JPH09302017A - Olefin polymerization catalyst and polymerization method for olefin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a catalyst which not only has a high polymerization activity, but also can be used for producing a polyolefin being easy to handle and having good powder characteristics. SOLUTION: This olefin polymerization catalyst comprises (A) a polymer particle comprising a polymer having, as at least a part thereof, a recurring unit represented by the formula: (wherein R<1> represents a 1-5C alkyl group, hydrogen atom or a halogen atom, m represents an an integer of 0 to 4, A<-> represents an anion residue of a boron compound and Z<+> represents a carbonium cation; and (B) a transition metal compound of a metal belonging to Group IVB of the Periodic Table which has a ligand containing a cyclopentadienyl skeleton. This polymerization method for an olefin comprises polymerizing an olefin in the presence of the above-mentioned catalyst).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an olefin polymerization catalyst and an olefin polymerization method, and more specifically, to an olefin polymerization catalyst comprising polymer particles having a specific repeating unit and a transition metal compound. The present invention relates to a method for polymerizing or copolymerizing an olefin in the presence of a catalyst.

[0002]

BACKGROUND OF THE INVENTION A catalyst comprising a transition metal compound such as a metallocene compound and an aluminoxane has been known as a catalyst for olefin polymerization. It is also known to polymerize olefins using a catalyst in which at least one of the transition metal compound and aluminoxane is supported on a carrier such as silica. By thus supporting the catalyst component on the carrier, the catalytic activity can be improved,
In addition, a catalyst comprising a transition metal compound such as a metallocene compound and an ionized ionic compound such as an organic boron compound has been conventionally known as a catalyst for olefin polymerization. It has also been attempted to support the catalyst component on a carrier such as silica. However, it is difficult to support an ionized ionic compound such as an organic boron compound on a carrier, and it is difficult to obtain a catalyst component supported by the ionized ionic compound on the carrier.

The present inventor has conducted extensive studies in view of the above problems in the prior art, and as a result, for example, at least a part of the phenyl group in the polymer having a styrene unit is a residue of a carbonium cation and a boron compound anion. The present inventors have completed the present invention by finding that particles made of a polymer substituted with a group consisting of and become a cocatalyst component when used in olefin polymerization together with a transition metal compound.

[0004]

An object of the present invention is to provide a catalyst for olefin polymerization which comprises polymer particles having a specific repeating unit and a transition metal compound, has a high polymerization activity and is easy to handle, and an olefin polymerization using the catalyst. It is intended to provide a way.

[0005]

SUMMARY OF THE INVENTION An olefin polymerization catalyst according to the present invention comprises (A) polymer particles comprising a polymer having a repeating unit represented by the following formula (I) in at least a part thereof:

[0006]

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(Wherein R ^{1 s} may be the same or different from each other and represent an alkyl group having 1 to 5 carbon atoms, a hydrogen atom or a halogen atom, and m is an integer of 0 to 4, A ⁻ represents a residue of a boron compound anion, Z
⁺ Represents a metal cation, an organometallic cation, a carbonium cation, a tripium cation, an oxonium cation, a sulfonium cation, an ammonium cation, an anilinium cation, or a phosphonium cation. ) (B) A transition metal compound of Group IVB of the periodic table containing a ligand having a cyclopentadienyl skeleton.

In the present invention, the (A) polymer particles are preferably particles of a styrene polymer having at least a part of the repeating unit represented by the formula (I).

The catalyst according to the present invention may further contain (C) an organoaluminum compound in addition to the (A) polymer particles and (B) transition metal compound. Further, it may be a catalyst containing a prepolymerized polyolefin obtained by prepolymerizing an olefin in the presence of the olefin polymerization catalyst.

The olefin polymerization catalyst according to the present invention has a high polymerization activity and is easy to handle. Further, with the olefin polymerization catalyst according to the present invention, a polyolefin having good particle properties can be obtained.

The olefin polymerization method according to the present invention is characterized in that the olefin is polymerized or copolymerized in the presence of the olefin polymerization catalyst. According to the olefin polymerization method of the present invention, a polyolefin having a high polymerization activity and good particle properties can be obtained.

[0012]

DETAILED DESCRIPTION OF THE INVENTION The olefin polymerization catalyst and the olefin polymerization method according to the present invention will be specifically described below.

The olefin polymerization catalyst according to the present invention comprises:
Group (IV) of the periodic table containing (A) polymer particles comprising a polymer having a repeating unit represented by the following formula (I) in at least a part thereof, and (B) a ligand having a cyclopentadienyl skeleton. And a transition metal compound thereof.

First, each component forming the olefin polymerization catalyst of the present invention will be described. (A) Polymer Particle The (A) polymer particle used in the present invention has the following formula (I).
It is a polymer particle having a repeating unit represented by at least a part thereof.

[0015]

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In the formula, R ^{1 s} may be the same or different and each represents an alkyl group having 1 to 5 carbon atoms, a hydrogen atom or a halogen atom, and preferably 1 carbon atom.
To 3 alkyl groups or hydrogen atoms.

M is an integer of 0 to 4, preferably 0 to 2. A ⁻ represents a residue of a boron compound anion. Examples of the residue of the boron compound anion include groups represented by the following general formula (II).

--B ^-- R ³ R ⁴ R ⁵ (II) In the formula, R ³ , R ⁴ and R ⁵ may be the same or different and each represents a phenyl group or a fluorine atom. It may have a substituent such as a fluorine atom, a methyl group or a fluoromethyl group.

Specific examples of the residue of the boron compound anion represented by the general formula (II) include trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl). ) Boron, tris (4-fluoromethylphenyl) boron, tris (pentafluorophenyl) boron, tris (p-tolyl) boron, tris (o-tolyl) boron, tris (3,5-
Residues of anions such as dimethylphenyl) boron are included. Among these, the residue of tris (pentafluorophenyl) boron anion is particularly preferable.

Z ⁺ is a cation, specifically, a metal cation, an organometallic cation, a carbonium cation, a tripium cation, an oxonium cation, a sulfonium cation, an ammonium cation, an anilinium cation, a phosphonium cation and the like. Can be mentioned.

