Polimerization process

invention field

The This invention relates to a process for olefin polymerization. In general, the invention relates to polymerization catalyst compositions and to methods for introducing the catalyst compositions in a polymerization reactor. More specifically, the method combines a catalyst component slurry with a catalyst component solution to a finished catalyst composition for the introduction to form a polymerization reactor. The invention relates to methods for preparing the catalyst component slurries, the catalyst component solutions and the catalyst compositions, to methods of control the properties of polymer products utilizing the catalyst compositions and to polymers that are formed by.

Background of the Invention

progress in polymerization and catalysis have resulted in it is capable of many new polymers having improved physical produce and chemical properties, which for many quality products and applications are useful. With the development of new catalysts has been the choice of types of polymerization (Solvents, slurry, High pressure or gas phase polymerization) for the manufacture of a particular Polymers very extended. The advances have in the polymerisation efficient, highly productive and economically enhanced processes provided. Especially illustrative of these advances is the Development of technology, wherein one metallocene catalyst systems with spatially sophisticated ligands and other improved metallocene-type Catalyst systems.

Around these systems in industrial slurry or gas phase process to use, it is useful when the catalyst compound on a support material or carrier such as z. B. immobilized silica or alumina. The Usage of heterogeneous catalysts or supported catalysts increases process performance, by ensuring that the polymeric particles formed achieve a shape and density which reactor operability, the improve and manageability. However, metallocene catalysts show with spatially demanding ligand and metallocene-type catalysts typically lower activity, when used together with a carrier present than when no carrier or be used in a homogeneous form. This "carrier effect" makes the commercialization of this promising Catalyst systems difficult.

The <patcit><text>US Patent Nos. 5,317,036</text></patcit> and <patcit><text>5,693,727</text></patcit> and the European publication <patcit><text>EP-A-0593083</text></patcit> and PCT Publication <patcit><text>WO 97/46599</text></patcit> describe all different methods and techniques for the introduction of liquid Unsupported catalysts in a polymerization reactor.

<patcit><text>US Pat. No. 6,069,213</text></patcit> disclosed contacting a metallocene catalyst with the carrier, and a metallocene catalyst without support in the polymerization of olefins, European publication <patcit><text>EP 0965601 A</text></patcit> disclosed contacting a solid Ziegler-Natta catalyst with a liquid Catalyst in toluene or Kaydol activated with methylalumoxane or modified methyl alumoxane, and <patcit><text>Chinese Patent Application No. 97116451.7</text></patcit> discloses contacting a metallocene without support with a methylalumoxane with carrier. None of these documents discloses a catalyst composition, which is prepared by a catalyst component slurry continuously is contacted with a catalyst component solution, and then introducing these Composition in an ongoing polymerization.

While these Methods have been described in the prior art, there is a need to Carrier effect for compositions of metallocene polymerization catalyst with spatially demanding ligand and metallocene-like polymerization reducing, for an improved method for introducing catalyst compositions and especially for introducing mixed catalyst compositions in polymerization and method for controlling the Properties of polymer products utilizing such catalyst compositions.

Summary of the Invention

The Invention generally provides polymerization catalyst compositions and procedures &lt;?page 3?&gt;for introducing the catalyst compositions in a polymerization prepared. In particular, in the Process a catalyst component-containing slurry and brought together a catalyst component-containing solution to the final catalyst composition for introduction into the polymerization reactor to form. The invention is also directed to methods for the preparation of the catalyst component slurry, the catalyst component solution and the catalyst compositions on procedures for controlling the properties of polymer products using the catalyst compositions and directed to polymers formed therefrom.

According to a Aspect, the invention provides a method for olefin polymerization comprising: <ul><li>(A) continuously contacting a catalyst component slurry with a catalyst component solution, to form a catalyst composition wherein the catalyst component solution a C₅- To C₃₀Alkane diluent and at least one catalyst compound; and wherein the Catalyst component slurry mineral oil or silicone oil, a carrier, an activating agent and an element of Group 15 containing includes catalyst compound containing a metal M with a metal atom Group 4, 5 or 6 contains;</li><li>(B) introducing of the catalyst composition and one or more olefin (s) in an ongoing polymerization reactor; and</li><li>(C) isolating a polymer.</li></ul>

Brief Description of Drawings

<figref idrefs="S127">1</figref> illustrated an embodiment a system configuration for use of the invention.

<figref idrefs="S128">2</figref> illustrated catalyst feed configuration for the application of the comparative example . 2

<figref idrefs="S129">3</figref> illustrated The catalyst feed configuration for the application of Comparative example . 3

<figref idrefs="S130">4</figref> illustrated The catalyst feed configuration for the application of Comparative example . 4

<figref idrefs="S131">5</figref> is a typical SEC curve of a polymer of the invention.

<figref idrefs="S132">6</figref> illustrated the catalyst feed configuration used for Examples 11-14 has been.

<figref idrefs="S133">7</figref> is a diagram on particle size flow into the collection chamber effects depending shows the time.

Detailed description the invention

I. Introduction

The Components of the catalyst composition of the invention include catalyst compounds, Activator compounds and support materials. The catalyst components be in a slurry and a solution used, the slurry and the solution are brought together and then introduced into a polymerization reactor.

II. Catalyst compounds

The Catalyst compounds in the catalyst compositions of the invention can be used conclude A: Group 15 containing metal compounds; Metallocene compounds with spatially sophisticated ligands; Phenoxide catalyst compounds; additionally up fund border Catalyst compounds; and transition metal catalysts the conventional Type.

A. Group 15 containing metal catalyst compound

The The catalyst composition of the invention, one or more an element of Group 15-containing metal catalyst compound (s) contain. The a Group 15 element-containing compound closes usually a metal atom of Group 3 to 14, preferably a Metal atom of Group 3 to 7, more preferably a metal atom of Group 4 to 6, and even more preferably a metal atom of the group &lt;?page 4?&gt;4 one which at least at least one leaving group and also at two atoms of Group 15 is bound, at least one of them by another group also attached to an atom of group 15 or 16 is bound.

According to a embodiment is at least one of the atoms of the group 15 by means of another group, which C a₁-C₂₀hydrocarbon group, a hetero atom-containing group, silicon, germanium, tin, lead may be or phosphorus, also on an atom of group 15 or 16 bound, the atom of Group 15 or 16 and nothing or Hydrogen, a group 14 atom containing group, halogen containing or a heteroatom Group can be attached, and each of the two atoms of the group 15 is also bound to a cyclic group and optionally hydrogen, Halogen, a heteroatom or a hydrocarbon group or a Hetero atom-containing group can be attached.

According to a another embodiment can containing an element of Group 15 metal compound be of the present invention represented by the formulas: <img img-content="cf" img-format="tif" he="115" wi="58" file="00060001.tif" />wherein M a transition metal Group 3 to 12 or a main group metal of group 13 or 14 is preferably a metal of Group 4, 5 or 6 and more preferably a Group 4 metal, and most preferably zirconium, Titanium or hafnium, each X is independently a leaving group, preferably an anionic leaving group, and more preferably hydrogen, Hydrocarbon group, a hetero atom or a halogen and at most preferably an alkyl. y is 0 or 1 (when y is 0, is the group L 'is not exists), n is the oxidation state of M, preferably +3, +4, Or +5, preferably +4 more, m is the formal charge of the YZL- or YZL' ligands is preferably 0, -1, -2 or -3, and more preferably -2, L an element of group 15 or 16 is, preferably nitrogen, L 'is an element of Group 15 or 16 or an element of Group 14 containing Group, preferably carbon, silicon or germanium, Y a group 15 element, preferably nitrogen or phosphorus, and more preferably nitrogen, Z is a group 15 element is, preferably nitrogen or phosphorus, and more preferably nitrogen, R¹ and R² independently a C₁-C₂₀hydrocarbon group, a heteroatom containing group having up to 20 carbon atoms, Silicon, germanium, tin, lead, or phosphorus, preferably a &lt;?page 5?&gt;C₂-C₂₀Alkyl, aryl or Aralkyl group, more preferably a linear, branched or cyclic C₂-C₂₀alkyl, most preferably a C₂-C₆Hydrocarbon group. R¹ and R² can also be interconnected. R³ not exists or a hydrocarbon group, hydrogen, halogen, a hetero atom-containing group, preferably a linear, cyclic, is or branched alkyl group having 1 to 20 carbon atoms, more preferably, R³ No, hydrogen or an alkyl group, and most preferably hydrogen R⁴ and R⁵ independently a Alkyl group, an aryl group, a substituted aryl group, an cyclic alkyl group, a substituted cyclic alkyl group, a cyclic aralkyl group, a substituted cyclic aralkyl or a multiple ring system, preferably having up to 20 carbon atoms, more preferably between 3 and 10 carbon atoms, are, and more preferably a C₁-C₂₀hydrocarbon group, a C₁-C₂₀aryl or a C₁-C₂₀aralkyl or a hetero atom-containing group, z. B. PR₃. wherein R is an alkyl group, R¹ and R² can be joined together and / or R⁴ and R⁵ can be joined together, R⁶ and R⁷ independently from each other are absent, hydrogen, an alkyl group, halogen, Hetero atom or a hydrocarbon group, preferably a linear, cyclic or branched alkyl group having 1 to 20 carbon atoms mean, and are preferably absent more, and R * is not exists or is hydrogen, a group 14 atom containing Group, halogen, or a heteroatom containing group.

By "formal Charge of the YZL- or YZL' ligand "is the charge of the whole ligand without the metal and the leaving groups X meant.

With "R¹ and R² can also be connected "is meant that R¹ and R² directly bonded or bonded by other groups together could be. With "R⁴ and R⁵ can also be connected "is meant that R⁴ and R⁵ directly bonded or bonded by other groups together could be.

A Alkyl group may be linear, branched alkyl radicals, alkenyl radicals, alkynyl radicals, Cycloalkyl, aryl, acyl, aroyl, alkoxy, Aryloxy, alkylthio, dialkylamino, alkoxycarbonyl, aryloxycarbonyl, Carbomoylreste, alkyl or Dialkylcarbamoylreste, acyloxy, Acylamino, Aroylaminoreste, straight-chain, branched or cyclic Alkylene, or combinations thereof. An aralkyl group is a substituted aryl group.

According to a preferred embodiment, are R⁴ and R⁵ independently for a Group which is represented by the following formula: <img img-content="cf" img-format="tif" he="56" wi="69" file="00090001.tif" /> formula 1 wherein R^8th to R¹² are each independently hydrogen, a C₁-C₄₀Alkyl group, a Halide, a heteroatom, a heteroatom containing group containing mean up to 40 carbon atoms, preferably a C₁-C₂₀ linear or branched alkyl group, preferably a methyl, ethyl, propyl or butyl group, any two R groups may form a cyclic group and / or form a heterocyclic group. The cyclic groups can aromatic. In a preferred embodiment, R⁹. R¹⁰ and R¹² independently a methyl, ethyl, propyl or butyl group (including all BE isomers), in a&lt;?page 6?&gt;preferred embodiment, R⁹. R¹⁰ and R¹² methyl groups and R^8th and R¹¹ are Hydrogen.

In a particularly preferred embodiment R⁴ and R⁵ both a group represented by the following formula group: <img img-content="cf" img-format="tif" he="48" wi="70" file="00090002.tif" /> formula 2

In this embodiment M is a Group 4 metal, preferably zirconium, titanium or Hafnium, and even more preferably zirconium; each of L, Y and Z is nitrogen; each of R¹ and R² is -CH₂-CH₂-; R³ is hydrogen; and R⁶ and R⁷ are unavailable.

In a particularly preferred embodiment the metal compound containing a Group 15 element by Compound 1 shown below: <img img-content="cf" img-format="tif" he="103" wi="56" file="00100001.tif" />

In Compound 1 represents Ph is phenyl.

The an element of Group 15 containing metal compounds, in which the catalyst composition of the invention can be used be prepared by known methods in the art such. B. those described in <patcit><text>EP 0 893 454 A1</text></patcit>. <patcit><text>US Pat. No. 5,889,128</text></patcit> and in <patcit><text>US Patent No. 5,889,128</text></patcit> cited references are disclosed. US Application Serial No. 09 / 312.878, filed on 17 May 1999, discloses a gas or Suspensionsphasenpolymerisationsverfahren using a Bisamidkatalysators with carrier.

&lt;?page 7?&gt;

A preferred direct synthesis of these compounds comprises reacting the neutral ligand (see, for example YZL or YZL 'of Formula I or II) with MⁿX_n (M is a metal the group 3-14, n is the oxidation state of M, each X is an anionic group such. as halide), in a non-coordinating or weakly coordinating solvent, such. as ether, toluene, xylene, benzene, methylene chloride and / or hexane, or another solvent having a boiling point above 60 ° C, at 20 to 150 ° C (preferably 20 to 100 ° C), preferably for 24 h or more, then treating the mixture with an excess (Such as. For example, 4 or more equivalents) an alkylating agent such. as methylmagnesium bromide in ether. The magnesium salts are removed by filtration and the metal complex is isolated by standard procedures.

In one embodiment the containing an element of Group 15 metal compound prepared by a method comprising reacting a neutral Ligands (see for example YZL or YZL 'of Formula I or II) with a by the formula MⁿX_n Compound represented (wherein M is a metal Group 3 to 14, n is the oxidation state of M, each X is an anionic leaving group) in a non-coordinating or weakly coordinating solvent at 20 ° C or above, preferably at 20 to 100 ° C, then treating the mixture with an excess of alkylating agent, then recovering the metal complex. In a preferred embodiment has the solvent a boiling point above 60 ° C, such as. for example, toluene, xylene, benzene, and / or hexane. In another embodiment the solvent comprises ether and / or methylene chloride, both of which are preferred.

For further Metal compounds information about an element of Group 15 containing see Mitsui Chemicals, Inc. in <patcit><text>EP 0893454 A1</text></patcit>Which combines Übergangsmetallamide disclosed with activating agents for the polymerization of olefins.

In one embodiment allowed to which containing an element of Group 15 metal compound age, before it is used in a polymerization. In at least one case has been found that such a catalyst compound (Aged at least 48 h) are better behaved than a fresh prepared catalyst compound.

B. metallocene compounds with spatially sophisticated ligands

The The catalyst composition of the invention, one or more Metallocene compounds with spatially demanding ligand (also referred to herein as metallocenes) contain.

in the include general Metallocene compounds with spatially demanding ligand half and full sandwich compounds one in which one or more spatially demanding ligands bonded to at least one metal atom / are. Typical metallocene compounds with spatially demanding ligands are generally described so as to one or more spatial contain sophisticated ligands and one or more leaving group (s) which is bonded to at least one metal atom / are.

The spatial demanding ligands are generally represented by a or more open / n, acyclic / n or condensed / n ring / s or Ring systems or a combination thereof. This spatially demanding ligands, Preferably the rings or ring systems are typically composed of atoms selected are made up of atoms of groups 13-16 of the Periodic Table, preferably selected atoms from the group consisting of carbon, nitrogen, oxygen, Silicon, sulfur, phosphorous, germanium, boron and aluminum, or a combination thereof. Most preferred is / are of the ring / Rings or / the ring system (s) composed of carbon atoms such. as, but not limited on cyclopentadienyl or cyclopentadienyl-type ligand structures or other similar acting ligand structures such. B. pentadiene, a cyclooctatetraendiyl or Imidligand. The metal atom is preferably selected from Groups 3-15 and the lanthanide or actinide of the periodic table. Preferably the metal is a transition metal groups of 4-12, more preferably Groups 4, 5 and 6, and at the Most preferably, the transition metal is from the group. 4

According to a embodiment closes the catalyst composition of the invention, one or more Metallocene catalyst compounds with spatially demanding ligands a which are represented by the formula: <st32:che xmlns:st32="http://lighthouseip.com/">L^AL^BMQ_n (III)</st32:che>&lt;?page 8?&gt;wherein M is a metal atom of the periodic table and a metal of Group 3-12 may be or is of the lanthanides or actinides of the periodic table, preferably M is a transition metal Group 4, 5 or 6, M is more preferably a transition metal group 4, and more preferably M is zirconium, hafnium or titanium. The spatially demanding ligand, L^A and L^B, Are open, acyclic or fused Rings or ring systems and any additional Ligand system, including unsubstituted or substituted cyclopentadienyl or Cyclopentadienyl-type ligands, heteroatom substituted and / or Heteroatom containing cyclopentadienyl-type ligands. Not restrictive Examples of spatially sophisticated include ligands Cyclopentadienyl Cyclopentaphenathrenylliganden, indenyl, Benzindenyl, fluorenyl, octahydrofluorenyl, Cyclooctatetraendiylliganden, Cyclopentacyclododecenliganden, Azenylliganden, Azulenliganden, pentalene, Phosphoylliganden, Phospinimin (<patcit><text>WO 99/40125</text></patcit>) Pyrrolylliganden, Pyrozolylliganden, carbazolyl, Bora benzene ligands and the like, including hydrogenated forms thereof, z. B. tetrahydroindenyl, a. According to a embodiment can L^A and L^B any be other ligand structure which is the π-bond to M in the position. In yet another embodiment, is the atomic weight (MW) of L^A or L^B more than 60 amu, preferably greater than 65 amu In another execution form can L^A and L^B one or more Heteroatoms include, for. Example, nitrogen, silicon, boron, germanium, Sulfur and phosphorous, in combination with carbon atoms to an open, acyclic, or preferably a / s condensed / s forming ring or ring system, z. B. a heterocyclopentadienyl ancillary ligands. Other spatially demanding ligands L^A and L^B conclude , but are not limited spatially demanding amides, phosphides, alkoxides, aryloxides, imides, Carbolide, Borolide, porphyrins, phthalocyanines, Corrine and other Polyazomakrocyclen. independently , each L^A and L^B the same or a different kind of spatially demanding ligands be bound to M. According to a embodiment of formula III is either L^A or L^B available.

Independently each L^A and L^B unsubstituted or be substituted with a combination of substituent groups R. Non-limiting examples of substituent groups R include one or more from the group selected from hydrogen, or linear, branched alkyl or alkenyl, alkynyl, cycloalkyl or aryl radicals, acyl radicals, aroyl radicals, alkoxy radicals, aryloxy radicals, Alkylthio, dialkylamino, alkoxycarbonyl, aryloxycarbonyl, Carbomoylreste, alkyl or Dialkylcarbamoylreste, acyloxy, Acylamino, Aroylaminoreste, geradketttige, branched or cyclic alkylene groups or combinations thereof. In a preferred embodiment have substituent groups R up to 50 non-hydrogen atoms, preferably 1 to 30 carbon atoms, which may also be substituted by halogens or heteroatoms or the like may be substituted. Non-limiting examples close of alkyl substituents R Methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, Benzyl or phenyl groups and the like, including all their isomers, z. B. tertiary butyl, Isopropyl, and the like. More carbon hydrogen radicals conclude Fluoromethyl, fluoroethyl, difluoroethyl, iodopropyl, bromohexyl, chlorobenzyl and hydrocarbon-substituted organometalloid including trimethylsilyl, Trimethylgermyl, methyldiethylsilyl and the like; and halocarbyl-substituted organometalloid including Tris (trifluoromethyl) silyl, methyl-bis (difluoromethyl) silyl, and Brommethyldimethylgermyl like; and disubstituted boron radicals including dimethylboron z. B .; and disubstituted pnictogen radicals including dimethylamine, Dimethylphosphine, diphenylamine, methylphenylphosphine, chalcogen including Methoxy, ethoxy, propoxy, phenoxy, methylsulfide and ethylsulfide, on. Non-hydrogen substituents R close the atoms carbon, silicon, boron, aluminum, nitrogen, phosphorous, Oxygen, tin, sulfur, germanium and the like, including olefins such. as, but not limited on olefinically unsaturated Substituents including vinyl-terminated Ligands, for. Example, but-3-enyl, prop-2-enyl, hex-5-enyl and the like. Also, at least two R groups, preferably two adjacent R groups connected to selected a ring structure having 3-30 atoms selected from Carbon, nitrogen, oxygen, phosphorus, silicon, germanium, to form aluminum, boron, and a combination thereof. can also a substituent R as 1-butanyl a carbon sigma bond form to the metal M.

It can Other ligands may be bonded to the metal M, such. as least a leaving group Q. In one embodiment, Q is a monoanionic labile ligand having a sigma-bond to M. Depending on the oxidation state of the metal, the value for n is 0.1 or 2 such that Formula III above a neutral metallocene catalyst compound with spatially is demanding ligands.

Not restrictive Examples of Q ligands weak bases such as amines, phosphines, ethers, carboxylates, dienes, Hydrocarbon radicals with 1-20 carbon atoms, hydrides or Halogens and the like or a combination thereof. In a another embodiment forming two or more Q part of a fused ring or ring system. Other examples of Q ligands include the substituents for R a, as described above and include cyclobutyl, cyclohexyl, Heptyl, tolyl, Triflu&lt;?page 9?&gt;ormethyl, tetramethylene, pentamethylene, methylidene, Methyloxy, ethyloxy, propoxy, phenoxy, bis (N-methylanilide), dimethylamide, Dimethylphosphidreste and the like.

In a further embodiment may comprise a catalyst composition of the invention or more Metallocene catalyst compound / s with spatially demanding ligands contain, where L^A and L^B the Formula III by at least one bridging group A, as represented by formula represented IV, are bridged together. <st32:che xmlns:st32="http://lighthouseip.com/">L^AAL^BMQ_n (IV)</st32:che>

The Compounds of formula IV are known as bridged metallocene catalyst compounds with spatial demanding ligands. L^A, L^B. M, Q and n are as defined above. Non-limiting examples of bridging group A close bridge groups containing at least one atom of group 13-16, a, often referred to as a divalent unit such. as, but not limited to at least one of carbon, oxygen, nitrogen, silicon, Aluminum, boron, germanium and tin atom or a combination from that. preferably contains the bridging group A is a carbon, silicon or Germanium atom, most preferably A contains at least one silicon atom or at least one carbon atom. The bridging group A may also substituent R contain as defined above including halogens and iron. Nonlimiting Examples of the bridging group A can by R '₂C, R '₂Si, R '₂SiR '₂Si, R '₂Ge, R'P be shown, where R 'is independently a Group which hydride, hydrocarbon, substituted hydrocarbon, Halohydrocarbon, substituted halocarbon, Hydrocarbon-substituted organometalloid, halogenated hydrocarbon-substituted Oganometalloid, disubstituted boron, disubstituted pnictogen, substituted chalcogen, or halogen, or wherein two or more R 'connected could be, to form a ring or ring system. In one embodiment, have bridged Metallocene catalyst compounds of formula IV with spatially sophisticated ligands two or more bridging groups A (<patcit><text>EP 664 301 B1</text></patcit>).

In a further embodiment the metallocene catalyst compounds with spatially sophisticated Ligands are those wherein the R substituent the space demanding ligand L^A and L^B of formula III and IV with the same or a different number of substituents on each of the spatially challenging Ligands are substituted. In a further embodiment are spatially demanding ligand L^A and L^B of the formulas III and IV different each other.

More Metallocene catalyst compounds with spatially demanding ligands and catalyst systems useful in the invention include those one which in the <patcit><text>US Patent Nos. 5,064,802</text></patcit>. <patcit><text>5,145,819</text></patcit>. <patcit><text>5,149,819</text></patcit>. <patcit><text>5,243,001</text></patcit>. <patcit><text>5,239,022</text></patcit>. <patcit><text>5,276,208</text></patcit>. <patcit><text>5,296,434</text></patcit>. <patcit><text>5,321,106</text></patcit>. <patcit><text>5,329,031</text></patcit>. <patcit><text>5,304,614</text></patcit>. <patcit><text>5,677,401</text></patcit>. <patcit><text>5,723,398</text></patcit>. <patcit><text>5,753,578</text></patcit>. <patcit><text>5,854,363</text></patcit>. <patcit><text>5,856,547</text></patcit>. <patcit><text>5,858,903</text></patcit>. <patcit><text>5,859,158</text></patcit>. <patcit><text>5,900,517</text></patcit> and <patcit><text>5,939,503</text></patcit> and PCT publications <patcit><text>WO 93/08221</text></patcit>. <patcit><text>WO 93/08199</text></patcit>. <patcit><text>WO 95/07140</text></patcit>. <patcit><text>WO 98/11144</text></patcit>. <patcit><text>WO 98/41530</text></patcit>. <patcit><text>WO 98/41529</text></patcit>. <patcit><text>WO 98/46650</text></patcit>. <patcit><text>WO 99/02540</text></patcit> and <patcit><text>WO 99/14221</text></patcit> and European publications <patcit><text>EP-A-0578838</text></patcit>. <patcit><text>EP-A-0638595</text></patcit>. <patcit><text>EP-B-0513380</text></patcit>. <patcit><text>EP-A1-0 816 372</text></patcit>. <patcit><text>EP-A2-0 839 834</text></patcit>. <patcit><text>EP-B1-0 632 819</text></patcit>. <patcit><text>EP-B1-0 748 821</text></patcit> and <patcit><text>EP-B1-0 757 996</text></patcit> described are.

In a further embodiment can The catalyst compositions of the invention metallocene compounds with bridged heteroatom spatially and with a Include sophisticated ligands. These types of catalysts and catalyst systems are, for. example, in PCT publications <patcit><text>WO 92/00333</text></patcit>. <patcit><text>WO 94/07928</text></patcit>. <patcit><text>WO 91/04257</text></patcit>. <patcit><text>WO 94/03506</text></patcit>. <patcit><text>WO 96/00244</text></patcit>. <patcit><text>WO 97/15602</text></patcit> and <patcit><text>WO 99/20637</text></patcit> and the <patcit><text>U.S. Patents No. 5,057,475</text></patcit>. <patcit><text>5,096,867</text></patcit>. <patcit><text>5,055,438</text></patcit>. <patcit><text>5,198,401</text></patcit>. <patcit><text>5,227,440</text></patcit> and <patcit><text>5,264,405</text></patcit> and European Publication <patcit><text>EP-A 0420436</text></patcit> described.

In a further embodiment closes the catalyst composition of the invention, one or more Metallocene catalyst compounds with spatially demanding ligands a which are represented by the formula V: <st32:che xmlns:st32="http://lighthouseip.com/">L^CAJMQ_n (V)</st32:che>wherein M a metal of group 3-16, or a metal is selected from the group of actinides and lanthanides of the Periodic Table, preferably M is a transition metal the group 4-12 and more preferably M is a transition metal of Group 4, M 5 or 6, and most preferably a transition metal of Group 4 in any oxidation state, especially titanium; L^C is a substituted or unsubstituted sterically demanding ligand that is bound to M; J is bonded to M; A is at J and L^C bound; J&lt;?page 10?&gt;is an additional Heteroatom ligand; and A is a bridging group; Q is a monovalent anionic ligand; and n is an integer 0, 1 or 2. In formula V top form L^C, A and J form a fused Ring system. In one embodiment, is L^C of formula V as defined above for L^A defined. A, M and Q are of the formula V as defined above in formula III.

In Formula V J is a heteroatom containing ligand in which J is an element Group 15 with a coordination number 3 or an element of Group 16 of the periodic table with a coordination number 2 is. Preferably contains J is a nitrogen, phosphorus, oxygen or sulfur atom, wherein Nitrogen being most preferred.

According to a embodiment the invention, the metallocene catalyst compounds with spatially sophisticated Ligand complexes with heterocyclic ligands, wherein the spatially demanding ligands, the rings or ring systems, one or more hetero atoms or a Include combination thereof. Nonlimiting Examples of hetero atoms include an element of group 13-16 a, preferably nitrogen, boron, sulfur, oxygen, aluminum, Silicon, phosphorus or tin. Examples of these catalyst compounds with spatially demanding ligands are described in <patcit><text>WO 96/33202</text></patcit>. <patcit><text>WO 96/34021</text></patcit>. <patcit><text>WO 97/17379</text></patcit> and <patcit><text>WO 98/22486</text></patcit> and <patcit><text>EP-A1-0 874 005</text></patcit> and <patcit><text>US Pat. No. 5,637,660</text></patcit>. <patcit><text>5,539,124</text></patcit>. <patcit><text>5,554,775</text></patcit>. <patcit><text>5,756,611</text></patcit>. <patcit><text>5,233,049</text></patcit>. <patcit><text>5,744,417</text></patcit> and <patcit><text>5,856,258</text></patcit>,

In one embodiment the metallocene catalyst compounds with spatially demanding ligands the complexes, the transition metal catalysts are known which on bidentate Ligands based containing pyridine or quinoline moieties, such as those in U.S. Application Ser. No. 09 / 103.620, filed June 23, 1998, are. In a further embodiment the metallocene catalyst compounds with spatially sophisticated Ligands such as described in PCT publications <patcit><text>WO 99/01481</text></patcit> and <patcit><text>WO 98/42664</text></patcit> are described.

In a further embodiment the metallocene catalyst compound with spatially demanding ligands a complex of a metal, preferably a transition metal, a spatially demanding ligand, preferably a substituted or unsubstituted pigebundenen ligands and one or more Heteroallyleinheiten, such as those in the <patcit><text>U.S. Patents No. 5,527,752</text></patcit> and <patcit><text>5,747,406</text></patcit> and <patcit><text>EP-B1-0 735 057</text></patcit> described are.

