Method of polymerization

POLYMERIZATION METHOD

Full description

Background of the invention

This invention relates to spray dried olefin polymerization catalysts and their use in a gas phase or slurry phase to produce polyolefins.

The extensive use of metallocene-type polyolefin catalysts (metallocene cyclopentadienyl-based transition metal catalyst compounds) on a commercial scale has led to widespread interest in the design of non-metallocene, homogenous catalysts. catalysts, in particular for use in gas-phase and slurry-phase processes on an economical scale. In addition to this being a particularly new academic topic, gas-phase or slurry-phase non-metalloacene catalysts may provide an easier and more economically viable way to obtain currently available products and may also provide opportunities for a superior product and process. Metallocene catalysts in the gas phase or slurry phase.

However, the new catalysts cannot be used independently in the gas phase as some catalysts are too reactive and dirty the reactor. Other catalysts cannot be carried and therefore cannot be introduced into the reactor in such a way that fouling does not occur. And so on

There is a technical need for a way to supply catalysts to a gas-phase or slurry-phase reactor, especially catalysts that are difficult or impossible to carry.

In US Patent No. 5,889,128, Schrock and his collaborators described a process for sustaining the polymerization of olefins in solution using initiators comprising a metal atom and a ligand containing two group 15 atoms and a group 6 atom or three group 1 atoms. Group 15. Specifically, a solution polymerization of ethylene using [3(NON]ZrMe} [Me(C6F5)]} or [4(NON]ZrMe (PhNMe2)]} [B (C6F5]}) is described in Examples 9 and 10.

European Patent No. Al 454 893 describes unsupported transition metal amide conrpounds used in combination with activators to polymerize olefins in the solution phase.

European Patent No. Al 454 893 0 of Mitsui Chemicals describes,

Mitsui Chemicals, In c Amides containing transition metals combined with activators for the polymerization of olefins.

European Patent No. Al 874 005 describes phenoxide compounds containing an imine substituent for use as a polymerization catalyst.

European Patent No. Al 454 893 describes unloaded amide compounds containing a transition metal used in combination with activators for the solution-phase polymerization of olefins.

US patent application serial number 09/312,878 filed on May 17, 1999 describes a polymerization process conducted in a gas or slurry phase using a supported bisamide catalyst.

The abstract of Japanese Patent No. 6A 41 03301 describes amide catalysts containing a transition metal in combination with Ziegler-Natta catalysts. The abstract of Japanese patent No. 2A 041 1033 describes amide catalysts containing a metal

Transition in combination with cyclopentadienyl catalysts containing a group 4 transition metal.

Ethylene dichloride (salicylidenciminato) zirconium dichloride combined with methyl alumoxane deposited on portable and non-mobile forms was used to polymerize ethylene by Repo and his collaborators in the journal Macromolecules, Skin 30, pp. 171-175, 1997. .

US Patent Nos. 5,672,669 and 5,674,795 and European Patent No. Bl 295 668 0 describe spray dried filled metallocene catalyst compositions for use in gas-phase polymerization processes. General description of the invention

This invention relates to a catalytic molecule and a spray-dried catalytic system comprising a particulate filler, an activator, and a metal catalyst compound.

In one respect, the particulate filler may be any known particulate filler containing carbon black, talc; inorganic oxides such as silica; magnesium chloride, alumina, silica-alumina; Polymeric materials such as polyethylene, polypropylene, polystyrene, cross linked polystyrene; And so on.

Preferred doping over conventional co-catalysts includes alkyl aluminum compounds (such as diethylaluminum chloride), alumoxanes, modified alumoxanes, non-coordinating anions, and metal or semi-coordinated anions. Metals from Group 13, non-coordinating group 13, metal or metalloid anions, borane compounds, borate compounds, and the like. The use of Alumoxan is considered

alumoxane or modified alumoxane as an activator within the scope of this invention, and/or also using ionizing activators, neutral or ionic, such as tri-(p-butyl)ammonium tetra(pentafluorophenyl)boron

tri(n-butyl)ammonium tetrakis teentafluorophenyl)boron or a semi-metallic source of trisperfluorophenyl boron metalloid precursor that ionizes the neutral metallocene compound. Other useful compounds include triphenyl boron, triethyl boron, tri-n-butylammoniumtetraethylborate, triaryl borane, and the like. Other beneficial compounds include aluminate salts as well.

Some of the many metal catalyst compounds that may be used in this statement include a metal compound containing a Group 15 metal as described below and/or phenoxide-based catalysts as described below. Brief explanation of fees

Figure 1: shows a horizontally mixed reactor system in use

In comparison example 9 and examples 22 to 28.

Detailed description of the invention

The present invention relates to a spray drying catalyst system comprising a particulate filler,

Activator, and one or more metal catalytic compounds. Metallic catalyst compounds show an amazing ability to be stabilized using a filler, activated by a dopant, and have amazing structural durability and catalytic activity.

In a preferred embodiment herein, the particulate filler is furned silica. It is preferable that the filler be Cabosoil TS 610, available from Cabot Corporation, which is fumed silica with a particle size ranging from 7 to 0.3 nanometers and treated with dimedrylsilyldichloride so that it covers the majority of the filler. groups

hydroxyl. Spray-dried particles are usually fed to the polymerization reactor as a mineral oil slurry. The concentrations of solids in the oil range from about 10 to 15% by weight, and preferably between 11 and 14% by weight. In some embodiments, the spray dryer particle size is less than approximately 10 µm from a laboratory-scale Buchi spray-dryer, while large-scale rotary atomizers may produce particles of approximately 25 µm, compared to conventional portable catalysts with a particle size of Approximately 50 micrometers. In a preferred embodiment, the particulate filler has an average particle size

Ranges between 0.001 and 1 micron, preferably between 0.001 and 0.1 micron.

In a preferred embodiment the metal catalyst complex comprises one or more of the following catalysts:

Preferred catalysts or catalyst systems that may be used in this statement include a metal compound containing a Group 15 element and/or phenoxide catalysts as described below. Other catalysts that can be used in combination with a metal complex containing a Group 15 element and/or phenoxides include bulky ligand metallocene type catalysts with an activator

news.

Once the catalysts described in this statement are spray dried, they can be combined with one or more conventional catalysts and introduced into the reactor. For example, a spray-dried catalyst or mixture of catalysts can be combined with conventional type transition metal catalysts (such as one or more Ziegler-Natta catalysts, vanadium catalysts and/or chromium catalysts) in mineral oil and the resulting mixture is fed to The reactor is in the form of a slurry.

For more information on conventional transition metal catalysts, see Ziegler-Natta Catalysts and Polymerization, published by John Boor, Inc.

Academic Press, New York State, 1979. Examples of transition metal catalysts of a conventional type are also described in US Patent No. 4,115,639,

٤.٠٧٧.٩٠٤، ٤.٤٨٢.٦٨٧، ٤٠٥٦٤.٦٠٥، ٤٠٧٢١٠٧٦٣، ٤,٨٧٩,٣٥٩، ٤,٩٦٠,٧٤١،

٤,٣٠٢٠٥٦٥، ٤,٣٠٢.٥٦٦، ٥,٣١٧,٠٣٦، ٣.٧٠٩,٨٥٣، ٣.٧٠٩,٩٥٤، ٣.٢٣١,٥٥٠،

٣٠٢٤٢,٠٩٩، ٤,٠٧٧,٩٠٤، ٤,١٢٤,٥٣٢، ٤,٣٠٢,٥٦٥، ٤,٣٠٢,٥٦٦، ٤,٣٧٦,٠٦٢،

403790758, 660737.,00 AH, 507630723, 508490655, 508520144, 508540164,

5,869,585, 3,487,112, 4,472,559, 4,182,814 and 4,689,437 and European Patent Application No. 815 0416 A2 and European Patent Application No. 436 420 0 Al and Patent Application No. 815 0416 A2. British No. 5,355 2.10.

To achieve the purposes of this invention, the cyclopentadienyl group is defined to include indenyls and fluorenyls. A metal compound containing an element from group 15

The mixed catalyst composition according to the present invention includes a metal compound containing an element of group 15. A compound containing an element from Group 15 usually includes a metal atom from Group 3 to Group 14, preferably from Group 3 to Group 7, preferably from Group 4 to Group 6, best of all a metal atom from Group 4, bonded to an easy group. Removal leaves at least one group further bonded to at least two atoms of group 15, at least one of which is further bonded to an atom of group 15 or 16 through another group.

In a preferred embodiment, at least one atom of group 15 is further linked to an atom of group 15 or 16 through another group which may be a hydrocarbon group having from one to 20 carbon atoms, a group containing a heteroatom, silicon, germanium germanium, tin, lead or phosphorus, where the atom of group 15 or 16 is not also bonded to another atom or may be bonded

With a hydrogen, or a group containing an atom from group 14, a halogen, or a group containing a heteroatom, whereby each of the two atoms of group 15 is also bonded to a cyclic group, and each of them may optionally be bonded to hydrogen, a halogen, a heteroatom or a group. A hydrocarbyl group, or a group containing a heteroatom.

In a preferred embodiment, the metallic compound containing an element of group 15 according to the present invention may be represented by the following two formulas: Formula I

<img file="SA687B1_D0001.tif" />

<img file="SA687B1_D0002.tif" />

or

Formula II

M represents a transition metal from group 3 to group 12 or one of the main metals of group 13 or 14, preferably a metal from group 4, 5 or 6, and the best metal from group 4, and the most preferred is zirconium, titanium or hafnium.

Each group 'L does not exist), n represents the oxidation state of M, preferably +3, +4, or +5, preferably +4, m represents the formal charge of the ligand YZL or 'YZL, preferably zero, -1, -2 or -3, and better -2,

L represents an element of group 15 or 16, preferably nitrogen; 'L represents an element of group 15 or 16 or a group containing an element of group 14, preferably carbon, silicon or germanium; Y represents an element of group 15, preferably nitrogen nitrogen, or phosphorus, and preferably nitrogen,

Z represents an element from group 15, preferably nitrogen or phosphorus, preferably nitrogen.

R1 and R2 each individually represent a hydrocarbon group containing from one to 20 carbon atoms, a group containing a heteroatom containing no more than 20 carbon atoms, silicon, germanium, tin, lead or phosphorus. The preferred alkyl group, aryl or aralkyl, contains from two to 20 carbon atoms, and the best alkyl group contains from two to 20 carbon atoms, linear, branched, or cyclic, and the most preferred is a hydrocarbon group. The hydrocarbon group contains from 2 to 6 atoms. carbon carbon. R1 and R2 may also be related to each other.

