JP2001517714A - Modified aluminoxane catalyst activator - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a catalyst activator useful for activating a metal complex of a Group 3-10 metal for the polymerization of an ethylenically unsaturated polymerizable monomer, preferably an olefin. The present invention provides a composition comprising a mixture of aluminum containing Lewis acids, the mixture has the ^{formula: [(- AlQ 1 -O-)} z (-AlAr f -O-) z '] (Ar f z "Al ₂ Q ¹ _{6-z ")} wherein Q ¹ is selected from C _1-20 alkyl independently in each case; the Ar ^f is a fluorinated aromatic hydrocarbyl group having carbon atoms of 6-30; z is 1 -50, preferably 1.5-40, more and is preferably a number from 2-30, and the group (-AlQ ¹ -O-) is a cyclic or linear oligomer with a repeat unit of 2-30; z 'it is 1-50, preferably 1.5-40, more preferably an number of 2-30, and the group (-AlAr ^f -O-) in the cyclic or linear oligomers having repeating units of 2-30 there; z "is a number from 0-6, and the group _{^{(Ar f z" Al 2 Q}} 1 6-z ") Which is either tri (fluoroarylaluminum), trialkylaluminum, or an adduct of tri (fluoroarylaluminum) with a less than stoichiometric to greater than stoichiometric amount of trialkylaluminum. I do.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD OF THE INVENTION

The present invention relates to compounds useful as catalyst activator components. More specifically, the present invention relates to those compounds which are particularly suitable for use in the polymerization of unsaturated compounds with improved activation efficiency and performance. These compounds are particularly effective for use in polymerization processes in which a catalyst, a catalyst activator and at least one polymerizable monomer are combined under polymerization conditions to produce a polymerization product.

[0002]

[Prior art]

It is already known in the art to activate a Ziegler-Natta polymerization catalyst, in particular a Group 3-10 metal complex containing a delocalized π-linked ligand group, with an activator. In general, little or no polymerization activity is observed without these activators, also called cocatalysts. A suitable class of activators are alumoxanes or alkylalumoxanes, which are generally said to be oligomeric or polymeric alkylaluminoxy compounds, including cyclic oligomers. One skilled in the art understands that the exact chemical structure of individual alumoxane molecules, including methylalumoxane, is not well characterized. The structure of methylalumoxane appears to consist of interchangeable linear chains, cyclic rings or polyhedra in solution. Generally, these compounds have an average of about 1.5 alkyls per aluminum atom and are made by reacting a tetraalkylaluminum compound or a mixture thereof with water (Redd
y et al., Prog. Poly. Sci. , 1995, 20, 309-367). The product is in fact a mixture of various substituted aluminum compounds, in particular containing trialkylaluminum compounds. The amount of these free trialkylaluminum compounds in the mixture is usually 1-50% by weight of the total composition. Examples of aluminoxanes include methylalumoxane (MAO) made by hydrolysis of trimethylaluminum and modified methylalumoxane (MMAO) made by hydrolysis of a mixture of trimethylaluminum and triisobutylaluminum. MMA
O is effective in that it is more soluble in aliphatic solvents than MAO.

[0003] A different type of activator is the Bronsted acid salt, which is capable of transferring a proton to the active derivative after other catalysis of a cationic derivative or a Group 3-10 metal complex. Preferred Bronsted acid salts are those having a cation / anion pair that can activate the Group 3-10 metal complex after catalysis. Preferred activators are those comprising a fluorinated aryl borate anion, most preferably a tetrakis (pentafluorophenyl) borate anion. Further preferred anions include US-A-5
, 447, 895:

[0004]

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Wherein S is hydrogen, alkyl, fluoroalkyl, aryl or fluoroaryl, Ar ^F is fluoroaryl, and X ¹ is either hydrogen or halide. There is a boron anion.

Examples of preferred charge separation (cation / anion pair) activators include US-A-
5,198,401, US-A-5,132,380, US-A-5,470,
927 and U.S. Pat. No. 5,153,157, and protonated ammonium, sulfonium or phosphonium salts capable of transferring hydrogen ions, and U
SA-5,350,723, US-A-5,189,192 and US-A-5
Oxidizing salts such as the salts of carbonium, ferrocenium and silylium disclosed in U.S. Pat.

[0007] Further preferred activators of the above metal complexes include (trisperfluorophenyl)
There are strong Lewis acids including borane and tris (perfluorobiphenyl) borane and the like. The former composition is disclosed in EP-A-520,732 and others for the above-mentioned end uses, while the latter composition is disclosed in Marks et al. Am. Chem. Soc
. , 118, 12451-12452 (1996). Further disclosure regarding the former activator can be found in the following publications: Chen et al. Am. Chem. Soc. 1997, 119, 2582-2
583, Jia et al., Organometallics, 1997, 16, 842.
-857, and Coles et al. Am. Chem. Soc. 1997, 119
, 8126-8126. Both the salts and Lewis acid activators described above are based on perfluorophenyl substituted boron compounds. Although the amounts of these activators used are very small, the residual boron and fluorinated benzene valuables remaining in the polymer can have a significant effect on the properties of the final polymer, such as applications requiring high dielectric properties.

In US-A-5,453,410, alumoxanes, especially methylalumoxane, are used in combination with a cationic constrained geometry metal complex, preferably in a molar ratio of metal complex to alumoxane of 1: 1-1: 50. It is disclosed. This combination results in improved polymerization efficiency. Similarly, US-A-5, 527, 929, U
SA-5,616,664, US-A-5,470,993, US-A-5
556,928, US-A-5,624,878 discloses that various combinations of a metal complex and a trispentafluorophenylboron cocatalyst and optionally an alumoxane are used as catalyst compositions for olefin polymerization. ing.

[0009]

[Problems to be solved by the invention]

While the catalyst activators described above exhibit satisfactory performance under various polymerization conditions, there is still a need for improved cocatalysts for use in activating various metal complexes under various reaction conditions. In particular, it is desirable to remove boron-containing contaminants from these activator compositions. These boron-containing contaminants mainly result from ligand exchange with alumoxanes and have trialkylboron compounds having 1-4 carbons in each alkyl group, such as trimethylboron, triisobutylboron or mixed trialkylboron products. . It would be desirable to provide a compound that can be used in solution, suspension, gas phase or high pressure polymerizations, can be used under homogeneous or heterogeneous conditions, has improved activation performance, and lacks trialkylboron species. It is known that the exchange reaction between an aluminum trialkyl compound and tris (pentafluorophenyl) borane occurs under certain conditions. This phenomenon is US-
A-5,602,269.

[0010]

[Means for Solving the Problems]

The present invention has the ^{formula: R 1 - (AlR 3 O} ) m -R 2 where R ¹ is in each case independently with C _1-40 aliphatic or aromatic group or a fluorinated derivative thereof; R ² is each or when independently a C _1-40 aliphatic or aromatic group or a fluorinated derivative, or in the case of cyclic oligomers wherein R ¹ and R ² forms a covalent bond together; R ³ is In each case independently a monovalent fluorinated organic group having 1-100 carbon atoms or R ¹ , but at least one R ³ per molecule is a monovalent fluorinated organic group having 1-100 carbon atoms. And m is a number from 1-1000, providing a novel composition having a fluorohydrocarbyl-substituted alumoxane corresponding to

The composition can be present in the form of a mixture of compounds of the above formula and also as a mixture with a trihydrocarbyl aluminum compound. It can also be present in the form of linear chains, cyclic rings or polyhedra that are compatible in solution. Further, the present invention also provides a catalyst composition for polymerizing an ethylenically unsaturated polymerizable monomer, comprising a combination of the above-mentioned combination with a Group 3-10 metal complex or a reaction product obtained from the combination. The present invention further provides one or more addition polymerizable monomers, optionally with an inert aliphatic,
There is also provided a polymerization method comprising contacting the catalyst composition or a supported derivative thereof in the presence of an alicyclic or aromatic hydrocarbon.

[0012] Finally, the invention also provides a composition comprising a reaction product of alumoxane and BAr ^f _3: where Ar ^f is a fluorinated aromatic group carbon atoms of 6-30; the reaction step is an alkyl the alumoxane and BAr ^f _3, and removing the at least a portion of and volatile byproducts are contacted ligand exchange conditions. The above combinations can be effectively used in the activation of various metal complexes, preferably Group 4 metal complexes, under standard and non-standard olefin polymerization conditions. In particular, the polymerization of Group 4 metal complexes and olefins having one or more cyclopentadienyl groups (including their substituted, polycyclic and partially hydrogenated derivatives), especially for use in polymerization under gas phase polymerization conditions. It is effectively used in polymerization processes in combination with an inert carrier to make a catalyst.

