Method of polymerization

IS 2 298 142 T3

DESCRIPTION

Polymerization procedure.

Field of the invention

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

Background of the invention

The intense commercialization of metallocene catalysts for polyolefins (the metallocene compounds being cyclopentadienyl-based transition metal catalysts) has led to widespread interest in the design of homogeneous, non-metallocene catalysts, particularly for use in economical gas phase and gas phase processes. of porridge. This field is more than an academic curiosity as new, gas or slurry non-metallocene catalysts can provide an easier, more economical route to currently available products and can also provide product and process opportunities that are beyond of the capacity of metallocene catalysts in the gas or slurry phase.

However, the new catalysts are not automatically usable in the gas phase. Some catalysts are too active and clog the reactor. Other catalysts cannot be deposited on a support and therefore cannot be introduced into the reactor in such a way that no plugging occurs. Therefore, there is a need in the art for a process for providing catalysts to a gas phase or slurry phase reactor, particularly with catalysts that are difficult or impossible to deposit on a support.

Schrock et al., In US 5,889,128 describe a process for the living polymerization of olefins in solution using initiators having one metal atom and a ligand having two group 15 atoms and one group 16 atom or three atoms. from group 15. In particular, the solution phase polymerization of ethylene using {[NON] ZrMe} [MeB (C6F₅) s] or {[NON] ZrMe (PhNMe2)]} [B (C6F₅) 4] is described in Examples 9 and 10.

EP 893 454 A1 describes unsupported transition metal amide compounds that are used in combination with activators to polymerize olefins in the solution phase.

Mitsui Chemicals, Inc., in EP 0 893 454 A1 describes transition metal amides combined with activators to polymerize olefins.

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

EP 893 454 A1 describes unsupported transition metal amide compounds that are used in combination with activators to polymerize olefins in the solution phase.

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

Japanese Abstract JP 10330416A makes it possible to deduce that it describes transition metal amide catalysts in combination with Ziegler-Natta catalysts. Japanese Abstract JP 10330412A allows to deduce that it describes transition metal amide catalysts in combination with group 4 transition metal cyclopentadienyl catalysts.

Ethylenebis (salicylidenoiminate) zirconium dichloride combined with supported methyl alumoxane and unsupported versions were used to polymerize ethylene by Repo et al., In Macromolecules 1997, 30, 171175.

US 5,672,669, US 5,674,795 and EP 0 668 295 B1 describe spray dried metallocene catalyst compositions with a filler for use in gas phase polymerizations.

Summary of the invention

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

In one aspect, the particulate filler can be any known particulate filler, including carbon black, talc; inorganic oxides such as silica; magnesium chloride, alumina, silica-alumina; polymeric materials such as polyethylene, polypropylene, polystyrene, cross-linked polystyrene; and the like.

Preferred activators include conventional cocatalysts, alkyl aluminum compounds (such as diethyl aluminum chloride), alumoxanes, modified alumoxanes, non-coordinating anions, metal or metalloid anions.

ES 2 298 142 T3 of group 13 non-coordinators, borans, borates and the like. It is within the scope of this invention to use alumoxane or modified alumoxane as the activator, and / or to also use ionizing, neutral or ionic activators, such as tri (nbutyl) ammonium tetrakis (pentafluorophenyl) boron or a metalloid precursor of trisperfluorophenyl boron which is ionized to the neutral metallocene compound. Other useful compounds include triphenyl boron, triethyl boron, tri-nbutyl ammonium tetraethylborate, triaryl borane, and the like. Other useful compounds also include aluminate salts.

The metal catalyst compounds used herein include a group 15 element containing metal compound as described below.

Brief description of the drawings

Figure 1 depicts the horizontal mixing reactor system used in Comparative 9 and Examples 22 to 28.

Detailed description of the invention

The present invention relates to a spray dried catalyst system comprising a particulate filler, an activator, and one or more metal catalyst compounds. Metal catalyst compounds show surprising ability to be immobilized with a charge, activated by an activator, and surprising robustness and catalytic activity.

The particulate filler comprises fumed silica. Preferably, the filler is Cabosil TS-610, available from Cabot Corporation, which is a 7 to 30 nanometer particle size fumed silica that has been treated with dimethylsilyl dichloride so that most of the hydroxyl groups are covered. The spray dried particles are generally supplied to the polymerization reactor as a slurry in mineral oil. Solids concentrations in oil are about 10-15% by weight, preferably 11-14% by weight. In some embodiments, spray-dried particles are <~ 10 microns in size from the lab-scale Buchi spray dryer, while larger-scale rotary atomizers can create ~ 25 micron particles, which are compared to supported catalysts. that are ~ 50 microns. In a preferred embodiment the particulate filler has an average particle size of 0.001 to 1 micron, preferably 0.001 to 0.1 micron.

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

Catalysts

The catalysts or catalyst systems used herein include a group 15 element containing metal compound and / or the phenoxide catalyst as described below. Other catalysts that can be used in combination with the group 15 element-containing metal compound include bulky ligand metallocene-type catalysts with optional activator.

Once the catalysts described herein have been spray dried they can be combined with other more conventional catalysts and can be introduced into a 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 a mineral oil and it can be introduced into a reactor in a slurry.

For more information on conventional-type transition metal catalysts see Ziegler-Natta Catalists and Polymerizations, John Boor, Academic Press, New York, 1979. Examples of conventional-type transition metal catalysts are also described in US Pat. USA N^you 4,115,639,4,077,904,4,482,687,4,564,605, 4,721,763, 4,879,359, 4,960,741, 4,302,565, 4,302,566, 5,317,036, 3,709,853, 3,709,954, 3,231. 550, 3,242,099, 4,077,904, 4,124,532, 4,302,565, 4,302,566, 4,376,062, 4,379,758, 5,066,737, 5,763,723, 5,849,655, 5,852,144, 5,854,164, 5,869,585, 3,487,112,4,472,559,4,182,814 and 4,689,437 and publications EP-A2 0 416 815 A2 and EP-A1 0 420 436, British patent application 2,105,355.

For the purposes of this invention, the cyclopentadienyl group is defined to include indenyls and fluorenyls.

Metal compound containing group 15 element

The mixed catalyst composition of the present invention includes a Group 15 element-containing metal compound. The Group 15 element-containing compound generally includes a Group 3 to 14 metal atom, preferably Group 3 to 7, more preferably Group 4 to 6, and even more preferably a Group 4 metal atom, bonded at least to a leaving group and also attached to at least two Group 15 atoms, at least one of which is also attached to a Group 15 or 16 atom through another group.

At least one of the Group 15 atoms is also attached to a Group 15 or 16 atom through another group which may be a Ci to C hydrocarbon group₂₀, a group containing heteroatom, silicon, germanium, tin, lead,

ES 2 298 142 T3 or phosphorus, in which the Group 15 or 16 atom can also be attached to nothing or hydrogen, a group containing a Group 14 atom, a halogen, or a group containing a heteroatom, and wherein each of the two Group 15 atoms is also attached to a cyclic group and may optionally be attached to hydrogen, a halogen, a heteroatom or a hydrocarbyl group, or a group containing a heteroatom.

The Group 15 element-containing metal compound of the present invention is represented by the formula:

R⁴ , z^RY\ r3 „L -------- MⁿXn + m

Formula I in which

M is a Group 4, 5 or 6 metal, and more preferably a Group 4 metal, and most preferably zirconium, titanium or hafnium, each X is independently an anionic leaving group, and more preferably hydrogen, a hydrocarbyl group, a heteroatom or a halogen, and most preferably an alkyl.

n is the oxidation state of M, preferably +3, +4, or +5, and more preferably +4, m is the formal charge of the ligand YZL or YZL ', preferably 0, -1, -2 or -3 , and more preferably -2,

L is a Group 15 or 16 element, preferably nitrogen,

Y is a Group 15 element, preferably nitrogen or phosphorus, and more preferably nitrogen,

Z is a Group 15 element, preferably nitrogen or phosphorus, and more preferably nitrogen,

R¹ and R² are independently a Ci to C hydrocarbon group₂₀, a group containing heteroatom having up to twenty carbon atoms, tin, lead, halogen or phosphorus, preferably a C alkyl₂ to C₂₀, an aryl or aralkyl group, more preferably a C alkyl group₂ to C₂₀ linear, branched or cyclic, most preferably a C hydrocarbon group₂ BC₆. R¹ and R² they can also be interconnected with each other.

