JPH05320237A - Solid catalyst for olefin polymerization and method for producing polyolefin using the same - Google Patents

Abstract

PURPOSE:To obtain a catalyst for olefin polymerization which is highly active and gives a polyolefin with a high bulk specific gravity by depositing a specific transition metal compd. and an ionic compd. on a carrier pretreated with an organometallic compd. CONSTITUTION:The catalyst is prepd. by depositing a transition metal compd. of formula I, II, or III and an ionic compd. of formula IV on a carrier pretreated with an organometallic compd. In those formulas, Cp is an unsatd. hydrocarbon residue coordinated with M; Cp' is an unsatd. hydrocarbon residue cross-linked with R and coordinated with M; R is a divalent residue having N, O, Si, P, or S or a linear satd. hydrocarbon residue; M is a metal atom of the group II, IV, or V; X is a ligand having N, O, Si, P, B, or S and coordinated with M; Q is a cation component of the ionic compd.; Y is an anion component of the ionic compd.; and m is 1, 2, or 3.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an olefin polymerization catalyst and an olefin polymerization method using the same, and more particularly to a method for producing a polyolefin with high activity by using an olefin polymerization catalyst in which a specific compound is combined. ..

[0002]

BACKGROUND OF THE INVENTION As a polymerization catalyst for olefins, a combination of a metallocene compound having a group having a conjugated π electron, particularly cyclopentadiene and its derivative as a ligand, and an alkylaluminoxane obtained by the reaction of trialkylaluminum and water. It has been known. For example, JP-A-58-19309 discloses a method for polymerizing biscyclopentadienyl zirconium dichloride and olefin using methylaluminoxane as a catalyst. In addition, JP-A-61-130
314, JP-A-61-264010, JP-A-1-301704 and JP-A-301704
2-41303 discloses a method for producing isotactic poly-α-olefins or syndiotactic poly-α-olefins and a polymerization catalyst for producing these stereoregular poly-α-olefins, All of the disclosed catalyst systems use aluminoxane as a cocatalyst.

On the other hand, research on homogeneous Ziegler-Natta catalysts that do not use aluminoxane has also been conducted,
A catalyst system mainly composed of a metallocene compound and an alkylaluminum compound has been investigated. Although this catalyst system has low activity, it is already known to have polymerization activity for olefins. It is considered that the active species of this catalyst is a cationic metallocene compound or an ion pair type metallocene complex.

Recently, it has been reported that an isolated cationic metallocene compound having cyclopentadiene or a derivative thereof as a ligand has a polymerization activity for an olefin by itself, even in the absence of coexisting methylaluminoxane. Has been done. For example, RF JORDAN et al., J. Am. Chem. Soc., 1986, Vol. 108, page 7410-7411, has tetraphenylborane as an anion, and has a zirconium cation having two cyclopentadienyl groups and a methyl group as ligands. It has been reported that the complex was isolated by using a donor such as tetrahydrofuran as a ligand, and the isolated complex had a polymerization activity of ethylene in methylene chloride.

Turner et al., J. Am. Chem. Soc., 1989
Volume 111, pages 2728-2729 and special table 1-501950, special table 1-5020
A transition metal compound having a cyclopentadienyl group having a substituent in 36 or a derivative thereof as a ligand and capable of reacting with at least one proton, and a compound providing a stable anion having a cation capable of giving a proton. It has been reported that the ion-pair type metallocene complex formed from OH has the polymerization activity of olefin. Further, JP-A-3-139504, JP-A-3-179005, JP-A-3-179006,
JP-A-3-207703 and JP-A-3-207704 also disclose olefin polymerization methods that do not use aluminoxane.

Further, Zambelli et al., Macromolecules, 1989.
Vol. 22, pp. 2186-2189, pp. 2186-2189, shows that isotactic polypropylene can be obtained by polymerizing propylene with a catalyst that combines a zirconium compound having a cyclopentadienyl group derivative as a ligand and trimethylaluminum and fluorodimethylaluminum. It has been reported, and in this case also, the active species is considered to be an ion pair type metallocene compound.