All citations to the Periodic Table of the Elements herein are incorporated by reference in CRC pres.
s, and copyrighted periodic table. Also, all citations about the tribe are the tribes shown in this periodic table using the IUPAC system for counting tribes.

The catalyst activator of the present invention combines an alkylalumoxane, which may also contain residual amounts of a trialkylaluminum compound, with a source of a fluoroaryl ligand, preferably a strong Lewis acid containing a fluoroaryl ligand, If desired, it can be easily prepared by removing by-products produced by ligand exchange. This reaction can be performed in or without a solvent or diluent. It is preferably carried out without them or with a solution as concentrated as possible where long reaction times are possible. The intimate contact of the raw reactants removes the volatile components from the reactant solution under reduced pressure to form a solid mixture of the reactants, optionally intermediate and desired final exchange products, and then optionally warming This is preferably performed by continuing the contact below. A preferred fluoroaryl ligand source is trifluoroarylboron, most preferably tris (), which provides a relatively volatile triarylborane exchange product that is easily removed from the reaction mixture.
(Pentafluorophenyl) boron or more preferably a trifluoroarylaluminum compound. Standard processes for the preparation of alkylalumoxanes, such as the reaction of a trialkylaluminum compound with water, are useful for industrially converting trifluoroarylaluminum compounds, especially tris (pentafluoro) phenylaluminum, from thermal instability and reactivity, ie, explosive properties. It is not directly possible to make the compositions according to the invention under analytical conditions.

The reactants can be combined in a suitable aliphatic, cycloaliphatic or aromatic liquid diluent or mixtures thereof. Preferred diluents are C _6-8 aliphatic and cycloaliphatic hydrocarbons and mixtures thereof, such as hexane, heptane, cyclohexane, or mixed fractions such as Isopar ^™ E available from Exxon Chemical Company. Preferably, however, the reactants are mixed without diluent. That is, the raw reactants are simply combined and heated. Preferred contact times are at least 1 hour, preferably at least 90
Minutes, the temperature is at least 25 ° C, preferably at least 30 ° C, most preferably at least 35 ° C. In order to suppress the formation of further derivatives having low catalytic performance or multiple metal exchange products, it is also preferable to carry out the contact before adding a metal complex catalyst such as metallocene. After contacting the alkylalumoxane with the fluoroaryl ligand source, the reaction mixture is preferably purified by any suitable method to remove ligand exchange products, especially trialkylboron compounds. Or the effectiveness is not great, but 1
The Group 3 metal complex catalyst may be first combined with the reaction mixture prior to removal of residual ligand exchange products. It is easily understood by those skilled in the art that the degree of fluoroaryl substitution of aluminoxane can be controlled in a wide range by the reaction conditions. Thus, low degrees of fluoroaryl substitution can be achieved using low temperatures, solvents and short contact times. Conversely, high degrees of substitution can be achieved by raw reactants, long reaction times, high temperatures and dynamic removal of volatile by-products under vacuum. By appropriately selecting the reaction conditions, a fluoroaryl-substituted aluminoxane having a wide range of properties can be produced, so that a design corresponding to various uses becomes possible.

Suitable techniques for removing transalkylation by-products from the reaction mixture include degassing, if desired under reduced pressure, distillation, solution exchange, solvent extraction, extraction with volatile agents, contact with zeolites or molecular sieves, and the like. There are combinations. The amount and nature of the residual boron-containing exchange by-product in the product can be determined by ¹¹ B NMR analysis. Preferably, the amount of residual trialkylboron exchange product is no more than 10% by weight, more preferably no more than 1.0% by weight, and most preferably no more than 0.1% by weight, based on the fluorohydrocarbyl-substituted alumoxane compound.

As mentioned above, the product contains a fluorinated organic substituted aluminoxy compound.
More specifically the product in can be defined as a mixture of aluminum containing Lewis acids, the mixture has the ^{formula: [(- AlQ 1 -O-)} z (-AlAr f -O
^{_{-) z '] (Ar f}} z "Al 2 Q 1 6-z") wherein Q ¹ is selected from C _1-20 alkyl independently in each case; Ar ^f is fluorine having carbon atoms of 6-30 is aromatic hydrocarbyl group; z is 1-50, preferably 1.5-40, more preferably a number from 2-30, and the group (-AlQ ¹ -O-) 2-30 of the repeating unit It is a cyclic or linear oligomer with a; z 'is 1-50, preferably 1.5-40, more preferably a number from 2-30, and the group (-AlAr ^f -O-) 2-30 is a cyclic or linear oligomer with a repeat unit; z "is a number from 0-6, and the group _{^{(Ar f z" Al 2 Q}} 1 6-z ") are tri (fluoroaryl aluminum), trialkyl Aluminum or tri (fluoroarylaluminum) and less than stoichiometric It is either an adduct of higher amounts of trialkylaluminum stoichiometric amount from the stomach content, which corresponds to.

[0018] group ^{_{(Ar f z "Al 2 Q}} 1 6-z") may be present as a separate product or dynamic exchange products. That is, the above-mentioned groups may be present in dimeric or other multi-center products in combination with metal complexes resulting from partial or complete ligand exchange, especially when combined with other compounds such as metallocenes. . These exchange products have variable properties, the concentration of which depends on time, temperature, solution concentration and the presence of other species capable of stabilizing the compound, thereby preventing or indicating further ligand exchange. . Preferably z ″ is 1-5, more preferably 1-3.

Preferred compositions of the present invention are those wherein Ar ^f is pentafluorophenyl and Q ¹ is C _1-4 alkyl. The most preferred compositions of the present invention are those wherein Ar ^f is pentafluorophenyl and Q ¹ is in each case methyl, isopropyl or isobutyl.

The compositions of the present invention are highly active cocatalysts for use in activating metal complexes for olefin polymerization, particularly Group 4 metallocenes. In these uses, it is preferable to use a homogeneous catalyst activator, particularly for use in solution polymerization, at a concentration diluted with a hydrocarbon liquid, especially an aliphatic hydrocarbon liquid. The composition of the present invention may also be deposited on an inert support, preferably a particulate metal oxide or polymer, together with the metal complex to be activated according to known methods to form a supported olefin polymerization catalyst which is then subjected to gas phase or suspension polymerization. Can be used.

When used as a catalyst activator, the ratio of metal complex to activator composition is preferably 0.1: 1-3: 1, more preferably 0.2: 3, based on the metal content of each component. 1-
2: 1, most preferably 0.25: 1-1: 1. The molar ratio of the metal complex to the polymerizable compound used in most polymerization reactions is 10 ^-12 : ^{1 -10 -1} : 1, more preferably 10 ^-12 : 1 ^{-10 -5} : 1.

The reactants used in the manufacture and use of the composition of the present invention, in particular the alumoxane reactant and the support (if used), are preferably before use, preferably at 200-500 ° C., optionally under reduced pressure, for 10 minutes to 100 hours. Should be dried well. This reduces the amount of residual aluminum trialkyl in the alumoxane as much as possible.

The support for the activator component is an inert particulate material, most suitably a metal oxide or a mixture thereof, preferably an alumina, silica, aluminosilicate or clay material. A suitable volume average particle size of the support is 1-1000 μM, preferably 10-100 μM. The most preferred support is calcined silica, which can be treated prior to use by reaction with silanes, trialkylaluminum or other reactive compounds to reduce hydroxyl groups on the surface.
Examples of the method of supporting the composition of the present invention on the surface of a support (including the gaps) include dispersing a cocatalyst in a liquid and contacting the support as a slurry, impregnating, spraying, or coating; Thereafter, the liquid may be removed, or the cocatalyst and the support material may be combined in a dry or paste form to bring the mixture into intimate contact and then form a dried granular product. In a preferred embodiment, the silica is tri (C _1-10 alkyl) aluminum, especially trimethylaluminum, triethylaluminum, triisopropylaluminum or triisobutylaluminum and aluminum 0.1-100.
More preferably in an amount of 0.2-10 mmol / g of silica, followed by a supported cocatalyst containing 0.1-1000, preferably 1-500 μmol / g of silica, of activator. Contact with a sufficient amount of the above activator composition or a solution thereof. The activated catalyst composition is then made by adding the metal complex to be activated or a mixture thereof to the surface of the support.

