JP3258702B2 - Solid catalyst for olefin polymerization and method for producing polyolefin using the same - Google Patents

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]

2. Description of the Related Art As an olefin polymerization catalyst, a combination of a metallocene compound having a conjugated π electron, particularly cyclopentadiene or a derivative thereof as a ligand, and an alkylaluminoxane obtained by reacting a trialkylaluminum with water. It has been known. For example, JP-A-58-19309 discloses a method for polymerizing olefins using biscyclopentadienyl zirconium dichloride and methylaluminoxane as catalysts. JP-A-61-130
314, JP-A-61-264010, JP-A-1-301704 and JP-A-Hei.
2-41303 discloses a method for producing isotactic poly-α-olefin or syndiotactic poly-α-olefin and a polymerization catalyst for producing these stereoregular poly-α-olefins, All of the disclosed catalyst systems use aluminoxane as a co-catalyst.

[0003] On the other hand, studies have been made on a homogeneous Ziegler-Natta catalyst which does not use aluminoxane.
A catalyst system mainly comprising a metallocene compound and an alkylaluminum compound has been studied. Although this catalyst system has low activity, it is already known to have polymerization activity for olefins. It is believed that the active species of this catalyst is a cationic metallocene compound or an ion-pair metallocene complex.

[0004] Recently, it has been reported that an isolated cationic metallocene compound having cyclopentadiene or a derivative thereof as a ligand has polymerization activity for olefins alone without the coexistence of methylaluminoxane as a cocatalyst. Have been. For example, RFJORDAN et al. In J. Am. Chem. Soc., 1986, 108: 7410-7411, zirconium cation having tetraphenylborane as an anion and having two cyclopentadienyl groups and a methyl group as ligands. The complex was isolated by using a donor such as tetrahydrofuran as a ligand, and it was reported that the isolated complex had ethylene polymerization activity in methylene chloride.

Also, Turner et al., J. Am. Chem. Soc., 1989
Volume 111, pages 2728-2729 and Tokiohei 1-501950, Tokiohei 1-5020
A transition metal compound capable of reacting with at least one proton having a cyclopentadienyl group or a derivative thereof having a substituent at 36 as a ligand, and a compound providing a stable anion having a cation capable of providing a proton It has been reported that an ion-pair type metallocene complex formed from has olefin polymerization activity. In addition, JP-A-3-139504, JP-A-3-17905, JP-A-3-17906,
JP-A-3-207703 and JP-A-3-207704 also disclose olefin polymerization methods without using aluminoxanes.

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

[0007]

An olefin polymerization method using a combination catalyst of a metallocene compound and an alkylaluminoxane is characterized by high polymerization activity per transition metal. However, the high polymerization activity per metallocene compound unit in these methods is due to the use of a large amount of expensive aluminoxane as a cocatalyst, and the activity per aluminoxane unit is not very high. Therefore, there is a problem that the production cost of the polymer increases, and further, 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, the above-mentioned problems relating to alkylaluminoxane are eliminated by the method using a cationic zirconium complex as a catalyst without using alkylaluminoxane, but these catalyst systems are more effective in reducing olefins than catalyst systems using alkylaluminoxane. There was a problem that the polymerization activity was very small. Furthermore, in these methods, it is necessary to use a dimethyl complex obtained by alkylating the dichloro complex with an expensive alkylating reagent such as methyllithium or methyl Grignard reagent, and there is a problem in the alkylation yield. Therefore, there was a problem that the production cost of the catalyst was increased. Furthermore, many of these alkylated metallocene compounds are unstable, especially in a solution dissolved in a hydrocarbon solvent, etc. Impurities contained in the solvent must be minimized.

In the case of polymerizing an olefin using a Ziegler catalyst, it is possible to remove impurities contained in the monomer and / or solvent by treating the monomer and / or solvent with an organometallic compound, particularly an alkylaluminum compound. . It is possible to apply this method when using these ion-pair type catalysts, using a monomer and / or a solvent treated with alkylaluminum, or using a transition metal compound and a compound that provides a stable anion having a cation. After forming the ion-pair type metallocene complex to be formed, adding an organometallic compound to remove the influence of impurities, the polymerization activity of olefins can be improved to some extent even with these catalysts JP-A-3-17905, This is disclosed in JP-A-3-207704 and the like. However, even such a method is inferior in activity as compared to a 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 and easily available at a low cost and can be easily synthesized, can be used as it is, and that olefin polymerization can be highly active. In addition to these problems, any of the above catalysts are homogeneous, and the resulting polymer particles are fine and fine, and have a low bulk density, making it difficult to handle, resulting in poor productivity, Polymerization adhered to the surface, making it difficult to control the polymerization due to poor heat transfer, causing problems such as interruption of continuous polymerization, and the production on an industrial scale could not be performed stably.

