating curve. The term may be used to permit exchange or substitution with the term "semicrystalline". The term "chain transfer agent" refers to a chemical that is capable of transferring a growing polymer chain to all or a portion of the agent, thus replacing the catalyst site with a catalytically inactive species. The term "chain exchange agent" means a chain transfer agent which is capable of transferring the growing polymer chain to the agent and thereafter transferring the polymeric chain back to the same or to a different active catalyst site at which the polymerization can start over. A decade exchange agent is distinguished from a decade transfer agent in that polymeric growth is disrupted but not generally terminated due to interaction with said agent.

The invention relates to previously identified novel metal complexes and catalyst compositions comprising them. The invention also relates to an olefin polymerization process, especially to a polypropylene polymerization process having improved operability and production capabilities using the present metal complexes. According to the invention, the preferred metal complexes are those according to the formula. (I) above wherein X is a C 1-20 alkyl or aralkyl group, and most preferably all X groups are the same and are C 1-12 alkyl or aralkyl groups, most preferably methyl, benzyl, n-butyl, octyl or n-dodecyl.

In accordance with the present invention, the most preferred metal complexes are imidazoldiyl derivatives corresponding to the formula: <formula> formula see original document page 10 </formula>

wherein each occurrence of R 1 is independently a C 3-12 alkyl group in which the carbon attached to the amphenyl is secondary or tertiary substituted, preferably each R 1 is isopropyl; each occurrence of independently is hydrogen or a C 1-12 alkyl group R 2, preferably at least one C 3-12 orthoethyl, ethyl or C 1-12 alkyl group wherein the carbon attached to the phenyl ring is secondary or tertiary substituted; halogen or R 1, R 4 is C 1-4 alkyl, and X and T are as defined above for the compounds of formula (I).

Even more preferred metal complexes correspond to the formula:

<formula> formula see original document page 10 </formula> <formula> formula see original document page 11 </formula>

wherein: each occurrence of R 1 is independently a C 3-12 alkyl group in which the carbon attached to the amphenyl is secondary or tertiary substituted, more preferably each R 1 is isopropyl; each occurrence of R 2 is independently hydrogen or a C 1-12 alkyl group, more preferably at least one ortho R2 group is methyl, ethyl or C 3-12 alkyl group in which the carbon ring bonded to the phenyl ring is secondary or tertiary substituted; R4 is methyl or isopropyl; R5 is hydrogen, or C1-6 alkyl, most preferably ethyl; R6 is hydrogen, C1-6 alkyl or cycloalkyl, or two adjacent R6 groups join together to form a fused aromatic ring, preferably two R6 groups together form a 5-membered ring a benzo substituent; T 'is oxygen, sulfur, or a C1-20 hydrocarbyl substituted nitrogen or phosphorus group; T 'is nitrogen or phosphorus; X is previously defined with respect to formula (I), most preferably X is methyl or benzyl.

The most preferred metal complexes are dibenzopyrol derivatives of formula (III):

<formula> formula see original document page 11 </formula> wherein each occurrence of R1 is independently isopropyl; each occurrence of R2 is independently a C1-12 alkyl group, preferably C1-4 alkyl, most preferably ethyl or isopropyl; R4 is C1-4 alkyl; R6 is hydrogen, C1-6 alkyl or cycloalkyl; and each occurrence of X is independently methyl or benzyl.

Metal complexes are prepared by applying well-known organometallic synthetic procedures. Compounds having improved methylcyclohexane solubility, especially those containing C4-20 n-alkyl ligands, are readily prepared using an aliphatic or cycloaliphatic hydrocarbon diluent to extract the metal complex after the final stage of relaxation. This assists in the recovery of very pure complexes, free from magnesium salt byproducts resulting from the Grignard alkylating agent. That is, the process may involve combining HfCl4 with a lithium derivative of the heterocyclic binder followed by alkylation using an alkylmagnesium chloride or bromide and alkylation product recovery. The resulting products may be recovered in extremely high purity using aliphatic hydrocarbons such as hexane, cyclohexane, methylcyclohexane, heptane, or mixtures thereof, to extract and recover the metal complex.

The recovered metal complexes normally form the tri-substituted metal compound, preferably a trihydrocarbyl-substituted metal compound, separated from reaction by-products. Thereafter, aortometallization involving an adjacent carbon of the "Τ" group, especially the C4 carbon of a ligandibenzopyrroyl, results in the loss of one of the three originally formed "X" ligands. Although orthometallization may occur due to room temperature, it is hastened by the use of elevated temperatures. Alternatively, the orthometallization step may be performed prior to the recovery of the metal complexes as part of the initial synthesis. Loss of a ligand X and internal bond formation are believed to be significant in achieving desirable properties, particularly improved productivity and decatalyst efficiency. The orthometallization step simultaneously generates a neutral hydrocarbon such as methane or toluene, due to the combination with an available hydrogen atom. Removal of this by-product from the reactant mixture generally results in rapid formation of the orthometalized product. If desired, anionic, diionic, and alternative neutral diene ligands may be substituted by the remaining groups using known disubstitution techniques.

Polymers of the invention which are formed from C3 or higher alpha olefins may have substantially isotactic polymeric sequences. "Substantially isotactic and thermosimilar polymeric sequences" mean that the sequences have a 13 C NMR triad (mm) of greater than 0.85, preferably greater than 0.90, more preferably greater than 0.93, and most preferably greater than 0.95. Measurement of isotactic triads by prior art is known in the art and previously disclosed in USP 5,504,172, WO 00/01745 and elsewhere.

The previously described metal complexes according to the invention are typically activated in various ways to produce catalyst compounds having a vague coordinating site which will coordinate, insert and polymerize by addition polymerizable monomers, especially olefins. For the purposes of this patent application and the appended claims, the term "activator" or "cocatalyst" is defined as any compound or component or method that can activate any of the above-described catalyst compounds of the invention. Non-limiting examples of suitable activators include Lewis acids, non-coordinating ion activators, ionizing activators, organometallic compounds, and combinations of the above substances that can convert a neutral catalyst compound into a catalytically active species.

It is believed, without wishing to be bound by such belief, that an embodiment of the invention, catalyst activation may involve formation of a cationic, partially cationic, or zuiterionic species by proton transfer, oxidation, or other appropriate reactivation process. It is understood that the present invention is operable and fully capable independently of whether or not such identifiable cationic, partially cationic, or zuiterionic species actually results during the activation process, also referred to herein as a "ionization" or "ionization process" process.

An appropriate class of organometallic cocatalysts or activators is aluminoxanes, also referred to as alkyl aluminoxanes. Aluminoxanes are Lewis acid activators well known for use with metallocene-type catalyst compounds for preparing addition polymerization catalysts. There are a variety of methods for preparing modified aluminoxanes and modified aluminoxanes, non-limiting examples of which are described in U.S. Patent Nos. 4,665,208,4,952,540, 5,091,352, 5,206,199, 5,204,419, 4,874,734,4,924,018, 4,908,463, 4,968,827, 5,308,815, 5,329,032,5,248,801, 5,235,081, 5,157,137, 5,103,031, 5,391,7793,5,391,529, 5,693,838, 5,731,253, 5,731. 451, 5,744,656; European Publications EP-A-561476, EP-A-279586 and EP-A-594218; and PCT publication WO 94/10180. Preferred aluminoxanes are tri (C3-6 alkyl) aluminum modified methyl aluminoxane, especially tri (isobutyl) aluminum modified methylaluminoxane, commercially available as MMAO-3A or tri (n-octyl) aluminum modified methylaluminoxane, commercially available as MMAO-12 , by Akzo Nobel, Inc.

It is within the scope of this invention to use aluminoxanes or modified aluminoxanes as an activator or as a tertiary component in the inventive process. That is, the compound may be used alone or in combination with other activators, neutral or ionic, such as tri (alkyl) ammonium tetrakis (pentafluorophenyl) borate compounds, tris (perfluoroaryl) compounds, polyhalogenated heteroborane anions (WO 98 / 43983), and combinations thereof. When used as a tertiary component, the amount of aluminoxane employed is generally less than that required to actively activate the metal complex when used alone. In this embodiment, it is believed, without wishing to be bound by this belief, that aluminoxane does not contribute significantly to actual decatalyst activation. Not resisting the above, it is understood that some participation of aluminoxane in the activation process is not necessarily excluded.

Ionizing cocatalysts may contain a protonative, or some other cation associated with, but uncoordinated to or only poorly coordinated to, an ionizing compound anion. Such compounds are described in European publications EP-A-570982, EP-A-520732, EP-A-495375, EP-A-500944, EP-A-277003 and EP-A-277004 and US Pat. Nos. 5,153. 157, 5,198,401, 5,066,741.5,206,197, 5,241,025, 5,384,299 and 5,502,124. Among the above preferred activators are the ammonium-containing salts, especially those containing trihydrocarbyl-substituted cationsammonium containing one or two C10-40 alkyl groups / especially methylbis (octadecyl) ammonium and methyl bis (tetradecyl) ammonium and an uncoordinating anion, especially an anionetrachion (). perfluoro) aryl borate, especially tetrakis (pentafluorophenyl) borate. It is further understood that the oction may comprise a mixture of hydrocarbyl groups of different lengths. For example, commercially obtainable long chain amine-derived protonated ammonium ocation comprising a mixture of C1 -C16 or C1-8 alkyl groups and a methyl group. Such amines are available from Chemtura Corp., under the trade name ΚΕΜΑΜΙΝΕ ™ T9701, and from Akzo Nobelsob a. trade name ARMEEN ™ M2HT. A most preferred desal ammonium activator is methyl (C14-20 alkyl) ammonium tetrakis (pentafluorophenyl) borate.

Activation methods using ionizing compounds not containing an active proton but capable of deforming active catalyst compositions such as ferrocene salts of the above non-coordinating anions are also considered for use herein, and are described EP-A-426637, EP-A-573403 and patent No. 5,387,568. A class of cocatalysts comprising non-coordinating anions generically referred to as pending anions, further disclosed in US Patent No. 6,395,671, may suitably be employed to activate metal complexes of the present invention for olefin polymerization. Generally, these cocatalysts (illustrated by those having anionsimidazolide, substituted imidazolide, imidazolinide, substituted imidazolinide, benzimidazolide, or substituted benzimidazolide) can be represented as follows:

<formula> formula see original document page 16 </formula>

wherein: A is a cation, a cation preferably is a proton-containing cation, and preferably and a cationtrihydrocarbyl ammonium containing one or two C10-40 alkyl groups / especially a methyl di (C14-20 alkyl) ammonium cation / each occurrence of R4 is independently hydrogen or a halogen group, hydrocarbyl, halocarbyl, halohydrocarbyl, silyl hydrocarbyl, ousilyl, (including mono, di and trihydrocarbyl silyl) deaté 30 atoms not containing hydrogen, preferably C1-20 / alkyl and J * 'is tris (pentaf luorophenyl) borane other (pentafluorophenyl) human.

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

bis (tris (pentafluorophenyl) borane) imidazolide, bis (tris (pentafluorophenyl) borane) -2-undecyl imidazolide, bis (tris (pentafluorophenyl) borane) -2-heptadecyl imidazolide, bis (tris (pentafluorophenyl) -4-borane) , 5-bis (undecyl) imidazolide, bis (tris (pentafluorophenyl) borane) -4,5-bis (heptadecyl) imidazolide,

bis (tris (pentafluorophenyl) borane) imidazolinide, bis (tris (pentafluorophenyl) borane) -2-undecyl imidazolinide, bis (tris (pentafluorophenyl) borane) -2-heptadecyl imidazolinide, bis (tris (pentafluorophenyl) -4 , 5-bis (undecyl) imidazolinide, bis (tris (pentafluorophenyl) borane) -4,5-bis (heptadecyl) imidazolinide, bis (tris (pentafluorophenyl) borane) -5,6-dimethyl benzimidazolide, bis (tris (pentafluorophenyl) borane) -5,6-bis (undecyl) benzimidazolide, bis (tris (pentafluorophenyl) alumino) imidazolide, bis (tris (pentafluorophenyl) alumano) -2-undecyl imidazolide, bis (tris (pentafluorophenyl) human) -2-heptadecyl -imidazolide, bis (tris (pentafluorophenyl) aluman) -4,5-bis (undecyl) imidazolide, bis (tris (pentafluorophenyl) aluman) -4,5-bis (heptadecyl) imidazolide,

bis (tris (pentafluorophenyl) alumano) imidazolinide, bis (tris (pentafluorophenyl) aluman) -2-undecyl imidazolinide, bis (tris (pentafluorophenyl) aluman) -2-heptadecyl imidazolinide, bis (tris (pentafluorophen) -4 , 5-bis (undecyl) imidazolinide, bis (tris (pentafluorophenyl) aluman) -4,5-bis (heptadecyl) imidazolinide, bis (tris (pentafluorophenyl) aluman) -5,6-dimethyl benzimidazolide, and bis (tris (pentafluorophenyl) ) human) -5,6-bis (undecyl) benzimidazolide.

Other activators include those described in PCT publication WO 98/07515 such as tris (2,2 ', 2' -nonafluorobiphenyl) fluoroaluminate. Combinations of activators may also be considered by the invention, for example aluminoxanes and ionizing activators in combinations, see for example EP -A-0573120, PCT Publications WO 94/07928 and WO 95/14044 and US Patent Nos. 5,153,157 and 5,453,410, AWO 98/09996 describes activating catalyst compounds with perchlorates, periodates and iodates, including their hydrates. 18135 describes the use of boron aluminum boron activators EP-A-781299 describes the use of a silyl salt in combination with a non-coordinating compatible anion Other activators or methods for activating a catalyst compound are described, for example, in US Pat. 5,849,852, 5,859,653, and 5,869,723, in EP-A-615981, and PCT publication WO 98/32775.

It is also within the limits of this invention that the metal complexes described above may be combined with more than one of the activators or activation methods described above. The molar ratio of the reactive component to the metal complex in the catalyst compositions of the invention is suitably in the range 0.3: 1 to 2000: 1, preferably from 1: 1 to 800: 1, most preferably from 1: 1 to 500: 1. Where the activator is an ionizing activator such as those based on the anion-based tetrakis (pentafluorophenyl) boron outris (pentafluorophenyl) strong Lewis acid boron, metal molar azazole or activating component metalloid for the metal complex will preferably be in the range 0.3: 1 to 3. :1.