Specifically, metal cations such as ferrocenium cations; cations of triarylcarboniums such as triphenylcarbonium; cations of dialkylammoniums such as dimethylammonium, di (n-propyl) ammonium, dicyclohexylammonium; triethyl. Trialkylammonium cations such as ammonium, tripropylammonium, tri (n-butyl) ammonium, trimethylammonium, trimethylammonium, tributylammonium; N, N-
Dimethylanilinium, N, N-diethylanilinium, N,
N, N-dialkylanilinium cations such as N-2,4,6-pentamethylanilinium; triarylphosphoniums such as triphenylphosphonium, tri (methylphenyl) phosphonium, tri (dimethylphenyl) phosphonium The cations of

Of these, the carbonium cation is preferred. The polymer particle (A) used in the present invention is not particularly limited as long as it is a polymer having at least a part of the repeating unit represented by the formula (I), and examples thereof include ethylene, propylene, 1-butene and 4 A repeating unit derived from a chain olefin such as -methyl-1-pentene, a cyclic olefin such as cycloheptene and norbornene, a styrene derivative such as styrene, a halogenated styrene and an alkylated styrene, and a repeating unit represented by the above formula (I) And a polymer composed of units. These repeating units may be bonded at random or in a block form.

Of these, a styrene polymer having a repeating unit represented by the above formula (I) in at least a part thereof is preferable. Examples of the styrene polymer include crosslinked polystyrene; polymers of styrene derivatives such as methylated polystyrene, polystyrylcyclopentadiene, and methylated polystyrylcyclopentadiene; polystyrene having functional groups such as halogenated polystyrene. And so on.

The proportion of the repeating unit represented by the formula (I) in the polymer forming the polymer particles (A) is not particularly limited, but is usually 0.1 to 0.1.
100 mol%.

The (A) polymer particles usually have a particle size of 10
To 300 μm, preferably 20 to 200 μm. Examples of the method for producing the (A) polymer particles used in the present invention include metallized polystyrene and a boron compound BR ³ R ⁴ R ⁵ (III) represented by the following general formula (III) (wherein , R ³ R ⁴ and R ⁵ may be the same or different from each other and are the same as the above.), And then the reaction product is further reacted with the general formula Z ⁺ X ⁻ (in the formula,
Z ⁺ represents a cation similar to the above, and X represents halogen. ) And a compound represented by the formula (1).

The metallized polystyrene used for producing the polymer particles (A) may be commercially available or may be prepared by the method described in the literature.

As a method for obtaining metallized polystyrene,
For example, there is a method of reacting polystyrene with an alkali metal compound. A preferable example of the alkali metal compound is a compound represented by the following formula (IV).

AR (IV) In the formula, A represents an alkali metal, specifically, Li, N
a and K are mentioned, and Li is preferable.

R represents a hydrocarbon group having 1 to 12 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms. As the alkali metal compound represented by the formula (IV), alkyl lithium having 1 to 8 carbon atoms is preferable. Specifically as such an alkyl lithium,
Methyl lithium, ethyl lithium, propyl lithium,
Butyl lithium, pentyl lithium, hexyl lithium and the like can be mentioned. Of these, n-butyllithium is preferable.

The reaction conditions for reacting polystyrene with an alkali metal compound can be widely selected. Generally, the alkali metal compound is polystyrene 1k.
About 0.1 mol to about 50 mol, preferably about 0.2 to about 25 mol, and more preferably about 0.5 to about 20 mol per g.
It is used in the molar range and the reaction temperature is from about 0 ° C to about 100 ° C.
C. is preferred.

As a method for effectively obtaining metallized polystyrene, there is a method of reacting the alkali metal compound with halogenated polystyrene. As a method for obtaining a halogenated polystyrene, J.Org.Chem.Vo
The method shown in l.41, No.24, 3877-3882 (1976), or the method shown in the cited document is known. That is, a method is known in which polystyrene, bromine, and iron chloride are reacted in chloroform. These reaction conditions are
Although a wide choice can be made, bromine is generally about 0.1 moles to about 5 moles per kg of halogenated polystyrene.
It is used in the range of 0 mol, preferably about 0.2 to about 25 mol, more preferably about 0.5 to about 20 mol, and the reaction temperature is preferably in the range of about 0 ° C to about 100 ° C. The halogenated polystyrene thus obtained and the alkali metal compound are reacted under the same conditions as above to obtain metallized polystyrene.

Further, as a method of obtaining metallized polystyrene, a method of reacting chloromethylated polystyrene with a metallized cyclopentadiene compound is known.
It is known that chloromethylated polystyrene can be obtained by reacting polystyrene with chloromethyl alkyl ethers. The alkyl group of chloromethyl alkyl ethers has 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms.

The metallized cyclopentadiene compound is an alkali metal salt of an alkali metal and a cyclopentadiene compound such as cyclopentadiene, substituted cyclopentadiene and substituted indene.

The metallized cyclopentadiene compound may be a commercially available one, or may be one synthesized by a method known in the literature or the like. Examples of commercially available metallized cyclopentadiene compounds include sodium cyclopentadiene and sodium indene.

The metallized cyclopentadiene compound is generally an alkali metal such as sodium, metallized polystyrene, and an alkali metal compound as shown in J. Am. Chem. Soc. Vol 73, 5135-5138. It can be obtained by reacting with the cyclopentadiene compound. As the alkali metal compound, for example, the number of carbon atoms is 1 to
Alkyl lithium and alkyl sodium of 8 are preferable.

