JPH10110009A - Catalyst for preparation of olefin polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a catalyst precursor which can be easily prepd. at a low cost and is useful for preparation of a novel single site olefin polymn. catalyst compsn. having excellent polymn. activity and productivity by selecting a particular catalyst precursor. SOLUTION: A catalyst precursor (e.g. cinnamyl-cyclopentadienyl dianion) represented by the formula (wherein L represents a cycloalkadienyl ligand; and W, X, Y, and Z are each H, a 1-20 C hydrocarbyl group, or a silyl group, provided that they can be bonded to L through a crosslinking group contg. two or more IVA group atoms of the periodic table, and one of X, Y, and Z is a negative charge stabilizing group selected from among a group IVA trialkyl group, an aryl group, a heteroarom. group, an ethylenically unsatd. hydrocarbon group, an acetylenically unsatd. hydrocarbon group, a ketone group, and an arom. organometal portion) is selected. The catalyst precursor is reacted with a compd. contg. a metal selected from group IIIB to VIII or lanthanide metals (e.g. ZrCl4 ) and an activation co-catalyst (e.g. methylaluminoxane) to prepare a catalyst compsn.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a catalyst precursor for the production of olefin polymers such as polymers of ethylene, higher α-olefins (hereinafter simply referred to as higher α-olefins), dienes and mixtures thereof. The present invention relates to a new class of conjugated allyl-cycloalkadienyl dianions useful as a body.

[0002]

BACKGROUND OF THE INVENTION Recently, single site catalysts for producing olefin polymers have been developed. Typically, the single-site catalyst is a metallocene, i.e., an organometallic coordination containing one or more pi-bonded moieties associated with a metal atom from Groups IIIB-VIII of the Periodic Table of the Elements or from the lanthanide group. Complex. Catalyst compositions containing single-site catalysts are very useful in the production of polyolefins,
It is reported to provide a homogenous polymer at an excellent rate of polymerization, making it possible to make a polymer with final properties close to the desired final properties.

[0003] European Patent Publication No. 0586167A1
Item and the No. 0586168A1 has the _{formula: M [XR n] x Y} p or

Embedded image (Where R is a hydrocarbyl optionally containing oxygen, silicon, phosphorus, nitrogen or boron atoms, X is an organic group containing a cyclopentadienyl nucleus, M is a Group IVA metal, Y is Is a monovalent anionic ligand, and Z is a bridging group). According to these applications, at least one of the R groups must contain a polymerizable (ie polymerizable) group, preferably having at least 3 carbon atoms. Preferred metallocene complexes are zirconium complexes where the polymerizable group is vinyl. The following formula:

Embedded image Such compounds are disclosed.

[0004] DE-A-3840772 A1 is prepared by reacting a zirconium, titanium or hafnium metallocene compound with poly (methhydrogenosiloxane) in the presence of a hydrosilation catalyst.
It relates to a metallocene catalyst component for use in olefin polymerization. The following formula:

Embedded image Such compounds are disclosed.

[0005]

SUMMARY OF THE INVENTION Described herein is a novel single-site olefin polymerization catalyst composition that is easily and inexpensively manufactured and has good polymerization activity and productivity. The catalyst composition comprises (1) a conjugated allyl-cycloalkadienyl dianion catalyst precursor and (2) IIIB-V
It includes the reaction product of a compound containing a metal from the group III or lanthanide group and (3) an activating co-catalyst.

[0006]

SUMMARY OF THE INVENTION The present invention provides the following formula:

Wherein L is a cycloalkadienyl ligand, W, X, Y and Z are each hydrogen, a hydrocarbyl or silyl group having from 1 to 20 carbon atoms, and at least two It can be attached to L via a bridging group containing a Group IVA atom, provided that one of X, Y and Z is a Group IVA trialkyl group, an aryl group, a heteroaromatic group, an ethylenically unsaturated group. A catalyst group selected from a hydrocarbon group, an acetylenic unsaturated hydrocarbon group, a ketone group and an aromatic organometallic moiety).

[0007] The present invention also relates to the catalyst precursor and IIIB
There is also provided a catalyst composition comprising a reaction product of a compound containing a metal from Groups VIII or lanthanides and an activating cocatalyst.

Further, the present invention provides a method for producing an olefin polymer comprising contacting an olefin monomer with the catalyst composition under polymerization conditions, and an olefin polymer such as an ethylene polymer produced by the method.

[0009]

DETAILED DESCRIPTION OF THE INVENTION Detailed description The catalyst precursor of the invention has the formula:

A conjugated allyl-cycloalkadienyl dianion having the formula: In this formula, L is a cycloalkadienyl ligand such as cyclopentadienyl, indenyl or fluorenyl, which may be one or more of a hydrocarbyl group such as alkyl, aryl, alkylaryl or arylalkyl, a silyl group, etc. It may be substituted or unsubstituted. L is preferably a substituted or unsubstituted cyclopentadienyl or indenyl ligand.