Tertiary Components

In addition to the metal complex and the catalyst or activator, it is contemplated that certain ester components or mixtures thereof may be added to the catalyst composition or reagent mixture in order to obtain improved or other beneficial catalyst performance. Examples of such tertiary components include sweepers designed to react with contaminants in the reagent mixture to prevent catalyst adhesion. Appropriate tertiary components may also activate or assist in the activation of one or more of the metal complexes employed in the catalyst composition or act as chain transfer agents.

Examples include Lewis acids, such as detrialkyl aluminum compounds, dialkyl zinc compounds, dialkyl aluminum alkoxides, dialkyl aluminum aryloxides, N, N-dialkylammonium dialkylamides, N, N (N-dialkyl silyl) aluminum, N, N-di (trialkylsilyl) dialkyl aluminum amides, alkyl aluminum dialkoxides, alkyl aluminum di (N, N-dialkyl amides), N, N-dialkyl amides detri (alkyl) silyl aluminum, N, N-di (trialkyl) silyl) alkyl aluminum amides, alkyl aluminum diaryloxides, μ-bridged alkyl aluminum bis (amides) such as bis (ethyl aluminum) -1-phenylene-2- (phenyl) starch μ-bis (diphenylamide), and / or aluminoxanes ; as well as Lewis bases such as organic compounds of ether, polyether, amine, and polyamine. Many of the foregoing compounds and their use in polymerizations are disclosed in U.S. Patent Nos. 5,712,352 and 5,763,543, and WO 96/08520. Preferred examples of the above tertiary components include trialkyl aluminum compounds, dialkyl aluminum aryloxides, alkyl aluminum diaryloxides, alkyl aluminum diamide oxides, alkyl aluminum diamides, dialkyl aluminum tri (hydrocarbyl silyl) amides, alkyl aluminum bis (tri (hydrocarbyl silyl) amides) , aluminoxanes, and modified aluminoxanes. Most preferred are tertiary compounds: aluminoxanes, modified aluminoxanes or compounds corresponding to the formula Re2Al (ORf) or Re2Al (NRg2) wherein Re is C1-4 alkyl; at each occurrence Rf is independently C6-2 aryl, preferably phenyl or 2,6-di-tertiary butyl-4-methylphenyl, and R9 is C1-4 alkyl or tri (C1-4 alkyl) silyl, preferably trimethylsilyl. Most preferred tertiary components include methyl aluminoxane, tri (isobutyl aluminum) modified methyl aluminoxane, di (n-octyl) aluminum 2,6-di-tertiary butyl-4-methylphenoxide, and di (2) N, N-bis (trimethylsilyl) amide -methyl propyl) aluminum.

Another example of a suitable tertiary component is a metal hydroxycarboxylate salt, which means any hydroxy-substituted mono, di or tricarboxylic acid salt in which the metal portion is a cationic derivative derived from a metal of Groups 1-13 of the Periodic Table of Elements. This compound can be used to improve polymer morphology especially in a gas phase polymerization. Non-limiting examples include salts of saturated, saturated, unsaturated, aliphatic, aromatic or saturated cyclic carboxylic acids where the ligandecarboxylate has from one to three hydroxy substituents and from 1 to 24 carbon atoms. Examples include: hydroxyacetate, hydroxy propionate, hydroxy butyrate, hydroxyvalerate, hydroxy pivalate, hydroxy caproate, hydroxycaprylate, hydroxy heptanate, hydroxy pelargonate, hydroxy undecanoate, hydroxy oleate, hydroxy paltoate, hydroxy myristate, hydroxyareate, hydroxy margarate and hydroxytercosanoate. Non-limiting examples of the metal portion include a metal selected from the group consisting of Al, Mg, Ca, Sr, Sn, Ti, V, Ba, Zn, Cd, Hg, Mn, Fe, Co, Ni, Pd, Li and Na. Preferred metal salts are dezinco salts.

In one embodiment, the hydroxy carboxylate metal salt is represented by the following general formula:

M (Q) x (OOCR) y

where M is a metal from Groups 1 to 16 and from the lanthanides and actinides series, preferably from Groups 1 to 7 and 12 to 16, more preferably from Groups 3 to 7 and 12 to 14, most preferably from Group 12, most preferably Zn. ; Q is hydrogen, hydroxide, or an alkyl, alkoxy, siloxy, silane, sulfonate or siloxane group of up to 20 atoms not containing hydrogen; R is a hydrocarbyl radical having from 1 to 50 carbon atoms, preferably from 1 to 20 carbon atoms, and optionally substituted by one or more hydroxy, alkoxy, N, N-dihydrocarbilamino, or halogen groups, provided that in one instance R is substituted with a hydroxy group or N, N-dihydrocarbilamino, preferably a hydroxy group which is coordinated to the metal M by non-shared electrons thereof; χ is an integer from 0 to 3; y is an integer from 1 to 4. In a preferred embodiment, M is Zn, χ is 0 and y is 2.

Preferred examples of the hydroxycarboxylate metal salts include compounds of the formulas:

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

wherein each occurrence of Raindependently, hydrogen, halogen, or C1-6 alkyl.

Other additives may be incorporated into the catalyst compositions or employed simultaneously in the polymerization reaction for one or more advantageous purposes. Examples of additives which are known in the art include metal salts of fatty acids such as mono, di, and tri stearates, octoates, oleates and cyclohexyl butyrates. aluminum, zinc, calcium, titanium or magnesium. Examples of such additives include # 18 aluminum stearate, # 22 aluminum stearate, # 132 aluminum stearate, and food grade aluminum stearate, all of which are obtainable from Chemtura Corp. The use of such additives in a catalyst composition is disclosed in U.S. Patent No. 6,306,984.

Suitable additional additives include antistatic agents such as fatty amines, for example AS 990 ethoxylated stearyl amine, AS990 / 2 zinc additive, zinc ethoxylated stearyl amine mixture, or AS 990/3, ethoxylated stearylamine, stearate mixture of zinc and octadecyl-3,5-di-tertiary butyl 4-hydroxyhydrocinnamate, also obtainable from Chemtura Corp.

The catalyst compounds and catalyst compositions described above may be combined with one or more carrier materials or carriers using one of the carrier methods well known in the art or described below. The supported catalysts are particularly useful in semifluid paste or fasegasosa polymerizations. Either the catalyst composition or the individual components thereof may be in a supported form, for example deposited on, contacted with or incorporated into a carrier or carrier.

The terms "carrier" and "carrier" are used to permit exchange or replacement and are any porous or nonporous carrier materials, preferably a porous carrier material, for example, inorganic oxides, carbides, nitrides, and halides. Other carriers include resinous support materials such as polystyrene, crosslinked or functionalized organic supports such as polymeric compounds or polystyrene / divinyl benzene polyolefins, or any other organic or inorganic support material, or mixtures thereof. Porous materials are preferred because of their larger pore-attributable surface areas.

Preferred carriers are inorganic oxides which include those Group 2, 3, 4, 5, 13or 14 metal oxides. Preferred supports include silica, alumina, silica / alumina, silicon carbide, boron nitride, and mixtures thereof. Other useful supports include magnesia, titania, zirconia, and clays. Also, combinations of these support materials may be used, for example silica / chromium and silica / titania.

It is preferred that the carrier has a surface area in the range of 10 to 700 m2 / g, pore volume in the range of 0.1 to 4.0 cm3 / g and average particle size in the range of 10 to 500 μιτι. More preferably, the carrier surface area is in the range of 50 to 500 m 2 / g, pore volume of 0.5 to 3.5 cm 3 / g and average particle size of 20 to 200 μτη. Most preferably, the surface area of the carrier is in the range of 100 to 400 m2 / g, pore volume of 0.8 to 3.0 cm3 / g and the average particle size of 20 to 10 μπι. The pore size of a carrier of the invention is typically in the range 1 to 100 nm, preferably 5 to 50 nm, and most preferably from 7.5 to 35 nm.

Examples of supported catalyst compositions suitably employed in the present invention are described in U.S. Patent Nos. 4,701,432, 4,808,561,4,912,075, 4,925,821, 4,937,217, 5,008,228, 5,238,892,5,240,894, 5,332. 706, 5,346,925, 5,422,325, 5,466,649,5,466,766, 5,468,702, 5,529,965, 5,554,704, 5,629.253,5,639,835, 5,625,015, 5,643,847, 5,665,665, 5,698,487,5,714,424, 5,723,400, 5,723,402, 5,731,261, 5,759,940,5,767,032 and 5,770,664; and in PCT publications WO 95/32995, WO 95/14044, WO 96/06187 and WO 97/02297.

Examples of techniques for supporting catalyst compositions of conventional types which may also be employed in the present invention are described in U.S. Patent Nos. 4,894,424, 4,376,062, 4,395,359,4,379,759, 4,405,495, 4,540,758 and 5,096 .869. It is contemplated that the catalyst compounds of the invention may be deposited on the same support together with an activator, or that the activator may be used in an unsupported form, or deposited on a support different from the supported catalyst compounds of the invention, or any combination thereof.

There are several other methods in the art for supporting a catalyst compound or polymerization catalyst compositions suitable for use in the present invention.

For example, the catalyst compound of the invention may contain a polymer-bound binder as described in USP 5,473,202 and USP 5,770,755. The supports used with the catalyst assembly of the invention may be functionalized as described in European publication EP-A-802203. At least one substituent or catalyst leaving group may be selected as described in USP 5,688,880. The supported catalyst composition may include a surface modifier as described in WO 96/11960.

A preferred method for producing a supported catalyst composition according to the invention in PCT publications WO 96/00245 and WO 96/00243 is described. In this preferred method, the catalyst compound and activators are combined in separate liquids. The liquids may be any compatible or other liquid solvent capable of forming a semifluid solution or paste with the catalyst and / or activator compounds. In the most preferred embodiment, the liquids are the same or aliphatic cyclic aromatic or aliphatic hydrocarbon, most preferably hexane or toluene. Mixtures or solutions of catalyst and activator compound are mixed together and optionally added to a porous support or alternatively the porous support is added to the respective mixtures. If desired, the resulting supported composition may be dried to remove diluent, or used separately or combined in a polymerization. Most desirably the total volume of the catalyst compound solution and activator solution or mixtures thereof is less than five times the pore size of the pore support, more preferably less than four times, even more preferably less than three times; with very preferred ranges being from 1.1 times to 3.5 times the pore volume of the support. The catalyst composition of the present invention may also be spray dried using techniques described in USP 5,648,310 to produce a particulate porous solid, optionally containing surfactants. structural reinforcement such as certain silica or alumina compounds, especially vaporized silica. In these compositions silica acts as a thixotropic agent for sizing and droplet formation as well as a reinforcing agent in the spray dried particles.

Procedures for measuring the total pore volume of a porous material are well known in the art. The preferred procedure is nitrogen absorption by BET. Another suitable method well known in the art is described in Innes, Total Porosity and Particle Density of Fluid Catalysts by Liquid Titration, Analytical Chemistry, (1956) 28 , 332-334.

The invention further considers that other catalysts may be combined with the inventive catalyst compounds. Examples of such other catalysts are disclosed in U.S. Patent Nos. 4,937,299, 4,935,474,5,281,679, 5,359,015, 5,470,811, 5,719,241, 4,159,965,4,325,837, 4,701,432, 5,124. 418, 5,077,255, 5,183,867,5,391,660, 5,395,810, 5,691,264, 5,723,399 and 5,767,031; in PCT publication WO 96/23010. In particular, compounds which may be combined with the metal complexes of the invention to produce polymer mixtures in an embodiment of the invention include conventional Ziegler-Natta transition metal compounds as well as coordination complexes, including transition metal complexes.

Conventional Ziegler-Nattad transition metal compounds include the well known magnesium dichloride supported compounds, devanadium compounds, and chromium catalysts (also known as "Phillips type catalysts"). Examples of descalers are discussed in U.S. Patent Nos. 4,115,639, 4,077,904, 4,482,687, 4,564,605, 4,721,7633,4,879,359 and 4,960,741. Suitable transition metal complexes that may be used in the present invention include Groups 3 to 8 transition metal compounds, preferably Group 4 of the Periodic Table of Elements containing inert linking groups capable of reactivation by contact with a cocatalyst.

Suitable Ziegler-Natta catalyst compounds include alkoxy, phenoxy, bromide, effluoride chloride derivatives of the above metals, especially titanium. Preferred titanium compounds include TiCl4, TiBr4, Ti (OC2H5) 3Cl, Ti (OC2H5) Cl3, Ti (OC4H9) 3Cl, Ti (OC3H7) 2Cl2, Ti (OC2H5) 2Br2, TiCl3 * 1/3 Al Cl3 and Ti (OC12H25) ) Cl 3, and mixtures thereof, preferably supported on an inert support, usually MgCl 2. Other examples are described in U.S. Patent Nos. 4,302,565, 4,302,566, and 6,124,507, for example.

Non-limiting examples of such catalyst compounds include vanadyl trihalide, alkoxy alkoxide halides such as VOCl3, VOCl2 (OBu) where Bu is butyl and VO (OC2H5) 3; vanadium tetrahalide and vanadium 25 alkoxy halides such as VCl4 and VCl3 (OBu); vanadium acetylvanadyl acetonates and chloroacetyl acetonates such as V (AcAc) 3 and VOCI 2 (AcAc) where (AcAc) is a deacetyl acetonate.

Chromium catalyst compounds of conventional types suitable for use in the present invention include CrO 3, chromocene, silyl chromate, chromyl chloride (CrO 2 Cl 2), chromium 2-ethyl hexanoate, and chromium acetonate (Cr (AcAc) 3). Non-limiting examples are disclosed in U.S. Patent Nos. 2,285,721, 3,242,099 and 3,231,550.

Still other conventional metal-transferring catalyst compounds are disclosed in U.S. Patent Nos. 4,124,532, 4,302,565, 4,302,566 and 5,763,723 and EP-A-4168145 and EP-A-420436.