The reaction conditions for the synthesis vary depending on the starting materials used, but the upper limit of the reaction temperature is 200 ° C, preferably about 0 ° C to about 100 ° C. A metallized polystyrene was obtained by reacting a metallized cyclopentadiene compound with chloromethylated polystyrene to produce polystyrene with cyclopentadiene, and then reacting this polystyrene with an alkali metal compound to obtain metallized polystyrene. For example, J. Am. Chem. Soc. Vol. 95, 2373 (1973), JA
m. Chem. Soc. Vol. 97: 8, 2128 (1975). The reaction conditions for the synthesis are generally that the alkali metal compound is polystyrene 1 with cyclopentadiene.
About 0.1 mol to about 50 mol, preferably about 0.2 to about 25 mol, and more preferably about 0.5 to about 20 mol per kg.
Used in the molar range. The reaction temperature in each step of the metallized polystyrene preparation process is about 0 ° C to about 100 ° C.
Is preferred.

An example of the method for producing the polymer for forming the polymer particles (A) is shown below.

[0038]

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In the above reaction, the boron compound (ii) represented by the general formula (III) is usually about 0.1 to about 50 moles, preferably about 0.1 to about 1 kg of the metallized polystyrene (i). 2 to about 25 moles, more preferably about 0.
It is used in the range of 5 to about 20 mol. The reaction temperature is usually in the range of about 0 ° C to about 100 ° C.

The reaction product (iii) and the general formula Z ⁺
In the reaction with the compound (iv) represented by X ⁻ , the compound (iv) is converted to 1 mole of boron in the reaction product (iii),
It is usually used in an amount of 0.8 to 1.1 mol, preferably 0.9 to 1.0 mol. The reaction temperature is usually in the range of 0 to 100 ° C.

(B) Transition Metal Compound Periodic Table IV containing a ligand having a (B) cyclopentadienyl skeleton which forms the olefin polymerization catalyst of the present invention
Examples of the transition metal compound of Group B include transition metal compounds represented by the following general formula (V).

M ¹ L _x (V) In the formula, M ¹ represents a transition metal atom selected from Group IVB of the Periodic Table, specifically zirconium, titanium or hafnium, preferably zirconium. .

[0043] x is the valence of the transition metal atom M ^1, illustrating a coordinated number of ligands L to the transition metal atom M ^1. L represents a ligand coordinated to a transition metal atom, and at least one L is a ligand having a cyclopentadienyl skeleton, and L other than a ligand having a cyclopentadienyl skeleton.
Is a hydrocarbon group having 1 to 20 carbon atoms, 1 carbon atom
To 20 halogenated hydrocarbon groups, oxygen-containing groups, sulfur-containing groups, silicon-containing groups, halogen atoms or hydrogen atoms.

Examples of the ligand having a cyclopentadienyl skeleton include cyclopentadienyl group, methylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, tetramethylcyclopentadienyl group. Group, pentamethylcyclopentadienyl group, ethylcyclopentadienyl group, methylethylcyclopentadienyl group, propylcyclopentadienyl group, methylpropylcyclopentadienyl group, butylcyclopentadienyl group, methylbutylcyclo Examples thereof include an alkyl-substituted cyclopentadienyl group such as a pentadienyl group and a hexylcyclopentadienyl group, an indenyl group, a 4,5,6,7-tetrahydroindenyl group, and a fluorenyl group. These groups may be substituted with a (halogenated) hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group, a halogen atom, or the like.

When the compound represented by the general formula (V) contains two or more ligands having a cyclopentadienyl skeleton, the two ligands having a cyclopentadienyl skeleton among them are , A (substituted) alkylene group, a (substituted) silylene group and the like may be bonded via a divalent bonding group. As the transition metal compound in which such a ligand having two cyclopentadienyl skeletons is bonded via a divalent bonding group, a transition metal compound represented by the following general formula (V) Is mentioned.

Specific examples of the ligand L other than the ligand having a cyclopentadienyl skeleton include the following. Examples of the hydrocarbon group having 1 to 20 carbon atoms include an alkyl group, a cycloalkyl group, an alkenyl group, an arylalkyl group, and an aryl group. More specifically, methyl, ethyl, propyl, butyl, and hexyl Alkyl groups such as octyl, nonyl, dodecyl and eicosyl; cycloalkyl groups such as cyclopentyl, cyclohexyl, norbornyl and adamantyl; vinyl,
Alkenyl groups such as propenyl and cyclohexenyl; arylalkyl groups such as benzyl, phenylethyl and phenylpropyl; phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, naphthyl, methylnaphthyl, anthryl and phenanthryl Aryl groups.

Examples of the halogenated hydrocarbon group having 1 to 20 carbon atoms include groups in which the above hydrocarbon group having 1 to 20 carbon atoms is substituted with halogen. A hydroxy group as the oxygen-containing group; methoxy, ethoxy, propoxy,
Alkoxy groups such as butoxy; aryloxy groups such as phenoxy, methylphenoxy, dimethylphenoxy and naphthoxy; and arylalkoxy groups such as phenylmethoxy and phenylethoxy.

As the sulfur-containing group, a substituent in which oxygen of the oxygen-containing group is replaced with sulfur, and methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, p-toluene sulfonate. , Trimethylbenzene sulfonate,
Sulfonate groups such as triisobutylbenzene sulfonate, p-chlorobenzene sulfonate and pentafluorobenzene sulfonate; methylsulfinate, phenylsulfinate, benzenesulfinate, p-toluenesulfinate, trimethylbenzene Examples thereof include sulfinate groups such as sulfinate and pentafluorobenzene sulfinate.

As the silicon-containing group, monohydrocarbon-substituted silyl such as methylsilyl and phenylsilyl; dihydrocarbon-substituted silyl such as dimethylsilyl and diphenylsilyl;
Trihydrosilyl substituted silyls such as trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, dimethylphenylsilyl, methyldiphenylsilyl, tritolylsilyl, and trinaphthylsilyl; silyls of hydrocarbon substituted silyls such as trimethylsilyl ether Ether; a silicon-substituted alkyl group such as trimethylsilylmethyl; and a silicon-substituted aryl group such as trimethylphenyl.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Such a transition metal compound has, for example, a transition metal valence of 4
Is more specifically represented by the following general formula (V ′).

R ¹¹ R ¹² R ¹³ R ¹⁴ M ¹ (V ′) In the formula, M ¹ represents a transition metal atom selected from Group IVB of the periodic table as described above, and preferably a zirconium atom. .