[0007]

The method for polymerizing olefins using a combination catalyst of a metallocene compound and an alkylaluminoxane is characterized by high polymerization activity per transition metal. However, in these methods, the polymerization activity per metallocene compound unit is high because a large amount of expensive aluminoxane is used as a cocatalyst, and the activity per aluminoxane unit is not so high. Therefore, there is a problem that the production cost of the polymer becomes high, and it is very difficult to remove the aluminoxane from the polymer produced after the polymerization, and there is a problem that a large amount of catalyst residue remains in the polymer.

[0008] On the other hand, in the method in which a cationic zirconium complex is used as a catalyst without using an alkylaluminoxane, the above-mentioned problems relating to the alkylaluminoxane are eliminated, but these catalyst systems are different from olefins in comparison with the catalyst system using an alkylaluminoxane. There was a problem that the polymerization activity of was very small. Furthermore, in these methods, it is necessary to use a dimethyl complex or the like obtained by alkylating a dichloro complex with an expensive alkylating reagent such as methyllithium or methyl Grignard reagent, and there is a problem in the yield of alkylation. Therefore, there is a problem that the production cost of the catalyst increases. Further, many of these alkylated metallocene compounds are unstable, and particularly in a solution dissolved in a hydrocarbon solvent or the like, they are easily decomposed by a trace amount of impurities such as water and oxygen, or light, so that the monomer or the monomer during polymerization may be easily decomposed. The impurities contained in the solvent should be minimized.

When olefins are polymerized using a Ziegler type catalyst, it is possible to remove impurities contained therein by treating the monomer and / or the solvent with an organometallic compound, particularly an alkylaluminum compound. .. This method can be applied to the case of using these ion pair catalysts, using a monomer and / or a solvent treated with alkylaluminum, a transition metal compound, and a compound that donates a stable anion having a cation. After forming the ion pair type metallocene complex to be formed, and removing the influence of impurities by adding an organometallic compound, the polymerization activity for olefins can be improved to some extent even with these catalysts JP-A-3-179005, It is shown in JP-A-3-207704. However, even such a method is inferior in activity as compared with the combined catalyst system using an alkylaluminoxane as a cocatalyst.

It has been desired that a transition metal compound having a transition metal-heteroatom bond, which is relatively stable, inexpensively available, and easy to synthesize, can be used as it is, and that the olefin polymerization can be highly active. In addition to these problems, since all of the above catalysts are homogeneous, the resulting polymer particles become fine fine powder, and the bulk density is low, which makes handling difficult and results in poor productivity. Polymerized polymer adheres to the surface, and it is difficult to control polymerization due to poor heat transfer, resulting in interruption of continuous polymerization, etc., and production on an industrial scale cannot be stably performed.

In order to solve these problems, in a catalyst system using methylaluminoxane as a cocatalyst, insolubilization of methylaluminoxane or loading of a transition metal compound on a carrier is disclosed, for example, in JP-A-61-108610. Kaisho 61-276805
, JP-A-61-296008, JP-A-63-199206 and the like. However, these methods cannot reduce the amount of catalyst residue contained in the produced polymer because the polymerization activity per solid catalyst is low.

Further, the above-mentioned ion-pair type catalyst has a small activity from the beginning, is easily affected by impurities, and becomes inactive due to a small amount of impurities, so that it is very difficult to synthesize a supported catalyst.

[0013]

Means for Solving the Problems The present inventors have intensively studied a method for producing a polyolefin with high activity by solving the above problems and using a specific transition metal compound and a specific compound in combination, and completed.