Examples of metal complexes suitable for use in combination with the cocatalysts described above include those of metals of groups 3-10 of the Periodic Table of the Elements that can be activated to polymerize monomers, especially olefins, by the activators of the present invention. It is an appropriate complex. These examples have the formula:

[0025]

Embedded image

M ^* is Ni (II) or Pd (II); X ′ is halogen, hydrocarbyl or hydrocarbyloxy; Ar ^* is an aryl group, particularly preferably a 2,6-diisopropylphenyl or aniline group. ; CT-CT is 1,2-ethanediyl, forms a fused ring system 2,3-butanediyl or two T groups are taken together form 1,8-naphthalene-diyl group; and a ^- Is the anionic component of the charge-separated activator described above.

Complexes similar to those described above are described in M.E. Brookhart et al. Am. Chem. So
c. , 118, 267-268 (1996); Am. Chem. Soc.
, 117, 6414-6415 (1995), which are especially described as active polymerization catalysts for the homopolymerization of α-olefins or their copolymerization with polar comonomers such as vinyl chloride, alkyl acrylates and alkyl methacrylates. ing.

Examples of further complexes include 3, 4 having 1-3 π-linked anionic or neutral ligand groups, which may be cyclic or acyclic delocalized π-linked anionic ligand groups.
Or a derivative of a lanthanide group metal. Examples of these π-bonded anionic ligand groups include conjugated or non-conjugated cyclic or non-cyclic dienyl groups, allyl groups, boratabenzene groups, and arene groups. Here, “π-bonded” means that the ligand group is bonded to the transition metal by sharing electrons from the partially localized π-bond.

Each atom of the delocalized π-bonded group is independently selected from the group consisting of hydrogen, halogen, hydrocarbyl, halohydrocarbyl, and hydrocarbyl substituted metalloid groups (metalloids are selected from Group 14 of the Periodic Table of the Elements). Group. And the above-mentioned hydrocarbyl- or hydrocarbyl-substituted metalloid group may be further substituted with a group 15 or 16 group hetero atom-containing group. Here, “hydrocarbyl” includes C _1-20 linear or branched and cyclic alkyl groups, C _6-20 aromatic groups, C _7-20 alkyl-substituted aromatic groups and C _7-20 aryl-substituted alkyl groups. Groups are included. Also, two or more of these groups may together form a fused ring system, including a partially or completely fused ring system, or may form a metallocycle with the metal. . Examples of preferred hydrocarbyl-substituted organic metalloid groups include mono-, di- and tri-substituted organic metalloid groups of Group 14 elements, where each hydrocarbyl group is 1-
(Having 20 carbon atoms). Specific examples of preferred hydrocarbyl-substituted organic metalloid groups include trimethylsilyl, triethylsilyl, ethyldimethylsilyl, methyldiethylsilyl, triphenylgermyl and trimethylgermyl groups. Examples of groups 15 or 16 heteroatom-containing groups include amine, phosphine, ether or thioether groups or divalent derivatives thereof, such as those bonded to the transition metal or lanthanide metal, and to hydrocarbyl groups or hydrocarbyl-substituted metalloid containing groups. There is an amide, phosphide, ether or thioether group attached to the attached group.

Examples of preferred anionic delocalized π-linking groups include cyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl, tetrahydrofluorenyl, octahydrofluorenyl, pentadienyl, cyclohexadienyl, There are dihydroanthracenyl, hexahydroanthracenyl, decahydroanthracenyl groups, and borabenzene groups, as well as C _1-10 hydrocarbyl-substituted or C _1-10 hydrocarbyl-substituted silyl-substituted derivatives thereof. Preferred anionic delocalized π-linking groups are cyclopentadienyl, pentamethylcyclopentadienyl, tetramethylcyclopentadienyl, tetramethylsilylcyclopentadienyl, indenyl, 2,3-dimethylindenyl, Fluorenyl, 2-methylindenyl, 2-methyl-4-phenylindenyl, tetrahydrofluorenyl, octahydrofluorenyl and tetrahydroindenyl.

Boratabenzene is the anionic ligand of the boron-containing homolog of benzene.
They are known and are described in Organometalli by Herberich et al.
cs, 1995, 14, 1, 471-480. Preferred boratabenzenes have the formula:

[0032]

Embedded image

Wherein R ″ is selected from the group consisting of hydrocarbyl, silyl or germyl, and said R ″ has no more than 20 non-hydrogen atoms. In complexes involving divalent derivatives of these delocalized π-bonded groups, one atom is bonded to another atom of the complex by a covalent or covalently bonded divalent group, thereby forming a bridged system. Has formed.

Suitable metal complexes for use in the catalyst of the present invention are any suitable transition metals, including lanthanides, preferably 3,4 in +2, +3 or +4 formal oxidation state meeting the above requirements.
Derivatives of group metals or lanthanide metals. Examples of preferred compounds include 1-3 π, which can be cyclic or acyclic, delocalized π-linked anionic ligand groups.
A metal complex (metallocene) having a bound anionic ligand group. Examples of these π-linked anionic ligand groups include conjugated or non-conjugated, cyclic or acyclic dienyl, allyl and allene groups. “Π-bonded” means that the ligand group is bonded to the transition metal by the delocalized electron present in the π bond.

Each atom in the delocalized π-bonded group is independently a group selected from the group consisting of hydrogen, halogen, hydrocarbyl, and hydrocarbyl-substituted metalloid group (metalloid is selected from Group 14 of the Periodic Table of the Elements). Can be replaced. Here, “hydrocarbyl” includes C _1-20 linear or branched and cyclic alkyl groups, C _6-20 aromatic groups, C _7-20 alkyl-substituted aromatic groups and C _7-20 aryl-substituted alkyl groups. Groups are included. Also, two or more of these groups may together form a fused ring system, including a partially or completely fused ring system, or may form a metallocycle with the metal. . Examples of preferred hydrocarbyl-substituted organic metalloid groups include mono-, di- and tri-substituted organic metalloid groups of Group 14 elements, where each hydrocarbyl group is 1-
(Having 20 carbon atoms). Specific examples of preferred hydrocarbyl-substituted organic metalloid groups include trimethylsilyl, triethylsilyl, ethyldimethylsilyl, methyldiethylsilyl, triphenylgermyl and trimethylgermyl groups.

Examples of preferred anionic delocalized π-linking groups include cyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl, tetrahydrofluorenyl, octahydrofluorenyl, pentadienyl, cyclohexadienyl , Dihydroanthracenyl, hexahydroanthracenyl, decahydroanthracenyl groups, and borabenzene groups, as well as C _1-10 hydrocarbyl-substituted or C _1-10 hydrocarbyl-substituted silyl-substituted derivatives thereof. Preferred anionic delocalized π-linking groups are cyclopentadienyl, pentamethylcyclopentadienyl, tetramethylcyclopentadienyl, tetramethylsilylcyclopentadienyl, indenyl, 2,3-dimethylindenyl, Fluorenyl, 2-methylindenyl, 2-methyl-4-phenylindenyl, tetrahydrofluorenyl,
Octahydrofluorenyl and tetrahydroindenyl.

More preferred is a metal complex corresponding to the formula: L ₁ MX _m X ′ _n X ″ _p or 2
Wherein L is an anionic delocalized π-bonded group having no more than 50 non-hydrogen atoms attached to M, optionally wherein two L groups are one or more substituents May form a bridged structure together, and if desired, one L
May be attached to X via one or more substituents of L; M is +2, +3 or +
X is any divalent substituent having no more than 50 non-hydrogen atoms which together with L forms a metallocycle with M; X 'is any neutral Lewis base with up to 20 non-hydrogen atoms; X "
Is a monovalent anionic group having up to 40 non-hydrogen atoms in each case, and the two X ″ groups are covalently linked together to form a divalent dianionic group having both valences bonded to M Or may form a neutral conjugated or non-conjugated diene π-bonded to M, wherein M is in the +2 oxidation state, or, if desired, one or more X
"And one or more X 'groups together may be divalently linked to M and form a group which is coordinated thereto by a Lewis base function; l is 1 or 2
M is 0 or 1; n is a number from 0-3; p is an integer from 0-3; and the sum of l + m + p equals M formal oxidation states.

Some of these preferred complexes have one or more L groups. 2 for the latter complex
Some have a bridging group connecting two L groups. Preferred bridging groups have the formula: (ER ^* _Two )_x Is equivalent to: where R^* Are independently hydrogen or silicon in each case.
Selected from ril, hydrocarbyl, hydrocarbyloxy and combinations thereof
R "has up to 30 carbon or silicon atoms and x is 1-8
is there. Preferably R^* Are each independently methyl, benzyl, tertiary butyl
Or phenyl.