Except as specified in the next paragraph, W, X, Y and Z are each hydrogen, hydrocarbyl or silyl having 1 to 20 carbon atoms.
One or more of W, X, Y and Z can be linked to L via a bridging group containing two or more Group IVA atoms.

One of X, Y and Z must be a negative charge stabilizing group. Examples of negative charge stabilizing groups include
There are a group IVA trialkyl group, an aryl group, a heteroaromatic group, an ethylenically unsaturated hydrocarbon group, an acetylene unsaturated hydrocarbon group, a ketone group and an aromatic organometallic moiety.

Group IVA trialkyl groups have the formula: (Group IVA elements) (R ₃ ) where R represents an alkyl group having from 1 to about 20 carbon atoms, for example, Cyril, Stanyl, Germill or Planville.

Examples of aryl groups include phenyl, naphthyl, biphenyl, anthracenyl, and substituted phenyl groups such as tolyl, methoxyphenyl and tert-butylphenyl. Examples of heteroaromatic groups include pyridyl,
There are furyl, pyryl and thienyl.

Examples of the ethylenically unsaturated hydrocarbon group include a vinyl group, a substituted vinyl group, an allene group, a substituted allene group,
There are a dienyl group and a substituted dienyl group. Examples of acetylenically unsaturated hydrocarbon groups include phenylalkynyl, trimethylsilylalkynyl, propynyl, hexynyl and 3,3-dimethylbutynyl.

Examples of ketone-based groups include benzoyl and pivaloyl. Examples of aromatic organometallic moieties include ferrocene, titanocene, chromocene, and vanadocene.

Preferred negative charge stabilizing groups are aryl groups, especially phenyl groups.

[0017] The catalyst precursor can be in the form of monomers, dimers, oligomers and polymers.

In a preferred embodiment of the present invention, the catalyst precursor has the formula:

Embedded image Cinnamyl-cyclopentadienyl dianion (including any isomers thereof).

In another preferred embodiment of the present invention,
The catalyst precursor is of the following formula:

Embedded image Cinnamyl-indenyl dianion (including any isomers thereof).

[0020] The catalyst precursor can be made by any synthetic method, and the method of making the catalyst precursor is not critical to the present invention. One useful method of preparing a catalyst precursor is to contact a cycloalkadienyl-containing salt with an allyl-containing halide and convert the resulting product to a metallizing reagent, preferably methyllithium or n-butyllithium. This is due to metallization with an alkyl lithium compound. Contact is at atmospheric pressure and about -78 ° C.
It can be carried out at a temperature in the range of room temperature, preferably in the range of -30C to room temperature.

For example, the preferred cinnamyl-
When preparing the cyclopentadienyl dianion catalyst precursor, sodium cyclopentadienide can be reacted with cinnamyl chloride or cinnamyl bromide. The product cinnamylcyclopentadiene can then be metallized with one equivalent of n-butyllithium in a suitable solvent to produce the monoanionic cinnamylcyclopentadienide (as a monolithium salt). Examples of useful solvents include tetrahydrofuran (THF), monoglyme, diglyme, triglyme, tetraglyme and methyl t
Ethers such as -butyl ether (MTBE), N,
There are chelating amines such as N, N ', N'-tetramethylethylenediamine and amides such as hexamethylphosphoramide. This monoanion can then be converted to the cinnamyl-cyclopentadienyl dianion by a second metallization with a second equivalent of n-butyllithium in a solvent. Alternatively, cinnamyl chloride or cinnamyl bromide and 2 equivalents of an alkyllithium compound are sequentially added to sodium cyclopentadienide to convert the cinnamyl cyclopentadiene into a cinnamyl-cyclopentadienyl dianion catalyst precursor in a one-vessel synthesis. Can be directly converted to

The catalyst composition comprises a conjugated allyl-cyclopentadienyl dianion catalyst precursor, a compound containing a metal from Groups IIIB-VIII or the lanthanide group (hereinafter referred to as "metal compound"), Includes reaction products with co-catalysts. In producing the reaction product, a catalyst precursor, which can be in the form of a salt containing a conjugated allyl-cycloalkadienyl dianion and a metal cation from a metallizing reagent, a metal compound and an activating agent The cocatalyst is contacted at atmospheric pressure at a temperature in the range of about -78C to room temperature, preferably in the range of about -30C to room temperature. The contacting is preferably carried out in the presence of a suitable solvent, ie an ether such as THF or a hydrocarbon such as hexane or toluene. The catalyst precursor, metal compound and activating cocatalyst can be contacted in any order,
However, first contact the catalyst precursor with the metal compound,
It is preferred to then contact the activating cocatalyst, or first contact the catalyst precursor with the activating cocatalyst, and then contact the metal compound.

When first contacting the catalyst precursor with the activating cocatalyst, a metal compound is added to adjust the overall ratio of activating cocatalyst to metal in the catalyst composition. Further activation co-catalysts can later be added to the reaction product, which is preferred.