That is, the present invention provides (a) an unsaturated hydrocarbon coordinated to M, wherein (C5), (C6) or (C7) of the following general formula (wherein Cp is the same or different from each other). A residue, Cp ′ is an unsaturated hydrocarbon residue, which is the same or different from each other and is coordinated to M, which is bridged by R, and R is 2
A linear saturated hydrocarbon residue which may have a residue or side chain containing a valent nitrogen atom, oxygen atom, silicon atom, phosphorus atom or sulfur atom, or a part or all of its linear carbon atom A residue substituted with a silicon atom, a germanium atom or a tin atom, M is a metal atom selected from Group 3, 4 or 5 of the periodic table, and X is a nitrogen atom coordinated with M. Represents a ligand containing an oxygen atom, a silicon atom, a phosphorus atom, a boron atom or a sulfur atom).

[0015]

Embedded image CpMXn

[0016]

[Chemical 6]

[0017]

[Chemical 7] (B) Represented by the following general formula (Formula 8) (wherein Q represents a cation component of an ionic compound, Y represents an anion component of the ionic compound, and m represents an integer of 1, 2 or 3). An ionic compound,

[0018]

Embedded image [Q] m [Y] m ⁻ (c) A solid catalyst for olefin polymerization, which is supported on a carrier treated with an organometallic compound. Further, the present invention is a method for producing a polyolefin, which comprises polymerizing an olefin by using the solid catalyst in the presence of an organometallic compound.

In the present invention, the transition metal compound is
Examples thereof include transition metal compounds represented by (Formula 5), (Formula 6) or (Formula 7) in the above general formula.

In the formula, the unsaturated hydrocarbon residue represented by Cp is a monocyclic or polycyclic hydrocarbon having 5 to 50 carbon atoms and a conjugated π electron or some of them are heteroatoms. Examples thereof include a residue substituted with, and specifically, cyclopentadienyl or a part or all of hydrogen thereof substituted with a hydrocarbon residue having 1 to 10 carbon atoms (here, a hydrocarbon residue). May have a structure in which its terminal is again bound to the cyclopentadiene ring, or may be a residue in which a part of the carbon atoms of a hydrocarbon residue is replaced with a hetero atom), or indenyl, fluorenyl, etc. Ring aromatic hydrocarbon residue or some or all of the hydrogen thereof is replaced by a hydrocarbon residue having 1 to 10 carbon atoms (wherein the hydrocarbon residue has its end bound to the aromatic ring again) did May be a concrete, also ligands some of the carbon atoms of the hydrocarbon residue is coordinated to the transition metal atom M, etc. may also be) at residue substituted with heteroatoms are exemplified. In the case of (Formula 6) in the above general formula, these may be the same as or different from each other.

The unsaturated hydrocarbon residue represented by Cp 'is a monocyclic or polycyclic conjugated π having 5 to 50 carbon atoms.
Examples include hydrocarbons having electrons or residues in which some of them are substituted with heteroatoms. Specifically, cyclopentadienyl or a part or all of hydrogens thereof is a carbon atom having 1 to 10 carbon atoms. Substituted with a hydrogen residue (wherein the hydrocarbon residue may have a structure in which its end is again bound to the cyclopentadiene ring, and some of the carbon atoms of the hydrocarbon residue are replaced with heteroatoms) Or a polycyclic aromatic hydrocarbon residue such as indenyl or fluorenyl or a part or all of the hydrogen thereof is replaced by a hydrocarbon residue having 1 to 10 carbon atoms (wherein The hydrocarbon residue may have a structure in which the end is again bound to the aromatic ring, or may be a residue in which a part of carbon atoms of the hydrocarbon residue is replaced with a hetero atom). The ligand coordinated to the atom M is exemplified. These may be the same or different from each other,
Two Cp's have a structure bridged by R.

The divalent group represented by R includes -O- and -S-.
, -SS-, -SO-, -SO _2- , -CO-, -NR-, -PR-, -POR-
, -OSiR ₂ O- or a methylene group represented by the following formula (Formula 9) or a silylene group or a germylene group in which some or all of the carbon atoms of the methylene group are substituted with silicon atoms, germanium atoms, or tin atoms. , Those having a stannylene group are exemplified.