Co-catalyst compounds for use with the above conventional type compost catalysts are typically organometallic metal derivatives of Groups 1, 2, 12 or 13. Non-limiting examples include methyl lithium, butyl lithium, dihexyl mercury, butyl magnesium, diethyl cadmium, benzyl potassium, diethyl zinc, tri-n-butyl aluminum, diisobutyl ethyl boron, di-n-butyl zinc, and tri-n-amyl boron, and in particular trialkyl aluminum compounds such as trihexyl aluminum, triethyl aluminum, trimethyl aluminum, and triisobutyl aluminum. Other suitable cocatalyst compounds include Group 13 organic monohalides and metal hydrides, Group 13 organic emo- or dihalides, and Group 13 metal hydrides. Nonlimiting examples of such conventional cocatalyst compounds include isobutylaluminum bromide, isobutyl dichloride. boron, methylmagnesium chloride, ethyl beryllium chloride, ethyl calcium calcium bromide, diisobutyl aluminum hydride, methyl cadmium hydride, diethyl boron hydride, dipropyl boron hydride, magnesium octyl hydride, butyl zinc hydride, hydride of dichloro boron, dibromo aluminum hydride and cadmium bromine hydride. Organometallic catalyst compounds of conventional types are known to those skilled in the art and a more complete discussion of these compounds can be found in U.S. Patent Nos. 3,221,002 and 5,093,415. Appropriate transition metal coordination complexes include metallocene catalyst compounds, which are semi or semi-compound. fully intercalated having one or more π-bonded ligands including cyclopentadienyl-like or other similarly functioning structures such as pentadiene, cyclo-octatetraendiyl and imides. Typical compounds are generally described as coordination complexes containing one or more ligands capable of π bonding with a transition metal atom, usually portions or ligands derived from cyclopentadienyl, in combination with a transition metal selected from Groups 3 to 8, preferably 4, 5 or 5. 6 or the eactinidae series of lanthanides. Periodic Table of the Elements. Examples of tipometalocene catalyst compounds are described in U.S. Patent Nos. 4. 530 914.4. 871. 705.4. 937,299.5. 017. 714, 5,055,438.5. 096, 867, 5.120. 867.5. 124,418.5. 198,401, 5. 210,352, 5,229. , 478, 5,264,405,5,278,264, 5,278. 119, 5,304. 614, 5,324. , 800, 5347. 025.5 .350. 723.5384.299.5. 391,790, 5,391. , 789, 5,399. 636.5.408. 017, 5,491,207, 5. 455,366, 5,534. , 473, 5,539,124.5. 554. 775.5. 621. 126.5. 684,098, 5,693. , 730.5. 698,634.5. 710,297.5. 712,354.5. 714,555, 5,728. , 641.5. 728. 839.5. 753. 577.5. 767. 209, 5,770,753 and 5,770. 664; European publications: EP-A-0591756, EP-A-0520732, EP-A-0420436, EP-A-0485822, EP-A-0485823, EP-A-0743324, EP-A-0518092; PCT publications WO 91/04257, WO 92/00333, WO 93/08221, WO93 / 08199, WO 94/01471, WO 96/20233, WO 97/15582, WO20 97/19959, WO 97/46567, WO 98/01455 , WO 98/06759 and WO98 / 01144.

Preferred examples of metallocenes used in combination with the metal complexes of the present invention include compounds of the formulas:

<formula> formula see original document page 28 </formula>

wherein: M is titanium, zirconium or hafnium, preferably zirconium or hafnium, in the formal oxidation state +2 or +4; each occurrence of R3 is independently selected from the group consisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halogen and combinations thereof, said R3 having up to 20 non-hydrogen atoms, or adjacent R3 groups together form a bivalent derivative (i.e. a hydrocarbadiyl, siladiyl or germadiyl group) thereby forming a fused ring system; each occurrence of X "is independently an anionic ligand group of up to 40 non-hydrogen atoms, or two X groups" together form an anionic ligand group of up to 40 non-hydrogen atoms or together are a conjugated diene having from 4 to 30 non-hydrogen atoms. hydrogen forming a complex π with M, where M is in the formal oxidation state +2; each occurrence of R * is independently C1-4 alkyl or phenyl; each occurrence of E is independently carbon or silicon; and χ is an integer from 1 to 8.

Additional examples of coordination complexes used in combination with the metal complexes of the present invention are those of the formula:

<formula> formula see original document page 29 </formula>

where: M is titanium, zirconium or hafnium in the formal oxidation state +2, +3 or +4; each occurrence of R3 is independently selected from the group consisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halogen and combinations thereof, said R3 having up to 20 non-hydrogen atoms, or adjacent R3 groups together form a bivalent derivative (i.e. a hydrocarbadiyl, siladiyl or germadiyl group) thereby forming a fused ring system; each X "is a halogen, hydrocarbyl, hydrocarbyloxy, hydrocarbylamino, orsilyl group, said group having up to 20 non-hydrogen atoms, or two X groups" together forming a C5-30 dienoconjugate or a divalent derivative thereof; Y is -O-, -S-, -NR * -, -PR * -; Z is SIR * 2, CR * 2, SiR * 2SIR * 2, CR * 2CR * 2, CR * = CR *, CR * 2SIR * 2, or GeR * 2, where R * is previously defined; and η is an integer from 1 to 3. The foregoing types of coordination complexes are described, for example, in U.S. Patent Nos. 5,703,187,5,965,756, 6,150,297, 5,064,802, 5,145,819, 5,149 819,5,243,001, 5,239,022, 5,276,208, 5,296,434, 5,321,106.5,329,031, 5,304,614, 5,677,401, and 5,723,398; PCT publications WO 93/08221, WO 93/08199, WO 95/07140, WO98 / 11144, WO 02/02577, WO 02/38628; and in European publications EP-A-578838, EP-A-638595, EP-A-513380 and EP-A-816372.

Additional suitable metal coordination complexes used in combination with the metal complexes of the present invention are substituted or unsubstituted π-bond transition metal complexes, one or more heteroalkyl moieties, such as those described in US Patent Nos. 5,527,752 and 5,747,406, eEP-A-73 5,057. Preferably, these compostcatalysts are represented by one of the following

formulas:

<formula> formula see original document page 30 </formula>

or wherein M 'is a metal of the Periodic Groups 4, 5 or 6 of the Elements, preferably zirconium or hafnium, most preferably zirconium or hafnium; L 'is an unsubstituted substituted π-linked substituted ligand to M' and, when T is present, attached to T, L 'will preferably be a cycloalkadienyl ligand, optionally with one or more hydrocarbyl substituents having from 1 to 20 carbon atoms, or derivatives thereof. a fused ring thereof, for example, a cyclopentadienyl, indenyl or fluorenyl binder; each Q 'is independently selected from the group consisting of -O-, -NR'-, -CR'2- and -S-, preferably oxygen; Y7 is either C or S, preferably carbon; Z7 is selected from the group consisting of -OR ', -NR'2, -CR73, -SR7-, -SiR73, -PR72, -H, and aryl groups substituted or unsubstituted, provided that when Q7 is -NR7 - then Z7 will be selected from the group consisting of: -OR7-, -NR72, -SR7-, -SiR73, -PR72, and -H, preferably Z7 will be selected from the group consisting of -OR7-, -CR73 and -NR72; n7 is 1 or 2, preferably 1; A7 will be a monovalent anionic group when n7 is 2 or A7 will be a bivalent anionic group when n7 is 1, preferably A7 is carbamate, hydroxycarboxylate, or another heteroalkyl moiety described by the combination of Q7, Y7 and Z7 ; each R7 is independently a group containing carbon, silicon, nitrogen, oxygen, and / or phosphorus and one or more groups R7 may also be attached to the substituent L7, preferably R7 is a hydrocarbon group containing from 1 to 20 carbon atoms, most preferably a group. alkyl, cycloalkyl, or aryl; T is a bridging group selected from the group consisting of alkylene or arylene groups containing from 1 to 10 carbon atoms optionally substituted with carbon or heteroatom, germanium, silicon and alkyl phosphine; and m is from 2 to 7, preferably from 2 to 6, most preferably 2 or 3.

In the above formulas, the support substituent formed by Q7, Y7 and Z7 is an unloaded polyidentate binder exerting electronic effects due to its high bias capability, similar to the doliclant cyclopentadienyl. In the most preferred embodiments of this invention, disubstituted carbamates and hydroxycarboxylates are employed. Non-limiting examples of these catalyst compounds include indenyl zirconium tris (diethyl carbamate), indenyl zirconium tris (trimethylacetate), tris (trimethyl acetate) demethyl cyclopentadienyl zirconium, deindenyl zirconium tris (p-toluate), deis (benzoate) tris (1-methyl indenyl) zirconium trimethyl acetate, (2-methyl indenyl) zirconium tris (diethyl carbamate), tetrahydroindenyl zirconium tris (trimethyl acetate), (methyl cyclopentadienyl) zirconium etris (benzoate). Preferred examples are indenylzirconium tris (diethyl carbamate), indenyl zirconium tris (trimethyl acetate), (methyl cyclopentadienyl) zirconium etris (trimethyl acetate).

In another embodiment of the invention additional compost catalysts are those nitrogen-containing heterocyclic delignant complexes based on bidentate linkers containing equinoline pyridine moieties, such as those described in WO 96/33202, WO99 / 01481, WO 98/42664 and US Patent No. 5,637. 660.

In one embodiment, it is within the scope of this invention that complexes of Ni2 + and Pd2 + catalyst compounds described in the articles by Johnson et al., "New Pd (II) - and Ni (II) - Based Catalysts for Polymerization of Ethylene and α-Olefins" , JACS (1995) 117, 6414-6415 and Johnson et al., "Copolymerization of Ethylene and Propylene with Functionalised Vinyl Monomers by Palladium (II) Catalysts" J.A.C.S. (1996) 118, 267-268 and WO96 / 23010 may be combined with the present metal complexes for use in the process of the invention. These complexes may be either dialkyl ether adducts, or alkylated reaction products of the described dihalide complexes which may be activated to a cationic state by conventional type co-catalysts or by the activators of this invention described below.

Additional suitable catalyst compounds for use in prior mixtures of diimine-based binder catalyst compositions containing Group 8-10 metal compounds disclosed in PCTWO 96/23010 and WO 97/48735 and Gibson, et al., Chem.Comm., (1998 ) 849-850.

Other catalysts are those Group 5 and 6 oxide demetal complexes described in EP-A-0816384 and U.S. Patent No. 5,851,945. In addition, catalysts include bridged group 4 bis (aryl starch) compounds described by D. H. McConville, et al. , Organometallics (1995) 14, 5478-5480. Other catalysts are described as bis (hydroxyaromatic nitrogen ligands) in U.S. Patent No. 5,852,146. Other metallocene catalysts containing one or more Group 15 atoms include those described in WO98 / 46651. Still other metallocene type catalysts include those multinuclear catalysts described in WO 99/20665.

In some embodiments, it is contemplated that the catalyst compounds employed in addition to those of the invention described above may be substituted asymmetrically in terms of additional substituents or substituent types, and / or unbalanced in terms of additional substituent numbers on the ligand-bonding groupsπ. It is also contemplated that such additional catalysts may include their structural or optical or enantiomeric isomers (meso and racemic isomers) and mixtures thereof, or they may be bridged / or bridged catalyst compounds.

In one embodiment of the invention, one or more olefins, preferably one or more C2-30 olefins, preferably ethylene and / or propylene are prepolymerized in the presence of the main polymerization catalyst composition. Prepolymerization may be carried out by batch or continuously in a flask, solution or semi-fluid paste including at high pressures. Prepolymerization may occur with any olefin monomer or combination and / or in the presence of any molecular weight controlling agent such as hydrogen. For examples of prepolymerization procedures see US Patent Nos. 4,748,221,4,789,359, 4,923,833, 4,921,825, 5,283,278 and 5,705,578, European Publication EP-A-279863, and PCT Publication WO97 / 44371. For the purposes of this patent application and the appended claims, the prepolymerized catalyst composition is preferably a supported catalyst system.

Generally, the method for preparing the catalyst composition involves combining, contacting, mixing and / or stirring the respective catalyst components, optionally in the presence of the polymerized monomer or monomers. Ideally, contact is performed under inert conditions or under polymerization conditions at a temperature in the range of 0 to 200 ° C, more preferably 15 to 190 ° C, and preferably at pressures from ambient (600 kPa) to 7 MPa (1000 psig). Desirably, contact is performed in an inert gaseous atmosphere such as nitrogen, however, it is also considered that the combination can be performed in the presence of olefin (s), solvents, and hydrogen.

The mixing equipment and techniques considered for use in the method of the invention are well known. Mixing techniques may involve any mechanical demixing means, for example vibration, shaking, drumming, and lamination. Another technique considered involves the use of fluidization, for example in a fluid bed reactor where circulating gases provide mixing.

For supported catalyst compositions, the catalyst composition is substantially dried and / or free flowing. In a preferred embodiment, the various components are contacted in a rotary mixer, double blender, or in a leitofluidized mixing process in a nitrogen atmosphere, and subsequently any liquid diluent is removed. employing the catalyst compositions include solution, gas phase, semifluid paste phase, high pressure, or combinations thereof. Particularly preferred is a solution in semifluid paste solution of one or more olefins at least one of which is ethylene, 4-methyl-1-pentene, or propylene. The invention is particularly well suited for processes in which propylene, propylene, 1-butene are homopolymerized. , or 4-methyl-1-pentene, polymerize ethylene and propylene, or copolymerize ethylene, propylene, or a mixture thereof with one or more monomers selected from the group consisting of 1-octene, 4-methyl-1-pentene, butadiene, norbornene , noridene ethylidene, 1,4-hexadiene, 1,5-hexadiene, norbornadiene, and 1-butene. The homopolymers of 1-butene and 4-methyl-1-pentene and copolymers thereof, especially with ethylene or propylene are desirably very isotactic.

Other monomers useful in the process of the invention include ethylenically unsaturated monomers, diolefins having from 4 to 18 carbon atoms, conjugated or unconjugated dienes, polyenes, vinyl monomers and olefinscyclics. Non-limiting monomers useful in the invention include norbornene, isobutylene, vinyl benzocyclobutane, styrene, alkyl substituted styrene, ethylidenonorbornene, isoprene, 1-pentene, di-cyclopentadiene and cyclopentene.