R3 does not exist or represents a hydrocarbon group, a hydrogen, a halogen, a group containing a heteroatom, and preferably a linear, cyclic or branched alkyl group containing from one to 20 carbon atoms. It is preferable for R3 to be non-existent.

Exists, or represents hydrogen or an alkyl group, most preferably hydrogen,

R4 and R5 each represent an alkyl group, an aryl group, a substituted aryl group, a cyclic alkyl group, a substituted alkyl group, aralkyl group, aralkyl group with substituted aryls, or a multiple ring system. ring system, preferably a group containing no more than 20 carbon atoms, preferably containing carbon atoms whose number ranges between 3 and 10, and best of all a hydrocarbon group containing from one to 20 carbon atoms. carbon, an aryl group with one to 20 carbon atoms, an aralkyl group with one to 20 carbon atoms, or a group containing a heteroatom, for example PR3, where R represents an alkyl group, and R1 may be linked and R2 with each other, and/or R5 and R4 may be connected with each other,

R6 and R7 may not be present, or each of them separately represents a hydrogen, an alkyl group, a halogen, a heteroatom or a hydrocarbyl group, preferably a linear, cyclic or branched alkyl group with from one to 20 carbon atoms. It is better that they do not exist, and

*R does not exist, or represents hydrogen, a group containing a group 14 atom, halogen, a group containing a heteroatom.

The 'formal charge of the ligand YZL' or 'YZL&amp;' means the total charge of the ligand in the absence of the metal and the easily removed groups X.

The phrase &amp;R1 and R2 may also be linked to each other' means that R1 and R2 may be linked directly to each other or may be linked to each other through other groups. The phrase &amp;R4 and R5 may also be related to each other&amp; means that R4 and R5 may

They are directly linked to each other or may be linked to each other through groups

Other.

The alkyl group may be linear or branched alkyl radicals, linear or branched alkenyl radicals, alkynyl radicals, cycloalkyl radicals, aryl radicals, acyl radicals, aroyl radicals, alkoxy radicals, aryloxy radicals, Alkylthio radicals, dialkylamino radicals, alkoxycarbonyl radicals, aryloxycarbonyl radicals, carbomoyl radicals, dialkyl-carbamoyl radicals, dialkyl-carbamoyl radicals Aryloxy, acyloxy radicals, acylamino radicals, aroylamino radicals, linear, branched or cyclic alkylene radicals, or a combination thereof. An aralkyl group is defined as an aryl group bearing substituents.

In a preferred embodiment, R4 and R5 are each individually represented by a group in the following form:

Formula 1

<img file="SA687B1_D0003.tif" />

R8 to R12 individually represent hydrogen, an alkyl group containing from one to 40 carbon atoms, a halide, a heteroatom, a group containing a heteroatom containing no more than 40 carbon atoms, and a linear alkyl group is preferred. Or branched from one to 20 carbon atoms, preferably a methyl, ethyl, propyl, or butyl group, and any two groups may form

R A ring group and/or a heterocyclic ring group. The ring groups may be aromatic. In a preferred embodiment, R9, R10 and R12 individually represent a methyl, ethyl, propyl or butyl methyl group (including all blue isomers), and in a preferred embodiment R9, R10 and R12 represent methyl groups, and R8 and R11 represent hydrogen

hydrogen.

In a particularly preferred embodiment, R4 and R5 represent a representative group

In the following format:

Formula 2

<img file="SA687B1_D0004.tif" />

In this embodiment, M represents a group 4 metal, preferably zirconium,

Titanium or hafnium, and best of all zirconium; Y, L and Z represent nitrogen; R1 and R2 represent the -CH2-CH2- cleft; R3 represents hydrogen; R6 and R7 do not exist.

In a particularly preferred embodiment, the metallic compound containing an element from group 15 is lysed with the following formula: Compound I

<img file="SA687B1_D0005.tif" />

In compound I, Ph refers to phenyl.

Metallic compounds containing elements of group 15 according to the invention are prepared using known methods of purification, such as those described in European Patent No. Al 0893454; U.S. Patent No. 5,889,128 and references cited in U.S. Patent No. 5,889,128 are all cited herein for reference. US Patent Application Serial No. 09/312,878, filed on May 17, 1999, describes a gas-phase or slurry-phase polymerization process using a portable bisamide catalyst, which is also cited herein for reference.

A preferred direct synthesis method for these compounds involves the reaction of the neutral ligand (see for example ligand YZL or 'YZL' for formulas 1 or 2) with MnXn (M represents a metal from group 3 to group 14, n represents the oxidation state of M, each represents an anionic group, such as a halide), in a non-coordinating or weakly coordinating solvent, such as ether, toluene, xylene, benzene, methylene chloride, and/or hexane or another solvent It has a boiling point point above 60°C, at a temperature ranging from about 20 to about 150°C (preferably from 20 to 100°C), preferably for 24 hours or more, then treat the mixture with an excess amount (e.g. four equivalents or more) of An alkylating agent, such as methyl magnesium bromide in ether. The magnesium salts are removed by filtration, and the metal complex is separated using standard techniques.

In an embodiment, the metal compound containing a group 15 element is prepared using a method comprising reacting a neutral ligand, (see for example ligand YZL or 'YZL of formulas 1 or 2) with a compound represented by the formula MnXn (where M represents a group 3 metal to Group 14, n represents the oxidation state of M, each

About 20 °C or higher, preferably at about 100 °C, then treating the mixture with an excess amount of alkylating agent, then extracting the metal complex. In a preferred embodiment the solvent has a boiling point greater than 60°C, such as toluene, xylene, and/or hexane. In another embodiment, the solvent consists of ether and/or methylene chloride, preferably

ether.

For additional information on metallic compounds containing a group 15 element, see European Patent No. Al 454 893. Mitsui Chemicals, Inc. describes transition metal amides combined with activators to polymerize olefins. Phenoxide Catalysts

Another group of catalysts that may be used in the process of this invention includes one or more catalysts represented by the following two formulas:

<img file="SA687B1_D0006.tif" />

or

Where R1 represents hydrogen or a group containing from 4 atoms to 100 carbon atoms, preferably a tertiary alkyl group, preferably an alkyl group containing from 4 atoms to 20 carbon atoms, and preferably a tertiary alkyl group containing from 4 to 20 atoms. A carbon atom, preferably a neutral group containing from 4 to 100 carbon atoms, which may or may not be bonded to M. At least one moiety from R2 to R5 represents a group containing a heteroatom, and the remaining moieties from R2 to R5 represent each of them separately. Hydrogen or a combination thereof One to 100 carbon atoms, preferably an alkyl group with from 4 to 20 carbon atoms (preferably butyl, isobutyl, pentyl hexyl, heptyl, isohexyl, octyl, isooctyl, decyl, nonyl nonyl, dodecyl) and any of the R2 to R5 moieties may also be bonded to M or may not be bonded to M, and O indicates oxygen, and M represents a transition metal from group 3 to group 10 or lanthanide metal, preferably a group 4 metal, preferably Zr,Ti or Hf; The n is the valence state of the metal M, preferably 2, 3, 4 or 5, and Q represents an alkyl group, a halogen, a benzyl, an amide, a carboxylate, a carbamate, a thiolate, a hydride, an alkoxide, or a bond. For an R group containing a heteroatom, it may be any of the radicals from R1 to R5. The group containing a heteroatom may be any heteroatom, a heteroatom bonded to carbon silica, or another heteroatom. Favorite heteroatoms include boron, aluminum, silicon, nitrogen, phosphorus, arsenic, tin, lead, antimony, and oxygen. selenium, tellurium. Particularly favored heteroatoms include nitrogen, oxygen, phosphorus, and sulfur. The best heteroatoms in particular include oxygen and nitrogen. The heteroatom itself may be directly bonded to the phenoxide ring, or it may be bonded to another atom or atoms bonded to the phenoxide ring. It may include

A group that contains a heteroatom on one or more identical or different heteroatoms. The preferred heteroatom groups include imines, amines, oxides, phosphines, ethers, ketenes, mixed cyclic oxoazolines, heterocyclics, oxazolines, and thioethers. thioethers and the like. Particularly favored heteroatom groups include imines. Any two adjacent R groups may form a ring structure, preferably a five- or six-membered ring. Likewise, R groups may form multi-ring structures. In an embodiment, any two or more R groups do not form a five-membered ring.

These phenoxide catalysts may be activated using activators that include alkyl aluminum compounds (such as diethylaluminum chloride), alumoxanes, modified alumoxanes, non-coordinating anions, group 13 chiral metal anions, or semi-coordinated anions. Asymmetric metalliod anions, borane compounds, borate compounds, and the like. For more information about stimulants, see the Steroids section below.

This invention can also be applied using the catalysts described in European Patent No. Al 5 0 0 874 0, which is mentioned in this statement for reference. Steroids

The catalysts, preferably a compound containing an element from Group 15 and/or the phenoxide catalysts described herein, are preferably combined with one or more activators to form catalyst systems for olefin polymerization. Preferred activators include alkyl aluminum compounds (such as diethylaluminum chloride), alumoxanes, modified alumoxanes, chiral anions, chiral Group 13 metal anions or chiral metalliod anions, and boranes. , vehicles

borates and the like. Within the scope of the present invention is the use of alumoxane or modified alumoxane as an activator, and/or the use of ionizing activators, neutral or ionic, such as

Tri-(p-butyl)ammonium quaternary (pentafluorophenyl)boron

Tri(n-butyl) ammonium teteakis (pentafluorophenyl) boron or a semi-metallic precursor source of trisperfluorophenyl boron ionizes the neutral metallocene compound. Other useful compounds include triphenyl boron, triethyl boron, tri-n-butyl ammonium tetraethylborate, triaryl borane and the like. Other beneficial compounds also include aluminate salts.

In one embodiment the modified alumoxanes are combined with catalysts to form a catalytic system. In a preferred embodiment MMA03A is incorporated (e.g. methyl alumoxane modified in heptane, commercially available from Akzo

Chemicals, Inc. Akzo Chemicals, Inc. (trade name Modified Methylalumoxane Type 3A, protected in US Patent No. 5,584,041) with the first and second metal compounds to form a catalytic system. MMAO-4 and MMAO-12 can also be used.