R ¹¹ represents a group (ligand) having a cyclopentadienyl skeleton, and R ¹² , R ¹³ and R ¹⁴ may be the same or different from each other and are groups having a cyclopentadienyl skeleton. (Ligand), a (halogenated) hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group, a halogen atom or a hydrogen atom.

In the present invention, in the transition metal compound represented by the general formula (V ′), at least one of R ¹² , R ¹³ and R ¹⁴ is a group (ligand) having a cyclopentadienyl skeleton. A compound, for example, a compound in which R ¹¹ and R ¹² are groups (ligands) having a cyclopentadienyl skeleton is preferably used. When R ¹¹ and R ¹² are a group (ligand) having a cyclopentadienyl skeleton, R ¹³ and R ¹⁴ are a group having a cyclopentadienyl skeleton, an alkyl group, a cycloalkyl group, an alkenyl group,
It is preferably an arylalkyl group, an aryl group, an alkoxy group, an aryloxy group, a trialkylsilyl group, a sulfonate group, a halogen atom or a hydrogen atom.

In the following, represented by the general formula (V), M ¹
Specific examples of the transition metal compound in which zirconium is zirconium will be illustrated. Bis (indenyl) zirconium dichloride, bis (indenyl) zirconium dibromide, bis (indenyl) zirconium bis (p-toluenesulfonate), bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, bis (fluorenyl) )
Zirconium dichloride, bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dibromide, bis (cyclopentadienyl) methylzirconium monochloride, bis (cyclopentadienyl) ethylzirconium monochloride,
Bis (cyclopentadienyl) cyclohexyl zirconium monochloride, Bis (cyclopentadienyl) phenyl zirconium monochloride, Bis (cyclopentadienyl) benzyl zirconium monochloride, Bis (cyclopentadienyl) zirconium monochloride, Bis (Cyclopentadienyl) methylzirconium monohydride, bis (cyclopentadienyl) dimethylzirconium, bis (cyclopentadienyl) diphenylzirconium, bis (cyclopentadienyl) dibenzylzirconium, bis (cyclopentadienyl) zirconium Methoxy chloride, bis (cyclopentadienyl) zirconium ethoxy chloride, bis (cyclopentadienyl) zirconium bis (methanesulfonate), Bis (cyclopentadienyl) zirconium bis (p-toluene sulfonate), bis (cyclopentadienyl) zirconium bis (trifluoromethane sulfonate), bis (methylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclo) Pentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium ethoxy chloride, bis (dimethylcyclopentadienyl) zirconium bis (trifluoromethanesulfonate), bis (ethylcyclopentadienyl) zirconium dichloride, bis ( Methylethylcyclopentadienyl) zirconium dichloride, bis (propylcyclopentadienyl) zirconium dichloride, bis (methylpropylcyclopentadienyl) zirconium dichloride Chloride, bis (butylcyclopentadienyl) zirconium dichloride, bis (methylbutylcyclopentadienyl) zirconium dichloride, bis (methylbutylcyclopentadienyl) zirconium bis (methanesulfonate),
Bis (trimethylcyclopentadienyl) zirconium dichloride, bis (tetramethylcyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (hexylcyclopentadienyl) zirconium dichloride, bis (trimethylsilylcyclo) Pentadienyl) zirconium dichloride and the like.

In the above example, the disubstituted form of the cyclopentadienyl ring includes 1,2- and 1,3-substituted forms, and the trisubstituted form is 1,2,3- and 1,2,4. -Includes substitutions. Alkyl groups such as propyl and butyl are n-, i-, sec-, tert.
-Including isomers such as.

In addition, in the zirconium compound as described above, a compound in which zirconium is replaced with titanium or hafnium can be exemplified. Examples of the transition metal compound compound in which two ligands having a cyclopentadienyl skeleton are bound via a divalent linking group include compounds represented by the following formula (VI).

[0057]

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In the formula, M ¹ represents a transition metal atom of Group IVB of the periodic table, specifically zirconium, titanium or hafnium, preferably zirconium. R <^15> , R <^16> , R <^17> and R < ¹⁸ >, which may be the same or different, are each a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group. Group, sulfur-containing group, silicon-containing group, nitrogen-containing group,
A phosphorus-containing group, a halogen atom or a hydrogen atom is shown.
Of the groups represented by R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ , some of the groups adjacent to each other may be bonded to each other to form a ring together with the carbon atom to which those groups are bonded. In addition, R ¹⁵ ,
Each of R ¹⁶ , R ¹⁷ and R ¹⁸ is shown at two places. For example, R ¹⁵ and R ¹⁵ may be the same group or different groups. The same suffixes among the groups represented by R indicate preferred combinations in the case where they are joined to form a ring.

Examples of the hydrocarbon group having 1 to 20 carbon atoms include the same alkyl groups, cycloalkyl groups, alkenyl groups, arylalkyl groups and aryl groups as those described above for L.

The ring formed by combining these hydrocarbon groups is a benzene ring, a naphthalene ring, an acenaphthene ring,
Examples thereof include a condensed ring group such as an indene ring, and a group in which a hydrogen atom on the condensed ring group is substituted with an alkyl group such as methyl, ethyl, propyl and butyl.

Examples of the halogenated hydrocarbon group having 1 to 20 carbon atoms include groups in which the aforementioned hydrocarbon group having 1 to 20 carbon atoms is substituted with halogen. As the oxygen-containing group, a hydroxy group and an alkoxy group similar to the aforementioned L,
Examples include an aryloxy group and an arylalkoxy group.

Examples of the sulfur-containing group include a substituent in which oxygen of the oxygen-containing group is replaced with sulfur. Examples of the silicon-containing group include the same mono-hydrocarbon-substituted silyl, di-hydrocarbon-substituted silyl, tri-hydrocarbon-substituted silyl,
Examples include a silyl ether of a hydrocarbon-substituted silyl, a silicon-substituted alkyl group, and a silicon-substituted aryl group.