R³ is absent or is a hydrocarbon group, hydrogen, a halogen, a heteroatom-containing group, preferably a linear, cyclic or branched alkyl group having 1 to 20 carbon atoms, more preferably R³is absent or is hydrogen or an alkyl group, and most preferably hydrogen,

R⁴ and R⁵ they are independently an alkyl group, an aryl group, a substituted aryl group, a cyclic alkyl group, a substituted cyclic alkyl group, a cyclic aralkyl group, a substituted cyclic aralkyl group or multiple ring system, preferably having up to 20 carbon atoms, more preferably between 3 and 10 carbon atoms and even more preferably a C1 to C20 hydrocarbon group, a C1 to C20 aryl group or a C1 to C20 aralkyl group, or a group containing heteroatom, for example PR3, where R is an alkyl group, R¹ and R² can be interconnected with each other, and / or R⁴ and R⁵ can be interconnected with each other, and

R⁶ and R⁷ they are independently absent or are hydrogen, an alkyl, halogen, heteroatom or a hydrocarbyl group, preferably a linear, cyclic or branched alkyl group having 1 to 20 carbon atoms, more preferably they are absent.

By "formal charge of the ligand YZL or YZL '" is meant the charge of the entire ligand absent from metal and leaving groups X.

By “R¹ and R² they can also be interconnected with each other ”is meant to imply that R¹ and R² they can be directly linked to each other or they can be linked to each other through other groups. By “R⁴ and R⁵ they can also be interconnected with each other ”is meant to imply that R⁴ and R⁵ they can be directly linked to each other or they can be linked to each other through other groups.

An alkyl group can be linear or branched alkyl radicals, or 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, carbomocarbonyl radicals , alkyl- or dialkylcarbamoyl radicals, acyloxy radicals, acylamino radicals, aroylamino radicals, linear alkylene radicals, branched or cyclic, or combinations thereof. An aralkyl group is defined as a substituted aryl group.

IS 2 298 142 T3

In a preferred embodiment R⁴ and R⁵ are independently a group that is represented by the following formula:

<img file="ES2298142T3_D0001.tif" />

in which

R⁸ to R¹² are each independently hydrogen, a Ci to C alkyl group₄₀, a halide, a heteroatom, a group containing heteroatom and containing up to 40 carbon atoms, preferably a C alkyl group₁ to C₂₀ linear or branched, preferably a methyl, ethyl, propyl or butyl group, either of the two R groups can form a cyclic group and / or a heterocyclic group. Cyclic groups can be aromatic. In a preferred embodiment R⁹, R¹⁰ and R¹² are independently a methyl, ethyl, propyl or butyl group (including all isomers), in a preferred embodiment R⁹, R¹⁰ and R¹² are methyl groups, and R⁸ and R¹¹ they are hydrogen.

In a particularly preferred embodiment R⁴ and R⁵ they are both a group that is represented by the following formula:

<img file="ES2298142T3_D0002.tif" />

In this embodiment, M is a Group 4 metal, preferably zirconium, titanium, or hafnium, and even more preferably zirconium; each of L, Y, and Z is nitrogen; each of R¹ and R² is -CH₂-CH₂-; R³ is hydrogen; R⁶ and R⁷They are absent.

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

<img file="ES2298142T3_D0003.tif" />

In compound I, Ph equals phenyl.

IS 2 298 142 T3

The Group 15 element-containing metal compounds of the invention are prepared by procedures known in the art, such as those described in EP 0 893 454 A1, US Patent No. 5,889,128 and References cited in US Patent No. 5,889,128, all of which are incorporated herein by reference. The US request Serial No. 09 / 312,878, filed May 17, 1999, describes a slurry or gas phase polymerization process using a supported bisamide catalyst, which is also incorporated herein by reference.

A preferred direct synthesis of these compounds comprises reacting the neutral ligand, (see for example YZL or YZL 'of formula 1 or 2) with MⁿX_n (M is a Group 3 to 14 metal, n is the oxidation state of M, each X is an anionic group such as a halide), in a weakly coordinating or non-coordinating solvent, such as ether, toluene, xylene, benzene, methylene chloride, and / or hexane or other solvent that has a boiling point above 60 ° C, at 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 methyl magnesium 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 element-containing metal compound is prepared by a process comprising reacting a neutral ligand, (see for example YZL or YZL 'of formula 1 or 2) with a compound that is represented by formula MⁿX_n (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 weakly or non-coordinating solvent, at about 20 ° C or above, preferably at about 20 to about 100 ° C, then treat the mixture with an excess of an alkylating agent, then recover the metal complex. In a preferred embodiment the solvent has a boiling point above 60 ° C, such as toluene, xylene, benzene, and / or hexane. In another embodiment the solvent comprises ether and / or methylene chloride, which are interchangeably preferable:

For additional information on Group 15 element containing metal compounds, see Mitsui Chemicals, Inc., in EP 0 893 454 A1 which describes transition metal amides combined with activators to polymerize olefins.

Activators

The catalysts, preferably the group 15 element metal compound and / or the phenoxide catalysts described herein, are preferably combined with one or more activators to form olefin polymerization catalyst systems. Preferred activators include alkyl aluminum compounds (such as diethyl aluminum chloride), alumoxanes, modified alumoxanes, non-coordinating anions, non-coordinating Group 13 metal or metalloid anions, borans, borates, and the like. It is within the scope of this invention to use alumoxane or modified alumoxane as the activator, and / or to also use ionizing, neutral or ionic activators, such as tri (n-butyl) ammonium tetrakis (pentafluorophenyl) boron or a metalloid precursor of trisperfluorophenyl boron which ionizes to the neutral metallocene compound. Other useful compounds include triphenyl boron, triethyl boron, tri-n-butyl ammonium tetraethylborate, triaryl borane, and the like. Other useful compounds also include aluminate salts.

In one embodiment, modified alumoxanes are combined with the catalysts to form a catalyst system. In a preferred embodiment MMA03A (Heptane-modified methyl alumoxane, commercially available from Akzo Chemicals, Inc., under the trade name Modified Methylalumoxane type 3A, covered by US Patent No. 5,041,584) is combined with the metal compounds first and second to form a catalyst system. MMAO -4 and MMAO -12 can also be used.

There are a variety of processes for preparing alumoxane and modified alumoxanes, non-limiting examples of which are described in US Pat. N^you 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, 5,391,793, 5,391,529, 5,041,584, 5,693,838, 5,731,253, 5,041,584 and 5,731,451 and the European publications EP-A0 561 476, EP-B1 -0 279 586 and EP-A-0 594 218, PCT publication WO 94/10180, all of which are fully incorporated herein by reference.

Ionizing compounds may contain an active proton, or some other cation associated but not coordinated thereto or only weakly coordinated to the remaining ion of the ionizing compound. Compounds of this type and the like are described in European publications EP-A-0 570 982, EP-A-0 520 732, EP-A-0 495 375, EP-A-0 426 637, EP-A-500 944 , EP-A-0 277 003 and EP-A-0 277 004 and US patents No.^you 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 fully incorporated herein by reference. Other activators include those described in PCT publication WO 98/07515 such as tris (2,2 ', 2 "-nonafluorobiphenyl) fluoroaluminate, which is fully incorporated herein by reference. Also contemplated by the invention are combinations of activators, eg, alumoxanes and ionizing activators in combinations, see eg, PCT publications WO 94/07928 and WO 95/14044 and US Patent Nos.^you 5,153,157 and 5,453,410 all of which are fully incorporated herein by reference. Also, activation procedures such as those using radiation and the like are contemplated as activators for the purposes of this invention.

IS 2 298 142 T3

When using two different catalysts, the first and second catalyst compounds can be combined in molar ratios of 1: 1000 to 1000: 1, preferably 1:99 to 99: 1, preferably 10:90 to 90:10, more preferably 20:80 at 80:20, more preferably 30:70 to 70:30, more preferably 40:60 to 60:40. The particular ratio chosen will depend on the desired end product and / or the activation procedure. A practical procedure to determine which ratio is best for obtaining the desired polymer is to start with a 1:11 ratio, measure the desired property in the product obtained, and adjust the ratio accordingly.

