Method of polymerization

Description of the invention

The present invention relates to spray dried olefin polymerization catalysts and their use in the gas phase or in suspension for the production of polyolefins.

The strong commercialization of metallocene polyolefin catalysts (metallocenes are cyclopentadienyl-based transition metal catalysts) has led to widespread interest in the development of homogeneous non-metallocene catalysts, especially for use in cost-effective gas or slurry processes. The field is more than an academic curiosity as new, non-metallocene gas or slurry phase catalysts can provide an easier, more economical route to products available today and can also provide a product and process that is impossible to obtain with gas phase metallocene catalysts or suspension.

However, the new catalysts are not automatically usable in the gas phase. Some catalysts are too active and contaminate the reactor. The other catalysts cannot be supported and therefore cannot be introduced into the reactor without impurities appearing. Therefore, there is a need to develop a method of supplying catalysts to the gas or slurry phase of the reactor, especially catalysts that are difficult or impossible to support.

Schrock et al. in US 5,889,128 describes the process of the instant polymerization of olefins in solution using initiators having a metal atom, an atom and a ligand containing two group 15 and 16 element atoms or three Group 15 element atoms. [MeB (C6F5) 3] or {[NON] ZrMe (PhNMe2)]} [B (C6F5) 4] in Examples 9 and 10.

EP 893 454 A1 describes unsupported transition metal amide compounds used in conjunction with activators for the polymerization of olefins in the liquid phase.

Mitsui Chemicals, Inc. EP 0 893 454 A1 describes transition metal amides in combination with activators for olefin polymerization.

EP 0 874 005 A1 discloses phenoxide compounds with an imino substituent for use as a polymerization catalyst.

EP 893 454 A1 discloses unsupported transition metal amide compounds used in conjunction with activators for liquid phase olefin polymerization.

USSN 09 / 312,878 filed on May 17, 1999 describes a gas or slurry phase polymerization process using a deposited bisamide catalyst.

The abstract of JP 10330416A describes transition metal amide compounds in combination with Ziegler-Natta catalysts. The abstract of JP 10330412A describes transition metal amide compounds in combination with cyclopentadienyl Group 4 metal catalysts.

Repo et al., Macromolecules 1997, 30, 171-175 used ethylene bis (salicylideneimininate) zirconium dichloride combined with methylalumoxane supported and unsupported in the polymerization of ethylene.

Nos. 5,672,669, 5,674,795 and EP 0 668 295 B1 describe spray dried metallocene catalyst compositions for gas and slurry phase polymerization.

The present invention relates to a catalyst composition and a spray-dried catalyst system comprising a solid filler, an activator and a metal catalytic compound.

The catalytic composition according to the invention is characterized in that it is a suspension containing a mineral oil, a solid filler, a catalytic metallocene compound, an activator and a catalytic metal compound represented by the formula:

PL 199 568 B1

<img file="PL199568B1_D0001.tif" />

wherein

M is a Group 4 metal;

each X is independently an anionic leaving group; n is the oxidation state M; m is the formal charge of the Y, Z and L ligand;

Y is a Group 15 element;

Z is a Group 15 element;

L is a Group 15 element;

R¹ and r² independently represent a C1 to C20 hydrocarbyl group or a group containing a heteroatom such as silicon, germanium, tin, lead or phosphorus; possibly R.¹ and r² they can also be connected to each other;

R³ represents a hydrogen atom, a straight, cyclic or branched alkyl group containing from 1 to 20 carbon atoms, halogen, or a group containing nitrogen, oxygen, phosphorus and sulfur, such as imine, amine, oxide, phosphine, ether, ketene, oxazoline, oxazoline heterocycle , thioether;

R⁴ and r⁵ independently represent an alkyl, aryl, substituted aryl, cyclic alkyl, or substituted cyclic alkyl group having 1 to 20 carbon atoms;

wherein the activator is selected from the group consisting of aluminum alkyls, alumoxanes, modified alumoxanes, non-coordinating anions, boron hydrides, boranes, ionizing compounds and combinations thereof;

the solid filler includes a finely divided polyolefin, talc, silicon oxide, magnesium oxide, titanium oxide, alumina, or silica-alumina, and has an average particle size of 0.001 to 1 micrometer;

and wherein the activator, solid filler and catalyst are spray-dried.

Preferably the metallocene type compound is a metallocene compound of zirconium or hafnium.

Preferably R.⁴ and r⁵ independently represent a group of formula:

<img file="PL199568B1_D0002.tif" />

in which each of the R.⁸ to r¹² are independently hydrogen or a C1-20 alkyl group, a halide, or a group of up to 40 carbon atoms and including nitrogen, oxygen, phosphorus and sulfur, and each two R groups⁸ - R¹² can combine to form a cyclic or heterocyclic group.

Preferably the composition is a suspension with a solids content in the range of 10 to 15% by weight.

Preferably, the particles of the composition are up to 25 µm in size.

PL 199 568 B1

Preferably, the solid filler is colloidal silica.

Preferably the solid filler is silica and the activator is alumoxane, with silica accounting for from 50 to 60% by weight of the dry composition of the carrier, catalyst compound and activator.

The invention also relates to a polymerization process which comprises combining in a gas phase or slurry reactor a C2-20 olefin and a catalytic composition as defined above.

Preferably, the product of the process is a polyolefin with a molecular weight of 200,000 or greater.

Preferred activators are conventional co-catalysts, alkyl aluminum compounds (such as diethyl aluminum chloride), alumoxanes, modified alumoxanes, non-coordinating anions, non-coordinating Group 13 metal anions or metalloid anions, boron hydrides, borates etc. It is within the scope of this invention to use alumoxane or a modified alumoxane as an activator, and / or also to use ionizing activators, neutral or ionic, such as tri (nbutyl) ammoniotetrakis (pentafluorophenyl) boron or the metalloid precursor trisperfluorophenyl boron which ionizes a neutral metallocene compound. Other useful compounds are triphenylboron, triethylboron, tri-n-butylammonium tetraethylborate, triarylborohydride, etc. Other useful compounds include the aluminate salts.

Figure 1 shows the horizontally agitated reactor system used in Comparative Example 9 and Examples 22 to 28.

The catalytic metal compounds of the invention show unexpected ability to be immobilized with a filler, activated by an activator, and unexpected catalytic power and activity.

In a preferred embodiment, the solid filler is colloidal silica, especially Cabosil TS-610, available from Cabot Corporation, which is a colloidal silica having a particle size of 7 to 30 nanometers and treated with dimethylsilyl dichloride such that most of the hydroxyl groups are covered. The spray-dried particles are generally introduced into the polymerization reactor as a mineral oil slurry. The concentration of the solids in the oil is about 10-15% by weight, preferably 11-14% by weight. In some embodiments, the lab-scale Buchi spray-dried particles have a size of &lt;~ 10 microns, while the scaled-up rotary atomizers can form particles of ~ 25 microns compared to conventional deposited catalysts of ~ 50 microns. In a preferred embodiment, the solid filler has an average particle size of 0.001 to 1 micrometer, preferably 0.001 to 0.1 micrometer.

Preferred catalysts or catalyst systems that can be used herein include the Group 15 metal containing compound. Other catalysts that may be used in conjunction with the Group 15 metal containing compound and / or phenoxides include the bulky ligand metallocene type catalysts and optionally an activator.

When the catalysts described herein are spray dried, they may be combined with other more conventional catalysts and introduced into the reactor. For example, the spray-dried catalyst or catalyst mixture may be combined with conventional transition metal catalysts (such as one or more Ziegler-Natta catalysts, vanadium catalysts, and / or chromium catalysts) in mineral oil and introduced into a slurry reactor.

Typical transition metal catalysts are described in Ziegler-Natta Catalysts and Polymerizations, John Boor, Academic Press, New York, 1979. Examples of typical transition metal catalysts are also described in US Pat. 4115639, 4077904, 4482687, 4564605, 4721763, 4879359, 4960741, 4302565, 4302566, 5317036, 3709853, 3709954, 3231550, 3242099, 4077904, 4124532, 4302565, 4302566, 4376062, 4379758, 582373714655, 582373714 5869585, 3487112, 4472559, 4182814 and 4689437 and EP-A2 publication 0416815A2 and EP-A1 0420436, and GB-A 2105355.

For the purposes of this invention, a cyclopentadienyl group is defined as the group consisting of indenyl and fluorenyl.

The mixed catalyst composition of the invention comprises a Group 15 metal containing compound. The Group 15 metal containing compound generally comprises a metal from Groups 3 to 14, preferably from Groups 3 to 7, more preferably from Groups 4 to 6 and preferably from Group 4 , bonded to at least one leaving group and also bonded to at least two atoms of an element of Group 15, one of which is bonded to an atom of an element of Group 15 or 16 via another group.

PL 199 568 B1

In one preferred embodiment, at least one of the Group 15 atoms is also bonded to a Group 15 element or 16 atom via another group which may be a C1 to C20 hydrocarbyl group, a heteroatom-containing group, silicon, germanium, tin, lead, or phosphorus. wherein the Group 15 or 16 atom may also be unbound or bonded to a hydrogen atom, a group containing a Group 14 element, a halogen atom, or a group containing a heteroatom, and wherein each of the two atoms of an element of Group 15 is bonded to a cyclic group and may optionally be bonded to a hydrogen atom, a halogen atom, a heteroatom or a hydrocarbyl group, or a heteroatom-containing group.

The formal charge of the YZL ligand "is understood to be the charge of the entire ligand without the metal and the leaving groups X.

By specifying R.¹ and r² can also be linked with each other, it is understood that R.¹ and r²they can be linked directly to each other or by other groups. By specifying R.⁴ and r⁵ can also be linked with each other, it is understood that R.⁴ and r⁵ they can be linked directly to each other or by other groups.

The alkyl group can be straight, branched alkyl, or alkenyl, alkynyl, cycloalkyl or aryl groups, acyl, aroyl, alkoxyl, aryloxy, alkylthio, dialkylamino, alkoxycarbonyl, aryloxycarbonyl, carbamoylamino, straight aralkyl or dialkylcarboxyl groups branched or cyclic, alkylene, or combinations thereof. An aralkyl group is referred to as a substituted aryl group.