For the purpose of solving these problems, in a catalyst system using methylaluminoxane as a co-catalyst, it is necessary to insolubilize methylaluminoxane or to carry a transition metal compound on a carrier, for example, as described in JP-A-61-108610. Kaikai 61-276805
And Japanese Patent Application Laid-Open Nos. 61-296008 and 63-199206. However, in these methods, since the polymerization activity per solid catalyst is low, the amount of catalyst residue contained in the produced polymer cannot be reduced.

Furthermore, the above-mentioned ion-pair type catalyst has a low activity from the beginning and is easily affected by impurities, and the activity is lost with a trace amount of impurities, so that it was very difficult to synthesize a supported type catalyst.

[0013]

Means for Solving the Problems The present inventors have solved the above-mentioned problems, and have earnestly studied a method for producing a polyolefin with high activity using a combination of a specific transition metal compound and a specific compound. completed.

That is, the present invention relates to (a) a compound represented by the following general formula (5), (6) or (7), wherein Cp is the same or different from each other, and is an unsaturated hydrocarbon coordinated to M: Cp 'is an unsaturated hydrocarbon residue coordinating to M, which is the same or different and is bridged by R, R is 2
A residue containing a divalent nitrogen atom, an oxygen atom, a silicon atom, a phosphorus atom or a sulfur atom or a linear saturated hydrocarbon residue which may have a side chain, or a part or all of the linear carbon atoms thereof; A residue substituted with a silicon atom, a germanium atom or a tin atom, M represents a metal atom selected from Group 4 of the periodic table, and X represents a general formula OR ′ coordinated with M
R 'is hydrogen or a hydrocarbon having 1 to 20 carbon atoms or
Some of which are substituted with heteroatoms)
1 shows the ligand represented. )

[0015]

[Image Omitted] CpMXn

[0016]

Embedded image

[0017]

Embedded image (B) The following general formula (Formula 8) (wherein Q is a cation component of an ionic compound, and Y is a boron compound
Nion, aluminum compound anion and gallium compound
M represents an integer of 1, 2 or 3; ) And an ionic compound represented by

[0018]

Embedded image (C) A solid catalyst for olefin polymerization, which is supported on a support treated with an organometallic compound of a metal belonging to Group 1, 2, 12, or 13 of the periodic table. Further, the present invention provides a polyolefin characterized in that an olefin is polymerized using the solid catalyst in the presence of an organometallic compound of a metal belonging to Group 1, 2, 12, or 13 of the periodic table. It is a manufacturing method of.

In the present invention, the transition metal compound includes
A transition metal compound represented by the following general formula (Chemical Formula 5), (Chemical Formula 6) or (Chemical Formula 7) can be exemplified.

In the formula, the unsaturated hydrocarbon residue represented by Cp is a monocyclic or polycyclic hydrocarbon having a conjugated π-electron having 5 to 50 carbon atoms, or some of them are heteroatoms. And more specifically, those wherein cyclopentadienyl or a part or all of hydrogen thereof is substituted by a hydrocarbon residue having 1 to 10 carbon atoms (here, the hydrocarbon residue May have a structure in which the terminal is again bonded to the cyclopentadiene ring, or may be a residue in which a part of a carbon atom of a hydrocarbon residue is substituted with a hetero atom), or a multi-chain such as indenyl and fluorenyl. Ring-aromatic hydrocarbon residues or those in which part or all of the hydrogen has been replaced by a hydrocarbon residue having 1 to 10 carbon atoms (here, the hydrocarbon residue has its terminal bonded to its 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 the above formula (Chem. 6), these may be the same 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 thereof include a hydrocarbon having an electron or a residue in which some of them are substituted with a hetero atom. Specifically, cyclopentadienyl or a part or all of the hydrogen is a hydrocarbon having 1 to 10 carbon atoms. Those substituted with a hydrogen residue (here, the hydrocarbon residue may have a structure in which the terminal is bonded to the cyclopentadiene ring again, and a part of the carbon atom of the hydrocarbon residue is replaced with a hetero atom) Or a polycyclic aromatic hydrocarbon residue such as indenyl, fluorenyl or the like or a part or all of the hydrogens of which are substituted with a hydrocarbon residue having 1 to 10 carbon atoms (wherein The hydrocarbon residue may have a structure in which the terminal is again bonded to the aromatic ring, or may be a residue in which a part of a carbon atom of the hydrocarbon residue is substituted with a hetero atom. A ligand coordinated to the atom M is exemplified. These may be the same or different from each other,
Two Cp's have a structure cross-linked by R.