Typically, in a gas phase polymerization process a continuous cycle is employed where in a part of the cycle of a reactor system, a cycling gas stream, also known as a recycle or meiofluidizing stream, is heated in the reactor by the heat of polymerization. This heat is removed from the recycle composition in another part of the cycle by a cooling system external to the reactor. Generally, in a fluidized bed process for producing polymers, a stream containing one or more monomers is continuously directed through a fluidized bed in the presence of a catalyst under reactive conditions. The gas stream is withdrawn from the fluidized bed and recycled back to the reactor. Simultaneously, the reactor polymer product is removed and new monomer is added to replace the polymerized omomer. Examples of such processes are disclosed in U.S. Patent Nos. 4,543,399, 4,588,790,5,028,670, 5,317,036, 5,352,749, 5,405,922, 5,436,304,5,453,471, 5,462,999, 5,616. 661 and 5,668,228.

The reactor pressure in a gas phase process could range from 700 kPa (100 psig) to 3500 kPa (500 psig), preferably in the range of 1400 kPa (200 psig) to 2800kPa (400 psig), more preferably in the range of 1700 kPa ( 250 psig) to 2400 kPa (350 psig). In the phasing process, the reactor temperature may range from 30 to 120 ° C, preferably from 60 to 115 ° C, more preferably from 70 to 110 ° C, and most preferably from 70 to 95 ° C.

In general, a slurry polymerization process uses pressures in the range 100 kPa to 5 MPa, and temperatures in the range 0 to 120 ° C. In a semi-fluid pasted polymerization, a solid particulate polymer suspension is formed in a liquid polymerization diluent to which monomers and often hydrogen are added together with catalyst. The diluent is intermittently or continuously removed from the reactor where volatile components separate from the polymer and are recycled to the reactor. The liquid diluent employed should remain a liquid under polymerization conditions and be relatively inert. Preferred diluents are aliphatic or cycloaliphatic hydrocarbons, preferably employed are propane, n-butane, isobutane, pentane, isopentane, hexane, cyclohexane, or one or the same. For use herein, examples of semi-fluid paste polymerization processes are disclosed in U.S. Patent Nos. 3,248,179 and 4,613,484.

Examples of solution processes which are suitably employed with the catalyst compositions of the present invention are described in U.S. Patent Nos. 4,271,060, 5,001,205, 5,236,998 and 5,589,555. Most preferably, the solution process is an ethylene polymerization or a continuously operated or continuously continuous ethylene / propylene copolymerization with high ethylene conversion, preferably greater than 90 percent, more preferably ethylene conversion greater than 92 percent. Typical temperatures for solution polymerizations are 70 to 200 ° C, more preferably 100 to 150 ° C.

Irrespective of the process conditions employed (gas phase, slurry or solution) in order to achieve the benefits of the present invention, the present polymerization is desirably carried out at a temperature greater than or equal to 100 ° C, more preferably greater than or equal to 100 ° C, and most preferably. greater than or equal to 115 ° C.

Polymer Properties

The polymers produced by the process of the invention may be used in a wide variety of end use products and applications. The process-produced polymers of the invention include high density polyethylenes, low density polyethylene, linear low density polyethylene, ethylene / α-olefin copolymers, polypropylene, ethylene / propylene copolymers, ethylene / propylene / diene etherolymers. Particularly preferred polymers are interpolymers of

propylene / ethylene or propylene / ethylene / diene containing 65 percent or more, preferably 85 percent or more, of polymerized propylene or substantially isotactic propylene segments.

The ethylene homopolymers and the high ethylene content copolymers formed by the present process preferably have a density in the range of 0.85 g / cm3 to 0.97 g / cm3, more preferably in the range of 0.86 g / cm3 to 0.92 g / cm3. cm3. Desirably, they additionally have a melt index (I2) determined according to ASTM D-1238, condition E, from 1 to 100 dg / min, preferably from 2 to 10 dg / min. Propylene / ethylene prepared copolymers according to the present process desirably have an AHf (in J / g) of 25 to 55, preferably 29 to 52. Most desirably, the polymers prepared according to the present invention are propylene / ethylene copolymers. containing from 85 to 95 percent, preferably 87 to 93 percent polymerized depropylene, a density of 0.860 to 0.885g / cm3, and a melt flow rate (MFR) determined according to ASTM D-1238, condition L from 0.1 to 500, preferably from 1.0 to 10. Typically, polymers produced by the process of the invention have a molecular weight distribution or polydispersion index (Mw / Mn or PDI) of 2.0 to 15.0, preferably preferably from 2.0 to 10.0.

"Broad polydispersion", "broad molecular weight distribution", "broad MWD" and similar terms mean an IDP greater than or equal to 3.0, preferably from 3.0 to 8.0.

Polymers for use in extrusion-coating and fiber applications typically have relatively wide polydispersion. Catalysts comprising a complex according to formula (I) are especially adapted to prepare such propylene / ethylene interpolymers having a wide molecular weight distribution for this end use.

"Narrow polydispersion", "narrow molecular weight distribution", "narrow MWD" and similar terms mean an PDI of less than 3.0, preferably from 2.0 to 2.7. The polymers for use in adhesive applications preferably have a narrower polydispersion. Catalysts comprising a complex according to formula (I) are especially adapted to prepare such propylene / ethylene interpolymers having a narrow molecular weight distribution for this purpose.

A suitable technique for determining the molecular weight distribution of polymers is gel-permeation chromatography (GPC) using a PL-GPC-220 high temperature chromatographic unit from Polymer Laboratories equipped with four linear mixed-bed columns (dePolymer Laboratories). 20μηη)). The oven temperature is set at 160 ° C with automatic sample collector hot azone at 160 ° C and the warm zone at 145 ° C. The solvent is 1,2,4-trichlorobenzene containing 200 ppm 2,6-di-tertiary butyl-4-methylphenol. The flow rate is 1.0 milliliter / minute and the injection volume is 100 microliters. About 0.2 percent of the samples for injection are prepared by dissolving the sample in 1,2,4-trichlorobenzene purged in nitrogen containing 200 ppm 2,6-di-terciobutyl-4-methylphenol for 2.5 hours at 160 ° C with gentle mixing.

Molecular weight is determined using ten narrow molecular weight distribution polystyrene standards (EasiCal PSI from Polymer Laboratories ranging from 580 to 7.50 0.000 g / mol) along with their elution volumes. Equivalent molecular weights of polypropylene are determined using coefficients of Mark-Houwink appropriate for polypropylene (J. Appl. Polym. Sci., 29,3763-3782 (1984)) and for polystyrene (Macromolecules, 4,507 (1971)) in the Mark-Houwink equation: {n} = KMa, whereKpp = 1.90 χ 10 "4, aPP = 0.725 and Kps = 1.26 χ 10" 4, aPS = 0.702.

A suitable technique for measuring thermal properties of polymers is by differential scanning calorimetry (DSC). The general principles of DSC measurements and DSC applications for studying crystalline polymers are described in standard texts such as, E. A. Turi, Ed., "Thermal Characterization of Polymeric Materials", Academic Press, (1981). A suitable technique for performing DSC analyzes is using a Q1000 DSC device from TA Instruments, Inc. To calibrate the instrument, a first baseline is obtained using the -90 ° C to 290 ° C DSC without any sample in the aluminum pan. DSC. Then 7 grams of a fresh sample of indium are analyzed by heating the sample to 180 ° C, cooling the sample to 140 ° C at a cooling rate of 10 ° C / min followed by keeping the sample isothermally at 140 ° C for 1 minute, followed by by heating the sample from 140 ° C to 180 ° C at a heating rate of 10 ° C / min. The melting heat and melting initiation of the indios sample was determined and checked to be within the 0.5 ° C of 156.6 ° C for the onset of melting within the limits of 0.5 J / g of 28.71. J / g for fusion heat. Deionized water is then analyzed by cooling a small drop of fresh sample into the 25 ° C -30 ° C DSC pan at a cooling rate of 10 ° C / min. The sample is kept at -30 ° C for 2 minutes and heated to 30 ° C in a heating rate of 10 ° C / min. The onset of melting is determined and checked to be within the range of 0.5 ° C to 0 ° C.

Samples are prepared by compressing the polymer into a thin film at a temperature of 190 ° C. About 5 to 8 mg of film sample is weighed and placed in the DSC panel. Lid the lid on the pan to ensure the atmosphere is closed. Place the pan with the DSC cell sample and then heat at a rate of 100 ° C / min to a temperature of 30 ° C above the melting temperature. The sample is kept at this temperature for about 3 minutes and then cooled at a rate of 10 ° C / min to -40 ° C, and held at that temperature for 3 minutes. Then heat again at a rate of 10 ° C / min until completion of the fusion. The enthalpy resulting curves are analyzed for maximum melting temperature, starting and maximum crystallization temperatures, melting heat, and crystallization heat.

The present interpolymers of propylene with ethylene and optionally C4-20 α-olefins have a relatively broad melting point evidenced by the DSC heating curve. It is believed that this may be due to the unique distribution of polymeric ethylene sequences within the polymeric chains. As a consequence of the foregoing, melting point data, Tm, are not generally reported here or used to describe polymeric properties. Crystallinity is determined based on the AHfi measurements with the crystallinity percentage determined by the formula: AHf / 165 (J / g) χ 100. Generally, a relatively narrow melting peak is observed for depropylene / ethylene interpolymers prepared using a metallocene catalyst while Polymers according to the present invention have a relatively wide melting point curve. It has been found that polymers having an extended melting point are very useful in applications requiring a combination of elasticity and high temperature performance, such as fibers or elastomeric adhesives, for example.

A feature on the DSC curve of depropylene / ethylene polymers having a relatively broad melting point is that Tme, temperature at which melting ends, remains essentially the same and Tmax, maximum melting temperature, decreases as the amount of ethylene in the copolymer is increased. An additional feature of such polymers is that the TREF curvature asymmetry is generally greater than -1.60, preferably greater than -1.00.

Determination of crystallizable sequence length distribution in a copolymer can be measured by the High Temperature Elution Fractionation (TREF) technique, disclosed by L. Wild, et al., Journal of Polymer Science, Physics Ed., 20, 441 (1982). , Hazlitt, Journal of Applied Polymer Science: Appl. Polym.Symp., 45, 25 (1990), and elsewhere. One version of this technique, Temperature Elevated Elution Analytical Fractionation (ATREF), does not address actual isolation of fractions but rather more accurately ends fraction weight distribution, and is especially suitable for use with small sample sizes.

While TREF and ATREF were originally applied to the analysis of ethylene and higher α-olefin copolymers, they can also be adapted to the analysis of propylene-ethylene (or higher α-olefin) copolymers. Analysis of depropylene copolymers may require the use of higher temperatures for the dissolution and crystallization of pure isotactic polypropylene, but most copolymerization products of interest elute at temperatures similar to those observed for ethylene copolymers. The following table summarizes the conditions used for propylene / ethylene copolymer analysis.

<table> table see original document page 42 </column> </row> <table>

Data obtained from TREF and ATREF analysis are expressed as a normalized polymer weight fraction plot as a function of elution temperature. The separation mechanism is analogous to that of ethylene copolymers, whereby the molar content of the crystallizable component (ethylene) is the major determinant of the elution temperature. In the case of depropylene copolymers, the molar content of propylene isotactic units basically determines the elution temperature.

The TREF or ATREF curve of a metallocene-catalyzed homogeneous depropylene / ethylene copolymer is characterized by gradual tail formation at lower elution temperatures compared to the accuracy or sharpness of the curve at higher elution temperatures. One statistic that reflects this type of asymmetry is obliquity. The equity index, Six, determined by the following formula, may be employed as a measure of this asymmetry.

The Tmax value is defined as the maximum fractional temperature eluting between 50 and 900C on the TREF curve. Ti and Wi are, respectively, the elution temperature and the weight fraction of the ith arbitrary fraction of the TREF distribution. The distributions are normalized (the sum of Wi equals 100 percent) with respect to the total area of the curve eluting above 30 ° C. Therefore, the index reflects only the properties of the crystallized polymer and any influence due to the non-crystallized polymer (polymer still in solution or at or below 30 ° C) is omitted from the calculation.

Certain polymers according to the invention having a relatively broad melting point on the DSC curve are desirably characterized by an yield index greater than -1.6, more preferably greater than -1.2.

Polymer tacticality, propylene content, regio-errors and other properties are determined as standard NMR techniques. Tactics (mm) or (rr) are calculated based on meso or region triads, and may be expressed as ratios smaller than one or with percentages. The isotacticity of propylenone triad level (mm) is determined from integrals of triadm (22.70-21.28 ppm), triad mr (21.28-20.67 ppm) and datriad rr (20.67 -19.74 ppm). The isotacticity is determined by dividing the intensity of the triad mm by the sum of the triads mm, mr, and rr. For ethylene-containing interpolymers, the mr region is corrected by subtracting the depic integral from 37.5-39 ppm. For copolymers with other peak producing monomers in the mm, mw, and rr triad regions, integrals for these regions are similarly corrected by subtracting the interfering peak intensity using standard NMR techniques once the peaks are identified. This can be accomplished, for example, by analyzing a series of copolymers at various levels of monomer incorporation, by literature work, by isotopic labeling, or by other means known in the art.

Specific Incorporations

The following specific embodiments of the invention and combinations thereof are especially desirable and described herein in order to provide detailed disclosure of the appended claims.

1. Metal complex corresponding to the formula:

<formula> formula see original document page 44 </formula>

wherein each occurrence of X is independently an anionic ligand, or two groups X together form a diionic grouping, or a neutral diene; T is a grouped aromatic or aromatic group containing one or more rings, each occurrence of R1 independently being hydrogen, halogen, or a monovalent polyatomic anionic ligand, or two or more R1 groups thus forming a polyvalent fused ring system; each occurrence of R2 is independently hydrogen, halogen, or a monovalent polyatomic anionic ligand, or two or more R2 groups together forming a polyvalent fused ring system; R4 is hydrogen, alkyl, aryl, aralkyl, trihydrocarbylsilyl, or methyl trihydrocarbyl silyl of 1 to 20 carbons.

2. Metal complex according to embodiment 1, wherein T is a bivalent fused polycyclic ring aromatic group, R4 being C1-4 alkyl, and each occurrence of X being C1-20 alkyl, cycloalkyl or aralkyl.

3. Metal complex according to embodiment 1, corresponding to the formula:

<formula> formula see original document page 145 </formula>

wherein each occurrence of R 1 is independently a C 3-12 alkyl group in which the carbon attached to the amphenyl is secondary or tertiary substituted, preferably each R 1 is isopropyl; each occurrence of R2 is independently hydrogen or a C1-12 alkyl group; R3 is hydrogen, halogen or R1; R4 is C1-4 alkyl; and X and T are previously defined for compounds of formula (I).