There are many methods for preparing alumoxane and modified alumoxanes, and examples of these methods are described, but are not limited to, in US Patent Nos. 4,665,208, 4,952,540, 5,091,352, 5,206,199, 5,204,419, 4,874,734, 4,9240.18, 4.9.80463, 4,968,827, 5,308,815,

٥٠٣٢٩.٠٣٢، ٥٠٢٤٨,٨٠١، ٥,٢٣٥,٠٨١، ٥,١٥٧,١٣٧، ٥,١٠٣,٠٣١، ٥,٣٩١,٧٩٣،

٥,٣٩١,٥٢٩، ٥,٢٤٨,٨٠١، 081,٢35,5، ٥.١٥٧.١٣٧، ٥.١٠٣.٠٣١، ٥.٣٩١.٧٩٣،

5,391,529, 5,041,584, 5,693,838, 5,731,253, 5,041,584 and 5,731,451 and European Patent Publications Nos. 476,561 0-A, 586,279. -B1

And 218,594. -A and the international patent application pursuant to the Patent Cooperation Treaty No. 94/10180, all of which are mentioned herein for full explanation for reference.

for reference.

Ionizing compounds may contain an active proton or another cation that is associated with the remaining ion in the ionized compound but is not coordinately bonded to it, or is only loosely bonded to it. Compounds of this and similar types are described in European Patent Publications Nos. 982 570 0-A, 732 520 0-A, A-0 277004 A-0 277003 A-0 500944 A-0 426 637 A-0 495 375, and Patents American patent numbers 5,153,157 5,198.401 5,066,741,

5,206,197, 5,241,025, 5,387,568, 5,384,299, 5,502,124 and 5,643,847, all of which are mentioned in this statement in full for reference. Other stimulants include those described in the International Patent Publication pursuant to Patent Cooperation Treaty No. 98/07515, such as tris-fluoroaluminate (2,2',2&amp;-nonafluorobiphenyl)-'''''2-''nonafluorobiphenyl)tris fluoroaluminate 2,2 which are mentioned in this statement for reference. The invention further includes combinations of activators, for example, alumoxanes and ionized activators in combinations, see, for example, Patent Cooperation Treaty International Patent Publications Nos. 07928/94 and 14044/95 and US Patent No. 5,153. 157 and No. 0 5,453.41, all of which are mentioned in this statement in full for reference. For the purposes of this invention, activation methods such as radiation and the like may also be used as activators.

When two different catalysts are used, the first catalyst compound and the second catalyst compound can be combined in molar ratios ranging from 1000:1 to 1:1000, preferably from 99:1 to 1:99, preferably from 10:90 to 10:90, and preferably from 80:20 to 20:80, preferably 30:70 to 30:70, and preferably 60:40 to 40:60. It depends on the specific percentage chosen

on the desired end product and/or activation method. A practical way to determine the best ratio to obtain the desired polymer is to start with a 1:1 ratio, measure the desired property of the formed product and adjust the ratio accordingly.

In some embodiments, one or more of the above metal catalyst compounds may be used in combination with a metallocene compound containing a bulky ligand metallocene compound (activated by the above mentioned activators). A metallocene compound containing a bulky ligand

A metallocene compound containing a bulky ligand (also referred to hereinafter as metallocenes) may also be used in an application of this invention.

It includes metallocene-type compounds containing a bulky ligand, generally half and full sandwich compounds containing one or more bulky ligands bound to at least one metal atom. Typical bulky ligand-containing metallocene-type compounds are generally described as containing one or more bulky ligands and one or more eluting groups attached to at least one metal atom. In a preferred embodiment, at least one bulky ligand is η-bonded to the metal atom, most preferably η-bonded to the metal atom at the 5η-bonded position.

Large ligands are usually represented by an open ring, acyclic ring, one or more fused rings, one or more ring systems, or a combination thereof. These large ligands, preferably represented by the ring(s) or ring system(s), are typically composed of atoms chosen from groups 13 to 1.6 of the Periodic Table of Elements. Made of carbon, nitrogen, oxygen, silicon, sulfur, phosphorus, germanium, boron, and aluminum, or a combination thereof. It is most preferable that the ring(s) or ring system(s) be made of carbon atoms

carbon such as, but not limited to, cyclopentadienyl ligands, cyclopentadienyl ligand structures, or another similar functioning ligand structure such as pentadiene, cyclooctatetraendiyl, or imide. It is preferable to choose the metal atom from groups 3 to 15 and the lanthanide or actinide series from the periodic table of the elements. It is preferable for the metal to be a transition metal, chosen from groups 4 to 12, preferably from groups 4, 5, and 6, and most preferable for the transition metal to be chosen from group 4.

In one embodiment, metallocene catalyst compounds containing a bulky ligand are represented by the formula:

LALBMQn (III)

Where M represents a metal chosen from the periodic table of elements. It may be chosen from groups 3 to 21 or from the lanthanide or actinide series from the periodic table of elements. It is preferable that M represents a transition metal from group 4, 5 or 6, and it is preferable that M represents a metal. Transitionally from group 4, M is best represented by zirconium, hafnium or titanium. The bulky ligands, LB and LA, represent an open, acyclic or compact ring(s) or system(s) and represent any additional ligand system, including cyclopentadienyl ligands with or without substituents or cyclopentadienyl ligands with or without substituents. Substituted, cyclopentadienyl ligands bearing heteroatom substituents and/or containing a heteroatom. Examples of bulky ligands include, but are not limited to, cyclopentadienyl ligands, cyclopentaphenanthreneyl ligands, indenyl ligands, benzindenyl ligands,

Fluorenyl ligands, octahydrofluorenyl ligands, cyclooctatetraendiyl ligands, cyclopentacyclododecene ligands, azenyl ligands, azulene ligands, pentalene ligands, phosphoyl ligands Phosphenimine (see application

International Patent No. 0125 99/4), pyrrolyl ligands, pyrozolyl ligands, carbazolyl ligands, borabenzene ligands and the like, including hydrogenated versions thereof, for example tetrahydroindenyl ligands. In an embodiment, LA and LB may represent any other ligand structure that has the ability to bind to M eta bond, preferably to bind to M eta bond at position 3 and most preferably at position 5. In yet another embodiment, the atomic molecular weight increases

The atomic molecular weight (MW) of LA and LB is less than 60 atomic mass units (amu unit), preferably greater than 65 atomic mass units. In another embodiment, La and LB may contain one or more heteroatoms, for example nitrogen silicon, boron, germanium, sulfur and phosphorus, in combination with carbon atoms to form an open, acyclic, or preferably compact ring or ring system, for example, an additional heterocyclopentadienyl ligand. Other bulky La and LB ligands include, but are not limited to, bulky ligands of amides, phosphides, alkoxides, aryloxides, imides, carbolides, borollides, porhyrins, phhalocyanines, corrins and other macrocyclic polyazomacrocycles. Individually, LA and LB represent identical or different types of a bulky ligand bound to M. In an embodiment according to formula (III) there is only one bond of LA and LB

Independently, LA and LB may carry substituents from a combination of R-substituents or be devoid of them. Examples of alternative R groups include, but are not limited to, one or more hydrogen-selected groups, linear or hollow alkyl radicals, linear or hollow alkenyl radicals, alkynyl radicals, cycloalkyl radicals, or aryl radicals. Acyl radicals, aroyl radicals, alkoxy radicals, aryloxy radicals, alkylthio radicals, dialkylamino radicals, alkoxycarbonyl radicals, aryloxycarbonyl radicals

aryloxycarbonyl, carbomoyl, alkyl or dialkyl-carbamoyl, acyloxy, acylamino, aroylamino or straight, branched or cyclic alkylene, or a combination thereof. In a preferred embodiment, the substituent R groups contain no more than 50 non-hydrogen atoms, preferably from one to 30 carbon atoms, and may also have substituents of halogens, heteroatoms, or the like. Examples of R alkyl substituents include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, benzyl or phenyl groups and the like, including all Its counterparts, for example tertiary butyl, isopropyl, and the like. Other hydrocarbyl radicals include organometalloid radicals bearing a substituent of fluoromethyl, fluroethyl, difluoroethyl, iodopropyl, bromohexyl, chlorobenzyl, and hydrocarbyls including trimethylsilyl, trimethylgermyl, and Diethyl methyldiethylsilyl and the like; Semi-metallic organic moieties bearing a halocarbyl substituent, including tri(tert fluoromethyl-tris(trifluoromethyl)-silyl, methyl-bis(difluoromethyl)silyl, bromomethyldimethylgermyl and the like; disubstituted boron moieties, including dimethylboron, for example; Di-substituent pnictogen moieties include dimethylamine, dimethylamine

dimethylphosphine, diphenylamine, methylphenylphosphine

methylphenylphosphine, chalcogen radicals including methoxy, ethoxy, propoxy, phenoxy, methylsulfide and ethyl sulfide. Non-hydrogen R substituents include carbon atoms.

carbon, silicon, boron, aluminum, nitrogen,

phosphorus, oxygen, tin, sulfur, germanium and the like, including olefins such as, but not limited to, olefinically unsaturated substitients including vinyl-terminated ligands, e.g. Example: but-3-enyl, propenyl(2), prop-2-enyl, hex-5-enyl, and the like. Likewise, at least two groups of R, and preferably two adjacent groups of R, are linked to form a ring structoe with from 3 to 30 atoms chosen from carbon, nitrogen, oxygen, phosphorus, silicon, germanium, aluminum. Boron, or a combination thereof. Also, a substituted R group such as l-butanyl may form a carbon sigma bond with the metal M.

Other ligands may bind to the metal M, such as at least one easily eluted group symbolized by Q. In an embodiment, Q represents a monoanionic labile ligd containing a sigma bond with M. Depending on the oxidation state of the metal, the value of n is zero, 1 Or 2, so that formula (III) above represents a metallocene catalytic compound containing a bulky neutral ligand.

Examples of Q include, but are not limited to, weak bases such as amines, phosphines, ethers, carboxylates, dienes, hydrocarbyl moieties containing from one to 20 carbon atoms, hydrides or halogens, and the like. A combination thereof. In another embodiment, two or more Q-ligands may form part of a compact ring or ring system. Other examples of Q ligands include those substituents for the R moiety described above and include cyclobutyl, cyclohexyl, heptyl, tolyl, trifluoromethyl, tetramethylene, pentamethylene, methylidene, methoxy, ethoxy, propoxy. propoxy, phenoxy

phenoxy, bis(N-methyl anilide),

dimethylphosphide and the like.