As an example of the above bis (L) -containing complex, the formula:

[0040]

Embedded image

Where M is titanium, zirconium or hafnium, preferably zirconium or hafnium, in the +2, +3 or +4 type oxidation state; R ³ is independently in each case hydrogen, hydrocarbyl, silyl, germyl, cyano, selected from halogen and combinations thereof, and said R ³ is 20
X or X having the following non-hydrogen atoms or together with adjacent R ³ groups may form a divalent derivative (ie, a hydrocarbadiyl, siladiyl or germadiyl group), thereby forming a ring system; "Is independently in each case an anionic ligand group having no more than 40 non-hydrogen atoms, or two X" groups taken together form a divalent anionic ligand group having no more than 40 non-hydrogen atoms. And may form together or together form a conjugated diene having 4-30 non-hydrogen atoms to form a π-complex with M (M is a +2 formal oxidation state); and R ^* , E and x is as defined above.

Examples of bridged ligands having two π-linking groups include:
(Dimethylsilyl-bis-cyclopentadienyl), (dimethylsilyl-bis-
Methylcyclopentadienyl), (dimethylsilyl-bis-ethylcyclopentadienyl), (dimethylsilyl-bis-t-butylcyclopentadienyl), (
Dimethylsilyl-bis-tetramethylcyclopentadienyl), (dimethylsilyl-bis-indenyl), (dimethylsilyl-bis-tetrahydroindenyl)
, (Dimethylsilyl-bis-fluorenyl), (dimethylsilyl-bis-tetrahydrofluorenyl), (dimethylsilyl-bis-2-methyl-4-phenylindenyl), (dimethylsilyl-bis-2-methylindenyl) ), (Dimethylsilyl-cyclopentadienyl-fluorenyl), (1,1,2,2-tetramethyl-1,2-disilyl-bis-cyclopentadienyl), (1,2-bis (cyclopentadienyl) Enyl) ethane) and (isopropylidene-cyclopentadienyl-
Fluorenyl).

Preferred X ″ groups are selected from hydride, hydrocarbyl, silyl, germyl, halohydrocarbyl, halosilyl, silylhydrocarbyl and aminohydrocarbyl groups, or two X ″ groups taken together to form a divalent divalent conjugated diene. Derivatives are formed or neutral π-bonded conjugated dienes are formed. Most preferred X "groups are _C1-20 hydrocarbyl groups.

Yet another class of metal complexes used in the present invention are those corresponding to the formula L _l MX _m X ′ _n X ″ _p or a dimer thereof: where L is bound to M An anionic delocalized π-bonded group having the following non-hydrogen atoms; M is a Group 4 metal of the Periodic Table of the Elements in +2, +3 or +4 formal oxidation state; X 'is a divalent substituent having 50 or less non-hydrogen atoms forming a metallocycle;
Any neutral Lewis base ligand having no more than 0 non-hydrogen atoms; X "is a monovalent anionic group having in each case no more than 20 non-hydrogen atoms, optionally 2
X "groups may be covalently linked together to form a divalent anionic group having both valences bonded to M or a neutral _C5-10 conjugated diene, and further optionally, X ' X
"Together may form a group which is divalently bonded to M and which is coordinated thereto by a Lewis base function; l is 1 or 2; m is 1; n is a number from 0-3; p is an integer from 0-2; and the sum of l + m + p equals M formal oxidation states.

Examples of preferred divalent X substituents include oxygen, sulfur, boron or at least one atom which is a member of Group 14 of the Periodic Table of Elements and M directly bonded to a delocalized π-linking group. There is a group containing up to 30 non-hydrogen atoms with another atom selected from the group consisting of nitrogen, phosphorus, oxygen or sulfur covalently bonded. A preferred class of Group 4 metal coordination complexes for use in the present invention include those of the formula:

[0046]

Embedded image

There is a complex corresponding to: wherein M is titanium or zirconium in the +2 or +4 type oxidation state; R ³ is in each case independently hydrogen, hydrocarbyl, silyl,
Wherein R ³ has no more than 20 non-hydrogen atoms, or adjacent R ³ groups taken together are divalent derivatives (ie, hydrocarbadiyl, A siladiyl or gelaziyl group), thereby forming a ring system; each X ″ is halogen, hydrocarbyl,
A hydrocarbyloxy or silyl group, and the group has no more than 20 non-hydrogen atoms, or two X ″ groups together form a C _5-30 conjugated diene; -, -S-, -NR "-, -PR"-; and Z is SiR ^* ₂ , CR ^* ₂ , SiR ^* ₂ SiR ^* ₂ , CR ^* ₂ CR ^* ₂ , CR ^* = CR ^* , C
R ^* ₂ SiR ^* _2, or a GeR ^* _2, wherein R ^* is as defined above.

Examples of Group 4 metal complexes that can be used in the practice of the invention include: cyclopentadienyl titanium trimethyl, cyclopentadienyl titanium triethyl, cyclopentadienyl titanium triisopropyl, cyclopentadienyl Titanium triphenyl, cyclopentadienyl titanium tribenzyl, cyclopentadienyl titanium-2,4-pentadienyl, cyclopentadienyl titanium dimethyl methoxide, cyclopentadienyl titanium methyl chloride, pentamethylcyclopentadienyl titanium trimethyl, Indenyl titanium trimethyl, indenyl titanium triethyl, indenyl titanium triisopropyl, indenyl titanium triphenyl, tetrahydroindenyl titanium tribenzyl, pentamethylcyclopentadienyl titanium Li isopropyl, pentamethylcyclopentadienyl titanium tribenzyl, pentamethylcyclopentadienyltitanium dimethyl methoxide,
Pentamethylcyclopentadienyltitanium dimethyl chloride, (η ⁵ -2,4-
Dimethyl-1,3-pentadienyl) titanium trimethyl, octahydrofluorenyltitanium trimethyl, tetrahydroindenyltitanium trimethyl, tetrahydrofluorenyltitanium trimethyl, (1,1-dimethyl-2,3,4,9,10)
-Η-1,4,5,6,7,8-hexahydronaphthalenyl) titanium trimethyl, (1,1,2,3-tetramethyl-2,3,4,9,10-η-1, 4,5,
6,7,8-hexahydronaphthalenyl) titanium trimethyl, (t-butylamido) (tetramethyl-η ⁵ -cyclopentadienyl) dimethylsilanetitanium dichloride, (t-butylamido) (tetramethyl-η ⁵ -cyclo Pentadienyl)
Dimethylsilanetitanium dimethyl, (t-butylamide) (tetramethyl-η ⁵ −
Cyclopentadienyl) -1,2-ethanediyltitanium dimethyl, (t-butylamide) (hexamethyl-η ⁵ -indenyl) dimethylsilanetitanium dimethyl,
(T-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) dimethylsilanetitanium (III) 2- (dimethylamido) benzyl, (t-butylamido)
(Tetramethyl-η ⁵ -cyclopentadienyl) dimethylsilanetitanium (III)
Allyl, (t-butylamido) (tetramethyl-eta ⁵ - cyclopentadienyl)
Dimethylsilanetitanium (II) 1,4-diphenyl-1,3-butadiene, (t-
Butylamido) (2-methylindenyl) dimethylsilanetitanium (II) 1,4-
Diphenyl-1,3-butadiene, (t-butylamido) (2-methylindenyl) dimethylsilanetitanium (IV) 1,3-butadiene, (t-butylamido) (
2,3-dimethylindenyl) dimethylsilanetitanium (II) 1,4-diphenyl-1,3-butadiene, (t-butylamide) (2,3-dimethylindenyl)
Dimethylsilanetitanium (IV) 1,3-butadiene, (t-butylamide) (2
3-dimethylindenyl) dimethylsilanetitanium (II) 1,3-pentadiene,
(T-butylamido) (2-methylindenyl) silanetitanium (II) 1,3-pentadiene, (t-butylamido) (2-methylindenyl) dimethylsilanetitanium (IV) dimethyl, (t-butylamido) (2 -Methyl-4-phenylindenyl) dimethylsilanetitanium (II) 1,4-diphenyl-1,3-butadiene;
(T-butylamido) (tetramethyl-eta ⁵ - cyclopentadienyl) dimethylsilane titanium (IV) 1,3-butadiene, (t-butylamido) (tetramethyl-eta ⁵ - cyclopentadienyl) dimethylsilane titanium ( II) 1,4-dibenzyl-1,3-butadiene, (t-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) dimethylsilanetitanium (II) 2,4-hexadiene, (t-butylamide) (tetra Methyl-η ⁵ -cyclopentadienyl) dimethylsilanetitanium (II) 3-methyl-1,3-pentadiene, (t-butylamide) (2,4
-Dimethyl-1,3-pentadien-2-yl) dimethylsilanetitanium dimethyl, (t-butylamide) (1,1-dimethyl-2,3,4,9,10-η-1,
4,5,6,7,8-Hexahydronaphthalen-4-yl) dimethylsilanetitanium dimethyl, (t-butylamide) (1,1,2,3-tetramethyl-2,3
4,9,10-η-1,4,5,6,7,8-hexahydronaphthalen-4-yl) dimethylsilanetitanium dimethyl, (t-butylamido) (tetramethylcyclopentadienyl) dimethylsilanetitanium 1 , 3-pentadiene, (t-butylamido) (2-methyl-S-intersen-1-yl) dimethylsilanetitanium 1,
3-pentadiene and (t-butylamido) (3,4-cyclopenta (1) phenanthren-2-yl) dimethylsilanetitanium 1,4-diphenyl-1,3-butadiene.