The divalent group represented by R includes -O-, -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 germylene group in which part or all of the carbon atoms of the methylene group are substituted with a silicon atom, a germanium atom, or a tin atom And those having a stannylene group.

[0023]

Embedded image Wherein R represents a hydrogen atom or a hydrocarbon residue having 1 to 20 carbon atoms, and each R may be the same or different; k, l, p, and q are integers of 0 to 4; 1
Represents an integer satisfying ≦ k + 1 + p + q ≦ 4. ) X is OR 'coordinated to M (R' is hydrogen or a hydrocarbon having 1 to 20 carbon atoms or a residue in which some of them are substituted with a hetero atom). n depends on the valence of M,
1, 2, or 3. When n is 2 or more, Xs may be mutually cross-linked, and a chelating 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 above 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 cation and the like. Specific examples of these cations include triphenylcarbonium, diphenylcarbonium, cycloheptatrienium, tributylammonium, N, N-dimethylanilinium, dipropylammonium, dicyclohexylammonium, triphenylphosphonium, trimethylphosphonium, triphenyl Examples include cations such as sulfonium, triphenyloxonium, triethyloxonium, pyrylium, silver, and ferrocenium.

Further, Y is an anion component of the ionic compound, boron compound anions, aluminum compound anions, selected from gallium compound anions. Specifically, tetraphenylboron, tetrakis (pentafluorophenyl) boron, tetrakis (3,4,5-trifluorophenyl) boron, tetraphenylaluminum, tetrakis (pentafluorophenyl) aluminum, tetrakis (3,5-bistrifluoro) Anions such as phenyl) 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 carries 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 in a solvent or in a solid phase. As a method for bringing them into contact with each other in a solvent, there is a method in which a carrier compound is suspended in an inert solvent such as a hydrocarbon solvent, an organic metal compound is added, and the mixture is stirred.

Examples of the method of contacting with a solid phase include a method of co-grinding. The method of co-grinding is not particularly limited, and examples thereof include a commonly used method of grinding using a ball mill, a vibration mill, or the like. Also,
At the time of pulverization, various organic compounds can be used in combination as a pulverization aid. Further, it is also possible to treat the pulverized product with a solvent after co-pulverization. The temperature at the time of co-milling is not particularly limited, and may be at a temperature of -100 to 100 ° C, usually at a temperature around normal temperature.

In the present invention, the organometallic compound which is first reacted with the carrier compound is a metal atom belonging to Group 1, 2, 12, or 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 when there are a plurality of ligands, they are different even if they are the same. And at least one of them is an alkyl group. For example, an alkyl metal compound in which one or two or more alkyl residues having 1 to 12 carbon atoms are coordinated, an alkyl metal halide in which the above-described alkyl residue is coordinated with another atom or residue, an alkyl metal alkoxide, and the like. Is exemplified. Among them, an alkyl boron compound or an alkyl aluminum compound in which at least one alkyl residue having 2 or more carbon atoms is coordinated is preferably used.

Examples of preferred organometallic compounds in which the metal atom is aluminum include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tributylaluminum, triisobutylaluminum, tripentylaluminum, and 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 any of an organic compound, an inorganic compound, and a solid, and may be a fine powdery polymer compound, an inorganic oxide, an inorganic halide, an inorganic oxide, or a carbonate. 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. Therefore, it is preferable that the carrier compound is dried before being treated with the organometallic compound except for a carrier which is industrially available as an anhydride. The drying method is usually under reduced pressure or under a dry atmosphere at 0 to 1000 ° C, preferably 100 to 800 ° C.
Heat treatment for a predetermined time. These carrier compounds having a size of usually about 1 μm to 0.1 mm can be preferably used.