The two groups L may be bridged to each other via group A, as will be known below.

In an embodiment, the metallocene catalyst compounds containing a bulky ligand according to the invention include those compounds of formula (III) wherein LA and LB are bridged to each other by at least one bridging group, A, such that formula B represents:

(IV) (LaALbMQn)

These bridged compounds, represented by formula (IV), are known as metallocene bridge catalytic compounds containing a bulky ligand. LB, LA, n, Q, and M are known as above. Examples of bridge group A include, but are not limited to, bridge groups containing at least one atom from group 3 1 through 16, often referred to as a divalent moiety, such as, but not limited to, at least one atom of carbon, oxygen, Nitrogen, silicon, aluminum, boron, germanium, tin, or a combination thereof. Preferably, the bridge group A must contain a carbon atom, silicon, or germanium, and most preferably, the bridge group A must contain at least one silicon atom or at least one carbon atom. The bridge group A may also contain alternative R groups as defined above, including halogens and iron. Examples of bridge group A may be represented, but not limited to, by R'2Si, R'2C, R'p, R'2Ge, R'2SiR'2Si, where 'R' each represents a radical group representing a hydride, a hydrocarbyl. hydrocarbyl, hydrocarbyl with substituents, halocarbyl, halocarbyl with substituents, semi-metallic organic compound with a hydrocarbyl substituent hydrocarbyl, semi-metallic organic compound with a halocarbyl substituent,

A di-substituted boron, a di-substituted pnictogen, a chalcogen carrying substituents, or a halogen or two or more R's may be linked to form a ring or ring system. In an embodiment, metallocene catalytic compounds containing a bulky bridged ligand of formula (IV) comprise two or more bridge groups A (see European Patent No. Bl 301 664).

In an embodiment, metallocene catalytic compounds containing a bulky ligand include those compounds where the R substituents on the bulky ligands LA and LB in strands (III) and (IV) carry a similar or different number of substituents on each of the bulky ligands. In another embodiment, the bulky ligands LA and LB in forms (III) and (IV) are different from each other.

Other metallocene catalyst compounds containing a bulky ligand and catalytic systems useful in the invention include those described in U.S. Patent Nos. 5,064,802, 5,145,819, 5,149,819, 5,243,001, and 5,239,022. , 5,276,208, 5,296,434, 5,321,106, 5,329,031, 5,304,614, 5,677,401, 5,723,398, 5,753,578, 5 ,854,363, 5,856,547, 5,858,903, 5,859,158 5,900,517 and 5,939,503 and International Patent Cooperation Treaty Publications Nos. 93/08199, 93/08221, 07140/95, 98/11144, A1-0 816 372 B-0 513 380, A-0 638 B1- 0 757 996 and B2-0 748 821, all of which are mentioned in this statement in full for reference.

to it for reference.

In an embodiment, other metallocene catalyst compounds containing a bulky ligand suitable for use in this invention include metallocene bridge compounds containing a heteroatom, a mono-bulky ligand.

Examples of these catalytic types and catalytic systems have been described, for example, in international patent publications according to Patent Cooperation Treaty Nos. 00333/92, 94/07928, 91/04257, 03506/94, 00244/96, 97/15602. And 99/20637

and US Patent Nos. 5,057,475, 5,096,867, 5,055,438, 5,198,401, 5,227,440 and 5,264,405 and European Patent Publication No. 436 420 0-A, which They are all incorporated herein fully by reference.

In this embodiment, the metallocene catalytic compound containing a bulky ligand is represented by the formula:

(V)LCAJMQn

Where M represents a metal atom from groups 3 to 16 or a metal chosen from the group consisting of actinides and lanthanides of the periodic table of elements, and it is preferable for M to represent a transition metal from groups 4 to 12, and it is preferable for M to represent a transition metal from groups 4, 5 or 6, and it is most preferable that M represents a group 4 transition metal in any oxidation state, particularly titanium; LC extends a bulky bond with or without substituents attached to M; J is linked to M; A is linked to M and J, and J represents an additional heteroatom ligand; And A represents a set gantry; Q represents an univalent anionic ligand; n represents an integer equal to zero, 1, or 2. In formula (V) above, A, Lc and J form a compact ring system. In an embodiment, Lc is in the form (V) as defined above for LA and LA, A, M and Q are in the form (V) as defined above in the form (III).

In formula (v), J represents a ligand containing a dust atom, where J represents an element with a coordination number of 3 from group 15 or an element with a coordination number of 2 from group 16 of the periodic table of elements. Preferably, J should contain a nitrogen atom, phosphorous, oxygen or sulfur, and preferably nitrogen.

nitrogen.

In one embodiment according to the invention, the metallocene catalytic compounds containing a bulky ligand are heterocyclic ligand complexes where the bulky ligands, the ring(s) or ring system(s), include one or more heteroatoms or A combination thereof. Examples of heteroatoms include, but are not limited to, elements of groups 13 through 16, preferably nitrogen, boron, sulfur, oxygen, aluminum, silicon, phosphorous, and tin. Examples of metallocene catalyst compounds containing this bulky ligand are described in International Patent Applications Nos. 96/33202, 97/17379, 96/34021 and 98/22486, European Patent No. 874005 0-A1, and US Patent Nos. 5,637. 660, 5,539,124, 0,554,775, 5,756,611, 5,233,049, 5,744,417 and 5,856,258, all of which are mentioned in this statement for reference.

In an embodiment, metallocene catalyst compounds containing a bulky ligand include those complexes known as transition metal catalysts based on bidentate ligands containing pyridine or quinoline moieties, such as those described in U.S. Patent Application Serial No. 103,620/09. Filed on Ponyo 23, 1998, US Patent No. 6,103,657 filed on August 5, 2000, which is mentioned in this statement for reference. In another embodiment, metallocene catalyst compounds containing a bulky ligand include compounds described in PCT international patent applications Nos. 99/01481 and 98/42664, which are set forth in this statement in full by reference.

In a preferred embodiment, the metallocene catalytic compound comprising a bulky ligand is a complex of a metal, preferably a transition metal, a bulky ligand, preferably a pi-bonded ligand bearing or devoid of substituents, and a heteroallyl moiety

One or more, such as those described in US Patent Nos. 5,527,752 and 5,747,406 and European Patent No. 57 0 735 0-Bl, all of which are incorporated herein by reference.

In a particularly preferred embodiment, the other metal or dimetallic compound is a metallocene catalytic compound containing a bulky ligand which is represented by the formula:

LdMQ2(YZ)Xn(VI)

Where M represents a metal from groups 3 to 16, preferably a transition metal from group 4 to 12, and most preferably a transition metal from groups 4, 5 or 6; LD represents a bulky ligand bound to M; Each Q is individually bound to M and forms a ligand, preferably a unicharged polydentate ligand; A or Q represents a monovalent anionic ligand also bound to M;

And x represents a monovalent anionic group when n equals 2, or X represents a divalent anionic group when n equals 1; n represents a value of 1 or 2.

And in formula (L), (VI and M) as defined above for formula (III). And Q is as defined above for formula (III), and it is preferable to choose Q from the group consisting of -Y; S-F-CR2,-NR,-O represents C or S; Z is chosen from the group consisting of H, -PR2, -SiR3, -SR, -CR3, -NR2, -OR-, and aryl groups with or without substituents, provided that when Q represents -NR-, Z chooses from the group that It consists of H and -PR2,-SiR3,-SR,-NR2,OR-; R is chosen from a group containing carbon, silicon, nitrogen, oxygen, and/or phosphorous, and R is preferred to represent a hydrocarbon group containing One to 20 carbon atoms, most preferably an alkyl group, a cycloalkyl, or an aryl; n represents an integer ranging from 1 to 4, preferably 1 or 2; X represents a monovalent anionic group when n equals 2, or X represents a divalent anionic group when n equals 1;

Preferably, X represents a carbamate, carboxylate, or other heteroallyl moiety described by the combination of Y, Q, and z. SPRAY-DRYWG

Then, by mixing metal compounds and/or activators with a particulate filler material, the resulting mixture is then preferably spray dried to form a free flowing powder.

Spray drying may be any method known in technology. See European Patent No. Bl 0 668,295, US Patent No. 5,674,795 and US Patent No. 5,672,669 which specifically describe spray drying of portable catalysts. In general, one can spray-dry catalysts by placing the metal catalyst and activator complex in a solution and allowing them to react, then adding a filler such as silica or Cabosil™, and then pushing the solution at high pressures through the nozzle. The catalyst may be sprayed on a surface or sprayed so that the droplets dry in midair. The commonly used method is to disperse silica in toluene, stir in the activator solution and then stir in the catalyst source solution. Typical slurry concentrations range from about 5 to 8% by weight. This composition may remain in slurry form for up to 30 minutes with moderate agitation or manual shaking to maintain it in suspension before spray drying. In a preferred embodiment, the compensated amount of desiccant ranges from about 40-50% by weight of the activator (preferably alumoxane), Sio2 50-60% and about 2% by weight of the metal catalyst compound.

To obtain simple mixtures of metal catalyst compounds, the two or more metal catalyst compounds can be added to each other in the desired ratio in the final step. In another embodiment, a more complex procedure may be followed such as adding a first metal catalyst compound to the mixture of activator and filler for a specified reaction time t and then adding a solution of the second metal catalyst compound and mixing for a specified period of time x and then co-spraying the mixture. Finally, it can

Another additive such as 1-hexene is present at approximately 10% by volume in the activator and filler mixture before the first metal catalyst compound is added.

In another embodiment, a metallocene-type compound containing a bulky ligand metallocene type and an optional activator can be mixed with spray-dried catalysts according to this invention and the resulting mixture is then fed to a reactor.

In another embodiment, binders are added to the mixture. These binders can be added as a means of improving particle shape, i.e. to narrow the particle size distribution, reduce the porosity of the particles, and allow the use of a reduced amount of alumoxane that acts as a binder. Polymerization process according to the present invention

The catalysts and catalyst systems described above are suitable for use in any polymerization process,

Including processes in solution, gas phase, slurry or a combination thereof, preferably phase process

Ghazi or gassy.