In a further embodiment closes the catalyst composition of the invention, one or more Metallocene catalyst compounds with spatially demanding ligands a, which is represented by formula VI: <st32:che xmlns:st32="http://lighthouseip.com/">L^DMQ₂(YZ) X_n (VI)</st32:che>wherein M is a metal of group 3-16, preferably a transition metal the group 4-12, and most preferably a transition metal of Group 4, 5 or 6; L^D is a spatially demanding ligand, is bound to M; each Q is independently bonded to M and Q₂(YZ) forms a ligand, preferably a singly charged multidentate Ligands; or Q is a univalent anionic ligand also is bound to M; X is a univalent anionic group when n is 2, or X is a divalent anionic group when n is 1 is; n is 1 or the second

In Formula VI, L and M are as defined above for Formula III. Q is above for formula III defined, preferably Q is selected from the group consisting of -O-, -NR-, -CR₂- And -S-; Y is either C or S; Z is selected from the group consisting of -OR, -NR₂. -CR₃, -SR, -SiR₃. -PR₂, -H, And substituted or unsubstituted Aryl groups, with the proviso that when Q is -NR- selected Z is selected from the group consisting of -OR, -NR₂. -SR, -SiR₃, -PR₂ and -H; R is selected from a group containing carbon, silicon, nitrogen, oxygen and / or phosphorus, preferably where R is a hydrocarbon group containing from 1 to 20 carbon atoms, more preferably an alkyl, Cycloalkyl or an aryl group; n is an integer from 1 to 4, preferably 1 or 2; X is a univalent anionic group when n is 2 or X is a divalent anionic group when n is 1; preferably X is a carbamate, carboxylate or other Heteroallyleinheit described, by combining Q, Y and Z.

In a further embodiment the metallocene catalyst compounds with spatially sophisticated Ligands such as described in PCT publications <patcit><text>WO 99/01481</text></patcit> and <patcit><text>WO 98/42664</text></patcit> are described.

&lt;?page 11?&gt;

Useful Metallocene catalyst systems of Group 6 with spatially demanding ligands are in <patcit><text>US Pat. No. 5,942,462</text></patcit> described.

Still more useful include catalysts polynuclear metallocene catalysts, as in <patcit><text>WO 99/20665</text></patcit> and <patcit><text>6,010,794</text></patcit> described, and transition metal Metaaracyclusstrukturen, described in <patcit><text>EP 0 969 101 A2</text></patcit>, on. Other metallocene catalysts include those as in <patcit><text>EP 0950667 A1</text></patcit> described, double cross-linked metallocene catalysts (<patcit><text>EP 0970074 A1</text></patcit>) linked metallocenes (<patcit><text>EP 970 963 A2</text></patcit>) And Sulfonylkatalysatoren as in <patcit><text>US Pat. No. 6,008,394</text></patcit> described are a.

It is also contemplated that in one embodiment the metallocene catalysts, with spatial demanding ligand, as described above, their structural isomers or optical isomers or enantiomers (meso and racemic Isomers. See, for example, <patcit><text>US Patent No. 5,852,143</text></patcit>Include), and mixtures thereof.

It it is further provided that each of the metallocene catalyst compounds with spatially sophisticated ligands as described above, at least one fluoride or fluorine-containing leaving group as described in US Application Serial Ser. No. 09 / 191.916, filed on 13 November 1998, have.

Illustrative and not beschänkende Examples of the metallocene catalyst compounds with spatially Close sophisticated ligands a bis (cyclopentadienyl) titanium, bis (cyclopentadienyl) titanium, Bis (cyclopentadienyl) zirconium, bis (cyclopentadienyl) zirkoniumdiphenyl, Bis (cyclopentadienyl) hafnium or diphenyl, bis (cyclopentadienyl) titandineopentyl, Bis (cyclopentadienyl) zirkoniumdineopentyl, bis (cyclopentadienyl) titanium, Bis (cyclopentadienyl) zirconium dibenzyl, bis (cylcopentadienyl) vanadiumdimethyl, Bis (cyclopentadienyl) titanium methyl chloride, bis (cyclopentadienyl) titanethylchlorid, bis (cyclopentadienyl) titanphenylchlorid, Bis (cyclopentadienyl) zirkoniummethylchlorid, bis (cyclopentadienyl) zirkoniumethylchlorid, Bis (cyclopentadienyl) zirkoniumphenylchlorid, bis (cyclopentadienyl) titanmethylbromid, Cyclopentadienyltitantrimethyl, Cyclopentadienylzirkoniumtriphenyl, Cyclopentadienylzirkoniumtrineopentyl, Cyclopentadienylzirkoniumtrimethyl, Cyclopentadienylhafniumtriphenyl, Cyclopentadienylhafniumtrineopentyl, Cyclopentadienylhafniumtrimethyl, pentamethylcyclopentadienyltitanium trichloride, Pentaethylcyclopentadienyltitantrichlorid, bis (indenyl) titanium or dichloride, bis (methylcyclopentadienyl) titanium or dihalide, Bis (1,2-dimethylcyclopentadienyl) titanium diphenyl or dichloride, Bis (1,2-diethylcyclopentadienyl) titanium diphenyl or dichloride, bis (pentamethylcyclopentadienyl) titanium or dichloride, or Dimethylsilyldicyclopentadienyltitandiphenyl Dichloride Methylphosphindicyclopentadienyltitandiphenyl or dichloride, Methylendicyclopentadienyltitandiphenyl or dichloride, isopropyl (cyclopentadienyl) (fluorenyl) zirconium dichloride, Isopropyl (cyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, Diisopropylmethylen (cyclopentadienyl) (fluorenyl) zirconium dichloride, Diisobutylmethylen (cyclopentadienyl) (fluorenyl) zirconium dichloride, Ditertbutylmethylen (cyclopentadienyl) (fluorenyl) zirconium dichloride, Cyclohexyli the (cyclopentadienyl) (fluorenyl) zirconium dichloride, Diisopropylmethylen (2,5-dimethylcyclopentadienyl) (fluorenyl) zirconium dichloride, Isopropyl (cyclopentadienyl) (fluorenyl) hafnium dichloride, diphenylmethylene (cyclopentadienyl) (fluorenyl) hafnium dichloride, Diisopropylmethylen (cyclopentadienyl) (fluorenyl) hafnium dichloride, Diisobutylmethylen (cyclopentadienyl) (fluorenyl) hafnium dichloride, Ditertbutylmethylen (cyclopentadienyl) (fluorenyl) hafnium dichloride, Cyclohexylidene (cyclopentadienyl) (fluorenyl) hafnium dichloride, Diisopropylmethylen (2,5-dimethylcyclopentadienyl) (fluorenyl) hafnium dichloride, Isopropyl (cyclopentadienyl) (fluorenyl) titanium dichloride, diphenylmethylene (cyclopentadienyl) (fluorenyl) titanium dichloride, Diisopropylmethylen (cyclopentadienyl) (fluorenyl) titanium dichloride, Ditertbutylmethylen (cyclopentadienyl) (fluorenyl) titanium dichloride, Cyclohexylidene (cyclopentadienyl) (fluorenyl) titanium dichloride, Diisopropylmethylen (2,5-dimethylcyclopentadienylfluorenyl) titanium dichloride, racemic ethylenebis (1-indenyl) zirconium (W) dichloride, racemic Ethylenebis (4,5,6,7-tetrahydro-1-indenyl) zirconium (IV) dichloride, racemic dimethylsilyl bis ((1-indenyl) zirconium (IV) dichloride, racemic dimethylsilyl bis (4,5,6,7-tetrahydro-1-indenyl) zirconium (IV) dichloride, racemic 1,1,2,2-tetramethylsilanylenbis (1-indenyl) zirconium (IV) dichloride, racemic 1,1,2,2-tetramethylsilanylenbis (4,5,6,7-tetrahydro-1-indenyl) zirconium (IV) dichloride, Ethylidene (1-indenyltetramethylcyclopentadienyl) zirconium (IV) dichloride, racemic dimethylsilylbis (2-methyl-4-t-butyl-1-cyclopentadienyl) zirconium (IV) dichloride, racemic ethylenebis (1-indenyl) hafnium (IV) dichloride, racemic ethylenebis (4,5,6,7-tetrahydro-1-indenyl) hafnium (IV) dichloride, racemic Dimethylsilylbis (1-indenyl) hafnium (IV) dichloride, racemic dimethylsilyl bis (4,5,6,7-tetrahydro-1-indenyl) hafnium (IV) dichloride racemic 1,1,2,2-tetramethylsilanylenbis (1-indenyl) hafnium (IV) dichloride, racemic 1,1,2,2-tetramethylsilanylenbis (4,5,6,7-tetrahydro-1-indenyl) hafnium (IV) dichloride, Ethylidene (1-indenyl-2,3,4,5-tetramethyl-1-cyclopentadienyl) hafnium (IV) dichloride racemic ethylenebis (1-indenyl) titanium (IV) dichloride, racemic Ethylenebis (4,5,6,7-tetrahydrol-indenyl) titanium (IV) dichloride, racemic Dimethylsilylbis (1-indenyl) titanium (IV) dichloride, racemic dimethylsilyl bis (4,5,6,7-tetrahydro-1-indenyl) titanium (IV) dichloride, racemic 1,1,2,2-tetramethylsilanylenbis (1-indenyl) titanium (IV) dichloride, racemic 1,1,2,2-tetramethylsilanylenbis (4,5,6,7-tetrahydro-1-inde&lt;?page 12?&gt;nyl) titanium (IV) dichloride, and Ethylidene (1-indenyl-2,3,4,5-tetramethyl-1-cyclopentadienyl) titanium (IV) dichloride.

Preferred Metallocene catalyst compounds with spatially demanding ligands are diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, racemic dimethylsilylbis (2-methyl-1-indenyl) zirconium (IV) dichloride racemic dimethylsilylbis (2-methyl-4- (1-naphthyl-1-indenyl) zirconium (IV) dichloride and racemic dimethylsilyl bis (2-methyl-4-phenyl-1-indenyl) zirconium (IV) dichloride. Further preferred metallocene catalyst compounds with spatially sophisticated include ligands Indenyl zirconium tris (diethyl carbamate), indenyl zirconium tris (pivalate) Indenyl zirconium tris (p-toluate), indenyl zirconium tris (benzoate), (1-methylindenyl) zirkoniumtris (pivalate), (2-methylindenyl) zirkoniumtris (diethylcarbamate), (methylcyclopentadienyl) zirkoniumtris (pivalate), Cyclopentadienyltris (pivalate), and (pentamethylcyclopentadienyl) zirkoniumtris (benzoate) on.

C. Phenolatkatalysatorverbindung

The The catalyst composition of the invention, one or more Phenolatkatalysatorverbindungen represented by the following formula are shown, containing: <img img-content="cf" img-format="tif" he="42" wi="71" file="00230001.tif" /> formula (VII) or <img img-content="cf" img-format="tif" he="77" wi="113" file="00240001.tif" /> formula (VIII) wherein R¹ hydrogen or a C₄-C₁₀₀-Group means, preferably a tertiary alkyl group, preferably a C₄-C₂₀alkyl, preferably a tertiary C₄-C₂₀ alkyl group, preferably a neutral C₄-C₁₀₀-Group, and also may or may not be bound to M, and at least one of R² to R⁵ a Grupp e means containing a heteroatom, with the remaining R² to R⁵ independently Is hydrogen or a C₁-C₁₀₀-Group are preferably a C₄-C₂₀alkyl (Preferably butyl, isobutyl, pentyl, hexyl, heptyl, isohexyl, Octyl, isooctyl, decyl, nonyl, dodecyl), and wherein each of R² to R⁵ also to M can be attached or not, O is oxygen, M is a transition metal Group 3 to Group 10 or a lanthanide, preferably a Group 4 metal, preferably Ti, Zr or Hf, n is the valence state of the metal M is, before&lt;?page 13?&gt;preferably 2, 3, 4 or 5, Q is an alkyl, halogen, Benzyl, amide, carboxylate, carbamate, thiolate, hydride or alkoxide , or a bond to an R group containing a heteroatom is that any of R¹ to R⁵ can be. A hetero atom-containing Group may be any heteroatom or a heteroatom is bound to carbon, silicon or another heteroatom, be. Preferred heteroatoms include boron, aluminum, silicon, Nitrogen, phosphorus, arsenic, tin, lead, antimony, oxygen, selenium, Tellurium. Particularly preferred heteroatoms include nitrogen, Oxygen, phosphorus and sulfur. Even more preferred heteroatoms conclude Oxygen and nitrogen. The heteroatom itself may be directly be bonded to the Phenolatdring or it may be to another atom or be bonded to other atoms, which bound to the Phenolatring are. The heteroatom containing group may contain one or more identical or different hetero atoms. Preferred heteroatom groups conclude Imines, amines, oxides, phosphines, ethers, ketenes, oxazoline heterocycles, Oxazolines, thioethers, and the like. Particularly preferred heteroatom groups conclude Imines one. Each of any two adjacent R groups may be a Ring structure, preferably a 5- or 6-membered ring. Just like that can the R groups form multi-ring structures. According to one embodiment form any two or more R groups do not 5-membered Ring.

In a preferred embodiment, Q represents a bond to any group R² to R⁵ represents, and the R group, to which bound Q is a hetero atom-containing group.

These Invention can also use the catalysts in <patcit><text>EP 0874005 A1</text></patcit> disclosed are to be performed.

In a preferred embodiment, comprises the phenoxide catalyst compound comprises one or more of: bis (N-methyl-3,5-di-t-butylsalicylimino) zirconium (IV) dibenzyl; Bis (N-ethyl-3,5-di-t-butylsalicylimino) zirconium (IV) dibenzyl; Bis (N-iso-propyl-3,5-di-t-butylsalicylimino) zirconium (IV) dibenzyl; Bis (Nt-butyl-3,5-di-t-butylsalicylimino) zirconium (IV) dibenzyl; Bis (N-benzyl-3,5-di-t-butylsalicylimino) zirconium (IV) dibenzyl; Bis (N-hexyl-3,5-di-t-butylsalicylimino) zirconium (IV) dibenzyl; Bis (N-phenyl-3,5-di-t-butylsalicylimino) zirconium (IV) dibenzyl; Bis (N-methyl-3,5-di-t-butylsalicylimino) zirconium (IV) dibenzyl; Bis (N-benzyl-3,5-di-t-butylsalicylimino) zirconium (IV) dichloride; Bis (N-benzyl-3,5-di-t-butylsalicylimino) zirconium (IV) dipivalate; Bis (N-benzyl-3,5-di-t-butylsalicylimino) titanium (IV) dipivalate; Bis (N-benzyl-3,5-di-t-butylsalicylimino) zirconium (IV) di (bis (dimethylamide)); Bis (N-iso-propyl-3,5-di-t-amylsalicylimino) zirconium (IV) dibenzyl; Bis (N-iso-propyl-3,5-di-t-octylsalicylimino) zirconium (IV) dibenzyl; Bis (N-iso-propyl-3,5-di- (1 ', 1'-dimethylbenzyl) salicylimino) zirconium (IV) dibenzyl; Bis (N-iso-propyl-3,5-di- (1 ', 1'-dimethylbenzyl) salicylimino) titanium (IV) dibenzyl; Bis (N-iso-propyl-3,5-di- (1 ', 1'-dimethylbenzyl) salicylimino) hafnium (IV) dibenzyl; Bis (N-iso-butyl-3,5-di- (1 ', 1'-dimethylbenzyl) salicylimino) zirconium (IV) dibenzyl; Bis (N-iso-butyl-3,5-di- (1 ', 1'-dimethylbenzyl) salicylimino) zirconium (IV) dichloride; Bis (N-hexyl-3,5-di- (1 ', 1'-dimethylbenzyl) salicylimino) zirconium (IV) dibenzyl; Bis (N-phenyl-3,5-di- (1 ', 1'-dimethylbenzyl) salicylimino) zirconium (IV) dibenzyl; Bis (N-iso-propyl-3,5-di (1'-methylcyclohexyl) salicylimino) zirconium (IV) dibenzyl; Bis (N-benzyl-3-t-butylsalicylimino) zirconium (IV) dibenzyl; Bis (N-benzyl-3-triphenylmethylsalicylimino) zirconium (IV) dibenzyl; Bis (N-iso-propyl-3,5-di-trimethylsilylsalicylimino) zirconium (IV) dibenzyl; Bis (N-iso-propyl-3- (phenyl) salicylimino) zirconium (IV) dibenzyl; Bis (N-benzyl-3- (2 ', 6'-di-iso-propylphenyl) salicylimino) zirconium (IV) dibenzyl; Bis (N-benzyl-3- (2 ', 6'-di-phenylphenyl) salicylimino) zirconium (IV) dibenzyl; Bis (N-benzyl-3-t-butyl-5-methoxysalicylimino) zirconium (IV) dibenzyl; Bis (2- (2H-benzotriazol-2-yl) -4,6-di-t-amylphenolat) zirconium (IV) dibenzyl; Bis (2- (2H-benzotriazol-2-yl) -4,6-di-t-amylphenolat) zirconium (IV) dichloride; Bis (2- (2H-benzotriazol-2-yl) -4,6-di-t-amylphenolat) zirconium (IV) di (bis (dimethylamide)); Bis (2- (2H-benzotriazol-2-yl) -4,6-di- (1 ', 1'-dimethylbenzyl) phenoxide) zirconium (IV) dibenzyl; Bis (2- (2H-benzotriazol-2-yl) -4,6-di-t-amylphenolat) titanium (IV) dibenzyl; Bis (2- (2H-benzotriazol-2-yl) -4,6-di- (1 ', 1'-dimethylbenzyl) phenoxide) titanium (IV) dibenzyl; Bis (2- (2H-benzotriazol-2-yl) -4,6-di- (1 ', 1'-dimethylbenzyl) phenoxide) titanium (IV) di chloride; &lt;?page 14?&gt;Bis (2- (2H-benzotriazol-2-yl) -4,6-di- (1 ', 1'-dimethylbenzyl) phenoxide) hafnium (IV) dibenzyl; (N-phenyl-3,5-di- (1 ', 1'-dimethylbenzyl) salicylimino) zirconium (IV) tribenzyl; (N- (2 ', 6'-di-iso-propylphenyl) -3,5-di- (1', 1'-dimethylbenzyl) salicylimino) zirconium (IV) tribenzyl; (N- (2 ', 6'-di-iso-propylphenyl) -3,5-di- (1', 1'-dimethylbenzyl) salicylimino) titanium (IV) tribenzyl); and (N- (2 ', 6'-di-iso-propylphenyl) -3,5-di- (1', 1'-dimethylbenzyl) salicylimino) zirconium (IV) trichloride.

D. Additional Catalyst Compounds

The Catalyst compositions of the invention may include one or more complexes included, which as transition metal catalysts based on bidentate Ligands containing pyridine or quinoline moieties, are known as such, in US application Ser. No. 09 / 103.620, filed June 23, 1998 are described.

According to a embodiment these catalyst compounds are represented by the formula: <st32:che xmlns:st32="http://lighthouseip.com/">((Z) XA_t(YJ))_qMQ_n (IX)</st32:che>wherein M is a metal, the selected is selected from the metals of groups 3-13 or from the lanthanide or actinide of the Periodic Table; Q is bonded to M and each Q is a monovalent, divalent or trivalent anion; X and Y bonded to M are; and one or more of X and Y are heteroatoms, preferably X and Y are both heteroatoms; Y in a heterocyclic ring is J, where J 2-50 non-hydrogen atoms includes, preferably 2-30 carbon atoms; Z is bonded to X, where Z comprises 1 to 50 non-hydrogen atoms, preferably 1-50 carbon atoms, preferably Z is a cyclic group containing 3-50 atoms, preferably 3-30 carbon atoms; t is 0 or 1; when t is 1, A is a bridging group at least at a bound of X, Y or J, preferably X and J; q is 1 or 2; n is an integer from 1 to 4 depending on the oxidation state is of M. According to one embodiment Z is optional, when X is oxygen or sulfur. According to a another embodiment Z is present when X is nitrogen or phosphorus. According to a embodiment Z is preferably an aryl group, more preferably a substituted Aryl group.

in the Scope of the invention is contemplated that according to an embodiment the catalyst compounds complexes of Ni²⁺ and Pd²⁺ Include which in Articles Johnson, et al., "New Pd (II) - and Ni (II) -Based Catalysts for Polymerization of Ethylene and a-olefin " J. Am. Chem. Soc. 1995, 117, 6414-6415 and Johnson, et al., "Copolymerization of Ethylene and Propylene with Functionalized Vinyl monomer by Palladium (II) Catalysts " J. Am. Chem. Soc., 1996, 118, 267-268, and<patcit><text>96/23010</text></patcit>, Published on 1 August 1996, <patcit><text>WO 99/02472</text></patcit>, in the <patcit><text>US Patent Nos. 5,852,145</text></patcit>. <patcit><text>5,866,663</text></patcit> and <patcit><text>5,880,241</text></patcit> are described. These complexes can either Dialkyletheraddukte or alkylated reaction products of be Dihalogenkomplexe described, which means the activation means of this invention, as described below, to the cationic State can be activated.

Other include catalyst compounds the nickel complexes in <patcit><text>WHERE 99/50313</text></patcit> describes a.

also includes those diimine based ligands of the catalyst compounds are with metals of group 8-10, as described in PCT publications <patcit><text>96/23010</text></patcit> and <patcit><text>WO 97/48735</text></patcit> and Gibson et al., Chem. Comm. S. 849-850 (1998) are disclosed.

More useful Catalyst compounds are the imido complexes with metals Group 5 and 6, which in <patcit><text>EP-A2-0 816 384</text></patcit> and <patcit><text>US Patent No. 5,851,945</text></patcit> are described. In addition, include metallocene catalysts bridged bis (arylamido) compounds Group 4, as described by DH McConville, et al., in Organometallics 1195, 14, 5478-5480 describes a. In addition, are bridged bis (amido) -Katalysatorverbindungen in <patcit><text>WO 96/27439</text></patcit> described. Other useful Catalysts are as bis (hydroxyaromatic nitrogen ligands) in <patcit><text>US Pat. No. 5,852,146</text></patcit> described. Other useful Catalysts, containing one or more Group 15 atoms, conclude are those as described in <patcit><text>WO 98/46651</text></patcit> are described.

E. Conventional transition metal catalysts

In a further embodiment can during execution this invention transition metal catalysts the conventional Type are used. Transition metal catalysts the conven&lt;?page 15?&gt;union Type are the well-known in the art traditional Ziegler-Natta, Vanadium and Phillips-type catalysts. Such as. For example, Ziegler-Natta catalysts, as, in Ziegler-Natta Catalysts and Polymerization, John Boor Academic Press, New York, are described 1979th Examples of transition metal catalysts the conventional Type are also known in the <patcit><text>U.S. Patents No. 4,115,639</text></patcit>. <patcit><text>4,077,904</text></patcit>. <patcit><text>4,482,687</text></patcit>. <patcit><text>4,564,605</text></patcit>. <patcit><text>4,721,763</text></patcit>. <patcit><text>4,879,359</text></patcit> and <patcit><text>4,960,741</text></patcit> described. The transition metal catalyst compounds of usual Type, which can be used in the present invention include transition metal compounds of Groups 3-17, preferably 4-12, more preferably 4-6, of the Periodic Table.

Preferred transition metal catalysts the conventional type can by the formula MR_x be presented with M is a metal of Groups 3-17, preferably Groups of 4-6, more preferably Group 4, most preferably titanium; R a Halogen or a Hydroxycarbyloxygruppe, and x is the oxidation state of the metal M is. Nonlimiting Examples of R include Alkoxy, phenoxy, bromide, chloride and fluoride. Non-limiting examples the transition metal catalysts the conventional Type, wherein M is titanium include, TiCl₄, TiBr₄, Ti (OC₂H₅)₃Cl, Ti (OC₂H₅) Cl₃, Ti (OC₄H₉)₃Cl, Ti (OC₃H₇)₂Cl₂, Ti (OC₂H₅)₂Br₂. TiCl₃, 1 / 3AlCl₃ and Ti (OC₁₂H₂₅) Cl₃ on.

Transition metal catalyst compounds the conventional Type based on magnesium / titanium electron-donor complexes that useful in the invention are, are,. as in the <patcit><text>U.S. Patents No. 4,302,565</text></patcit> and <patcit><text>4,302,566</text></patcit> described. The MgTiCl₆(Ethyl acetate)₄-Derivative is particularly preferred.

The <patcit><text>British Patent Application 2,105,355</text></patcit> and the <patcit><text>US Pat. No. 5,317,036</text></patcit> describe various vanadium catalyst compounds of conventional Type. Nonlimiting Examples of the vanadium catalyst compounds of conventional close type Vanadyltrihalid, alkoxy halides and alkoxides such as VOCl₃. VOCl₂(OBu) where Bu = butyl, and VO (OC₂H₅)₃; Vanadiumtetrahalogenid and Vanadiumalkoxyhalogenide as VCl₄ and VCl₃(OBu); Vanadium and Vanadylacetylacetonate and Chloracetylacetonate as V (AcAc)₃ and VOCl₂(AcAc) wherein (AcAc) is an acetylacetonate, a. The preferred vanadium catalyst compounds the conventional Type are VOCl₃, VCl₄ and VOCl₂-OR, Wherein R is a hydrocarbon radical means, preferably an aliphatic or aromatic C₁-C₁₀hydrocarbon such as. for example, ethyl, phenyl, isopropyl, butyl, propyl, n-butyl, iso-butyl, Tertiary butyl, Hexyl, cyclohexyl, naphthyl, etc., and Vanadiumacetylacetonate.

Chromium catalyst compounds the conventional Type which often are referred to as Phillips-type catalysts, which for Use useful in the present invention include CrO₃, Chromocene, silyl, chromyl (CrO₂Cl₂), Chromium-2-ethylhexanoate, Chromium acetylacetonate (Cr (AcAc)₃) and the same on. Nonlimiting Examples are described in <patcit><text>U.S. Patents No. 3,709,853</text></patcit>. <patcit><text>3,709,954</text></patcit>. <patcit><text>3,231,550</text></patcit>. <patcit><text>3,242,099</text></patcit> and <patcit><text>4,077,904</text></patcit> disclosed.

Still Other transition metal catalyst compounds the conventional Type and catalyst systems for use in the present Invention are suitable are described in <patcit><text>U.S. Patents No. 4,124,532</text></patcit>. <patcit><text>4,302,565</text></patcit>. <patcit><text>4,302,566</text></patcit>. <patcit><text>4,376,062</text></patcit>. <patcit><text>4,379,758</text></patcit>. <patcit><text>5,066,737</text></patcit>. <patcit><text>5,763,723</text></patcit>. <patcit><text>5,849,655</text></patcit>. <patcit><text>5,852,144</text></patcit>. <patcit><text>5,854,164</text></patcit> and <patcit><text>5,869,585</text></patcit> and published in the <patcit><text>EP-A2-0 416 815 A2</text></patcit> and <patcit><text>EP-A1-0 420 436</text></patcit> disclosed.

Other catalysts include cationic catalysts such. as AlCl₃ and other cobalt, iron, nickel and Palladiumkatalyatoren which are well known in the art. See z. B. <patcit><text>US Patent Nos. 3,487,112</text></patcit>. <patcit><text>4,472,559</text></patcit>. <patcit><text>4,182,814</text></patcit> and <patcit><text>4,689,437</text></patcit>,

also is contemplated that other catalysts with the catalyst compounds be combined in the catalyst composition of the invention can. See z. B. <patcit><text>US Patent Nos. 4,937,299</text></patcit>. <patcit><text>4,935,474</text></patcit>. <patcit><text>5,281,679</text></patcit>. <patcit><text>5,359,015</text></patcit>. <patcit><text>5,470,811</text></patcit> and <patcit><text>5,719,241</text></patcit>,

It is further comprises that a / s or more of the above-described Catalyst compounds or catalyst systems in combination with a / m or more conventional Catalyst compounds or catalyst systems may be used can / can. Nonlimiting Examples of mixed catalysts and catalyst systems are described in the <patcit><text>US Patent Nos. 4,159,965</text></patcit>. <patcit><text>4,325,837</text></patcit>. <patcit><text>4,701,432</text></patcit>. <patcit><text>5,124,418</text></patcit>. <patcit><text>5,077,255</text></patcit>. <patcit><text>5,183,867</text></patcit>. <patcit><text>5,391,660</text></patcit>. <patcit><text>5,395,810</text></patcit>. <patcit><text>5,691,264</text></patcit>. <patcit><text>5,723,399</text></patcit> and <patcit><text>5,767,031</text></patcit> and in PCT Publication <patcit><text>96/23010</text></patcit>, released described on 1 August 1996,.