Examples of bis (L) -containing complexes containing bridged complexes suitable for use in the present invention include: biscyclopentadienyl zirconium dimethyl, biscyclopentadienyl titanium diethyl, biscyclo Pentadienyl titanium diisopropyl, biscyclopentadienyl titanium diphenyl, biscyclopentadiethyl zirconium dibenzyl, biscyclopentadienyl titanium-2,4-pentadienyl, biscyclopentadienyl titanium methyl methoxide, biscyclopentadienyl Titanium methyl chloride, bispentamethylcyclopentadienyltitaniumdimethyl, bisindenyltitaniumdimethyl, indenylfluorenyltitaniumdiethyl, bisindenyltitaniummethyl (2- (dimethylamino) benzyl),
Bisindenyl titanium methyltrimethylsilyl, bistetrahydroindenyl titanium methyltrimethylsilyl, bispentamethylcyclopentadienyl titanium diisopropyl, bispentamethylcyclopentadienyl titanium dibenzyl, bispentamethylcyclopentadienyl titanium methyl methoxide, bispenta Methylcyclopentadienyl titanium methyl chloride, (dimethylsilyl-bis-cyclopentadienyl) zirconium dimethyl, (dimethylsilyl-bis-pentamethylcyclopentadienyl) titanium-2,4-pentadienyl), (dimethylsilyl-bis -T-butylcyclopentadienyl) zirconium dichloride, (methylene-bis-pentamethylcyclopentadienyl) titanium (III) 2- (dimethylamino) benzyl, (Dimethylsilyl-bis-indenyl) zirconium dichloride, (dimethylsilyl-bis-2-methylindenyl) zirconium dimethyl, (dimethylsilyl-bis-2-methyl-4-phenylindenyl) zirconium methyl, (dimethylsilyl-bis -2-methylindenyl) zirconium-
1,4-diphenyl-1,3-butadiene, (dimethylsilyl-bis-2-methyl-4-phenylindenyl) zirconium (II) 1,4-diphenyl-1,3
-Butadiene, (dimethylsilyl-bis-tetrahydroindenyl) zirconium (II) 1,4-diphenyl-1,3-butadiene, (dimethylsilyl-bis-
(Fluorenyl) zirconium dichloride, (dimethylsilyl-bis-tetrahydrofluorenyl) zirconium di (trimethylsilyl), (isopropylidene)
(Cyclopentadiethyl) (fluorenyl) zirconiumindenyl and (dimethylsilylpentamethylcyclopentadienylfluorenyl) zirconiumdimethyl.

Examples of polymerizable monomers that can be used include ethylenically unsaturated monomers, acetylenic compounds, conjugated or non-conjugated dienes and polyenes. Preferred monomers include olefins, for example α-olefins having 2 to 20,000, preferably 2 to 20, more preferably 2 to 8 carbon atoms and combinations of two or more of these α-olefins. Examples of particularly preferred α-olefins are ethylene, propylene,
1-butene, 1-pentene, 4-methylpentene-1, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene , 1-pentadecene or a combination thereof,
Furthermore, long-chain vinyl-terminated oligomeric or polymeric reaction products formed during the polymerization, and C _10-30 α-olefins specially added to the reaction mixture to form relatively long branches in the resulting polymer There is. More preferred α-olefins are ethylene, propene, 1-butene, 4-methyl-pentene-1, 1-hexene,
-A combination of octene and ethylene and / or propene with one or more other α-olefins. Other preferred monomers include styrene, halogen- or alkyl-substituted styrene, tetrafluoroethylene, vinylcyclobutene, 1,4-hexadiene, dicyclopentadiene, ethylidene norbornene, and 1,7-octadiene. Mixtures of the above monomers may also be used.

In general, the polymerization can be carried out under well-known conditions in a Ziegler-Natta or Kaminskysin type polymerization reaction. The conditions of these known polymerization processes are described in WO 88/02009,
US-A-5,084,534; 5,405,922; 4,588,790; 5
4,032,652; 4,543,399; 4,564,647; 4,522,9
87, etc. The preferred polymerization temperature is 0-250 ° C. The preferred polymerization pressure is atmospheric-3000 atm.

[0052] A molecular weight controller may be used with the cocatalyst of the present invention. Examples of these molecular weight controlling agents include hydrogen, silane or other known chain transfer agents. A great advantage of the cocatalysts of the present invention is that homopolymers and copolymers of α-olefins having a narrow molecular weight distribution can be used.
It is obtained with significantly improved cocatalyst efficiency and purity, especially with respect to residual aluminum-containing contaminants. The preferred polymer is 2.5
It has Mw / Mn of 2.3 or less, more preferably 2.3 or less. Polymer products having these narrow molecular weight distributions are particularly desirable in that they have improved tensile strength properties.

Polymerization of C _2-6 olefins, especially homopolymerization and copolymerization of ethylene and propylene, and ethylene and C _3-6 α-olefins such as 1-butene, 1-hexene,
Gas phase methods for copolymerization of 4-methyl-pentene 1 and the like are well known. These methods are used industrially on a large scale for the production of high density polyethylene (HDPE), medium density polyethylene (MDPE), linear low density polyethylene (LLDPE) and polypropylene.

Examples of the gas phase method used include a type using a mechanically stirred bed or a gas fluidized bed as a polymerization reaction bed. In particular, a method in which polymerization is carried out in a vertical cylindrical polymerization reactor having a fluidized bed of polymer particles in which a polymerization reaction is supported on a plate having apertures by a flowing gas stream is used.

The bed fluidizing gas consists of the monomers to be polymerized and also serves as a heat exchange medium for removing the heat of reaction from the bed. Hot gas exits the top of the reactor through a stabilization zone, also known as a velocity reduction zone, where fine particles, usually larger in diameter than the fluidized bed and suspended in the gas stream, return to the bed under their own weight. . The use of cyclones to remove ultrafine particles from the hot gas stream is also desirable. The gas is then circulated to the bed, usually by a blower or compressor and a heat exchanger to remove the heat of polymerization from the gas.

In addition to the cooling provided by the cooled recycle gas, a preferred method of cooling the bed is to provide a volatile liquid to the bed to provide a cooling effect by evaporation. Examples of volatile liquids used in this case are volatile inert liquids, for example saturated hydrocarbons having 3-8, preferably 4-6, carbon atoms. If the monomers or comonomers themselves are volatile or condense into these liquids, they can be fed to the bed to provide an evaporative cooling effect. Examples of olefin monomers that can be used in this way include olefins having 3-8, preferably 3-6, carbon atoms. These volatile liquids evaporate in the hot fluidized bed to form a gas that mixes with the fluidizing gas.
If the volatile liquids are monomers or comonomers, they polymerize to some extent in the bed. The evaporated liquid then exits the reactor as part of the heat recycle gas and enters the recycle loop compression / heat exchange section. The recycle gas is cooled in a heat exchanger and liquid precipitates out of the gas if the temperature at which the gas is cooled is below the dew point. Preferably, the liquid is continuously circulated through the fluidized bed.

It is also possible to recycle the precipitated liquid to the bed as droplets associated with the recycle gas stream, which is described in EP-A-89691, US-A-4543399.
, WO 94/25495 and US-A-5352747. A particularly preferred method of circulating liquid to the bed is to separate the liquid from the recycle gas stream and
Preferably, it is a method in which fine droplets are generated in the bed, and the liquid is directly re-injected into the bed. A method of this type is disclosed in WO 94/28032. The polymerization taking place in the gas fluidized bed is catalyzed by the continuous or semi-continuous addition of the catalyst. The catalyst may be subjected to a prepolymerization step, for example, by polymerizing a small amount of an olefin monomer in a liquid inert diluent, to form a catalyst composite composed of catalyst particles embedded in olefin polymer particles. .