In a preferred embodiment, R.⁴ and r⁵ denote groups represented by formula 1:

<img file="PL199568B1_D0003.tif" />

a binding to Z or Y where

R⁸ to r¹² independently represent a hydrogen atom, a C1 to C40 alkyl group, a halogen, a heteroatom, a heteroatom-containing group of up to 40 carbon atoms, preferably a straight or branched C1 to C20 alkyl group, especially methyl, ethyl, propyl or butyl, each two R groups may form cyclic and / or heterocyclic group. Cyclic groups can be aromatic. In a preferred embodiment, R.⁹, R¹⁰ and r¹² are independently methyl, ethyl, propyl or butyl (including all isomers 9 10 12 8 11 ml), preferably R⁹, R¹⁰ R¹² represent methyl groups and R.⁸ and r¹¹ are hydrogen.

In a particularly preferred embodiment, R.⁴ and r⁵ denote the group represented by the formula 2:

<img file="PL199568B1_D0004.tif" />

PL 199 568 B1

In this case, M is a Group 4 metal, preferably zirconium, titanium or hafnium, especially zircon; L, Y, and Z are each nitrogen; each of the R.¹ and r² is -CH2-CH2-; R³ is a hydrogen atom; and R.⁶and r⁷ do not occur .

In a particularly preferred embodiment, the Group 15 metal containing compound is represented by the formula:

<img file="PL199568B1_D0005.tif" />

In relation I, Ph is phenyl.

Group 15 metal compounds of the invention are prepared by known methods such as those disclosed in EP 0893454 A1, US No. 5,889,128, and references cited in US No. 5,889,128, all of which are incorporated herein by reference. US Application No. 09/312878, filed May 17, 1999, discloses a gas or slurry phase polymerization process using a supported bisamide catalyst, which is hereby incorporated by reference.

A preferred direct route for the synthesis of these compounds is to react a neutral ligand (e.g. YZL of formula 1 or 2) with MⁿXn (M is a metal of Groups 3 to 14, n is the oxidation state of M, each X is an anionic group such as a halogen group in a non-coordinating or weakly coordinating solvent such as ether, toluene, xylene, benzene, methylene chloride, and / or hexane or other solvent with a boiling point above 60 ° C, at a temperature of about 20 to about 150 ° C (preferably 20 to 100 ° C), preferably for 24 hours or more, then treating the mixture with an excess (such as four or more equivalents) of an alkylating agent such as methylmagnesium bromide in ether. The magnesium salts are removed by filtration and the metal complex is isolated by standard techniques.

In one embodiment, the Group 15 metal compound is prepared by a method that comprises reacting a neutral ligand (e.g., YZL of Formula 1 or 2) with a compound represented by Formula MⁿXn (where M is a Group 3 to 14 metal, n is the oxidation state of M, each X is an anionic leaving group) in a non-coordinating or weakly coordinating solvent at a temperature of about 20 ° C or higher, preferably at a temperature of about 20 to about 100 ° C, then treating the mixture with an excess of alkylating agent and separating the metal complex. Preferably, a solvent with a boiling point above 60 ° C is used, such as toluene, xylene, benzene, and / or hexane. In another embodiment, the solvent comprises ether and / or methylene chloride, both of which are preferred.

Additional information on Group 15 metal-containing compounds can be found in Mitsui Chemicals, Inc., in EP 0 893 454 A1, which discloses transition metal amides combined with activators used in olefin polymerization.

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

PL 199 568 B1

<img file="PL199568B1_D0006.tif" />

₁ in which R.¹ represents a hydrogen atom or a C4 to C100 group, preferably a tertiary alkyl group, more preferably a C4 to C20 alkyl group, especially a C4 to C20 tertiary alkyl group, especially a neutral C4 to C100 group, and may or may not be bonded to M, and at least one of R² to r⁵ is a heteroatom-containing group and the rest are R² to r⁵ are independently hydrogen or a C1 to C100 group, preferably a C4 to C20 alkyl group (preferably butyl, iso-butyl, pentyl hexyl, heptyl, isohexyl, octyl, isooctyl, decyl, nonyl, dodecyl), and each R² to r⁵ also may or may not be related to M,

O is oxygen, M is a Group 3 to 10 transition metal or a lanthanide metal, preferably a Group 4 metal, preferably Ti, Zr or Hf, n is the value state of the metal M, preferably 2, 3, 4, or 5, Q is an alkyl group, halogen atom, benzyl, amide, carboxylate, carbamate, thiolane, hydride or alkoxide group, or a bond to R of the heteroatom-containing group which can be any R¹ to r⁵. The heteroatom-containing group can be a heteroatom or a heteroatom bonded to carbon, silicon or other heteroatom. Preferred heteroatoms are boron, aluminum, silicon, nitrogen, phosphorus, arsenic, tin, lead, antimony, oxygen, selenium, tellurium. Particularly preferred heteroatoms include nitrogen, oxygen, phosphorus, and sulfur. The most preferred heteroatoms are oxygen and nitrogen. The heteroatom may be bonded directly to the phenoxide ring or it may be bonded to another atom or atoms that are bonded to the phenoxide ring. A heteroatom-containing group may contain one or more of the same or different heteroatoms. Preferred heteroatom-containing groups include imines, amines, oxides, phosphines, ethers, ketenes, oxoazoline heterocycles, oxazolines, thioethers, and the like. Imines are particularly preferred. Any two adjacent R groups may form a ring structure, preferably a 5- or 6-membered ring. Similarly, R groups can form multi-ring structures. In one embodiment, each two or more R groups do not form a 5-membered ring.

Phenoxide catalysts can be activated with activators including alkylaluminum compounds (such as diethylaluminum chloride), alumoxanes, modified alumoxanes, non-coordinating anions, non-coordinating Group 13 metal or non-metal anions, borates, borohydrides, etc. More information on activators is provided in the section below on Activators.

The present invention may also be practiced with the catalysts disclosed in EP 0 874 005 A1, which is hereby incorporated by reference.

Catalysts, preferably Group 15 metal compounds and / or phenoxide catalysts described herein, are preferably combined with one or more activators to form a catalyst system for an olefin polymerization process. Preferred activators include aluminum-alkyl compounds

(Such as diethylaluminum chloride), alumoxanes, modified alumoxanes, non-coordinating anions, anions of non-coordinating metals or group metalloids, borohydrides, borates, etc. It is within the scope of this invention to use alumoxane or a modified alumoxane as an activator, and / or also to use ionizing activators, neutral or ionizing, such as tri (n-butyl) ammonium-tetrakis (pentafluorophenyl) boron or the trisperfluorophenyl boron metalloid precursor, which ionize a neutral metallocene compound . Other useful compounds include tri-phenylboron, triethylboron, tri-n-butylammonium tetraethylborate, triarylborohydride, etc. Other useful compounds include the aluminum salts.

In one embodiment, modified alumoxanes are combined with catalysts to form a catalyst system. In a preferred embodiment, MMAO3A (modified methylalumoxane in heptane, commercially available from Akzo Chemicals, Inc. under the trade name Modified Methylalumoxane type 3A, protected by US Patent 5,041,584) in combination with the first and second metal compounds forms a catalyst system. MMAO-4 and MMAO-12 can also be used.

Various methods are known for the preparation of alumoxanes and modified alumoxanes, non-limiting examples of which are shown in US patents. No. 4,665,208, 4,952,540, 5,091,352, 5,206,199, 5,204,419, 4,874,734, 4,924,018, 4,908,463, 4,968,827, 5,308,815, 5,329,032, 5,248,801, 5,235,081, 5,157,137, 5,103,031, 5,391,529,631, 5,391,529,631, 5,391,529,631, 5,391, 529,631, 5,391, 529,631, 5,391, 529,631, 5,391, 529,631, 5,391, 573, 5,391,793, 5,391, 734. 0 561 476, EP-B1-0 279 586 and EP-A-0 594-218, and PCT publications WO 94/10180, all incorporated herein by reference.

Ionizing compounds may contain an active proton or other cation bound to, but not coordinated with, or only loosely coordinated with the remaining ion of the ionizing compound. Such compounds and the like are described in EP-A-0570982, EP-A-0520732, EP-A-0495375, EP-A-0426637, EP-A-500944, EP-A-0277003 and EP-A-0277004, and U.S. Patent Nos. 5,153,157, 5198401, 5066741, 5206197, 5.241025, 5387568, 5384299, 5502124, and 5643847, incorporated herein by reference. PCT publication WO 98/07515 describes other activators such as tris (2,2 ', 2' 'nonafluorobiphenyl) fluoroaluminate, incorporated herein by reference. A combination of activators has also been contemplated in the present embodiment, for example, alumoxanes in combination with ionizing activators, for example, PCT publications WO 94/07928 and WO 95/14044 and US Patent Nos. 5153157 and 5453410 all incorporated herein by reference. Also, activation methods such as applying radiation etc. are considered activators for the purposes of this invention.

When two different catalysts are used, the first and second catalyst compounds may be combined in molar ratios of 1: 1000 to 1000: 1, preferably 1:99 to 99: 1, more preferably 10:90 to 90:10, especially 20:80 to 80 : 20, especially 30:70 to 70:30, preferably 40:60 to 60:40. The choice of a particular ratio will depend on the final product and / or mode of activation. A practical way to determine what ratio is best to obtain the desired polymer is to start with a 1: 1 ratio, measure the properties of the product formed, and adjust the ratio accordingly.

In some embodiments, one or more of the above catalytic metal compounds may be used in combination with a hindered ligand metallocene (which is activated by the above-mentioned activators).

Hindered ligand metallocene compounds (hereinafter referred to as metallocenes) may also be used in the present invention

Generally, hindered-ligand metallocene compounds include sandwich and semi-sandwich compounds having one or more hindered ligands bound to at least one metal atom. Typical hindered-ligand metallocene compounds are described as having one or more hindered ligands and one or more leaving groups bound to at least one metal atom. In a preferred embodiment, the at least one bulky ligand is η-linked to a metal atom, most preferably n⁵- bound to a metal atom.