As the nitrogen-containing group, an amino group; an alkylamino group such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, dicyclohexylamino; phenylamino, diphenylamino,
Examples thereof include arylamino groups such as ditolylamino, dinaphthylamino and methylphenylamino, and alkylarylamino groups.

Examples of the phosphorus-containing group include phosphino groups such as dimethylphosphino and diphenylphosphino. As the halogen atom, those similar to the aforementioned L can be mentioned.

Of these, a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom is preferable, and particularly, a hydrocarbon group having 1 to 4 carbon atoms such as methyl, ethyl, propyl and butyl, or a hydrocarbon group. A benzene ring formed by bonding, a hydrogen atom on the benzene ring formed by bonding a hydrocarbon group is methyl, ethyl, n-propyl, iso-propyl,
It is preferably a group substituted with an alkyl group such as n-butyl, iso-butyl and tert-butyl.

X ¹ and X ² may be the same or different from each other, and are a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group,
It represents a sulfur-containing group, a silicon-containing group, a hydrogen atom or a halogen atom.

Examples of the hydrocarbon group having 1 to 20 carbon atoms include the same alkyl groups, cycloalkyl groups, alkenyl groups, arylalkyl groups and aryl groups as those described above for L.

Examples of the halogenated hydrocarbon group having 1 to 20 carbon atoms include groups in which the above hydrocarbon group having 1 to 20 carbon atoms is substituted with halogen. Examples of the oxygen-containing group include a hydroxy group and the same alkoxy group, aryloxy group, and arylalkoxy group as those described above for L.

Examples of the sulfur-containing group include a substituent in which oxygen of the oxygen-containing group is substituted with sulfur, and the same sulfonate group and sulfinate group as those in L above. Examples of the silicon-containing group include a silicon-substituted alkyl group and a silicon-substituted aryl group as described above for L.

As the halogen atom, the same groups and atoms as the above L can be mentioned. Of these, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a sulfonate group is preferable.

Y¹Is a divalent carbon having 1 to 20 carbon atoms
Hydrogenated group, divalent halogenated carbon having 1 to 20 carbon atoms
Hydrogen-containing group, divalent silicon-containing group, divalent germanium-containing group
Group, divalent tin-containing group, -O-, -CO-, -S-,
-SO-, -SO_Two-, -Ge-, -Sn-, -NR¹⁹
-, -P (R¹⁹)-, -P (O) (R¹⁹)-, -BR ¹⁹
-Or-AlR¹⁹-[However, R¹⁹Are identical to each other
Hydrocarbon water having 1 to 20 carbon atoms
Elementary groups, halogenated hydrocarbon groups having 1 to 20 carbon atoms,
A hydrogen atom or a halogen atom].

Specific examples of the divalent hydrocarbon group having 1 to 20 carbon atoms include methylene, dimethylmethylene and 1,2-
Ethylene, dimethyl-1,2-ethylene, 1,3-trimethylene, 1,4-tetramethylene, 1,2-cyclohexylene, 1,4-
Examples include alkylene groups such as cyclohexylene; arylalkylene groups such as diphenylmethylene and diphenyl-1,2-ethylene.

Specific examples of the divalent halogenated hydrocarbon group having 1 to 20 carbon atoms include a group obtained by halogenating the above divalent hydrocarbon group having 1 to 20 carbon atoms such as chloromethylene. Is mentioned.

As the divalent silicon-containing group, silylene,
Methyl silylene, dimethyl silylene, diethyl silylene, di (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, methylphenyl silylene, diphenyl silylene, di (p-tolyl) silylene, di (p- Alkylsilylylene groups such as chlorophenyl) silylene; Alkylarylsilylene groups; Arylsilylene groups; Tetramethyl-1,2-disilirene, tetraphenyl-1,2-disilylene and other alkyldisilylene groups; Alkylaryldisilylene groups; Aryldiyl Examples thereof include a silylene group.

Examples of the divalent germanium-containing group include groups obtained by substituting germanium for silicon in the above-mentioned divalent silicon-containing group. Examples of the divalent tin-containing group include groups obtained by substituting tin for silicon in the divalent silicon-containing group.

R ¹⁹ is a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, or a halogen atom similar to L. Of these, substituted silylene groups such as dimethylsilylene, diphenylsilylene, and methylphenylsilylene are particularly preferable.

Specific examples of the transition metal compound represented by the above formula (VI) are shown below. ethylene-
Bis (indenyl) dimethyl zirconium, ethylene-
Bis (indenyl) zirconium dichloride, ethylene
-Bis (indenyl) zirconium bis (trifluoromethanesulfonate), ethylene-bis (indenyl) zirconium bis (methanesulfonate), ethylene-bis (indenyl) zirconium bis (p-toluenesulfonate), ethylene-bis (Indenyl) zirconium bis (p-chlorobenzene sulfonate),
Ethylene-bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, isopropylidene- (cyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene- (cyclopentadienyl) (methylcyclopentadienyl) Zirconium dichloride,
Dimethylsilylene-bis (cyclopentadienyl) zirconium dichloride, dimethylsilylene-bis (methylcyclopentadienyl) zirconium dichloride, dimethylsilylene-bis (dimethylcyclopentadienyl)
Zirconium dichloride, dimethyl silylene-bis (trimethylcyclopentadienyl) zirconium dichloride, dimethyl silylene-bis (indenyl) zirconium dichloride, dimethyl silylene-bis (indenyl)
Zirconium bis (trifluoromethanesulfonate), dimethylsilylene-bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, dimethylsilylene- (cyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylsilylene-bis ( Indenyl) zirconium dichloride, methylphenylsilylene-bis (indenyl) zirconium dichloride, rac-
Dimethylsilylene-bis (2,3,5-trimethylcyclopentadienyl) zirconium dichloride, rac-Dimethylsilylene-bis (2,4,7-trimethylcyclopentadienyl) zirconium dichloride, rac-Dimethylsilylene-
Bis (2-methyl-4-tert-butylcyclopentadienyl)
Zirconium dichloride, isopropylidene- (cyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilylene- (3-tert-butylcyclopentadienyl) (indenyl) zirconium dichloride, isopropylidene- (4-methylcyclopentadienyl) (3
-Methylindenyl) zirconium dichloride, isopropylidene- (4-tert-butylcyclopentadienyl)
(3-Methylindenyl) zirconium dichloride, isopropylidene- (4-tert-butylcyclopentadienyl)
(3-tert-butylindenyl) zirconium dichloride, dimethylsilylene- (4-methylcyclopentadienyl) (3-methylindenyl) zirconium dichloride,
Dimethylsilylene- (4-tert-butylcyclopentadienyl) (3-methylindenyl) zirconium dichloride,
Dimethylsilylene- (4-tert-butylcyclopentadienyl) (3-tert-butylindenyl) zirconium dichloride, dimethylsilylene- (3-tert-butylcyclopentadienyl) (fluorenyl) zirconium dichloride,
Isopropylidene- (3-tert-butylcyclopentadienyl) (fluorenyl) zirconium dichloride, etc.