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

Bulky ligand metallocene-like compound

Bulky ligand metallocene-type compound (hereinafter also referred to as metallocenes) can also be used in the practice of this invention.

Generally, bulky ligand metallocene-type compounds include semi or fully sandwich compounds having one or more bulky ligands attached to at least one metal atom. Typically bulky ligand metallocene-type compounds are generally described as containing one or more bulky ligands and one or more leaving groups attached to at least one metal atom. In a preferred embodiment, at least one of the bulky ligands is η-bonded to the metal atom, most preferably η⁵-joined to the metal atom.

Bulky ligands are generally represented by one or more open, acyclic, or fused rings or ring systems, or a combination thereof. These bulky ligands, preferably rings and ring systems are typically composed of atoms that are selected from atoms in Groups 13 to 16 of the Periodic Table of the Elements, preferably the atoms are selected from the group consisting of carbon, nitrogen, oxygen, silicon, sulfur, phosphorus, germanium, boron, and aluminum or a combination thereof. Most preferably the rings or ring systems are composed of carbon atoms such as, but not limited to, cyclopentadienyl ligands or cyclopentadienyl-type ligand structures or other similarly functioning ligand structure such as a pentadienyl ligand. , a cyclooctatetraendiyl or an imide. The metal atom is preferably selected from Group 3 to 15 and the lanthanide and actinide series of the Periodic Table of the Elements. Preferably the metal is a Group 4 to 12 transition metal, more preferably Groups 4, 5 and 6, and most preferably the transition metal is Group 4.

In one embodiment, bulky ligand metallocene-type catalyst compounds are represented by the formula:

L^TOL^BMq_n (III) where M is a metal atom of the Periodic Table of the Elements and can be a metal of Group 3 to 12, or of the series of lanthanides and actinides of the Periodic Table of the Elements, preferably M is a metal of Group 4, 5 or 6 transition, more preferably M is a Group 4 transition metal, even more preferably M is zirconium hafnium or titanium. The bulky ligands, L^TO and L^B, are open, acyclic, or fused rings or ring systems and are any auxiliary ligand system, including cyclopentadienyl ligands or substituted or unsubstituted cyclopentadienyl-type ligands, substituted with heteroatoms and / or cyclopentadienyl-type ligands containing heteroatoms. Non-limiting examples of bulky ligands include cyclopentadienyl ligands, cyclopentaphenanthrenyl ligands, indenyl ligands, bencindenyl ligands, fluorenyl ligands, octahydrofluorenyl ligands, cyclooctatetraendiyl ligands, cyclopentacyclododecene ligands, azenylene ligands, , phosphoyl ligands, phosphinimine ligands (WO 99/40125), pyrrolyl ligands, pyrozolyl ligands, carbazolyl ligands, borabenzene ligands and the like, even hydrogenated versions thereof, for example tetrahydroindenyl ligands. In one embodiment, L^TO and L^B they can be any other ligand structure capable of forming η-bonds with M, preferably capable of forming η³-links with M and most preferably, capable of forming η⁵-links to M. In still another embodiment, the atomic molecular weight (MW) of L^TO and L^B exceeds 60 amu, preferably is greater than 65 amu In another embodiment, L^TO and L^B they may comprise 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 fused ring or ring system, for example a heterocyclopentadienyl auxiliary ligand . Other bulky ligands of L^TO and L^B They include, but are not limited to, amides, phosphides, alkoxides, aryloxides, imides, carbolides, borolides, porphyrins, phthalocyanines, corrins, and other polyazomacrocycles. Regardless, each L^TO and L^B may be of the same or a different type of bulky ligand that binds to M. In one embodiment of formula (III) only one of L is present^TO or L^B indistinctly.

Regardless, each L^TO and L^B may be substituted or unsubstituted with a combination of R substituent groups. Non-limiting examples of substituent groups R include one or more of the group selected from hydrogen, or linear or branched alkyl radicals, or 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, carbomoyl radicals, alkyl- or dialkyl radicals

ES 2 298 142 T3 carbamoyl, acyloxy radicals, acylamino radicals, aroylamino radicals, linear, branched or cyclic alkylene radicals, or combinations thereof. In a preferred embodiment, the R substituent groups have up to 50 non-hydrogen 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 substituents include methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, benzyl, or phenyl groups and the like, including all of their isomers, for example tertiary butyl, isopropyl, and the like. Other hydrocarbyl radicals include fluoromethyl, fluoroethyl, difluoroethyl, iodopropyl, bromohexyl, chlorobenzyl, and hydrocarbyl-substituted organometalloid radicals including trimethylsilyl, trimethylgermil, methyldiethylsilyl, and the like; and halocarbyl-substituted organometalloid radicals including tris (fluoromethyl) -silyl, methyl-bis (difluoromethyl) silyl, bromomethyldimethylgermil, and the like; and disubstituted boron radicals including dimethylboron for example; and disubstituted nitrogenid radicals including dimethylamine, dimethylphosphine, diphenylamine, methylphenylphosphine, amphigenic radicals including methoxy, ethoxy, propoxy, phenoxy, methylsulfide, and ethylsulfide. Non-hydrogen substituents R include carbon, silicon, boron, aluminum, nitrogen, phosphorus, oxygen, tin, sulfur, germanium, and the like, including olefins such as, but not limited to, olefinically unsaturated substituents including end-terminated ligands. vinyl, for example but-3-enyl, prop-2-enyl, hex-5-enyl and the like. In addition, at least two R groups, preferably two adjacent R groups, join together to form a ring structure having 3 to 30 carbon atoms selected from carbon, nitrogen, oxygen, phosphorus, silicon, germanium, aluminum, boron. or a combination thereof. Furthermore, a substituent group R, group such as 1-butanyl can form a sigma carbon bond with the metal M.

Other ligands can be attached to metal M, such as at least one leaving group Q. In one embodiment, Q is a labile monoanionic ligand that has a sigma bond to M. Depending on the oxidation state of the metal, the value for n is 0 , 1 or 2 such that formula (III) above represents a neutral bulky ligand metallocene-type catalyst compound.

Non-limiting examples of Q ligands include weak bases such as amines, phosphines, ethers, carboxylates, dienes, hydrocarbyl radicals having 1 to 20 carbon atoms, hydrides or halogens and the like or a combination thereof. In another embodiment, two or more Q's are part of a fused ring or ring system. Other examples of Q ligands include the R substituents as described above and include cyclobutyl, cyclohexyl, heptyl, tolyl, trifluoromethyl, tetramethylene, pentamethylene, methylidene, methoxy, ethoxy, propoxy, phenoxy, bis (N-methylanilide), dimethylamide radicals, dimethylphosphide and the like.

The two L groups can be bridged via group A as defined below.

In one embodiment, the bulky ligand metallocene-type catalyst compounds of the invention include those of formula (III) wherein L^TO and L^B are bridged together by at least one bridging group, A, such that the formula is represented by

L^TOTO THE^BMq_n (IV)

These bridged compounds which are represented by formula (IV) are known as bridged bulky ligand metallocene-type catalyst compounds. L^TO, L^B, M, Q and n are as defined above. Non-limiting examples of bridging group A include bridging groups containing at least one atom from Group 13 to 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, and tin or a combination thereof. Preferably the bridging group A contains a carbon, silicon or germanium atom, most preferably A contains at least one silicon atom or at least one carbon atom. The bridging group A may also contain substituent groups R as defined above which include halogens and iron. Non-limiting examples of bridging group A can be represented by R'2C, R'2Si, R'2Si R'2Ge, R'P, where R 'is independently, a radical group which is hydride, hydrocarbyl, substituted hydrocarbyl, halocarbyl, Substituted halocarbyl, hydrocarbyl substituted organometalloid, halocarbyl substituted organometalloid, disubstituted boron, disubstituted nitrogen, substituted antigen, or halogen or two or more R 'can be joined to form a ring or ring system. In one embodiment, the bridged bulky ligand metallocene-type catalyst compounds of formula (IV) have two or more bridging groups A (EP 664 301 B1).

In one embodiment, bulky ligand metallocene-type catalyst compounds are those in which the R substituents on the bulky L ligands^TO and L^B of formulas (III) and IV) are substituted with the same number or with a different number of substituents on each of the bulky ligands. In another embodiment, the bulky ligands L^TO and L^B of formulas (III) and IV) are different from each other.