The compound containing a metal from Groups IIIB-VIII or the lanthanide group is preferably a compound containing a Group IVB metal. More preferably, the metal compound is a zirconium compound. Suitable zirconium compounds include zirconium halides, alkyl zirconium halides, alkyl zirconiums, zirconium amides, zirconium diketonates, zirconium alkoxides, zirconium carboxylate, and the like. Specific examples of zirconium compounds include zirconium tetrachloride, cyclopentadienyl zirconium trichloride, pentamethylcyclopentadienyl zirconium trichloride, tetrabenzyl zirconium, tetrakis (diethylamino) zirconium, acetylacetonato zirconium, hexafluoro Zirconium acetoacetonate, zirconium bis (acetylacetonato) dichloride,
Zirconium isopropoxide, zirconium 2-ethylhexanoate, ClZr [CH (SiMe ₃ ) ₂ ] ₃ , [Me ₃ SiCH ₂ ] ₂ ZrCl ₂
(Et ₂ O) ₂ , [PhCH ₂ ] ₂ ZrCl ₂ , (Me ₃ CH ₂ ) ₂ ZrCl ₂ (Et ₂ O) ₂ and [ZrCl ₂ (THF) (η-C ₈ H ₈ )] are included. .

When a catalyst precursor is synthesized using a strong metallizing reagent such as an alkyllithium compound, the catalyst precursor is contacted with a metal exchange compound before the catalyst precursor is contacted with the metal compound. Can and is useful to do so. Compounds for metal exchange are IIA, IIB, II
It is preferably a Group IA or IVA halide or alkoxide. The metal exchange compound removes metal cations (from the metallizing reagent) associated with the catalyst precursor,
This is replaced with a more reactive metal. This promotes the reaction between the catalyst precursor and the metal compound. Particularly preferred metal replacement compounds are halides and alkoxides of silicon, aluminum and tin.

The activating cocatalyst can activate the catalyst composition. Preferably, the activating cocatalyst is one of the following or a mixture thereof: (a) the general formula-(Al (R ^* ) O)-, wherein R ^* is hydrogen, 1 to about 12 A branched or cyclic oligomeric poly (hydrocarbylaluminum oxide) containing a repeating unit of an alkyl group having 10 carbon atoms or an aryl group such as a substituted or unsubstituted phenyl or naphthyl group); _{^{[a +] [BR ** 4}} -] ( wherein, a ⁺ is a cationic Lewis or Bronsted acid capable of extracting an alkyl, a halogen or hydrogen from the metallocene catalysts, B is boron, R ^{* *} Is a substituted aromatic hydrocarbon,
(C) alkyl borons of the general formula BR ^** ₃ , wherein R ^** is as defined above.

[0027] formula _{^{[A +] [BR ** 4}} -] When used as a cocatalyst for activating the ionic salt or alkyl boron is
Prior to contacting the metal compound with the catalyst precursor and the activating cocatalyst, the metal compound can be contacted with an alkylaluminum such as trimethylaluminum or triisobutylaluminum to alkylate the metal compound. It is desirable to do.

The activating cocatalyst is preferably a branched or cyclic oligomeric poly (hydrocarbyl aluminum oxide) or alkyl boron. More preferably, the activating cocatalyst is methylaluminoxane (MAO) or modified methylaluminoxane (MMAO) or alkylboron.

Aluminoxanes are well known in the art and have the formula:

Embedded image And an oligomeric linear alkylaluminoxane represented by the following formula:

Embedded image Wherein s is 1 to 40, preferably 10 to 20, p is 3 to 40, preferably 3 to 20, and R ^*** is 1 to 1.
An alkyl group having 2 carbon atoms, preferably methyl, or an aryl group such as a substituted or unsubstituted phenyl or naphthyl group).

Aluminoxanes can be produced in various ways. Generally, in the production of aluminoxanes from, for example, trimethylaluminum and water, a mixture of linear and cyclic aluminoxanes is obtained. For example, the alkyl aluminum may be treated with water in the form of a water-containing solvent. Alternatively, an alkylaluminum such as trimethylaluminum may be contacted with a hydrated salt such as hydrated ferrous sulfate. The latter method is
For example, treating a dilute solution of trimethylaluminum in toluene with a suspension of ferrous sulfate heptahydrate. Further, a tetraalkyldialuminoxane containing C ₂ or higher alkyl groups, by reacting a stoichiometric excess of the amount less than the amount of trimethylaluminum, may also be produced methylaluminoxane. Further, by the tetraalkyldialuminoxane or trialkylaluminum compound containing C ₂ or higher alkyl groups are reacted with water to produce a polyalkyl aluminoxane and then reacted it with trimethylaluminum, methylaluminoxane Synthesis can also be achieved. Further modified methylaluminoxanes containing both methyl and higher alkyl groups are described, for example, in US Pat.
As disclosed in 584 Pat, a polyalkyl aluminoxane containing C ₂ or higher alkyl groups is reacted with trimethyl aluminum followed by reaction with water, it can be synthesized.