&lt;?page 16?&gt;

III. Activation means and activation procedures for catalyst compounds

The be Polymerisationskatalysatorverbindungen described above typically activated in various ways to provide compounds to obtain, which have a free coordination site, the olefin (s) coordinated inserted and polymerized. For purposes of this specification and the appended claims the term "activating agent" is any compound, which activate one of the catalyst compounds described above may, by the neutral catalyst compound to a catalytically active catalyst compound cation is converted. Non-limiting activators include,. B. Alumoxanes, aluminum alkyls, ionizing activators, which may be neutral or ionic, and co-catalysts of the conventional Type one.

A. aluminoxane and aluminum alkyl activators

According to a embodiment be alumoxane activating agent as an activating agent in the The catalyst composition of the invention. alumoxanes are generally oligomeric compounds containing -Al (R) -O-subunits, wherein R represents an alkyl group. Examples of alumoxanes include methylalumoxane (MAO), modified methylalumoxane (MMAO), and isobutyl ethylalumoxane a. alumoxanes can produced by hydrolysis of the corresponding trialkylaluminium will. MMAO can be prepared by the hydrolysis of trimethylaluminum and a higher Trialkylaluminum such as triisobutylaluminum are produced. MMAOs are generally soluble in aliphatic solvents and while storage stable. There are a variety of methods for preparing alumoxane and modified alumoxanes from, wherein non-limiting examples thereof in the <patcit><text>US Patent Nos. 4,665,208</text></patcit>. <patcit><text>4,952,540</text></patcit>. <patcit><text>5,091,352</text></patcit>. <patcit><text>5,206,199</text></patcit>. <patcit><text>5,204,419</text></patcit>. <patcit><text>4,874,734</text></patcit>. <patcit><text>4,924,018</text></patcit>. <patcit><text>4,908,463</text></patcit>. <patcit><text>4,968,827</text></patcit>. <patcit><text>5,308,815</text></patcit>. <patcit><text>5,329,032</text></patcit>. <patcit><text>5,248,801</text></patcit>. <patcit><text>5,235,081</text></patcit>. <patcit><text>5,157,137</text></patcit>. <patcit><text>5,103,031</text></patcit>. <patcit><text>5,391,793</text></patcit>. <patcit><text>5,391,529</text></patcit>. <patcit><text>5,693,838</text></patcit>. <patcit><text>5,731,253</text></patcit>. <patcit><text>5,731,451</text></patcit>. <patcit><text>5,744,656</text></patcit>. <patcit><text>5,847,177</text></patcit>. <patcit><text>5,854,166</text></patcit>. <patcit><text>5,856,256</text></patcit> and <patcit><text>5,939,346</text></patcit> and in European publications <patcit><text>EP-A-0561476</text></patcit>. <patcit><text>EP-B1-0 279 586</text></patcit>. <patcit><text>EP-A-0594218</text></patcit> and <patcit><text>EP-B1-0 586 665</text></patcit> and PCT publications <patcit><text>WO 94/10180</text></patcit> and <patcit><text>WO 99/15534</text></patcit> disclosed. Another alumoxane is a modified methyl alumoxane (MMAO) cocatalyst Type 3A (commercially available from Akzo Chemicals, Inc. under the trade name Modified methylalumoxanes Type 3A, includes Pat. <patcit><text>US 5,041,584</text></patcit>).

aluminum alkyl or organoaluminum compounds which as an activating agent may be used conclude Trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminium and like.

B. Ionizing activators

It is included within the scope of this invention, or ionizing stoichiometric Activators, neutral or ionic, such as. For example, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) boron, a Trisperfluorphenylbormetalloid precursor or a precursor Trisperfluornaphthylbormetalloid polyhalogenated, Heteroborananionen (<patcit><text>WO 98/43983</text></patcit>) boric acid (<patcit><text>US Pat. No. 5,942,459</text></patcit>) or to use combinations thereof. It is also within the scope of this Invention included, neutral or ionic activators alone or in combination with alumoxane or modified alumoxane activators to use.

Examples for neutral stoichiometric include activating agent tri-substituted boron, tellurium, aluminum, gallium and indium, or Mixtures thereof. The three substituent groups are each independently selected from Alkyl, alkenyl, halo, substituted alkyl, aryl, aryl halides, Alkoxy and halides. Preferably, the three groups are independently selected from Halogen, mono or multicyclic (including halo-substituted) are aryl, alkyl, and alkenyl compounds and mixtures thereof, preferably Alkenyl groups having 1-20 carbon atoms, alkyl groups having 1-20 carbon atoms, Alkoxy groups having 1-20 carbon atoms and aryl groups having 3-20 Carbon atoms (including substituted aryl). More preferably, the three groups are alkyls having 1-4 carbon atoms, phenyl, naphthyl or mixtures thereof. Even more preferably, the three groups halogenated, preferably fluorinated, aryl groups. Most preferably, the neutral stoichiometric Activating agent or trisperfluorophenylboron Trisperfluornaphthylbor.

Ionian stoichiometric Activating compounds may contain an active proton, or some other cation with the remaining ion of the ionizing compound is connected to but is not coordinated or only loosely to it. Such compounds and the like are described in European Publications <patcit><text>EP-A-0570982</text></patcit>. <patcit><text>EP-A-0520732</text></patcit>. <patcit><text>EP-A-0495375</text></patcit>. <patcit><text>EP-B1-0 500 944</text></patcit>. <patcit><text>EP-A-0277003</text></patcit> and <patcit><text>A-EP-0277004</text></patcit> and the <patcit><text>US Patent Nos. 5,153,157</text></patcit>. <patcit><text>5,198,401</text></patcit>. <patcit><text>5,006,741</text></patcit>. <patcit><text>5,206,197</text></patcit>. <patcit><text>5,241,025</text></patcit>. <patcit><text>5,384,299</text></patcit> and <patcit><text>5,502,124</text></patcit>&lt;?page 17?&gt;and in US Patent Application Ser. No. 08 / 285.380, filed on August 3, 1994..

In a preferred embodiment, conclude the stoichiometric Activating agent is a cationic and an anionic component and can be represented by the following formula: <st32:che xmlns:st32="http://lighthouseip.com/">(LH)_d⁺(A^d-) (X)</st32:che>wherein L a neutral Lewis base; means H is hydrogen; (LH)⁺ a Bronsted acid is A^d- on non-coordinating anion having the charge d- d is an integer 1-3 is.

The cationic component (LH)_d⁺ can Bronsted acids, such as Protons or protonated Lewis bases or reducible Lewis acids are capable of protonating or a unit such as. for example, alkyl or aryl of the metallocene bulky ligand or a transition metal the group to abstract 15-containing catalyst precursor, resulting in a cationic transition metal species leads, lock in.

the activating cation (LH)_d⁺ can is a Bronsted acid be, which is in the position, on the transition metal catalyst precursor is a deliver proton, resulting in a transition metal cation leads, including Ammonium, oxonium, phosphonium, and mixtures Silyliumgruppen thereof, preferably ammonium groups of methylamine, aniline, dimethylamine, Diethylamine, N-methylaniline, diphenylamine, trimethylamine, triethylamine, N, N-dimethylaniline, Methyldiphenylamine, pyridine, p-bromo-N, N-dimethylaniline, p-nitro-N, N-dimethylaniline, Phosphonium from triethylphosphine, triphenylphosphine and diphenylphosphine, Oxoniumgruppen ethers such as dimethyl ether, diethyl ether, tetrahydrofuran and Dioxane, sulfonium from thioethers such. B. Diethylthioethern and tetrahydrothiophene and mixtures thereof. The activating cation (LH)_d⁺ can also a leaving group such. as silver, Carboniumgruppen, tropylium, Carbeniumgruppen, Ferroceniumgruppen and mixtures thereof, preferably Carboniumgruppen and Ferroceniumgruppen be. Most preferably, is (LH)_d⁺ on Triphenylcarbonium.

The anionic component A^d- includes such having the formula [M^{k +}Q_n]^d- on, wherein k is an integer from 1 to 3; n is an integer of 2 is up to 6; nk = d; M is an element selected from the group 13 of the periodic table of the Elements, preferably boron or aluminum, and Q is independently a Hydride, a bridged or unbridged Dialkylamide, halide, alkoxide, aryloxide, a hydrocarbon radical, a substituted hydrocarbon radical, a halogenated hydrocarbon radical, halogen substituted hydrocarbon radical, and a halogen-substituted Hydrocarbon radical, said Q having up to 20 carbon atoms, with the proviso Q that in not more than one occasion is a halide. Preferably each Q is a fluorinated hydrocarbon group having 1-20 carbon atoms, more preferably each Q is a fluorinated aryl group, and most preferably each Q is an aryl group pentafluorierte. Examples A suitable^d- also include diboron compounds, as in <patcit><text>US Pat. No. 5,447,895</text></patcit> disclosed are a.

Exemplary but not limiting examples for Boron compounds which as activating cocatalyst in the preparation of the improved catalysts of the invention can be used are tri-substituted Ammonium salts such as. B .: trimethylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, tri (t-butyl) ammonium tetraphenylborate, N, N-dimethylanilinium, N, N-Diethylaniliniumtetraphenylborat, N, N-dimethyl- (2, 4,6-trimethylanilinium) tetraphenylborate, trimethylammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, tri (sec-butyl) ammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-Diethylaniliniumtetrakis (pentafluorophenyl) borate, &lt;?page 18?&gt;N, N-dimethyl- (2,4,6-trimethylanilinium) tetrakis (pentafluorophenyl) borate, Trimethylammoniumtetrakis- (2,3,4,6-tetrafluorophenyl) borate, triethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate , Tripropylammoniumtetrakis- (2,3,4,6-tetrafluorophenyl) borate, tri (n-butyl) ammoniumtetrakis- (2,3,4,6-tetrafluorophenyl) borate, dimethyl (t-butyl) ammoniumtetrakis- (2,3, 4,6-tetrafluorophenyl) borate, N, N-dimethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate, N, N-Diethylaniliniumtetrakis- (2,3,4,6-tetrafluorophenyl) borate, and N, N-dimethyl- (2,4,6-trimethylanilinium) tetrakis- (2,3,4,6-tetrafluorophenyl) borate; dialkylammonium such. B .: di- (i-propyl) ammonium tetrakis (pentafluorophenyl) borate, and dicyclohexylammonium tetrakis (pentafluorophenyl) borate and tri-substituted Phosphonium salts such as. For example, triphenylphosphonium tetrakis (pentafluorophenyl) borate, Tri (o-tolyl) phosphonium tetrakis (pentafluorophenyl) borate, and tri (2,6-dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate.

At the Most preferably, the ionic stoichiometric activator (LH)_d⁺(A^d-) N, N-dimethylanilinium tetra (perfluorophenyl) borate or triphenylcarbenium tetra (perfluorophenyl) borate.

According to a embodiment is an activation method includes, after ionizing ionic compounds are used which contain an active proton but in capable of providing a cation of a metallocene catalyst with spatially demanding ligands and to form the non-coordinating anion to what in <patcit><text>EP-A-0426637</text></patcit>. <patcit><text>EP-A-0573403</text></patcit> and <patcit><text>US Pat. No. 5,387,568</text></patcit> described is.

C. cocatalysts of conventional type

Typically , conventional transition metal catalyst compounds except some chromium catalyst compounds of conventional Type, with one or more of the conventional cocatalysts activated, represented by the formula M³M⁴_vX²_cR³_bc illustrated could be, wherein M³ a metal of Group 1-3 and 12-13 of the Periodic Table; M⁴ is a metal of Group 1 of the periodic table; v is a number from 0 to 1; each X² a halogen; c is a number from 0 to 3; each R³ a monovalent hydrocarbon radical is or hydrogen; b is a number from 1 to 4 and wherein bc is at least 1. Other organometallic catalyst compounds for the above transition metal catalysts of the conventional type have the formula M³R³_kWherein M³ a metal Group IA, IIA, IIB or IIIA is such., lithium, sodium, beryllium, Barium, boron, aluminum, zinc, cadmium, and gallium; k 1, 2, or 3, depending on the valence of M³What the value in turn normally depends upon the particular Group to which M³ belongs; and wherein each R³ , any monovalent hydrocarbon radical can be.

Not restrictive examples for Organometallic cocatalyst compounds of the conventional type, which with the Catalyst compounds of conventional Type as described above useful are close Methyllithium, butyllithium, Dihexylquecksilber, butylmagnesium, Diethylcadmium, benzylpotassium, diethylzinc, tri-n-butylaluminum, Diisobutylethylbor, diethylcadmium, di-n-butylzink and tri-n-amylbor and in particular, the aluminum alkyls such. B. trihexylaluminum, Triethylaluminum, trimethylaluminum and triisobutylaluminum a. Additional cocatalyst of the conventional type include Monoorganohalogenide and hydrides of metals of group 2 and mono- or Diorganohalogenide and a hydrides of metals of groups 3 and 13. FIG. Non-limiting examples Such cocatalyst compounds of the conventional type include Diisobutylaluminiumbromid, Isobutylbordichlorid, methyl magnesium chloride, Ethylberylliumchlorid, Ethylcalciumbromid, diisobutylaluminum, Methylcadmiumhydrid, Diethylborhydrid, Hexylberylliumhydrid, Dipropylborhydrid, Octylmagnesiumhydrid, Butylzinkhydrid, Dichlorborhydrid, Dibromaluminiumhydrid and Bromcadmiumhydrid on. Organometallic cocatalyst compounds of the conventional type are known in the art and a more complete discussion of these compounds can in the <patcit><text>US Patent Nos. 3,221,002</text></patcit> and <patcit><text>5,093,415</text></patcit> being found.

D. Other activating agent

More include activating agent those described in PCT Publication <patcit><text>WO 98/07515</text></patcit> described are, one, such as tris (2,2 ', 2' '- nonafluorobiphenyl). fluoroaluminate. Combinations of activators are also of the invention includes, for. example, alumoxanes and ionizing activators in Combinations. See, for example, <patcit><text>EP-B1-0 573 120</text></patcit>, PCT publications <patcit><text>WO 94/07928</text></patcit> and <patcit><text>WO 95/14044</text></patcit> and <patcit><text>US Patent Nos. 5,153,157</text></patcit> and <patcit><text>5,453,410</text></patcit>,

More Suitable activating agents are in <patcit><text>WHERE 98/09996</text></patcit> disclosed, wherein the activation of Metal&lt;?page 19?&gt;locen catalyst compounds with spatially demanding ligands with perchlorates, periodates and iodates including their hydrates is described. <patcit><text>WHERE 98/30602</text></patcit> and <patcit><text>WO 98/30603</text></patcit> describe the use of lithium (2,2'-bisphenylditrimethylsilikat) · THF as Activating agent for a metallocene catalyst compound having spatially demanding ligands. <patcit><text>WO 99/18135</text></patcit> describes the use of organoboron-aluminum activators. <patcit><text>EP-B1-0 781 299</text></patcit> describes the use of a Silyliumsalzes in combination with not a coordinating compatible anion. Procedures for activation such. as using radiation (see <patcit><text>EP-B1-0 615 981</text></patcit>, here in by reference included), electrochemical oxidation, and the like are as activation method for the purpose provided, the neutral metallocene catalyst compound with spatially demanding ligand or precursor thereof to a metallocene with spatially to make demanding ligand, which is capable of olefins to polymerize. Other activators or methods for Activating a metallocene catalyst compound having spatially sophisticated Ligands are, for. Example, in the <patcit><text>U.S. Patents No. 5,849,852</text></patcit>. <patcit><text>5,859,653</text></patcit> and <patcit><text>5,869,723</text></patcit> and <patcit><text>WO 98/32775</text></patcit>. <patcit><text>WO 99/42467</text></patcit> (Dioctadecylmethylammonium-bis (tris (pentafluorophenyl) borane) benzimidazolide) described.

On Another suitable ion forming, activating cocatalyst comprises a salt of a cationic oxidizing agent and a non- noncoordinating, compatible anion represented by the formula (OX^e⁺)_d(A^d-) E represented is wherein: OX^{e +} a cationic oxidizing agent with a charge e + is; e is an integer from 1 to 3; and A^- and d are as previously defined. Examples of cationic oxidizing agents conclude A: ferrocenium, hydrocarbyl-substituted ferrocenium, Ag⁺ or Pb⁺², Preferred Embodiments of A^d- are the anions as previously containing Brönsted acids-in connection with the Activating agents have been defined, especially tetrakis (pentafluorophenyl) borate.

in the Scope of this invention is comprising that catalyst compounds with one or more activators or activation methods, as described above, may be combined. z. B. were a combination of activating agents in the <patcit><text>U.S. Patents No. 5,153,157</text></patcit> and <patcit><text>5,453,410</text></patcit>. in European publication <patcit><text>EP-B1-0 573 120</text></patcit> and PCT publications <patcit><text>WO 94/07928</text></patcit> and <patcit><text>WO 95/14044</text></patcit> described. These documents describe the use of an alumoxane and a ionizing activator with a metallocene catalyst compound with spatially demanding ligands.

IV. Carrier, support materials and general support techniques

The The catalyst composition of the invention includes a support material or carrier, and closes preferably an activating agent with a carrier. For example, the catalyst composition component, preferably the activator compound and / or the catalyst compound is deposited on a support material or carrier, brought into contact with, vaporized thus, bound thereto or therein incorporated, adsorbed or absorbed therein.

A. support material

the support material is any of the conventional Support materials. Preferably, the carrier material a porous Support material z. B. talc, inorganic oxides and inorganic chlorides. Other support materials conclude resinous support materials such. as polystyrene, functionalized or crosslinked organic Carrier, such. as polystyrene divinyl benzene polyolefins or polymeric compounds, Zeolites, clays, or any other organic or inorganic support material and the like or mixtures thereof.

The preferred support materials are inorganic oxides, which oxides of the metals of groups 2, 3, 4, 5, 13 and 14 include. The preferred carriers conclude Silicon dioxide, which may be dehydrated or not, fumed silica, alumina (<patcit><text>WO 99/60033</text></patcit>) Silica-alumina and mixtures thereof. More useful carrier conclude Magnesia, titania, zirconia, magnesium chloride (<patcit><text>US Pat. No. 5,965,477</text></patcit>), Montmorillonite (European patent <patcit><text>EP-B1-0 511 665</text></patcit>), Phyllosilicate, zeolites, talc, clays (<patcit><text>US Pat. No. 6,034,187</text></patcit>) and the like. can also Combinations of these support materials be used, for. example, silica-chromium, silica-alumina, Silica-titania and the like. Other support materials can in the <patcit><text>EP-0767184 B1</text></patcit> porous described include acrylic polymers. Other support materials conclude Nanocomposites as in <patcit><text>PCT-WO 99/47598</text></patcit> describes aerogels as in <patcit><text>WO 99/48605</text></patcit> describes spherulites as in <patcit><text>US Pat. No. 5,972,510</text></patcit> and Polymer beads as described in <patcit><text>WO 99/50311</text></patcit> described on.

It is preferred that the support material, most preferably an inorganic oxide, an upper&lt;?page 20?&gt;area in the field from 10-700 m²/ G, a pore volume in the range of 0.1-4.0 cc / g and has an average particle size in the range of 5-500 microns. More preferably, the surface is the carrier material in the range of 50-500 m²/ G, the pore volume is 0.5-3.5 cc / g and the mean particle size is 10-200 microns. Most preferably, the surface is the carrier material in the range of 100-400 m²/ G, the pore volume is 0.8-3.0 cc / g and the average particle size is 5-100 microns. The middle Pore ​​size of the support of the Invention typically has a pore size in the range of 1-100 nm (10-1000 Å), preferably 5-50 nm (50-500 Å) and the most preferably from 7.5 to 35 nm (75-350 Å), on.

The support materials can be chemically treated, eg. B. with a fluoride compound such as in <patcit><text>WO 00/12565</text></patcit> described. Other activating agents with carriers such. B. <patcit><text>WO 00/13792</text></patcit> describes what is on boron containing solid acid complex with support relates.

In a preferred embodiment, is fumed silica, available under the trade name Cabosil^TM TS-610, available from Cabot Corporation, as a nucleating agent or as a viscosity builder described in Katalysatorkomponentenaufschlämmung below, used. Fumed silica is typically a silica with Particles having a size of 7-30 nm, which has been treated with dimethylsilyldichloride such that the majority of the surface hydroxy protected is. In a further embodiment , the fumed silica used has a particle size less than 40 microns (microns), preferably less than 20 microns (Microns) or preferably less than 10 micrometers (microns).

In a preferred method of forming a catalyst composition component with support is the amount of liquid, in which the activating agent is present, is less than four times the pore volume of the support material, more preferably less than three times, even more preferably less than twice; preferred ranges are 1.1 to 3.5 times, and most preferred is the range from 1.2 to 3 times. According to a alternative embodiment is the amount of liquid, in which the activating agent is present, once or less once as the pore volume of the support material, the formation during the the activating agent with carrier is used.

procedures for measuring the total pore volume of a porous support are well known in the art. Details of these procedures are in Volume 1, Experimental Methods in Catalytic Research (Academic Press, 1968) (in particular see described p 67-96). This preferred approach looks Require the use of a classical BET apparatus for nitrogen absorption. Another method, which is well known in the art, is in Innes, Total Porosity and Particle Density of Fluid Catalysts by Liquid Titration, Vol. 28, no. 3, Analytical Chemistry 332-334 (March 1956).

B. activating agent with carrier

According to a embodiment closes the catalyst composition comprises a carrier with an activating agent. Many activating agent with carrier are described in various patents and publications, including: <patcit><text>US Pat. No. 5,728,855</text></patcit>. which refers to the formation of an oligomeric alkylaluminoxane with carriers, formed by treating a trialkylaluminum with carbon dioxide prior to hydrolysis; <patcit><text>US Patent No. 5,831,109</text></patcit> and <patcit><text>5,777,143</text></patcit> describe a methylalumoxane with carriers, which is prepared by using a non-hydrolytic process becomes; <patcit><text>US Pat. No. 5,731,451</text></patcit> refers by a method for the preparation of an alumoxane with carrier Oxygenation with a trialkylsiloxy; <patcit><text>US Pat. No. 5,856,255</text></patcit> describes the formation of an auxiliary catalyst with support (alumoxane or organoboron compound) at elevated temperatures and pressures; <patcit><text>US Pat. No. 5,739,368</text></patcit> refers to a method of heat treatment alumoxane and applying it to a support; <patcit><text>EP-A-0545152</text></patcit> refers and the addition of a metallocene to an alumoxane with carrier Adding more methylalumoxane; <patcit><text>US Pat. No. 5,756,416</text></patcit> and <patcit><text>6,028,151</text></patcit> describe a catalyst composition of a alumoxane impregnated carrier and a metallocene and a bulky aluminum alkyl and methylalumoxane; <patcit><text>EP-B1-0 662 979</text></patcit> discusses the use of a metallocene with a catalyst support silica reacted with alumoxane. <patcit><text>PCT WO 96/16092</text></patcit> refers to a heated carrier, which is treated with alumoxane and washing to unfixed Alumoxane to remove; <patcit><text>U.S. Patents No. 4,912,075</text></patcit>. <patcit><text>4,937,301</text></patcit>. <patcit><text>5,008,228</text></patcit>. <patcit><text>5,086,025</text></patcit>. <patcit><text>5,147,949</text></patcit>. <patcit><text>4,871,705</text></patcit>. <patcit><text>5,229,478</text></patcit>. <patcit><text>4,935,397</text></patcit>. <patcit><text>4,937,217</text></patcit> and <patcit><text>5,057,475</text></patcit> and <patcit><text>PCT WO 94/26793</text></patcit> are on the addition a metallocene directed to an activating agent with the carrier; <patcit><text>US Pat. No. 5,902,766</text></patcit> refers to an activating agent with carrier with a certain distribution alumoxane on the silica; <patcit><text>US Pat. No. 5,468,702</text></patcit> refers to to the aging of an activating agent with the carrier and adding a metallocene; <patcit><text>US Patent No. 5,968,864</text></patcit> discusses the treatment of a solid with alumoxane and introducing a metallocene; <patcit><text>EP-0747430 A1</text></patcit> refers to a process using a metallocene on a Methylalumoxane and trimethylaluminum on a &lt;?page 21?&gt;Carrier; <patcit><text>EP-0969019 A1</text></patcit> discussed the use of a metallocene and an activating agent with Carrier; <patcit><text>EP-B2-0 170 059</text></patcit> refers to a polymerization process under Use of a metallocene and an organoaluminum compound, which is formed by aluminum trialkyl with a water-containing carrier is implemented; <patcit><text>US Pat. No. 5,212,232</text></patcit> discusses the use of an alumoxane with carrier and a metallocene for producing styrene polymers-based; <patcit><text>US Pat. No. 5,026,797</text></patcit> discussed a Polymerization using a solid component a zirconium compound and a water-insoluble porous inorganic oxide, which previously treated with alumoxane; <patcit><text>US Patent No. 5,910,463</text></patcit> refers to a process for preparing a catalyst carrier, by a dehydrated support material, an alumoxane and a polyfunctional organic cross-linking agent be combined; the<patcit><text>U.S. Patents No. 5,332,706</text></patcit>. <patcit><text>5,473,028</text></patcit>. <patcit><text>5,602,067</text></patcit> and <patcit><text>5,420,220</text></patcit> discuss a method for the preparation of an activating agent with carrier, wherein the volume of alumoxane solution is less is defined as the pore volume of the support material; <patcit><text>WO 98/02246</text></patcit> describes Silica, which with a solution containing an aluminum source and a metallocene was treated; <patcit><text>WHERE 99/03580</text></patcit> refers to the use of an alumoxane with support and a metallocene; <patcit><text>EP-A1-0 953 581</text></patcit> discloses a heterogeneous catalytic system an alumoxane with carrier and a metallocene; <patcit><text>US Patent No. 5,015,749</text></patcit> discusses a process for preparing a polyhydrocarbon alumoxane using a porous organic or inorganic recording material; <patcit><text>US Patent Nos. 5,446,001</text></patcit> and <patcit><text>5,534,474</text></patcit> refer to a process for preparing one or more alkylaluminoxanes the particulate on a solid, inert carrier are immobilized; and<patcit><text>EP-A1-0 819 706</text></patcit> refers to a method for preparing a solid silica, treated with alumoxane. The following products are fully herein incorporated by reference to useful Activating agent with carrier to reveal and processes for their preparation, including: W. Kaminsky, et al., "Polymerization of Styrene with Supported Half-Sandwich Complexes ", Journal of Polymer Science Vol. 37, 2959-2968 (1999) describes a method of adsorbing a methylalumoxane to a support followed by the adsorption a metallocene; Junting Xu, et al. "Characterization of isotactic polypropylene prepared with dimethylsilyl bis (1-indenyl) zirconium dichloride supported of methylaluminoxane pretreated silica ", European Polymer Journal 35 (1999) 1289-1294, discloses the use of silica, which with Methylalumoxane and metallocene was treated; Stephen O'Brien, et al., "EXAFS analysis of a chiral alkene polymerization Catalyst Incorporated in the mesoporous silicate MCM-41 "Chem. Commun. 1905-1906 (1997), discloses an immobilized alumoxane on a modified mesoporous silica, and F. Bonini, et al., "Propylene Polymerization through Supported metallocene / MAO Catalysts: Kinetic Analysis and Modeling "Journal of Polymer Science, Vol. 33 2393-2402 (1995) describes the use of a silica support with methylalumoxane with a metallocene. Each of these references discussed method is to produce the activation component with support that used in the catalyst composition of the invention is useful.

In a further embodiment is the activating agent with carrier such. B. alumoxane with Carrier, for some Time prior to use herein aged. See<patcit><text>US Patent Nos. 5,468,702</text></patcit> and <patcit><text>5,602,217</text></patcit>,

In one embodiment is the activating agent with the carrier in the dry state or a solid. In a further embodiment, the activation means with support in a substantially dry state or a slurry, preferably in a mineral oil slurry.

In a further embodiment two or more separately coated onto a carrier activation means used, or alternatively two or more different Activation means on a single carrier.

According to a another embodiment the carrier material, preferably partially or completely dehydrated support material, preferably 200 ° C to 600 ° C dehydrated silica, then with an organoaluminum or alumoxane compound contacted. Preferably, in one embodiment, in which an organoaluminum compound is used, the activation means as a result of the reaction of z. B. trimethyl aluminum and water in situ on or in the carrier material educated.

In a further embodiment are Lewis base-containing support with a Lewis acid activating agent reacted to a support-bound Lewis acid compound to form. The Lewis base hydroxyl groups of silica exemplify Metal / metalloid oxides, in which this method of binding to a carrier occurs. This embodiment is described in US patent application Ser. No. 09 / 191.922, filed on 13. November 1998 describes.