Other bulky ligand metallocene-type catalyst compounds useful in the invention may include those described in US Patent Nos. No.^you 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, 5,858,903, 5,859,158, 5,900,517 and 5,939,503 and PCT publications WO 93/08221, WO 93/08199, 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 of which are fully incorporated herein by reference.

IS 2 298 142 T3

In one embodiment, bulky ligand metallocene-type catalyst compounds useful in the invention include heteroatom bridged mono-bulky ligand metallocene-type compounds. 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 in US Patent Nos.^you 5,057,475, 5,096,867, 5,055,438, 5,198,401, 5,227,440 and 5,264,405 and European publication EP-A-0 420 436, all of which are fully incorporated herein by reference.

In this embodiment, the bulky ligand metallocene-type catalyst compound is represented by the formula

LCAJMQn (V) where M is a metal atom of Group 3 to 16 or a metal that is selected from the Group of actinides and lanthanides of the Periodic Table of the Elements, preferably M is a transition metal of Groups 4 to 12 , and more preferably M is a Group 4, 5 or 6 transition metal, and most preferably M is a Group 4 transition metal in any oxidation state, especially titanium; L^C is a bulky substituted or unsubstituted ligand attached to M; J is linked to M; A is attached to M and J; J is a heteroatom helper ligand; and A is a bridging group; Q is a univalent anionic ligand; and n is an integer 0, 1 or 2. In formula (V) above L^C, A and J form a fused ring. In one embodiment, L^C of formula (V) is as defined above for L^TO, and A, M and Q of formula (V) are as defined above in formula (III).

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

In one embodiment of the invention, bulky ligand metallocene-type catalyst compounds are complexes of heterocyclic ligands in which the bulky ligands, the ring (s) or ring systems, include one or more heteroatoms or a combination 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 such bulky ligand metallocene catalyst compounds are disclosed in WO 96/33202, WO 96/34021, WO 97/17379 and WO 98/22486 and EP-A1-0 874 005 and US patents. N^you 5,637,660, 5,539,124, 5,554,775, 5,756,611, 5,233,049, 5,744,417, and 5,856,258, all of which are incorporated herein by reference.

In one embodiment, bulky ligand metallocene-type catalyst compounds are those complexes known as bidentate ligand-based transition metal catalysts containing pyridine or quinoline moieties, such as those described in US application No. Serial No. 09 / 103,620 filed June 23, 1998, which is incorporated herein by reference. In another embodiment, bulky ligand metallocene-type catalyst compounds are those described in PCT publications WO 99/01481 and WO 98/42664, which are fully incorporated herein by reference.

In a preferred embodiment, the bulky ligand metallocene-type catalyst compound is a complex of a metal, preferably a transition metal, a bulky ligand, preferably a substituted or unsubstituted pi-bond forming ligand, and one or more heteroalyl moieties , such as those described in US Patents No.^you 5,527,752 and 5,747,406 and EP-B1-0 735 057 all of which are fully incorporated herein by reference.

In a particularly preferred embodiment, the other metal compound or second metal compound is the bulky ligand metallocene-type catalyst compound which is represented by the formula

L^DMq₂(YZ) X_n (VI) where M is a Group 3 to 16 metal, preferably a Group 4 to 12 transition metal, and most preferably a Group 4, 5 or 6 transition metal; L^D it is a bulky ligand that binds to M; each Q is independently attached to M and Q₂(YZ) forms a ligand, preferably a uncharged polydentate ligand; A or Q is a univalent anionic ligand that also binds M; X is a univalent 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 indistinctly C or S; Z is selected from the group consisting of -OR, -Nr₂, -CR₃, -SR, -SiR₃, -PR₂, -H, and substituted or unsubstituted aryl groups, provided that when Q is -NR- then Z is selected from one of the groups consisting of -OR, -NR₂, -SR, -SiR₃, -PR₂, and -H; R is selected from a group containing carbon, silicon, nitrogen, oxygen and / or phosphorus, wherein preferably R is a hydrocarbon group containing from 1 to 20 carbon atoms, most preferably an alkyl, cycloalkyl, or aryl group ; n is an integer from 1 to 4,

ES 2 298 142 T3 preferably 1 or 2; X is a univalent anionic group when n is 2 or X is a divalent anionic group when n is 1; preferably X is a carbamate, carboxylate, or other heteroaryl moiety described by the combination of Q, Y, and Z.

Spray drying

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

Spray drying can be by any means known in the art. See, please, EPA 0 668 295 B1, US 5,674,795 and US 5,672,669 which particularly describe the spray drying of supported catalysts. In general, catalysts can be spray dried by placing the metal catalyst compound and activator in solution, allowing them to react, then adding a filler material such as silica or Cabosil.^®, then forcing the solution to pass at high pressures through a nozzle. The catalyst can be sprayed onto a surface or it can be sprayed so that the droplets dry in the air. The generally employed procedure is to disperse the silica in toluene, stir the activator solution, and then stir the catalyst precursor solution. Typical porridge concentrations are about 5-8% by weight. This formulation can remain as a slurry for 30 minutes with gentle shaking or manual shaking to keep it as a suspension prior to spray drying. In a preferred embodiment, the constitution of the dry material is about 40-50% activator, (preferably alumoxane), 50-60% SiO2, and about ~ 2% by weight metal catalyst compound.

For simple metal catalyst compound mixtures, the two or more metal catalyst compounds can be added together in the desired ratio in the last step. In another embodiment, more complex procedures are possible, such as adding a first metal catalyst compound to the charge / activator mixture for a specified reaction time t, followed by addition of the second metal catalyst compound solution, which is mix for another specified time x, after which the mix is ​​sprayed in a parallel stream. Lastly, another additive, such as 1-hexene at about 10% by volume, may be present in the activator / filler mixture prior to the addition of the first metal catalyst compound.

In another embodiment a bulky ligand metallocene-type compound and an optional activator can be combined with the spray-dried catalysts of this invention and then introduced into the reactor.

In another embodiment binders are added to the mixture. They can be added as a means of improving the morphology of the particles, that is, of narrowing the particle size distribution, lowering the porosity of the particles and allowing a reduction in the amount of alumoxane, which is acting as a "binder" .

Polymerization process of the invention

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

In one embodiment, this invention is directed to slurry or gas phase polymerization or copolymerization reactions involving the polymerization of one or more monomers having 2 to 30 carbon atoms, preferably 2-12 carbon atoms, and more preferably 2 to 8 carbon atoms. The invention is particularly well suited for copolymerization reactions involving the polymerization of one or more olefin 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 a combination thereof. Other monomers can include vinyl monomers, diolefins such as dienes, polyenes, norbornene, norbornadiene monomers. Preferably an ethylene copolymer is produced, in which the comonomer is at least one alpha-olefin having 4 to 15 carbon atoms, preferably 4 to 12 carbon atoms, more preferably 4 to 8 carbon atoms and so on. more preferably 4 to 7 carbon atoms. In an alternative embodiment, the geminally disubstituted olefins described in WO 98/37109 can be polymerized or copolymerized using the invention described herein.

In another embodiment, ethylene or propylene is polymerized with at least two different comonomers to form a tertpolymer. Preferred comonomers are a combination of alpha-olefin monomers having 4 to 10 carbon atoms, more preferably 4 to 8 carbon atoms, optionally with at least one diene monomer. Preferred tertpolymers include blends such as ethylene / butene-1 / hexene-1, ethylene / propylene / butene-1, propylene / ethylene / hexene-1, ethylene / propylene / norbornene, and the like.

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

IS 2 298 142 T3

Typically in a gas phase polymerization process a continuous cycle is employed in which in part of the cycle of a reactor system, a circulating gas stream, also known as a recycle stream or fluidizing medium, is heated in the reactor by means of the heat of polymerization. This heat is dissipated from the recycle composition in another part of the cycle through a cooling system external to the reactor. Generally, in a gaseous fluidized bed process for producing polymers, a gaseous stream containing one or more monomers is continuously circulated through a fluidized bed in the presence of a catalyst under reactive conditions. The gas stream is withdrawn from the fluidized bed and recirculated to the reactor. Simultaneously, polymer product is removed from the reactor and new monomer is added to replace the polymerized monomer. (See for example US patents No.^you 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 to this document for reference.)