In addition, compounds in which zirconium in the above compounds is replaced by titanium or hafnium can also be mentioned. In the present invention, the transition metal compound represented by the formula (VI) is more specifically represented by the following general formula (VI
Examples thereof include transition metal compounds represented by I) or (VIII).

[0079]

[Chemical 6]

In the formula, M ² represents a transition metal atom belonging to Group IVB of the periodic table, and specifically, is titanium, zirconium or hafnium, preferably zirconium. R ^21's may be the same or different from each other and represent a hydrocarbon group having 1 to 6 carbon atoms, specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec- Examples thereof include alkyl groups such as butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl and cyclohexyl; alkenyl groups such as vinyl and propenyl.

Of these, an alkyl group having a primary carbon atom bonded to an indenyl group is preferable, an alkyl group having 1 to 4 carbon atoms is more preferable, and a methyl group and an ethyl group are particularly preferable.

R ²² , R ²⁴ , R ²⁵ and R ^{26, which} may be the same or different, each represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 6 carbon atoms similar to R ¹¹ . R ^{23, which} may be the same or different, each represents a hydrogen atom or an aryl group having 6 to 16 carbon atoms,
Specifically, phenyl, α-naphthyl, β-naphthyl, anthryl, phenanthryl, pyrenyl, acenaphthyl,
Examples include phenalenyl, aceanthrylenyl, tetrahydronaphthyl, indanyl, biphenylyl and the like. Of these, phenyl, naphthyl, anthryl, and phenanthryl are preferable.

These aryl groups include halogen atoms such as fluorine, chlorine, bromine and iodine; methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, octyl,
Alkyl groups such as nonyl, dodecyl, eicosyl, norbornyl and adamantyl; alkenyl groups such as vinyl, propenyl and cyclohexenyl; arylalkyl groups such as benzyl, phenylethyl, phenylpropyl; phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl , Propylphenyl, biphenyl,
Hydrocarbon group having 1 to 20 carbon atoms such as an aryl group such as α- or β-naphthyl, methylnaphthyl, anthryl, phenanthryl, benzylphenyl, pyrenyl, acenaphthyl, phenalenyl, aceanthrylenyl, tetrahydronaphthyl, indanyl and biphenylyl. It may be substituted with an organic silyl group such as trimethylsilyl, triethylsilyl and triphenylsilyl.

X ³ and X ⁴ may be the same or different from each other, and are a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group,
It represents a sulfur-containing group, a silicon-containing group, a hydrogen atom or a halogen atom, and specific examples thereof include the same atoms or groups as those of X ¹ and X ² .

Of these, halogen atom or carbon atom
It is preferably a hydrocarbon group having a child number of 1 to 20. Y
^TwoIs a divalent hydrocarbon group having 1 to 20 carbon atoms, carbon
Divalent halogenated hydrocarbon group having 1 to 20 atoms, divalent
A silicon-containing group, a divalent germanium-containing group, a divalent sulfur
Group containing group, -O-, -CO-, -S-, -SO-, -S
O_Two-, -Ge-, -Sn-, -NR¹⁹-, -P
(R¹⁹)-, -P (O) (R¹⁹)-, -BR ¹⁹-Or
-AlR¹⁹-[However, R¹⁹Are the same or different
A hydrocarbon group having 1 to 20 carbon atoms,
Halogenated hydrocarbon group having 1 to 20 elementary atoms, hydrogen atom
Or a halogen atom].
Y¹And the same atom or group as.

Of these, a divalent silicon-containing group is preferable, a divalent germanium-containing group is more preferable, and a divalent silicon-containing group is more preferable, and alkylsilylene, alkylarylsilylene or arylsilylene is preferable. Is more preferable.