Hindered ligands generally represent one or more open, acyclic, or fused rings or ring systems, or combinations thereof. These bulky ligands, preferably rings or ring systems, are typically composed of atoms selected from groups 13 to 16 of the Periodic Table of the Elements, preferably the atoms are selected from the group consisting of carbon, nitrogen, oxygen, silica, sulfur, phosphorus, germanium, boron and aluminum. or combinations thereof. Most preferably, the ring (s) or ring system (s) are composed of carbon atoms forming, but not limited to, the structures of cyclopentadienyl ligands or of the cyclopentadienyl ligand type, or other similarly functioning ligand structures such as pentadiene, cyclooctatetraenediyl or imide ligand. The metal atom is preferably selected from Groups 3 to 15

PL 199 568 B1 and a series of lanthanides or actinides of the Periodic Table of the Elements. Preferably the metal is a Group 4 to 12 transition metal, more preferably Group 4, 5 and 6 transition metal, especially a Group 4 transition metal.

In one solution, metallocene compounds with a spatially complex ligand are represented by the formula:

L.^ANDL.^BMQn (III) where M is a metal of the Periodic Table of the Elements and may be a Group 3 to 12 metal or a lanthanide or actinide series, preferably M is a Group 4, 5 or 6 transition metal, more preferably M is a Group 4 transition metal , most preferably M is zirconium, hafnium or titanium. Spatially expanded ligands, L.^AND and L.^Bare open, acyclic or fused ring (s) or ring system (s) and are any auxiliary ligand system, including unsubstituted or substituted cyclopentadienyl or cyclopentadienyl ligands, cyclopentadienyl type ligands containing a heteroatom and / or substituted with a heteroatom. Non-limiting examples of bulky ligands include cyclopentadienyl, cyclopentaphenanthrenyl, indenyl, benzindenyl, fluorenyl, octahydrofluorenyl, cyclooctatetraenediyl, cyclopentacyclododecene, azenyl, azulene, pentalene, pentalene, phosphinyl, etc. hydrogenated versions, for example tetrahydroindenyl ligands. In one embodiment, the LA and LB may be any other ligand structure capable of forming a η-bond to M, preferably a η-bond to M, and preferably a η-bond. In yet another embodiment, the atomic molecular weight (MW) of L^AND and L.^B exceeds 60 atomic mass units, preferably more than 65 atomic mass units. In a further embodiment, L.^AND and L.^B they may include one or more heteroatoms, for example nitrogen, silicon, boron, germanium, sulfur and phosphorus, combined with carbon atoms to form an open, acyclic, or preferably fused ring, or ring system, for example, an auxiliary heterocyclopentadienyl ligand. Other bulky ligands of L.^AND and L.^B include, but are not limited to, hindered amides, phosphides, alkoxides, aryl oxides, imides, carbolides, borolides, porphyrins, phthalocyanines, cortices, and other polyazomacrocycles. Independently, each L.^AND and L.^B may be a hindered ligand of the same or a different type that is linked to M. In one embodiment, only one of the L^AND or L.^B.

AB

Independently, each L.^AND and L.^B may be unsubstituted or substituted by a combination of R. Non-limiting examples of R substituents include one or more groups selected from hydrogen or straight branched alkyl or alkenyl, alkynyl, cycloalkyl or aryl, acyl, aroyl, alkoxy, aryloxy, alkylthio, dialkylamino, alkoxycarbonyl, aryloxycarbonyl, alkylcarbonyl, or dialkylcarbamoyl, acyloxy, acylamino, aroylamino, straight, branched or cyclic alkylene groups, or combinations thereof. In a preferred embodiment, the R groups have up to 50 non-hydrogen carbon atoms, preferably 1 to 30 carbon atoms, which may also be substituted with halogens or heteroatoms or the like. Non-limiting examples of alkyl R groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, benzyl or phenyl and the like, including all isomers thereof, for example tertiary butyl, isopropyl, etc. Other hydrocarbyl groups include fluoromethyl, fluroethyl, difluroethyl, iodopropyl, bromohexyl, chlorobenzyl, and hydrocarbyl substituted with a metalloid-organic group including trimethylsilyl, tri-methylgermyl, methyldiethylsilyl and the like; and halogenocarbyl substituted metalloid-organic groups including tris (trifluoromethyl) -silyl, methyl-bis (difluoromethyl) -silyl, bromomethyldimethylgermyl and the like; and disubstituted boron groups including, for example, dimethylboron; and disubstituted pentogen groups including dimethylamine, dimethylphosphine, diphenylamine, methylphenylphosphine, chalcogen groups including methoxy, ethoxy, propoxy, phenoxy, methylsulfide, and ethylsulfide. Non-hydrogen R substituents include carbon, silicon, boron, aluminum, nitrogen, phosphorus, oxygen, tin, sulfur, germanium and the like, along with olefins such as, but not limited to, olefinically unsaturated substituents including vinyl-terminated ligands, for example, but- 3-enyl, prop-2-enyl, hex-5-enyl etc. Also, at least two R groups, preferably two adjacent R groups, are linked to form a ring structure having from 3 to 30 atoms selected from carbon, nitrogen, oxygen, phosphorus, silicon, germanium, aluminum, boron or combinations thereof. Also, R substituent groups such as 1-butanyl can form a sigma carbon bond with metal M.

PL 199 568 B1

Other ligands may be bonded to the metal M, such as at least one leaving group Q. In one embodiment, Q is a monoanion labile ligand having a sigma bond with M. Depending on the oxidation state of the metal, the value of n is 0, 1, or 2 so that the above formula (III) represents a neutral metallocene-like catalytic compound with a hindered ligand.

Non-limiting examples of ligands Q weak bases such as amines, phosphines, ethers, carboxylates, dienes, hydrocarbyl groups of 1 to 20 carbon atoms, hydrides or halogens and the like, or combinations thereof. In another embodiment, two or more Q groups form part of a fused ring or ring system. Other examples of Q ligands include those substituents for R as described above and include cyclobutyl, cyclohexyl, heptyl, tolyl, trifluromethyl, tetramethylene, pentamethylene, methylidene, methoxy, ethoxy, propoxy, phenoxy, bis (N-methylanilide), dimethylamide, dimethyl phosphide etc. .

Two L groups may be bridged to each other by at least one A group as defined below.

In one embodiment, the hindered ligand metallocene-like catalysts of the invention include those of formula (III) wherein L^AND and L.^B are bridged between themselves by at least one group, A, so that they are represented by a pattern

L.^ANDAL^BMQn (IV)

These bridged compounds represented by formula (IV) are known as hindered metallocene-like catalytic compounds with bulky. L.^AND, L.^B, M, Q and n are as defined above. Non-limiting examples of a bridging group A include bridging groups containing at least one atom of an element from Groups 13 to 16, often referred to as a divalent group such as, but not limited to, at least one carbon, oxygen, nitrogen, silicon, aluminum, boron, germanium, and tin atom. or a combination of them. Preferably the bridging group A comprises a carbon, silicon or germanium atom, most preferably the group A comprises at least one silicon atom or at least one carbon atom. The bridging group A may also contain R substituent groups as defined above, including halogens and iron. Non-limiting examples of bridging groups A may be represented by R'2C, R'2Si, R'2Si R'2Si, R'2Ge, R'P, where R 'is independently a group such as hydride, hydrocarbyl, substituted hydrocarbyl , halocarbyl, substituted halocarbyl, hydrocarbyl-substituted organic metalloid, halocarbyl-substituted organic metalloid, disubstituted boron, disubstituted pnictogen, substituted chalcogene, or a halogen or two or more R 'can be joined to form a ring or ring system. In one embodiment, the bridged, metallocene-like catalyst compounds with a hindered ligand of formula (IV) have two or more bridging groups A (EP 664 301 B1).

In one embodiment, the hindered ligand metallocene catalyst compounds are compounds in which the R groups on the hindered ligand L^AND and L.^B formulas (III) and (IV) are substituted with the same number of substituents in each bulky ligand. In another embodiment, the hindered ligands of L^AND and L.^B formulas (III) and (IV) differ from each other.

Other hindered-ligand metallocene catalysts and catalyst systems useful in the invention include those described in the US Patent Nos. 5,064,802, 5,145,819, 5,149,819, 5,243,001, 5,239,022, 5,276,208, 5,296,434, 5,321,106, 5,329,031, 5,304,614, 5,677,401, 5,723,398, 5,753,578, 5,854,363, 5,856,547, 5,859,558,903, and WO 5,999,081, and, WO 5,999 / 08, 93/05, 93/05, 93/05, and WO 5995, 93 WO 95/07140, WO 98/11144, WO 98/41530, WO 98/41529, WO 98/46650, WO 99/02540 and WO 99/14221 and European publications EP-A-0 578 838, EP-A-0 638 595, EP-B-0 513 380, EP-A1-0 816 372, EP-A2-0 839 834, EP-B1-0 632 819, EP-B1-0 748 821 and EP-B1-0 757 996, all incorporated herein by reference.

In another embodiment, the hindered ligand metallocene catalyst compounds useful in the present invention include heteroatom bridged metallocene-like catalysts. These types of catalysts and catalyst systems are described, for example, in PCT publications WO 92/00333, WO 94/07928, WO 91/04257, WO 94/03506, WO 96/00244, WO 97/15602 and WO 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 publications EP-A-0 420 436, all of which are incorporated herein by reference.

In this solution, the catalytic compound of the metallocene type with the bulky ligand is represented by the formula:

PL 199 568 B1

L.^C.AJMQn (V) where M is a metal from Groups 3 to 16 or a metal selected from the Actinide and Lanthanide Groups of the Periodic Table of the Elements, preferably M is a transition metal from Groups 4 to 12, especially from Groups 4, 5 or 6, especially from Group 4 at any oxidation state, especially titanium; L.^C. is a substituted or unsubstituted hindered ligand linked to M; J is related to M; A is related to M and J; J is an auxiliary ligand heteroatom; and A is a bridging group; Q is a monovalent anionic ligand; and n is 0, 1 or 2. In the above formula (V), L^C.A and J form a fused ring system. In one solution, L.^C. of formula (V) is as defined above for L.^AND, A, M and Q of formula (V) are as defined above for formula (III).