In one embodiment, this invention directs toward polymerization or copolymerization reactions including the polymerization of one or more monomers containing from 2 to 30 carbon atoms, preferably from 2 to 12 carbon atoms, and preferably from 2 to 8 carbon atoms. This invention is well suited to copolymerization reactions involving the polymerization of one or more olefin monomers of ethylene, propylene, butene-l, pentene-l, and 4-methyl-pentene. -l, hexene-l, octene-l, decene-l, 3-methyl-pentene -3

3,5,5-trimethyl-hexane:1: 3,5,5-trimethyl-hexane-l and cyclic olefins. A combination thereof. Other monomers may include vinyl monomers, diolefins such as dienes, polyenes, norbornene, and norbornadiene. It is preferable to produce a copolymer from ethylene, where the copolymer is alpha-olefin.

At least one alpha-olefin contains 3 to 15 carbon atoms, preferably 4 to 12 carbon atoms, preferably 4 to 8 carhon atoms and most preferably 4 to 7 carbon atoms. In an alternative embodiment, the olefins bearing the geminally disubstitated twin substituents in IPC No. 99/37109 may be polymerized or copolymerized using the invention process described herein.

In another embodiment the ethylene or propylene is polymerized with at least two different comonomers to form a terpolymer. A preferred co-monomer is a combination of alpha-olefin monomers containing 4 to 10 carbon atoms, preferably 4 to 8 carbon atoms, optionally with at least one diene monomer. Preferred terpolymers include combinations such as ethylene/butene-l/hexene-l, ethylene/propylene/butene-l, propylene/ethylene/hexene-l, Ethylene/propylene/norbornene and the like.

In a particularly preferred embodiment the process according to the invention relates to the polymerization of ethylene and at least one comonomer containing from 4 to 8 carbon atoms, preferably from 4 to 7 carbon atoms. In particular, the comonomers include butene-l, 4-methyl-pentene-l, hexene-l and octene-l, the preferred comonomer of all being hexene-l. 1-hexene and/or 1-butene

butene-l.

Typically, a continuous cycle is used in gas-phase polymerization, where in one part of the cycle of a reactor system, a cycling gas stream, also called a recycle stream or fluidizing medium, is heated in the reactor by the heat generated by the polymerization process. . This heat is removed from the recycled composition in another part of the cycle by a cooling system located outside the reactor. Typically, a gas stream containing one or more monomers is circulated continuously in a fluidized bed process

Fluidized bed process is a gas phase used to produce polymers through a fluidized bed in the presence of a catalyst exposed to reactive conditions. The gaseous stream is drawn from the fluidized bed and recycled to the reactor. At the same time, the polymer product is withdrawn from the reactor and a fresh monomer is added to replace the polymerized monomer (see for example US Patents Nos. 4,543,399, 4,588,790, 5,028,670, 5,317,036 , 5,352,749, 5,405,922, 5,436,304, 5,453,471, 5,462,999, 5,616,661 and 5,668,228, all of which are fully incorporated into this Statement for reference.

Reactor pressure in the gas-phase process may vary from about 69 kPa (kilo pascals) (10 psig) pound per square inch) to about 3448 kilopascals (500 psi), preferably in the range of about 690 kPa. (100 psi) to about 2759 kPa (400 psi), best in the range from about 1379 kPa (200 psi) to about 2759 kPa (400 psi), best in the range from about 1724 kPa (250 psi) to about 2414 kPa (350 psi standard).

The reactor temperature in the gas-phase process may vary from about 30°C to about 120°C, preferably from about 60°C to about 115°C, preferably from about 70°C to 110°C, and most preferably from about 0.7°C to about 95°C.

The productivity of the catalyst or catalytic system is affected by the partial pressure of the parent monomer. The preferred mole percent of the main monomer, ethylene or propylene, with ethylene being preferred, ranges from about 25 to 90 mole percent, and the partial pressure of the monomer ranges from about 75 pounds per square inch absolute (psia) (517 kilopascals). to about 300 psi absolute (2069 kPa), which are typical conditions for a gas-phase polymerization process.

In a preferred embodiment, the reactor used in the present invention and the process of the invention produces from 227 kg/hr (500 pounds (lbs) of polymer per hour) to about 90,900 kg/hr (200,000 lb/hr) or More than polymer, preferably in excess of 455 kg/h (1,000 lb/h), best in excess of 4,540 kg/h (10,000 lb/h), best in excess of 11,300 kg/h (25,000 lb/h) Better yet, no more than 15,900 kg/hour (35,000 lb/hour), and best of all, no more than 22,700 kg/hour. 50,000 lb/h), most preferably over 29,000 kg/h (65,000 lb/h) to over 45,500 kg/h (100,000 lb/h).

Other gas-phase processes considered within the scope of the process of the invention include those described in U.S. Patent Publications Nos. 5,627,242, 5,665,818, and 5,677,375 and European Patent Publications Nos. 794,200 0-A, 202,802 0-A. and 421 634-B, all of which are mentioned in this statement for reference.

The slurry-phase polymerization process typically uses pressures in the range from about 1 to about 50 atmospheres and even higher pressures and temperatures in the range from 0°C to about 120°C. In the process of polymerization in the slurry phase, it forms

A suspension of a solid, particulate polymer in a dilute liquid polymerization medium to which ethylene, co-monomers, and often hydrogen are added along with the catalyst. The suspension containing the diluent is removed intermittently or continuously from the reactor where the volatile components are separated from the polymer and recycled, optionally after distillation to the reactor. It includes the liquid diluent. The polymerization medium used is usually an alkane with 3 to 7 carbon atoms, and preferably a branched alkane. The medium used should be liquid under polymerization conditions and relatively inert. When propane media is used, the process should be operated at a temperature and pressure above the temperature and pressure

Critical to the reaction buffer. It is preferable to use a medium of hexane or isobutane.

In an embodiment, a preferred polymerization technique according to the invention is referred to as particle form polymerization, or a worm-phase process where the temperature is maintained below the temperature at which the polymer turns into solution. A technique of this nature is well known in the art, and is described, for example, in US Patent No. 3,248,179, which is cited herein by reference. The preferred temperature for particle polymerization ranges from about 185 F (85 C) to about 230 F (110 C). Two preferred polymerization methods for a worm-phase process include those that use a loop reactor and those that use multiple stirred reactors arranged in series, parallel, or a combination thereof. Examples of slurry-phase processes include, but are not limited to, continuous-loop or stirred-tank processes. Other examples of slurry-phase processes are also described in US Patent No. 4,613,484, which is cited herein for reference.

In another embodiment, the process is conducted in the slurry phase continuously in a toroidal reactor.

The catalyst in the form of a solution, suspension, emulsion or slurry in isobutane or as a dry free flowing powder is uniformly injected into the reactor loop, which itself fills a circulating slurry of growing polymer particles in a diluent of A monomer and a comonomer containing isobutane. Hydrogen is optionally added as a molecular weight control. The reactor is maintained at a pressure ranging from about 525 standard psi to 625 standard psi (3620 kPa to 4309 kPa) and at a temperature ranging from about 140 F to about 220 F (about 60 C to about 140 C) based on The desired polymer density. The heat of reaction is removed through the loop wall, as most of the reactor is in the

Picture of a double-jacketed pipe and allows the slurry to exit the reactor on

Regular intervals or continuously to a heated low-pressure flash vessel, rotary dryer and nitrogen purge column sequentially to remove the isobutane diluent and all unreacted monomers and comonomers. The resulting hydrocarbon free powder is then prepared in the form of compounds for use in various applications.

In an embodiment, the reactor used in the slurry-phase process according to the invention and the process of the invention is capable of producing in excess of 2,000 pounds of polymer per hour (907 kg/hour), preferably in excess of 2,268 kg/hour (5,000 lb/hour), and most preferably in excess of 2,268 kg/hour (5,000 lb/hour). About 4,540 kg/hour (10,000 lb/hour).

In another embodiment, the slurry phase reactor used in the process of the invention produces more than 15,000 lb of polymer per hour (6,804 kg/h), with a yield of from more than 11,340 kg/h (25,000 lb/h) to about 45,500 kg/h (100,000 lb/h). / hour). In another embodiment, in the slurry-phase process of the invention the total reactor pressure ranges from 2758 kPa (400 psi) to 5516 kPa (800 psi), preferably from 3103 kPa (450 psi) to about 4827 kPa ( 700 psi (standard), best from about 3448 kPa (500 psi) to about 4482 kPa (650 psi), best from about 3620 kPa (525 psi) to 4309 kPa (625 psi). 2 inch standard).

In another embodiment, in the slurry-phase process of the invention the concentration of ethylene in the liquid reactor medium ranges from about 1 to 10% by weight, preferably from about 2 to about 7% by weight, preferably from about 2.5 to about 6% by weight, and most preferably from about 3 to about 6% by weight.

The preferred process according to the invention is the process, preferably the slurry or gas-phase process,

Which operate in the absence of or which are essentially devoid of any scavengers, such as triethylaluminum, trimethylaluminum, tri-isobutylaluminum, tri-n-hexylaluminum, and diethylaluminum chloride. diethyl aluminum chloride, dibutyl zinc and the like. This preferred process is described in the International Patent Bulletin pursuant to Patent Cooperation Treaty No. 96/08520 and US Patent No. 5,712,352, which are cited herein by reference.

In another preferred embodiment, one or all of the catalysts are mixed with not more than 10% by weight of metal stearate (preferably aluminum stearate, preferably aluminum distearate) based on the weight of the catalyst (or its components), any carrier and the stearate. . In an alternative embodiment, a solution of metal stearate is fed to the reactor, preferably 2 to 3% by weight. In another embodiment, the metal stearate is mixed with the catalyst and the product is fed separately to the reactor. These agents may be mixed with the catalyst or may perish into the reactor in solution or slurry with or without the catalyst system or its components.

In a preferred embodiment, the extracted polyolefin typically has a melt index according to the American Society for Testing ASTM D-1238 Materials method, state E, at a temperature of 190°C, of 3000 g/10 minutes or less. In a preferred embodiment, the polyolefin is a homopolymer or copolymer of ethylene. In a preferred embodiment for certain applications, such as films, molded material, and the like, the magma index is preferably 100 g/10 minutes or less. For some films and molded materials, it is preferable that the magma index be 100 g/10 minutes. In a preferred embodiment the resulting polymer has a molecular weight of 200,000 daltons or more.