4. Metal complex according to embodiment 2, characterized in that it corresponds to the formula: <formula> formula see original document page 46 </formula>

wherein: each occurrence of R 1 is independently a C 3-12 alkyl group in which the carbon attached to the amphenyl is secondary or tertiary substituted; each occurrence of R 2 is independently hydrogen or a C 1-12 alkyl; R4 is methyl or isopropyl; R5 is hydrogen or C1-6 alkyl; R 6 is hydrogen, C 1-6 alkyl or cycloalkyl, or two adjacent R 6 groups together form a fused aromatic ring; T 'is oxygen, sulfur, or a C1-20 hydrocarbyl substituted nitrogen or phosphorus group; T "is nitrogen or phosphorus; X is methyl or benzyl.

5. Metal complex according to embodiment 1, corresponding to the formula:

<formula> formula see original document page 46 </formula> wherein each occurrence of R1 is independently isopropyl; each occurrence of R2 is independently hydrogen or a C1-12 alkyl group; R4 is C1-4 alkyl; R6 is hydrogen, C1-6 alkyl or cycloalkyl; Each occurrence of X is independently methyl or benzyl.

6. Metal complex according to Incorporation 1, selected from the group consisting of: [N- [2,6-bis (1-methylethyl) phenyl] -a- [2,4,6-tri (1-methyl ethyl) ) phenyl] -5- (2-ethylbenzofuran-3-yl-K-C4) -2- (N'-methyl) imidazol-2-yl) methanaminate (2-) - κΝ1, κΝ2] di (methyl) hafnium, [N- [2,6-bis (1-methylethyl) phenyl] -a- [2,6-di (1-methylethyl) phenyl] -5- (2-ethylbenzofuran-3-yl-K-C4) -2- (N'-methyl) imidazol-2-yl) methanaminate (2-) - KN1KN2] di (methyl) hafnium, [N- [2,6-bis (1-methylethyl) phenyl] -a- [ 2,4,6-tri (1-methylethyl) phenyl] -5- (carbazol-1-yl-K-C2) -2- (N'-methyl) imidazol-2-yl) methanaminate (2-) - KN1iKN2] di (methyl) hafnium, [N- [2,6-bis (1-methylethyl) phenyl] -a- [2,4,6-tri (1-methylethyl) phenyl] -5- (2- ethyl benzofuran-3-yl-K-C4) -2- (N'-methyl) imidazol-2-yl) methanaminate (2-) - KN1KN2] di (benzyl) hafnium, [N- [2,6-bis ( 1-methylethyl) phenyl] -a- [2,6-di (1-methylethyl) phenyl] -5- (2-ethyl benzofuran-3-yl-K-C4) -2- (N'-methyl) imidazol-2-yl) (2 -) -κΝ1, κΝ2] di (benzyl) hafnium, [N- [2,6-bis (1-methylethyl) phenyl] -a- [2,4,6-tri] (1-methyl 1-ethyl) phenyl] -5- (carbazol-1-yl-K-C2) -2- (N'-methyl) imidazol-2-yl) methanaminate (2-) -KN1KN2] di (benzyl) hafnium, [ N- [2,6-bis (1-methylethyl) phenyl] -a- [2,6-di (1-methylethyl) phenyl] -5- (carbazol-1-yl-K-C2) -2- (N'-methyl) imidazol-2-yl) (2-) - KN11KN2] di (benzyl) hafnium or a mixture thereof.

7. Suitable catalyst composition for use in coordinating olefin polymerization comprising a metal complex as defined by any one of embodiments 1-6 and a cocatalyst activator.

Catalyst composition according to the 7-incorporation, wherein the activating cocatalyst is a Lewis acid.

A catalyst composition according to embodiment 8 wherein the Lewis acid is methyl aluminoxane or modified methylaluminoxane.

Catalyst composition according to embodiment 7, further comprising a support.

A catalyst composition according to embodiment 10, wherein the support is a selected particulate compound of Group 13 or 14 metal or metalloid oxides, sulfides, nitrides or carbides.

A catalyst composition according to embodiment 11 wherein the support is silica-containing methyl aluminoxane containing the metal complex deposited on the same surface.

13. Addition polymerization process comprising contacting one or more olefinic monomers under polymerization conditions with a catalyst composition as defined by incorporation 7.

Process according to embodiment 13, being a gas phase polymerization process.

Process according to embodiment 13, being a semi-fluid paste polymerization process.

Examples

The invention is further illustrated by the following examples which are not to be construed as limiting the present invention. The skilled artisan will understand that the invention disclosed herein may be practiced in the absence of any component which has not been specifically disclosed. If used, the term "overnight" refers to a time interval of approximately 16-18 hours; the terms "ambient temperature" and "ambient air temperature" refer to temperatures of 20-25 ° C; and the term "mixed alkanes" refers to a commercially obtained mixture of aliphatic hydrocarbons obtainable under the tradename ISOPAR E® from Exxon Mobil Chemicals, Inc. Where the name of a compound is not in accordance with the structural representation thereof, structural representation will dominate. The synthesis of all metal complexes and preparation of all shredding experiments were performed in a dry nitrogen atmosphere using dry box techniques. All solvents used were HPLC grade and dried before use.

Example 1

[N- (2,6-bis (1-methylethyl) phenyl] -a- [2,4,6-tri (1-methylethyl) phenyl] -5- (2-ethyl benzofuran-3,4-diyl) K-C4) -2- (N'-methyl) imidazol-2-yl) methanaminate (2 -) - KN11KN2] di (methyl) hafnium

<formula> formula see original document page 49 </formula>

(a) To a 250 mL glass flask equipped with magnetic stirring is added 100 mL of diethyl ether and 2-ethylbenzofuran (20.0 g, 137 mmol). The reaction flask is then cooled to 0 ° C. Then bromine (8.40 mL, 164 mmol) is added to an addition funnel containing 50 mL of ethyl acetate. The mixture is added dropwise in the reactor while maintaining the temperature of 0 ° C. The addition funnel is rinsed with an additional 20 mL of ethyl acetate. The resulting mixture is stirred for 2 hours and kept at 0 ° C. The reaction is quenched with 50 mL of water. The reactor contents are then transferred to a 1 L separatory funnel and rinsed with 2 χ 50 mL of water. The organic layers are combined and rinsed with 200 mL of a saturated sodium thiosulfate solution. The layers are separated and the organic layer is dried over MgSO4 to give an amber colored solution. The solvent is removed under vacuum to give the product, 3-bromo-2-ethylbenzofuran, as a pale yellow liquid which is used without further purification (yield: 27.1 g, 88.0 percent).

(b) To a 500 mL glass flask equipped with magnetic stirring is added 200 mL of diethyl ether and 3-bromo-2-ethyl benzofuran (50.0 g, 223 mmol). The spinning flask is purged with nitrogen and then cooled to -780C. Then, nBuLi (146 mL, 234mmol) is added dropwise via an addition funnel. The reaction is maintained at -780C from the beginning of the addition of nBuLi and then stirred for 1 hour. Then, deisopropyl boronate pinacolate (45.8 g, 246 mmol) is added to the addition funnel added dropwise to the reaction mixture. The mixture is stirred at -780 ° C for 1.5 h. The cooling bath is then removed and the mixture allowed to warm to room temperature. Temper sand with 200 mL of water. The reactor contents are then transferred to a 1 L separatory funnel and extracted with 4 χ 50 mL of ethyl acetate. The organic layers are combined and the solvent removed in vacuo. The product is redissolved in methylene chloride and extracted with an aqueous NaOH solution to remove phenolic byproducts. The organic layer is then dried over MgSO 4 to give a yellow solution. The solvent is removed in vacuo to give 50.0 g of 3-pinacolate boronate-2-ethylbenzofuran as a pale yellow liquid (yield: 82.2 percent, GC / MS purity: 96 percent).

(c) To a dry, N2-purged 500-neck three-necked glass flask is added 200 mL of dry ethyl ether and 4-bromo-N-methyl imidazole (50.0 g, 311mmol). The flask is then cooled to -10 ° C with a deacetone / ice bath. Then a 2M solution of lithium diisopropyl amide (171 mL, 342 mmol) in heptane / THF / ethyl benzene is added via syringe while maintaining the temperature at 0 ° C or below. After 1 hour, dimethylformamide (DMF) (36.1 mL, 466 mmol) is added dropwise over 5 minutes. The reaction mixture is stirred for 45 minutes at or below 50 ° C and then quenched with saturated aqueous citric acid solution. Gently stir the resulting mixture until the two phases are separated. The organic layer is recovered and washed (3 χ 200mL) with water. The solvent is removed in vacuo to afford the desired product, 2-formyl-4-bromo- (1) N-methyl imidazole as a brown crystalline solid (yield: 55.7 g, 95 percent, 86 percent purity by GC). Further purification may be performed by elution through alumina using the methylene chloride solvent.

(d) Add 3-pinacolato boronate-2-ethyl benzofuran (61.6 g, 378 mmol), Na 2 CO 3 (40.0 g, 378 mmol) and 2-formyl-4-bromo- (1) N-methyl imidazole (28.4 g, 151 mmol) in a 3 L glass flask equipped with mechanical stirring containing a degassed water solution (600 mL) and dimethyl ether (60 mL). Inside a dry box 1.41 g of tetrakis (triphenyl phosphine) palladium (0) is dissolved in 40 ml of anhydrous degassed toluene. The Pd solution in toluene is removed from the dry box and charged to the syringe via a layer of N2. The biphasic solution is stirred vigorously and heated at 730 ° C for 14 hours. On cooling to room temperature, the organic phase is separated. The aqueous layer is washed twice with 150 mL of ethyl acetate. All organic phases are combined and the solvent is removed under vacuum to an oil. Recrystallization from hexane gives the product 4- (2-ethyl benzofuran-3-yl) -2-formyl- (1) N-methyl imidazole as a brown solid (yield: 25.6 g, 66.8 percent) .

(e) A 250mL round-bottomed glass flask is charged with a neck with a solution of 4- (2-ethylbenzofuran) -2-formyl- (1) N-methyl imidazole (59.9 g, 236mmol) and 2,6-diisopropyl aniline (41.8 g, 236 mmol) in 50 mL of anhydrous toluene. To the reaction flask is added a catalytic amount (10 mg) of p-toluenesulfonic acid. The reactor is equipped with a Dean Stark trap with a condenser as well as a thermocouple. The mixture is heated to 100 ° C in N2 for 12 hours. The solvent is then vacuum removed to give 103 g of the product, 2- (2,6-diisopropyl phenyl) imine-4-3 (2-ethyl benzofuran) - (1) N-methyl imidazole as a brown solid. This material is dried under high vacuum, rinsed with hexane, and then recrystallized from hexane (yield: 68.0 g, 69.7 percent).

1H NMR (CDCl3) δ 1.2 (d, 12H), 1.5 (t, 3H), 3.0 (septet, 2H), 3.15 (q, 2H), 4.2 (s, 3H) 7.2 (m, 3H), 7.35 (m, 2H), 7.6 (d, 2H), 7.85 (d, 2H).

GC / MS 413 (M +), 398, 370, 227, 211, 186, 170, 155, 144,128, 115, 103.

(f) A 2-neck three-necked glass flask equipped with a magnetic stirrer and N2 spray with 2- (2,6-diisopropyl phenyl) imine-4-3 (2-ethylbenzofuran) - (1 ) N-methyl imidazole (122 g, 296 mmol) and 700 mL of anhydrous degassed toluene. The solution is cooled to -40 ° C after which time a solution of 2,4,6-triisopropyl phenyl lithium (127 g, 606 mmol) dissolved in diethyl ether is added dropwise for 30 minutes. Then the solution is heated to at room temperature for 1 hour and stirred at room temperature for an additional 1 hour. The reaction is then quenched with 300 mL of water and 50mL of ammonium chloride. The organic layer is separated, washed three times with 100 mL aliquots of water.

All organic layers are combined and the solvent is removed vacuum to yield 200 g of crude solid. Solid impurities are precipitated with filtered hexane. The mother liquors are reconcentrated and the material recrystallized with hexane to give 82 g of the product, N- [2,6-bis (1-isopropyl) phenyl] -a- [2,4,6- (triisopropyl) phenyl] -4- 3- (2-ethyl benzofuran) 2- (1) N-methylimidazole methanamine as a light yellow solid. Chromatographic separation gives an additional 7.03 g of product (yield: 89.0 g, 48.7 percent).

1H NMR (CDCl3) δ 0.5 (bs, 3H), 0.7 (bs, 3H), 0.95 (d, 6H), 1.25 (d, 6H), 1.3-1.4 ( m, 12H), 1.6 (t, 3H), 2.75 (septet, 1Η), 2.9 (septet, 1Η), 3.0 (s, 3Η), 3.1 (septet, 2Η), 3.25 (septet, 1Η), 3.35 (q, 2Η), 3.8 (bs, 1Η), 5.1 (s, 1Η), 5.7 (s, 1Η), 6.9 (s , 1Η), 6.95-7.1 (m, 3Η), 7.2 (m, 2Η), 7.45 (dd, 2Η), 7.75 (dd, 2H) ppm.

GC / MS 617 (δ +), 442, 425, 399, 281, 227, 162, 120.

(g) N- [2,6-bis (1-isopropyl) phenyl] -α- [2,4,6- (triisopropyl) phenyl] -4-3 (2-ethyl benzofuran 2- (I) is transferred ) N-Methyl imidazole methanamine (40.3 g, 65.2 mmol) into a 2L, 3-necked glass flask equipped with a magneticmagnet and a thermoelectric pair, and dissolved 300mL of toluene. 40 ml of 1.60 M BuLi solution in hexanes to the flask dropwise, the reaction mixture is stirred for 1 hour at room temperature.