[0023]

Embedded image _{- (R 2 C) k- (} R 2 Si) l - (R 2 Ge) p - (R 2 Sn) q - ( hydrocarbons to R is not hydrogen or C 1 -C formula 20 Representing a residue, each R may be the same or different, k, l, p and q are integers from 0 to 4 and the following formula 1
Represents an integer that satisfies ≦ k + l + p + q ≦ 4. ) X is a nitrogen atom, an oxygen atom, a silicon atom, a phosphorus atom coordinated to M,
A ligand containing a boron atom or a sulfur atom, NR ' ₂ , OR',
OCR ' ₂ , OSiR' ₃ , SiR ' ₃ , GeR' ₃ , PR ' ₂ , POR' ₂ , SR '
, SOR ', SO ₂ R', BR ' ₃ (R' is hydrogen or 1 to 2 carbon atoms
0 hydrocarbons or residues in which some of them have been replaced by heteroatoms). n is 1, 2 or 3 depending on the valence of M. When n is 2 or more, Xs may be crosslinked with each other, and a chelate type ligand is also exemplified.

The ionic compound used in the present invention is an ionic compound formed from an ion pair of a cation and an anion represented by the general formula (Formula 8).

In the formula, Q is a cation component of the ionic compound, and is a carbonium cation, tropylium cation, ammonium cation, oxonium cation, sulfonium cation, phosphonium cation, transition metal cation, ferrocenium cation. , Indenium cations, and the like. Specific examples of these cations include triphenylcarbonium, diphenylcarbonium, cycloheptatrienium, tributylammonium, N, N-dimethylanilinium, dipropylammonium, dicyclohexylammonium, triphenylphosphonium, trimethylphosphonium and triphenyl. Examples include cations such as sulfonium, triphenyloxonium, triethyloxonium, pyrylium, silver and ferrocenium.

Y is an anion component of an ionic compound, and examples thereof include a boron compound anion, an aluminum compound anion and a gallium compound anion. Specifically, tetraphenylboron, tetrakis (pentafluorophenyl) boron, tetrakis (3,4,5-trifluorophenyl) boron, tetraphenylaluminum,
Tetrakis (pentafluorophenyl) aluminum,
Examples include anions such as tetrakis (3,5-bistrifluorophenyl) aluminum, tetraphenylgallium, and tetrakis (pentafluorophenyl) gallium.

In the present invention, it is important that the carrier compound is treated with an organometallic compound in advance before the carrier compound is loaded with the transition metal compound and the ionic compound. Here, the method of treating the carrier compound with the organometallic compound is not particularly limited, and both components may be brought into contact with each other in a solvent or in a solid phase. Examples of the method of bringing them into contact with each other in a solvent include a method of suspending a carrier compound in an inert solvent such as a hydrocarbon solvent, adding an organometallic compound and stirring.

As a method of contacting with a solid phase, a method of co-milling and the like can be mentioned. The method of co-pulverization is not particularly limited, and examples thereof include commonly used methods of pulverizing using a ball mill, a vibration mill, or the like. Also,
At the time of crushing, various organic compounds can be used together as a crushing aid. It is also possible to treat the pulverized product with a solvent after co-pulverization. The temperature at the time of co-pulverization is not particularly limited, and it may be carried out at a temperature of -100 to 100 ° C, usually around room temperature.

In the present invention, the organometallic compound which is first reacted with the carrier compound is a metal atom of Groups 1, 2, 12 and 13 of the Periodic Table, preferably aluminum, boron, gallium, zinc or magnesium. When a halogen atom, an oxygen atom or a hydrogen atom or a residue such as alkyl, alkoxy, or aryl is coordinated to these metals and there are a plurality of ligands, they may be the same or different. However, at least one of them is an alkyl group. For example, an alkyl metal compound having 1 or 2 or more alkyl residues having 1 to 12 carbon atoms, an alkyl metal halide having the above alkyl residue and another atom or residue coordinated, an alkyl metal alkoxide, etc. It is illustrated. Among them, an alkylboron compound or an alkylaluminum compound in which at least one alkyl residue having 2 or more carbon atoms is coordinated is preferably used.