In a preferred embodiment, the catalytic system described above is used to make polyethylene with a density between 0.88 and 0.97 g/cm3 (as measured in accordance with ASTM2839), and having a magma index of 1 g/10 min or less (as measured in accordance with ASTM D-1238, Case E, at 910 AD). It is preferable to produce polyethylene with a magma index ranging from 0.01 to 10 dg/min. In some embodiments, its density is preferred to range from 0.915 to 0.940 g/cm3, and in other embodiments it is preferable for densities to range from 0.93 to 0.960 g/cm3.

Polyolefins can then be formed into films, molded materials,

Sheets, a coating for wires, cables, and the like. Films can be formed using any conventional method known to the technology including extrusion, co-extrusion, lamination, blowing and casting. The membrane can be obtained by a flat film or tubular process, which may be followed by uniaxial orientation or two mutually perpendicular directions in the plane of the membrane to a similar or different degree. The guidance may be the same degree in both directions or it may be to a different degree. Particularly preferred methods for forming polymers into films include extrusion or co-extrusion on a film line by blowing or casting.

Formed films may also contain additives such as slip, antiblock, antioxidants, pigments, fillers, antifog, UV stabilizers, antistatics, and auxiliary agents. For polymer processing aids, neutralizers, lubricants, surfactants, dyes, dyes, nucleating agents. Preferred additives include silicon dioxide, synthetic silica, titanium dioxide, and polydimethylsiloxane carbonate.

Calcium carbonate, metal stearates, calcium stearate

stearate, zinc stearate, talc, and BaSO4, diatomaceous earth, wax, carbon black, flame retarding additives, low molecular weight resins, hydrocarbon resins, glass beads, etc. Similar. Additives may be present in typical effective amounts well known in technology, such as 0.001% by weight to 10% by weight.

Examples

Mn and Mw were measured by gel permeation chromatography using a GPC waters instrument at a temperature of 150°C equipped with differential refraction index detectors. GPC columns were calibrated by pouring a series of polyethylene molecular weight standards and molecular weights were calculated using Mark Houwink coefficients for the biopsy polymer. Density was measured according to the ASTMD 1505 procedure.

Measure the temperature (Ml) for I2 and I21 according to ASTM D-1238 procedure, clauses E and F, at a temperature of 190°C.

The magma index ratio (Mir) represents the ratio of I21 over I2 as determined according to the ASTMD 1238-procedure.

The weight percentage of the copolymer was measured using proton nuclear magnetic resonance (NMR). Mn/Mw = MWD

{[2,4,6-Me3C6H2)NCH2CH2]2NH}ZrBz2=A

B=[(2-Me-naphthyl)NCH2CH2]2NH]ZrBz2[(naphthyl-Me-2)NCH2CH2]2NH]ZrBz2

C=[[(2,4,6-Me3C6H2)NCH2CH2]2NH] HfBz2

Example 1

Preparation of ligand 2,4,6-Me3C6H2)NHCH2CH2]2NH)

Add to a 2-liter one-armed Schlenk flask equipped with a magnetic stir bar 23.450 g (0.227 mol) of diethylenetrimine, 90.51 g (0.455 mol) of 2-bromomesitylene. , 1.041 g (1.14 mmol) of tris(dibenzylideneacetone)dipalladium, 2.123 g (3.41 mmol) of 2,2'-di(diphenylphospino)- 1,1-racemic dinaphthyl-'2,2-racemic binap) bis(diphenylphosphino)-l,l'-binaphthyl racemic), 65.535 g (0.682 mol) of sodium tert-butoxide, and 800 ml of toluene in a dry, oxygen-free nitrogen atmosphere. The reaction mixture was stirred and heated to 100°C. After 18 hours, the reaction was complete, as determined by proton (nuclear magnetic resonance) spectroscopy. All remaining treatments were performed in air. All solvent was removed in a vacuum and the ore was dissolved in 1 L of diethyl ether. The ether was washed three times with water, using 250 ml each time, then using (180 g in 500 ml) of saturated aqueous NaCl, and dried over 30 g of magnesium sulfate. Removing the ether in vacuum resulted in 71.10 g of red oil, which was dried at 70 C for 12 hours in vacuum (dissolution rate = 92%). 1H Rn m (c6D6) delta 6.83 (F, 4), 3.39 (F, 2), 2.86 (W, 4), 2.49 (W, 4), 2.27 (F, 12), 2.21 (F, 6), 0.68 (F, wide, 1).

Example 2 (Preparing Catalyst A)

Preparation of (2,4,6-Me3C6H2)NCH2CH2]2NH}Zr (CH7Ph)2)]}

Add to a 500 ml round bottom flask equipped with a magnetic stir bar 41.729 g (91.56 mmol) of tetrabenzyl zirconium (from Boulder Scientific) and 300 ml of toluene in a nitrogen atmosphere Dry nitrogen free of oxygen. 32.773 g (96.52 mmol) of solid NH3 ligand (Example 1) was added and stirred for one minute (thus precipitating the desired compound). The volume of the slurry was reduced to 100 ml and 300 ml of pentane was added while stirring. 44.811 g of a yellowish-orange solid product was collected by filtration and dried in vacuum. (Production rate = 280). 1H R N M (C6D6) delta 7.22-6.81 (H, 12), 5.90 (H, 2), 3.38 (H, 2), 3.11 (H, 2), 3. 01 (P, 1), 2.49 (P, 4), 2.43 (P, 6), 2.41 (P, 6), 2.18 (P, 6), 0.96 (P, 2 ).

Example 3 (Catalyst preparation C)

{[(2,4,6-Me3C6H2)NCH2CH2]2NH}Hf(CH2Ph)2)- Preparation

To a 250 ml round-bottom flask fitted with a magnetic stir bar, add 4.063 g (7.482 mmol) of tetrabenzylbafbium and 150 ml of toluene in a dry, oxygen-free nitrogen atmosphere. 2.545 g (7.495 mmol) of solid NH3 ligand (Example 1) was added and stirred for one minute (thus precipitating the desired compound). The volume of the slurry was reduced to 30 ml and 120 ml of pentane was added while stirring. 4.562 g of a pale yellow solid product was collected by filtration and dried in vacuum (production rate = 87%).

1H R N M (C6D6) delta 7.21-6.79(H, 12), 6.16(H, 2), 3.39(H, 2), 3.14(H, 2), 2. 65 (F, 6), 2.40 (F, 6), 2.35 (F, 2), 2.23 (F, 2), 2.19 (F, 6), 1.60 (F, 2) ), 1.26(f, 2), NH is unclear.

Example 4

Preparation of the ligand NHCH2CH2[2NH (-2-methylnaphthyl)]2-methylnaphthyl)NHCH2CH2[2NH)] Add to a 1-liter single-lever Schlenk flask equipped with a magnetic stir bar 6.026 g (58.41 mmol) of diethylenetriamine 25.892 g (116.8 mmol) of bromo-2-methylnaphthylene-2,

0.268 g (0.292 mmol) of tris(dibenzylidene-acetone)dipalladium, 0.547 g (0.878 mmol) of 2,2'-di(diphenyl) Phospho)-1,1'-racemic dinaphthyl-'2,2-racemic binap) bis(diphenylphosphmo)-l,l'-racemic binaphthyl) and 16.90 g (175.8 mmol) of sodium dibutoxide sodium tert-butoxide and 400 ml of toluene in a dry, oxygen-free nitrogen atmosphere. The reaction mixture was stirred and heated to 100°C. After 18 hours, the reaction was complete as determined by proton nuclear magnetic resonance spectroscopy. All remaining treatments were performed in air. All solvent was removed in a vacuum and the ore was dissolved in 500 ml of diethyl ether. The ether was washed three times with water, using 100 ml each time, then using (90 g in 250 ml) of saturated aqueous NaCl, and dried over 15 g of magnesium sulfate. Removing the ether in vacuum resulted in 19.1 g of red oil that was dried at 70 °C for 12 hours in vacuum (production rate = 85%). 1H R N M (C6D6) delta 8.32(G,2), 7.71(G,2), 7.40-7.18(H,8), 3.91(S,2),2. 99 (Z, 4), 2.41 (Z, 4), 2.30 (F, 6), 0.69 (Pent, 1).

(Example 5 (Preparing the catalyst c

{[(2-methylnaphthyl)NCH2CH2]NH}Zr(CH2Ph)2 Preparation

{[(2-methylnaphthyl)NCH2CH2]2NH}Zr(CH2Ph)2

To a 500 mL round-bottom flask fitted with a magnetic stir bar, add 3.00 g (6.582 mmol) of tetrabenzyl zirconium (from Boulder Scientific) and 300 mL of toluene in a dry, oxygen-free nitrogen atmosphere. 65 ml (0.102 mol, 6.63 mmol) of a solution of the 2-HN3 ligand (Example 4) was added and stirred for 1 minute (thus precipitating the desired compound). The volume of the slurry was reduced to 40 ml and 150 ml of pentane was added while stirring. 3,060 orange-colored solid products were collected. Zero by filtration and dried in vacuum (production rate = 71%). The product was a mixture of four compounds produced by the orientation of 2-methylnaphthyl groups 1H.2-methylnaphthyl RNM (C6D6) delta 8.50 (g), 8.39 (g), 8.35 (g),

7.70(G), 7.66-6.70(H), 6.53(W), 6.22(W), 5.63(H), 5.18(G), 4.70(G), 3 .62 (P), 3.50 (P), 3.30-3.11-(P), 2.68 (P), 2.60 (P), 2.55 (P), 2.52 ( q), 2.50(q), 2.10(q), 1.6(q), 1.29(ab quad), 1.03(q), 1.01(q), 1.00(ab quad ), other unclear ringtones.

Example (6)

Synthesis of [ortho-3,5-di-t-butyl C6H2)(OH)CH-NCHMe2)-Bu)]- -ortho-3,5-di-t-Bu]

[C6H2)(OH) CH=NCHMe2)

Add 3000 g of 5,3-di-t-butylsalicylaldehyde to 10 ml of iso-propylamine. The solution quickly turned bright yellow. After stirring at ambient temperature for 3 minutes

Hours, the volatiles were removed in a vacuum to produce a bright yellow crystalline solid (production rate = 97%).