The reactor pressure in a gas phase process can range from about 69 kPa to about 3448 kPa, preferably in the range of about 690 kPa to about 2759 kPa, preferably in the range of about 1379 kPa to about 2759 kPa, more preferably in the range from about 1724 kPa to about 2414 kPa.

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

The productivity of the catalyst or catalyst system is influenced by the partial pressure of the main monomer. The preferred mole percent of the major monomer, ethylene or propylene, preferably ethylene, is about 25 to 90 mole percent and the partial pressure of the monomer is in the range of about 517 kPa to about 2069 kPa, which are typical conditions in a process. gas phase polymerization.

In a preferred embodiment, the reactor used in the present invention and the process of the invention produce more than 227 kg of polymer per hour at approximately 90,900 kg / hr or more of polymer, preferably more than 455 kg / hr, more preferably more than 4540 kg / hr, even more preferably more than 11,300 kg / hr, still more preferably more than 15,900 kg / hr, even still more preferably more than 22,700 kg / hr and most preferably more than 29,000 kg / hr to more than 45,500 kg / hr.

Other gas phase processes contemplated by the process of the invention include those described in US Patents No.^you 5,627,242, 5,665,818 and 5,677,375, and European publications EP-A-0 794 200, EP-A-0 802 202 and EP-B-634 421 all of which are fully incorporated herein by reference.

A slurry polymerization process generally uses pressures in the range of about 101 kPa to 5066 kPa and even higher and temperatures in the range of 0 ° C to about 120 ° C. In a slurry polymerization, a suspension of solid, particulate polymer is formed in a liquid polymerization diluent medium to which ethylene and comonomers and often hydrogen are added along with catalyst. The suspension including diluent is intermittently or continuously withdrawn from the reactor where the volatile components are separated from the polymer and recycled, optionally after distillation, to the reactor. The liquid diluent employed in the polymerization medium is typically an alkane having 3 to 7 carbon atoms, preferably a branched alkane. The medium used should be liquid under the polymerization conditions and relatively inert. When using a propane medium the process has to be operated above the critical temperature and pressure of the reaction diluent. Preferably, a hexane or isobutane medium is used.

In one embodiment, a preferred polymerization technique of the invention is what is called particulate polymerization, or a slurry process in which the temperature is kept below the temperature at which the polymer goes into solution. Such a technique is well known in the art, and is described for example in US Patent No. 3,248,179 which is fully incorporated herein by reference. The preferred temperature in the particulate process is within the range of about 85 ° C to about 110 ° C. Two preferred polymerization processes for the slurry process are those that employ a recirculating reactor and those that use a plurality of stirred reactors in series, parallel, or combinations thereof. Non-limiting examples of slurry processes include continuous recirculation or stirred tank processes. In addition, other examples of slurry processes are described in US Patent No. 4,613,484, which is fully incorporated herein by reference.

In another embodiment, the slurry process is carried out continuously in a recirculating reactor. The catalyst, as an isobutane slurry or as a free-flowing dry powder, is regularly injected into the recirculation reactor, which is in turn filled with circulating slurry of growing polymer particles in an isobutane diluent containing monomer and comonomer. Optionally, hydrogen can be added as a molecular weight control. The reactor is maintained at a pressure of about 3620 kPa to 4309 kPa and at a temperature in the range of about 60 ° C to about 104 ° C depending on the desired polymer density. The heat of reaction is dissipated through the recirculation wall since most of the reactor is in the form of double-jacketed tubing. The slurry is allowed to drain out of the reactor at regular or

ES 2 298 142 T3 continuously to a low pressure hot flash tank, a rotary dryer and a nitrogen purge column in sequence for removal of the isobutane diluent and all unreacted monomer and comonomers. The resulting hydrocarbon-free powder is then conditioned for use in various applications.

In one embodiment the reactor that is used in the slurry process of the invention has capacity, and the process of the invention is producing, for more than 907 kg per hour, more preferably more than 2268 kg / hr, and most preferably more 4540 kg / hr. In another embodiment the slurry reactor used in the process of the invention is producing more than 6804 kg per hour of polymer, preferably more than 11,340 kg / hr at about 45,500 kg / hr.

In another embodiment in the slurry process of the invention the total pressure of the reactor is in the range of 2758 kPa to 5516 kPa, preferably 3103 kPa to about 4827 kPa, more preferably 3448 kPa to about 4482 kPa, most preferably about 3620 kPa to 4309 kPa.

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

A preferred process of the invention is the process, preferably a slurry or gas phase process, which is operated in the absence or essentially free of any scavenging agent, such as triethylaluminum, trimethylaluminum, tri-isobutylaluminum and tri-n-hexylaluminum and diethyl aluminum chloride, dibutylzinc, and the like. This preferred procedure is described in PCT publication WO 96/08520 and US Pat. No. 5,712,352, which are fully incorporated herein by reference.

In another preferred embodiment the catalyst or all catalysts are combined with up to 10% by weight of a metal stearate, (preferably an aluminum stearate, more preferably aluminum distearate) based on the weight of the catalyst, any support and the stearate, preferably 2 to 3% by weight. In an alternative embodiment, a metal stearate solution is supplied to the reactor. In another embodiment the metal stearate is mixed with the catalyst and supplied to the reactor separately. These agents can be mixed with the catalyst or they can be supplied to the reactor in a solution with or without the catalyst system or its components.

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

In a preferred embodiment the above-described catalyst system is used to make a polyethylene having a density between 0.88 and 0.970 g / cm³ (measured according to ASTM 2839), a melt index of 1.0 or less g / 10 min or less (measured according to ASTM D-1238, Condition E, at 190 ° C). Polyethylene having a melt index between 0.01 and 10 dg / min is preferably produced. In some embodiments, a density of 0.915 to 0.940 g / cm would be preferred.³ or less, in other embodiments densities of 0.930 to 0.960 g / cm are preferred³.

Polyolefins can be made into films, sheet molded articles, wire and cable coatings, and the like. Films can be formed by any conventional technique known in the art including extrusion, co-extrusion, lamination, blowing, and casting. The film can be obtained by the flat or tubular film process which can proceed by orientation in a uniaxial direction or in two mutually perpendicular directions in the plane of the film in the same amplitude or in different amplitudes. The orientation can be of the same amplitude in both directions or it can be of different amplitudes. Particularly preferred processes for forming the polymers into films include extrusion or coextrusion over a blown or cast film pipe.

The films produced may further contain additives such as glidants, antiblocks, antioxidants, pigments, fillers, antifogs, UV stabilizers, antistats, polymer processing aids, neutralizers, lubricants, surfactants, colorants 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 molecular weight resins, hydrocarbon resins, glass beads and the like. The additives may be present in typically effective amounts well known in the art, such as 0.001% by weight to 10% by weight.

This invention further relates to a panoply of a plurality of metal compounds that are represented by the above formula. These panoplies can then be used for simultaneous parallel screening of catalysts by combining the panoply with one or more olefins, preferably in order to determine the relative capacities of the different compounds.

IS 2 298 142 T3

Examples

Mn and Mw were measured by gel permeation chromatography with a Waters GPC instrument at 150 ° C fitted with differential refractive index detectors. The GPC columns were calibrated by passing a series of narrow polystyrene standards and molecular weights were calculated using Mark Houwink coefficients for the polymer in question.

Density was measured according to ASTM D 1505.

The Merger Indices (MI) I₂ and I₂₁ were measured according to ASTM D-1238, Condition E, at 190 ° C.

The Fusion Index Ratio (MIR) is the ratio of I₂₁ about I₂ as determined by ASTM D-1238.