Examples of preferred organometallic compounds for the metal atom being aluminum include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tributylaluminum, triisobutylaluminum, tripentylaluminum, trihexylaluminum. ,
Triheptyl aluminum, trioctyl aluminum, tridecyl aluminum, isoprenyl aluminum, diethyl aluminum hydride, diisopropyl aluminum hydride, diisobutyl aluminum hydride, diethyl aluminum chloride, di-n-propyl aluminum chloride, diisopropyl aluminum chloride, diisobutyl aluminum chloride, diethyl aluminum Ethoxide, diisopropyl aluminum isopropoxide, ethyl aluminum sesquichloride, isopropyl aluminum sesquichloride, isobutyl aluminum sesquichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride, isobutyl aluminum dichloride, ethyl acetate Mini Umm diisopropoxide, and the like.

The carrier compound used in the present invention may be an organic compound, an inorganic compound or a solid compound, and may be a fine powdery polymer compound, inorganic oxide, inorganic halide, inorganic oxide or carbonic acid. Examples thereof include various metal salts such as salts and perchlorates, and complexes thereof.

The carrier compound used in the present invention is preferably an anhydride, and therefore, it is preferable to dry it in advance before treating it with an organometallic compound except for a carrier industrially available as an anhydride. The drying method is usually under reduced pressure or in a dry atmosphere at 0 to 1000 ° C, preferably 100 to 800 ° C.
Then, heat treatment may be performed for a predetermined time. Those carrier compounds having a size of usually about 1 μm to 0.1 mm can be preferably used.

In the present invention, the method of synthesizing the solid catalyst by supporting the transition metal compound and the ionic compound is not particularly limited, and both may be contacted in a solvent or in a solid phase. As a method of bringing them into contact with each other in a solvent, a carrier compound treated with an organometallic compound is suspended in an inert solvent such as a hydrocarbon solvent, and a transition metal compound and an ionic compound are added and stirred. Is mentioned.

As the method of contacting with the solid phase, a method of co-pulverization and the like can be mentioned. The method of co-pulverization is not particularly limited, and examples thereof include commonly used methods of pulverizing using a ball mill, a vibration mill, or the like. Also,
At the time of crushing, various organic compounds can be used together as a crushing aid. It is also possible to treat the pulverized product with a solvent after co-pulverization. The temperature at the time of co-pulverization is not particularly limited, and it may be carried out at a temperature of -100 to 100 ° C, usually around room temperature.

Another important point in the present invention is to bring the organometallic compound into contact with the supported catalyst during the polymerization. Unless an organometallic compound is used, olefin is not polymerized at all, or even if polymerized, the activity becomes very low, and the reproducibility of polymerization is poor.

The ratio of the organometallic compound used in the polymerization to the transition metal compound is 1 to 100,000 mole times, usually 1 to 5000 mole times.

The ratio of the ionic compound to the transition metal compound used in the catalyst is 0.1 to the transition metal compound.
It is 100,000 mole times, usually 0.5-10000 mole times.

Further, in the present invention, hydrogen which is usually used in a Ziegler type catalyst for adjusting the molecular weight of the obtained polyolefin can be used. Furthermore, the presence of an internal olefin in the polymerization of the olefin can control the molecular weight of the produced polyolefin.

Specific examples of the internal olefin include 2-
Straight chain internal olefins such as butene, 2-pentene and 2-hexene, cyclic olefins such as cyclopentene, cyclohexene, cycloheptene and norbornene, 5-methylene-2-
Examples include dienes such as norbornene and 5-ethylidene norbornene.

Examples of the solvent used in the preparation or polymerization or treatment of the catalyst using the catalyst component in the present invention include propane, butane, isobutane, pentane, hexane, heptane, octane, nonane, decane, cyclopentane, cyclohexane, Saturated hydrocarbon compounds such as cycloheptane and methylcyclohexane, aromatic hydrocarbon compounds such as benzene, toluene and xylene, and halogenated hydrocarbon compounds such as methylene chloride and chlorobenzene can also be used. Further, an ether, a nitrile, an ester compound or the like can be used as long as the solvent itself does not bind to the produced transition metal cation compound or strongly coordinate to inactivate the polymerization activity.