Example (7) (preparation of catalyst D)

Synthesis of (CH2Ph)Zr[ortho-3,5-di-th-butyl-(C6H2(O)CH=NCHMe2)]

2(ortho-3,5-di-t-Bu-(C6H2) (O)CH-NCHMe2]2Zr(CH2Ph]

Add a solution of 605 mg (2.2 mmol) of N-iso-Pr-3,5-di-t-butylsalicylimine in 5 ml of toluene. Slowly add a solution of 500 mg (1.1 mmol) of Zr(CHPh) in 50 ml of toluene. The resulting dark yellow solution was stirred for 30 minutes. The solvent was removed under vacuum to produce a reddish-brown solid. 1H R N M (C6D6) Delta 8.07 (P,H1,HC=N), 7.77 (G,C=2.4 Hz, salicylimine), 7.1-6.95 (Ar,Ho,aryl) , 6073 (W, C = 7.2 Hz, H1, Benzyl), 4.17 (Hepta, C = 6.6 Hz, CHMe2, H1), 2.76 (AB, C = 10.2 Hz, ZrCH2Ph, H2 ), 1.78 (P, H9, th-butyl), 1.29 (P, H9, th-butyl), 0.76 (G, C-6.6 Hz, NCHMeAMeB, H3), 0. 52(g, c = 6.6 Hz, NCHMeAMeB, H3).

Catalyst 1: Spray drying of the compound 2,4,6-Me3C6H2)NCH2CH2]2NH}ZrBz2)]}

To 110 ml of toluene, add 5 g of Cabosil TS-610-TS, and remove the water in vacuum at a temperature exceeding 100°C. A solution of methylalumoxane (26 ml of 20% by weight MAO in toluene) was added to this slurry. A catalytic source solution of 0.075 g of 2.4.6-Me3C6H2)NCH2CH2[2NH]ZrBz2) in approximately 20 ml of toluene was added to the slurry and stirred for approximately 30 minutes. Spray dry this mixture in a Bucci Series dryer

190 Mini Spray Dryer Buchi Series 190 Mini Spray Dryer, housed in a dry box in an inert atmosphere. The following conditions were used: 0.7 mm diameter of the spray nozzle cap, 0.5 mm thickness of the mixing needle, nittogen flow at 16.7 liters/min for spray flow, aspirator position at 20 C, inlet temperature 120 C, exit temperature from

80 to 90 m, and the catalyst mixture feed rate is 0.6 liters/hour. The amount of solids collected was 6.55 g (production rate = 68%). The ICP was 13% by weight Zr, and the Zr:Al ratio was 536:1.

Catalyst 2: Spray drying of the compound Me-2)NCH2CH2]2NH}ZrBz2 - naphthyl)]}

2-Me-Naphthyl)NCH2CH2]2NH}ZrBz2)]}

To 110 ml of toluene, 5 g of Kabosil TS-610 was added and the water was removed in vacuum at a temperature of more than 100 °C. A solution of methylalumoxane (26 ml of 20% by weight MAO in toluene) was added to this slurry. A catalyst source solution of 0.084 g of Naphthyl Me-2)NCH2CH2]2NH]ZrBz2)- Me-2)]} was added.

Naphthyl)NCHCH2]2NH}ZrBz2 in about 20 mL of toluene to the slurry and stir/swirl for about 30 minutes. Spray dry this mixture as described above. The amount of solids collected was 5.77 g (production rate = 59%). The ICP was 0.15% by weight Zr, and the Zr:Al ratio was 1:458.

Catalyst 3. Spray drying compound 2,4,6-Me3C6H2)NC6H2CH2]2NH}ZrBz2)]}

To 110 ml of toluene, 4 g of Caposyl TS-610 were added, the water was removed in vacuum at a temperature of more than 100 °C, and a solution of methylalumoxane (26 ml of 20% by weight MAO in toluene) was added to this slurry. And I add

Catalytic source solution of 2 g of 2,4.6-Me3C6H2)NCH2CH2]2NH]ZrBz2 in about 20 ml

Add toluene to the slurry and stir for about 30 minutes. Spray dry this mixture as described above. The amount of solids collected was 5.18 g (production rate = 58%), and the ICP was 0.36% by weight Zr, and the Zr:Al ratio was 196:1.

Catalyst 4: Spray drying of the compound 214,6-Me3C6H2)NCH2CH2]2NH}HfBz2)]}

To 140 ml of toluene, add 4.6 g of Kabosil TS-610, and remove the water in vacuum, at a temperature exceeding 100°C. A solution of methylalumoxane (20.8 ml of 20% by weight MAO in toluene) was added to this slurry. A catalytic source solution of 0.229 g of 2.4.6-Me3C6H2)NCH2CH2]2NH}HfBz2)]} was added.

Apply 20 ml of toluene to the slurry and stir for about 30 minutes. Spray dry this mixture as described above.

Catalyst 5: Spray drying of the compound 2,4,6-Me3C6H2)NCH2CH2]2NH}ZrBz2)]}

Add to 280 ml of toluene 12.4 g of Caposyl TS-610.

The water was removed in vacuum at a temperature exceeding 100°C. A solution of methylalumoxane (57 ml of 20% by weight MAO in toluene) was added to this slurry. A catalytic source solution of 0.55 g of 2.4.6-Me3C6H2)NCH2CH2]2NH}HfBz2)]} was added.

Add about 2 ml of toluene to the slurry and stir for about 30 minutes. Spray dry this mixture as described above. The amount of solids collected was 1.3 g (production rate = 56%). The ICP was 0.38% by weight Zr and the Zr:Al ratio was 1:152.

Catalyst 6. Spray drying compound Me3C6H2)NCH2CH2}2NH]Hf)]}

To 125 ml of toluene, 6 g of Kabosil TS-610 was added, and the water was removed in vacuum at a temperature above 100°C. A solution of methylalumoxane (27 ml of 20% by weight MAO in toluene) was added to this slurry. A catalytic source solution of 0.30 g of 2,4,6-Me3C6H2)NCH2CH2[2NH]HfBz2) in about 20 ml of toluene was added to the slurry and stirred for about 30 minutes. Spray dry this mixture as described above. The amount of solids collected was 0.7 g (production rate = 63%). The ICP was 0.72% by weight Hf and the Hf:Al ratio was 1:120.

Catalyst 7: Spray drying of the compound Zr(CH2Ph)2 2[ortho-5,3-di-th-butyl-

(2[{ortho-3,5-di-t-Bu-(C6H2)(O)CH=NCTMe2]2}Zr(CH2Ph)2 [((C6H2)(O)CH=NCHMe]2

To 75 ml of toluene, 2.6 g of Kabosil TS-610 was added, and the water was removed in vacuum at a temperature above 100°C. A solution of methylalumoxane (12.4 ml of 20% by weight MAO in toluene) was added to this slurry. A catalytic source solution of 0.168 g of Zr(CH2Ph)2 {2[ortho-5,3-di-di-butyl {ortho-3,5-di-t-Bu-(C6H2)(O)CH=NCHMe2] was added. 2} C6H2)(O)CH=NCHMe2)]2)-)) Add about 20 ml of toluene to the slurry and stir for about 30 minutes. Spray dry this mixture as described above.

.

Catalyst 8: Spray drying of a 1:1 mixture of

2,4,6-Me3C6H2)NCH2CH2]2NH}ZrBz2)]} and n-C3H7-C5H4) (Me5C)ZrCl2)

To 110 ml of toluene, add 4 g of Kabosil TS-610, and remove the water in a vacuum at 100 °C. Temperature above 100°C. A solution of methylalumoxane (26 ml of 20% by weight MAO in toluene) was added to this slurry. A catalytic source solution of 10 g of M2e3C6H2)NCH2]2NH}ZrBz2 was added.

Add 0.067 g of n-C3H7-C5H4)(Me5C)ZrCl2 in about 20 mL of toluene to the slurry and stir for about 30 minutes. Spray dry this mixture as described above. The amount of solids collected was 5.31 g (production rate = 60%). The ICP was 0.37% by weight Zr and the Zr:Al ratio was 1:202.

Catalyst 9: Spray drying of a 1:1 mixture of 2.4.6-Me3C6H2)NCH2CH2]2NH}HfBz2)]} and

n-C3H7-C5H4)2ZrCl2)

To 110 ml of toluene, 4 g of Kabosil TS-610 were added, and the water was removed in vacuum at a temperature above 100 °C. A solution of methylalumoxane (26 ml of 20% by weight MAO in toluene) was added to this slurry. A catalytic source solution of 0.10 g of 2.4.6-Me3C6H2)NCH2CH2]2NH}HfBz2)]} and 0.056 was added.

g of n-C3H7-C5H4)2ZrCl2) in about 20 ml of toluene, to the slurry and heart/dome

For about 30 minutes. Spray dry this mixture as described above.

Catalyst 10: Spray drying of a 3.4:1 mixture of

2.4.6-Me3C6H2)NCH2CH2]2NH}HfBz2)]} and n-C3H7-C5H4)2 ZrCl2)

Add to 540 ml of toluene 21.4 g of Caposyl TS-610.

The water was removed in vacuum at a temperature above 100°C. A solution of methylalumoxane (97 ml of 20% by weight MAO in toluene) was added to this slurry. A catalytic source solution of 0.80 g of 2.4.6-Me3C6H2)NCH2CH2]2NH}HfBz2)]} was added to

Rye and stir fry for about 30 minutes. Spray dry this mixture as described above. The amount of solids collected was 21 g (production rate = 53%). The ICP was 0.44% by weight Zr and the Al:Zr ratio was 128.

Catalyst 11: Spray drying of a 1:5 mixture of 2.4.6-Me3C6H2)NCH2CH2]2NH}HfBz2)]}

Add to 570 ml of toluene 25.8 g of Caposyl TS-610.

The water was removed in vacuum at a temperature above 100°C. A solution of methylalumoxane (116 ml of 20% by weight MAO in toluene) was added to this slurry. A catalytic source solution of 0.93 g of 2.4.6-Me3C6H2)NCH2CH2]2NH}HfBz2)]} and 0.114 g of (n-C3H7-C5H4)2 ZrCl2 was added to

Add about 60 ml of toluene to the slurry and stir for about 30 minutes. Spray dry this mixture as described above. The total amount of solids collected was 29 g (production rate = 60%), with an ICP of 39.0% by weight Zr and a Zr:Al ratio of 156.