Monomer catalyst (co) on fluidized particles of catalyst, supported catalyst or prepolymer in bed
By conducting the polymerization, the polymer is made directly in the fluidized bed. The initiation of the polymerization reaction can be carried out using a bed of preformed polymer particles. The polymer particles are preferably similar to the target polyolefin and operate in a catalyst, monomer and other appropriate gas which is desirably included in the recycle gas stream, such as a diluent gas, a hydrogen chain transfer agent or a gas phase condensation mode. The bed is conditioned by drying with an inert gas or nitrogen before introducing the inert condensable gas at the time of the process. The resulting polymer is discharged continuously or discontinuously from the fluidized bed as desired, optionally exposed to a catalyst deactivator, and optionally pelletized.

Similarly, a supported catalyst used in suspension polymerization can be prepared by a known method. In general,
These catalysts can be made using the same techniques used to make the supported catalysts used in gas phase polymerization. Suspension polymerization conditions are generally those in which C _2-20 olefins, diolefins, cycloolefins or mixtures thereof are polymerized in an aliphatic solvent at a temperature below the temperature at which the polymer can be readily dissolved in the presence of a supported catalyst. Include.

The present invention can be carried out in the absence of any suitable components not disclosed herein. The following examples are intended to illustrate, but not limit, the invention. Parts and percentages are by weight unless otherwise specified. “Room temperature” means 20-25 ° C., “one night”
It refers to 12-18 hours and, refers to an aliphatic solvent Isopar ^(R) E, commercially available from Exxon Chemical Company as "mixed alkene".

[0061]

【Example】

Example: Tris (perfluorophenyl) borane (FAB) was applied to Boulder Sci.
Obtained as a solid from entific Inc and used without further purification. A heptane solution of modified metaalumoxane (MMAO-3A) was purchased from Akzo-Nobel. MAO in toluene and trimethylaluminum (TMA) in toluene were purchased from Aldrich Chemical Co. A toluene solution of tris (perfluorophenyl) aluminum (FAAL) was prepared by an exchange reaction between tris (perfluorophenyl) borane and trimethylaluminum. All solvents were purchased from Organometallics, Pangborn et al., 1996,15.
, 1518-1520. All compounds and solutions were handled under an inert atmosphere (dry box).

Example 1: Preparation of pentafluorophenyl-exchanged aluminoxane: Tris (pentafluorophenyl) borane (0.015M) mixed hexane (
Isoper ^(R) E, 5 mL) solution was added to MMAO-3A (5 mL of mixed hexane).
. (Diluted to 05M). The resulting solution was stirred and then the solvent was removed under vacuum. The residue was left at 25 ° C. for about 2 hours. This residue was then dissolved in 5 mL of toluene to obtain a solution of pentafluorophenyl-exchanged aluminoxane. Elemental analysis of this solution indicated 1000 ppm Al, 3600 ppm F, and 31 ppm B. This analysis shows that a molar ratio of F / Al = 5.1 and 83 mol% of boron were removed from the mixture as volatile trialkylborane compounds.

Example 2 Preparation of a Pentafluorophenyl-Exchanged Aluminoxane ^: Example 1 was repeated except that the residue after degassing and aging was dissolved in a mixed alkene (Isoper® E).

[0064] Polymerization: was introduced a gallon of computer control was stirred autoclave at about 1450g mixed alkanes solvent ^{(Isopar (R)} E) and about 125 g 1-octene.
10 mmol of H ₂ was added as a molecular weight control agent. The mixture was stirred at 130 ° C
Heated. This solution was saturated with ethylene at 450 psig (3.4 MPa). [(Tetramethylcyclopentadienyl) dimethylsilyl-N-t-butylamide] titanium (II) (1,3-pentadiene) (0.005 in mixed alkane)
M) and tris (pentafluorophenyl) borane (0.1 in mixed alkanes).
015M) and MMAO-3A (0.5M in mixed alkanes) without solvent degassing or aging (comparison); MMAO-3A alone (comparison); or Example 1 or Example 2 (
A catalyst / cocatalyst solution was made by combining any solution of pentafluorophenyl-exchanged alumoxane from the present invention). The catalyst solution was added to the reactor using a pump. The reactor temperature was determined by controlling the temperature of the reactor jacket. After a polymerization time of 10 minutes, the resulting solution was transferred from the reactor to a nitrogen purged collection vessel. After cooling, the container was taken out into the air and a solution of the phosphorus-containing antioxidant and the hindered phenol stabilizer was added. This stabilizing solution is commercially available from Iva (commercially available from Ciba-Gaiky).
6.67 g of RGAPHOS ^(TM) 168, 3.33 g of IRGANOX ^(TM) 1010 ⁽ commercially available from Ciba-Gaiky ⁾ and 500 mL of toluene were combined. The solvent was removed under reduced pressure in a vacuum oven for 2 days to recover the polymer. Table 1 shows the reaction conditions. Table 2 shows the polymer property data.

[0065]

[Table 1]

Catalyst solution A was made by adding 0.5 mL of 0.05 M MMAO-3A to 13 mL of mixed alkanes. To this was added 0.5 mL of 0.01 M tris (pentafluorophenyl) borane, and further, 0.005 M [(tetramethylcyclopentadienyl) dimethylsilyl-N-t-butylamido] titanium (II) (1,3-pentadiene) ) Was added.

Catalyst solution B combines the desired amount of pentafluorophenyl-exchanged aluminoxane from Example 1 with 13 mL of mixed alkanes, then [(tetramethylcyclopentadienyl) dimethylsilyl-Nt-butylamido] titanium ( II) It was prepared by adding a 0.005 M solution of (1,3-pentadiene).

Catalyst solution C combines the desired amount of pentafluorophenyl-exchanged alumoxane from Example 2 with 13 mL of mixed alkanes, then [(tetramethylcyclopentadienyl) dimethylsilyl-Nt-butylamido] titanium ( II) It was prepared by adding a 0.005 M solution of (1,3-pentadiene).

The catalyst solution D was prepared by adding 1.07 mL of 0.05 M MMAO-3A to a mixed alkane 1
It was made by combining with 3 mL. To this was added 0.005 M [(tetramethylcyclopentadienyl) dimethylsilyl-Nt-butylamido] titanium (II) (1,3-pentadiene).

The catalyst solution E was prepared by mixing 2.14 mL of 0.05M MMAO-3A with a mixed alkane 1
It was made by combining with 3 mL. To this was added 0.005 M [(tetramethylcyclopentadienyl) dimethylsilyl-Nt-butylamido] titanium (II) (1,3-pentadiene).

[0071]

[Table 2]

The above data in Tables 1 and 2 indicate that the compounds of the present invention are B (C ₆ F ₅ ) ₃ and MMAO-3
A shows that it produces a higher molecular weight polymer than the polymer obtained with a simple blending of A, which is due to the lower value of 12 of Nos. 2-6 compared to Nos. 1 and 7. It is shown. Also the 12.8 Al: pentafluorophenyl at Ti ratio - modified alumoxane catalyst system B (C ₆ F _{5) 3} and MMAO-3A
Shows higher efficiency compared to the simple mixture of Nos. 3, 5, 6, and 1 and 7. Finally, the compositions of the present invention are commonly used at Al: Ti ratios between 6.4 and 12.8, whereas MMAO-3A is completely inert at these low ratios (Comp. Nos. 8 and 9).

Example 3: 3 of methylalumoxane on silica (Witco 02794 / HL / 04)
. 01 g was suspended in 25 mL of toluene. To this slurry was added 0.511 g of [B (C ₆ F ₅ ) ₃ ] as a dry solid. The mixture was stirred for 3 days. At this point the solids were collected on a fritted funnel, washed three times with 15 mL each of toluene, once with 20 mL of pentane, and vacuum dried. 2.0 of this modified carrier material
The 0 g portion was suspended in 18 mL of pentane, and 1.0 mL of a 0.1 M pentane solution of (tetramethylcyclopentadienyl) dimethylsilyl (Nt-butylamido) titanium (II) (1,3-pentadiene) was added. Was. After 5 minutes, the solid was collected on a fritted funnel, washed twice with 10 mL of pentane, and dried in vacuo to give the supported catalyst product as a pale green solid.

Polymerization: The polymerization conditions of Example 2 were substantially repeated using a 0.1 g sample of the above supported catalyst to give about 200 g of ethylene / octene copolymer with a catalyst efficiency of 3.1 kg / Ti · g of polymer. . Comparative polymerization was carried out under the same conditions as indicated using the same metal complex and MAO supported on Witco 02794 / HL / 04 (not treated with [B (C ₆ F ₅ ) ₃ ]). The catalyst efficiency was 1.5 kg of polymer / Ti · g.