In formula (V), J is a heteroatom-containing ligand, wherein J is a coordination number three from Group 15 or an element with a coordination number two from Group 16 of the Periodic Table of the Elements. Preferably J is nitrogen, phosphorus, oxygen or sulfur, especially nitrogen.

In an embodiment of the invention, hindered ligand metallocene catalysts are complexes of heterocyclic ligands where the bulky ligands, ring (s) or ring systems include one or more heteroatoms or combinations thereof. Non-limiting examples of heteroatoms include a Group 13 to 16 element, preferably nitrogen, boron, sulfur, oxygen, aluminum, silicon, phosphorus, and tin. Examples of these hindered ligand metallocene catalyst compounds are described in WO 96/33202, WO 96/34021, WO 97/17379 and WO 98/22486 as well as EP-A1-0874005 and US Nos. 5637660, 5539124, 5554775, 5756611, 5233049, 5744417, and 5856258, all of which are incorporated herein by reference.

In one embodiment, the hindered ligand metallocene catalysts are complexes known as transition metal catalysts based on divalent ligands containing pyridine or quinoline groups, such as described in U.S. Application Serial No. 09 / 103,620 filed June 23, 1998, incorporated by reference here as a reference. In another embodiment, hindered ligand metallocene catalysts are described in PCT publications WO 99/01481 and WO 98/42664, incorporated herein by reference.

In another embodiment, the hindered ligand metallocene catalyst is a complex of a metal, preferably a transition metal, a hindered ligand, preferably a substituted or unsubstituted pi-linked ligand, and one or more heteroallyl groups such as those described in US Publication No. 5,527,752 and 5747406 and EP-B10735057, incorporated herein by reference.

In a particularly preferred embodiment, the one metal compound or the other metal compound is a metallocene catalytic compound with a hindered ligand represented by the formula:

L.^DMQ2 (YZ) Xn (VI) wherein M is a Group 3 to 16 metal, preferably a Group 4 to 12 transition metal, and preferably a Group 4, 5 or 6 transition metal; L.^D is a bulky ligand associated with M; each Q is independently associated with M and Q2 (YZ) forms a ligand, preferably a monovalent multifunctional ligand; A or Q is a monovalent anionic ligand also bound to M; X is a monovalent anionic group when n is 2 or X is a divalent anionic group when n is 1; n is 1 or 2.

In formula (VI), L and M are as defined above for formula (III). Q is as defined above for formula (III), preferably Q is selected from the group consisting of -O^-, -NR-, -CR₂- and -S-; Y is 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- then Z is selected from one from the groups consisting of -OR, -NR2, -SR, -SiR3, -PR2, and -H; R is selected from the group consisting of carbon, silicon, nitrogen, oxygen, and / or phosphorus, preferably R is a hydrocarbon group having 1 to 20 carbon atoms, especially an alkyl, cycloalkyl or aryl group; n is from 1 to 4, preferably 1 or 2; X is a monovalent anionic group when n is 2 or X is a divalent anionic group when n is 1; preferably X is carbaminiam, carboxylate, or another heteroallyl group described by the combination of Q, Y and Z.

The metal compounds and / or activators are preferably combined with solid filler material and then spray dried, preferably to form a free flowing powder.

PL 199 568 B1

Spray drying can be carried out by means known in the art. For example, EPA publications 0668295 B1, US 5674795 and US 5672669 describe in detail the spray drying of supported catalysts. In general, the catalysts can be spray dried by placing the catalytic metal compound and the activator in solution allowing them to react between them, then adding a filler material such as silica or Cabosil®, and by forcing the solution through a nozzle at high pressure. The catalyst may be surface dried or dried so that the droplets are air dried. The process is generally used to disperse silica in toluene, agitate in the activator solution, and then agitate in the catalyst precursor solution. Typical slurry concentrations are about 5-8% by weight. This formulation can be suspended for about 30 minutes by gentle agitation or by hand shaking to keep it suspended prior to spray drying. In a preferred embodiment, the composition of the dried material is about 40-50% by weight of activator, (preferably alumoxane), 50-60 SiO2 and about 2% by weight of the catalytic metal compound.

In simple metal catalytic compound mixtures, two or more catalytic metal compounds may be added together in the desired ratio in the last step. In another embodiment, more complex procedures are possible such as adding the first catalyst compound to the activator / filler mixture at a specific reaction time t followed by adding a second metal catalyst compound solution, mixing at another specific time x, and then the mixture is co-sprayed. Finally, another additive such as 1-hexene in an amount of about 10% by volume may be present in the activator / filler mixture prior to the addition of the first metal catalytic compound.

In another embodiment, the bulky ligand metallocene catalyst and optional activator may be combined with the spray dried catalysts of the invention and introduced into the reactor.

In another embodiment, binders are added to the mixture. They can be added as morphology-improving agents, ie, reducing the particle size distribution, lowering the porosity of the particles, and taking into account the amount of alumoxane which acts as a "binder."

The catalysts and catalyst systems described above are suitable for use in the polymerization process of the invention. The polymerization process of the invention comprises gas or slurry phase processes or a combination thereof, most preferably a gas or slurry phase process.

In one invention, this invention is directed to a gas or slurry phase polymerization or copolymerization process for the polymerization of one or more monomers having from 2 to 30 carbon atoms, preferably from 2-12 carbon atoms, especially from 2 to 8 carbon atoms. The invention is particularly suitable for a copolymerization comprising the polymerization of one or more olefinic monomers of ethylene, propylene, butene-1, pentene-1,4-methyl-pentene-1, hexene-1, octene-1, decene-1,3-methyl-pentene -1, 3,5,5-trimethyl-hexene-1 and cyclic olefins or combinations thereof. Other monomers may include vinyl monomers, diolefins such as diene, polyene, norbornene, norbornadiene monomers. Preferably an ethylene copolymer is prepared wherein the comonomer is at least one alpha-olefin having from 4 to 15 carbon atoms, preferably from 4 to 12 carbon atoms, more preferably from 4 to 8 carbon atoms, and preferably from 4 to 7 carbon atoms. In an alternative embodiment, geminal disubstituted olefins described in WO 98/37109 may be polymerized or copolymerized using the present invention.

In another embodiment, ethylene or propylene is polymerized with at least two different comonomers to form a terpolymer. Preferred comonomers are combinations of alpha-olefin monomers having from 4 to 10 carbon atoms, preferably from 4 to 8 carbon atoms, optionally with at least one diene monomer. Preferred terpolymers include combinations such as ethylene / butene-1 / hexene-1, ethylene / propylene / butene-1, propylene / ethylene / hexene-1, ethylene / propylene / norbornene etc.

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

Typically gas-phase polymerization processes are carried out in a continuous cycle in which, in one part of the reaction system, a recycle gas stream, otherwise known as a recycle stream or fluidization medium, is heated in the reactor by the heat of polymerization. This heat is removed from the recycle mixture in the second cycle part in the external cooling system

PL 199 568 B1 reactor. In general, in the preparation of fluidized bed polymers, a gaseous stream containing one or more is continuously recycled through the fluidized bed in the presence of a catalyst under reaction conditions. The gaseous stream is withdrawn from the fluidized bed and recycled to the reactor. Simultaneously, the polymer product is discharged from the reactor, fresh monomer is added to replace the polymerized monomer. (See, for example, U.S. Patent Nos. 4543399, 4588790, 5028670, 5317036, 5352749, 5405922, 5436304, 5453471, 5462999, 5,616,661, and 5,668,228 incorporated herein by reference).

Reactor pressure in the gas phase process may range from about 69 kPa (10 psig) to about 3448 kPa (500 psig), preferably in the range from about 690 kPa (100 psig) to about 2759 kPa (400 psig), more preferably in the range of from about 200 psig to about 2759 kPa (400 psig), even more preferably from about 250 psig to about 2414 kPa (350 psig).

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

The productivity of the catalyst or catalytic system is influenced by the partial pressure of the main monomer. A preferred mole percent of the main monomer, ethylene or propylene, preferably ethylene, is from about 25 to 90 mole percent and the monomer partial pressure is on the order of about 517 kPa (75 psia) to about 2069 kPa (300 psia), which is a typical operating condition. gas phase polymerization process.

In a preferred embodiment, the reactor used in the present invention and the process of the invention produces more than 500 Ibs / hr (227 Kg / h) polymer per hour to about 90,900 Kg / h (200,000 Ibs / hr) or more polymer, preferably greater than 455 Kg / h (1000 Ibs / h), more preferably greater than 4540 Kg / h (10,000 Ibs / h), especially greater than 11,300 Kg / h (25,000 Ibs / h), even more preferably greater than 15,900 Kg / h (35,000 Ibs / h). h), even more preferably above 22,700 Kg / h (50,000 Ibs / h), and most preferably greater than 29,000 Kg / h (65,000 Ibs / h) to greater than 45,500 Kg / h (100,000 Ibs / h).

Other gas-phase processes contemplated by the process of the invention include those described in U.S. Patent Nos. 5,627,242, 5,665,818 and 5,677,375, and EP-A-0 794 200, EP-A-0 802 202 and EP-B-634 421 all incorporated herein as references.

Pressures in the range of about 101 to about 5066 kPa and even higher and temperatures in the range of 0 ° C to about 120 ° C are generally used in the slurry phase polymerization process. In slurry polymerization, the solid polymer particles are suspended in a liquid diluent polymerization medium to which ethylene and comonomers, and often hydrogen, along with the catalyst, are added. The slurry containing the diluent is continuously or intermittently removed from the reactor, and volatile components are separated and returned, optionally after distillation, to the reactor. The liquid diluent used in the polymerization process is usually an alkane having from 3 to 7 carbon atoms, preferably a branched alkane. The medium used should be liquid under the polymerization conditions and relatively inert. When propane is used as the medium, the process must be operated above the critical temperature and critical pressure of the reaction diluent. Preferably hexane or isobutane is used as the medium.

In one embodiment, a preferred polymerization technique is particle or slurry polymerization, where the temperature is kept below the temperature at which the polymer enters solution. Such a technique is frequently used in the art, and is described, for example, in US Patent No. 3,248,179, which is hereby incorporated by reference. The preferred temperature for the particle polymerization process ranges from about 85 ° C (185 ° F) to about 110 ° C (230 ° F). The two preferred slurry processes are loop reactor processes and those using multiple agitated reactors in series, in parallel, or combinations thereof. Non-limiting examples of slurry processes include continuous loop or stirred reactor processes. Also, other slurry processes are described in US Patent No. 4,613,484, which is hereby incorporated by reference.