In the present invention, there is no particular limitation on the method of synthesizing the solid catalyst by supporting the transition metal compound and the ionic compound, and they may be brought into contact in a solvent or in a solid phase. These are brought into contact in a solvent, for example, by suspending a carrier compound treated with an organometallic compound in an inert solvent such as a hydrocarbon solvent, adding a transition metal compound and an ionic compound, and stirring the mixture. Is mentioned.

[0034] Examples of the method of contacting with a solid phase include a method of co-grinding. The method of co-grinding is not particularly limited, and examples thereof include a commonly used method of grinding using a ball mill, a vibration mill, or the like. Also,
At the time of pulverization, various organic compounds can be used in combination as a pulverization aid. Further, it is also possible to treat the pulverized product with a solvent after co-pulverization. The temperature at the time of co-milling is not particularly limited, and may be at a temperature of -100 to 100 ° C, usually at a temperature around normal temperature.

Another important point in the present invention is to bring the organometallic compound into contact with the supported catalyst during the polymerization. If an organometallic compound is not used, the olefin will not polymerize at all, or the activity will be very low even after polymerization, resulting in poor reproducibility of polymerization.

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

The ratio of the above ionic compound to the transition metal compound used for the catalyst is 0.1 to 0.1 with respect to the transition metal compound.
It is 100,000 molar times, usually 0.5-10000 molar times.

In the present invention, in order to adjust the molecular weight of the obtained polyolefin, hydrogen which is usually used in a Ziegler catalyst can be used. Furthermore, the molecular weight of the produced polyolefin can be controlled by the presence of an internal olefin during the polymerization of the olefin.

Specific examples of the internal olefin include 2-
Linear internal olefins such as butene, 2-pentene and 2-hexene, cycloolefins such as cyclopentene, cyclohexene, cycloheptene and norbornene, 5-methylene-2-
Dienes such as norbornene and 5-ethylidene norbornene are exemplified.

The solvent used in the preparation, polymerization or treatment of the catalyst using the catalyst component in the present invention includes, for example, 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. In addition, ethers, nitriles, ester compounds, and the like can be used as long as the solvent itself does not bind to the generated transition metal cation compound or strongly coordinate to inactivate the polymerization activity.

The polymerization conditions of the olefin using the 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, and a gas phase polymerization method can be used.

Examples of the olefin used for the polymerization include olefins having 2 to 25 carbon atoms, and specific examples thereof include 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, branched olefins such as 4,4-dimethylpentene-1 and cyclopentene, cyclooctene, and cyclic olefins such as norbornene are exemplified. An olefin can be homopolymerized or a copolymer of olefins can be copolymerized with each other. If necessary, a diene can be copolymerized. Further, in this polymerization system, an aromatic olefin such as styrene can be polymerized, and aromatic olefin alone or copolymerization with the above olefin can be performed.

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

[0044]

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

Example 1 10 g of anhydrous magnesium chloride and 0.1 g of triethylaluminum were used.
1.9 ml of a toluene solution containing 38 g was mixed with a vibrating mill (a SUS ball 2 k having a pot capacity of 1000 ml and a diameter of 12.7 mm)
g) and ground for 17 hours. Furthermore, 3.5 g of triphenylmethanetetrakis (pentafluorophenyl) boron and isopropyl (cyclopentadienyl-1-fluorenyl) zirconium dimethoxide 1.0 as a transition metal compound
g was crushed in a vibration mill 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, and 1.5 kg of propylene was added, followed by polymerization at 60 ° C. for 2 hours. Unreacted propylene was purged to remove the polymer, and dried to obtain 103 g of a polymer. Also 13 of polymer
The intrinsic viscosity (hereinafter referred to as η) measured with a tetralin solution at 5 ° C is 0.73, and the ratio of the weight average molecular weight to the number average molecular weight measured with 1,2,4-trichlorobenzene (hereinafter referred to as 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 Triphenylmethanetetrakis (pentafluorophenyl) boron and isopropyl (cyclopentadienyl-1-fluorenyl) zirconium dimethoxide were used as solid catalyst components without using a co-ground product of anhydrous magnesium chloride and triethylaluminum. Was polymerized in the same manner as in Example 1 except that the compound was used as it was (without pulverization). After the polymerization, the obtained slurry was taken out and dried to obtain 114 g of a polymer.
Obtained. The η of the polymer was 0.71, and the 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 Isopropyl (cyclopentadienyl-1-fluorenyl)
E) Instead of zirconium dimethoxide, ethylene bis
Trahydroindenyl) zirconium dimethoxide 4.0m
g in the same manner as in Example 1 except that
After the combination, 86 g of a polymer was obtained.