HfCl4 (19.8 g, 62.0 mmol) is added with stirring and the mixture is refluxed for three hours. After cooling, 67.4 mL of MeMgBr 3, OM in Et 2 O are added dropwise to the flask for 30 minutes. Vacuum is applied to the balloon and the volatiles are removed overnight. The remaining black solids are slurried with 500 mL of toluene and stirred for one hour, then the mixture is filtered through a 500 mL medium porosity frit funnel using a diatomaceous auxiliary filter. The solids are washed with toluenoaddiction (500 mL) until the filtrate is colorless. The residual solvent is removed in vacuo to give the tri-alkylated product, [N- (2,6-bis (1-methylethyl) phenyl] -a- [2,4,6-tri (1-methylethyl)) phenyl] -5- (2-ethyl benzofuran-3-yl) -2- (N'-methyl) imidazol-2-yl) methanaminate (2 -) - KN1 fKN2] trimethylphenium as a light brown solid (yield: 40.6 g 74 percent).

1H NMR (C6D6) δ 0.40 (d, 3H), 0.59 (s, 9H), 0.72 (d, 3H), 0.97 (d, 3H), 1.25 (d, 3H) 1.3-1.42 (bm, 12H), 1.5 (t, 3H), 1.64 (d, 6H), 1.71 (d, 6H), 2.54 (s, 3H), 2.9 (m, 4H), 3.12 (septet, 1H), 3.75 (septet, 1H), 3.86 (septet, 1H), 4.20 (septet, 1H), 6.1 (s) , 1H), 6.44 (s, 1H), 7.11 (s, 1H), 7.25-7.33 (bm, 4H), 7.6 (d, 2H), 7.8 (d, 2H) ppm.

(h) heating for several hours at 70 ° C results in complete metallization of the benzofuranyl group on the C4 carbon of the benzyl ring to cleanly form [N- (2,6-bis (1-methylethyl) phenyl] -a- [2 4,6-tri (1-methylethyl) phenyl] -5- (2-ethyl benzofuran-3-yl-K-C4) -2- (N'-methyl) imidazol-2,3-diyl) methanaminate ( 2 -) - KN1iKN2] dimethyl hafnium.

1H NMR (C6D6) δ 0.28 (d, 3H), 0.44 (d, 6H), 0.59 (d, 3H), 0.78 (s, 3H), 0.9 (s, 3H) 1.1 (d, 6H), 1.2 (d, 6H), 1.18 (t, 3H), 1.24 (d, 6H), 1.4 (d, 3H), 2.41 ( s, 3H), 2.59 (q, 2H), 2.65 (septet, 1H), 2.75 (septet, 1H), 3.28 (septet, 1H), 3.57 (septet, 1H), 4.05 (septet, 1H), 6.27 (s, 1H), 6.30 (s, 1H), 6.91 (s, 1H), 7.05 (m, 2H), 7.1 (m , 3H), 7.45 (m, 1H), 8.65 (d, 2H) ppm.

Example 2

[N- (2,6-bis (1-methylethyl) phenyl] -a- [2,4,6-tri (1-methylethyl) phenyl] -5- (2-ethyl benzofuran-3,4-diyl) K-C4) -2- (N'-methyl) imidazol-2-yl) methanaminate (2 -) - KN11KN2] di (n-butyl) hafnium

(a) A glass flask is charged with N- [2,6-bis (1-isopropyl) phenyl] -a- [2,4,6- (triisopropyl) phenyl] -4-3 (2-ethylbenzofuran) 2- (1) N-methyl imidazole methanamine ((Ex. 1, (f)), 0.81 mmol dissolved in 20 mL of toluene). To this solution is added 0.81 mmol n-BuLi (2.5 M solution in hexanes) per syringe. This solution is stirred for 30 minutes and toluene is removed using a dry box vacuum system. Hexane is added and removed by vacuum, added again, and the resulting semifluidic slurry is filtered to give the lithium salt as a white solid (0.20 g, 0.32 mmol; 40 percent). Then a glass jar with the white solid dissolved in 30 ml of toluene is charged. To this solution is added 0.32 mmol of solid HfCl4. The container is capped with a standard air-cooled reflux condenser and the reflux mixture is heated for about 4 hours. After cooling, 1.1 mmol BuMgCl (3.5 equivalents, solution 2, OM in diethyl ether) is added by syringe and the resulting mixture is stirred overnight at room temperature. Remove the reaction mixture solvent in vacuo. Toluene (30 mL) is added to the residue, the mixture is filtered, and the residue is washed with toluenoaddiction (30 mL). The solvent is removed under vacuum from combined toluene solutions and hexane is added and then removed under vacuum. This process is repeated again to give the tri-alkylated product, [N- (2,6-bis (1-methylethyl) phenyl] -a- [2,4,6-tri (1-methylethyl) phenyl ] -5- (2-ethyl benzofuran-3-yl) -2- (N'-methyl) imidazol-2-yl)

methanaminate (2 -) - κΝχ, κΝ2] tri (n-butyl) hafnium as white solid vitreous.

1H NMR (C6D6) δ 7.62 (d, J = 8Hz, 1H), 7.42 (d, J = 8Hz, 1H), 7.25-7.00 (multiplets, 6H), 6.93 (d, J = 2 Hz, 1H), 6.22 (s, 1H), 5.84 (s, 1H), 3.95 (septet, J = 7Hz, 1H), 3.71 (septet, J = 7 Hz, 1H), 3.60 (septet, J = 8 Hz, 1H), 2.89 (septet, J = 7 Hzi 1H), 2.85 (q, J = 8 Hz, 2H), 2.72 (septet, J = 7Hz, 1H), 2.32 (s, 3H), 2.0-0.8 (multiplets, alkyl chain protons), 1.55 (d, J = 7Hz1 3H), 1.54 (d, J = 7Hz 7H), 1.41 (d, J = 7Hz, 3H), 1.40 (d, J = 7Hz, 3H), 1.18 (d, J = 7 Hz, 3H), 1.17 (d, J = 7Hz 7H), 1.05 (d, J = 7Hz, 3H), 0.90 (t, J = 7Hz, 9H), 0.76 (t , J = 7Hz, 3H), 0.72 (d, J = 7Hz, 3H), 0.52 (d, J = 7Hz, 3H), 0.20 (d, J = 7Hz, 3H).

(b) The foregoing product is heated for several hours to 70 ° C resulting in metallization of the C4 benzofuranilane carbon binder to form [N- (2,6-bis (1-methylethyl) phenyl] -a- [2,4,6- tri (1-methylethyl) phenyl] -5- (2-ethylbenzofuran-3,4-diyl-K-C4) -2- (N'-methyl) imidazol-2-yl)

(2-) - KN1iKN2] di (n-butyl) hafnium methanaminate. The complex for solubility is tested by dissolving in methyl cyclohexane at 20 ° C. The solubility thus measured is greater than 5 per cent.

1H NMR (C6Ds) δ 8.88 (m, 1H), 7.52 (d, J = 4Hz, 2H), 7.20-7.05 (multiplets, 4H), 6.99 (d, J = 2 Hz, 1H), 6.36 (s, 2H), 3.99 (septet, J = 7 Hz, 1H), 3.65 (septet, J = 7 Hz, 1H), 3.30 (septet, J = 7 Hz 7 1H), 2.79 (septet, J = 7 Hz, 1H), 2.71 (septet, J = 7 Hz, 1H), 2.66 (qd, J = 8.3 Hz, 2H), 2.50 (s, 3H), 2.15 (multiplet, 2H), 1.86 (multiplet, 1H), 1.6-0.6 (multiplets, alkyl chain protons), 1.50 (d, J = 7Hz, 3H), 1.40 (d, J = 7Hz, 3H), 1.37 (d, J = 7Hz, 3H), 1.28 (d, J = 7Hz, 3H), 1 , 22 (t, J = 8Hz, 3H), 1.21 (d, J = 7Hz, 3H), 1.12 (d, J = 7Hz, 3H), 0.90 (t, J = 7Hz) 0.96 (t, J = 7Hz, 3H), 0.66 (d, J = 7Hz, 3H), 0.63 (d, J = 7Hz, 3H), 0.36 ( d, J = 7 Hz, 3H).

Example 3

[N- (2,6-bis (1-methylethyl) phenyl] -a- [2,6-di (1-methylethyl) phenyl] -5- (2-ethyl benzofuran-3-yl-K-C4) -2- (N'-methyl) imidazol-2-yl) (2-) -KN1iKN2] di (n-butyl) hafnium

The reaction conditions of Example 1 are repeated substantially except that in step (f), 2,4,6-diisopropyl phenyl lithium is replaced by 2,4,6-triisopropyl phenyl lithium. More particularly, a 2- (2,6-diisopropyl phenyl) imine-4- (2-ethyl benzofuran) - (1) N-methyl imidazole flask dissolved in 20 mL of toluene is charged. To this solution is added 0.78 mmol of n-BuLi (2.5M solution in hexanes) by syringe and immediately after addition toluene is removed in vacuo. Add hexane, remove in vacuo, then add again, and filter out the resulting semifluid to give 0.21 g, 0.35 mmol; 44 percent of the binder's lithium salt is free as a white solid. The solid is placed in a glass flask and dissolved in 30 mL of toluene. To this solution is added 0.35 mmol of solid HfCl4. The vessel is capped with an air-cooled reflux condenser and heats the mixture at reflux for about 4 hours. After cooling, 1.2 mmol BuMgCl (3.5 equivalents, solution 2, OM in diethyl ether) is added by syringe and the resulting mixture is stirred overnight at room temperature. Remove the solvent (toluene and diethyl ether) from the reaction mixture in vacuo. Hexane (30 mL) is added to the residue, then filtered off, and the solids are washed again with hexanoaddiction (30 mL). The white vitreous solid product is recovered from the combined hexane extracts and converted to the dibutyl derivative by heating in debenzene solution at 500 ° C overnight.

The solubility of the recovered dibutyl complex in methylcyclohexane measured at 20 ° C is greater than 5 per cent.1H NMR (CgD6) δ 8.88 (m, 1H), 7.52 (d, J = 4 Hz, 2H), 7.20-7.10 (multiplets, 4H), 6.97 (m, 2H), 6.32 (s, 1H), 6.30 (s, 1H), 4.01 (septet, J = 7Hz, 1H), 3.64 (septet, J = 7Hz, 1H), 3.26 (septet, J = 7Hz, 1H), 2.75 (septet, J = 7Hz, 1H), 2 , 61 (qd, J = 8.3 HZi 2H), 2.38 (s, 3H), 2.15 (multiplet, 2H), 1.86 (multiplet, 1H), 1.6-0.6 (multiplets , alkyl chain protons), 1.50 (d, J = 7Hz, 3H), 1.34 (d, J = 7Hz, 3H), 1.32 (d, J = 7Hz, 3H), 1.25 (d, J = 7Hz, 3H), 1.18 (t, J = 8Hz, 6H), 1.03 (d, J = 7Hz, 3H), 0.88 (d, J = 7 Hz, 3H), 0.83 (t, J = 7Hz, 9H), 0.61 (d, J = 7Hz, 3H), 0.55 (d, J = 7Hz, 3H), 0.38 (d, J = 7Hz, 3H).

Example 4

[N- (2,6-bis (1-methylethyl) phenyl] -a- [2,4,6-tri (1-methylethyl) phenyl] -5- (carbazol-1-yl-K-C2) - 2- (N'-methyl) imidazol-2-yl) methanaminate (2 -) -KN17 κΝ2] di (methyl) hafnium

<formula> formula see original document page 58 </formula>

(a) In a N2 atmosphere a 2.35 mmol glass flask of 2- (1) N-methyl imidazole methanamine-N- [2,6- (diisopropyl) phenyl] -a- [2, 4,6- (triisopropyl) phenyl] -4- (N-carbazole) and 60 mL of toluene is added. To this solution is added dropwise 2.35 mmol of n-BuLi (2.03M solution in cyclohexane) by syringe and the solution is stirred at room temperature for 2 hours. To this solution is added 2.35 mmol of solid HfCl4 in one portion.

The mixture is gradually warmed to 105 ° C for 30 minutes, then held at this temperature for 90 minutes. After cooling, 7.2 mmol MeMgBr (3.1 equivalents, solution3.0 OM in diethyl ether) is added dropwise and the resulting mixture is stirred for 30 minutes at room temperature. Volatile vacuum is removed from the reaction mixture overnight. The residue is stirred in 50 mL of filtered toluene and the volatiles of the combined toluene extracts are removed in vacuo. The resulting solids are stirred in 20 mL of sedan, allowed to settle, then separated from the supernatant by decantation. The ivory material is dried vacuum to provide 1.05 g of the tri-alkylated species, [N- (2,6-bis (1-methylethyl) phenyl] -a- [2,4,6-tri (1-methylethyl) ) phenyl] -5- (carbazol-1-yl) -2- (N'-methyl) imidazol-2-yl) methanaminate (2-) - KN1KN2] tri (methyl) hafnium in 51 percent yield.

1H NMR (500 MHz, 25 ° C, CeD6) δ 0.24 (d, J = 7 Hz, 3H), 0.53 (s, 9H), 0.92 (d, J = 7 Hz, 3H), 1.07 (d, J = 7Hz, 3H), 1.20 (d, J = 7Hz, 3H), 1.21 (d, J = 7Hz, 3H), 1.31 (d, J = 7Hz, 3H), 1.41 (d, J = 7Hz, 3H), 1.42 (d, J = 7Hz, 3H), 1.57 (d, J = 7Hz, 3Η), 2.30 (s, 3Η), 2.74 (septet, J = 7Hz, 1Η), 2.94 (septet, J = 7Hz, 1Η), 3.61 (septet, J = 7Hz, 1Η), 3, 67 (septet, J = 7Hz, 1Η), 3.99 (septet, J = 7Hz, 1Η), 5.58 (s, 1Η), 6.31 (s, 1Η), 6.95 (d, J = 2 Hz, 1Η), 7, 09-7.34 (multiplets, 7Η), 7.53 (td, J = 7.1 Hz7 1Η), 7.62 (d, J = 8 Hz, 1Η), 8.04 (apparent t, J = 8 Hzi 2Η). (B) An 800 mg (0.92 9 mmol) sample of [N- [2,6-bis (1-methylethyl) phenyl] -α [2,4,6-tri (1-methylethyl) phenyl] -5- (carbazol-1-yl) -2- (N'-methyl) imidazol-2-yl) methanaminate (2-) -kN1, kn2 ] tri (methyl) hafnium is stirred in 15mL of toluene and heated overnight at 100 ° C in an N 2 atmosphere. The volatiles are removed in vacuo and the resulting solids are washed with 10 ml of pentane. After vacuum drying, 688 mg of the title compound are obtained as an ivory solid (88 percent yield of the previous tri-alkylated compound).