The useful amounts of catalyst precursor, metal compound and activating cocatalyst in the catalyst composition can vary.
Generally, the ratio of catalyst precursor to metal compound can range from about 1: 5 to about 5: 1, and preferably ranges from about 1: 3 to about 3: 1, with about 1: 1. More preferably, it ranges from 2 to about 2: 1.

When the activating cocatalyst is a branched or cyclic oligomeric poly (hydrocarbyl aluminum oxide), the total number of aluminum atoms contained in the poly (hydrocarbyl aluminum oxide) to that contained in the metal compound is reduced. The molar ratio of metal atoms is about 2: 1 to 1
It is generally in the range of about 100,000: 1, preferably in the range of about 10: 1 to about 10,000: 1, and particularly preferably in the range of about 50: 1 to about 2000: 1. Cocatalyst wherein the activating _{^{[A +] [BR ** 4}} -] in the case of ionic salts or alkyl boron of formula BR ^** ₃ of boron atoms contained in the ionic salt or alkyl boron The molar ratio of all metal atoms contained in the metal compound is
It is generally in the range of about 0.5: 1 to about 10: 1, and preferably in the range of about 1: 1 to about 5: 1.

The catalyst composition may be supported or unsupported and may be spray dried with or without filler. In the case of the supported catalyst composition, the catalyst composition is 1 to 1 of the total weight of the catalyst composition and the carrier.
The catalyst composition is impregnated in or deposited on an inert substrate such as silicon dioxide, aluminum oxide, magnesium dichloride, polystyrene, polyethylene, polypropylene or polycarbonate to provide a range of 90% by weight. be able to.

The catalyst composition can be used for the polymerization of olefins by any suspension, solution, slurry or gas phase method using known equipment and reaction conditions, and is not limited to a particular type of reaction system. Generally, olefin polymerization temperatures range from about 0 ° C to about 200 ° C at atmospheric, subatmospheric, or superatmospheric pressures. Slurry or solution polymerization processes use subatmospheric or superatmospheric pressures and about 4
Temperatures ranging from 0 ° C to about 110 ° C can be used.
Useful liquid phase polymerization systems are described in U.S. Pat. No. 3,324,095. Liquid phase reaction systems generally include a reaction vessel to which an olefin monomer and a catalyst composition have been added and which contain a liquid reaction medium for dissolving or suspending the polyolefin. The liquid reaction medium may consist of a large amount of liquid monomer or of an inert liquid hydrocarbon which is non-reactive under the polymerization conditions used. Such an inert liquid hydrocarbon does not need to act as a solvent for the polymer obtained by the catalyst composition or method, but usually acts as a solvent for the monomers used in the polymerization. is there. Among the inert liquid hydrocarbons suitable for this purpose are isopentane, hexane, cyclohexane, heptane, benzene, toluene and the like. Constant agitation should maintain reactive contact between the olefin monomer and the catalyst composition. The reaction medium containing the olefin polymer product and unreacted olefin monomer is continuously removed from the reactor. The olefin polymer product is separated and the unreacted olefin monomer and liquid reaction medium are recycled to the reactor.

0.07 to 70 Kg / cm ² (1 to 100
0 psi), preferably 3.5-28 Kg / cm ² (5 psi).
0 to 400 psi), particularly preferably 7 to 21 Kg / c.
m ² (100~300psi) above atmospheric pressure and 30 to 130 ° C. in the range of, preferably to use a gas-phase polymerization at a temperature in the range of 65 to 110 ° C.. Stirred bed or fluidized bed gas phase reaction systems are particularly useful. Generally, conventional gas-phase fluidized bed processes involve suspending a stream containing one or more olefin monomers in a fluidized bed reactor under reaction conditions and in the presence of a catalyst composition, in a bed of solid particles. This is accomplished by passing continuously at a space velocity sufficient to maintain the condition. The stream containing unreacted monomers is continuously withdrawn from the reactor, compressed, cooled and recycled to the reactor. The product is removed from the reactor and refilled (make-
up) Monomer is added to the recycle stream. If desired for temperature control of the system, any gas which is inert to the catalyst composition and the reactants can be present in the gas stream. In addition, fluidizing aids such as carbon black, silica, clay or talc can be used, as disclosed in U.S. Pat. No. 4,994,534.

The polymerization can be carried out in a single reactor or in a series of two or more reactors and is carried out in the substantial absence of catalyst poisons. Organometallic compounds can be used as scavenging agents for catalyst poisons to enhance catalytic activity. Examples of scavengers are alkyl metals, preferably alkyl aluminum, particularly preferably triisobutyl aluminum.

Conventional auxiliaries can be included in the process, provided that they do not interfere with the operation of the catalyst composition in the production of the desired polyolefin. As a chain transfer agent in the process, hydrogen can be used in an amount up to about 10 moles of hydrogen per mole of total monomer feed.