More Embodiments, by an activating agent with a carrier to be brought into connection, &lt;?page 22?&gt;are in <patcit><text>US Pat. No. 5,427,991</text></patcit> described, wherein non-coordinating anions derived from trisperfluorophenyl boron derived, with support are described; <patcit><text>US Pat. No. 5,643,847</text></patcit> discussed the reaction of Lewis-acid compounds Group 13 metal oxides, such as, for example, silica, and illustrates the reaction of trisperfluorophenylboron with silanol groups (the hydroxyl of silicon) resulting in bound anions capable of transition metal organometallic catalyst compounds to protonate to catalytically active cations which by bound anions are compensated to form; immobilized Group IIIA Lewis acid catalysts, the for carbocationic polymerizations are suitable are <patcit><text>US Pat. No. 5,288,677</text></patcit> described; and James CW Chien, Jour. Poly. Sci. Pt A. Poly. Chem, Vol. 29, 1603-1607 (1991) describes the suitability of methylalumoxane (MAO), the with silica (SiO₂) Has been implemented, and Metallocenes for olefin polymerization and describes a covalent Bonding of the aluminum atom to the silica through an oxygen atom of the surface hydroxyl of the silica.

According to a preferred embodiment, is an activating agent formed with support by a stirred and temperature and pressure-controlled reaction vessel a solution of Activating agent and a suitable solvent is prepared, then the carrier material at temperatures from 0 ° C to 100 ° C was added is, the carrier with the activator solution up to 24 is brought into contact h, then a combination of heat and Pressure is applied to the solvent to remove, to a free-flowing prepare powders. The temperatures may range from 40 to 120 ° C and the pressures 34.5 to 138 kPa (5 psia to 20 psia) range. It can also an inert purge gas be used to assist in the removal of the solvent. Other Orders of addition, such slurry of the carrier material in a suitable solvent and then addition of the activating agent can be employed.

C. Spray dried Catalyst composition components

In a further embodiment is a carrier combined with one or more activating agents and spray-dried, to an activating agent with carrier to form. In a preferred embodiment, fumed silica combined with methyl alumoxane and then spray dried to methylalumoxane with support to form. Preferably a support is combined with alumoxane, and spray-dried then in mineral oil incorporated to form an appropriate slurry in the present invention.

In a further embodiment were the catalyst compounds described above with optional support materials brought together and / or optional activators and before matching with the Aufschlämmungsverdünnungsmittel spray dried.

In a further embodiment , the catalyst compounds and / or the activating agent preferably with a carrier material such. as a particulate filling material brought together and then spray dried, preferably to a free-flowing to form powder. spray can be done by any method known in the art methods. See also <patcit><text>EP-A-0 668 295 B1</text></patcit>. <patcit><text>US Pat. No. 5,674,795</text></patcit> and <patcit><text>US Patent No. 5,672,669</text></patcit> and US-Panentanmeldung Ser. No. 09 / 464.114, filed on 16 December 1999, which in particular spray drying catalysts with carriers describe. In general, the catalysts spray dried, by the catalyst compound and the optional activator in solution be introduced (so that the catalyst compound and the activator can react with each other, fals desired); a filler such. as silica or silica dust such. B. Gasil^TM or Cabosil^TM is added, then the solution at high pressures through a nozzle promoted is. The solution can on a surface sprayed be sprayed or so are that the droplets are dried in midstream. The in Commonly used methods is the silica in toluene disperse, stir in the activator solution, and then in the catalyst compound solution stir. Typical slurry concentrations 5-8 . Wt%. This formulation can be used as slurry for 30 minutes at moderate stirring or manual shaking remain to them spray before to maintain a suspension. According to a preferred embodiment, is the composition of the dried material 40-50 wt.% Activator (preferably alumoxane), 50-60 SiO₂ and about 2 wt.% Catalyst compound.

According to a another embodiment is fumed silica such. B. Gasil^TM or Cabosil^TM to a solution containing a catalyst compound added so that the fumed silica, if this solution added to the Katalysatorkomponentenaufschlämmung is or is injected into a polymerization reactor as Template for "in situ spray" drying furnaces acts.

For simple Catalyst compound mixtures, the two or more Katalysatorverbindun&lt;?page 23?&gt;gene in the desired relationship are added together in the last step. In another embodiment more complex procedures are possible, such. as the addition a first catalyst compound to the activator / filler mixture for a specified reaction time t, followed by the addition of the second Catalyst compound solution, mixing for another specified time x, after which the mixture is cogesprüht. After all , another additive, such as. for example, 1-hexene, with about 10 vol%, in the activating agent / filler mixture present before the addition of the first metal catalyst compound be.

In a further embodiment are added to the mixture binder. These can be added in order to improve the particle morphology, that is, the particle size distribution reducing, for a lower porosity And to enable the particles to a smaller amount of alumoxane which as "binder" acts.

In a further embodiment can a solution a metallocene compound with spatially sophisticated ligands and an optional activating agent with a different slurried spray dried catalyst compound are brought together and then introduced into the reactor.

The spray-dried Particles are generally referred to as mineral oil slurry to the polymerization reactor brought in. Solids concentration by weight in oil betragn 10-30.%, preferably 15-25 wt.%. In some embodiments, can the spray-dried Particles less than 10 microns up to 100 microns be great compared to conventional Supported catalysts, what about 50 microns in size. In a preferred embodiment , the support an average particle size of 1-50 microns (microns), preferably 10-40 microns (Micron) on.

V. Catalyst Compositions of the Invention

Around prepare the catalyst composition of the invention are the above-described catalyst components in a Katalysatorkomponentenaufschlämmung and / or in a catalyst component solution used. For purposes of this invention, a slurry is defined as a suspension of a solid, wherein the solid may be porous or not, in a liquid. The Katalysatorkomponentenaufschlämmung and the catalyst component solution brought together to form the catalyst composition, which is then introduced into a polymerization reactor.

A. Katalysatorkomponentenaufschlämmung

The Katalysatorkomponentenaufschlämmung closes mineral oil or silicone oil, a Carrier, an activating agent and a metal of the Group 15 containing Catalyst compound with a metal atom of Group 4, 5, or 6 a. According to a another embodiment contains the Katalysatorkomponentenaufschlämmung fumed. In a embodiment is mounted in the slurry to a carrier, the catalyst compound.

In a further embodiment closes the slurry one or more activating agents and carriers and / or activating agent with support and / or one or more catalyst compound is a (s). z. B. the slurry may two or more activators (such. as an alumoxane with carrier Include and a modified alumoxane) and a catalyst compound, or the slurry an activating agent with carrier and more than one catalyst compound lock in. Preferably, the slurry an activating agent with carrier and two catalyst compounds.

In a further embodiment includes slurry Activating agent with carrier and two different catalyst compounds, which separately, or together to the slurry can be given.

In a further embodiment is an alumoxane with carrier containing slurry contacted with a catalyst compound in contact, letting this react, and thereafter the slurry with another catalyst compound contacted. In a further embodiment, the an alumoxane with support containing slurry contacted with two catalyst compounds at the same time in contact and allowed they react.

In a further embodiment is the molar ratio of metal in the activator to metal in the catalyst compound in the slurry 1000: 1 to 0.5: 1, preferably 300: 1 to 1: 1, more preferably 150: 1 to 1: 1.

&lt;?page 24?&gt;

In a further embodiment contains the slurry a carrier material which any known in the art inert particulate carrier material may be, including, but not limited silica, fumed silica, alumina, clay, talc or other support materials as disclosed above. In a preferred embodiment the slurry contains a Activating agent with carrier such as those disclosed above, preferably methylalumoxane and / or modified Methyl alumoxane on a silica support.

The Katalysatorkomponentenaufschlämmung, which is used in the method of the invention is typically prepared by mixing the catalyst components, preferably the Carrier, the activating agent and the optional catalyst compounds in a liquid thinner are suspended. The liquid thinner is mineral oil or silicone oil. The diluent used under the polymerization preferably liquid and relatively inert. The concentration of the components in the slurry is controlled so that a desired relationship of catalyst compound (s) to activator, and / or catalyst compound is introduced to the catalyst compound in the reactor.

Typically allowed to the catalyst compound and the carrier and the activation means or the activating agent with the carrier and the Aufschlämmungsverdünnungsmittel for a Time to contact which is sufficient to provide at least 50% of the depositing catalyst compounds in or on the carrier, preferably at least 70%, preferably at least 75%, preferably at least 80%, more preferably at least 90%, preferably at least 95%, preferably at least 99%. According to a embodiment the Katalysatorkomponentenaufschlämmung before use produced in the catalyst feed system of the invention. mixing times be up to 10 h, typically up to 6 hours, typically 4-6 hours. In one embodiment of this Invention is the catalyst compound then in or on the carrier, if the concentration of the catalyst compound in the liquid portion the slurry after adding the catalyst compound to the slurry with the time is reduced. The concentration of the catalyst compound in the liquid thinner z can. B. by inductively coupled plasma spectroscopy (ICPS = Inductively Coupled Plasma Spectroscopy) or by ultraviolet (UV) spectroscopy after standardization with a case of a suitable concentration range Calibration curve produced are measured as known in the art is. So z. B. apply 70% of a catalyst compound as in or on the carrier deposited, if the concentration of the catalyst compound in the liquid (Not including of the carrier) by 70%, starting from the initial Concentration is reduced.

According to a embodiment can the catalyst compounds as a solution, slurry or Powder to the slurry be added. The Katalysatorkomponentenaufschlämmung is before being used in the polymerization process of the invention produced or can Katalysatorkomponentenaufschlämmung also be produced in-line.

According to a embodiment The slurry is by contacting the catalyst compounds such. as the Catalyst or the supported catalyst or the carrier and the activating agent or activating agent with support on once produced. According to a another embodiment The slurry is prepared by first a carrier material is added, and then the combination of a catalyst and an activation component is added.

According to a another embodiment includes slurry an activating agent with the carrier and at least one catalyst compound wherein the catalyst compound with the slurry as a solution is combined. A preferred solvent is mineral oil.

According to a another embodiment is alumoxane, preferably methylalumoxane or modified methylalumoxane with a carrier such. as calcined silica or fumed silica are brought together, to an activating agent with carrier to form, the activating agent with carrier is then in a liquid dispersed, such. as degassed mineral oil, and then one or more catalyst compound / s to the dispersion was added and mixed to form the Katalysatorkomponentenaufschlämmung. The catalyst compounds are preferably added to the dispersion as a solid, powder, solution or as slurry preferably a mineral oil slurry added. added when more than one catalyst compound to the dispersion is, can the catalyst compounds in succession or at the same time be added.

According to a another embodiment the catalyst compound in solid form or powder form to the slurry added. According to a preferred embodiment, a catalyst compound of group 15 to the slurry in Powder or solid form added. According to a&lt;?page 25?&gt;another embodiment is [(2,4,6-Me₃C₆H₂) NCH₂CH₂]₂NHZrBz₂ and / or [(2,4,6-Me₃C₆H₂) NCH₂CH₂]₂NHHfBz₂ added to the slurry as a powder.

According to a preferred embodiment, the Katalysatorkomponentenaufschlämmung includes mineral oil and has a viscosity of 130-2000 mPa.s (CP) at 20 ° C, more preferably 180-1500 mPa.s (CP) at 20 ° C and even more preferably 200-800 mPa.s (CP) at 20 ° C as measured with a Brookfield model LVDV-III Rheometer in a nitrogen-purged dry box (So ​​that the headspace is substantially free of moisture and oxygen , that is, less than a few ppmv of each). The Katalysatorkomponentenaufschlämmungen be purged nitrogen in a prepared drying chamber and in their closed glass containers until immediately before the viscosity measurements rolled, in order to ensure that they are fully suspended at the start of the experiment. The Temperature of the viscometer is controlled via an external temperature bath, wherein heat transfer fluid is circulated in the viscometer. The rheometer is suitable with the spindle for the test material according to the instructions the device equipped. Typically a SC4-34- or SC4-25 spindle was used. Data analysis was prepared using Rheocalc-VI.1 software, Copyright 1995, Brookfield Engineering Laboratories, preferably with which the were obtained and used unit is performed.

According to a embodiment the Katalysatorkomponentenaufschlämmung includes an activating agent with support and one or more or a combination of the catalyst compound (s) as defined in formula I-IX described above.

According to a another embodiment the Katalysatorkomponentenaufschlämmung includes an activating agent with support and one or more or a combination of the catalyst compound (s) Group 15, as represented by Formula I or II above.

According to a another embodiment the Katalysatorkomponentenaufschlämmung includes an activating agent with support and one or more or a combination of catalyst compound (s) with spatially demanding ligands, as represented by formula III-VI above are shown.

According to a another embodiment includes slurry an activating agent with the carrier, Catalyst compound (s) of group 15 above by Formula I. or illustrated II, and catalyst compound (s) with spatially sophisticated Ligands represented by Formula III-VI.

According to a another embodiment includes slurry Alumoxane with carrier and [(2,4,6-Me₃C₆H₂) NCH₂CH₂]₂NHMBz₂Wherein M a metal of group 4, each Bz is independently a benzyl and Me is methyl.

According to a another embodiment includes slurry alumoxane with support a catalyst compound of group 15 and one of the following Compounds: bis (n-propylcyclopentadienyl) -MX₂, (Pentamethylcyclopentadienyl) (n-propylcyclopentadienyl) MX₂, Bis (indenyl) MX₂. or (tetramethylcyclopentadienyl) (n-propylcyclopentadienyl) MX₂Wherein M is zirconium, hafnium or titanium, and X is chlorine, bromine or fluorine.

In the polymerization process of the invention as described below, , any of the above-described catalyst component containing slurries with any of the catalyst component-containing solutions as described below, are brought together. Additionally More than one catalyst component containing slurry used will.

B. catalyst component solution

According to a embodiment closes the catalyst component solution a catalyst compound a. According to another embodiment closes the solution and an activation agent in addition to the catalyst connection.

The Solution used in the method of this invention is typically prepared by the catalyst compound and optionally an activating agent in liquid solvent dissolved will. The liquid solvent is a C₅-C₃₀alkane, preferably a C₅-C₁₀Alkane. Cyclic alkanes such. As cyclohexane and aromatic compounds such. as toluene can also be used. also can also mineral oil as solvent be used. The solution used should under the polymerization liquid be and relatively inert. According to a embodiment is in the catalyst compound solution &lt;?page 26?&gt;liquid used different from the diluent, which is used in the Katalysatorkomponentenaufschlämmung. According to a another embodiment is the fluid used in the catalyst compound solution the same as the components used in the catalyst solution Diluent.

According to a preferred embodiment, is The relationship of metal in the activator to metal in the catalyst compound in the solution 1000: 1 to 0.5: 1, preferably 300: 1 to 1: 1, more preferably 150: 1 to 1: 1.

According to a preferred embodiment, is the activating agent and the catalyst compound in the solution . With up to 90 wt.%, Preferably with up to 50% by weight, preferably with up to 20 wt.%, preferably up to 10 wt.%, more preferably up to . To 5 wt.%, More preferably less than 1 wt%, more preferably between 100 ppm and 1 wt.%, Based on the weight of the solvent and the activating agent or catalyst compound present.

According to a embodiment the catalyst component solution comprises any of the catalyst compounds, the formula in I-IX are described above.

According to a another embodiment the catalyst component solution comprises a catalyst compound Group 15 that described by the formula I or II as described above is shown.

According to a another embodiment the catalyst component solution comprises a catalyst compound with spatially demanding ligands, as represented by formula III-VI as is shown above.

According to a preferred embodiment, includes the resolution Bis (n-propylcyclopentadienyl) -MX₂, (Pentamethylcyclopentadienyl) (n-propylcyclopentadienyl) MX₂, Bis (indenyl) -MX₂. (Tetramethylcyclopentadienyl) (n-propylcyclopentadienyl) MX₂Wherein M is a Group 4 metal, preferably Zirconium, hafnium or titanium and X is chlorine, bromine or fluorine.

In the below-described polymerization process of the invention, any of the above-described catalyst component containing solutions with any of the catalyst component containing slurry / slurries are brought together as described above. In addition, more than one catalyst component containing solution be used.

C. Catalyst Compositions

The The catalyst composition of the invention is formed by each any of Katalysatorkomponentenaufschlämmungen with any solutions of the catalyst components is brought together as described above. Generally the Katalysatorkomponentenaufschlämmung and the catalyst component solution in The method of the present invention blended to the ultimate catalyst composition to form, which is then introduced into a polymerization reactor is brought together and with one or more olefins.

Preferably the Katalysatorkomponentenaufschlämmung and the catalyst component solution are continuously and introduced into the polymerization reactor.

According to a embodiment contains the slurry at least one carrier and at least one activator, preferably an activating agent with support and the solution contains at least one catalyst compound.

According to a another embodiment contains the Katalysatorkomponentenaufschlämmung a support and an activating agent and / or an activating agent with the carrier, and the catalyst component solution contains at least one catalyst compound and at least one activating agent.

According to a embodiment contains the slurry at least one carrier and at least one activator, preferably an activating agent with support and the solution contains one or more catalyst compound (s) and / or one or more Activating compound (s).

According to a another embodiment contains the Katalysatorkomponentenaufschlämmung more &lt;?page 27?&gt;as a / s support, activating agent and / or activating agent with carrier and the catalyst component solution contains at least a catalyst compound.

According to a another embodiment contains the Katalysatorkomponentenaufschlämmung more than a / s support, activating agent and / or activating agent with carrier and the catalyst component solution contains at least a catalyst compound and at least one activating agent.

According to a another embodiment contains the Katalysatorkomponentenaufschlämmung more than a / s support, activating agent and / or activating agent with carrier and the catalyst component solution contains a or more catalyst compound (s) and / or one or more Activating compound (s).

According to a another embodiment contains the Katalysatorkomponentenaufschlämmung a carrier, Activating agent and / or an activating agent with the carrier, and contains a catalyst compound and / or a catalyst compound with support and the catalyst component solution contains at least one catalyst compound.

According to a another embodiment contains the Katalysatorkomponentenaufschlämmung a carrier, Activating agent and / or an activating agent with carrier and contains a catalyst compound and / or a catalyst compound with support and the catalyst component solution contains at least one catalyst compound and at least one activating agent.

According to a another embodiment contains the Katalysatorkomponentenaufschlämmung a carrier, Activating agent and / or an activating agent with carrier and contains a catalyst compound and / or a catalyst compound with support and the catalyst component solution contains one or more catalyst compound (s) and / or one or more Activating compound (s).

According to a another embodiment contains the Katalysatorkomponentenaufschlämmung a carrier, Activating agent and / or an activating agent with carrier and more than one catalyst compound (s) and / or catalyst compounds with support and the catalyst component solution contains at least one catalyst compound.

According to a another embodiment contains the Katalysatorkomponentenaufschlämmung a carrier, Activating agent and / or an activating agent with carrier and more than one catalyst compound and / or catalyst compounds with support and the catalyst component solution contains at least one catalyst compound and at least one activating agent.

According to a another embodiment contains the Katalysatorkomponentenaufschlämmung a carrier, Activating agent and / or an activating agent with carrier and more than one catalyst compound and / or catalyst compounds with support and the catalyst component solution contains one or more catalyst compound (s) and / or one or more Activating compound (s).

According to a another embodiment contains the Katalysatorkomponentenaufschlämmung more than one carrier, activating agent and / or Activating agent with carrier and more than one catalyst compound and / or catalyst compound (s) with support and the catalyst component solution contains at least one catalyst compound.

According to a another embodiment contains the Katalysatorkomponentenaufschlämmung more than one carrier, activating agent and / or activating agent with carrier and more than one catalyst compound and / or catalyst compound (s) with the carrier, and the catalyst component solution contains at least a catalyst compound and at least one activating agent.

According to a another embodiment contains the Katalysatorkomponentenaufschlämmung more than one carrier, activating agent and / or activating agent with carrier and more than one catalyst compound and / or catalyst compound (s) with the carrier, and the catalyst component solution contains one or more catalyst compound (s) and / or one or more activator compound (s).

According to a embodiment , the by contacting the Katalysatorkomponentenaufschlämmung and the catalyst component solution formed catalyst composition has a viscosity of 130-2000 mPa · s (cP) at 20 ° C on, more preferably 180-1500 mPa.s (CP) at 20 ° C, more before&lt;?page 28?&gt;given to 200-800 mPa.s (CP) at 20 ° C.

According to a another embodiment comprises the catalyst component solution up to 80 wt.%, preferably up to 50 wt.%, preferably up to 20 wt.%, preferably up 15 wt.%, More preferably between 1-10 wt.%, More preferably 3-8 wt.% the combination of the catalyst component solution and the Katalysatorkomponentenaufschlämmung based on the weight of the solution and the slurry. According to a further preferred embodiment, the catalyst component solution comprises mineral oil and comprises up to 90 wt.%, preferably up to 80 wt.%, more preferably between 1-50 wt.% and more preferably 1-20 Wt.% Of the combination of the catalyst component solution and the Katalysatorkomponentenaufschlämmung, based on the weight the solution and the slurry.

According to a embodiment the Katalysatorkomponentenaufschlämmung a using Aufschlämmungszufuhrvorrichtung introduced into the polymerization reactor. According to a further embodiment is the catalyst composition and the Katalysatorkomponentenaufschlämmung the catalyst component solution contains, using a Aufschlämmungszufuhrvorrichtung introduced into the polymerization reactor. A Aufschlämmungszufuhrvorrichtung is z. B. <patcit><text>US Pat. No. 5,674,795</text></patcit> described.

According to a embodiment is a catalyst compound comprising catalyst component solution so brought the Katalysatorkomponentenaufschlämmung in contact, that at least 50% of the original in the catalyst component solution deposited catalyst compound existing in or on the carrier are preferably at least 70%, preferably at least 75%, preferably at least 80%, more preferably at least 90%, preferably at least 95%, preferably at least 99%.

According to a another embodiment is a metallocene catalyst compound comprehensive catalyst component solution with a Katalysatorkomponentenaufschlämmung in brought contact comprising a support and an activating agent comprises, preferably an activating agent with the carrier to to form an immobilized catalyst composition. After the contacting is all or substantially all of preferably at least 50%, preferably at least 70%, preferably at least 75%, preferably at least 80%, more preferably at least 90%, preferably at least 95%, preferably at least 99% of the catalyst compound of the catalyst component solution in or on the carrier deposited, which initially is included in the Katalysatorkomponentenaufschlämmung. According to one embodiment a catalyst compound is then in or on the support if the concentration of the catalyst compound in the liquid portion of the composition is reduced with the time after the catalyst compound from the solution was added. The catalyst concentration as described above can be measured.

According to a another embodiment located bfindet the activating agent with the carrier in a mineral oil, which then with a metallocene catalyst solution in Is contacted before the catalyst composition is introduced into the reactor is, preferably where the contacting takes place in-line.

According to a another embodiment can / can the immobilized catalyst composition system or components of which have a carboxylate metal salt as described in PCT Publication <patcit><text>WO 00/02930</text></patcit> and <patcit><text>WO 00/02931</text></patcit> described, are brought into contact.

According to a another embodiment includes the resolution a catalyst compound and the slurry comprises an activating agent with support such. as alumoxane with carriers, and two or more catalyst compounds, which resemble the could be may be or different of the catalyst compound in the solution. The two catalyst compounds can added before or after the activating agent with the carrier to the slurry will. According to a preferred embodiment, first, the activation agent with carrier to the liquid diluent, added to a slurry to form, the catalyst compound is added to the slurry and thereafter another catalyst compound is added to the slurry. The second catalyst is preferably added after the first catalyst compound and the activating agent with support for at least 1 min, preferably at least 15 min, more preferably at least 30 min, more preferably at least 60 min, more preferably at least 120 min, more preferably at least 360 min in contact with each had been brought.

According to a another embodiment the two catalyst compounds are added simultaneously to the slurry, in the same or in different solutions. According to another Ausfüh&lt;?page 29?&gt;ment of a catalyst compound with an activating agent without carrier brought into contact, before it is introduced into the slurry. According to a preferred embodiment, is the activating agent without support a modified or unmodified alumoxane such. B. methylalumoxane.

According to a another embodiment , the catalyst compound to the solution or the slurry in added the form of their components as metal compound and ligands will. For example, cyclopentadienyl, z. B. substituted or unsubstituted cyclopentadiene, indene, Fluorene groups and metal compounds such. As Zirkoniumtetrahalogenid, to the slurry or the solution brought, or both may be added and in response to will. Similarly, one can also metal compounds and / or ligands to the solution and / or the slurry give that included catalyst compounds. The metal compounds and ligands can be the same or different from the components of the Catalyst compound in the solution or the slurry. According to a further embodiment can Ligands and / or metal compounds, both for the solution as also for slurry be added.

According to a another embodiment comprises the catalyst composition a "bisamide" -Katalysatorverbindung (Ie bridged Bis (aryl amide) compounds of Group 4, as described by DH McConville et al are. described in Organometallics 1195, 14, 5478-5480, or bridged Bis (amide) -Katalysatorverbindungen as in <patcit><text>WO 96/27439</text></patcit> ), in conjunction with an activating agent, which is spray-dried to powder form are and then with petroleum have been brought together to give a slurry. This combination can then be contacted with various catalyst component solutions are to form particularly effective multiple catalyst systems. Preferred catalyst compounds include those as above Metallocene catalysts with spatially demanding ligands have been described. According to a further preferred embodiment, includes slurry an activating agent with carrier and the solution comprises a catalyst compound. The catalyst compounds can selected are from various catalyst compounds as described above are, including Metallocenes with spatially demanding ligands.

According to a another embodiment comprises the slurry [(2,4,6-Me₃C₆H₂) NCH₂CH₂]₂NHZrBz₂ or [(2,4,6-Me₃C₆H₂) NCH₂CH₂]₂NHHfBz₂Wherein each Bz is a benzyl group independently, Me is methyl, and the solution comprises bis (n-propylcyclopentadienyl) -MX₂. (Pentamethylcyclopentadienyl) (n-propylcyclopentadienyl) MX₂, Bis (indenyl) -MX₂. or (tetramethylcyclopentadienyl) (n-propylcyclopentadienyl) MX₂Wherein M is zirconium, hafnium or titanium, and X is chlorine, bromine or fluorine.

According to a another embodiment includes the resolution [(2,4,6-Me₃C₆H₂) NCH₂CH₂]₂NHZrBz₂ or [(2,4,6-Me₃C₆H₂) NCH₂CH₂]₂NHHfBz₂Wherein each Bz is a benzyl group independently, Me is methyl, and the slurry includes: 1) alumoxane with carrier and 2) bis (n-propylcyclopentadienyl) -MX₂, (Pentamethylcyclopentadienyl) (n-propylcyclopentadienyl) MX₂, Bis (indenyl) -MX₂. or (tetramethylcyclopentadienyl) (n-propylcyclopentadienyl) MX₂. wherein M is zirconium, hafnium or titanium and X is chlorine, bromine or is fluorine.

According to a another embodiment comprising the slurry: 1) an alumoxane with the carrier, 2) bis (n-propylcyclopentadienyl) -MX₂, (Pentamethylcyclopentadienyl) (n-propylcyclopentadienyl) MX₂, Bis (indenyl) -MX₂(Tetramethylcyclopentadienyl) (n-propylcyclopentadienyl) MX₂Wherein M is zirconium, hafnium or titanium, and X is chlorine, bromine or fluorine, and 3) [(2,4,6-Me₃C₆H₂) NCH₂CH₂]₂NHZrBz₂ or [(2,4,6-Me₃C₆H₂) NCH₂CH₂]₂NHHfBz₂And the solution comprising a metallocene compound with spatially sophisticated Ligands.

According to a another embodiment includes slurry mineral oil and a spray-dried Catalyst compound. According to a another embodiment the spray-dried A catalyst compound containing an element of Group 15 Metal compound. According to a preferred embodiment, includes the spray-dried Catalyst compound [(2,4,6-Me₃O₆H₂)₂NCH₂OH₂]₂NHZrBz₂ or Hafniumanalogon thereof.

According to a another embodiment can the catalyst compound and the activating agent with carrier before or after the Aufschlämmungsverdünnungsmittel are brought together, are brought together.

According to a another embodiment includes the resolution a catalyst compound of bis-indenyl&lt;?page 30?&gt;zirconium dichloride, bis (n-propylcyclopentadienyl) zirconium dichloride, (Pentamethylcyclopentadienyl) (n-propylcyclopentadienyl) zirconium dichloride, (Tetramethylcyclopentadienyl) (n-propylcyclopentadienyl) zirconium dichloride or a mixture thereof.

According to a another embodiment a first catalyst compound with an activating agent with support in the slurry brought together and a second catalyst compound and an activating agent be the solution brought together, and then the two are mixed in-line. According to a another embodiment is the activation means an alumoxane and the other activator is a boron-based activating agent.

According to a another embodiment includes slurry Mineral oil, spray dried [(2,4,6-Me₃C₆H₂) NCH₂CH₂]₂NHZrBz₂And the solution comprises bis (n-propylcyclopentadienyl) zirconium.

According to a embodiment slurry of this invention comprises the activating agent with the carrier and a catalyst compound and the solution comprises a catalyst compound, which in some way is different from the catalyst compound in the slurry. For example, the Aufschlämmungskatalysatorverbindung be a compound described by Formula I or II as above is shown, during the solution catalyst compound a catalyst compound, as represented by formulas III, IV, V VI or VII is described, may be, or vice versa.