Specific examples of the transition metal compound represented by the above general formula (VII) are shown below. rac-dimethylsilylene
-Bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2
-Methyl-4- (α-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-methyl-4- (β-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛ 1- (2-methyl-
4- (1-anthryl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-methyl-4- (2
-Anthryl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-methyl-4- (9-
Anthryl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (9-phenanthryl) indenyl)} zirconium dichloride,
rac-Dimethylsilylene-bis {1- (2-methyl-4- (p-fluorophenyl) indenyl)} zirconium dichloride, rac-Dimethylsilylene-bis {1- (2-methyl-4- (pentafluorophenyl) indenyl) )} Zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-
4- (p-chlorophenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-
4- (m-chlorophenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-
4- (o-chlorophenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-
4- (o, p-dichlorophenyl) phenylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1
-(2-Methyl-4- (p-bromophenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1
-(2-Methyl-4- (p-tolyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- (m-tolyl) indenyl)} zirconium dichloride, rac-dimethylsilylene -Bis {1- (2-methyl-4- (o
-Tolyl) indenyl)} zirconium dichloride, rac
-Dimethylsilylene-bis {1- (2-methyl-4- (o, o'-dimethylphenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- (p -
Ethylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- (pi
-Propylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4-)
(p-benzylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-
4- (p-biphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- (m
-Biphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- (p-
Trimethylsilylenephenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-
Methyl-4- (m-trimethylsilylenephenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-phenyl-4-phenylindenyl)} zirconium dichloride, rac-diethylsilylene-bis {1-
(2-Methyl-4-phenylindenyl)} zirconium dichloride, rac-di- (i-propyl) silylene-bis {1- (2
-Methyl-4-phenylindenyl) zirconium dichloride, rac-di- (n-butyl) silylene-bis {1- (2-methyl-4-phenylindenyl) zirconium dichloride, rac-dicyclohexylsilylene-bis} 1- (2-methyl-4-phenylindenyl)｝ zirconium dichloride, rac-methylphenylsilylene-bis ｛1- (2-methyl-
4-phenylindenyl)} zirconium dichloride, ra
c-diphenylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-di (p-tolyl) silylene-bis {1- (2-methyl-4-phenylindenyl)} Zirconium dichloride, rac-di (p-chlorophenyl) silylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-methylene-bis {1- (2-methyl-4-phenylindenyl) )} Zirconium dichloride, rac-ethylene-bis {1- (2-methyl-4-)
Phenylindenyl) zirconium dichloride, rac-
Dimethylgermylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-Dimethylstanylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac- Dimethyl silylene
-Bis {1- (2-methyl-4-phenylindenyl)} zirconium dibromide, rac-dimethylsilylene-bis {1- (2
-Methyl-4-phenylindenyl)} zirconium dimethyl, rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium methyl chloride, rac-
Dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium chloride SO ₂ Me, rac-Dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium chloride OSO ₂ Me, rac-dimethylsilylene-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-ethyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-ethyl-4- (β-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-ethyl-4- (2-methyl-1-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4- (5-acenaphthyl) indenyl) ｝ Zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl-4- (9-anthryl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-ethyl-4- (9-phenanthryl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-ethyl-4- (o-methylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-ethyl-4- (m-methylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-ethyl-4- (p-methylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-ethyl-4- (2,3-dimethylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4- (2,4-dimethylphenyl)
Indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl-4- (2,5-dimethylphenyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl- 4- (2,4,6-trimethylphenyl) indenyl)｝ zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (o-chlorophenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (m-chlorophenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (p-chlorophenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (2,3-dichlorophenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4- (2,6
-Dichlorophenyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl-4-
(3,5-dichlorophenyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl
-4- (2-bromophenyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl
-4- (3-bromophenyl) indenyl) zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl
-4- (4-bromophenyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl
-4- (4-biphenylyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl-4
-(4-trimethylsilylphenyl) indenyl) zirconium dichloride, rac-dimethylsilylene-bis
(2-n-propyl-4-phenylindenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-n-propyl-4- (α-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene -Bis {1- (2-n-propyl-4- (β-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-n-propyl
-4- (2-methyl-1-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-n-propyl-4- (5-acenaphthyl) indenyl)｝ zirconium dichloride, rac-dimethyl Silylene-bis ｛1- (2-n-
Propyl-4- (9-anthryl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-n-
Propyl-4- (9-phenanthryl) indenyl) {zirconium dichloride, rac-dimethylsilylene-bis} 1-
(2-i-propyl-4-phenylindenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-i-propyl-4- (α-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene -Bis {1- (2-i-propyl-4- (β-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-i-propyl
-4- (8-methyl-9-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-i-propyl-4- (5-acenaphthyl) indenyl)｝ zirconium dichloride, rac-dimethyl Silylene-bis ｛1- (2-i-
Propyl-4- (9-anthryl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-i-
Propyl-4- (9-phenanthryl) indenyl) {zirconium dichloride, rac-dimethylsilylene-bis} 1-
(2-s-butyl-4-phenylindenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-s-butyl
-4- (α-naphthyl) indenyl) zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-s-butyl-4-
(Β-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-s-butyl-4- (2
-Methyl-1-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-s-butyl-4)
-(5-acenaphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-s-butyl-4)
-(9-anthryl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-s-butyl-4-
(9-phenanthryl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-n-pentyl)
-4-Phenylindenyl)} zirconium dichloride, r
ac-dimethylsilylene-bis ｛1- (2-n-pentyl-4- (α-
Naphthyl) indenyl) zirconium dichloride, ra
c-dimethylsilylene-bis {1- (2-n-butyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-n-butyl-4- (α-naphthyl) indenyl) )｝ Zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-n-butyl-4- (β-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-n-butyl-4- (2-methyl-1-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-n-butyl-4- (5- Acenaphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-n-butyl-4- (9-anthryl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-n -Butyl-4- (9-phenanthryl) indenyl) {zirconium dichloride, rac-dimethylsilylene-bis {1- (2-i-butyl-4-phenylindenyl)}
Zirconium dichloride, rac-dimethylsilylene-bis {1- (2-i-butyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis
-(2-i-butyl-4- (β-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-
i-butyl-4- (2-methyl-1-naphthyl) indenyl) {zirconium dichloride, rac-dimethylsilylene-bis} 1
-(2-i-butyl-4- (5-acenaphthyl) indenyl) {zirconium dichloride, rac-dimethylsilylene-bis} 1
-(2-i-butyl-4- (9-anthryl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1-
(2-i-butyl-4- (9-phenanthryl) indenyl) {zirconium dichloride, rac-dimethylsilylene-bis} 1
-(2-neopentyl-4-phenylindenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-neopentyl-4- (α-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛ 1- (2-n-
Hexyl-4-phenylindenyl) zirconium dichloride, rac-dimethylsilylene-bis {1- (2-n-hexyl)
-4- (α-naphthyl) indenyl) zirconium dichloride, rac-methylphenylsilylene-bis ｛1- (2-ethyl
-4-Phenylindenyl)} zirconium dichloride, r
ac-methylphenylsilylene-bis ｛1- (2-ethyl-4- (α
-Naphthyl) indenyl)} zirconium dichloride, r
ac-methylphenylsilylene-bis {1- (2-ethyl-4- (9-
Anthryl) indenyl)} zirconium dichloride,
rac-methylphenylsilylene-bis {1- (2-ethyl-4- (9
-Phenanthryl) indenyl)｝ zirconium dichloride, rac-diphenylsilylene-bis ｛1- (2-ethyl-4-
Phenylindenyl) zirconium dichloride, rac-
Diphenylsilylene-bis {1- (2-ethyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-diphenylsilylene-bis {1- (2-ethyl-4- (9-anthryl) indenyl)} zirconium Dichloride, rac-diphenylsilylene-bis {1- (2-ethyl-4- (9-phenanthryl) indenyl)} zirconium dichloride, rac-diphenylsilylene-bis {1- (2-ethyl-4- (4-biphenylyl) Indenyl) {zirconium dichloride, rac-methylene-bis {1- (2-ethyl-4-phenylindenyl)}
Zirconium dichloride, rac-methylene-bis {1- (2-ethyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-ethylene-bis {1- (2-ethyl-4-phenylindenyl)} zirconium Dichloride, rac-ethylene-bis {1- (2-ethyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-ethylene-bis
-(2-n-propyl-4- (α-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylgermyl-bis ｛1-
(2-ethyl-4-phenylindenyl) zirconium dichloride, rac-dimethylgermyl-bis ｛1- (2-ethyl-4-
(Α-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylgermyl-bis ｛1- (2-n-propyl-4-)
Phenylindenyl) zirconium dichloride.