In another slurry process, the process is carried out continuously in a loop reactor. The catalyst as a slurry in isobutane or as a dry free flowing powder is regularly introduced into a loop reactor which is fed with a circulating suspension of growing polymer particles in a conomer diluent containing isobutane and comonomer. Hydrogen, optionally, may be used as a standard molecular weight. The reactor is pressurized from about 3620 kPa to 4309 kPa (525 psig to 625 psig) and at a temperature on the order of about 60 ° C to about 104 ° C (140 ° F to about 220 ° F) depending on the desired polymer density. The heat of reaction is removed through the loop wall as most of the reactor is in the form of a double jacketed tube. Suspension 14

The flow is fed to the reactor outlet at regular intervals or continuously to a heated low pressure flow vessel, rotary dryer and nitrogen purge column sequentially to remove the isobutane diluent and all unconverted monomer and comonomers. The resulting free flowing hydrocarbon powder is then mixed for use in various applications.

In one embodiment, the reactor used in the slurry process of the invention allows the process of the invention to produce more than 907 Kg / h (2000 lbs / h) of polymer, preferably more than 2268 Kg / h (5000 lbs / h), more preferably 4540 Kg. / h (10,000 Ibs / h). In another embodiment, the slurry reactor used in the process of the invention produces greater than 6804 Kg / h (15,000 Ibs / hr) of polymer, preferably greater than 11,340 Kg / h (25,000 Ibs / hr) to about 45,500 Kg / hr (100,000 Ibs / hr).

In another slurry process of the invention, the total reactor pressure is in the order of about 2758 kPa (400 psig) to 5516 kPa (800 psig), preferably 3103 kPa (450 psig) to about 4827 kPa (700 psig), more preferably 3448 kPa (500 psig). to about 4,482 kPa (650 psig), most preferably from about 3,620 kPa (525 psig) to 4,309 kPa (625 psig).

In yet another embodiment of the slurry process of the invention, the concentration of ethylene in the liquid reactor medium is in the order of from about 1 to 10% by weight, preferably from about 2 to about 7% by weight, more preferably from about 2.5 to about 6% by weight, most preferably from about 3 to about 3% by weight. about 6% by weight.

A preferred process according to the invention is a process, preferably in the gas or slurry phase, carried out in the absence or substantially free of free radical scavengers such as triethyl aluminum, trimethyl aluminum, tri-iso-butyl aluminum and tri-n-hexyl aluminum and diethyl aluminum chloride, dibutyl zinc etc. This is preferred. the process is described in PCT Publication WO 96/08520 and US Patent No. 5,712,352, which are incorporated herein by reference.

In another preferred embodiment, one or all of the catalysts are combined with 10 wt% metal stearate (preferably aluminum stearate, more preferably aluminum distearate) based on the weight of catalyst, carrier and stearate, preferably 2 to 3 wt%. In an alternative embodiment, the metal stearate solution is charged to the reactor. In another embodiment, the metal stearate is mixed with the catalyst and charged to the reactor separately. These agents may be mixed with the catalyst or may be introduced into the reactor in solution with or without the catalyst system or its components.

In a preferred embodiment, the resultant polyolefin typically has a melt index of 3000 g / 10 min or less as measured according to ASTM D-1238, Condition E, at 190 ° C. In a preferred embodiment, the polyolefin is an ethylene homopolymer or copolymer. In a preferred embodiment, for certain applications such as films, shaped articles, etc., a melt index of 100 g / 10 min or less is preferred. A melt index of 10 g / 10 min is preferred for some films and shaped articles. In a preferred embodiment, the polymer produced has a molecular weight of 200,000 Daltons or more.

In a preferred embodiment, the catalyst system described above is used to produce polyethylene with a density between 0.88 and 0.970 g / cm.³ (measured according to ASTM 2839), melt index 1.0 or less g / 10 min or less (measured according to ASTM D-1238, Condition E, at 190 ° C). Preferably, polyethylene is produced having a melt index between 0.01 to 10 dg / min. In some embodiments, a density of 0.915 to 0.940 g / cm2 would be preferred³while in other embodiments, densities between 0.930 and 0.960 g / cm are preferred³.

Polyolefins can be made into films, shaped articles, sheets, coatings of wires and cables, etc. The films can be formed by conventional known techniques including extrusion, coextrusion, lamination, blow molding and casting. The film may be obtained by a flat head extrusion or tubular process and then oriented in one direction or in two mutually perpendicular directions in the plane of the film to the same or different sizes. Orientation can be performed to the same sizes in both directions or to different sizes. Particularly preferred methods of forming polymers into films include extrusion or coextrusion in a blown or cast film line.

The films produced may also contain additives such as glidants, anti-skid, antioxidants, pigments, fillers, anti-smoke, UV stabilizers, antistatic agents, polymer processing aids, neutralizers, lubricants, surfactants, pigments, dyes and nucleating agents. Preferred additives include silicon dioxide, synthetic silica, titanium dioxide, polydimethylsiloxane, calcium carbonate, metal stearates, calcium stearate, zinc stearate, talc, BaSO4, diatomaceous earth, wax, carbon black, flame retardant additives, low resins.

With molecular weight, hydrocarbon resins, glass spheres, and the like. The additives may be present in well-known, typically effective amounts, such as 0.001 wt% to 10 wt%.

The present invention also relates to a collection of a plurality of metal compounds represented by the above formula. These collections can be used for simultaneous parallel searches for catalysts by combining the collections with one or more olefins, preferably to determine the relative abilities of different compounds.

Examples:

Mn and Mw were measured by gel permeation chromatography on a "waters 150 ° C GPC instrument" equipped with differential refractive index detectors. GPC columns were calibrated with running series of narrow polystyrene standards and molecular weights were calculated using Mark Houwink factors for the polymer in question.

Density was measured according to ASTM D 1505.

The Melt Index (MI) of I2 and I21 was measured according to ASTM D-1238, Condition E, at 190 ° C.

The Melt Index (MIR) is the I21 / I2 ratio according to ASTM D-1238.

% by weight of comonomer was measured by proton NMR.

MWD = Mw / Mn

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

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

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

Example 1

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

Diethylenetriamine (23.450 g, 0.227 mol), 2-bromomethylene (90.51 g, 0.455 mol), tris (dibenzylidene-acetone) dipalladium (1.041 g, 1.14 mmol), racemic-2 were added to a 2 L Schlenk flask with a magnetic stir bar. , 2'-bis- (diphenylphosphino) -1,1'-binaphthyl (racemic BINAP) (2.123 g, 3.41 mmol), sodium tert-butoxide (65.535 g, 0.682 mol), toluene (800 mL) in dry, oxygen-free nitrogen. The reaction mixture was stirred and heated to 100 ° C. After 18 h the reaction was complete as judged by proton NMR spectroscopy. All other activities can be carried out in the air. All solvent was removed in vacuo and the residue was dissolved in diethyl ether (1 L). The ether was washed with water (3 x 250 mL) followed by aqueous NaCl (180 g in 500 mL) and dried with magnesium sulfate (30 g). Removal of the ether in vacuo gave a red oil which was dried at 70 ° C for 12 h in vacuo (yield: 71.10 g, 92%).

¹H NMR (C6D6) δ 6.83 (s, 4), 3.39 (br s, 2), 2.86 (t, 4), 2.49 (t, 4), 2.27 (s, 12), 2.21 (s, 6), 0.68 (br s, 1).

Example 2 (Preparation of Catalyst A)

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

Tetrabenzylzircon (Boulder Scientific) (41.729 g, 91.56 mmol), and 300 mL of toluene in oxygen-free nitrogen were added to a 500 mL round bottom flask with a magnetic stir bar. Solid HN3 ligand (Example 1) (32.773 g, 96.52 mmol) was added with stirring for 1 minute (desired compound precipitated). The volume of the suspension was reduced to 100 mL and 300 mL of pentane was added while stirring. The solid yellow-orange product was filtered off and dried in vacuo (44,811 g, 80% yield).

¹H NMR (C6D6) δ 7.22-6.81 (m, 12), 5.90 (d, 2), 3.38 (m, 2), 3.11 (m, 2), 3.01 (m, 1), 2.49 (m, 4), 2.43 (d, 6), 2.41 (d, 6), 2.18 (d, 6), 1.89 (d, 2), 0.96 (d, 2).

Example 3 (Preparation of Catalyst C)

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

Tetrabenzylohafnium (4.063 g, 7.482 mmol) and 150 mL of toluene in oxygen-free nitrogen were introduced into a 250 mL round bottom flask with a magnetic stir bar. Solid HN3 ligand (Example 1) (2.545 g, 7.495 mmol) was added with stirring for 1 minute (the desired compound precipitates). The volume of the suspension was reduced to 30 mL and 120 mL of pentane was added with stirring. The solid pale yellow product was filtered off and dried in vacuo (4.562 g, 87% yield).

¹H NMR (C6D6) δ 7.21-6.79 (m, 12), 6.16 (d, 2), 3.39 (m, 2), 3.14 (m, 2), 2.65 (s, 6), 2.40 (s, 6), 2.35 (m, 2), 2.23 (m, 2), 2.19 (s, 6), 1.60 (s, 2), 1.26 (s, 2), NH visible.

Example 4

Preparation of [(2-methylnaphthyl) NHCH2CH2] 2NH ligand

PL 199 568 B1

Into a Schlenk flask with a magnetic stir bar, diethylenetriamine (6.026 g, 58.41 mmol), 2-bromo-2-methylnaphthylene (25.829 g, 116.8 mmol), tris (dibenzylideneacetone) dipalladium (0.268 g, 0.292 mmol), racemic-2, 2'-bis- (diphenylphosphino) -1,1'-binaphthyl (racemic BINAP) (0.547 g, 0.878 mmol), sodium tert-butoxide (16.90 g, 175.8 mmol) and toluene (400 mL) in oxygen free nitrogen. The reaction mixture was stirred and heated to 100 ° C. After 18 h the reaction was complete as judged by proton NMR spectroscopy. All other activities can be carried out in the air. All solvents were removed in vacuo and the residue was dissolved in diethylether (500 mL). The ether was washed with water (3 x 100 mL) followed by saturated aqueous NaCl (90 g in 250 mL) and dried with magnesium sulfate (15 g). Removal of the ether in vacuo gave a red oil which was dried at 70 ° C for 12 h in vacuo (yield: 19.10 g, 85%).