The η of the polymer is 0.79 and the MW / MN is 4.6
Met. 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 Ethylene was polymerized in the same manner as in Example 1 except that dicyclopentadienyl zirconium dimethoxide was used instead of isopropyl (cyclopentadienyl-1-fluorenyl) zirconium dimethoxide. However, 43 g of a polymer was obtained. Η of the polymer is 3.04, MW / MN is 5.
0, indicating little adhesion of the polymer to the wall of the polymerization machine.

Example 4 A 2-liter four-necked flask purged with nitrogen was placed under reduced pressure at 600
50 g of γ-alumina heat-treated at 6 ° C. for 6 hours 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 three times with 50 ml of pentane, and dried under reduced pressure. Nitrogen replaced
10 g of this gamma-alumina treated with alkylaluminum is placed in a 500 ml four-necked flask, 100 ml of toluene is added, and 2.2 g of triphenylmethanetetrakis (pentafluorophenyl) boron and isopropyl (cyclo) are used as a transition metal compound while stirring. (Pentadienyl-1-fluorenyl) toluene solution containing zirconium dimethoxide 2
50 ml was added dropwise. After stirring at room temperature for 1 hour, the mixture was filtered through a glass filter, washed three times with 50 ml of pentane, and dried under reduced pressure.

300 mg of the above treated product and 0.23 g of triethylaluminum were placed in a 5-liter autoclave, and 1.5 kg of propylene was added, followed by polymerization at 60 ° C. for 2 hours. Unreacted propylene was purged to remove the polymer, and dried to obtain 132 g of a polymer. Η of polymer is 0.70, MW / MN
Was 2.4. In addition, the bulk specific gravity was 0.37 g / ml, and the adhesion of the polymer to the polymerization machine was small.

[0053]

According to the present invention, a polyolefin having a high activity and a high bulk specific gravity per catalyst can be obtained by carrying out the method of the present invention, which is extremely valuable industrially.

[Brief description of the drawings]

FIG. 1 is a flowchart for helping an understanding of the present invention.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP 5-148316 (JP, A) JP 5-155926 (JP, A) JP 5-125112 (JP, A) JP 3- 207703 (JP, A) JP-A-3-179005 (JP, A) JP-A-3-234709 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 4/60-4 / 70

Claims (2)

(57) [Claims] (A) a compound represented by the following general formula (Cp), (Cp) or (Cp) wherein Cp is the same or different from each other and is an unsaturated hydrocarbon residue coordinated to M; , Cp ′ are the same or different unsaturated hydrocarbon residues bridged by R and 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 part or all of the straight-chain carbon atoms are substituted with a silicon atom, a germanium atom or a tin atom, M is a metal atom selected from Group 4 of the periodic table, and X is M
Wherein R 'is hydrogen or carbon number
1 to 20 hydrocarbons or some of them
A residue represented by a terrorist atom) . ) And a transition metal compound represented by Embedded image Embedded image (B) The following general formula (Formula 4) (wherein Q is a cation component of an ionic compound, and Y is a boron compound
Nion, aluminum compound anion and gallium compound
M represents an integer of 1, 2 or 3; With an ionic compound represented by the formula: (C) Metals of Groups 1, 2, 12, and 13 of the periodic table
A solid catalyst for olefin polymerization, which is supported on a support treated with an organometallic compound. 2. The method according to claim 1, wherein the solid catalyst according to claim 1
A process for producing a polyolefin, comprising polymerizing an olefin in the presence of an organometallic compound of a Group 2, Group 12, Group 12, or Group 13 metal .