The olefin polymerization conditions using this catalyst component are not particularly limited, and a solvent polymerization method using an inert medium, a bulk polymerization method substantially free of an inert medium, or a gas phase polymerization method can also be used.

Further, examples of the olefin used for the polymerization include olefins having 2 to 25 carbon atoms, specifically, ethylene, propylene, butene-1, pentene-1, and hexene-.
1, heptene-1, octene-1, nonene-1, decene-1, undecene-1, dodecene-1, tridecene-1, tetradecene
-1, pentadecene-1, hexadecene-1, octadecene-1
In addition to linear olefins such as 3-methylbutene-1,4-methylpentene-1,4,4-dimethylpentene-1 and other branched olefins and cyclopentene, cyclooctene, norbornene and other cyclic olefins are exemplified. The olefins can be homopolymerized or copolymerized with each other, and if necessary, the diene can be copolymerized. Furthermore, in this polymerization system, an aromatic olefin such as styrene can be polymerized, and an aromatic olefin alone or a copolymer with the above-mentioned olefin can be also used.

As the polymerization temperature and the polymerization pressure, general conditions used in a known method are used. The polymerization temperature can be -20 to 150 ° C., and the polymerization pressure can be atmospheric pressure to 100 kg / cm ^2. ..

[0044]

EXAMPLES The present invention will be further described with reference to the following examples.

Example 1 10 g of anhydrous magnesium chloride and 0.3 g of triethylaluminum.
Mixing 1.9 ml of toluene solution containing 38 g, vibration mill (pot inner volume 1000 ml, SUS ball 2k with diameter 12.7 mm)
g) and co-ground for 17 hours. Furthermore, 3.5 g of triphenylmethanetetrakis (pentafluorophenyl) boron and 1.0 g of isopropyl (cyclopentadienyl-1-fluorenyl) zirconium dimethoxide as a transition metal compound.
g was placed in a vibration mill and pulverized for 4 hours to obtain a solid catalyst component.

300 mg of the above solid catalyst component and 0.51 ml of triethylaluminum were placed in an autoclave having an internal volume of 5 liters, 1.5 kg of propylene was added, and polymerization was carried out at 60 ° C. for 2 hours. Unreacted propylene was purged to take out the polymer, and the polymer was dried to obtain 103 g of the polymer. Also, the polymer 13
The intrinsic viscosity (hereinafter referred to as η) measured with a 5 ° C tetralin solution was 0.73, and the ratio of the weight average molecular weight to the number average molecular weight measured with 1,2,4-trichlorobenzene (hereinafter, MW / MN
Was 3.4). The bulk specific gravity was 0.32 g / ml, and the adhesion of the polymer to the wall of the polymerization machine was small.

Comparative Example 1 As a solid catalyst component, triphenylmethanetetrakis (pentafluorophenyl) boron and isopropyl (cyclopentadienyl-1-fluorenyl) zirconium dimethoxide were used without using a co-ground product of anhydrous magnesium chloride and triethylaluminum. Polymerization was carried out in the same manner as in Example 1 except that was used as it was (without co-pulverization). After the polymerization, the resulting slurry was taken out and dried to obtain 114 g of the polymer.
Obtained. Further, η of the polymer was 0.71 and MW / MN was 2.2. The bulk specific gravity was 0.1 or less, and a large amount of the polymer adhered to the wall of the polymerization machine.

Example 2 Triphenylmethanetetrakis (pentafluorophenyl) borane instead of tris (pentafluorophenyl)
Polymerization of propylene was carried out in the same manner as in Example 1 except that boron was used to obtain 16 g of a polymer. The η of the polymer was 0.80 and the MW / MN was 4.2. The bulk specific gravity was 0.32 g / ml, and the adhesion of the polymer to the wall of the polymerization machine was small.