¹H NMR (C6D6) δ 8.32 (d, 2), 7.71 (d, 2), 7.40-7.18 (m, 8), 3.91 (t, 2), 2.99 (dt, 4), 2.41 (dt, 4), 2.30 (p, 6), 0.69 (pentet, 1).

Example 5 (Preparation of Catalyst C)

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

Tetrabenzylzircon (Boulder Scientific) (3.000 g, 6.582 mmol), and 300 mL of toluene in oxygen-free nitrogen were introduced into a 500 mL round bottom flask with a magnetic stir bar. A solution of HN3-2 ligand (Example 4) (65 mL, 0.102 M, 6.63 mmol) was added with stirring for 1 minute (the desired compound precipitates). The volume of the suspension was reduced to 40 mL and 150 mL of pentane was added with stirring. The solid yellow-orange product was filtered off and dried in vacuo (3.060 g, 71% yield). The product is a mixture of four isomers obtained by the orientation of the 2-methylnaphthyl groups.

¹H NMR (C6D6) δ 8.50 (d), 8.39 (d), 8.35 (d), 7.70 (d), 7.66-6.70 (m), 6.53 (t), 6.22 (t), 5.63 (m), 5.18 ( d), 4.70 (d), 3.62 (m), 3.50 (m), 3.30-3.11 (m), 2.68 (m), 2.60 (s), 2.55 (m), 2.52 (s), 2.50 (s), 2.10 (s), 1.61 (s), 1.29 (AB quartet), 1.03 (s), 1.01 (s), 1.00 (AB quartet), other resonances are hardly visible.

Example 6

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

3,5-Di-t-butylsalicylaldehyde (3.00 g) was added to 10 mL of iso-propylamine. The solution turned light yellow quickly. After stirring at neutral temperature for 3 h, the volatiles were removed in vacuo to give a light yellow crystalline solid (97% yield).

Example 7 (Preparation of Catalyst D)

Synthesis of {[ortho-3,5-di-t-Bu- (C6H2) (O) CH = NCHMe2] 2Zr (CH2Ph) 2.

A solution of N-iso-Pr-3,5-di-t-butylsalicylimine (605 mg, 2.2 mmol) in 5 mL of toluene was slowly added to a solution of Zr (CH2Ph) 4 (500 mg, 1.1 mmol) in 50 mL of toluene. The resulting dark yellow solution was stirred for 30 min. The solvent was removed in vacuo to give a red-brown solid.

¹H NMR (C6D6) δ 8.07 (s, HC = N, 1H), 7.77 (d, J = 2.4 Hz, salicylimine), 7.1-6.95 (m, 5H, aryl), 6.73 (t, J = 7.2 Hz, 1H , benzyl), 4.17 (septet, J = 6.6 Hz, 1H, CHMe2), 2.76 (AB, J = 10.2 Hz, 2H, ZrCH2Ph), 1.78 (s, 9H, t-Bu), 1.29 (s, 9H, t -Bu), 0.76 (d, J = 6.6 Hz, 3H, NCHMeAMeB), 0.52 (d, J = 6.6 Hz, 3H, NCHMeAMeB).

Catalyst 1.

Spray drying {[(2,4,6-Me3C6H2) NCH2CH2] 2NH} ZrBz2

5.0 g of Cabosil TS-610, dehydrated in vacuo above 100 ° C, were added to 110 ml of toluene. A solution of methylalumoxane (26 ml of 20 wt% MAO in toluene) was added to this suspension. A catalyst precursor solution of 0.075 g [(2,4,6-Me3C6H2) NCH2CH2] 2NH] ZrBz2 in about 20 mL of toluene was added to the slurry, and stirred / vortexed for about 30 minutes. This mixture was spray dried in a Buchi Series 190 Mini Spray Dryer contained in a drying chamber under an inert atmosphere. The following conditions were used: 0.7 mm diameter sprayer cap, 0.5 mm mixing needle, 16.7 L / min nitrogen gas flow for spray flow, aspirator set to 20, inlet temperature 120 ° C, outlet temperature 80 to 90 ° C, and charge catalyst mixture 0.6 L / h. 6.55 g (68%) of the solid product was collected. ICP indicated 0.13 wt% Zr and the Al: Zr ratio was 536: 1.

PL 199 568 B1

Catalyst 2.

Spray drying {[(2-Me-Naphthyl) NCH2CH2] 2NH} ZrBz2

5.0 g of Cabosil TS-610, dehydrated in vacuo above 100 ° C, were added to 110 ml of toluene.

A solution of methylalumoxane (26 mL 20 wt% MAO in toluene) was added to this slurry, followed by the addition of a catalyst precursor solution of 0.083 g [(2-Me-naphthyl) NCH2CH2] 2NH] ZrBz2 in about 20 mL of toluene and stirred / swirled for about 30 minutes. This mixture was spray dried as above. 5.77 g of solid product (59%) were collected. ICP indicated 0.15 wt% Zr and Al: Zr ratio 458: 1.

Catalyst 3.

Spray drying {[(2,4,6-Me3C6H2) NCH2CH2] 2NH} ZrBz2

To 110 ml of toluene was added 4.0 g of Cabosil TS-610, dehydrated in vacuo above 100 ° C.

A solution of methylalumoxane (26 ml of 20 wt% MAO in toluene) was added to this suspension. A catalyst precursor solution of 0.20 g of [(2,4,6-Me3C6H2) -NCH2-CH2] 2NH] ZrBz2 in about 20 mL of toluene was added to this slurry and stirred / vortexed for about 30 minutes. This mixture was spray dried as above. 5.18 g (58%) of the solid product was collected. ICP indicated 0.36 wt% Zr and an Al: Zr ratio of 196: 1.

Catalyst 4.

Spray drying {[(2,4,6-Me3C6H2) NCH2CH2] 2NH} HfBz2

4.6 g of Cabosil TS-610, dehydrated in vacuo above 100 ° C, was added to 140 ml of toluene.

A solution of methylalumoxane (20.8 ml of 20 wt% MAO in toluene) was added to this suspension. A catalyst precursor solution of 0.229 g of [(2,4,6-Me3C5H2) NCH2CH2] 2NH] HfBz2 in approximately 20 ml of toluene was added to this slurry and stirred / vortexed for approximately 30 minutes. This mixture was dried as above.

Catalyst 5.

Spray drying {[(2,4,6-Me3C6H2) NCH2CH2] 2NH} ZrBz2

To 280 ml of toluene was added 12.4 g of Cabosil TS-610, dehydrated in vacuo above 100 ° C.

A solution of methylalumoxane (57 ml of 20 wt% MAO in toluene) was added to this suspension. A catalyst precursor solution of 0.55 g (2,4,6-Me3C6H2) NCH2CH2] 2NH] ZrBz2 in about 20 mL of toluene was added to this slurry and stirred / swirled for about 30 minutes. The mixture was spray dried as above. 13 g of solid product (56%) was collected. ICP indicated 0.38 wt% Zr and the Al: Zr ratio was 152: 1.

Catalyst 6.

Spray drying {[(2,4,6-Me3C6H2) NCH2CH2] 2NH} HfBz2

6.0 g of Cabosil TS-610, dehydrated in vacuo above 100 ° C, were added to 125 ml of toluene.

A solution of methylalumoxane (27 ml of 20 wt% MAO in toluene) was added to this suspension. A catalyst precursor solution of 0.30 g of [(2,4,6-Me3C6H2) NCH2CH2] 2NH] HfBz2 in about 20 mL of toluene was added to this slurry and stirred / vortexed for about 30 minutes. The mixture was spray dried as above. 7.0 g (63%) of the solid product was collected. ICP indicated 0.72 wt% Hf and the Al: Hf ratio was 120: 1.

Catalyst 7.

Spray drying {[ortho-3,5-di-t-Bu- (C6H2) (O) CH = NCHMe2] 2} Zr (CH2Ph) 2

2.6 g of Cabosil TS-610, dehydrated in vacuo above 100 ° C, were added to 75 ml of toluene. A solution of methylalumoxane (12.4 ml of 20 wt% MAO in toluene) was added to this suspension. To this slurry was added a catalyst precursor solution of 0.168 g {[ortho-3,5-di-t-Bu- (C6H2) (O) CH = NCHMe2] 2} Zr (CH2Ph) 2 in about 20 mL of toluene and stirred / swirled for about 30 minutes. This mixture was spray dried as above.

Catalyst 8.

Spray drying 1: 1 {[(2,4,6-Me3C6H2) NCH2CH2] 2NH) ZrBz2 and (n-C3H7-C5H4) (Me5C) ZrCl2

To 110 ml of toluene was added 4.0 g of Cabosil TS-610, dehydrated in vacuo above 100 ° C.

A solution of methylalumoxane (26 ml of 20 wt% MAO in toluene) was added to this suspension. To this slurry a catalyst precursor solution 0.10 g {[(2,4,6-Me3C6H2) NCH2CH2] 2NH} ZrBz2 and 0.067 g (n-C3H7-C5H4) (Me5C) ZrCl2 in about 20 mL of toluene was added and stirred / vortexed for approximately Thirty minutes. This mixture was spray dried as above. 5.31 g (60%) of the solid product was collected. ICP indicated 0.37 wt% Zr and the Al: Zr ratio was 202: 1.

PL 199 568 B1

Catalyst 9.