Comonomer Weight% 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

Ligand preparation [(2,4,6-Me₃C₆H₂) NHCH₂CH₂]₂NH

A 2 L one-arm Schlenk flask was charged with a magnetic stir bar, diethylenetriamine (23.450 g, 0.227 mol), 2-bromomesitylene (90.51 g, 0.455 mol), tris (dibenzylideneacetone) dipaladium (1.041 g, 1, 14 mol), 2,2'bis (diphenylphosphino) -1,1'binaphthyl-racemic (racemic BINAP) (2.123 g, 3.41 mmol), sodium tert-butoxide (65.535 g, 0.682 mol), and toluene ( 800 mL) under dry oxygen-free nitrogen. The reaction mixture was stirred and heated to 100 ° C. After 18 h the reaction was terminated, as verified by proton NMR spectroscopy. All other manipulations can be done in the air. All solvent was removed in vacuo and the residues were dissolved in diethyl ether (1 L). The ether was washed with water (3X250 mL) followed by saturated aqueous NaCl (150 g in 500 mL) and dried over magnesium sulfate (30 g). Extraction of ether in vacuo gave a red oil which was dried at 70 ° C for 12 h in vacuo (yield: 71.10 g, 92%). NMR¹H (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

A 500 mL round bottom flask was charged with a magnetic stir bar, tetrabenzyl zirconium (Boulder Scientific) (41.729 g, 91.56 mmol), and 300 mL of toluene under dry oxygen-free nitrogen. Solid HN3 ligand (Example 1) (32.773 g, 96.52 mmol) was added with stirring for 1 minute (the desired compound precipitates). The slurry volume was reduced to 100 mL and 300 mL of pentane was added with stirring. The yellow-orange solid product was collected by filtration and dried under vacuum (44.811 g, 80% yield). NMR¹H (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 (s, 6), 2.41 (s, 6), 2.18 (s, 6), 1.89 (s, 2), 0.96 ( s, 2).

Example 3 (Preparation of Catalyst C)

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

A 250 mL round bottom flask was charged with a magnetic stir bar, tetrabenzyl hafnium (4.063 g, 7.482 mmol), and 150 mL of toluene under dry oxygen-free nitrogen. 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 slurry was reduced to 30 mL and 120 mL of pentane was added with stirring. The pale yellow solid product was collected by filtration and dried under vacuum (4.562 g, 87% yield). RmN¹H (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 darkened.

IS 2 298 142 T3

Example 4

Preparation of ligand l (2-methylnaifthyls) NHCH-_:CH-_:l-_:NH

A 1 L one-arm Schlenk flask was charged with a magnetic stir bar, diethylenetriamine (6.026 g, 58.41 mmol), 2-bromo-2-naphthylene (25.829 g, 116.8 mmol), tris (dibenzylidene-acetone ) dipalladium (0.268 g, 0.292 mmol), 2,2'-bis (diphenylphosphino) -1,1'binaphthyl-racemic (racemic BINAP) (0.547 g, 0.878 mmol), sodium tert-butoxide (16.90 g, 175.8 mmol), and toluene (400 mL) under dry oxygen-free nitrogen. The reaction mixture was stirred and heated to 100 ° C. After 18 h the reaction was terminated, as verified by proton NMR spectroscopy. All other manipulations can be done in the air. All solvent was removed in vacuo and the residues were dissolved in diethyl ether (500 mL). The ether was washed with water (3X100 mL) followed by saturated aqueous NaCl (90 g in 250 mL) and dried over magnesium sulfate (15 g). Extraction of ether in vacuo gave a red oil which was dried at 70 ° C for 12 h in vacuo (yield: 19.10 g, 85%). NMR¹H (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 (s, 6), 0.69 (quintet, 1).

Example 5 (Preparation of Catalyst C)

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

A 500 mL round bottom flask was charged with a magnetic stir bar, tetrabenzyl zirconium (Boulder Scientific) (3,000 g, 6.582 mmol), and 300 mL of toluene under dry oxygen-free nitrogen. HN3-2 ligand solution (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 slurry was reduced to 40 mL and 150 mL of pentane was added with stirring. The yellow-orange solid product was collected by filtration and dried under vacuum (3.060 g, 71% yield). The product is a mixture of four isomers resulting from the orientation of the 2-methylnaphthyl groups. NMR¹H (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 obscured.

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 quickly turned bright yellow. After stirring at room temperature for 3 hours, the volatiles were removed in vacuo to give a bright 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-butylsalicillimine (605 mg, 2.2 mmol) in 5 ml of toluene was added slowly 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 reddish brown solid. NMR¹H (C₆D₆) δ 8.07 (s, HC = N, 1H), 7.77 (d, J = 2.4 Hz, salicillimin), 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, NCHMeAMes), 0.52 (d, J = 6.6 Hz, 3H, XCI IMle.% / &lt;-,).

Catalyst 1

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

To 110 mL of toluene 5.0 g of Cabosil TS-610, dehydrated under vacuum above 100 ° C, were added. A solution of methyl alumoxane (26 mL of 20% by weight MAO in toluene) was added to this slurry. A catalyst precursor solution of 0.075 g of {[(2,4,6-Me₃C₆H₂) NCH₂CH₂]₂NH} ZrBz₂ in about 20 mL of toluene, and stirred / stirred for about 30 minutes. This mixture was spray dried in a Buchi Series 190 Mini Spray Drier, contained in a dry booth with an inert atmosphere. The following conditions were employed: 0.7 mm diameter spray nozzle cap, 0.5 mm mixing needle, nitrogen gas flow rate at 16.7 L / min for spray flow, one aspirator setting at 20, inlet temperature of 120 ° C, outlet temperature of 80 to 90 ° C, and supply of catalyst mixture of 0.6 L / hr. The collected solids totaled 6.55 g (68%). ICP analysis indicated 0.13% by weight of Zr and an Al: Zr ratio of 536: 1.

IS 2 298 142 T3

Catalyst 2

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

To 110 mL of toluene 5.0 g of Cabosil TS-610, dehydrated under vacuum above 100 ° C, were added. A solution of methyl alumoxane (26 mL of 20% by weight MAO in toluene) was added to this slurry. A catalyst precursor solution of 0.083 g of {[(2-Me-naphthyl) NCH was added to the slurry₂CH₂] 2NH} ZrBz₂ in about 20 mL of toluene, and stirred / stirred for about 30 minutes. This mixture was spray dried as before. The collected solids totaled 5.77 g (59%). ICP analysis indicated 0.15% by weight of Zr and an Al: Zr ratio of 458: 1.

Catalyst 3

Spray drying {[(2,4,6-Me₃ C₆H₂) NCH₂CH₂]₂NH} ZrBz₂

To 110 mL of toluene 4.0 g of Cabosil TS-610, dehydrated under vacuum above 100 ° C, were added. A solution of methyl alumoxane (26 mL of 20% by weight MAO in toluene) was added to this slurry. A catalyst precursor solution of 0.20 g of {[(2,4,6-Me₃C₆H₂) NCH₂CH₂]₂NH} ZrBz₂ in about 20 mL of toluene, and stirred / stirred for about 30 minutes. This mixture was spray dried as before. The collected solids totaled 5.18 g (58%). ICP analysis indicated 0.36% by weight of Zr and an Al: Zr ratio of 196: 1.

Catalyst 4

Spray drying {[(2,4,6-Me₃ C₆H₂) NCH₂CH₂]₂NH} HfBz₂

To 140 mL of toluene 4.6 g of Cabosil TS-610, dehydrated under vacuum above 100 ° C, were added. A solution of methyl alumoxane (20.8 mL of 20% by weight MAO in toluene) was added to this slurry. A catalyst precursor solution of 0.229 g of {[(2,4,6-Me₃C₆H₂) NCH₂CH₂]₂NH} HfBz₂ in about 20 mL of toluene, and stirred / stirred for about 30 minutes. This mixture was spray dried as before.

Catalyst 5

Spray drying {[(2,4,6-Me₃ C₆H₂) NCH₂CH₂]₂NH} ZrBz₂

To 280 mL of toluene, 12.4 g of Cabosil TS-610, dehydrated under vacuum above 100 ° C, were added. A solution of methyl alumoxane (57 mL of 20% by weight MAO in toluene) was added to this slurry. A catalyst precursor solution of 0.55 g of {[(2,4,6-Me₃C₆H₂) NCH₂CH₂]₂NH} ZrBz₂ in about 20 mL of toluene, and stirred / stirred for about 30 minutes. This mixture was spray dried as before. The collected solids totaled 13 g (56%). ICP analysis indicated 0.38% by weight of Zr and an Al: Zr ratio of 152: 1.