Example 3 Ethylenebis (tetrahydroindenyl) zirconium dimethoxide 4.0 m instead of isopropyl (cyclopentadienyl-1-fluorenyl) zirconium dimethoxide
Polymerization of propylene was carried out in the same manner as in Example 1 except that g was used to obtain 86 g of a polymer. The polymer had an η of 0.79 and a MW / MN of 4.6. The bulk specific gravity is
It was 0.32 g / ml, and the adhesion of the polymer to the wall of the polymerization machine was small.

Example 4 Polymerization of ethylene was carried out in the same manner as in Example 1 except that dicyclopentadienyl zirconium dimethoxide was used instead of isopropyl (cyclopentadienyl-1-fluorenyl) zirconium dimethoxide. Then, 43 g of a polymer was obtained. Polymer η is 3.04, MW / MN is 5.
0, and the adhesion of the polymer to the wall of the polymerizer was small.

Example 5 A 2-liter four-necked flask purged with nitrogen was placed under a reduced pressure of 600.
50 g of γ-alumina heat-treated at 6 ° C. was added, 1 liter of toluene was added, and 25 ml of a toluene solution containing 5.0 g of trimethylaluminum was added dropwise with stirring. At room temperature
After stirring for 17 hours, the mixture was filtered through a glass filter, washed with 50 ml of pentane three times, and dried under reduced pressure. Replaced with nitrogen
Into a 500 ml four-necked flask, 10 g of this alkylaluminum-treated γ-alumina was added, and 100 ml of toluene was added to the mixture while stirring to add 2.2 g of triphenylmethanetetrakis (pentafluorophenyl) boron and isopropyl (cyclo Pentadienyl-1-fluorenyl) zirconium dimethoxide in toluene solution 2
50 ml was added dropwise. After stirring at room temperature for 1 hour, the mixture was filtered through a glass filter, washed with 50 ml of pentane three times, and dried under reduced pressure.

300 mg of the above treated product and 0.23 g of triethylaluminum were placed in an autoclave having an internal volume of 5 liters, and 1.5 kg of propylene was added thereto, followed by polymerization at 60 ° C. for 2 hours. Unreacted propylene was purged to take out the polymer, which was dried to obtain 132 g of the polymer. Polymer η is 0.70, MW / MN
Was 2.4. Further, the bulk specific gravity was 0.37 g / ml, and the adhesion of the polymer to the polymerization machine on the wall was small.

[0053]

Industrial Applicability By carrying out the method of the present invention, a highly active polyolefin having a large bulk specific gravity per catalyst can be obtained, which is extremely valuable industrially.

[Brief description of drawings]

FIG. 1 is a flow chart for facilitating understanding of the present invention.

Claims (2)

[Claims] (A) (Chemical formula 1), (Chemical formula 2) or (Chemical formula 3) of the following general formula (in the formula, Cp is the same or different from each other, an unsaturated hydrocarbon residue coordinated to M is , Cp ′ is an unsaturated hydrocarbon residue which is the same or different from each other and is bridged with R, which is coordinated to M, and R is a divalent nitrogen atom, oxygen atom, silicon atom, phosphorus atom or sulfur atom. A linear saturated hydrocarbon residue which may have a residue or a side chain or a residue in which some or all of the carbon atoms of the linear chain thereof are substituted with a silicon atom, a germanium atom or a tin atom, M is a metal atom selected from Group 3, 4 or 5 of the periodic table, and X is a nitrogen atom, an oxygen atom coordinated to M,
A transition metal compound represented by a ligand containing a silicon atom, a phosphorus atom, a boron atom or a sulfur atom) and CpMXn [Chemical 3] (B) represented by the following general formula (Formula 4) (wherein Q represents a cation component of an ionic compound, Y represents an anion component of the ionic compound, and m represents an integer of 1, 2 or 3). an ionic compound, embedded image [Q] m [Y] m - (c) comprising supported on a carrier treated with the organometallic compound solid catalyst. 2. A process for producing a polyolefin, which comprises polymerizing an olefin by using the solid catalyst according to claim 1 in the presence of an organometallic compound.