According to a another embodiment can, if a bimodal polymer product is desired, a first catalyst compound mixing with an activating agent in the slurry, and then on-line a solution a different catalyst compound present through which the same activating agent can be activated. Since the two Catalyst compounds independently from each other are introduced into the feed line, it becomes easier be, the amount of the two species in the final bimodal product to control, assuming that each catalyst contains at least a polymer species forms.

According to a another embodiment be a compound containing a metal of Group 15 compound and a metallocene catalyst compound having spatially demanding ligands alumoxane with carrier brought together in the process of this invention. Typically the two catalyst compounds in the slurry with the alumoxane with carrier brought together, and the solution includes an adjusting solution of one or the other of the two catalyst compounds.

According to a another embodiment be [(2,4,6-Me₃C₆H₂) NCH₂CH₂]₂NHHfBz₂ and bis (n-propylcyclopentadienyl) zirconium dichloride with methylalumoxane with carrier brought together in the process of this invention. Typically are the two catalyst compounds in the slurry the alumoxane with carrier brought together, and the solution includes one or the other of the two catalyst compounds. The solution is preferably used as adjusting solution used to regulate the product formed in the reactor, by matched the amount of the slurry on-line solution is varied, that is, to adjust the mixture. In one embodiment, is this catalyst composition then used the olefins, preferably ethylene, at a Polymerization temperature of 80-110 ° C and in the presence of little or no / n comonomer / comonomers z. B. witches polymerize.

According to a another embodiment is the slurry in more than 0-90% by weight. Solids, more preferably 1-50 %. By weight, more preferably 5-40 %. By weight, more preferably 10-30 .% By weight, based on the weight of the slurry maintained. According to a further preferred embodiment, is the activating means on the support with between 0.5-7 mmol / g, preferably 2-6 mmol / g, more preferably between 4-5 mmol / g available. According to a further preferred embodiment, is the total amount of the carrier to existing catalyst compound, preferably the activation means with support 1-40 micromol / g, preferably 10-48 mol / g, more preferably 30-36 mol / g.

In one embodiment is the final molar ratio (Ie after combining the solution and the slurry) of Metal compounds of the catalyst to the metal of the activating agent in the range 1000: 1 to 0.5: 1, preferably from 300: 1 to 1: 1, more preferably from 150: 1 to 1: 1; for Boranes, borates, aluminates, etc. the ratio is preferably 1: 1 to 10: 1, and for Alkyl ammonium compounds (eg. As diethylaluminum in connection with water) the ratio preferably 0.5: 1 to 10: 1.

According to a embodiment is the in the slurry used not catalyst compound &lt;?page 31?&gt;soluble in the solvent used in the solution. not with " soluble "is meant that not more than 5 wt.% of the substance in the solvent at 20 ° C and less than 3 minutes of stirring, to solve, preferably not more than 1 wt.%, preferably not more than 0.1 wt.%, preferably not more than 0.01 wt.%. According to a preferred embodiment is the in the slurry used catalyst compound only slightly in an aromatic Hydrocarbon soluble. In a particularly preferred embodiment, the slurry used in the Catalyst compound not soluble in mineral oil, aromatic solvent or aliphatic hydrocarbon (pentane, heptane, etc.).

D. transport of the catalyst composition

In the method of the invention, the Katalysatorkomponentenaufschlämmung with the catalyst component solution brought together and / or implemented in order to in-line to a catalyst composition form. The thus formed catalyst composition is then in the polymerization reactor is introduced. In general, the Catalyst composition introduced into the reactor by using a catalyst feed system is that a container, which can accommodate the Katalysatorkomponentenaufschlämmung, a container the catalyst component solution may take, and a Aufschlämmungszufuhrvorrichtung includes.

Referring on <figref idrefs="S127">1</figref> the Katalysatorkomponentenaufschlämmung, preferably a mineral oil slurry which at least one carrier and at least one activating agent, preferably at least one Activating agent with carrier and optional catalyst compound (s) includes, in a container (A) introduced. According to a preferred embodiment, is (A) a reservoir with stirring, which is designed so that the solid concentration kept homogeneous is. The catalyst component solution which is prepared using a solvent and at least one catalyst compound and / or an activating agent be mixed, is introduced into a container (C). The Katalysatorkomponentenaufschlämmung is then brought together in-line with the catalyst component solution, the to form final catalyst composition. A nucleating such as. for example, silica, alumina, fumed silica or any any other particulate Substance (B) may be in-line or in the container (A) or (C) to the slurry and / or to the solution be added. Accordingly, additional added activating agent or catalyst compounds in-line will. The Katalysatorkomponentenaufschlämmung and resolution preferably in-line at the point (E) for a certain period of time together mixed. z. B. can the solution and the slurry are mixed by a static mixer or a stirred tank be used. Mixing the Katalysatorkomponentenaufschlämmung and the catalyst component solution should be long enough to allow the catalyst compound in the catalyst component solution in the Katalysatorkomponentenaufschlämmung is dispersed, so that the catalyst component, which was originally in the solution, to the activating agent with carrier travels, which originally in the slurry was present. The composition is characterized in a uniform Dispersion of catalyst compounds on the activation means with support whereby the catalyst composition of the invention is formed. The period of time during the slurry, the and the solution are brought into contact, is typically up to 120 min, preferably 1-60 min, more preferably 5-40 min, more preferably 10-30 min.

According to a another embodiment be an aluminum alkyl, an ethoxylated aluminum alkyl, a Alumoxane, an antistatic agent or a Boraktivierungsmittel, such as. for example, a C₁-C₁₅-Alkylaluminium (Z. B. triisobutylaluminum, trimethylaluminum or the like), a C₁-C₁₅-ethoxyliertes alkylaluminum or methylalumoxane ethylalumoxane, isobutyl, modified Alumoxane, or the like, to the mixture of slurry and solution added in-line. The alkyls, antistatic agents, Boraktivierungsmittel and / or alumoxanes can (F) added directly to the combination of solution and slurry be, or may by means of an additional Alkan carrier stream added (such as. for example, isopentane, hexane, heptane and / or octane) (G) will. Preferably, the additional alkyls, antistatic Means Boraktivierungsmittel and / or alumoxanes with up to 500 ppm, more preferably up to 1-300 ppm, more preferably 10-300 ppm, more preferably 10-100 ppm. Preferred carrier streams include isopentane and / or Hexane one. The alkane can (G) to the mixture of slurry and solution be added, typically at a rate of 0.2 up to 27 kg / h (0.5 to 60 lbs / h). Just can Carrier gas, such as. for example, nitrogen, argon, ethane, propane and the like in-line (H) to the mixture of slurry and solution be added. Typically the carrier gas may at a rate of 0.4 to 45 kg / h (1-100 lb / hr), preferably 5 to 23 kg / h (1 to 50 lb / hr), more preferably from 0.4 to 11 kg / h was added (1 to 25 lb / hr) will.

According to a another embodiment is a liquid carrier power in the combination of solution &lt;?page 32?&gt;and slurry introduced which extends in a downward direction emotional. The mixture of solution, slurry and liquid carrier power may pass through an optional mixer or length of tube through to be mixed before with a gaseous carrier stream is brought into contact.

correspondingly may witches (or another α-olefin or diolefin) and in-line (J) to the mixture of slurry solution be added. The slurry / solution mixture is then preferably through an injection tube (O) to the reactor (Q) out. In some embodiments, can make the slurry / solution mixture to aerosol the injection pipe. In a preferred embodiment, the injection tube has a diameter of 0.16 cm to 1.27 cm (1/16 Inch to 1/2 inch) preferably 0.5 cm to 0.9 cm (3/16 inch to 3/8 inch), more preferably from 0.6 cm to 0.9 cm (1/4 inch to 3/8 inch) on.

In one embodiment Recycle gas (sometimes also referred to as recycle gas) into the support tube (S) introduced according to a Alternatively, is introduced into the support tube monomer gas such. as ethylene gas. nucleating (K), such. As fumed silica, may be added directly into the reactor.

According to a another embodiment this invention, a plenum may be used. A collection chamber is an apparatus to a particle lean zone in a fluidized bed gas phase reactor to form, as detailed in <patcit><text>US Patent No. 5,693,727</text></patcit> is described. A plenum may have one, two or more injection nozzles exhibit.

According to a Alternatively, , when a metallocene catalyst or other similar Catalyst is used in the gas phase reactor, oxygen or a fluorobenzene be fed directly to the reactor or the recycle gas, to affect the polymerization rate. Thus, when a metallocene catalyst (which with respect to oxygen or fluorobenzene sensitive is) in combination with another catalyst (which not against Oxygen sensitive) is used in a gas phase reactor is oxygen can be used to the metallocene polymerization rate relative to the polymerization rate of the other catalyst to change. An example of such a catalyst combination is bis (n-propylcyclopentadienyl) zirconium and [(2,4,6-Me₃C₆H₂) NCH₂CH₂]₂NHZrBz₂Wherein Me is methyl, or bis (indenyl) zirconium dichloride and [(2,4,6-Me₃C₆H₂) NCH₂CH₂]₂NHHfBz₂Wherein Me Methyl. For example, when the oxygen concentration in the Nitrogen flow of 0.1 ppm to 0.5 ppm is changed, is considerably less polymer from the bisindenyl ZrCl₂ arise, and the relative quantity of polymer that of [(2,4,6-Me₃C₆H₂) NCH₂CH₂]₂NHHfBz₂ is formed, is increased. <patcit><text>WO / 09328</text></patcit> discloses the addition of water and / or carbon dioxide to gas phase polymerization reactors.

According to a further embodiment, Still referring to <figref idrefs="S127">1</figref>, becomes the slurry comprising mineral oil, at least one catalyst compound, a support and an activating agent, in (A) were mixed and / or imported by (A). The catalyst component solution comprising a solvent, such as. for example, toluene, hexane, mineral oil or tetrahydrofuran, and a catalyst compound and / or a Activating agent is mixed in (C) and / or introduced from (C). nucleating (B) and (K), such. As fumed silica, may on-line at one or several position / s are added and may be wet or dry. The slurry and the solution are brought together and typically mixed at (E). Optional can lower alkyls (F), such as, for example triisobutyl aluminum, an alumoxane, modified methylalumoxane and / or trimethyl aluminum, right be added in-line to the combination or via an alkane, such. as isopentane, feed (G). Nitrogen (H) and / or olefin, such. as witches (J), can also be added in-line. The combination can then means an injection tube (O) (such as. for example, a 0.3 cm (1/8 inch) pipe) be injected in a gas phase reactor (Q). The injection pipe (O) can inside a larger support tube be introduced (S), such as. for example, a 2.54 cm (1 inch) pipe. It can added oxygen directly to the reactor (Q) or the recycle gas (P) be to enhance the activity of one or / to change several catalyst s. (R) means, a current (Monomer, recycle gas, alkane) to the support tube (S).

According to a another embodiment were the ball formation of catalyst and / or general deposits at the nozzle reduced by only a Isopentanträger via feedline (G) in the combination of solution and slurry is introduced, according to which the combination of solution, slurry and Isopentane preferably in the vertical direction with downward flow bwegt in the reactor, with a nitrogen stream (H) is used, the isopentane / slurry mixture to distribute in the reactor.

the Catalyst injection tube extends through a compressed chevron lock in the reactor and &lt;?page 33?&gt;ranging in length from 0.25 to 3.1 m (0.1 Inches to 10 feet) into the fluidized bed pure, preferably 2.5 cm to 1.8 m (1 inch to 6 feet), and more preferably from 5 cm to 1.5 m (2 inches to 5 feet). Typically, the penetration depth depends the diameter of the reactor from; typically on 1/20 to 1/2 of the reactor diameter, preferably 10/01 to 02/01 and more preferably 5/1 to 3/1 of the reactor diameter. The end of the tube may be cut perpendicular to the axis, a nozzle cone or a tip with an angle in the range of 0 to 90 degrees, preferably to form in the range 10 to 80 degrees.

Of the Edge of the hole can be brought to a new cutting edge. The tube may be positioned so that the reduced Harzadhäsion will or may antistatic with a deposit-prophylactic or be coated compound. The tube may also diagonally with a cut angle of 0 to 80 degrees from the axial orientation of the tube be, preferably 0 to 60 degrees. The opening of the tube can be the same be like the bore of the tube or expanded or reduced, a nozzle form, being added dropwise with sufficient pressure and with a Geometry, that a dispersed spray of a solution slurry and / or a powder is provided in the reactor, preferably in the fluidized bed.

the Injection tube can optionally contain in a structure within the fluid bed be to provide a structural whole. This support tube typically a tube with thick walls having an inner diameter of 0.64 cm to 12.7 cm (1/4 inch to 5 inches), preferably 1.3 cm to 7.6 cm (1/2 inch to 3 inches), and more preferably from 1.9 cm to 5 cm (3/4 inch to 2 inches). The support tube preferably extends through the reactor wall above about the length of Injektonsrohrs, thereby enabling is that the injection pipe just inside the terminal segment of the support tube ends or 25.4 cm (10 inches) extends beyond. Preferably extends the injection pipe 1.8 cm to 12.7 cm above the End of the support tube addition, preferably 2.5 cm to 7.6 cm (1 to 3 inches). The end of the support tube in the reactor may be cut flat and perpendicular to the axis of the tube may be or are tapered at an angle of 10 to 80 degrees. the End of the support tube can be polished or with an antistatic or deposits retardant Material to be coated.

On Purge flow of fluid (R) (typically fresh monomer, ethylene, Hexane, isopentane, recycle gas, and the like) is preferably from outside of the reactor, the support tube introduced along, to assist in the dispersion of the catalyst composition to be what the production of resinous grained particles with good morphology reduced agglomeration and an average particle size (APS = Average Particle Size) in the range of 0.01 cm to 0.3 cm (0.005 to 0.10 inches) allows. The fluid-purge stream helps deposits at the end of the catalyst injection tube and to support tubes to minimize. That in the support tube imported Fluid may comprise hydrogen, olefins or diolefins, including, but not limited on C₂-C₄₀-α-olefins and C₂-C₄₀diolefins, Ethylene, propylene, butene, hexene, octene, norbornene, pentene, hexadiene, Pentadiene, isobutylene, octadiene, cyclopentadiene, comonomer is used in the polymerization reaction, hydrogen; alkanes, such. B. C₁-C₄₀Alkanes, including but not limited to isopentane, hexane, ethane, propane, butane and the like; Mineral oil, cycle gas with or without condensed liquids or any combination thereof. Preferably, the current is in the supporting tube fresh ethylene or propylene that may be heated. In addition, % To the current present in an amount in the range of 0.001. To 50% of the Stream, an alkane, such. As isopentane or hexane, can be added. The alkane can be dispersed in the stream and can be used as dispersed Liquid droplets are present or at the exit of the support tube are evaporated. The presence of liquid may deposits on the reduce output.

The flow rate the fluid in the support tube ranges from 5 to 10,000 pph and is in some way dependent on the reactor size. The linear velocity of the fluid in the support tube ranges from 11 to 549 km / h (10 to 500 ft / sec), preferably 22 to 329 km / h (20 to 300 ft / sec) and more preferably 33-219 km / h (30 to 200 ft / sec).

alternative , the output of the support tube as a nozzle be designed in the end to a beam or a dispersion of to form gas to assist in the distribution of the catalyst composition to assist. According to a embodiment is the inner diameter of the support tube gradually by 3 to 80% reduced in the end, it is preferably tapered from 5 to 50%, in order a nozzle to form, so that the accelerated fluid flow and / or dispersed is. insertion the injection tube is not by the internal taper of the support tube impaired.

According to a another embodiment the invention can the contact time of slurry, and solution be varied to the formation of the active catalyst complex adjust or control. The contact time of the slurry and solution is preferably in the range of 1 min to 120 min, &lt;?page 34?&gt;preferably in the range of 2 min to 60 min, preferably 5 min to 45 min, more preferably from 10 min to 30 min.

According to a another embodiment is the contact temperature of the slurry and solution is in the range of 0 ° C to 80 ° C, preferably from 0 ° C to 60 ° C, more preferably from 10 ° C to 50 ° C and most preferably from 20 ° C to 40 ° C.

According to a another embodiment the invention provides the introduction the immobilized catalyst system in the presence of a mineral oil or a surface modifier or a combination thereof, as described in PCT Publication <patcit><text>WO 96/11960</text></patcit> and <patcit><text>USSN 09 / 113.261</text></patcit>, Registered on 10 July 1998, describes ready. According to a further embodiment A slurry or a surface modifier like an aluminum stearate in mineral oil) with the combination of slurry and solution introduced into the reactor (T). According to a another embodiment was the surface modifier such. as aluminum in the slurry tank (A) was added.

According to a another embodiment be of a catalyst or catalysts all having up to 6 .% By weight of a metal stearate (preferably a aluminum stearate, more preferably aluminum distearate) or an anti-static agent merged based on the weight of the catalyst, any support and the stearate or anti-static agent, preferably 2 to 3 wt.%. In one embodiment, A solution or slurry the metal stearate or anti-static agent introduced into the reactor. the Stearate or anti-static agent may with the slurry (A) or the solution merged (C) are or may be introduced with the combination of slurry and solution together (R). In a preferred embodiment , the catalyst compounds and / or activating agents with 0.5 to 4 wt.% Anti-static agent, such as. For example, methoxylated Amine, such. As Witco's Kemamine AS-990 from ICI Specialties in Bloomington Delaware, merged.

In a further embodiment be the catalyst system or the components thereof with benzil, Xylitol, Irganox^TM 565, sorbitol or the like merged and then introduced into the reactor. These funds can brought together the catalyst compounds and / or activating agents or can be in a solution with or without the catalyst system or the components thereof in the introduced reactor will. According to this means with the slurry (A) or the solution (C) can be brought together or with the combination slurry and solution are introduced together (R).

According to a another embodiment the process of this invention may further comprise additional solutions and slurries include. For example, according to a preferred embodiment, a slurry with two or more solutions with the same or different catalyst compounds and / or Activating agents are combined. Accordingly, the solution can with two or more slurries, these are the same or different carriers and the same or different catalyst compounds and / or activating agent, are combined. Similarly, the process of this invention, two or more slurries include, combined with two or more solutions, preferably in-line, the slurries each comprise the same or different carriers and the same or different catalyst compounds and / or activator include, and the solutions include the same or different catalyst compounds and / or activating agent. For example, a slurry Activating agent with carrier and contain two different catalyst compounds, and two Solutions, wherein each one of the catalysts contains in the slurry, are each independently in-line with the slurry brought together.

E. Use of the catalyst composition, to control the product properties

Of the Timing, temperature, concentrations, and the order mixing the solution, the slurry and any optionally added material (nucleating agents, catalyst compounds, Activating agent, etc.), as described above, can be used in order to change the product characteristics. The melt index, the relative amount of polymer, which is formed of each catalyst is, and other properties of the polymer produced may also changed be by process parameters are set, which the Adjusting the hydrogen concentration in the polymerization system lock in, or by: <ul><li>1) the amount of the first catalyst changes in the polymerization system and / or</li><li>2) the amount of the second catalyst in the polymerization changed and / or</li><li>3) the concentration of hydrogen in the polymerization changed becomes; and or </li>&lt;?page 35?&gt;<li>4) the relative proportion of the catalyst is changed in the polymerization (And possibly the individual feed rates to be adjusted to a stable or constant resin production rate to maintain); and or</li><li>5) the amount of liquid and / or gas, which is removed from the process and / or delivered is changed becomes; and or</li><li>6) the amount and / or composition of a recovered liquid and / or a recovered gas, which the polymerization recycled is changed is, wherein the liquid obtained or the gas obtained is obtained from polymer of the Polymerization is removed; and or</li><li>7) a hydrogenation catalyst in the polymerization process is used; and or</li><li>8) the polymerization temperature is changed; and or</li><li>9) of the ethylene partial pressure is changed in the polymerization process; and or</li><li>10) the ethylene to comonomer ratio in the polymerization process changed becomes; and or</li><li>11) the ratio of activating agent to transition metal changes in the activation sequence becomes; and or</li><li>12) changing the relative feed rates of the slurry and / or solution; and or</li><li>13) the mixing time, the temperature or degree of mixing the slurry and the solution in-line changed becomes; and or</li><li>14) different types of activation compounds to the polymerization process are added; and or</li><li>15) oxygen or fluorobenzene or other catalyst poison is added to the polymerization process.</li></ul>

Around z. B. the flow index and / or a melt index according to the invention polymer produced using a slurry of Methylalumoxane with carrier and [(2,4,6-Me₃C₆H₂) NCH₂CH₂]₂NH} ZrBz₂ and a solution of bis (n-propylcyclopentadienyl) zirconium dichloride to change, can the temperature of the reaction in the polymerization reactor, the Concentration of hydrogen in the reactor or the concentration of bis (n-propylcyclopentadienyl) zirconium in solution before the solution with the slurry is brought into contact, modify, or one may the relative feed rate of the catalyst component solution and / or change the Katalysatorkomponentenaufschlämmung.

According to a preferred embodiment, is the flow index (I₂₁ according to ASTM D-1238, Condition E, at 190 ° C measured) of the polymer product is measured at regular intervals, and it is one of the factors mentioned above, preferably the Temperature, the catalyst connection feed rate, the ratio of the two or more Catalysts to each other, the monomer partial pressure, oxygen concentration and / or the hydrogen concentration changes, to the flow index to the desired Level bring, if necessary. Preferably, the samples for the flow index measurements melt homogenized by extruding in an extruder, which can be either with a screw, preferably with a mixing head or a twin screw, is equipped to either bands or strands to make. The tape and / or the strands are typically in cut narrow parts to perform flow property measurements.

According to a embodiment is a polymer product property is measured in-line, and in response it is the ratio of the combined catalysts changed. According to one embodiment the molar ratio the catalyst compound in the Katalysatorkomponentenaufschlämmung to the catalyst compound in the catalyst component solution, after the slurry and the solution mixed to form the final catalyst composition were 500: 1 to 1: 500, preferably 100: 1 to 1: 100, more preferably 50: 1 to 1:50, and most preferably 40: 1 to 1:10. According to a another embodiment the molar ratio a catalyst compound of group 15 in the slurry to a metallocene catalyst compound having spatially demanding ligands in the solution, after the slurry and the solution were mixed to form the catalyst composition, 500: 1, preferably 100: 1, more preferably 50: 1, more preferably 10: 1 and even more preferably 5: 1. Preferably, the measured product property the flow index, Melt index, density, MWD, comonomer content and combinations of the polymer product. According to a are another embodiment, if the ratio changing the catalyst compounds is, the import rate of the catalyst composition to the reactor or other process parameter is changed to a desired production rate maintain.

correspondingly can also the design of the carrier, the number of functional groups on the support (such as. for example, -OH groups of silica), loading with the activating agent and the loading &lt;?page 36?&gt;preimpregnated Catalyst affect the product formed.

correspondingly the variation change of Ethylenpartialdruckes product characteristics. For example, increased the increase of Ethylenpartialdruckes in the gas phase reactor of 1.5 to 1.7 MPa (220 to 240 psi) in a system, wherein the solution of bis (n-propylcyclopentadienyl) zirconium dichloride and the slurry [(2,4,6-Me₃C₆H₂) NCH₂CH₂]₂NHZrBz₂ and methylalumoxane with support included, the flow index of 100 up over 700 dg / min.

While not wishing to be bound by any theory, the inventors believe that the methods described herein, the solution catalyst compound in and on a support, preferably an activating agent with support, immobilize. herein described in-line immobilization preferably lead to a catalyst system with the carrier, which, when the reactor supplied is a better particle morphology, bulk density and / or higher catalyst activities, and leads, that no additional equipment is necessary to ensure the catalyst compound solution into a reactor, in particular a gas phase or slurry phase, introduce. It is known in the trade area that typical support techniques for metallocene catalyst compounds with support to provide, to a lower overall productivity of the educated Supported catalysts to lead. In some cases makes the process with carrier indeed certain of these catalyst compounds useless for commercial Polymerization process, wherein in particular the use of Supported catalysts is preferred. This is particularly the case when the insertion of a Catalyst system without carrier in a gas phase process over a conventional Ka lytic system with carrier is compared. with conventional Catalyst system are those catalyst systems meant by carrier, which by contacting a support material, an activating agent and a catalyst compound in various ways under a variety by conditions outside a catalyst supply apparatus are formed.

Examples conventional A method to provide metallocene catalyst systems with carriers, in the <patcit><text>US Patent Nos. 4,701,432</text></patcit>. <patcit><text>4,808,561</text></patcit>. <patcit><text>4,912,075</text></patcit>. <patcit><text>4,925,821</text></patcit>. <patcit><text>4,937,217</text></patcit>. <patcit><text>5,008,228</text></patcit>. <patcit><text>5,238,892</text></patcit>. <patcit><text>5,240,894</text></patcit>. <patcit><text>5,332,706</text></patcit>. <patcit><text>5,346,925</text></patcit>. <patcit><text>5,422,325</text></patcit>. <patcit><text>5,466,649</text></patcit>. <patcit><text>5,466,766</text></patcit>. <patcit><text>5,468,702</text></patcit>. <patcit><text>5,529,965</text></patcit>. <patcit><text>5,554,704</text></patcit>. <patcit><text>5,629,253</text></patcit>. <patcit><text>5,639,835</text></patcit>. <patcit><text>5,625,015</text></patcit>. <patcit><text>5,643,847</text></patcit>. <patcit><text>5,665,665</text></patcit>. <patcit><text>5,698,487</text></patcit>. <patcit><text>5,714,424</text></patcit>. <patcit><text>5,723,400</text></patcit>. <patcit><text>5,723,402</text></patcit>. <patcit><text>5,731,261</text></patcit>. <patcit><text>5,759,940</text></patcit>. <patcit><text>5,767,032</text></patcit>. <patcit><text>5,770,664</text></patcit>. <patcit><text>5,846,895</text></patcit> and <patcit><text>5,939,348</text></patcit> and the US-sign-serial numbers 271.598, registered on 7 July 1994 and 788.736, filed on January 23, 1997 and PCT publications <patcit><text>WO 95/32995</text></patcit>. <patcit><text>WO 95/14044</text></patcit>. <patcit><text>WO 96/06187</text></patcit> and <patcit><text>WO 97/02297</text></patcit> and <patcit><text>EP-B1 0685494</text></patcit> described. It was also surprisingly found that catalyst systems not commercially in a gas phase process with carrier can be provided, particularly useful are, when using the method according to the invention are immobilized.

VI. polymerization

The prepared catalyst systems and the method of adding a Catalyst system as described above, for use in any Prepolymerisations- and / or polymerization process over a suitable broad range of temperatures and pressures. The temperatures can in the range of 60 ° C to 280 ° C, preferably from 50 ° C to 200 ° C lie, and the pressures used can in Ranging from 1 atmosphere to 500 atmospheres or higher be.

polymerization conclude solution, Gas phase, slurry and high pressure process or a combination thereof. especially preferred is a gas phase or slurry phase of one or more olefins, including at least one ethylene or Propylene and more preferably ethylene.

In one embodiment refers to the process of this invention in a solvent, High pressure, slurry or gas phase polymerization process of one or more olefin monomers having 2 to 30 carbon atoms, preferably 2 to 12 carbon atoms and more preferably 2 to 8 carbon atoms. The invention is especially for the polymerization of two or more olefin monomers selected from Ethylene, propylene, butene-1, pentene-1, 4-methylpentene-1, hexene-1, Octene-1 and decene-1 well suited.

More Monomers which are useful in the method of the invention include ethylenically unsaturated Monomers, diolefins having 4 to 18 carbon atoms, conjugated or nonconjugated dienes, polyenes, vinyl monomers and cyclic Olefins. Nonlimiting Monomers useful in the invention are able Norbornene, norbornadiene, isobutylene, isoprene, Vinylbenzocylcobutan, Styrene, alkyl substituted Sty&lt;?page 37?&gt;rol, ethylidenenorbornene, dicyclopentadiene and include cyclopentene.

In the most preferred embodiment, the method of the invention, a copolymer of ethylene is produced, wherein a comonomer having at least one α-olefin having 3 to 15 carbon atoms, preferably 4 to 12 carbon atoms and most preferably 4 to 8 carbon atoms is polymerized in a gas phase process with ethylene.

According to a another embodiment the method of the invention is ethylene or propylene with at least two different comonomers polymerized, optionally one of which a diene, to form a terpolymer.

In one embodiment the molar ratio of comonomer to ethylene, C_x/ C₂. wherein C_x the amount of comonomer and C2 Amount of ethylene is between 0.001 to 0.200, and more preferably between .002 to .008.

In one embodiment the invention relates to a polymerization process, particularly a Gas phase or slurry for the polymerization of propylene alone or with one or more other monomers including Ethylene and / or other olefins having from 4 to 12 carbon atoms. Polypropylene polymers may be prepared by mixing the particular bridged metallocene catalysts with spatially demanding ligands such as in the <patcit><text>U.S. Patents No. 5,296,434</text></patcit> and <patcit><text>5,278,264</text></patcit> described, be used.