1H NMR (500 MHz, 25 ° C, C6D6) δ 0.34 (d, J = 7 Hz, 3H), 0.38 (d, J = 7 Hz, 3H), 0.64 (d, J = 7 Hz, 3H), 0.77 (s, 3H), 0.96 (s, 3H), 1.09 (d, J = 7Hz, 3H), 1.16 (d, J = 7Hz, 3H) 1.17 (d, J = 7Hz, 3H), 1.22 (d, J = 7Hz, 3H), 1.24 (d, J = 7Hz, 3H), 1.38 (d, J = 7Hz, 3H), 1.47 (d, J = 7Hz, 3H), 2.51 (s, 3H), 2.71 (septet, J = 7Hz, 1H), 2.80 (septet, J = 7Hz, 1H), 3.27 (septet, J = 7Hz, 1H), 3.53 (septet, J = 7Hz, 1H), 4.09 (septet, J = 7Hz, 1H), 6 , 31 (s, 1H), 6.44 (s, 1H), 6.97 (d, J = 2 Hz, 1H), 7.07 (d, J = 2 Hz, 1H), 7, 11-7 19 (multiplets, 3H), 7.33 (m, 2H), 7.44 (m, 1H), 7.60 (dd, J = 8.7 Hz, 1H), 8.07 (dq, J = 8.1 Hz, 1H), 8.11 (dd, J = 8.1 Hz, 1H), 9.02 (dd, J = 7.1 Hz, 1H) ppm.

Example 5

[N- (2,6-bis (1-methylethyl) phenyl] -a- [2,6-di (1-methylethyl) phenyl] -5- (carbazol-1-yl-k-C2) -2- (N'-methyl) imidazol-2-yl) methanaminate (2 -) -KN17KN2] di (methyl) hafnium <formula> formula see original document page 60 </formula>

(a) In an N2 atmosphere, dissolve in a glass flask equipped with a Dean Stark apparatus, dissolve a crude reagent mixture which is mainly 2-formyl-4-bromo- (1) N-methyl imidazole (20.5 g) in toluene (250 mL) with traces of p-toluene sulfonic acid (4-5 mg). Using GC and NMR analyzes, 2,6-diisopropyl aniline (total addition of 16.5 g, 93.0 mmol) is added portionwise until the aldehyde is converted entirely to imine. The reaction mixture is cooled and the solvent removed under reduced pressure. The product 2- (2,6-diisopropylphenyl) imine-4-bromo- (1) N-methyl imidazole (35.3 g) is used without further purification. Alternatively, the product is recrystallized using hexane.

1H NMR (C6Ds) δ 8.14 (s, 1H), 7.12-7.22 (m, 3H), 7.03 (s, 1H), 4.13 (s, 3H), 2.93 (septet) , J = 7Hz, 2H), 1.16 (d, J = 7Hz, 12H).

(b) In a N2 atmosphere, a magnetic co-absorber equipped with 2- (2,6-diisopropyl phenyl) imine-4-bromo- (1) N-methyl imidazole (3.0 g, 8.6) is charged. mmol), carbazole (1.44 g, 8.61 mmol), Δ, Ν'-dimethyl ethylenediamine (0.30 g, 3.45 mmol), copper (I) iodide (0.16 g, 0, 86 mmol), tri-basic potassium phosphate (3.84 g, 18.09 mmol) etoluene (25 mL). This mixture is refluxed overnight. After cooling the reaction is diluted with water (25 mL) and more toluene (100 mL). The organic layer is washed once with water and once with brine. The solution in toluene is dried over Na 2 SO 4 and evaporated under reduced pressure. The product, 2- (2,6-diisopropylphenyl) imine-4- (carbazol-1-yl) - (1) N-methyl imidazole (3.4 g) is purified by washing and filtering from cold pentane. 1 H NMR (C6D6) δ 8.29 (s, 1H), 8.08 (d, J = 7Hz, 2H), 7.72 (d, J = 8Hz, 2H), 7.43 (t, J = 7 Hz, 2H), 7.08-7.29 (m, 6H), 4.26 (s, 3H), 3.04 (septet, J = 7 Hz, 2H), 1.22 (d, J = 7Hz, 12H).

(c) The imine, 2- (2,6-diisopropyl phenyl) imine-4- (N-carbazolyl) - (1) N-methyl imidazole (2.80 g, 6.44 mmol) is dissolved, in toluene (20-25 mL) in an N2 atmosphere charged glove box. Aryl lithium sodium, 2,6-diisopropyl phenyl lithium, is added portionwise (1.63 g and 1.0 g) after dissolving in ether (5-7 mL). After evaporation, an aliquot of the reaction is analyzed by NMR to check for the disappearance of the imine proton signal. Analysis after the second portion of aryl lithium indicates that the imina was consumed and the reaction was completed. The reaction mixture is removed from the glove box and mixed with NH4Cl 1N solution (15 mL). The organic layer is separated, dried over Na 2 SO 4 and evaporated under reduced pressure. The product, N- [2,6- (diisopropyl) phenyl] -a- [2,6- (diisopropyl) phenyl] -4- (carbazol-1-yl) -2- (I) N- Methyl imidazole methanamine (2.9 g) is purified by washing with cold pentane.

1H NMR (C6D6, probe at 80 ° C) δ 8.01 (d, J = 7 Hz, 2H), 7.80 (d, J = 8 Hz, 2H), 7.39 (t, J = 7 Hz) , 2H), 7.20 (t, J = 7Hz, 2H), 7.0-7.15 (m, 6H), 6.30 (s, 1H), 5.66 (s, 1H), 5 , 32 (s, 1H), 3.49 (t, J = 7Hz, 4H), 2.53 (s, 3H), 1.15 (d, J = 7Hz, 12H), 0.90 (d , J = 7Hz, 6H), 0.71 (d, J = 7Hz, 6H).

(d) Inside a N2-loaded glovebox dissolve the binder, N- [2,6- (diisopropyl) phenyl] -a- [2,6- (diisopropyl) phenyl] -4- ( carbazol-1-yl) -2- (1) N-methylimidazol methanamine (2.9 g, 4.86 mmol) in hexane (50 mL) and slowly added by 2.5 M n-butyllithium syringe (2 mL, 5.0 mmol) and the mixture is allowed to stir for more than 1 hour. The mixture is placed in the glove box freezer (-40 ° C) overnight. The solution is warmed to room temperature and the hexane removed under reduced pressure and replaced with toluene (50 mL). Add hafnium tetrachloride (1.56 g, 4.86 mmol) and reflux the mixture for 2 hours and then cool After cooling to room temperature, 3N methyl magnesium bromide in ether (5.65 ml, 17.0 mmol) is added by syringe and the reaction mixture is allowed to stir overnight. The mixture is heated at 110 ° C for 3 to 4 hours and then cooled again. The solids are removed by vacuum filtration and washed thoroughly with more toluene until the filter becomes colorless. The toluene solution is evaporated under reduced pressure. NMR analysis of crude product suggests from multiple isopropyl methyl signals that methyl magnesium bromide sandblasting is incomplete. The crude product is redissolved in toluene and the 3N methyl magnesium bromide (1 mL, 3 mmol) is added again. The reaction is stirred at room temperature overnight, filtered, extracted under reduced pressure and the crude product is isolated after washing. and cold hexane filtration. The product, [N- (2,6-bis (1-methylethyl) phenyl] -a- [2,6-di (1-methylethyl) phenyl] -5- (carbazol-1-yl-K-C2 ) -2- (N'-methyl) imidazol-2-yl) methanaminate (2-) -

KN1, KN2] di (methyl) hafnium (700 mg), is a white powder. 1 H NMR (C 6 D 6) δ 8.98 (d, J = 7 Hz, 1H), 8.09 (d, J = 7 Hz, 1H), 8.04 (d, J = 7Hz, 1H), 7.58 (t, J = 8Hz, 1H), 7.40 (m, 1H), 7.27-7.33 (m, 2H), 6.93-7.18 (many multiplets, 6H), 6.42 (s, 1H), 6.27 (s, 1H), 4.11 (septet, J = 7 Hz, 1H), 3, 52 (septet, J = 7Hz, 1H), 3.24 (septet, J = 7Hz, 1H), 2.73 (septet, J = 7Hz, 1H), 2.43 (s, 3H), 1 .03 (d, J = 7Hz, 3H), 0.94 (s, 3H), 0.76 (s, 3H), 0.61 (d, J = 7Hz, 3H), 0.38 (d , J = 7 Hz 7 3H), 0.32 (d, J = 7 Hz, 3H). Example 6

[N- (2,6-bis (1-methylethyl) phenyl] -a- [2,4,6-tri (ethyl) phenyl] -5- (carbazol-1-yl-K-C 2) -2- (N'-methyl) imidazol-2-yl) (2-) -KN1iKN2] di (methyl) hafnium <formula> formula see original document page 63 </formula>

(a) In a N2 atmosphere, a glass flask is charged with 2- (1) N-methyl imidazole methanamine-N- [2,6 (diisopropyl) phenyl] -a- [2,4,6-tri ( ethyl) phenyl] -4- (N-carbazole) and add 75 mL of toluene. To this solution is added dropwise 3.05 mmol of n-BuLi (2.03M solution in cyclohexane) by syringe and the solution is stirred overnight at room temperature. To this solution is added 3.02 mmol of solid HfCl4 in one portion.

The mixture is gradually warmed to 105 ° C for 30 minutes, then kept at this temperature for 2.5 hours. After cooling, 10.2 mmol MeMgBr (3.4 equivalents, solution3.0 OM in diethyl ether) is added dropwise and the resulting mixture is stirred for 40 minutes at room temperature. Volatile vacuum is removed from the reaction mixture overnight. The residue is stirred in 50 mL of toluene for 30 minutes, filtered, and volatiles of toluene-combined extracts are removed in vacuo. The resulting solids are stirred in 15 mL of pentane, allowed to settle, then separated from the supernatant by decantation. After washing twice with an additional 15-20 mL of pentane the solid and meat are vacuum dried to provide 1.52 g of the tri-alkylated species in 61.5 percent yield.

1H NMR (500 MHz, 25 ° C, C6D6) δ 0.28 (d, J = 7Hz, 3H), 0.29 (s, 9H), 0.84 (d, J = 8Hz, 3H) , 1.15 (t, J = 8Hz, 3H), 1.30 (t, J = 8Hz, 3H), 1.31 (d, J = 7Hzi 3H), 1.45 (d, J = 7Hz, 3H), 1.47 (d, J = 7Hz, 3H), 2.07 (m, 1H), 2.25 (s, 3H), 2.30 (m, 2H, 2.46 (q apparent, J = 8 Hz, 2H), 3.48 (septet, J = 7 Hzi 1Η), 3.52 (m, 1Η), 3.75 (septet, J = 7 Hz, 1Η), 5,669 (s, 1Η), 6.20 (s, 1Η), 6.68 (d, J = 7Hz, 1Η), 7.01 (d, J = 7Hz, 1Η), 7, 02-7.40 (multiplets, 7Η), 7.45 (d, J = 7Hz, 1Η), 7.53 (apparent t, J = 7Hz, 1Η), 8.05 (apparent t, J = 7Hz, 1H).

(b) In an N2 atmosphere, a 1.27 g (1.55 mmol) sample of the tri-alkylated compound, [N- [2,6-bis (1-methylethyl) phenyl] -a- [2,4, 6-tri (ethyl) phenyl] -5- (carbazol-1-yl) -2- (N'-methyl) imidazol-2-yl) methanaminate (2-) -KN17KN2] tri (methyl) hafnium is stirred at 40 ° C. mL of toluene and heated for 17 hours at 100 ° C. The volatiles are removed under vacuum and the resulting solids are washed twice with 15 ml of depentan. After vacuum drying, 1.06 g of the dialkyl compound is obtained as an ivory solid (yield 81.5 percent).

1H NMR (500 MHz, 25 ° C, C6D6) δ 0.36 (d, J = 7Hz, 3H), 0.73 (d, J = 8Hz, 3H), 0.78 (s, 3H), 0.87 (t, J = 8Hz, 3H), 0.96 (s, 3H), 1.13 (t, J = 8Hz, 3H), 1.23 (d, J = 7Hz, 3H) 1.40 (d, J = 7Hz, 3H), 1.46 (d, J = 7Hz, 3H), 2.03 (m, 1H), 2.19 (m, 2H), 2.44 (apparent q, J = 8Hz, 2H), 2.48 (s, 3H), 2.93 (m, 1H), 3.37 (septet, J = 7Hz, 1H), 3.86 (septet, J = 7Hz, 1H), 6.18 (s, 1H), 6.44 (s, 1H), 6.72 (d, J = 2Hz, 1H), 6.87 (d, J = 2Hz , 1H), 7.12-7.22 (multiplets, 4H), 7.33 (m, 2H), 7.44 (td, J = 7.1 Hz, 1H), 7.61 (t, J = 8Hz, 1H), 8.07 (d, J = 8Hz, 1H), 8.12 (dd, J = 8.1Hz7 1H), 9.00 (dd, J = 7.1Hz7 1H).

Propylene homopolymerizations in batch reactor (Catalyst not supported)

Polymerizations are performed in a computer controlled, stirred, Lensized, 3.8-liter stainless steel autoclave batch reactor. The reactor bottom is prepared with a wide orifice deep discharge valve, which empties the reactor contents into a 6L stainless steel container. The container is vented to a 100L bleed tank, both the container and the tank bleed with nitrogen. . All chemicals used for polymerization and catalyst composition are passed through purification columns to remove any impurities. Propylene and solvents pass through 2 columns, the first containing alumina, the second containing a purifying reagent (obtainable from Englehardt Corporation). Nitrogen and hydrogen gases pass through a single column containing Q5 ™ reagent. The reactor is cooled to 50 ° C before loading. It is charged with 1400 g of mixed alkanes, hydrogen (using a 50 mL loading tank calibrated at differential pressure in a 0.4 MPa pressurized loading tank), followed by 600 g of propylene using a micromotion flowmeter. The reactor is then conducted to the desired temperature before addition of the catalyst composition.