Spray drying 1: 1 {[(2,4,6-Me3C6H2) NCH2CH2] 2NH} ZrBz2 and (n-C3H7-C5H4) 2ZrCl2

To 110 ml of toluene was added 4.0 g of Cabosil TS-610, dehydrated in vacuo above 100 ° C. A solution of methylalumoxane (26 ml of 20 wt% MAO in toluene) was added to this suspension. A catalyst precursor solution of 0.10 g {[(2,4,6-Me3C6H2) NCH2CH2] 2NH} ZrBz2 and 0.056 g (n-C3H7-C5H4) 2-ZrCl2 in about 20 mL of toluene was added to this slurry and stirred / vortexed for about 30 minutes. This mixture was spray dried as above.

Catalyst 10.

Spray drying 3.4: 1 {[(2,4,6-Me3C6H2) NCH2CH2] 2NH} ZrBz2 and (n-C3H7-C5H4) 2ZrCl2

To 540 ml of toluene was added 21.4 g of Cabosil TS-610, dehydrated in vacuo above 100 ° C. A solution of methylalumoxane (97 ml of 20 wt% MAO in toluene) was added to this suspension. A catalyst precursor solution of 0.80 g {[(2,4,6-Me3C6H2) NCH2CH2] 2NH} ZrBz2 and 0.143 g (n-C3H7-C5H4) 2-ZrCl2 in about 60 mL of toluene was added to this slurry and stirred / vortexed for about 30 minutes. This mixture was spray dried as above. 21 g (53%) of the solid product was collected. ICP indicated 0.44 wt% Zr and an Al: Zr ratio of 128.

Catalyst 11.

Spray drying 5: 1 {[(2,4,6-Me3C6H2) NCH2CH2] 2NH} ZrBz2 and (n-C3H7-C5H4) 2ZrCl2

To 570 ml of toluene was added 25.8 g of Cabosil TS-610, dehydrated in vacuo above 100 ° C. A solution of methylalumoxane (116 ml of 20 wt% MAO in toluene) was added to this suspension. A catalyst precursor solution of 0.93 g of {[(2,4,6-Me3C6H2) NCH2CH2] 2NH} ZrBz2 and 0.114 g (n-C3H7-C5H4) 2-ZrCl2 in about 40 mL of toluene was added to this slurry and stirred / swirled for about 30 minutes. The mixture was spray dried as above. 29 g (60%) were collected. ICP indicated 0.39 wt% Zr and an Al: Zr ratio of 156.

Catalyst 12.

Spray drying 3: 1 {[(2,4,6-Me3C6H2) NCH2CH2] 2NH} HfBz2 and (n-C3H7-C5H4) 2ZrCl2

To 570 ml of toluene was added 25.8 g of Cabosil TS-610, dehydrated in vacuo above 100 ° C. A solution of methylalumoxane (116 ml of 20 wt% MAO in toluene) was added to this suspension. To this slurry a catalyst precursor solution of 0.96 g {[(2,4,6-Me3C6H2) NCH2CH2] 2NH} HfBz2 and 0.17 g (n-C3H7-C5H4) 2ZrCl2 in about 40 mL of toluene was added and stirred / vortexed for about 30 minutes. This mixture was spray dried as above. 32 g (67%) of the solid product was collected. ICP indicated 0.51 wt% Hf, 0.094 wt% Zr and an Al: M ratio of 161.

Polymerization Examples 1-15

The polymerization in the slurry reactor was carried out as follows. After sufficient drying and cooling time, 490 cm³ hexanes were charged to a 1 liter autoclave reactor. Hexene was added as needed and 0.17 cm2 to the reactor prior to heating³ 0.87 mmoles of triisobutylaluminum in heptane as a radical scavenger and a hydrogen atom if needed. The reactor contents were heated to the desired temperature. The spray-dried catalyst was inserted into a 10 cm bomb that was installed into a 20 cm bomb³to which 10 cm has been added³ hexanes. Each bomb was pressurized with nitrogen prior to attachment to the reactor. The spray-dried catalyst was injected under pressure into the reactor followed immediately by the release of hexanes. Thus, quantitative delivery can be ensured. Ethylene filled this system immediately and has since been introduced on demand. Polymerizations were carried out for 30 minutes.

Comparative polymerization

A reactor was prepared and charged with hexane, hexene, hydrogen and a free radical scavenger as above. The following procedure for Comparative Example 1 is general: A solution of 2.1 mg {[(2,4,6-Me3C6H2) NCH2CH2] 2NH} ZrBz2 was dissolved in 4.5 cm³ toluene. Part of the solution of 0.50 cm³removed and added to 0.50 cm³ 0.5 M methylaluminoxane (MAO) in toluene. The solutions were mixed for about five minutes before being injected into the reactor on demand followed immediately by ethylene and thereafter being fed on demand. All polymerizations were carried out for 30 minutes. The data is given in the table below.

PL 199 568 B1

Table

<td>Ex.</td><td>Catalan blockage</td><td>μιτοί M</td><td>By- cho- quote (days)</td><td>Al / Zr</td><td>rxn temp. (° C)</td><td>cm³ H2</td><td>cm³ C6</td><td>C2 PP</td><td>g PE</td><td>Ak- tywn.¹</td><td>J21²</td><td>Mw 10⁵</td><td>PDI³</td>

<td> 1</td><td> 1</td><td> 0.38</td><td> 15</td><td></td><td> 65</td><td> 0</td><td> 0</td><td> 128</td><td> 45.7</td><td> 187900</td><td></td><td></td><td></td>

<td> 2</td><td> 1</td><td> 0.38</td><td> 15</td><td></td><td> 65</td><td> 0</td><td> 0</td><td> 77</td><td> 34.2</td><td> 233800</td><td></td><td></td><td></td>

<td> 3</td><td> 1</td><td> 0.50</td><td> 33</td><td></td><td> 65</td><td> 0</td><td> 20</td><td> 60</td><td> 27.9</td><td> 186000</td><td> 10.3</td><td> 1.98</td><td> 4.01</td>

<td> 4</td><td> 1</td><td> 0.50</td><td> 34</td><td></td><td> 65</td><td> 0</td><td> 10</td><td> 56</td><td> 28.1</td><td> 200700</td><td> 2.36</td><td> 3.07</td><td> 5.55</td>

<td> 5</td><td> 1</td><td> 0.38</td><td> 55</td><td></td><td> 65</td><td> 0</td><td> 0</td><td> 62</td><td> 23.8</td><td> 202000</td><td></td><td></td><td></td>

<td> 6</td><td> 1</td><td> 0.50</td><td> 56</td><td></td><td> 85</td><td> 0</td><td> 0</td><td> 60</td><td> 12.2</td><td> 81300</td><td> 051</td><td></td><td></td>

<td> 7</td><td> 2</td><td> 2.3</td><td></td><td></td><td> 65</td><td> 0</td><td> 0</td><td> 128</td><td> 10.3</td><td> 7000</td><td></td><td></td><td></td>

<td> 8</td><td> 2</td><td> 3.0</td><td></td><td></td><td> 65</td><td> 0</td><td> 20</td><td> 129</td><td> 12.4</td><td> 6400</td><td></td><td></td><td></td>

<td> 9</td><td> 3</td><td> 0.50</td><td></td><td></td><td> 65</td><td> 0</td><td> 0</td><td> 57</td><td> 24.3</td><td> 170500</td><td></td><td></td><td></td>

<td> 10</td><td> 3</td><td> 0.50</td><td></td><td></td><td> 65</td><td> 0</td><td> 10</td><td> 58</td><td> 24.6</td><td> 169700</td><td> 1.67</td><td> 3.14</td><td> 4.51</td>

<td> 11</td><td> 3</td><td> 0.50</td><td></td><td></td><td> 85</td><td> 0</td><td> 0</td><td> 55</td><td> 18.4</td><td> 133800</td><td></td><td></td><td></td>

<td> 12</td><td> 8</td><td> 0.50</td><td></td><td></td><td> 65</td><td> 0</td><td> 0</td><td> 55</td><td> 26.6</td><td> 193400</td><td>bp</td><td></td><td></td>

<td> 13</td><td> 8</td><td> 0.50</td><td></td><td></td><td> 65</td><td> 0</td><td> 10</td><td> 57</td><td> 21.9</td><td> 153700</td><td> 1.29</td><td> 3.21</td><td> 3.81</td>

<td> 14</td><td> 8</td><td> 0.50</td><td></td><td></td><td> 85</td><td> 0</td><td> 0</td><td> 54</td><td> 9.9</td><td> 73300</td><td>bp</td><td></td><td></td>

<td> 15</td><td> 9</td><td> 0.50</td><td></td><td></td><td> 65</td><td> 100</td><td> 0</td><td> 65</td><td> 8.7</td><td> 53500</td><td></td><td></td><td></td>

<td>Winner 1</td><td>AND</td><td> 0.38</td><td></td><td> 667</td><td> 65</td><td> 0</td><td> 0</td><td> 62</td><td> 22.1</td><td> 187600</td><td></td><td></td><td></td>

<td>Winner 2</td><td>AND</td><td> 0.38</td><td></td><td> 667</td><td> 65</td><td> 0</td><td> 20</td><td> 60</td><td> 29.1</td><td> 255300</td><td></td><td></td><td></td>

<td>Winner 3</td><td>B</td><td> 3.0</td><td></td><td> 500</td><td> 65</td><td> 0</td><td> 0</td><td> 135</td><td> 3.2</td><td> 1580</td><td></td><td></td><td></td>

<td>Winner 4</td><td>B</td><td> 3.0</td><td></td><td> 500</td><td> 65</td><td> 0</td><td> 20</td><td> 135</td><td> 3.2</td><td> 1580</td><td></td><td></td><td></td>

¹ Units of activity in g PE mmol M^-1 h^-1 100 psi C2^-1.

² bp = no flow.

³ PDI = Mw / Mn.

A = {[(2,4,6-Me3C6H2) NCH2CH2] 2NH} ZrBz2 was injected as activated MAO solution.

B = [(2-Me-naphthyl) NCH2CH2] 2NH] ZrBz2 was injected as an activated MAO solution

Polymerization Examples 16-21

After an appropriate drying time of a 4L bench reactor with gas phase side agitation and nitrogen cooling, the reactor was charged with Davison 955-600 silica as starting bed. Hydrogen, 1-hexene, and a free radical scavenger were added before heating to 85 ° C. Thereafter, hydrogen was introduced by filling with 50 cm³ bombing to 150 psig (1.03 MPa) with 5% H2 / N2 and introducing into the reactor slightly above ambient pressure. Spray-dried catalysts were injected into the reactor using the same equipment as used to inject the catalyst into the slurry reactor. Following catalyst injection, ethylene was immediately introduced into the reactor and fed on demand for the remainder of the run. The ethylene partial pressure was 100 psig.