Typically is in a gas phase polymerization process a continuous Circuit used, wherein in one part of the cycle of a reactor system a circulating gas stream, otherwise known as the recycle stream or fluidising medium through the heat of polymerization in the Reactor is heated. This heat is of the circulation composition in another part of the Cycle by a cooling system outside the reactor removed. Generally, in a gas fluidized bed process for producing polymers, a gaseous stream containing a or more monomers continuously in the presence of a catalyst under reactive conditions circulated through a fluidized bed. The gas stream is of the fluidized bed removed and circulated in the reactor. Simultaneously, polymer product is of the reactor is removed and fresh monomer is added to the polymerized monomer to replace. (See, eg. B.<patcit><text>US Pat. No. 4,543,399</text></patcit>. <patcit><text>4,588,790</text></patcit>. <patcit><text>5,028,670</text></patcit>. <patcit><text>5,317,036</text></patcit>. <patcit><text>5,352,749</text></patcit>. <patcit><text>5,405,922</text></patcit>. <patcit><text>5,436,304</text></patcit>. <patcit><text>5,453,471</text></patcit>. <patcit><text>5,462,999</text></patcit>. <patcit><text>5,616,661</text></patcit> and <patcit><text>5,668,228</text></patcit>.)

Of the Reactor pressure in a gas phase process may vary from 690 kPa to 4138 kPa (100 psig to 600 psig) may vary, preferably in the range of 1379 kPa to 2759 kPa (200 psig to 400 psig), more preferably in Range from 1724 kPa to 2414 kPa (250 psig to 350 psig).

The Reactor temperature in a gas phase process may vary from 30 ° C to 120 ° C, preferably 60 ° C to 115 ° C, more preferably in the range of 70 ° C to 110 ° C, and most preferably vary in the range from 70 ° C to 95 ° C.

More Gas phase process, who presided chat advantage of the method of the invention are close Series or multi-stage polymerization, a. Also include gas phase process, which are encompassed by the invention, those disclosed in the <patcit><text>US Patent Nos. 5,627,242</text></patcit>. <patcit><text>5,665,818</text></patcit> and <patcit><text>5,677,375</text></patcit> and European publications <patcit><text>EP-A-0,794,200</text></patcit>. <patcit><text>EP-B1-0,649,992</text></patcit>. <patcit><text>EP-A-0,802,202</text></patcit> and <patcit><text>EP-B-634.421</text></patcit> on.

According to a preferred embodiment, is the reactor used in the present invention in the Capable of producing more than 227 kg (500 lbs) of polymer per hour to 90,900 kg / h (200,000 lbs / h) or more to produce polymer and the The method produces these amounts, preferably more than 455 kg / h (1000 lbs / h), more preferably more than 4540 kg / h (10,000 lbs / h), and even more preferably greater than 11300 kg / hr (25000 lbs / hr), even more preferably greater than 15900 kg / hr (35000 lbs / hr), and still more preferably more than 22700 kg / h (50,000 lbs / hr) and most preferably greater 29,000 kg / h (65000 lbs / hr) to greater than 45500 kg / h (100,000 lbs / h).

In a slurry polymerization are generally pressures in the range 1 to 50 atmospheres and even greater and Temperatures in the range of 0 ° C to 120 ° C used. In a slurry, a suspension of a solid, particulate polymer is in a liquid Polymerisationsverdünnungsmittelmedium, to which ethylene and comonomers and often hydrogen along with be added to the catalyst is formed. The suspension thinner &lt;?page 38?&gt;including, will at intervals or continuously removed from the reactor, wherein the volatile Components separated from the polymer and the reactor, optionally after fed to a distillation again will. The liquid diluent employed in the polymerization is typically an alkane having from 3 to 7 carbon atoms, preferably a branched alkane. The medium employed should, under the conditions the polymerization liquid be and relatively inert. When a propane medium is used, the method above the critical temperature and the critical Pressure of the reaction diluent to be performed. Preferably, a hexane or an isobutane medium is employed.

A preferred polymerization technique of the invention is a particle-forming Polymerization or a slurry, the temperature being kept below the temperature at wherein the polymer in solution goes. Such art is the art well known and z. B. in<patcit><text>US Pat. No. 3,248,179</text></patcit> described. Other slurry processes conclude are those which use a loop reactor and those a plurality of reactors with agitators in series, parallel or Combinations thereof use. Non-limiting examples of slurry conclude continuous loop or stirred tank processes a. also are other examples of slurry in the <patcit><text>US Patent Nos. 4,613,484</text></patcit> and <patcit><text>5,986,021</text></patcit> described.

In one embodiment is in the slurry the invention used reactor capable of more than 907 kg / h (2000 lbs) of polymer per hour, more preferably more than 2268 kg / h (5000 lbs / hr) and most preferably 4540 kg / h (10,000 lbs / h) form, and the method of the invention produces these quantities. In a further embodiment produces the slurry reactor used in the process of the invention more than 6404 kg (15,000 lbs) of polymer per hour, preferably more than 11340 kg / hr (25000 lbs / hr) to 45500 kg / h (100,000 lbs / h).

Examples Solution method are in the <patcit><text>US Patent Nos. 4,271,060</text></patcit>. <patcit><text>5,001,205</text></patcit>. <patcit><text>5,236,998</text></patcit>. <patcit><text>5,589,555</text></patcit> and <patcit><text>5,977,251</text></patcit> and PCT <patcit><text>WO 99/32525</text></patcit> and PCT <patcit><text>WO 99/40130</text></patcit> described.

On preferred method of the invention is one, wherein the method, preferably a slurry or gas phase process in the presence of a metallocene catalyst system with spatially sophisticated Ligands of the invention and without or substantially without Scavenger accomplished is such. as triethylaluminum, trimethylaluminum, triisobutylaluminum and tri-n-hexylaluminum and diethyl aluminum chloride, dibutyl zinc and the same. This preferred process is described in PCT publication<patcit><text>WO 96/08520</text></patcit> and the <patcit><text>US Patent Nos. 5,712,352</text></patcit> and <patcit><text>5,763,543</text></patcit> described.

In one embodiment of the invention are olefins, preferably C₂- -C₃₀Olefins or α-olefins, preferably ethylene or propylene or combinations thereof, in the presence of the metallocene catalyst system of the invention as described above, before the main polymerization, prepolymerized. The prepolymerization can take place batchwise or continuously in gas, solution or slurry phase, including at increased To press, accomplished will. The prepolymerization can with any olefin monomer or Combinations and / or in the presence of any molecular weight controlling agent, such. as hydrogen performed will. For examples for Prepolymerisationsvorgehensweisen see <patcit><text>US Patent Nos. 4,748,221</text></patcit>. <patcit><text>4,789,359</text></patcit>. <patcit><text>4,923,833</text></patcit>. <patcit><text>4,921,825</text></patcit>. <patcit><text>5,283,278</text></patcit> and <patcit><text>5,705,578</text></patcit> and European Publication <patcit><text>EP-B-0279863</text></patcit> and PCT Publication <patcit><text>WO 97/44371</text></patcit>,

In one embodiment is not toluene at the manufacturing or polymerization of this invention.

VII. Polymer Products

The Polymers, which are produced in the method of the invention, can in a wide variety of products and end-use applications be used. The products produced in the method of the invention include polymers linear low density polyethylene, elastomers, plastomers, High density polyethylenes, medium density polyethylenes, Low density polyethylenes, multimodal or bimodal polyethylenes high molecular weight, polypropylene and polypropylene copolymers on.

The Polymers, typically ethylene based polymers, have a Density in the range of 0.86 g / cc to 0.97 g / cc, depending on the desired Use on. For some applications a density in the range of 0.88 g / cc to 0.920 g / cc is preferred, while in other applications, such. as pipe, film and blow molding, a density in the range of 0.930 g / cc to 0.965 g / cc is preferred. For polymers low density, such as. for example, for film applications, is a Density of 0.910 g / cc to 0.940 g / cc preferred. The&lt;?page 39?&gt;density according to standard ASTM method measured.

The Polymers produced by the process of the invention, can a molecular weight distribution, a ratio of weight Molecular weight to number-averaged molecular weight (M_w/ M_n) Of greater than 1.5 to 70 exhibit. In some embodiments, the formed Polymer a narrow M_w/ M_n from 1.5 to 15, whereas the polymer formed in other embodiments, a M_w/ M_n has from 30 to 50. The polymers of the invention can also have a narrow or broad composition distribution, measured by the composition distribution breadth index (CDBI = Composition Distribution Breadth Index). Further details of determining the CDBI of a copolymer are known in the art. See, eg., PCT Patent Application<patcit><text>WO 93/03093</text></patcit>, released February 18, 1993. In some embodiments, the can produced Polymer having a CDBI of 80% or more, or may have a CDBI have 50% or less.

According to a embodiment the polymers of the invention CDBI's generally in the range of greater than 50% to 100%, preferably 99%, preferably in the range of 55% to 85% and more preferably 60% to 80%, even more preferably greater than 60%, even more preferably greater than 65%.

According to a another embodiment have polymers which are prepared using this invention be a CDBI of less than 50%, more preferably less than 40% and most preferably less than 30%.

The Polymers of the present invention have according to an embodiment a melt index (MI) or (I₂) Measured, by ASTM-D-1238-E, in the range from 0.01 dg / min to 1000 dg / min, more preferably from 0.01 dg / min to 100 dg / min, even more preferably of 0.01 dg / min to 50 dg / min, and most preferably from 0.1 dg / min to 10 dg / min.

The Polymers of the invention have in one embodiment a melt index ratio (I₂₁/ I₂) (I₂₁ is measured by ASTM-D-1238-F) of 10 to less than 25, more preferably from 15 to less than 25th

The Polymers of the invention have in a preferred embodiment a melt index ratio (I₂₁/ I₂) (I₂₁ is measured by ASTM-D-1238-F) of preferably greater than 25, more preferably greater than 30, even more preferably greater than 40, even more preferably greater than 50, and most preferably greater than 65. In one embodiment, the polymer of the invention has a narrow molecular weight distribution and a broad composition distribution or vice versa comprise, and it may in one of the <patcit><text>US Patent No. 5,798,427</text></patcit> be described polymers.

In one embodiment , the polymers produced by this invention, a multimodal molecular weight distribution (M_w/ M_n) or one typical bimodal molecular weight distribution. In a preferred embodiment the polymer produced has a density of 0.93 to 0.96 g / cc, an MI (I₂) From 0.03 to 0.10 g / 10 min, an SI (I₂₁) 4 to 12 g / 10 min, a MFR (I₂₁/ I₂) from 80 to 180, a total Mw 200000-400000, a total M_n 5000-10000, an M_w/ M_n from 20 to 50. Preferably, the Group has low molecular weight (~ 500 to ~ 50,000) has a density of From 0.935 to 0.975 g / cc, and the fraction of high molecular weight (~ 50,000 to ~ 8000000) has a density of 0.910 to 0.950 g / cc on. These polymers are particularly useful for film and pipe, especially useful for PE-100 pipe applications. More preferably, this embodiment the polymer, the following Molekulargewichtsverteilungs- (MWD) characteristics on. The MWDs, as obtained by Size Exclusion Chromatography (SEC = size exclusion chromatography) are obtained, may under Using the bimodal setting program to be deployed. The preferred distribution of the polymer, the ratio of weight percent of the HMW fraction and weight percent of the LMW fraction is 20-80 to 80-20, more preferably 30-70 to 70-30 and more preferably 40-60 to 60-40. Higher Weight percent HMW than LMW weight percent are preferred. The SEC curve can be further are analyzed to determine the percentage of weight%&gt; 1MM what weight the of the total MWD that has a molecular weight greater than has 1 million, and by wt%&gt; 100 K, which are the weight percent of the total MWD that is greater than 100,000 molecular weight. The weight ratio is simply wt%&gt; 1MM divided by wt%&gt; 100 K to. 100000 was as an approximate means of dividing the total MWD into a HMW (high molecular weight) and LMW (low Molecular weight) region used. This ratio is a simple, but sensitive indication of the relative amount of particles having very high molecular weight in the HMW region of the MWD. The preferred embodiment the polymer has the preferred range of weight percentage (WPR = Weight Percent ration) higher than 10, but less than 30, preferably higher than 15, but less than 25. It has been found that the stability of an inflated bladder while the Folienextru&lt;?page 40?&gt;sion depends on this WPR as shown in the table is shown below. A preferred catalyst system for the preparation of these polymers in accordance with this Invention comprises [(2,4,6-Me₃C₆H₂) NCH₂CH₂]₂NH} HfBz₂ or [(2,4,6-Me₃C₆H₂) NCH₂CH₂]₂NH} ZrBz₂ combined with bis (indenyl) zirconium dichloride, (Pentamethylcyclopentadienyl) (n-propylcyclopentadienyl) zirconium dichloride or (tetramethylcyclopentadienyl) (n-propylcyclopentadienyl) zirconium dichloride and methylalumoxane with carrier. <tables><table frame="all"><tgroup cols="10" colsep="1" rowsep="1"><colspec colname="1" colwidth="1*" /><colspec colname="2" colwidth="1*" /><colspec colname="3" colwidth="1*" /><colspec colname="4" colwidth="1*" /><colspec colname="5" colwidth="1*" /><colspec colname="6" colwidth="1*" /><colspec colname="7" colwidth="1*" /><colspec colname="8" colwidth="1*" /><colspec colname="9" colwidth="1*" /><colspec colname="10" colwidth="1*" /><tbody><row><entry colname="1">sample</entry><entry colname="2">FI</entry><entry colname="3">MI</entry><entry colname="4">MFR</entry><entry colname="5">HMW Mw</entry><entry colname="6">HMW% Split</entry><entry colname="7">Wt.%&gt; 1MM</entry><entry colname="8">. Wt%&gt; 100K</entry><entry colname="9">. Wt% ratio</entry><entry colname="10">bubble stability</entry></row><row><entry colname="1">No. 1</entry><entry colname="2">8.32</entry><entry colname="3">0,051</entry><entry colname="4">167.3</entry><entry colname="5">605500</entry><entry colname="6">53.5%</entry><entry colname="7">9.7%</entry><entry colname="8">41.8%</entry><entry colname="9">23%</entry><entry colname="10">low</entry></row><row><entry colname="1">No. 2</entry><entry colname="2">7.45</entry><entry colname="3">0.06</entry><entry colname="4">124</entry><entry colname="5">584000</entry><entry colname="6">50.1%</entry><entry colname="7">8.7%</entry><entry colname="8">41.7%</entry><entry colname="9">21%</entry><entry colname="10">Good</entry></row><row><entry colname="1">No. 3</entry><entry colname="2">7.99</entry><entry colname="3">0,047</entry><entry colname="4">168.7</entry><entry colname="5">549900</entry><entry colname="6">53.3%</entry><entry colname="7">8.7%</entry><entry colname="8">40.9%</entry><entry colname="9">21%</entry><entry colname="10">Good</entry></row><row><entry colname="1">No. 4</entry><entry colname="2">9.16</entry><entry colname="3">0,076</entry><entry colname="4">121.2</entry><entry colname="5">454 700</entry><entry colname="6">58.3%</entry><entry colname="7">7.5%</entry><entry colname="8">42.1%</entry><entry colname="9">18%</entry><entry colname="10">Good</entry></row><row><entry colname="1">No. 5</entry><entry colname="2">8.11</entry><entry colname="3">0.094</entry><entry colname="4">86.7</entry><entry colname="5">471 800</entry><entry colname="6">53.7%</entry><entry colname="7">6.6%</entry><entry colname="8">43.3%</entry><entry colname="9">15%</entry><entry colname="10">low</entry></row></tbody></tgroup></table></tables>

A typical SEC curve of the embodiment the polymer is in <figref idrefs="S131">5</figref> shown.

Two different peaks of HMW and LMW fractions can with extended curves be seen. <tables><table frame="all"><tgroup cols="4" colsep="1" rowsep="1"><colspec colname="1" colwidth="1*" /><colspec colname="2" colwidth="1*" /><colspec colname="3" colwidth="1*" /><colspec colname="4" colwidth="1*" /><tbody><row><entry colname="2">LMW</entry><entry colname="3">HMW</entry><entry colname="4">total</entry></row><row><entry colname="1">Mn:</entry><entry colname="2">3,231</entry><entry colname="3">91514</entry><entry colname="4">8076</entry></row><row><entry colname="1">Mw:</entry><entry colname="2">12307</entry><entry colname="3">505 322</entry><entry colname="4">291217</entry></row><row><entry colname="1">Mw / Mn:</entry><entry colname="2">3.81</entry><entry colname="3">5.52</entry><entry colname="4">36.06</entry></row><row><entry colname="1">. Wt%</entry><entry colname="2">43.57%</entry><entry colname="3">56.43%</entry></row></tbody></tgroup></table></tables>

It it was found that this multimodal or bimodal polymer an excellent bubble stability and good film extrusion properties shows. The polymer showed excellent stretch properties and there was a film of 8.89 micron (0.85 mil) was obtained. The film appearance rate was excellent, without gel patch. The arrow film impact was excellent, thereby placing them on Grocery bag applications suitable is.

According to a another embodiment made under this Invention produced polymer has a bimodal molecular weight distribution (M_w/ M_n). In a preferred embodiment, , the polymer produced has a density of 0.93 to 0.97 g / cc, an MI (I₂) Of 0.02 to 0.5 g / 10 min, a FI (I₂₁) Of 10 to 40 g / 10 min, a MFR (I₂₁/ I₂) from 50 to 300, an M_w 100,000 to 500,000, a M_n 8000-20000, an M_w/ M_n 10-40 on. These polymers are particularly useful for blow molding applications. These bimodal polymers exhibited extraordinary Bent Strip ESCR behavior (ESCR = Environmental Stress Crack Resistance), which power the of unimodal HDPE far surpasses. The blow-molded bottles could be easily cut and reported an opaque surface on which opposes translucent surfaces is preferably unimodal HDPE.

In yet another embodiment, are produced in the process of the invention, propylene-based polymers. These polymers include atactic polypropylene, isotactic polypropylene, halbisotaktisches and syndiotactic polypropylene or mixtures thereof, which using two or more different catalysts are produced when using this invention. Other propylene polymers conclude Propylenblock- or impact-resistant Copolymers. Propylene polymers of this type are in the art well known. See, for example, <patcit><text>U.S. Patents No. 4,794,096</text></patcit>. <patcit><text>3,248,455</text></patcit>. <patcit><text>4,376,851</text></patcit>. <patcit><text>5,036,034</text></patcit> and <patcit><text>5,459,117</text></patcit>,

The Polymers of the invention can blended with any other polymer and / or co-extruded will. Nonlimiting examples for include other polymers a linear polyethylenes of low density, which by means of conventional Ziegler-Natta catalysis and / or catalysis with metallocene with spatially sophisticated Ligands are prepared, elastomers, plastomers, high density polyethylene low density, high density polyethylenes, polypropylenes and the same.

polymers which are prepared by the method of the invention, and Mixtures thereof, &lt;?page 41?&gt;useful in processing operations as film, sheet, and fiber extrusion and co-extrusion as well as blow molding, injection molding and rotational molding process. include films blown or cast Films which is formed by co-extrusion or by laminating be that useful are as shrink film, adhesive film, stretch film, sealing film, stretched films, snack packaging, heavy duty bags, grocery sacks, packaging for baked and frozen food, medical packaging, industrial coverings, Membranes, etc., in applications with food come into contact or not. Fibers include melt extrusion, solution spinning and Schmelzblasfaseranwendungen for use in woven or non-woven form, to filter, diaper fabrics, medical garments, geotextiles etc. produce a. Close Extruded articles include medical tubing, wire and cable coatings, pipe, geomembranes, and pond liners on. Shaped articles conclude Monolayer and multilayer structures in the form of bottles, Tanks, large Hollow objects, solid food containers and toys, etc., a.

According to a another embodiment the polymer of the invention by known methods in the art processed into a pipe. For Pipe applications, the polymers of the invention, an I₂₁ 2-10 dg / min, and preferably from 2 to 8 dg / min. According to a another embodiment met the tube of the invention ISO qualifications. According to a further embodiment The present invention is applied to a polyethylene tube produce, which has a predetermined S-4T_c for a 110 mm tube of less than -5 ° C, preferably less than -15 ° C and more preferably less than -40 ° C (ISO DIS 13477 / ASTM F1589).

According to a another embodiment the polymer has an extrusion rate of greater than 1.12 g / s / cm (17 lbs / hr / inch) Peripheral shape, and preferably greater than 1.32 g / s / cm (20 lbs / hr / inch) mold circumference and more preferably greater than 1.46 g / s / cm (22 lbs / hour / inch) form peripheral.

The Polyolefins of the invention can in films, moldings (Including tubes) Plates, wire and cable coatings, and the like processed will. The films may by any conventional technique, which in the art is known to be formed, including extrusion, coextrusion, lamination, Blowing and casting. The film may be obtained by the flat film or tubular process, whereafter in uniaxial direction or in two mutually perpendicular directions oriented in the plane of the film to the same or varying degrees is. The alignment can be in both directions with the same held extent or may contain various proportions have. Particularly preferred methods for processing of the polymers close in films Extrusion or coextrusion on a blown or cast film line on.

According to a another embodiment the polymer of the invention by known methods in the art processed into a film. For Film applications, the polymers of the invention, an I₂₁ from 2 to 50 dg / min, preferably from 2 to 30 dg / min, even more preferably 2 to 20 dg / min, even more preferably 5 to 15 dg / min and even more preferably from 5 to 10 dg / min.

The articles produced (Such as films, pipes, etc.) further additives such as lubricants, anti-blocking agents, antioxidants, Pigments, fillers, Schleierverhinderndes agents, UV stabilizers, antistats, polymer processing aids, Neutralizing agents, lubricants, surfactants, pigments, Dyes and nucleating agents included. Preferred additives conclude Silica, synthetic silica, titanium dioxide, polydimethylsiloxane, Calcium carbonate, metal stearates, calcium stearate, zinc stearate, talc, BaSO₄, Diatomaceous earth, wax, carbon black, Flame retardant additives, resins with low molecular weight, Hydrocarbon resins, glass beads and the like. The additives can in the typically effective amounts, which is well known in the art are be present, such as, for example, 0.001 percent to 10 weight percent.

According to a another embodiment the polymer of the invention by known methods in the art into a shaped body processed z. B. by blow molding and injection stretch forms. For molding applications the polymers of the invention, an I₂₁ from 20 dg / min to 50 dg / min and preferably from 35 dg / min to 45 dg / min on.

While is not bound by any theory, it is believed that The polymers produced by this invention has the unique have advantage that the two polymer products are mixed so intimately, that a uniform distribution of the two polymers over the polymer particles is away yet when the reactor leaving. The unprocessed, untreated granular polymer is as pure polymer designated. The pure polymer is then Standardsiebgrößen ASTM D 1921 particles&lt;?page 42?&gt;size (sieve analysis) of Plastic Materials, Method A or PEG method 507 in fractions separated. <tables><table frame="all"><tgroup cols="3" colsep="1" rowsep="1"><colspec colname="1" colwidth="1*" /><colspec colname="2" colwidth="1*" /><colspec colname="3" colwidth="1*" /><tbody><row><entry colname="1">screen size</entry><entry colname="2">collected fraction</entry><entry colname="3">Group name</entry></row><row><entry colname="1">10 mesh</entry><entry colname="2">&gt; 2000 .mu.m</entry><entry colname="3">fraction 1</entry></row><row><entry colname="1">18 mesh</entry><entry colname="2">2000-1000 microns</entry><entry colname="3">fraction 2</entry></row><row><entry colname="1">35 mesh</entry><entry colname="2">&lt;1000-500 microns</entry><entry colname="3">fraction 3</entry></row><row><entry colname="1">60 mesh</entry><entry colname="2">&lt;500-250 microns</entry><entry colname="3">fraction 4</entry></row><row><entry colname="1">120 mesh</entry><entry colname="2">&lt;250-125 microns</entry><entry colname="3">fraction 5</entry></row><row><entry colname="1">200 mesh / pan</entry><entry colname="2">&lt;125 microns</entry><entry colname="3">fraction 6</entry></row><row><entry colname="1">total</entry><entry colname="3">fraction 6</entry></row></tbody></tgroup></table></tables>

The individual fractions (Group 2, 3, 4, 5) are then on their tested for physical properties. The melt index is according to ASTM 1238, Condition E, 190 ° C measured.

On unique feature of the polymer produced herein is that the Melt indices of the different fractions do not vary significantly.

According to a preferred embodiment, not vary more the melt indices of Fractions 3, 4 and 5 than 40% relative, preferably not more than 30% relative, preferably not more than 10% relative, preferably not more than 8% relative, preferably not more than 6% relative, preferably not more than 4% relative. Relative means relative to the mean of the values ​​for Fractions 3, 4 and 5. FIG.

According to a another embodiment include fractions 2, 3, 4 and 5 more than 90% of the total weight the resin sample, preferably fractions comprise 2, 3, and 4 more than 90% of the total weight of the resin sample.

On Another desirable Feature of the polymer produced herein is that the M_w/ M_n the various Fractions does not vary significantly. In a preferred embodiment vary the M_w/ M_n of fractions 1, 4, 5 and 6 are not more than 20% relative, preferably not more than 10% relative, preferably not more than 8% relative, preferably not more than 6% relative, preferably not more than 4% relative, preferably not more than 2% relative. In a preferred embodiment vary the M_w/ M_n from Fractions 1, 4 and 6 are not more than 20% relative, preferably not more than 10% relative, preferably not more than 8% relative, preferably not more than 6% relative, preferably not more than 4% relative, preferably not more than 2% relative. Relative means relative to the mean of the values ​​for Fractions 1, 4 and 6. According to a preferred embodiment, vary the M_w/ M_n from Fractions 2, 3, 4 and 5 is not more than 20% relative, preferably not more than 10% relative, preferably not more than 8% relative, preferably not more than 6% relative, preferably not more than 4% relative, preferably not more than 2% relative. Relative means relative to the mean of the values ​​for Fractions 2, 3, 4 and 5. FIG. According to a further preferred embodiment, vary M_w/ M_n from Fractions 3, 4 and 5 is not more than 20% relative, preferably not more than 10% relative, preferably not more than 8% relative, preferably not more than 6% relative, preferably not more than 4% relative, preferably not more than 2% relative. Relative means relative to the mean of the values ​​for Fractions 3, 4 and 5 M_n and M_w will by gel permeation chromatography on a Waters 150 ° C GPC instrument equipped with Differentialrefraktionsindexdetektoren measured. The GPC columns calibrated by a series of polystyrene standards having a narrow one running molecular weight, and the molecular weights are determined by using polyethylene standards with a broad molecular weight according to National Bureau of Standards in 1496 for the polymer in question is calculated.

According to a further preferred embodiment, comprises according to this Invention produced polymer 10-90.% Of polymer with low Molecular weight (low means 50,000 or less, preferably 40000 or less), preferably 20-80 wt.%, More preferably 40-60 wt.%, based on the weight of the polymer.

In one embodiment , the fractions on the following properties. &lt;?page 43?&gt;<tables><table frame="all"><tgroup cols="7" colsep="1" rowsep="1"><colspec colname="1" colwidth="1*" /><colspec colname="2" colwidth="1*" /><colspec colname="3" colwidth="1*" /><colspec colname="4" colwidth="1*" /><colspec colname="5" colwidth="1*" /><colspec colname="6" colwidth="1*" /><colspec colname="7" colwidth="1*" /><tbody><row><entry colname="1">screen size</entry><entry colname="2">collected fraction</entry><entry colname="3">. Wt%</entry><entry colname="4">I21</entry><entry colname="5">I5</entry><entry colname="6">I2</entry><entry colname="7">Group name</entry></row><row><entry colname="1">10 mesh</entry><entry colname="2">&gt; 2000 .mu.m</entry><entry colname="3">0.5</entry><entry colname="7">fraction 1</entry></row><row><entry colname="1">18 mesh</entry><entry colname="2">2000-1000 microns</entry><entry colname="3">1.02</entry><entry colname="4">23.9</entry><entry colname="5">0.75</entry><entry colname="6">0.14</entry><entry colname="7">fraction 2</entry></row><row><entry colname="1">35 mesh</entry><entry colname="2">&lt;1000-500 microns</entry><entry colname="3">15,11</entry><entry colname="4">37.6</entry><entry colname="5">1.18</entry><entry colname="6">0.22</entry><entry colname="7">fraction 3</entry></row><row><entry colname="1">60 mesh</entry><entry colname="2">&lt;500-250 microns</entry><entry colname="3">44,05</entry><entry colname="4">41.0</entry><entry colname="5">1.28</entry><entry colname="6">0.20</entry><entry colname="7">fraction 4</entry></row><row><entry colname="1">120 mesh</entry><entry colname="2">&lt;250-125 microns</entry><entry colname="3">33,62</entry><entry colname="4">40.8</entry><entry colname="5">0.93</entry><entry colname="6">0.18</entry><entry colname="7">fraction 5</entry></row><row><entry colname="1">200 Mesh / pan</entry><entry colname="2">&lt;125 microns</entry><entry colname="3">5.70</entry><entry colname="7">fraction 6</entry></row><row><entry colname="1">total</entry><entry colname="3">100.0</entry><entry colname="4">41.6</entry><entry colname="5">1.18</entry><entry colname="6">0.23</entry><entry colname="7">fraction 6</entry></row></tbody></tgroup></table></tables>

According to a another embodiment it was found that the produced polyolefin least Two types of molecular weights which weight with more than 20th% based on the weight of the polymer are present, contains.