The olefin polymers which can be prepared according to the invention include ethylene homopolymers, from 3 to about 2
Linear or branched higher α- having 0 carbon atoms
Olefin homopolymer and ethylene and such higher α
-Interpolymer with olefin (about 0.8
Having a density in the range of 6 to about 0.95). Suitable high α
-Olefins include, for example, propylene, 1-butene, 1
-Pentene, 1-hexene, 4-methyl-1-pentene, 1-octene and 3,5,5-trimethyl-1-hexene. The olefin polymers according to the invention may also be based on conjugated or non-conjugated dienes, such as linear, branched or cyclic hydrocarbon dienes having about 4 to about 20, preferably 4 to 12 carbon atoms. Or may contain such a diene. Preferred dienes include 1,4-pentadiene, 1,5-hexadiene, 5-vinyl-2-norbornene, 1,7-octadiene, vinylcyclohexene, dicyclopentadiene,
Butadiene, isobutylene, isoprene, ethylidene norbornene and the like are included. Also, aromatic compounds having vinyl unsaturation such as styrene and substituted styrene, and acrylonitrile, maleic ester, vinyl acetate, acrylate ester, methacrylate ester,
Polar vinyl monomers such as vinyltrialkylsilanes and the like can also be polymerized according to the present invention. Specific olefin polymers that can be made in accordance with the present invention include, for example, polyethylene, polypropylene, ethylene / propylene rubber (EPR), ethylene / propylene / diene terpolymer (EPDM), polybutadiene, polyisoprene, and the like.

[0039]

The following examples further illustrate the invention.

The term activity is measured in kg of polyethylene / mmol of Zr / hour · 100 psi ethylene. I2 is AS
It is a melt index (dg / min) measured at 190 degreeC using TM method D-1238 conditions E. I21
Is a flow index (dg / min) measured using ASTM method D-1238 condition F. The MFR is the melt flow ratio I21 / I2. MMAO is Akzo Chemi
A solution of modified methylaluminoxane in heptane (aluminum about 1.9 mol) (type 3) commercially available from cal Inc. BBF is the butyl branching frequency (number of butyl branches per 1000 main chain carbon atoms). M _w is the weight average molecular weight and is measured by gel permeation chromatography (140 ° C.) using a cross-linked polystyrene column (the order of pore size is one column smaller than 1000 ° and three columns of mixed 5 × 10 ⁷ ). ,
1,2,4-trichlorobenzene solvent, refractive index detection). PDI is the polydispersity index, which is equal to the molecular weight distribution ( _Mw / _Mn ).

EXAMPLES 1 TO 10 Catalyst compositions containing the reaction products of cinnamyl-cyclopentadienyl dianion, modified methylaluminoxane and various zirconium compounds were prepared as follows:
It was used to copolymerize ethylene and 1-hexene.

Cinnamyl-cyclopentadienyl diani
Preparation and Isolation A solution of 102 mmol of cinnamyl bromide in 95 ml of THF was cooled to 0 ° C. An equimolar amount of sodium cyclopentadienide (2.0 in THF) is added to the cooled solution.
M) was added slowly under an argon atmosphere. After the addition, the reaction of cinnamylcyclopentadiene was completed according to GC analysis. The reaction mixture was concentrated under vacuum to a residue to give a brown oil.

Cinnamyl cyclopentadiene residue (10
(2 mmol) was then placed under an argon atmosphere, diluted with 100 ml of ether and stirred. The mixture was then vacuum filtered (to remove sodium bromide) in an oven dried double-ended glass filter and the solid was washed with ether. The filtrate was placed under an argon atmosphere and cooled to -78 ° C. 0.6 equivalent of n-
Butyllithium (3.089M in hexane 1
9.4 ml, 60 mmol). The mixture was stirred overnight. The solid monoanion product is
Vacuum filtration was performed using a dry double-ended glass filter, and the resultant was washed with dry ether. The solid was vacuum dried and stored in a drying box.

The resulting solution of lithium cinnamyl cyclopentadienide in THF was placed under an argon atmosphere. To this was added 3 equivalents of methyllithium (in ether) at room temperature. The resulting solution was stirred at room temperature for 2 hours, then concentrated under strong vacuum to a residue.
Dry ether was added to the residue, and the obtained product was filtered to obtain a dianion as a dilithium salt.

Preparation of Catalyst Composition Next, the cinnamyl-cyclopentadienyl dianion (as a dilithium salt) prepared as described above was converted to zirconium tetrachloride and cyclopentadienyl zirconium trichloride (CpZrCl ₃ ) as follows. Or pentamethylcyclopentadienyl zirconium trichloride (Cp
^{* A} series of catalyst compositions were prepared by reacting with ZrCl ₃ ) and MMAO.

Equimolar amounts of dilithium cinnamyl cyclopentadienide and a zirconium compound were charged to the flask in a dry box. To this mixture, with stirring,
About 1 milliliter of chilled ether or room temperature ether as shown in Table 1 was added. The resulting mixture was concentrated under vacuum to a residue.