Gas phase polymerization: 6 liter gas phase with a 2 inch diameter, 12 inch long flow zone and an 8 inch diameter, 8 inch long velocity reduction zone connected by a transition section with tapered walls Continuous gas phase polymerization was performed using a reactor. Typical operating conditions are 40-100 ° C, 1
Total pressure of 00-300 psig (0.7-2.4 MPa) and reaction time within 8 hours. Monomers, comonomers and other gases are passed through a gas distribution plate to the bottom of the reactor. The gas flow has a minimum particle flow velocity [Fluidization Engine]
ering, 2nd Ed. , D. Kunii and O.M. Levenspiel,
1991, Butterworth-Heinemann].
Most of the suspended solids are separated in the velocity reduction zone. The gas exits the top of the velocity reduction zone and removes any fines present through the dust filter. The gas then passes through a gas booster pump. The polymer remains in the reactor throughout the reaction. The overall pressure of the system is kept constant during the reaction by regulating the monomer flow to the reactor. A series of valves located at the bottom of the flow zone are opened to transfer the polymer from the reactor to a collection vessel maintained at a lower pressure than the reactor. Monomer, comonomer and other gas pressures are given as partial pressures.

[0076] 0.05 g of the catalyst prepared above is placed in a glove box in an inert atmosphere into a catalyst injector. The injector is removed from the glove box and inserted at the top of the reactor. The catalyst is maintained at an ethylene (monomer) pressure of 6.5 bar (0.6
5 MPa), a 1-butene (comonomer) pressure of 0.14 bar (14 kPa), a hydrogen pressure of 0.04 bar (4 kPa) and a nitrogen pressure of 2.8 bar (0.28 MPa) in a semi-batch gas phase reactor. The polymerization temperature during the experiment is 70 ° C. 90 polymerization
Do for a minute. The total system pressure is kept constant during the reaction by regulating the monomer flow to the reactor.

The yield of the ethylene / 1-butene copolymer was 43 g, which was 37 g / gH
It corresponds to an activity of rBar (0.22 kg / g HrMPa). Comparative polymerization was performed using the same metal complex and MAO supported on Witco 02794 / HL / 04 (not treated with [B (C ₆ F ₅ ) ₃ ]) to obtain 19 g of an ethylene / hexene copolymer. This corresponds to an activity of 6 g / g HrBar (0.06 kg / g HrMPa).

Example 4 Tris (pentafluorophenyl) boron (5.775 g, 11.3 mmol) was dissolved in toluene (100 mL). Heptane solution of MMAO-3A (7.
(11.6 mL of a 1 wt% Al solution) was added and the mixture was stirred for 15 minutes. The volatile components were removed under reduced pressure to obtain a pale yellow glass. After several hours at 25 ° C., 200 mL of toluene was added to dissolve this material and the resulting solution was dried at 250 ° C. in air for 3 hours.
To 2 g of silica that had been heat treated for a period of time (Davison ^(TM) 948, commercially available from Grace Division Company ⁾ The slurry was filtered and the resulting solid was washed with 50 mL of toluene and dried in vacuo. 9g
, [Al] = 8.2% by weight.

1 g of the above treated support was suspended in 10 mL of hexane. (Tetramethylcyclopentadienyl) dimethylsilyl (Nt-butylamido) titanium (II
) (1,3-pentadiene) in 0.2 mL of a mixed solution of alum in 0.2 M was added and the mixture was shaken for 30 minutes to form a green solid phase and a colorless supernatant. The slurry was filtered, washed with 30 mL of hexane, and dried under vacuum to obtain a solid supported catalyst. Comparative catalysts were similarly prepared using a support silica-supported MMAO with a corresponding aluminum concentration similar to the support used to make the above catalyst.

Polymerization: The gas-phase polymerization conditions of Example 3 were essentially repeated using the supported composition prepared above as a catalyst. The yield of dry free-flowing powder after 90 minutes of operation is 64.7 g, corresponding to an activity of 96.7 g / g HrBar (0.97 Kg / g of HrMPa). The comparative catalyst was 3.4 g / g HrBar (0.03 kg / g Hr) under the same polymerization conditions.
Gives the activity of MPa).

Example 5: In a glove box, tris (pentafluorophenyl) boron and trimethyl
Replacement of aluminum (TMA) in accordance with US-A-5,602,269 technology
The correspondingly prepared trispentafluorophenylaluminum (0.25 g, 0.
403 mmol) of toluene adduct in a flask with 50 mL of dry toluene.
Add solid MAO (0.49 g) and heat at 80 ° C. under reduced pressure for 8 hours.
To remove TMA and volatile components (8.06 mmol Al). This reaction mixture is
The mixture was stirred at room temperature for 4 hours, and the solvent was removed under reduced pressure. Dry the residue under reduced pressure for several hours
A colored solid was obtained (83% yield). Reagent in toluene-d in glove box₈ Inside
Using the corresponding NMR-scale at the same ratio in a J-Young NMR tube
The reaction was performed. Monitor the reaction throughout the NMR study as indicated.
The reaction was essentially complete in 20 minutes at room temperature (FAAL not detectable in reaction mixture)
The product was found to be a mixture of two species: FAAL and stoichiometric
Stoichiometric adduct of TMA: empirical formula: ((C₆ F_Five )_{z "}・ Al_Two (CH_Three )_{6- z "} ) Where z ″ is about 1 and pentafluorophenyl-substituted aluminoxy
Mixtures of Gomer and methyl-substituted aluminoxy oligomers; [(MeAlO)_z ((C₆ F_Five ) AlO)_{z '}], Z / z 'ratio was about 6/1. Two products
The ratio of (aluminum compound / aluminoxy compound) was about 1.2 / 1. Long
There was no noticeable spectral change during the long reaction time. Spectral data: [(MeAlO)_z ((C₆ F_Five ) AlO)_{z '}The spectrum is¹⁹AlC typical for F NMR₆ F_Five AlC that resonates in the region₆ F _Five It shows a very broad peak of the group.¹⁹F NMR (C₇ D₈ , 23 ° C): δ-12
3.09 (s, br, 2F, o-F), -15.15 (s, br, 1F, p-
F), -16.19 (s, br, 2F, m-F). (C₆ F_Five )_{z "}Al_Two Me_{6-z "} ¹ H NMR (C₇ D₈ , 23 ° C): δ-0.29 (overlaps with s, br, MeAlO groups)¹⁹ F NMR (C₇ D₈ , 23 ° C): δ-121.94 (d,^ThreeJ_FF = 15.
3 Hz, 2F, oF), -152.61 (s, br, 1F, pF), -16
1.40 (s, br, 2F, m-F).

Example 6 FAB (0.005 g, 0.01 mmol) and solid M in a glove box
AO (0.017 g, toluene and free TMA were removed under vacuum drying for 8 hours.
l 0.20 mmol) was dissolved in 0.7 mL of toluene-d ₈ at room temperature.
ng NMR tubes. NMR spectra of these reagents
Recorded after mixing for 20 minutes in the tube. No FAB was detected in the reaction mixture and 4
It was found that two new species were formed by the alkyl / aryl B / Al exchange reaction: BMe ₃ , ¹ H NMR (C ₇ D ₈ , 23 ° C.): δ 0.73 ppm MeB (C ₆ F ₅ ) ₂ , ¹ H NMR (C ₇ D ₈ , 23 ° C.): δ 1.39 pp
m; ¹⁹ F NMR (C ₇ D ₈ , 23 ° C.): δ-129.99 (d, ³ J _FF = 2)
1.4 Hz, 2F, o-F), -147.00 (t, ³ J _FF = 18.3 Hz,
1F, p-F), -161.39 (tt, ³ J _FF = 21.4 Hz, 2F, m-
_{F) (C 6 F 5)} z "Al 2 Me 6-z", (NMR data Example 5 substantially the same), and _{[(MeAlO) z ((C} 6 F 5) AlO) z '] (NMR data Is almost the same as in Example 5.) After 1.5 hours of reaction at room temperature, BMe ₄ and MeB (C ₆ F ₅ ) ₂ are converted to ¹⁹ F N
It could not be detected by MR.