According to a another embodiment this invention is the bi- or multimodal polymer produced (On the SEC graph). With bi- or multimodal is meant that the SEC graph of the polymer, two or more positive slopes, two having or more negative slopes, and three or more inflection points (An inflection point is the point at which the second derivative of Curve becomes negative), or the chart has at least one positive Slope, a negative slope, one inflection point and a change in the positive and / or negative slope greater than 20% of the slope before the change on. According to a another embodiment , the SEC graph has a positive slope, one negative slope, a turning point and a M_w/ M_n from 10 or more, preferably 15 or more, more preferably 20 or more on. The SEC Chart 150 ° C GPC instrument equipped by gel permeation chromatography on a Waters, with Differentialrefraktionsindexdetektoren generated. The columns calibrated by a series of polystyrene standards having a narrow one running molecular weight, and the molecular weights were determined using Mark Houwink coefficients for the concerned polymer calculated.

The Films produced using the polymers of this invention have extremely good appearance properties, on. The films have a low gel content have and / or good opacity and good gloss. According to a preferred embodiment, has the 0.25 micron (1 mil) film (1.0 mil = 0.25 microns) a 45 ° gloss of 7 or more, preferably 8 or more as measured by ASTM D 2475. According to a preferred embodiment, has the 0.25 micron (1 mil) film (1.0 mil = 25 microns) cloudiness measured of 75 or less, preferably 70 or less, by ASTM D 1003, condition A.

Around to facilitate a better understanding of the present invention and representative to understand advantages thereof, the following examples are provided.

Examples

M_n and M_w were ... By Gel permeation chromatography on a Waters 150 ° C GPC instrument equipped with Differentialrefraktionsindexdetektoren measured. The GPC columns were calibrated by a series of molecular weight standards ran, and the molecular weights were determined using Mark Houwink coefficients for the concerned polymer calculated. <ul><li>The density was measured according to ASTM D 1505 measured.</li><li>The melt index (MI) and the flow index (FI) I₂ and I₂₁ were in accordance with ASTM D 1238, Condition E, measured at 190 ° C.</li><li>The melt index ratio (MIR) is the ratio of I₂₁ about I₂, As determined by ASTM D-1238th</li><li>Wt.% Comonomer was measured by proton NMR. <st32:df xmlns:st32="http://lighthouseip.com/">MWD = M<st32:sub>w</st32:sub>/ M<st32:sub>n</st32:sub></st32:df></li>&lt;?page 44?&gt;<li>Impact strength was measured according to ASTM D 1709 measured.</li><li>MD and TD Elmendorf Tear Strength were in accordance with ASTM D 1922 measured.</li><li>MD and TD 1% secant modulus were measured according to ASTM D 882nd</li><li>MD and TD tensile strength and tensile strength were measured according to ASTM D 882 measured.</li><li>MD and TD elongation and ultimate elongation were measured according to ASTM D 412 measured.</li><li>MD and TD modulus were measured according to ASTM 882-91 measured.</li><li>The pulp was in accordance with ASTM 1003-92, A condition measured.</li><li>45 ° gloss was determined according to ASTM D 2457 measured.</li><li>BUR is blow.</li><li>"PPH" is pounds per hour. "MPPH" means Milli Pounds per hour.</li><li>"Ppmw" is parts per Weight per million (parts per million by weight).</li></ul>

example 1

Manufacture of activating agent with SMAO carrier

For one Batch of 1 kg 1158.43 g of 30 wt% -. Strength MAO in toluene (7.3 wt.% Al) available additional from Albemarle Corporation, Baton Rouge, LA, and 2400 g Toluene in a 8 liter mixing vessel equipped with helical Bandrührgerät introduced. 984 g of Davison 955-600 silica be at the MAO in toluene added room temperature. An exotherm of 10 ° C occurs by the reaction of the MAO with the hydroxyl groups on. The slurry is for 30 min mixed at room temperature. Dried then by heating the mixing tank to approximately 70 ° C and by reducing the pressure to 0.00 mm / Hg. When the slurry is thickened, the U / min the mixing machine to be the minimum rotation speed, 40-60 U / min, reduced. Then stirring is increased slowly (At approximately 600 U / min) and the temperature is raised to 95 ° C when the slurry is converted into a dry powder. It can be a stream of nitrogen (about 0.5 cc / min per gram of added silica) during the final stage of drying be used to control the removal of the toluene from the silica pores to support. The material is typically held at 95 ° C until the distance the toluene ceases and the material temperature settles at the jacket temperature on. The material temperature changes not in at least 30 min before the methylalumoxane with carrier (SMAO) for dry is found. Toluolreste be at less than 2 wt.% Of solids reduced.

Comparative Example 2

Solution catalyst compound activated with slurry comprising activating agent with support in fluidized bed gas phase reactor with a shorter contact time

The Polymerization performance of in-line on a support is shrunk bis (n-propylcyclopentadienyl) zirconium (P-MCN) -Fließbett pilot plant reactor was examined in a 20.3 cm (8 inches). The catalyst feed setting is shown schematically in <figref idrefs="S128">2</figref> shown. P-MCN (1.7 mol / ml in hexane) was introduced in line at 0.65 g / h. 0.5 wt.% In isopentane TiBA (200-250 cc / h Isopentanträger and 75-90 cc / hr 0.5 wt.% TiBA) were introduced in-line. After that A slurry comprising Kaydol petroleum and 16 wt.% SMAO prepared in Example 1 (4.5 mmol / g solids) inserted in-line, and mixing the solution with the solution of P-MCN and TiBA for 25-35 min. After mixing, the catalyst was measured using a standard 0.3 cm (1/8 inch) -Injektionsrohrs with 1.05 pph N₂ reverse current injected.

Of the Catalyst was dried at LLDPE conditions, 75 ° C, 2.4 MPa (350 psig) total pressure, 0.8 MPa (120 psi) ethylene, 0.017 hexene-1 comonomer to ethylene ratio investigated. The reactor was no hydrogen is supplied, since this catalyst enough developed hydrogen to 2-5 dg / min melt index polymer under the conditions used to manufacture. The superficial gas velocity (SGV = Superficial Gas Velocity) was measured at 0.47 m / s (1.54 ft / sec) held and the stationary bed weight was held to 12.3 kg (27 lbs). The reactor was continuously operated, ie for about wherein the bed weight in general kept constant for 13 hours per day, been to a bed height near to get the tip of the straight part. Where possible, the reactor was about Night kept closed, the bed in a nitrogen atmosphere fluidified has been. As scavenger was TiBA (triisobutylaluminum) in isopentane with about 75 ppm is added to the bed, to give a commercially relevant catalyst productivity.

the Product had a 6.1 dg / min (I₂), on 17.6 MFR and a density of 0.93 g / cc. The average particle size of the resin was 0.056 cm (0.022 inches) with 2.4 wt.% fines (&lt;120 mesh). The Density of Stripping was 438.9 kg / m³ (27.4 lb / cu ft). A residual of 0.66 ppm zirconium, 33 ppm aluminum and 75 &lt;?page 45?&gt;ppm silica were determined by ICP (Inductively Coupled Plasma Spectroscopy) measured.

Comparative Example 3

Solution catalyst compound activated with slurry comprising activating agent with support in fluidized bed gas phase reactor with a longer contact time

The Polymerization performance of in-line on a support is shrunk bis (n-propylcyclopentadienyl) zirconium (P-MCN) -Fließbett pilot plant reactor was examined in a 20.3 cm (8 inches). The catalyst feed setting is shown schematically in <figref idrefs="S129">3</figref> shown. P-MCN introduced 0.56 g / hr with 65-100 cc / hr 0.5 wt.% TiBA in isopentane upstream, was charged with 16 wt.% SMAO (Prepared as in Example 1) in Kaydol mineral oil upstream of the 150 ml mixer contacted. Was allowed to solution and the slurry for 90-130 min mix. 200-250 There were cc / h Isopentanträger used the catalyst exiting the mixer to to rinse the reactor. After mixing, the catalyst was measured using a standard 0.32 cm (1/8 inch) -Injektionsrohrs with 1.1 pph N₂ reverse current injected.

Of the Catalyst was dried at LLDPE conditions, 75 ° C, 3.4 MPa (350 psig) total pressure, 0.8 MPa (120 psi) ethylene, 0.017 hexene-1 comonomer to ethylene ratio investigated. The reactor was no hydrogen is supplied, since this catalyst enough developed hydrogen to 2-5 dg / min melt index polymer under the conditions used to manufacture. The superficial gas velocity (SGV = Superficial Gas Velocity) was measured at 0.42 m / s (1.38 ft / sec) held and the stationary bed weight was maintained at 13.6 kg (30.5 lbs). The reactor was continuously operated, ie for about wherein the bed weight in general kept constant for 13 hours per day, been to a bed height near to get the tip of the straight part. Where possible, the reactor was about Night kept closed, the bed in a nitrogen atmosphere fluidified has been. As scavenger was TiBA (triisobutylaluminum) in isopentane with about 75 ppm is added to the bed, to give a commercially relevant catalyst productivity.

the Product had a 5.3 dg / min (I₂), on 18.9 MFR and a density of 0.928 g / cc. The average particle size of the resin was 0.053 cm (0.021 inches) with 2.8 wt.% fines (&lt;120 mesh). The Density of the deposited mass was 416.5 kg / m³ (26.0 lb / cu ft). A residual of 0.55 ppm zirconium, aluminum and 35 ppm 78 ppm silica were measured by ICP.

The data for Examples 2 and 3 are summarized in Table 1 below. &lt;?page 46?&gt; TABLE 1: 20.3 CM (8 INCH) -FLIEßBETTDATEN ROUNDUP <tables><table frame="all"><tgroup cols="3" colsep="1" rowsep="1"><colspec colname="1" colwidth="1*" /><colspec colname="2" colwidth="1*" /><colspec colname="3" colwidth="1*" /><tbody><row><entry colname="1">reaction conditions</entry><entry colname="2">example 2</entry><entry colname="3">example 3</entry></row><row><entry colname="1">production rate (Kg / h) ((lbs / hr)) stationary</entry><entry colname="2">3.5 (7,7)</entry><entry colname="3">3.2 (7,1)</entry></row><row><entry colname="1">Fluidized bulk density (kg / m³) ((Lb / ft³)</entry><entry colname="2">192-223 (12-13,9)</entry><entry colname="3">256-296 (16-18,5)</entry></row><row><entry colname="1">Grain bed quantity (Kg) ((lb))</entry><entry colname="2">5 (11)</entry><entry colname="3">10 (22)</entry></row><row><entry colname="1">sales the bed in decommissioning</entry><entry colname="2">2.2</entry><entry colname="3">1.6</entry></row><row><entry colname="1">Theoretical %. Weight grains the bed in decommissioning</entry><entry colname="2">0.11</entry><entry colname="3">0.19</entry></row><row><entry colname="1">Catalyst feed-parameter</entry></row><row><entry colname="1">Catalyst feed rate (G / h) at SS, dry basis</entry><entry colname="2">0.65</entry><entry colname="3">0.56</entry></row><row><entry colname="1">Catalyst support upstream of the mixer</entry></row><row><entry colname="1">isopentane (Cc / h)</entry><entry colname="2">200-250</entry><entry colname="3">n / A</entry></row><row><entry colname="1">0.5 . Wt% TiBA in iC₅ (Cc / h)</entry><entry colname="2">45-90</entry><entry colname="3">65-100</entry></row><row><entry colname="1">Catalyst support downstream of mixer</entry></row><row><entry colname="1">isopentane (Cc / h)</entry><entry colname="2">n / A</entry><entry colname="3">200-250</entry></row><row><entry colname="1">N₂ kg / h ((lb / hr))</entry><entry colname="2">0.5 (1.05)</entry><entry colname="3">0.5 (1,1)</entry></row><row><entry colname="1">Resin properties:</entry></row><row><entry colname="1">melt index I₂ dg / min</entry><entry colname="2">6.1</entry><entry colname="3">5.3</entry></row><row><entry colname="1">MFR (I₂₁/ I₂)</entry><entry colname="2">17.6</entry><entry colname="3">18.9</entry></row><row><entry colname="1">density (G / ml)</entry><entry colname="2">0.93</entry><entry colname="3">0.928</entry></row><row><entry colname="1">mass density (Kg / m³) (Lb / ft³)</entry><entry colname="2">439 (27.4)</entry><entry colname="3">416 (26)</entry></row><row><entry colname="1">middle Particle size (cm) ((in))</entry><entry colname="2">0.06 (0.022)</entry><entry colname="3">0.05 (0.021)</entry></row><row><entry colname="1">Fines &lt;120 mesh (wt.%)</entry><entry colname="2">2.4</entry><entry colname="3">2.8</entry></row></tbody></tgroup></table></tables><tables><table frame="all"><tgroup cols="3" colsep="1" rowsep="1"><colspec colname="1" colwidth="1*" /><colspec colname="2" colwidth="1*" /><colspec colname="3" colwidth="1*" /><tbody><row><entry colname="1">reaction conditions</entry><entry colname="2">example 2</entry><entry colname="3">example 3</entry></row><row><entry colname="1">amount (Kg) ((lb)) Net</entry><entry colname="2">31.3 (69)</entry><entry colname="3">23.1 (51)</entry></row><row><entry colname="1">rest Zr (ppmw as determined by ICP)</entry><entry colname="2">0.66</entry><entry colname="3">0.55</entry></row><row><entry colname="1">rest Al (ppmw as determined by ICP)</entry><entry colname="2">33</entry><entry colname="3">35</entry></row><row><entry colname="1">rest Si (ppmw as determined by ICP)</entry><entry colname="2">75</entry><entry colname="3">78</entry></row></tbody></tgroup></table></tables>

Comparative Example 4

Solution catalyst compound activated with slurry comprising activating agent with support in fluidized bed gas phase reactor

The Polymerization performance of in-line on a support is shrunk bis (n-propylcyclopentadienyl) zirconium (P-MCN) -Fließbett pilot plant reactor was examined in a 35.6 cm (14 inches). The Catalyst supply arrangement for in-line activation of P-MCN is used with SMAO, is in <figref idrefs="S130">4</figref> shown. Catalyst solution supplied with 10 cc / hr, was pph 1.0 Isopentanträger and 10 cc / h 15 wt% -. strength SMAO (as produced in Example 1) in Kaydol mineral oil upstream of the 100 ml mixer &lt;?page 47?&gt;stirrer contacted. After stirring the catalyst using a standard 0.3 cm (1/8 was Inch) -Injektionsrohrs with 2.0 pph N₂ reverse current injected.

the Catalyst system was at LLDPE conditions, 85 ° C, 2.4 MPa (350 psig) total pressure 4 MPa (200 psi) ethylene, 0.0185 hexene-1 comonomer to ethylene molar ratio (C₆/ C₂) Was investigated. There was a concentration of 200 ppm of hydrogen in the reactor kept. The superficial gas velocity (SGV = Superficial Gas Velocity) was measured at 0.6 m / sec (2.0 ft / sec) held and the stationary bed weight was kept at 50 kg (110 lbs). The reactor production rate was 31 pph.

The for the used in-line activation of P-MCN with SMAO activator- Catalyst supply arrangement is in <figref idrefs="S130">4</figref> shown. After stirring the catalyst using a standard 0.3 cm (1/8 was Inch) -Injektions tube with 2.0 pph N₂ reverse current injected. Catalyst, which was supplied with 10 cc / hr, was charged with 1.0 pph Isopentanträger and 10 cc / h wt.% SMAO (as produced in Example 1) in Kaydol mineral oil upstream of the 100 ml mixer with stirrer contacted.

the Product had an I₂ of 5.89 dg / min, a MSR of 16.6 and a density of 0.926 g / cc. The average particle size of the resin was 0.084 cm (0.033 inches) with 0.56 wt.% fines (&lt;120 mesh). The remote bulk density was 17.1 lb / cu-ft. A residual of 0.28 ppm zirconium and 35 ppm Aluminum were measured by X-ray fluorescence measured.

Comparative Example 5

Bis-indenyl solution catalyst compound activated with slurry comprising activating agent with support in fluidized bed gas phase reactor

The Polymerization performance of a bis-indenylzirkoniumdichlorid solution catalyst (Bis-indenyl) with carrier -Fließbett Pilot plant reactor was examined in a 35.6 cm (14 inches). The Catalyst feed configuration for the in-line activation Bis-indenyl metallocene catalyst compound solution with SMAO was used (from Example 1), is in <figref idrefs="S130">4</figref> shown. The catalyst fed, . With 15 cc / hr, 15 wt% was pph 0.5 Isopentanträger and 15 cc / h - sodium SMAO in Kaydol petroleum upstream the 100 ml mixer with stirrer contacted. After the mixer, the catalyst was Using a standard 0.32 cm (1/8 inch) -Injektionsrohrs with 1.5 pph Isopentanträger and 4.0 pph N₂ Reverse current injected.

the Catalyst system was at LLDPE conditions, 85 ° C, 2.4 MPa (350 psig) total pressure 4 MPa (200 psi) ethylene, 0.016 hexene-1 comonomer to ethylene molar ratio (C₆/ C₂) Was investigated. There was a concentration of 195 ppm of hydrogen in the reactor kept. The superficial gas velocity (SGV = Superficial Gas Velocity) was measured at 0.6 m / sec (2.0 ft / sec) held, and the stationary bed weight was kept at 50 kg (110 lbs). The reactor production rate was 38 pph.

the Product had an I₂ of 8.4 dg / min, a MSR of 16.5 and a density of 0.9273 g / cc. The average particle size of the resin was 0.091 cm (0.0357 inches) with 0.44 wt.% fines (&lt;120 mesh). The remote bulk density was 294.7 kg / m³ (18.4 lb / cu-ft). On Rest of &lt;0.10 ppm zirconium and 37 ppm aluminum were analyzed by X-ray fluorescence measured.

example 6

P-MCN solution catalyst compound activated with slurry comprising SMAO and second catalyst compound in fluidized bed gas phase reactor

The A solution polymerization performance comprising bis (n-propylcyclopentadienyl) zirconium catalyst compound and a slurry comprising SMAO and [(2,4,6-Me₃C₆H₂) NCH₂CH₂]₂NHZrBz₂ was in a 35.6 cm (14 inch) pilot plant reactor -Fließbett- examined. When for the catalyst feed configuration used in-line activation the solution was bis (n-propylcyclopentadienyl) zirconium dichloride with 0.5 Wt.% And a slurry comprising 17.3 wt.% SMAO (from Example 1) in Kaydol. (The SMAO contained 4.5mmol Al per gram of solid) used. The [(2,4,6-Me₃C₆H₂) NCH₂CH₂]₂NHZrBz₂ was off-line added to the slurry, a 150: 1 molar ratio Al: Zr to form. The remaining portion of the slurry was Kaydol petroleum. The catalyst fed, 4 cc / h, was charged with 75 cc / h to SMAO / [(2,4,6-Me₃C₆H₂) NCH₂CH₂]₂NHZrBz₂Mixture in Kaydol mineral oil upstream of the Series of two 25.4 cm (10 inch) diameter Kinecs-static mixers &lt;?page 48?&gt;(from Chemineer) contacted. The contact time between the solution and the slurry was about 5 min. After the mixer, the catalyst was measured using a Standard 0.32 cm (1/8 inch) -Injektionsrohrs pph 3 Isopentanträger and 5 pph N₂Carrier gas injected.

the Catalyst system was investigated in the following conditions, 105 ° C, 2.4 MPa (350 psig) total pressure, 1.5 MPa (220 psi) ethylene and a molar relationship 0.0035 hexene-1 to ethylene. There was a concentration of 1800 ppm of hydrogen retained in the reactor. The superficial gas velocity (SGV) was 0.6 m / sec (2.0 ft / sec) is held, and the bed weight was at 34 kg (75 lbs) held. The reactor production rate was 21 pph.

the Product had a (I₂) Of 0.051 dg / min, a flow index of 7.74 dg / min, a MFR of 151 and a density of 0.9502 g / cc on. The average particle size of the resin was 0.04 cm (0.016 inches) with 1.25 wt.% fines (&lt;120 mesh). The Contrasting bulk density was 382.8 kg / m³ (23.9 lb / cu-ft). On Zirkoniumrest of &lt;3.25 ppm and aluminum of 109 ppm were measured by X-ray fluorescence.

The Data of Examples 4, 5 and 6 are summarized in Table 2 below. TABLE 2: 35.6 CM (14 INCH) -FLIEßBETTDATEN ROUNDUP<tables><table frame="all"><tgroup cols="4" colsep="1" rowsep="1"><colspec colname="1" colwidth="1*" /><colspec colname="2" colwidth="1*" /><colspec colname="3" colwidth="1*" /><colspec colname="4" colwidth="1*" /><tbody><row><entry colname="2">example 4</entry><entry colname="3">example 5</entry><entry colname="4">example 6</entry></row><row><entry colname="1">Fluidized bed bulk density kg / m³ (Lb / ft³)</entry><entry colname="2">176 (11.0)</entry><entry colname="3">208 (13.0)</entry><entry colname="4">247 (15.4)</entry></row><row><entry colname="1">Bed turnover at standstill</entry><entry colname="2">10.3</entry><entry colname="3">8.7</entry><entry colname="4">12</entry></row><row><entry colname="1">resin properties</entry></row><row><entry colname="1">melt index (I₂ (Dg / min)</entry><entry colname="2">5.89</entry><entry colname="3">8.4</entry><entry colname="4">0,051</entry></row><row><entry colname="1">Flow index (I₂₁) (Dg / min)</entry><entry colname="2">97.65</entry><entry colname="3">138.7</entry><entry colname="4">7.74</entry></row><row><entry colname="1">MFR (I₂₁/ I₂)</entry><entry colname="2">16.6</entry><entry colname="3">16.5</entry><entry colname="4">151</entry></row><row><entry colname="1">density (G / cc)</entry><entry colname="2">0.926</entry><entry colname="3">.9273</entry><entry colname="4">.9502</entry></row><row><entry colname="1">bulk density kg / m³ (Lb / ft³)</entry><entry colname="2">274 (17.1)</entry><entry colname="3">295 (18.4)</entry><entry colname="4">383 (23.9)</entry></row><row><entry colname="1">middle Particle size cm (in)</entry><entry colname="2">0.08 (0.033)</entry><entry colname="3">0,090 (0.0357)</entry><entry colname="4">0.04 (0.016)</entry></row><row><entry colname="1">Fines &lt;120 mesh (wt.%)</entry><entry colname="2">0.56</entry><entry colname="3">0.44</entry><entry colname="4">1.25</entry></row></tbody></tgroup></table></tables><tables><table frame="all"><tgroup cols="4" colsep="1" rowsep="1"><colspec colname="1" colwidth="1*" /><colspec colname="2" colwidth="1*" /><colspec colname="3" colwidth="1*" /><colspec colname="4" colwidth="1*" /><tbody><row><entry colname="2">example 4</entry><entry colname="3">example 5</entry><entry colname="4">example 6</entry></row><row><entry colname="1">rest Zr (ppm, by X-ray)</entry><entry colname="2">0.28</entry><entry colname="3">&lt;0.10</entry><entry colname="4">3.25</entry></row><row><entry colname="1">rest Al (ppm, by X-ray)</entry><entry colname="2">34.7</entry><entry colname="3">27</entry><entry colname="4">109</entry></row></tbody></tgroup></table></tables>

example 7

Several Product samples comprising by polymerization with a slurry SMAO and [(2,4,6-Me₃C₆H₂) NCH₂CH₂]₂NHZrBz₂ and solution catalyst to (n-propylcyclopentadienyl) zirconium dichloride (P-MCN) were screened for Film applications examined. This bimodal HMW HDPE granular polymer was performed on a single screw machine with 6.35 cm (2.5 inch) 24: 1 L / D, equipped a double mixing head, at 210 ° C after the mixing drum with a Stabilisierpackung comprising 1000 ppm Irganox 1076, 1500 ppm Irgafos 168 and 1500 ppm calcium stearate, mixed. Two pelleted Samples showed a FI of 8.4 and 9.9 and an MFR of 155 and 140. The density was 0.0524 or 0.9490. The pelletized polymer was produced on an Alpine film line equipped with a 50 mm, 18: 1 L / D Einfachschne&lt;?page 49?&gt;blocks, a 100 mm die with a 1 mm die gap extruded. The temperature was set at 210 ° C. The work rate was at about 45.4 kg / h (100 lb / h) is kept, the blow-up ratio of the bubble was 4.0 to asked and crystallization limits height was 91.44 cm (36 inches). As shown in Table 3 below, the bimodal polymer exhibited a excellent bubble stability and excellent film extrusion properties. The film impact strength was over 200 g or above 300 g for a strength 25.4 microns (1.0 mil) and 12.7 microns (0.5 mil). The film samples also exhibited excellent tensile strength and an excellent tensile modulus. TABLE 3<tables><table frame="all"><tgroup cols="7" colsep="1" rowsep="1"><colspec colname="1" colwidth="1*" /><colspec colname="2" colwidth="1*" /><colspec colname="3" colwidth="1*" /><colspec colname="4" colwidth="1*" /><colspec colname="5" colwidth="1*" /><colspec colname="6" colwidth="1*" /><colspec colname="7" colwidth="1*" /><tbody><row><entry colname="1">Sample No..</entry><entry namest="2" nameend="3">Escorene HD 7755 * (comparison)</entry><entry namest="4" nameend="5">A</entry><entry namest="6" nameend="7">B</entry></row><row><entry colname="1">Rxn Temp. (° C)</entry><entry colname="4">105</entry><entry colname="6">105</entry></row><row><entry colname="1">Rx pressure</entry><entry colname="4">350</entry><entry colname="6">350</entry></row><row><entry colname="1">C2 PP</entry><entry colname="4">220</entry><entry colname="6">220</entry></row><row><entry colname="1">H2 / C2 (Molar)</entry><entry colname="4">0.003</entry><entry colname="6">0.003</entry></row><row><entry colname="1">H2 ppm</entry><entry colname="4">1800</entry><entry colname="6">1800</entry></row><row><entry colname="1">comonomer</entry><entry colname="4">C6</entry><entry colname="6">C6</entry></row><row><entry colname="1">Comonomer / C2 (Molar)</entry><entry colname="4">0,004</entry><entry colname="6">0.0044</entry></row><row><entry colname="1">MI (I2)</entry><entry colname="2">0,068</entry><entry colname="4">0,055</entry><entry colname="6">0,071</entry></row><row><entry colname="1">M (I5)</entry><entry colname="6">0,341</entry></row><row><entry colname="1">FI (I21)</entry><entry colname="2">10</entry><entry colname="4">8.37</entry><entry colname="6">9.93</entry></row><row><entry colname="1">MFR (I21 / I2)</entry><entry colname="2">146.6</entry><entry colname="4">155</entry><entry colname="6">140</entry></row><row><entry colname="1">density (G / cc)</entry><entry colname="2">.9518</entry><entry colname="4">0.9524</entry><entry colname="6">.9490</entry></row><row><entry colname="1">Throughput (kg / h) ((lb / hr))</entry><entry colname="2">45.4 (100)</entry><entry colname="4">45.8 (101)</entry><entry colname="6">47.2 (104)</entry></row><row><entry colname="1">Head pressure (MPa) ((Psi))</entry><entry colname="2">50.6 (7230)</entry><entry colname="4">51.5 (7350)</entry><entry colname="6">53.2 (7600)</entry></row><row><entry colname="1">engine load (Amp)</entry><entry colname="2">58</entry><entry colname="4">58.5</entry><entry colname="6">59.5</entry></row><row><entry colname="1">BUR</entry><entry colname="2">4</entry><entry colname="4">4</entry><entry colname="6">4</entry></row><row><entry colname="1">FLH (Cm) ((inch))</entry><entry colname="2">91.4 (36)</entry><entry colname="4">91.4 (36)</entry><entry colname="6">91.4 (36)</entry></row><row><entry colname="1">melt fracture</entry><entry colname="2">no</entry><entry colname="3">no</entry><entry colname="4">no</entry><entry colname="5">no</entry><entry colname="6">no</entry><entry colname="7">no</entry></row><row><entry colname="1">FAR</entry><entry colname="2">40</entry><entry colname="3">40</entry><entry colname="4">40</entry><entry colname="5">40</entry><entry colname="6">40</entry><entry colname="7">40</entry></row><row><entry colname="1">bubble stability</entry><entry colname="2">Good</entry><entry colname="3">Acceptable</entry><entry colname="4">Good</entry><entry colname="5">Good</entry><entry colname="6">Good</entry><entry colname="7">Good</entry></row></tbody></tgroup></table></tables>&lt;?page 50?&gt;<tables><table frame="all"><tgroup cols="7" colsep="1" rowsep="1"><colspec colname="1" colwidth="1*" /><colspec colname="2" colwidth="1*" /><colspec colname="3" colwidth="1*" /><colspec colname="4" colwidth="1*" /><colspec colname="5" colwidth="1*" /><colspec colname="6" colwidth="1*" /><colspec colname="7" colwidth="1*" /><tbody><row><entry colname="1">Sample No..</entry><entry namest="2" nameend="3">Escorene HD 7755 * (comparison)</entry><entry namest="4" nameend="5">A</entry><entry namest="6" nameend="7">B</entry></row><row><entry colname="1">recording speed (Fpm)</entry><entry colname="2">92</entry><entry colname="3">182</entry><entry colname="4">92</entry><entry colname="5">184</entry><entry colname="6">92</entry><entry colname="7">184</entry></row><row><entry colname="1">Film thickness (micron) ((mil))</entry><entry colname="2">25.4 (1)</entry><entry colname="3">12.7 (0.5)</entry><entry colname="4">25.4 (1)</entry><entry colname="5">12.7 (0.5)</entry><entry colname="6">25.4 (1)</entry><entry colname="7">12.7 (0.5)</entry></row><row><entry colname="1">impact strength (G)</entry><entry colname="2">250</entry><entry colname="3">330</entry><entry colname="4">200</entry><entry colname="5">340</entry><entry colname="6">230</entry><entry colname="7">340</entry></row><row><entry colname="1">tensile strenght (MPa) ((psi))</entry></row><row><entry colname="1">MD</entry><entry colname="2">70 (10000)</entry><entry colname="3">77 (11000)</entry><entry colname="4">59.5 (8500)</entry><entry colname="5">82.7 (11820)</entry><entry colname="6">60.2 (8600)</entry><entry colname="7">89.6 (12800)</entry></row><row><entry colname="1">TD</entry><entry colname="2">52.5 (7500)</entry><entry colname="3">52.5 (7500)</entry><entry colname="4">44.1 (6300)</entry><entry colname="5">59.1 (8440)</entry><entry colname="6">70 (10000)</entry><entry colname="7">62.3 (8900)</entry></row><row><entry colname="1">Strain (%)</entry></row><row><entry colname="1">MD</entry><entry colname="2">490</entry><entry colname="3">380</entry><entry colname="4">400</entry><entry colname="5">325</entry><entry colname="6">530</entry><entry colname="7">300</entry></row><row><entry colname="1">TD</entry><entry colname="2">570</entry><entry colname="3">390</entry><entry colname="4">630</entry><entry colname="5">370</entry><entry colname="6">430</entry><entry colname="7">380</entry></row><row><entry colname="1">TD</entry><entry colname="2">570</entry><entry colname="3">390</entry><entry colname="4">630</entry><entry colname="5">370</entry><entry colname="6">430</entry><entry colname="7">380</entry></row><row><entry colname="1">Elmendorf tear strength (N / m) (G / mil)</entry></row><row><entry colname="1">MD</entry><entry colname="2">8.7 (22)</entry><entry colname="3">4.7 (12)</entry><entry colname="4">8.7 (22)</entry><entry colname="5">4.3 (11)</entry><entry colname="6">8.3 (21)</entry><entry colname="7">4.7 (12)</entry></row><row><entry colname="1">TD</entry><entry colname="2">73.3 (186)</entry><entry colname="3">14.2 (36)</entry><entry colname="4">141.8 (360)</entry><entry colname="5">16.6 (42)</entry><entry colname="6">70.9 (180)</entry><entry colname="7">10.2 (26)</entry></row><row><entry colname="1">module (MPa) ((psi))</entry></row><row><entry colname="1">MD</entry><entry colname="2">912.8 (130400)</entry><entry colname="3">905.8 (129400)</entry><entry colname="4">812 (116000)</entry><entry colname="5">1170.4 (167200)</entry><entry colname="6">777 (111000)</entry><entry colname="7">798 (114000)</entry></row><row><entry colname="1">TD</entry><entry colname="2">1121.4 (160200)</entry><entry colname="3">1141 (163000)</entry><entry colname="4">1028.3 (146900)</entry><entry colname="5">1148 (164000)</entry><entry colname="6">889 (127000)</entry><entry colname="7">952 (136000)</entry></row></tbody></tgroup></table></tables><ul><li>* Escorene HD7755 is a polyethylene polymer, available ExxonMobil Chemical Company in Mt. Belvue, Texas, with a I₂₁ of 7.5, a MIR of 125 and a M_w of 180,000, a density of 0.95 g / cc, produced using a dual reactor system.</li></ul>