Catalyst 6

Spray drying {[(2,4,6-Me₃ C₆H₂) NCH₂CH₂]₂NH} HfBz₂

To 125 mL of toluene 6.0 g of Cabosil TS-610, dehydrated under vacuum above 100 ° C, were added. A solution of methyl alumoxane (27 mL of 20% by weight MAO in toluene) was added to this slurry. A catalyst precursor solution of 0.30 g of {[(2,4,6-Me₃C₆H₂) NCH₂CH₂]₂NH} HfBz₂ in about 20 mL of toluene, and stirred / stirred for about 30 minutes. This mixture was spray dried as before. The collected solids totaled 7.0 g (63%). ICP analysis indicated 0.72% by weight of Hf and an Al: Hf ratio of 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 under vacuum above 100 ° C, were added to 75 mL of toluene. A solution of methyl alumoxane (12.4 mL of 20% by weight MAO in toluene) was added to this slurry. A catalyst precursor solution of 0.168 g of {[ortho-3,5-di-t-Bu- (C₆H₂) (O) CH = NCHMe2]₂} Zr (CH₂Ph)₂ in about 20 mL of toluene, and stirred / stirred for about 30 minutes. This mixture was spray dried as before.

Catalyst 8

Spray drying {[(2,4,6-Me₃ C₆H₂) NCH₂CH₂]₂NH} ZrBz₂ and (nC₃H₇-C₅H₄)(I₅C) ZrCl₂1:1

To 110 mL of toluene 4.0 g of Cabosil TS-610, dehydrated under vacuum above 100 ° C, were added. A solution of methyl alumoxane (26 mL of 20% by weight MAO in toluene) was added to this slurry. A catalyst precursor solution of 0.10 g of {[(2,4,6-Me₃C₆H₂) NCH₂CH₂]₂NH} ZrBz₂ and 0.067 g of (nC₃H₇15

IS 2 298 142 T3

C₅H₄)(I₅C) ZrCl₂ in about 20 mL of toluene, and stirred / stirred for about 30 minutes. This mixture was spray dried as before. The collected solids totaled 5.31 g (60%). ICP analysis indicated 0.37% by weight of Zr and an Al: Zr ratio of 202: 1.

Catalyst 9

Spray drying {[(2,4,6-Me₃C₆H₂) NCH₂CH₂]₂NH} ZrBz₂ and (nC₃H₇-C₅H₄)₂ZrCl₂1:1

To 110 mL of toluene 4.0 g of Cabosil TS-610, dehydrated under vacuum above 100 ° C, were added. A solution of methyl alumoxane (26 mL of 20% by weight MAO in toluene) was added to this slurry. A catalyst precursor solution of 0.10 g of {[(2,4,6-Me₃C₆H₂) NCH₂CH₂]₂NH} ZrBz₂ and 0.056 g of (nC₃H₇C₅H₄)₂ZrCl₂ in about 20 mL of toluene, and stirred / stirred for about 30 minutes. This mixture was spray dried as before.

Catalyst 10

Spray drying {[(2,4,6-Me₃C₆H₂) NCH₂CH₂]₂NH} ZrBz₂ and (nC₃H₇-C₅H₄)₂ZrCl₂ 3,4:1

To 540 mL of toluene, 21.4 g of Cabosil TS-610, dehydrated under vacuum above 100 ° C, were added. A solution of methyl alumoxane (97 mL of 20% by weight MAO in toluene) was added to this slurry. A catalyst precursor solution of 0.80 g of {[(2,4,6-Me₃C₆H₂) NCH₂CH₂]₂NH} ZrBz₂ and 0.143 g of (nC₃H₇-C₅H₄)₂ZrCl₂ in about 60 mL of toluene, and stirred / stirred for about 30 minutes. This mixture was spray dried as before. The collected solids totaled 21 g (53%). ICP analysis indicated 0.44% by weight of Zr and an Al: Zr ratio of 128.

Catalyst 11

Spray drying {[(2,4,6-Me₃C₆H₂) NCH₂CH₂]₂NH} ZrBz₂ and (nC₃H₇-C₅H₄)₂ZrCl₂ 5:1

To 570 mL of toluene, 25.8 g of Cabosil TS-610, dehydrated under vacuum above 100 ° C, were added. A solution of methyl alumoxane (116 mL of 20% by weight MAO in toluene) was added to this slurry. A catalyst precursor solution of 0.93 g of {[(2,4,6-Me₃C₆H₂) NCH₂CH₂]₂NH} ZrBz₂ and 0.114 g of (nC₃H₇-C₅H₄)₂ZrCl₂ in about 40 mL of toluene, and stirred / stirred for about 30 minutes. This mixture was spray dried as before. The collected solids totaled 29 g (60%). ICP analysis indicated 0.39% by weight of Zr and an Al: Zr ratio of 156.

Catalyst 12

Spray drying {[(2,4,6-Me₃C₆H₂) NCH₂CH₂]₂NH} HfBz₂ and (nC₃H₇-C₅H₄)₂ZrCl₂ 5:1

To 570 mL of toluene, 25.8 g of Cabosil TS-610, dehydrated under vacuum above 100 ° C, were added. A solution of methyl alumoxane (116 mL of 20% by weight MAO in toluene) was added to this slurry. A catalyst precursor solution of 0.96 g of {[(2,4,6-Me₃C₆H₂) NCH₂CH₂]₂NH} HfBz₂ and 0.17 g of (nC₃H₇-C₅H₄)₂ZrCl₂ in about 40 mL of toluene, and stirred / stirred for about 30 minutes. This mixture was spray dried as before. The collected solids totaled 32 g (67%). ICP analysis indicated 0.51 wt% Hf, 0.094 wt% Zr and an Al: M ratio of 161.

Polymerization Examples 1-15

Polymerizations were carried out in a slurry reactor as follows. After a period of heating with degassing and subsequent cooling under nitrogen, 490 cm³ of hexanes to a 1 L autoclave reactor. Before heating, hexene, if applicable, and 0.17 cm³ 0.87 mmolar triisobutylaluminum in heptane as scavenger, and hydrogen, if applicable. The contents of the reactor were heated to the desired temperature. Spray dried catalyst was added to a 10 cm pump³ which was connected to a 20 cm pump³ to which 10 cm were added³ of hexanes. Each bomb was pressurized with nitrogen before coupling to the reactor. The spray dried catalyst was injected under pressure into the reactor, immediately followed by the release of the hexanes. In this way, a quantitative contribution could be ensured. The system was immediately filled with ethylene and this was supplied on demand thereafter. Polymerizations were carried out for 30 minutes.

Comparative polymerizations

The reactor was set up and charged with hexane, hexene, hydrogen, and scavenger as above. The following preparation for Comparative 1 is general: A 2.1 mg stock solution of {[(2,4,6-Me₃C₆H₂) NCH₂CH₂]₂NH} ZrBz₂ dissolved in 4.5 cm³ of toluene. A 0.50 cm aliquot was removed³ and was added to 0.50 cm³ 0.5M methyl alumoxane (MAO) in toluene. The solutions were mixed for approximately five minutes prior to injection into the desired reactor, after which ethylene was immediately introduced and supplied on demand thereafter. All polymerizations were carried out for 30 minutes.

The data are summarized in the following table.

IS 2 298 142 T3

<img file="ES2298142T3_D0004.tif" />

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<td>Γ-</td><td>CN</td><td>in</td><td>T-</td><td> 00</td><td>CN</td><td>CO</td><td></td><td>co_</td><td>CO_</td><td>xt</td><td>CD</td><td>in</td>

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<td>'t</td><td>CO</td><td>CN</td><td>CN</td><td>CN</td><td></td><td>T—</td><td></td><td>CN</td><td>CN</td><td>t—</td><td>CN</td><td>CN</td>

<td> 00</td><td>OR</td><td>OR</td><td> 00</td><td>or</td><td></td><td></td><td>or</td><td>or</td><td>or</td><td>or</td><td>or</td><td>or</td><td>or</td><td> 00</td><td> 00</td>

<td>CO</td><td>IO</td><td>IT</td><td>co</td><td>IT</td><td>co</td><td>or</td><td>IT</td><td>IT</td><td>IT</td><td>IT</td><td>IT</td><td>IT</td><td>IT</td><td>co</td><td>co</td>

<td>or</td><td>or</td><td>or</td><td>or</td><td>or'</td><td>CN</td><td>co</td><td>or</td><td>or</td><td>or</td><td>or</td><td>or</td><td>or</td><td>or</td><td>or</td><td>or</td>