Example 7: In a glove box, FAB (0.15 g, 0.293 mmol) was dissolved in 50 mL of dry toluene in a flask and solid MAO was added (toluene and TM
After removing A by vacuum drying for 8 hours, 1.70 g, 29.3 mmol Al). The reaction mixture was stirred at room temperature for 2 hours, and the solvent was removed under reduced pressure. The residue was dried in vacuo for several hours to give a white solid (85% yield). The product was a mixture of the following _{two: (C 6 F 5) z} "Al 2 Me 6-z", minor product, Example 5 substantially the same spectral data, and [(MeAlO) _z ((C _{6 F 5) AlO) z '} ], the major product. ¹⁹ F
The NMR peaks overlapped and no clearer ratio of product was determined. The spectral data of [(MeAlO) _z ((C ₆ F ₅ ) AlO) _{z ′} ] are as follows; ¹ H NMR (C ₇ D ₈ , 23 ° C.): δ-0.24 (s, br, MeAl)
O _{group) [(MeAlO) z ((} C 6 F 5) AlO) z '] is ¹⁹ F NMR spectrum in typical AlC ₆ F very broad peaks of AlC ₆ F ₅ groups resonated in the ₅ region (W _{1 / 2} > 600 Hz). ¹⁹ F NMR (C ₇ D ₈ , 23 ° C.): δ-122.
01 (s, br, 2F, oF), -151.72 (s, br, 1F, pF)
, -16.34 (s, br, 2F, m-F).

Example 8: In a glove box, MMAO-3A (11.48 mL, 0.5 in heptane
6M, 6.42 mmol) into a flask, remove the solvent under reduced pressure and remove the residue in vacuo.
One liquid was dried in the solution to obtain a white solid. A solvent (hexane 20 mL and toluene
(5 mL) and FAB (0.077 g, 0.15 mmol) were added. reaction
The mixture was stirred for 4 hours and the solvent was removed under reduced pressure. The residue was dried under reduced pressure for several hours,
A white solid was obtained (85% yield). This product was found to be a mixture of the following two:
Was: [(Q^Three AlO)_z ((C₆ F_Five ) AlO)_{z '}] And (C₆ F_Five )_{z "}Al_Two O ^Three _{6-z "}(Where Q^Three Is a mixture of methyl and isobutyl, and z 'is about 1)
These ratios are¹⁹Not clear because of overlapping peaks in F NMR. Spectral data: [(Q^Three AlO)_z ((C₆ F_Five ) AlO)_{z '}The spectrum is¹⁹AlC typical for F NMR₆ F_Five AlC that resonates in the region₆ F _Five It shows a very broad peak of the group and is almost the same as in Example 7.¹ H NMR (C₆ D₆ , 23 ° C): δ-0.05 (s, br, (C₆ F_Five )_ThreeA
lx (trimethylaluminum), 0.15 (d), 0.99 (d) and (C ₆ F_Five )_Three Al.x (1.84 septets of triisobutylaluminum).¹⁹ F NMR (C₆ D₆ , 23 ° C): δ-122.74 (d, 2F, o-F),-
152.18 (s, br, 1F, pF), -16.09 (t, 2F, mF
).

Polymerization: Before introducing all the components into the reactor, the alumina and decontaminant (Engele)
hardt Chemicals Inc. (available from Q-5 ^™ catalyst). The catalyst and cocatalyst were handled in a glove box with an atmosphere of argon or nitrogen. About 740 g of the mixed alkane solvent and 118 g of 1-octene comonomer were charged into a stirred 2.0 liter reactor. Hydrogen at 25 psi (2070p
Ka) was added as a molecular weight regulator from the 75 mL addition tank by differential pressure expansion. The reactor was heated to a polymerization temperature of 130 ° C. and saturated with ethylene at 500 psig (3.4 MPa).

A catalyst ((t-butylamide) (tetramethylcyclopentadienyl) dimethylsilanetitanium 1,3-pentadiene) and a cocatalyst were mixed as a dilute toluene solution, transferred to a catalyst tank, and injected into a reactor. The polymerization conditions were maintained for 15 minutes while adding ethylene as desired. The resulting solution was discharged from the reactor and about 67 mg of a hindered phenol antioxidant (Irganox ^™ 1010 commercially available from Ciba Geigy).
And 133 mg of a phosphorus stabilizer (Irgafo available from Ciba Geigy)
The toluene solution containing s ^™ 168) was added. The polymer was dried and recovered in a vacuum oven set at 140 ° C. for about 20 hours. The density was determined by immersing in air and methyl ethyl ketone and measuring the polymer mass. The micromelt index value (MMI) was calculated using Custom Scientific Instrument I.
Measured at 190 ° C. using an nc model CS-127MF-015 instrument and calculated unitless values: MMI = 1 / (0.00343t-0.00251), where t is the time (sec) measured with the instrument. . Table 3 shows the results.

[0087]

[Table 3]

──────────────────────────────────────────────────続 き Continued on front page (31) Priority claim number 60 / 059,574 (32) Priority date September 19, 1997 (September 19, 1997) (33) Priority claim country United States (US) ( 81) Designated countries EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CU, CZ, DE, DK, EE, ES, FI, GB, GE, GH, GM, HR, HU, ID, IL, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU , LV, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, US, UZ, VN, YU, ZW (72) Inventor Jacobsen, Grant Bee 77081 Houston Newcastle Drive, Texas, USA # 1845, 5454 (72) Inventor Stevens, James Sea 77469 Richmond, Texas, United States Pecan Trail drive 2026 F term (reference) 4H048 AA03 AB40 VA11 VA20 VA80 VB10 4J002 CQ031 EZ006 GT00 4J028 AA01A AB01A AC01A AC02A AC09A AC10A AC19A AC20A AC22A AC27A AC28A AC29A AC4 9A BA00A BA01B BB00A BB01B BC12B BC25B CA28C EB01 EB02 EB03 EB04 EB05 EB07 EB08 EB09 EB10 EB12 EB15 EC01 EC02 EC03 ED03 FA02 FA03 FA04 GA06

Claims (10)

[Claims] 1. A composition having a mixture of aluminum containing Lewis acid, the mixture has the _{^{formula: [(-AlQ 1 -O-) Z}} (-AlAr f -O-) Z '] (Ar f Z " ^{_{al 2 Q 1 6-Z "}} ) wherein Q ¹ is selected from C _1-20 alkyl independently in each case; the Ar ^f is a fluorinated aromatic hydrocarbyl group having carbon atoms of 6-30; z is 1-50, preferably 1.5-40, more preferably a number from 2-30, and the group (-AlQ ¹ -O-) is a cyclic or linear oligomer with a repeat unit of 2-30; Z 'is 1-50, preferably 1.5-40, more preferably a number from 2-30, and the group (-AlAr ^f -O-) are cyclic or linear oligomers having repeating units of 2-30 it is; Z "is a number from 0-6, and the group ^{_{(Ar f Z" Al 2 Q}} 1 6-Z ") Any of tri (fluoroarylaluminum), trialkylaluminum, or an adduct of tri (fluoroarylaluminum) with a less than stoichiometric to greater than stoichiometric amount of trialkylaluminum; A composition characterized by the corresponding. Wherein ^{formula: R 1 - (AlR 3 O} ) m -R 2 where R ¹ is in each case independently with C _1-40 aliphatic or aromatic group or a fluorinated derivative thereof; R ² is or in each case independently is a C _1-40 aliphatic or aromatic group or a fluorinated derivative, or in the case of cyclic oligomers wherein R ¹ and R ² forms a covalent bond together; R ³ is in each case independently a monovalent fluorinated organic radical having 1-100 carbon atoms or R ¹ , wherein at least one R ³ per molecule is a monovalent fluorinated organic radical having 1-100 carbon atoms. A composition having a fluorohydrocarbyl-substituted alumoxane corresponding to an organic group; and m is a number from 1 to 1000. 3. The composition of claim 2 wherein the residual trialkylboron content is less than 10.0% by weight. 4. A catalyst system for polymerization of an addition-polymerizable monomer, comprising a combination of a Group 3-10 metal complex and the composition of Claim 1 or 3, or a reaction product thereof. 5. A polymerization method comprising bringing an addition-polymerizable monomer into contact with the catalyst system of claim 4 under polymerization conditions. 6. The method of claim 5, which is a solution polymerization. 7. The polymerization method according to claim 6, which is a continuous solution polymerization. 8. The process according to claim 5, wherein the process is gas phase, powder bed or suspension polymerization. 9. The polymerization method according to claim 8, wherein the catalyst composition further has a support. 10. The support reacts the silica with tri (C _1-10 alkyl) aluminum in an amount of 0.1-100 mmol of aluminum / g of silica, followed by 0.1-1000 μmol of activator. 10. The process of claim 9 obtained by contacting the activator composition of claim 1 or a solution thereof in an amount sufficient to provide a supported cocatalyst having g of silica / g.