example 8

A spray-dried [(2,4,6-Me₃C₆H₂) NCH₂CH₂] NHZrBz₂Catalyst with pentamethylcyclopentadienyl (n-propylcyclopentadienyl) ZrCl₂ Online pruned (trimmed)

On Ethylene-hexene copolymer was dissolved in a 35.6 cm (14 inch) fluidized bed reactor -Gasphasen in pilot plant size, which at 100 ° C and 2.45 MPa (350 psig) total reactor pressure was, and with a water-cooled heat exchanger produced. Ethylene at a rate of approximately 22.7 introduced kg (50 pounds) per hour into the reactor, the reactor was hexane at a rate of about 0.23 kg (0.5 pounds) per supplied hour, and hydrogen was added to the reactor at a rate of 20 mPPH supplied. Ethylene was supplied to an ethylene partial pressure in the reactor of 1.4 MPa (200 psi) maintain. Hexene was continuously fed to a C6 / C2 molar ratio of 0.01 maintain. The hydrogen feed rate was controlled, an H2 / C2 molar gas ratio to retain in the recycle gas of 0.0035. The production rate was about 28 PPH. The reactor was equipped with a plenum having about 544.3 kg / hr (12000 lb / h) equipped to recycle gas flow. (The plenum is a Device that is used to create a particle lean zone in a Fluidized bed gas phase reactor to bil&lt;?page 51?&gt;the. See<patcit><text>US Patent 5,693,727</text></patcit>). A tapered Katalysatorinjektionsdüse with a hole size of 0.14 cm (0.055 '') was in the plenum gas flow positioned.

A spray-dried slurried [(2,4,6-Me₃C₆H₂) NCH₂CH₂] NHZrBz₂ (HN3-Zr) catalyst (20 wt.% Solids) was prepared. The desired composition for the Catalyst should be: 34.2% Cabosil, 12.8% Gasil, 50.7% MAO, 2.3% HN3-Zr, 8.7 mmol Al / g, 0.037 mmol Zr / g and 234 Al / Zr. The resulting Powder was dissolved in petroleum added to a 25 wt% -. prepare slurry.

Of the Catalyst was further diluted with hexane to a 20 wt% -. A slurry to form, and for mixed for 24 h before it was fed to the reactor.

Of the slurried Catalyst was continuously passed through a 0.32 cm (1/8 '') - with a line speed supplied from 35 cc / h. An additional flow rate of 0.45 kg / h (1 lb / hr) isopentane helped carry the catalyst to the mixing point "T". There were 3 cc / h of a 0.5 wt.% Pentamethylcyclopentadienyl (n-propylcyclopentadienyl) ZrCl₂ ((Cp *) (n-propCp) ZrCl₂) Catalyst in purified Kaydol petroleum added to the mix point "T", and the Catalysts were in 5.7 cm (2 ¼ '') Chemineer Kinecs-static mixers placed in series in contact. The Contact time between the two catalysts was less than 5 min. The catalysts were finally together by the tapered injection nozzle with additional 0.45 kg / h (1 lb / hr) isopentane and 1.8 kg / h (4 lbs / hr) purified nitrogen injected. The molar ratio of HN3 / (Cp *) (n-propCp) ZrCl₂-Catalyst was about . 7

the resulting polymer was after the processing of the grains a Brabender extruder analyzed. The flow index was 6.5 and the melt index was 0.049, which led to a MFR of 133rd The density was 0.9528 g / cc.

example 9

HN3-Zr-spray-dried catalyst (Cp *) (n-propCp) ZrCl₂ dipped off-line

On Ethylene-hexene copolymer was dissolved in a 35.6 cm (14 inch) fluidized bed reactor -Gasphasen in pilot plant size, which at 85 ° C and 2.45 MPa (350 psig) total reactor pressure was, and with a water-cooled heat exchanger produced. Ethylene at a rate of approximately 16.3 introduced kg (0.7 pounds) per hour into the reactor, the reactor was hexane at a rate of about 0.23 kg (0.5 pounds) per supplied hour, and hydrogen was added to the reactor at a rate of 18 mPPH supplied. Ethylene was supplied to an ethylene partial pressure in the reactor of 1.4 MPa (200 psi) maintain. Hexene was continuously fed to a C6 / C2 molar ratio of 0.015 maintain. The hydrogen feed rate was controlled, an H2 / C2 molar gas ratio to retain in the recycle gas of 0.0035. The production rate was about 19 PPH. The reactor was equipped with a plenum having about 544.3 kg / hr (12000 lb / h) equipped to recycle gas flow. (The plenum is a Device that is used to create a particle lean zone in a Fluidized bed gas phase reactor to form. See<patcit><text>US Patent 5,693,727</text></patcit>). A tapered Katalysatorinjektionsdüse with a hole size of 0.14 cm (0.055 '') was in the plenum gas flow positioned.

A spray-dried HN3-Zr-slurried Catalyst with (Cp *) (n-propCp) ZrCl₂ (17 wt.% Solids, molar ratio HN3 / (Cp *) (n-propCp) ZrCl₂ 8) off-line was prepared. The aimed composition for the catalyst should be: 34.2% Cabosil, 12.8% Gasil, 50.7% MAO, 2.3% HN3-Zr, 8.7 mmol Al / g, 0.037 mmol Zr / g and 234 Al / Zr. The resulting Powder was dissolved in petroleum added to a 20 wt% -. to produce slurry. (Cp *) (n-propCp) ZrCl₂ the mixture was added to provide a molar ratio of Catalyst HN3- (Cp *) (n-propCp) ZrCl₂ from 8: 1 to produce. The catalyst was further diluted with hexane to give a 17 wt% -. solids slurry to obtain. It was continuously passed through a 0.32 cm (1/8 '') - with a line speed supplied from 30 cc / h. An additional Flow rate of 0.45 kg / h (1 lb / hr) isopentane helped the catalyst to the reactor to carry. The catalyst was finally together by the tapered injection nozzle with additional 0.45 kg / h (1 lb / hr) isopentane and 1.13 kg / h (2.5 lb / h) of purified Nitrogen injected.

the resulting polymer was after the processing of the grains a Brabender extruder analyzed. The flow index was 9.7 and the melt index was 0.041, leading to a MFR of 237th The density was 0.9501 g / cc.

&lt;?page 52?&gt;

example 10

Catalyst preparation (HN3-Zr / MMAO / Cabosil slurry) for Examples 11-14

It A catalyst slurry containing HN3-Zr, modified methylalumoxane (MMAO) and fumed silica (TS-610 Cabosil) prepared in hexane and heptane. 468 g of MMAO Albemarle as a 7 wt.% Al in heptane were mixed with 1 liter of purified hexane diluted. There were 30.1 g Cabosil for a 3 wt.% solids concentration added. The mixture was for 30 stirred. 3.6 g HN3-Zr powder was added, stirred and in a clean 2-liter vessel made of stainless Steel filled. The molar ratio Al / Zr was 150 and the HN3-Zr was 0.35 wt.%. HN3- (Cp *) (n-propCp) ZrCl₂ was dissolved in purified hexane at a concentration dissolved of 0.15 wt.%.

example 11

On Ethylene-hexene copolymer was dissolved in a 35.6 cm (14 inch) fluidized bed reactor -Gasphasen in pilot plant size, which at 85 ° C and 2.45 MPa (350 psig) total reactor pressure was, and with a water-cooled heat exchanger produced. Ethylene at a rate of approximately 27.2 kg introduced (60 pounds) per hour into the reactor, the reactor was hexane at a rate of about 0.43 kg (0.95 pounds) per supplied hour, and hydrogen was added to the reactor at a rate of 20 mPPH supplied. Ethylene was supplied to an ethylene partial pressure in the reactor of 1.54 MPa (220 psi) maintain. Hexene was continuously fed to a molar ratio of C6 / C2 maintain 0.005. The hydrogen feed rate was controlled to maintain a H2 / C2 in the recycle gas of 0.003. The production rate was about 30 PPH.

Of the Reactor was equipped with a plenum with 725.8 kg / hr (1600 lb / hr) of recycle gas flow equipped. (The Plenum is a device used to create a particle lean Zone in a fluidized bed gas phase reactor to form. See<patcit><text>US Patent 5,693,727</text></patcit>). The catalyst system was a in a tapered catalyst injection nozzle having Hole size of 0.14 cm (0.055 ''), prepared from a stainless steel tube with 0.32 cm (1/8 ''), positioned in the center of an additional casing tube 0.64 cm (¼ ''). The shroud tube contained nitrogen, the fed with 4.5 kg / h (10 lb / h) has been.

The catalyst slurry (HN3-Zr / MMAO / Cabosil, prepared in Example 10) was dissolved in a continuously touching container placed, performed through a tube with 0.32 cm (1/8 '') using 120 cc / hr of isopentane. The Katalysatoraufschlämmungs-flow rate was 16 cc / hr. she got with a 0.15% by weight -. solution of (Cp *) (n-propCp) ZrCl₂ in hexane (24 cc / hr) and additional 0.09 kg / h (0.2 lb / h) brought witches in contact and in-line with two 0.64 cm (¼ '') mixed Kinecs-static mixers in series. Optionally isopentane was between the two Kinecs mixers at a rate from 0 to 0.45 kg / hr (0-1 lb / hr). the molar ratio of HN3-Zr / (Cp *) (n-propCp) ZrCl₂Catalyst was 1.4. The contact time the (Cp *) (n-propCp) ZrCl₂-Solution and the HN3-Zr / MMAO / Cabosil slurry before entering the reactor was 5-10 min, depending of the isopentane flow rate. additionally the catalysts and isopentane, nitrogen was the injection tube fed to the slurry at a rate of 1.36 kg / hr (3 lb / hr) to obscure. all Materials have been merged and through the 0.32 cm (1/8 '') - and the injection nozzle pipe in the fluidized bed out. A diagram describing the entire feed delivery system, is in <figref idrefs="S132">6</figref> shown.

the produced polyethylene had an FI of 1.6, a MI of 0.022 and a density of 0.9487. The particle size was 0.035 cm (0.0139 Inch) and contained 5 wt.% Fines. The resin contained 0.2% material which is greater than a 10 mesh sieve was. The catalyst activity was excellent, containing 18 ppm Al and 1.29 ppm Zr, determined by X-rays.

example 12

On Ethylene-hexene copolymer was dissolved in a 35.6 cm (14 inch) fluidized bed reactor -Gasphasen- in pilot plant size, which at 90 ° C and 2.45 MPa (350 psig) total reactor pressure was, and with a water-cooled heat exchanger produced. Ethylene at a rate of approximately 22.7 introduced kg (50 pounds) per hour into the reactor, the reactor was hexane at a rate of about 0.45 kg (1 pound) per hour fed and hydrogen was added to the reactor at a rate of 14 mPPH supplied. Ethylene was supplied to an ethylene partial pressure in the reactor of 1.54 MPa (220 psi) maintain. Hexene was continuously fed to a molar ratio of C6 / C2 maintain 0.007. The hydrogen feed rate was controlled to a H2 / C2 in the cycle gas from 0.0035 &lt;?page 53?&gt;maintain. The production rate was about 25 PPH.

Of the Reactor was equipped with a plenum chamber with 476.3 kg / h (1050 lb / h) Circulation gas flow equipped. (The plenum is a device used to create a particle lean zone in a fluidized bed gas phase reactor to form. See<patcit><text>US Patent 5,693,727</text></patcit>). The catalyst system was a in a tapered catalyst injection nozzle having Hole size of 0.14 cm (0.055 ''), prepared from a stainless steel tube with 0.32 cm (1/8 ''), positioned in the center of an additional casing tube 0.64 cm (¼ ''). The shroud tube contained nitrogen, the fed with 4.5 kg / h (10 lb / h) has been.

The catalyst slurry (HN3 / MMAO / Cabosil, prepared in Example 10) was dissolved in a continuously touching container placed, performed through a tube with 0.32 cm (1/8 '') using 300 cc / hr of isopentane. The Katalysatoraufschlämmungs-flow rate was 16 cc / hr. she got with a 0.15% by weight -. solution of X-catalyst in hexane (31 cc / hr) and additional 0.09 kg / hr (0.2 lb / h) brought witches in contact and in-line with two 0.64 cm (¼ '') Kinecs-static mixers mixed in series. Isopentane was between the two Kinecs mixers at a rate of 1.36 kg / h (3 lb / hr). The molar ratio of HN3 to X catalyst was 1.06. The contact time of the X-catalyst solution and the HN3 / MMAO / Cabosil slurry before entering the reactor was 1.5 min. In addition to the catalysts and isopentane, nitrogen for injection tube fed to the slurry with a rate of 2.3 kg / h (5 lb / hr) to obscure. all Materials have been merged and through the 0.32 cm (1/8 '') - and the injection nozzle pipe in the fluidized bed out. A diagram describing the entire feed delivery system, is in <figref idrefs="S132">6</figref> shown.

the produced polyethylene had an FI of 2.2, a MI of 0.28 and a density of 0.9439. The particle size was 0.17 cm (0.0662 inch) and containing 0.2 wt.% fines. The resin contained 43.5% material which is greater than a 10 mesh sieve was. The catalyst activity was excellent, containing 24 ppm Al and 1.07 ppm Zr, determined by X-rays.

example 13

On Ethylene-hexene copolymer was dissolved in a 35.6 cm (14 inch) fluidized bed reactor -Gasphasen in pilot plant size, which at 90 ° C and 2.45 MPa (350 psig) total reactor pressure was, and with a water-cooled heat exchanger produced. Ethylene at a rate of approximately 22.7 introduced kg (50 pounds) per hour into the reactor, the reactor was hexane at a rate of about 0.45 kg (1 pound) per hour fed and hydrogen was added to the reactor at a rate of 14 mPPH supplied. Ethylene was supplied to an ethylene partial pressure in the reactor of 1.54 MPa (220 psi) maintain. Hexene was continuously fed to a molar ratio of C6 / C2 maintain of 0.0068. The hydrogen feed rate was controlled to maintain a H2 / C2 in the recycle gas of 0.0035. The production rate was about 35 PPH.

Of the Reactor was equipped with a collection chamber with a cycle gas flow of up to 544.3 kg / h (1200 lb / h) as standard. (The plenum is a device which is used to provide a particle lean zone in a fluidized bed gas phase reactor to form. See<patcit><text>US Patent 5,693,727</text></patcit>). The catalyst system was a in a tapered catalyst injection nozzle having Hole size of 0.14 cm (0.055 ''), made of a stainless steel tube with 0.32 cm (1/8 ''), positioned in the center of an additional casing tube with 0.64 cm (¼ ''). The shroud tube contained nitrogen, the fed with 4.5 kg / h (10 lb / h) has been.

The catalyst slurry (HN3 / MMAO / Cabosil, prepared in Example 10) was dissolved in a continuously touching container placed, performed through a tube with 0.32 cm (1/8 '') using of 120 cc / hr of isopentane. The Katalysatoraufschlämmungs-flow rate was 12 cc / hr. she got with a 0.15% by weight -. solution of X-catalyst in hexane (22 cc / hr) and additional 0.09 kg / hr (0.2 lb / h) brought witches in contact and in-line with two 0.64 cm (¼ '') Kinecs-static mixers mixed in series. Isopentane was between the two Kinecs mixers at a rate of 0.23 kg / h (0.5 lb / hr). The molar ratio of HN3 to X catalyst was 1.12. The contact time of the X-catalyst solution and the HN3 / MMAO / Cabosil slurry before entering the reactor was 6 minutes. In addition to the catalysts and isopentane, nitrogen for injection tube fed to the slurry at a rate of 1.36 kg / hr (3 lb / hr) to obscure. all Materials have been merged and through the 0.32 cm (1/8 '') - and the injection nozzle pipe in the fluidized bed out. A diagram describing the entire feed delivery system, is in <figref idrefs="S132">6</figref> shown.

the produced polyethylene had an FI of 7.1, a MI of 0.046 and a density of 0.951. &lt;?page 54?&gt;The particle size was 0.03175 cm (0.0125 Inch) and contained 9.4 wt.% Fines. The resin contained no material which is greater than a 10 mesh sieve was. The catalyst activity was excellent.

example 14

On Ethylene-hexene copolymer was dissolved in a 35.6 cm (14 inch) fluidized bed reactor -Gasphasen in pilot plant size, which at 90 ° C and 2.45 MPa (350 psig) total reactor pressure was, and with a water-cooled heat exchanger produced. Ethylene at a rate of approximately 20.4 kg introduced (45 pounds) per hour into the reactor, the reactor was hexane at a rate of about 0.36 kg (0.8 pounds) per supplied hour, and hydrogen was added to the reactor at a rate of 12 mPPH supplied. Ethylene was supplied to an ethylene partial pressure in the reactor of 1.54 MPa (220 psi) maintain. Hexene was continuously fed to a molar ratio of C6 / C2 maintain of 0.0068. The hydrogen feed rate was controlled to maintain a H2 / C2 in the recycle gas of 0.0035. The production rate was about 23 PPH.

Of the Reactor was equipped with a collection chamber with a cycle gas flow of 290.3 kg / h (640 lb / h) as standard. (The plenum is a device used to create a particle lean zone in a fluidized bed gas phase reactor to form. See<patcit><text>US Patent 5,693,727</text></patcit>). The catalyst system was a in a tapered catalyst injection nozzle having Hole size of 0.14 cm (0.055 ''), prepared from a stainless steel tube with 0.32 cm (1/8 ''), positioned in the center of an additional casing tube 0.64 cm (¼ ''). The shroud tube contained nitrogen, the fed with 4.5 kg / h (10 lb / h) has been.

The catalyst slurry (HN3 / MMAO / Cabosil, prepared in Example 10) was dissolved in a continuously touching container placed, performed through a tube with 0.32 cm (1/8 '') using of 120 cc / hr of isopentane. The Katalysatoraufschlämmungs-flow rate was 16 cc / hr. she got with a 0.15% by weight -. solution of X-catalyst in hexane (25 cc / hr) and additional 0.09 kg / hr (0.2 lb / h) brought witches in contact and in-line with two 0.64 cm (¼ '') Kinecs-static mixers mixed in series. isopentane was between the two Kinecs mixers at a rate of 0.23 kg / h (0.5 lb / hr). the molar ratio of HN3 to X catalyst was 1.32. The contact time of the X-catalyst solution and the HN3 / MMAO / Cabosil slurry before entering the reactor was 6 minutes. In addition to the catalysts and isopentane, nitrogen for injection tube fed to the slurry at a rate of 1.36 kg / hr (3 lb / hr) to obscure. all Materials have been merged and through the 0.32 cm (1/8 '') - and the injection nozzle pipe in the fluidized bed out. A diagram describing the entire feed delivery system, is in <figref idrefs="S132">6</figref> shown.

the produced polyethylene had an FI of 4.7, a MI of 0.045 and a density of 0.9493. The particle size was 0.06 cm (0.0231 inch) and contained 2 wt.% fines. The resin contained 0.1 wt.% Material which is greater than a 10 mesh sieve was. The catalyst activity was excellent, with Al residues in 19 ppm and Zr residues at 1.31 ppm, determined by X-ray fluorescence.

The Table 4 below summarizes the data of Examples 11-14. The examples 12 and 13 demonstrate that the different flow rates of the Isopentane and nitrogen affect the particle size formed. Examples 13 and 14 show that the plenum flow used can be to control the particle size. additionally is <figref idrefs="S133">7</figref> a diagram showing change in the the fines and the particle size with the change the collection chamber circulation gas flow rate is illustrated. &lt;?page 55?&gt; TABLE. 4 <tables><table frame="all"><tgroup cols="5" colsep="1" rowsep="1"><colspec colname="1" colwidth="1*" /><colspec colname="2" colwidth="1*" /><colspec colname="3" colwidth="1*" /><colspec colname="4" colwidth="1*" /><colspec colname="5" colwidth="1*" /><tbody><row><entry colname="1">example</entry><entry colname="2">11</entry><entry colname="3">12</entry><entry colname="4">13</entry><entry colname="5">14</entry></row><row><entry colname="1">FI (I21)</entry><entry colname="2">1.6</entry><entry colname="3">2.2</entry><entry colname="4">7.1</entry><entry colname="5">4.7</entry></row><row><entry colname="1">MI (I2)</entry><entry colname="2">0,022</entry><entry colname="3">0,028</entry><entry colname="4">0,046</entry><entry colname="5">0,045</entry></row><row><entry colname="1">density (G / cc)</entry><entry colname="2">.9487</entry><entry colname="3">.9439</entry><entry colname="4">0,951</entry><entry colname="5">.9493</entry></row><row><entry colname="1">APS cm (inch)</entry><entry colname="2">0.0139</entry><entry colname="3">.0662</entry><entry colname="4">0.0125</entry><entry colname="5">0.0231</entry></row><row><entry colname="1">fines (Less than 120 mesh)</entry><entry colname="2">5</entry><entry colname="3">0.2</entry><entry colname="4">9.4</entry><entry colname="5">2.0</entry></row><row><entry colname="1">Greater than 10 mesh</entry><entry colname="2">0.2</entry><entry colname="3">43.5</entry><entry colname="4">0</entry><entry colname="5">0.1</entry></row><row><entry colname="1">reactor temperature (° C)</entry><entry colname="2">85</entry><entry colname="3">90</entry><entry colname="4">90</entry><entry colname="5">90</entry></row><row><entry colname="1">C2 MPa (psi)</entry><entry colname="2">1.54 (220)</entry><entry colname="3">1:54 (220)</entry><entry colname="4">1.54 (220)</entry><entry colname="5">1.54 (220)</entry></row></tbody></tgroup></table></tables><tables><table frame="all"><tgroup cols="5" colsep="1" rowsep="1"><colspec colname="1" colwidth="1*" /><colspec colname="2" colwidth="1*" /><colspec colname="3" colwidth="1*" /><colspec colname="4" colwidth="1*" /><colspec colname="5" colwidth="1*" /><tbody><row><entry colname="1">example</entry><entry colname="2">11</entry><entry colname="3">12</entry><entry colname="4">13</entry><entry colname="5">14</entry></row><row><entry colname="1">H2 / C2 molar ratio in the cycle gas</entry><entry colname="2">0.003</entry><entry colname="3">0.0035</entry><entry colname="4">0.0035</entry><entry colname="5">0.0035</entry></row><row><entry colname="1">C6 / C2 molar ratio in the cycle gas</entry><entry colname="2">0.005</entry><entry colname="3">0,007</entry><entry colname="4">0.0068</entry><entry colname="5">0.0068</entry></row><row><entry colname="1">HN3-Zr / (Cp *) (n-propCp) ZrCl₂ molar ratio</entry><entry colname="2">1.4</entry><entry colname="3">1.06</entry><entry colname="4">1.12</entry><entry colname="5">1.3</entry></row><row><entry colname="1">Isopentanträger g / h (Lb / hr total)</entry><entry colname="2">0.36 (0,8)</entry><entry colname="3">1.59 (3,5)</entry><entry colname="4">0.32 (0,7)</entry><entry colname="5">0.32 (0,7)</entry></row><row><entry colname="1">Nitrogen carrier g / h (lb / h)</entry><entry colname="2">1.36 (3)</entry><entry colname="3">2.3 (5)</entry><entry colname="4">1.36 (3)</entry><entry colname="5">1.36 (3)</entry></row><row><entry colname="1">N2 / IC5-weight ratio</entry><entry colname="2">3.75</entry><entry colname="3">1.66</entry><entry colname="4">4.3</entry><entry colname="5">4.3</entry></row><row><entry colname="1">Plenum flow (Cycle gas kg / h (lb / h))</entry><entry colname="2">725.8 (1600)</entry><entry colname="3">476.3 (1050)</entry><entry colname="4">544.3 (1200)</entry><entry colname="5">290.3 (640)</entry></row></tbody></tgroup></table></tables>

While the present invention by reference to certain embodiments has been described and illustrated, the expert knows that the invention even lead to variations may not necessarily illustrated herein. That's why should only to the attached Examples may be referred to the true scope of the present to determine invention. It is also includes that Immobilis Innovative technique the combination of the slurry and the solution this invention can be used to substantially z. B. to form a metallocene catalyst compound with an Activating agent is combined and a polymerization reactor supplied is.

all herein mentioned documents are incorporated by reference herein, including any priority document and / or test procedure. Based on the foregoing general Description and the specific embodiments, it is obvious that embodiments of the invention have been illustrated and described, various Modifications can be made, without departing from the spirit and scope of the invention departing. Accordingly, should the Invention is not limited to, be.