For Examples 6 and 10, the flask was first removed from the box and cooled in a low temperature bath (-78 ° C.)
Treat with 10 ml of ether while stirring. The mixture was then allowed to slowly warm to room temperature overnight and then concentrated in vacuo to a residue.

For each example, the dianion / zirconium complex obtained was then dissolved in dry toluene. In Examples 4, 5, 9 and 10, an oven-dried (oven-dried) glass vial was charged with stirring with 500 equivalents of MMAO, to which a dianion / zirconium complex in toluene solution was added. In Examples 1, 2, 3, 7 and 8, toluene 1 was first added before the introduction of MMAO.
0 ml was charged to the vial. In Example 6, the vial was charged with the dianion / zirconium complex, 10 milliliters of toluene were added with stirring, and then 500 equivalents of MMAO was added to the vial. In each case, a catalyst composition having an MMAO / zirconium molar ratio of 1000 was formed.

Polymerization The polymerization using these catalyst compositions was carried out in a 1 liter stainless steel autoclave equipped with a mechanical stirrer.
Performed in the slurry phase. The reaction was carried out under ethylene pressure of 85 psia with 43 ml of 1-hexene and 600 ml of hexane solvent also present in the reactor,
Performed at 75 ° C. The reaction time was 30 minutes each. Table 1 shows the results.

[0050]

[Table 1]

EXAMPLES 11-16 Further catalyst compositions containing the reaction products of cinnamyl-cyclopentadienyl dianion with modified methylaluminoxane and various zirconium compounds were prepared as described in Examples 1-10, Used to copolymerize with 1-hexene. Table 2 shows the results.

[0052]

[Table 2]

EXAMPLES 17-24 Further catalyst compositions containing the reaction products of cinnamyl-cyclopentadienyl dianion with a modified methylaluminoxane and various zirconium compounds were prepared as follows to form ethylene and 1-hexene. Used for copolymerization.

For each of Preparation Examples 17 to 24 of the catalyst composition, 0.0452 mmol of the cinnamyl-cyclopentadienyl dianion prepared in Examples 1 to 10 was combined with 1.5 mL of MMAO at room temperature and stirred for 4 days. About 5 micromoles of the resulting dianion / MMAO complex was added to an oven-dried vial containing about 5 micromoles of the zirconium compound shown in Table 3 (provided that Examples 22 and 23 were used).
Used only about 2.5 micromoles of the zirconium compound). For Examples 17, 18, 20, 21 and 22, toluene was also added to the vial. The resulting mixture was stirred for 20-55 minutes to form a catalyst composition.

For each of Polymerization Examples 17 to 24, the catalyst composition was introduced into the autoclave reactor with an additional 2 mmol of MMAO (except for Examples 22 and 23, which were 1 mmol and 0.33 mmol, respectively). Was additionally used).
Polymerization using these catalyst compositions was carried out as in Example 1. The results are shown in Table 3 below.

[0056]

[Table 3]

[0057] Example was prepared as follows additional catalyst composition comprising the reaction product of 25 1-cinnamyl Lewin Denis distearate anion modified methylaluminoxane and ZrCl _4, and ethylene 1-
Used to copolymerize with hexene.

Preparation of 1-cinnamylindenyl dianion
A solution of 98% indene 364 mmol was cooled to -78 ° C. under an argon atmosphere forming THF300 ml. An equimolar amount of n-butyllithium was added to this solution. The resulting mixture was warmed to room temperature. It was then charged at -30 DEG C. with an equimolar amount of 58% cinnamyl chloride (58.45 g) in 100 ml of THF. The mixture was then warmed to room temperature and reacted for 1 hour to produce cinnamylindene. The cinnamylindene was concentrated under strong vacuum to a residue, then washed twice with 100 ml of hexane and concentrated. The residue was washed three times with 100 ml of hot hexane and filtered hot. The filtrate was again concentrated under vacuum to a residue. The filtrate, cinnamylindene, melted at 55-69 ° C. The recovery yield was 62%.

A solution of 224 mmol of cinnamylindene in 300 ml of ether was placed under an argon atmosphere and cooled to 0.degree. 0.89 equivalent of n-
Butyllithium (200 mmol) was added and the solution was warmed to room temperature. Hexane was added to the mixture, which was concentrated to almost a residue. Hexane was added to the mixture, and the mixture was stirred overnight. The product solid lithium cinnamyl indenide was later filtered, washed and dried in vacuo. The recovery yield was 44 g.

To form a dianion, THF5
A solution of 11 mmol of lithium cinnamyl indenide in 0.0 ml was placed under an argon atmosphere and cooled to 0 ° C. This was charged with 1.0 equivalent of butyllithium and then stirred at room temperature for 1 hour.

Preparation of the Catalyst Composition The dianion solution was then charged with 2.0 equivalents of zirconium tetrachloride (5.0 g, 21.4) in 50 ml of THF.
(Mmol) at -30 ° C with a double-ended needle and stirred for 3 days. The reaction mixture was concentrated to a residue under vacuum and combined with 500 equivalents of MMAO in an oven-dried glass vial with stirring.