<td>or</td><td>T— T— X— χ— χ— 04</td><td>CN</td><td>CO</td><td>co</td><td>CO</td><td> 00</td><td> 00</td><td>CO</td><td>in</td><td> &lt;</td><td> &lt;</td><td>CQ</td><td></td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>φ</td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>Τ-</td><td>CN</td><td>co</td><td>ro</td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>Ο.</td><td>former</td><td>or.</td><td>O. Ό</td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>AND</td><td>AND</td><td>AND</td><td>Ε Έ</td>

<td></td><td></td><td></td><td></td><td>or</td><td>χ—</td><td>CN</td><td>CO</td><td>Tj-</td><td>IT</td><td>, Q</td><td>or</td><td>or</td><td>or ZD</td>

<td>LU</td><td>T- 04 CO Tt IO CD N.</td><td> 00</td><td>σ&gt;</td><td></td><td>t—</td><td></td><td>τ—</td><td></td><td></td><td>OR</td><td>OR</td><td>OR</td><td>Or -</td>

IS 2 298 142 T3

Polymerization Examples 16-21

After appropriate heating with degassing of a side stirred 4L gas phase laboratory reactor and cooling under nitrogen, the reactor was charged with Davison 955-600 silica as the starting bed. Before heating to 85 ° C hydrogen, 1-hexene and scavenger were added to the reactor. Hydrogen was charged by filling a 50 cm bomb³ at 1.03 MPa with 5% H₂/ N₂ and discharging it into the reactor at a pressure slightly above ambient. The spray dried catalyst was injected into the reactor using the same device that was used for injecting catalyst into the slurry reactor. Immediately after catalyst injection, ethylene was fed to the reactor and supplied on demand for the remainder of the experiment. The partial pressure of ethylene was 0.69 MPa.

Comparative polymerizations

Supported catalysts were tested identically to the above. Catalysts in solution were injected in the same way as for slurry polymerizations.

The data are summarized in the following table.

<td>Ahem-</td><td>catalyst/</td><td>umol</td><td>Al / M</td><td>h₂</td><td>TIBA</td><td>C6</td><td>silica</td><td>PE 9</td><td>weather</td>

<td>plo</td><td>precursor</td><td>M</td><td></td><td></td><td>ml_</td><td>ml_</td><td> 9</td><td></td><td>min</td>

<td> 16</td><td> 4</td><td> 4,0</td><td></td><td>any</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>any</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 = {[(2₁4.6-Me₃C6H₂) NCH₂CH2] 2NH} HfBz2 injected as activated MAO solution. C '= {[(2₁4,6-Me3C6H2) NCH₂CH2] 2NH} HfBz2 supported on Davison 948 silica, 0.38 umol Hf / g, AI / Hf = 120.

D = [ortho-3,5-di-t-Bu- (C₆H₂) (O) CH = NCHMe2] 2Zr (CH2Ph) 2 injected as activated MAO solution.

Polymerization Examples 22-28

Polymerization procedure

In Comparative 9 and Examples 22 to 28, polyethylene was prepared in a stirred bed horizontal mixing reactor with various catalyst compositions. The table below summarizes the polymerization conditions for each example.

Figure 1 depicts the horizontal mixing reactor system used in Comparative 9 and Examples 22 to 28. The reactor was a two phase (gas / solid) stirred bed return mixing reactor. A system of four "plows" 100 was mounted horizontally on a central shaft rotating at 180 rpm to keep the particles mechanically fluidized in reactor 110. The reactor cylinder swept by these four plows was 46 cm long by 39.7 cm in diameter, resulting in a mechanically fluidizable volume of 46 liters. The gas volume, greater than the mechanically fluidizable volume due to the vertical cylindrical chamber, totaled 54.6 liters.

IS 2 298 142 T3

The reactor pressure in all examples was 2.4 MPa. Ethylene monomer, hexene comonomer and hydrogen (for molecular weight control) were continuously supplied to the reactor via control valves through line 120. The partial pressure of the ethylene monomer was 1.5 MPa. The comonomer content in the polyethylene product was controlled by adjusting the feed rates to maintain a constant comonomer / monomer molar ratio (shown in the Table) in the gas phase. The gas composition was measured at 1-4 minute intervals by a chromatographic analyzer. The molecular weight of the polyethylene was controlled by adjusting the hydrogen supply rate to maintain a constant hydrogen to monomer molar ratio in the gas phase. Nitrogen made up the majority of the gas composition equilibrium in the reactor, entering with the catalyst composition through line 130 and exiting via a small vent 140 with the reactor gases that included volatilized solvents. The vent opening was adjusted by computer to keep the total pressure in the reactor constant.

The reactor was cooled by an outer jacket of cold glycol. The temperature of the bed was measured with a thermometer probe 150 in a thermowell protruding into the bed at an angle of 60 ° above the horizontal, between the inner set of plows. The temperature in Comparative 9 was 85 ° C, while the reactor temperature in Examples 22 to 28 was 80 ° C.

For Comparative 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 metered in pulses via line 160 and mixed with a continuous stream of modified methyl aluminoxane cocatalyst solution which was introduced via line 170. The concentration of Akzo type 3A MMAO 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 and MMAO solutions was supplied through a coil. 180 of 0.32 cm tube in which the catalyst and cocatalyst reacted for about 4 minutes. After exiting this pre-contact coil, the mixed catalyst composition solution was sprayed into the reactor by a constant flow of nitrogen from line 130.

For Examples 22 to 28, a spray dried catalyst slurry was prepared by mixing the catalyst powder with light mineral oil, and the resulting slurry was stored in a stirred tank connected to line 160. The catalyst slurry was metered in pulses via line 160 and mixed with a continuous stream of modified methyl aluminoxane cocatalyst solution which was introduced via line 170. For these examples, coil 180 was replaced with a straight piece of 0.32 cm OD tubing approximately 10.2 cm long. The Akzo type 3A MMAO concentration in isopentane was 2.1% and the MMAO solution delivery rate was kept fixed at approximately 50 mL / hr. The mixture of catalyst and MMAO solution was supplied to the reactor via a 0.32 cm OD injection tube using a constant flow of nitrogen to disperse the mixture.

The reactor was run in both batch and continuous modes. Typical batch yields of granular polyethylene in the reactor were 3.2-9.1 kg. Each experiment typically lasted 3-6 hours. In continuous mode, granular polymer was removed at valve 190 typically in 0.2 kg portions while polymerization proceeded. In continuous mode, the product discharge system was activated after the bed weight accumulated 5.4-9.1 kg, and the discharge flow was changed to keep the bed weight constant based on what was calculated by balance of materials.

In all of Comparative 9 and Examples 22-28, the polymerization process began by charging the monomers to the reactor and adjusting the supplies until the desired gas composition was achieved. An initial charge of cocatalyst was added prior to the start of catalyst delivery in order to flush out any poisons present in the reactor. After the catalyst feed was started, the monomers were added to the reactor in amounts sufficient to maintain the gas concentrations and ratios. As catalyst stocks accumulated, the polyethylene production rate increased to 2.3-4.5 kg / hr, at which point the catalyst supply was adjusted to maintain a constant polyethylene production rate. For Comparative 9, the cocatalyst feed rate was kept in proportion to the catalyst feed rate. After the desired batch weight was made, the reactor was rapidly vented, and the monomers were purged from the polyethylene resin with nitrogen. The batch was then discharged through valve 190 to open atmosphere.

IS 2 298 142 T3

<td>example</td><td>catalyst</td><td>temp (° C)</td><td>H2 / C2</td><td>C6 / C2</td><td>rend. pound</td><td>rend. kg</td><td>Ml dg / min</td><td>FI dg / min</td><td>density g / cm³</td>

<td>Comp 9</td><td>TO</td><td> 85</td><td> 0,0015</td><td> 0,0057</td><td> 6,6</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> 15,9</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> 36,7</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> 37,9</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> 27,7</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> 6,6</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> 15,9</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> 36,7</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 injected as activated MAO solution.

Indenyl zirconium tris pivalate which had been spray dried as described herein produced polymer, but had low activity.

All documents described herein are incorporated by reference into this document, including priority documents and / or test procedures. As is apparent from the foregoing general description and specific embodiments, as well as from the forms of the invention that have been illustrated and described, various modifications can be made without departing from the spirit and scope of the invention. Accordingly, the invention is not intended to be so limited.