PL 199 568 B1

Comparative polymerizations

The examples with supported catalysts were identical to those above. The catalyst solution was injected in the same manner as in the suspension polymerization.

The data is given in the table below.

Table

<td>Ex.</td><td>catalyst/ precursor</td><td>umol M.</td><td>AI / M</td><td>H2</td><td>TIBA ml</td><td>C6 ml</td><td>silica g</td><td>PE g</td><td>time min</td>

<td> 16</td><td> 4</td><td> 4.0</td><td></td><td>no</td><td> 5</td><td> 1.2</td><td> 30</td><td> 210</td><td> 66</td>

<td> 17</td><td> 4</td><td> 2.0</td><td></td><td>Yes</td><td> 4</td><td> 0.6</td><td> 30</td><td> 141</td><td> 94</td>

<td> 18</td><td> 5</td><td> 4.0</td><td></td><td>no</td><td> 5</td><td> 1.2</td><td> 50</td><td> 120</td><td> 60</td>

<td> 19</td><td> 5</td><td> 20</td><td></td><td>Yes</td><td> 4</td><td> 0.6</td><td> 30</td><td> 107</td><td> 75</td>

<td> 20</td><td> 7</td><td> 2.0</td><td></td><td>Yes</td><td> 4</td><td> 0.6</td><td> 30</td><td> 148</td><td> 60</td>

<td> 21</td><td> 8</td><td> 2.0</td><td></td><td>Yes</td><td> 4</td><td> 0.6</td><td> 30</td><td> 174</td><td> 62</td>

<td>Comp. 5</td><td>C.</td><td> 2.0</td><td> 120</td><td>Yes</td><td> 4</td><td> 0.6</td><td> 30</td><td> 31</td><td> 60</td>

<td>Comp. 6</td><td>C.</td><td> 2.0</td><td> 200</td><td>Yes</td><td> 4</td><td> 0.6</td><td> 30</td><td> 56</td><td> 132</td>

<td>Comp. 7</td><td>C '</td><td> 2.0</td><td> 120</td><td>Yes</td><td> 4</td><td> 0.6</td><td> 30</td><td> 38</td><td> 62</td>

<td>Comp. 8</td><td>D</td><td> 2.0</td><td> 200</td><td>Yes</td><td> 4</td><td> 0.6</td><td> 30</td><td> 15</td><td> 60</td>

C = {[(2,4,6-Me3C6H2) NCH2CH2] 2NH} HfBz2 was injected as activated MAO solution.

C '= {[(2,4,6-Me3C6H2) NCH2CH2] 2NH} HfBz2 supported on Davison 948 silica, 0.38 µmol Hf / gm, Al / Hf = 120. D = {[ortho-3,5-di-t -Bu- (C6H2) (O) CH = NCHMe2] 2Zr (CH2Ph) 2 was injected as activated MAO solution.

Polymerization Examples 22-28

Polymerization procedure

In Comparative Example 9 and Examples 22-28, polyethylene was produced in a mixed bed in a horizontally mixed reactor with different catalyst compositions.

The table below summarizes the polymerization conditions for each Example.

Figure 1 shows the horizontally agitated reactor system used in Comparative Example 9 and Examples 22-28. The reactor was a two-phase (gas / solid) backmixed bed reactor. A set of four scrapers 100 was mounted horizontally on a central rotating shaft at 180 rpm to keep the particles in reactor 110 mechanically fluidized. The reactor cylinder scraped off these scrapers was 40.6 cm (16 in.) Long and 39.7 cm (15.6 in.) In diameter, resulting in a mechanically fluidized volume of 46 liters (1.6 ft).³). The gas volume greater than the mechanically fluidizable volume due to the vertical cylindrical chamber is 54.6 liters (1.93 ft³).

The reactor pressure in each Example was 2.4 MPa. Ethylene mononer, hexene comonomer and hydrogen (for molecular weight control) were continuously fed to the reactor through control valves through line 120. The partial pressure of ethylene monomer was 1.5MPa. The comonomer content of the polyethylene product was controlled by adjusting the feed ratios keeping the comonomer / monomer molar ratio (shown in the table) constant in the gas phase. The gas composition was measured at 1-4 minute intervals using a gas chromatographic analyzer. The molecular weight of the polyethylene was controlled by adjusting the hydrogen feed ratio while keeping the molar ratio of hydrogen to gas phase monomer constant. The nitrogen formed most of the equilibrium of the gaseous composition in the reactor entering the catalyst composition through line 130 and exiting through the small vent 140 with the reactor gases containing volatile solvents. The vent was set by computer to maintain a constant total pressure in the reactor.

The reactor was cooled with an external jacket containing cooling glycol. The bed temperature was measured with a temperature probe 150 in a thermowell protruding 60 ° to the bed above the horizontal between the inner set of scrapers. The reactor temperature of Comparative Example 9 was 85 ° C, while the temperature of the reactor in Examples 22-28 was 80 ° C.

In Comparative Example 9, a catalyst 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 injected through line 160 and mixed with a continuous stream of modified methylaluminoxane cocatalyst solution fed through line 170. The concentration of Akzo MMAO type 3A in isopentane was 2.1% and the amount of MMAO used was such that the Al / Zr ratio in the reactor was 200. The mixture of catalyst solutions and MMAO was introduced through a 180 pipe coil 0.32 cm (1/8 inch) where the catalyst and the cocatalyst react for about 4 minutes. After exiting this coil for initial contact, the mixed catalyst composition solution was sprayed into the reactor under a constant flow of nitrogen from line 130.

For Examples 22-28, a spray-dried catalyst slurry was prepared by mixing the catalyst powder with a light mineral oil, and the resulting slurry was stored in a stirred tank attached to line 160. The catalyst slurry was injected through line 160 and mixed with a continuous stream of modified methylaluminoxane cocatalyst solution fed cable 170. In these Examples, the coil 180 is replaced with a straight tubular piece with an outside diameter of 0.32 cm (1/8 inch) and approximately 10 cm (4 inches) long. The concentration of Akzo MMAO type 3A in isopentane was 2.1%, and the MMAO solution feed rate was set to approximately 50 ml / h. The mixture of catalyst slurry and MMAO solution was supplied to the reactor via a 1/8 inch OD injection tube using a constant nitrogen flow to disperse the mixture.

The reactor was operated both continuously and batchwise. Typical batch sizes for granular polyethylene in the reactor were 7-20 lbs. Each run typically took 3-6 hours. In a continuous process, the granular polymer was removed with valve 190 in typically 0.2 kg (0.4 Ib) aliquots as the polymerization progressed. In the continuous process, the product discharge system was able to build up a bed mass up to 5.4-9.1 kg (12-20 lbs) and change the discharge rate to maintain a constant bed mass as calculated from the material balance.

In each of Comparative 9 and Examples 22-28, the polymerization process was carried out by introducing the monomers into the reactor and feeding the raw materials to the desired gas composition. The initial cocatalyst charge was added prior to the catalyst input to remove poisons present in the reactor. After the catalyst was charged, sufficient monomer was added to the reactor to maintain gas concentrations and proportions. After the catalyst was accumulated, the polyethylene production rate was increased to 2.3-4.5 kg / hr (5-10 lbs / hr), during which time the catalyst charge was modified to keep the polyethylene production rate constant. In Comparative Example 9, the cocatalyst feed rate remained in proportion to the catalyst feed rate. After the desired batch weight was reached, the reactor was vented rapidly and the monomers were removed from the polyethylene resin by purging it with nitrogen. The charge was then discharged through valve 190 into the open atmosphere.

Table

<td>Example</td><td>Catalysis.</td><td>Temp (° C)</td><td>H2 / C2</td><td>C6 / C2</td><td>Issue kg</td><td>Ml dg / min</td><td>Fl dg / min</td><td>Density g / cm³</td>

<td>Comp. 9</td><td>AND</td><td> 85</td><td> 0.0015</td><td> 0.0057</td><td> 3.0</td><td> 0.413</td><td> 20.2</td><td> 0.937</td>

<td> 22</td><td> 5</td><td> 80</td><td> 0.0013</td><td> 0.0030</td><td> 7.2</td><td> -</td><td> 1.15</td><td> 0.935</td>

<td> 23</td><td> 10</td><td> 80</td><td> 0.0013</td><td> 0.0057</td><td> 16.7</td><td> 2.62</td><td> 101.2</td><td> 0.942</td>

<td> 24</td><td> 11</td><td> 80</td><td> 0.0013</td><td> 0.0046</td><td> 17.2</td><td> 1.58</td><td> 70.4</td><td> 0.946</td>

<td> 25</td><td> 11</td><td> 80</td><td> 0.0012</td><td> 0.0041</td><td> 12.6</td><td> 0.71</td><td> 30.1</td><td> 0.944</td>

<td> 26</td><td> 6</td><td> 80</td><td> 0.0020</td><td> 0.0045</td><td> 3.0</td><td> -</td><td> 0.2</td><td> 0.937</td>

<td> 27</td><td> 12</td><td> 80</td><td> 0.0019</td><td> 0.0048</td><td> 7.2</td><td> 1.71</td><td> 130.7</td><td> 0.935</td>

<td> 28</td><td> 12</td><td> 80</td><td> 0.0008</td><td> 0.0055</td><td> 16.7</td><td> 1.56</td><td> 49.2</td><td> 0.942</td>

A = {[(2,4,6-Me3C6H2) NCH2CH2] 2NH} ZrBz2 was injected as activated MMAO-3A solution.

PL 199 568 B1

However, when spray-dried indenyl zirconium tris-pivalate as described herein, it had low activity.

All cited documents are incorporated herein by reference, including priority documents and / or testing procedures. As is apparent from the above general descriptions and specific embodiments, while embodiments of the invention are described and illustrated, various modifications can be made without departing from the spirit and scope of the invention. Accordingly, it is not intended to limit the invention.