Polymerization 1- Copolymerization of ethylene and 1-hexene was carried out as in Examples 1 to 10 above using a catalyst composition containing cinnamylindenyl dianion. The activity of the catalyst was 6,700. Butyl branching frequency of 11.9,
A copolymer having an I2 of 0.513 and a melt flow ratio of 26.3 was obtained.

Examples 26-29 A further catalyst composition comprising the reaction product of a cinnamyl-cyclopentadienyl dianion, a boron compound, a modified methylaluminoxane and various zirconium compounds was prepared as follows, and ethylene and 1- Used to copolymerize with hexene.

In each of Preparation Examples 26 to 29 of the catalyst composition , Examples 1 to 1 were added in THF.
A solution of 0.28 mmol of dilithium cinnamyl cyclopentadienide prepared in 0 was placed under an argon atmosphere and cooled to 0 ° C. Equimolar amounts of the boron compounds shown in Table 4 were added to this solution. The resulting mixture was stirred at 0 ° C. for 30 minutes, then warmed to room temperature. It was then charged at room temperature to a solution of the zirconium compound shown in Table 4 in THF. The mixture was stirred overnight and then concentrated under vacuum to a residue.

For each of Examples 26 to 29, the resulting dianion / boron / zirconium complex was then dissolved in dry toluene. In Example 28, 500 equivalents of MMAO were stirred into an oven-dried glass vial.
And a toluene solution of the dianion / boron / zirconium complex was added thereto. In Examples 26 and 27, the vials were initially charged with 10 milliliters of toluene before introducing MMAO. In Example 29, a dianion / boron / zirconium complex was charged to a vial,
With stirring, 10 milliliters of toluene was added, and then 500 equivalents of MMAO was added to the vial.

Polymerization Polymerization using these catalysts was carried out as in Examples 1-10. Table 4 shows the results.

[0067]

[Table 4]

Example 30 Cinnamyl-cyclopentadienyl dianion metal-exchanged with chlorotrimethylsilane and ZrC
l ₄ and modified methylaluminoxane was prepared as follows a catalyst composition comprising the reaction product of hexane, ethylene 1-
Used to copolymerize with hexene.

Examples 1 to 3 in about 1 ml of THF
The solution of 1.09 mmol of dilithium cinnamyl cyclopentadienide prepared in 10 was placed under an argon atmosphere. To this was charged 2.5 equivalents of chlorotrimethylsilane and then stirred for 1 hour. The mixture was concentrated under vacuum to a residue. The residue was washed twice with toluene and dried under vacuum to remove lithium chloride.

The filtrate was then charged at room temperature to an equimolar amount of zirconium tetrachloride and stirred. The mixture was concentrated to a residue under vacuum and combined with 500 equivalents of MMAO in an oven-dried glass vial with stirring.

Polymerization Using this catalyst composition, copolymerization of ethylene and 1-hexene was carried out as in Examples 1-10. The activity of the catalyst was 7211. I2 of 0.176, 3.35
A copolymer having a melt flow ratio of I21 and 22.05 was obtained.

Example 31 A catalyst composition containing the reaction product of cinnamyl-cyclopentadienyl dianion, metal-exchanged with trimethyltin chloride, ZrCl ₄ and modified methylaluminoxane was prepared as follows, Used to copolymerize with 1-hexene.

Example 1 in 5.0 ml of THF
A solution of 0.2 mmol of dilithium cinnamylcyclopentadienide prepared in to 10 was placed under an argon atmosphere and cooled to -78 ° C. This was charged with 1.0 equivalent of trimethyltin chloride and the resulting mixture was warmed to room temperature. The mixture was concentrated under vacuum to a residue.

The product obtained was then charged to an equimolar amount of zirconium tetrachloride at room temperature and stirred overnight to form a catalyst composition. This was concentrated to a residue under vacuum and combined with 500 equivalents of MMAO in an oven-dried glass vial with stirring.

Polymerization Using this catalyst composition, copolymerization of ethylene and 1-hexene was carried out as in Examples 1-10. The activity of the catalyst was 20,888. I2 of 0.294, 5.2
Of I21 and a melt flow ratio of 17.6.

Example 32 Cinnamyl-cyclopentadienyl dianion initially transmetalated with trimethylaluminum and ZrC
l ₄ and modified methylaluminoxane was prepared as follows a catalyst composition comprising the reaction product of hexane, ethylene 1-
Used to copolymerize with hexene.

Example 1 in 5.0 ml of THF
A solution of 0.124 mmol of dilithium cinnamyl cyclopentadienide prepared in to 10 was placed under an argon atmosphere and cooled to -30 ° C. This was charged with 2.0 equivalents of trimethylaluminum. It was then warmed to room temperature and stirred for 4 hours. The mixture was concentrated under strong vacuum to a residue.