Catalyst 12: Spray drying of a 3:1 mixture of 2.4.6-Me3C6H2)NCH2CH2]2NH}HfBz2)]} and

n-C3H7-C5H4)2ZrCl2)

Add to 570 ml of toluene 25.8 g of Caposyl TS-610,

The water was removed in vacuum at a temperature above 100°C. A solution of methylalumoxane (16 ml of 20% by weight MAO in toluene) was added to this slurry. A catalytic source solution of 0.96 g of 2.4.6-Me3C6H2)NCH2CH2]2NH}HfBz2)]} was added to

Add about 0.4 ml of toluene to the slurry and stir for about 30 minutes. Spray dry this mixture as described above. The amount of solids collected was 32 g (production rate = 67%). The ICP was 0.51 wt% Hf, 0.094 wt% Zr, and the M:Al ratio reached 161.

Polymerization examples 1 through 15

Polymerization reactions were carried out in a reflux-phase reactor as follows. After an appropriate drying period and subsequent cooling in a nitrogen atmosphere, 490 cc of hexane compounds were charged to a 1-litre autoclave reactor. Add hexene, if present, and 0.17 cm3 of triisobutyl aluminum with a concentration of 0.87 mol.

Heptane as a scavenger and hydrogen, if present, are added to the reactor before heating. The reactor contents were heated to the desired temperature. The spray-dried catalyst was carried in a 10 cm3 bomb tied to a 20 cm3 bomb to which 20 cm3 of hexane compounds were added. Each bomb was pressurized with nitrogen before being attached to the reactor. The spray-dried catalyst is injected under pressure into the reactor, and is immediately followed by the release of hexane compounds. In this way, quantitative discharge is ensured. The system is then immediately filled with ethylene and fed as needed. Polymerization reactions were carried out for 30 minutes.

Comparative polymerization reactions

The reactor was prepared and charged with hexane, hexene, hydrogen, and a scavenger as described above. The following preparation procedure for comparative example 1 is general: I dissolve a solution of 2.1 mg of 2,4,6-Me3C6H2)NCH2CH2]2NH}ZrBz2)]} in 405 cm3 of toluene. An amount of 0.50 cm of sapphire was removed and added to 0.5 cm3 of methylalumoxane (MAO) with a concentration of 0.5 mol in toluene. The solutions were mixed for about 5 minutes before being injected into the reactor as desired, after which ethylene was supplied directly and subsequently fed as needed. All polymerization reactions were carried out for 30 minutes. The data is shown in the following table.

<img file="SA687B1_D0007.tif" />

2,4,6-Me3C6H2)NCH2CH2]2NH}ZrBz2=A)]}, injected as a solution activated with MAO.

NCH2CH2]2 NH]ZrBz2 =B(2- [2-Me-naphthyl)NCH2CH2]2NH]ZrBz2 [[(2-Me- (naphthylMe)) injected as a solution activated with MAO.

Examples of polymerization 16 to 21

After proper drying of a 2-liter side-agitated laboratory gas-phase reactor and cooling in nitrogen, the reactor is charged with 955-600 Davison silica as the starting bed. Hydrogen, 1-hexene, and a scavenger were added before heating to 85°C. When hydrogen was added, it was charged by filling a 50 cm3 bomb to a pressure of 1.03 MPa absolute (150 psi) with 5% N2/H2 and discharging it into the reactor at a pressure slightly above atmospheric pressure. The spray-dried catalysts were injected into the reactor using the same tool used to inject the catalyst into the slurry reactor. When the catalyst was injected, ethylene was added directly to the reactor and fed as needed for the remainder of the experiment. The partial pressure of ethylene was 0.69 absolute MPa (100 psi).

Comparative polymerization reactions

I tested portable catalysts in the same manner as described above. The catalyst solutions were injected in the same way as in the reaction phase polymerization reactions.

The data is shown in the following table.

<img file="SA687B1_D0008.tif" />

Me3C6H2)NCH2 CH2]2NH}HfBz2=C-2.4.6 )]}Injected as a solution activated with MAO.

2,4,6-'Me3C6H2) NCH2 CH2]2 NH}HFBz2 =c)]} carried on Davison 948 silica, 0.38 μmol of Hf/g, Hf/Al= 120. Zr(CH2Ph)2=D{2[ortho-5,3-di-t-butylC6H2(O)CH=NCHMe2))]} -ortho-3.5-]} 2(di-t-Bu-(C6H2)( O)CH=NCHMe2]2}Zr(CH2Ph), injected as a solution activated with MAO.

Examples of polymerization 22 to 28

Polymerization procedure

In Comparative Example 9 and Examples 22 through 28, polyethylene was prepared in a stirred bed horizontally mixed reactor using different catalyst compositions. The table below summarizes the polymerization conditions for each example.

Figure 1 shows the horizontal mixing reactor system used in Comparative Example 9 and Examples 22 through 28. The reactor was a back-mixed reactor with a two-phase (gas/solid) stirred bed. A group of four “plows” 100 are mounted horizontally on a central shaft rotating at a speed of 180 rpm to keep the particles in the reactor 110 mechanically fluidized. The reaction cylinder swept by these lower accumulators was 40.6 cm (16 in) long and 39.7 cm (15.6 in) in diameter, resulting in a mechanically fluidizable volume of 46 liters (1.6 liters). ft3). The volume of gas, which exceeds the volume that can be diluted mechanically due to the vertical cylindrical chamber, was 54.6 liters.

(1.93 ft3).

The reactor pressure in each example was 2.4 MPa absolute. The ethylene monomer, hexene comonomer, and hydrogen (as a molecular weight control) were fed to the reactor continuously through control valves through Line 120. And he reached

The partial pressure of ethylene monomer is 5.1 MPa absolute. The content of the co-monomer in the polyethylene product is controlled by adjusting the feed rates to maintain a constant molar ratio of the Islamic monomer/monomer (shown in the table) in the gas phase. The gas composition was measured at intervals ranging from 1 to 4 minutes using a gas chromatographic analyzer. The molecular weight of polyethylene is adjusted by adjusting the hydrogen feed rate to maintain a constant molar ratio of hydrogen to the monomer in the gas phase. Nitrogen constitutes most of the balancing amount of the gas composition in the reactor, which enters with the catalyst composition through line 130 and exits through a small vent 140 with the reactor gases, including volatile solvents. The vent opening was adjusted by computer to maintain a constant total pressure in the reactor.

The reactor was cooled by an external jacket of chilled glycol. The layer temperature was measured using a temperatoe prohe 150 temperature probe in a thermowell protruding from the layer at an angle of 6.0 above the horizontal between the inner set of lower collectors. The temperature of the reactor in the comparative example was 9 85°C, while the temperature of the reactor in the examples from 22 to 28 was 80°C.

For comparative example 9, a catalytic solution was prepared by mixing catalyst A in toluene and the resulting solution was stored in a tank connected to line 160. The catalyst solution was bottled through line 160 and mixed with a continuous stream of modified methylaluminoxane co-catalyst solution fed through line 170. The concentration of Akzo MIO type 3A in isopentane was 2.1%, and the amount of MAO used was such that the ratio of Zr/Al in the reactor was 200. The mixture of catalyst and MMAO solutions was fed through an 810 coil with 0.32 cm (1/8 in) diameter tubing, where the catalyst and cocatalyst reacted for approximately 4 minutes. At the exit of this pre-contact coil, the mixed solution is sprayed from the catalyst composition into the reactor by a steady flow of nitrogen from line 130.

For Examples 22 through 28, spray-dried catalytic slurry is prepared by mixing the catalyst powder with light mineral oil and storing the resulting slurry in an agitated reservoir connected to line 160. The catalyst slurry was fed into line 160 and mixed with a continuous stream of modified methylaluminoxane co-catalyst solution fed through line 170. In these examples, the 180 coil was replaced with a straight piece of tubing with an outside diameter of 1/8 inch and a length of approximately 4 inches. The concentration of AkzoMMAO type 3A in isopentane reached 2.1%, and the feed rate of the MMAO solution was kept constant at approximately 50 ml/hour. The mixture of catalyst slurry and MMAO solution was fed to the reactor via an injection tube with an outer diameter of 32.0 cm (1/8 inch) using a constant flow of nitrogen to spread the mixture.

The reactor was operated continuously and in batches. Typical batch yields of granular polyethylene in the reactor ranged from 1.3 to 1.9 kg (7 to 20 lb). Each experiment lasted for a period of time ranging from 3 to 6 hours. In the continuous operation mode, the granular polymer is withdrawn at line 190 in typical portions weighing 0.2 kg (0.4 lb) while the polymerization process is in progress. In the continuous operation method, a product discharge system can be used after the layer weight has increased to From 5.4 to 9.1 kg (12 to 20 lb), the drainage rate was varied to maintain a constant layer weight as calculated by material balance.

In both Comparative Example 9 and Examples 22 through 28, the polymerization process began by charging the monomers to the reactor and adjusting the feed rates until the desired gas composition was obtained. An initial charge of co-catalyst was added before starting to feed the catalyst to clean up any toxic materials. present in the reactor. After the start of catalyst feeding, monomers were added to the reactor in sufficient amounts to maintain gaseous concentrations and ratios. Once the catalyst supply had built up, the polyethylene production rate was increased to range from 2.3 to 4.5 kg/hour (5 to 10 lb/hour), at which point the catalyst feed rate was adjusted to maintain a constant polyethylene production rate.

Ethylene polyethylene. For comparative example 9, the co-catalyst feed rate was kept directly proportional to the catalyst feed rate. After the desired batch weight was formed, the same reactor was quickly cleaned and the monomers were cleaned from the polyethylene resin using

Nitrogen. The batch is then discharged through valve 190 to the external atmosphere.

<img file="SA687B1_D0009.tif" />

2,4,6-A=Me3C6H2)NCH2CH2]2NH}ZrBz2)]}, injected as an activated solution.

B- MMAO-3A

By spray-drying indenyl zirconium trispivalate, a polymer was produced, but with low efficiency.

All documents mentioned in this statement are incorporated by reference, including any

Previous documentation and/or testing procedures. As is evident from the foregoing general description and specific embodiments, although variations of the invention have been stated and described, various modifications may be made without departing from the scope and principle of the invention. Accordingly, the invention is not limited to these forms.