The metal complex (catalyst) is used as a 0.2 mM solution in toluene. The tertiary component activator complexometallic and toluene solutions are handled in an inert glove box, mixed in a small vial, withdrawn into a syringe and transferred under pressure to the catalyst loading tank. This is followed by 3 toluene rinses of 5 mL each. The cocatalyst used is a long-chain stoichiometric alkyl ammonium borate of approximately equal methyl-di (octadecyl) ammonium tetrakis (pentafluorophenyl) borate (MDB) or an aromatic ammonium salt, 4-n-tetrakis (pentafluorophenyl) borate. butyl phenyl-Ν, Ν-di (hexyl) ammonium (PDB). The tertiary component used is tri (isopropyl) aluminum modified omethyl aluminoxane (MMAO-3α, obtainable from Akzo Nobel, Inc.) in a molar ratio (metal complex: cocatalyst: tertiary component) of 1: 1.2: 30. The loading tank is pressurized with N2 at 0.6 MPa above reactor pressure, and contents are rapidly blown into the reactor. Both reaction heat release and pressure drop are monitored from beginning to end of reaction time. . After 10 minutes of polymerization the stirrer is stopped, the reactor pressure is raised to 3.4 MPa with N2, and the bottom valve is opened to empty the reactor contents into the collection vessel. The contents are poured into trays and placed in a laboratory cover where the solvent is evaporated from day to day. The trays are then transferred to a vacuum oven where they are heated to 145 ° C vacuum to remove any remaining solvent. After cooling the trays to room temperature, the polymers are quantified and analyzed. The results are contained in Table 1.

Table 1

<table> table see original document page 66 </column> </row> <table>

Comparative, not an example of the invention

1- [N- (2,6-bis (1-methylethyl) phenyl] -a- [2- (1-methylethyl) phenyl] -6- (1,2-naphthalenediyl-K-C 2) -2-pyridinamethanaminate ( 2 -) - KN1iKN2] di (methyl) hafnium prepared according to US-A-2004/0220050

Catalyst Activation Profile Studies The thermal profiles of metallic complexes are compared by initiating polymerization under substantially diabetic conditions. In the test, 10 mL of polymerization grade 1-octenate is accurately added to a small 40 mL vial, a stir bar is added and the vial is placed in an insulated glove and placed on a magnetic stirrer. An amount of aluminoxane cocatalyst (ΜΑΟ obtainable from Albemarle, Corporation) is accurately added to the vial and then 0.2 µmol of the metal complex to be tested is added. The small vial is sealed with a top septum and a thermoelectric pair is pushed through the septum and below the surface of the 1-octenum. The temperature is recorded at 5 second intervals until at least the maximum temperature is reached. The time to maximum temperature (TMT) is a direct indication of the activation profile of the particular metal complex under the conditions tested. aluminoxane ratios for metal complex, 300/1, 150/1, 75/1 and 37.5 / 1. The results comparing the present dimethyl complex as the corresponding trimethyl complex are contained in Table 2, and demonstrate that the present invention complex has increased TMT as well as reduced heat release.

Table 2

<table> table see original document page 67 </column> </row> <table>

Comparative, not an example of the invention

1 [N- (2,6-bis (1-methylethyl) phenyl] -a- [2,4,6-tri (1-methylethyl) phenyl] -5- (2-ethyl benzofuran-3-yl) -benzamide 2- (N'-methyl) imidazol-2-yl) (2-) - KN1KN2] tri (methyl) hafnium.

Catalyst Support Preparation

A solution of MAO (methyl aluminoxane; AkzoNobel) in toluene is added to the precalcined silica of 25 μπι particle size (757, obtainable from Ineos, Inc.) Followed by isolation and drying as described in US patent application 2004 / 0220051 (A1). The calcination temperature is 200 ° C and the MAO percentage in the support after preparation is approximately 35 percent (6.0 μπιοί Al / g).

Propylene homopolymerizations in batch reactor (supported catalyst)

Polymerizations are performed in a computer controlled, agitated 3.8L stainless steel autoclave. Temperature control is maintained by heating or cooling an integrated reactor jacket with circulating water. The top of the reactor is unscrewed after registration in order to empty the contents after volatilization. All chemicals used for polymerization or catalyst preparation are passed through purification columns to remove any impurities. Propylene and 2-column passive solvents, the first containing alumina, the second containing a purifying reagent (Q5 ™ obtainable from Englehardt Corporation). Nitrogen and hydrogen gases pass through a single column containing the Q5 ™ reagent.

After fixing the top of the reactor to the bottom, the nitrogen purged reactor is simultaneously heated to 140 ° C and then cooled to approximately 30 ° C. The reactor is then charged with a 3-5 percent solution by weight of triethyl aluminum in isoctane and stirred for 45 minutes.

This cleaning solution is then poured into a recovery tank and the reactor is loaded with 1370 g of propylene. The desired amount of hydrogen, typically 2337 cm 3 (0 ° C; 0.1 MPa), is added using a Brooks flowmeter and the reactor is brought to 62 ° C. The catalyst is injected as a semi-fluid oil or light hydrocarbon slurry, and the injector is flushed with isoctan three times to ensure complete release. After injection, the reactor temperature is raised to 67 ° C for 5 minutes, or maintained at 67 ° C, by means of a large heat release cooling. After an operation time of 1 hour, the reactor is cooled to ambient temperature, vented, and then the upper part is removed and the contents are emptied. Polymer weights are measured after overnight drying or even constant in a vented smoke suction cup.

The semifluid catalyst slurry is prepared by premixing the desired amounts of a stock solution of the toluene metal complex (0.01 or 0.005M) and the catalyst support in 5 ml isoctane for 30 minutes providing a molar ratio of Al / Hf of 200 and 120.

All manipulations are performed in an inert atmosphere glove box. After preparation, the catalyst slurry is charged to the reactor injector of a small septum-capped vial using an integrated needle, then injected into the reactor. Duplicate series results are contained in Tables 3 and 4.

Table 3 (Al: Hf 200: 1)

<table> table see original document page 69 </column> </row> <table>

Comparative, not an example of the invention

1LN- [2,6-bis (1-methylethyl) phenyl] -a- [2,4,6-tri (1-methylethyl) phenyl] -5- (carbazol-1-yl) -2- (N ' (methyl) imidazol-2-yl) methanaminate (2-) -KN1KK2] tri (methyl) hafnium.

2 [N- [2,6-bis (1-methylethyl) phenyl] -a- [2- (1-methylethyl) phenyl] -6- (1,2-naphthalenediyl-κ-C2) -2-pyridine (2-) - kN1, KN2] di (methyl) hafnium methanaminate prepared according to U.S. 2004/0220050.

3 [N- (2,6-bis (1-methylethyl) phenyl] -a- [2,4,6-tri (ethyl) phenyl] -5- (carbazol-1-yl) -2- (N ' (methyl) imidazol-2-yl) methanaminate (2-) -KN1KN2] tri (methyl) hafnium.

4- [N- (2,6-bis (1-methylethyl) phenyl] -a- [2,4,6-tri (ethyl) phenyl] -5- (carbazol-1-yl-K-C2) -2 - (N'-methyl) imidazol-2-yl) methanaminate (2-) -KN1KN2] di (methyl) hafnium.Table 4 (Al: Hf 120: 1)

<table> table see original document page 70 </column> </row> <table>

Comparative, not an example of the invention

1CN- [2,6-bis (1-methylethyl) phenyl] -a- [2,4,6-tri (1-methylethyl) phenyl] -5- (carbazol-1-yl) -2- (N ' (methyl) imidazol-2-yl) methanaminate (2-) -KN1KN2] tri (methyl) hafnium.

2 [N- [2,6-bis (1-methylethyl) phenyl] -a- [2- (1-methylethyl) phenyl] -6- (1,2-naphthalenediyl-κ-C2) -2-pyridine (2-) - KN1fKN2] di (methyl) hafnium methanaminate prepared according to U.S. 2004/0220050.

3 [N- (2,6-bis (1-methylethyl) phenyl] -a- [2,4,6-tri (ethyl) phenyl] -5- (carbazol-1-yl) -2- (N ' (methyl) imidazol-2-yl) methanaminate (2-) - KN11KN2] tri (methyl) hafnium.

4- [N- (2,6-bis (1-methylethyl) phenyl] -a- [2,4,6-tri (ethyl) phenyl] -5- (carbazol-1-yl-K-C2) -2 - (N'-methyl) imidazol-2-yl) methanaminate (2-) -KN1KN2] di (methyl) hafnium.

Comparing the above results, it is observed that seating and improved catalytic efficiency when employed in a supported catalyst composition using orthometallized metal complexes, compared to the identical complex containing three alkyl- groups. In addition, an improved performance is also observed compared to orthophilized pyridyl ligand (HNP) -hafnium complexes.

Claims (15)

1. Metallic complex, characterized in that it corresponds to the formula: <formula> formula see original document page 71 </formula> in which each occurrence of X is independently an anionic ligand, or two groups X together form a diionic grouping. or a neutral diene; T is a grouped aromatic or aromatic group containing one or more rings, each occurrence of R1 independently being hydrogen, halogen, or a monovalent polyatomic anionic ligand, or two or more R1 groups thus forming a polyvalent fused ring system; each occurrence of R2 is independently hydrogen, halogen, or a monovalent polyatomic anionic ligand, or two or more R2 groups together forming a polyvalent fused ring system; R4 is hydrogen, alkyl, aryl, aralkyl, trihydrocarbylsilyl, or methyl trihydrocarbyl silyl of 1 to 20 carbons. Metal complex according to Claim 1, characterized in that T is a polycyclic fused ring aromatic group, R 4 is C 1-4 alkyl, and each occurrence of X is C 1-20 alkyl, cycloalkyl or aralkyl. Metal complex according to claim 1, characterized in that it corresponds to the formula: wherein each occurrence of R1 is independently a C3-12 alkyl group. wherein the carbon attached to the amphenyl is secondary or tertiary substituted, preferably each R 1 is isopropyl; each occurrence of R2 is independently hydrogen or a C1-12 alkyl group; R3 is hydrogen, halogen or R1; R4 is C1-4 alkyl; and X and T are previously defined for compounds of formula (I). Metal complex according to Claim 2, characterized in that it corresponds to the formula: <formula> formula see original document page 72 </formula> <formula> formula see original document page 73 </formula> where: The occurrence of R 1 is independently a C 3-12 alkyl group in which the carbon attached to the amphenyl is secondary or tertiary substituted; each occurrence of R2 is independently hydrogen or a C1-12 alkyl; R4 is methyl or isopropyl; R5 is hydrogen or C1-6 alkyl; R 6 is hydrogen, C 1-6 alkyl or cycloalkyl, or two adjacent R 6 groups together form a fused aromatic ring; T 'is oxygen, sulfur, or a C1-2 hydrocarbyl-substituted nitrogen or phosphorus group! T "is nitrogen or phosphorus; X is methyl or benzyl. Metal complex according to claim 1, characterized in that it corresponds to the formula: wherein each occurrence of R1 is independently isopropyl; each occurrence of R2 is independently hydrogen or a C1 -C2 alkyl group; R4 is C1-4 alkyl; R5 is hydrogen, C1-6 alkyl or cycloalkyl; Each occurrence of X is independently methyl or benzyl. Metal complex according to Claim 1, characterized in that it is selected from the group consisting of: [N- [2,6-bis (1-methylethyl) phenyl] -a- [2,4,6-tri (1-methylethyl) phenyl] -5- (2-ethyl benzofuran-3-yl-K-C4) -2- (N'-methyl) imidazol-2-yl) (2-) -KN1, KN2 ] di (methyl) hafnium, [N- [2,6-bis (1-methylethyl) phenyl] -a- [2,6-di (1-methylethyl) phenyl] -5- (2-ethyl benzofuran) 3-yl-K-C4) -2- (N'-methyl) imidazol-2-yl) methanaminate (2-) -KN1rKN2] di (methyl) hafnium, [N- [2,6-bis (1-methyl ethyl) phenyl] -a- [2,4,6-tri (1-methylethyl) phenyl] -5- (carbazol-1-yl-K-C2) -2- (N'-methyl) imidazol-2-one il) methanaminate (2 -) - KN1 fKN2] di (methyl) hafnium, [N- [2,6-bis (1-methyl ethyl) phenyl] -a- [2,4,6-tri (1-methyl ethyl) phenyl] -5- (2-ethyl benzofuran-3-yl-K-C4) -2- (N'-methyl) imidazol-2-yl) methanaminate (2-) -KN1iKN2] di (benzyl) hafnium, [Ν - [2,6-bis (1-methylethyl) phenyl] -a- [2,6-di (1-methylethyl) phenyl] -5- (2-ethyl benzofuran-3-yl-K-C4) - 2- (N'-methyl) imidazol-2-yl) (2-) -KN1KKN2] di (benzyl) hafnium, [N- [2,6-bis (1-methylethyl) 1) phenyl] -a- [2,4,6-tri (1-methylethyl) phenyl] -5- (carbazol-1-yl-K-C2) -2- (N'-methyl) imidazol-2-one yl) (2 -) - KN1iKN2] di (benzyl) hafnium, [N- [2,6-bis (1-methylethyl) phenyl] -a- [2,6-di (1-methylethyl) phenyl] -5- (carbazol-1-yl-K-C2) -2- (N'-methyl) imidazol-2-yl) (2-) -KN1KN2] di (benzyl) hafnium or a mixture thereof. A catalyst composition, suitable for use by coordinated olefin polymerization, comprising a complexometallic as defined by any one of claims 1-6 and an activating cocatalyst. Catalyst composition according to claim 7, characterized in that the activating cocatalyst is a Lewis acid. Catalyst composition according to Claim 8, characterized in that the Lewis acid is methylaluminoxane or modified methyl aluminoxane. Catalyst composition according to claim 7, characterized in that it further comprises a support. Catalyst composition according to Claim 10, characterized in that the carrier is a particulate compound selected from oxides, sulphides, nitrides or carbides of a Group 13 or 14 metal or metalloid. Catalyst composition according to claim 11, characterized in that the silicon-containing methyl aluminoxane supports having the complexometallic deposited on the surface thereof. 13. Addition polymerization process, characterized in that it comprises contacting one or more olefin monomers under polymerization conditions with a catalyst composition as defined by claim 7. Process according to Claim 13, characterized in that it is a gas phase polymerization process. Process according to Claim 13, characterized in that it is a semi-fluid paste polymerization process.