The product obtained was then charged at room temperature to 2 equivalents of zirconium tetrachloride and stirred for 3 days. This was concentrated to a residue under vacuum and combined with 500 equivalents of MMAO in an oven-dried glass vial with stirring.

Polymerization Using this catalyst composition, copolymerization of ethylene and 1-hexene was carried out as in Examples 1-10. The activity of the catalyst was 12205. I2 of 0.166, 3.0
A copolymer having an I21 of 8, a melt flow ratio of 18.5 and a BBF of 9.39 was obtained.

Example 33 A catalyst composition containing the reaction product of cinnamyl-cyclopentadienyl dianion, metal-exchanged with magnesium bromide, ZrCl ₄ and modified methylaluminoxane was prepared as follows, Used to copolymerize with 1-hexene.

An equimolar (0.22 mmol) mixture of dilithium cinnamyl cyclopentadienide and magnesium bromide prepared in Examples 1 to 10 above was stirred in a dry box at room temperature. The solid was cooled (-
(30 ° C.) About 1 ml of THF-d8 was added. The solution was stirred for 2 hours.

The obtained product was first treated with THF-d8
A solution of equimolar amount of zirconium tetrachloride in milliliter was charged at room temperature. The mixture was stirred overnight.
The solvent layer was concentrated under vacuum to a residue. To this residue was added 10 ml of toluene under stirring, and then 5
00 equivalent of MMAO was added. This produced a catalyst product.

Polymerization Using this catalyst composition, copolymerization of ethylene and 1-hexene was carried out as in Examples 1-10. The activity of the catalyst was 4345.

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Claims (17)

[Claims] (1) The following formula: Wherein L is a cycloalkadienyl ligand; W, X, Y and Z are each hydrogen, a hydrocarbyl or silyl group having from 1 to 20 carbon atoms, and at least two Group IVA atoms Can be linked to L via a bridging group that includes, provided that one of X, Y and Z is
A group for stabilizing a negative charge selected from a group IVA trialkyl group, an aryl group, a heteroaromatic group, an ethylenically unsaturated hydrocarbon group, an acetylene unsaturated hydrocarbon group, a ketone group and an aromatic organometallic moiety. A) catalyst precursor. 2. The following formula: Catalyst precursor. 3. The following formula: Catalyst precursor. (1) The following formula: Wherein L is a cycloalkadienyl ligand; W, X, Y and Z are each hydrogen, a hydrocarbyl or silyl group having from 1 to 20 carbon atoms, and at least two Group IVA atoms Can be linked to L via a bridging group that includes, provided that one of X, Y and Z is
A group for stabilizing a negative charge selected from a group IVA trialkyl group, an aryl group, a heteroaromatic group, an ethylenically unsaturated hydrocarbon group, an acetylene unsaturated hydrocarbon group, a ketone group and an aromatic organometallic moiety. Catalyst precursor) and (2)
III. A catalyst composition comprising a reaction product of a compound containing a metal from Groups B to VIII or a lanthanide group and (3) an activating cocatalyst. 5. The catalyst precursor is as follows: The catalyst composition according to claim 4, which is 6. A catalyst precursor according to the formula: The catalyst composition according to claim 4, which is 7. The catalyst composition according to claim 4, wherein the compound containing a metal from Groups IIIB-VIII or the lanthanide group is a zirconium compound. 8. The catalyst composition according to claim 4, wherein the activating cocatalyst is selected from the group consisting of methylaluminoxane, modified methylaluminoxane, alkylboranes and mixtures thereof. 9. Under polymerization conditions, at least one α-olefin is converted to (1) a compound of the formula: Wherein L is a cycloalkadienyl ligand;
W, X, Y and Z are each hydrogen, a hydrocarbyl group having 1 to 20 carbon atoms or a silyl group, which can be bonded to L via a bridging group containing at least two Group IVA atoms. However, one of X, Y and Z is
A group for stabilizing a negative charge selected from a group IVA trialkyl group, an aryl group, a heteroaromatic group, an ethylenically unsaturated hydrocarbon group, an acetylene unsaturated hydrocarbon group, a ketone group and an aromatic organometallic moiety. Catalyst precursor) and (2)
A process for producing an olefin polymer, which comprises contacting a compound containing a metal from Group III B to VIII or a lanthanide group with a catalyst composition containing a reaction product of (3) an activating cocatalyst. 10. The catalyst precursor is: The method of claim 9, comprising: 11. The catalyst precursor is The method of claim 9, comprising: 12. The method of claim 9, wherein the compound comprising a metal from Groups IIIB-VIII or the lanthanide group is a zirconium compound. 13. The method of claim 9, wherein the activating co-catalyst is selected from the group consisting of methylaluminoxane, modified methylaluminoxane, alkylboranes and mixtures thereof. 14. The method of claim 9, which is performed in the gas phase. 15. The method of claim 9, wherein the olefin monomer is selected from the group consisting of ethylene, higher α-olefins, dienes, and mixtures thereof. 16. An olefin polymer produced by the method of claim 9. 17. An ethylene polymer produced by the method of claim 9.