Further, compounds in which zirconium in the above compounds is replaced by titanium or hafnium can be also mentioned. In the present invention, a racemic transition metal compound represented by the general formula (VII) is usually used as a catalyst component, but an R type or an S type can also be used.

The transition metal compound represented by the general formula (VII) is prepared according to Journal of Organometallic Chem. 288 (1).
985), pages 63-67, European Patent Application Publication No. 0,320,76.
It can be produced according to the specification and Example.

Next, the transition metal compound represented by the general formula (VIII) will be described.

[0091]

[Chemical 7]

In the formula, M ³ represents a transition metal atom of Group IVB of the Periodic Table, specifically titanium, zirconium or hafnium, preferably zirconium. R ³¹ and R ³² may be the same or different from each other, and are a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, Represents a silicon-containing group, a nitrogen-containing group, a phosphorus-containing group, a halogen atom or a hydrogen atom, and specifically, the above R
The same atoms or groups as ^{15 to} R ¹⁸ can be mentioned.

Of these, R ³¹ has 1 to 2 carbon atoms.
It is preferably a hydrocarbon group having 0, and particularly preferably a hydrocarbon group having 1 to 3 carbon atoms such as methyl, ethyl and propyl.

R ³² has a hydrogen atom or a carbon atom number of 1 to
20 hydrocarbon groups are preferred, and particularly hydrogen atom or methyl, ethyl, propyl having 1 carbon atom
It is preferably from 3 to 3 hydrocarbon groups.

R ³³ and R ^{34, which} may be the same or different, each represents an alkyl group having 1 to 20 carbon atoms, specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, Examples thereof include alkyl groups such as isobutyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, cyclohexyl, octyl, nonyl, dodecyl and eicosyl; and cycloalkyl groups such as norbornyl and adamantyl.

Of these, R ³³ is preferably a secondary or tertiary alkyl group. X ⁵ and X ⁶ may be the same or different from each other, and are a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group. A group, a hydrogen atom or a halogen atom is shown, and specific examples thereof include the same atom or group as those of X ¹ and X ² .

Y^ThreeIs a divalent carbon having 1 to 20 carbon atoms
Hydrogenated group, divalent halogenated carbon having 1 to 20 carbon atoms
Hydrogen-containing group, divalent silicon-containing group, divalent germanium-containing group
Group, divalent tin-containing group, -O-, -CO-, -S-,
-SO-, -SO_Two-, -Ge-, -Sn-, -NR¹⁹
-, -P (R¹⁹)-, -P (O) (R¹⁹)-, -BR ¹⁹
-Or-AlR¹⁹-[However, R¹⁹Are identical to each other
Hydrocarbon water having 1 to 20 carbon atoms
Elementary groups, halogenated hydrocarbon groups having 1 to 20 carbon atoms,
A hydrogen atom or a halogen atom],
Is Y¹And the same atom or group as.

Specific examples of the transition metal compound represented by the above general formula (VIII) are shown below. rac-dimethylsilylene
-Bis {1- (2,7-dimethyl-4-ethylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1-
(2,7-dimethyl-4-n-propylindenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2,7
-Dimethyl-4-i-propylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-n-butylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis { 1- (2,7-dimethyl-4-
sec-Butylindenyl)} zirconium dichloride, ra
c-Dimethylsilylene-bis {1- (2,7-dimethyl-4-t-butylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-n-pentylindene) Nil)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-n-hexylindenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2,7-dimethyl-4-cyclohexylindenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2,7-dimethyl-4-methylcyclohexylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-phenylethylindenyl)} zirconium dichloride, rac-Dimethylsilylene-bis {1- (2,7-dimethyl-4-phenyldichloromethylindenyl)} zirconium dichloride, rac-Dimethylsilylene-bis {1- (2,7-dimethyl-4-chloromethylindenyl) )} Zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-trimethylsilylmethylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-) Trimethylsiloxymethylindenyl)} zirconium dichloride, ra
c-Diethylsilylene-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride, rac-di (i-propyl) silylene-bis {1- (2,7-dimethyl-4) -i-
Propylindenyl) zirconium dichloride, rac-
Di (n-butyl) silylene-bis {1- (2,7-dimethyl-4-i-
Propylindenyl) zirconium dichloride, rac-
Di (cyclohexyl) silylene-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride, rac-methylphenylsilylene-bis {1- (2,7-dimethyl-4-i- Propylindenyl)} zirconium dichloride, rac-methylphenylsilylene-bis {1- (2,7-dimethyl-4-t-butylindenyl)} zirconium dichloride, rac-diphenylsilylene-bis {1- (2,7 -Dimethyl-4-t-butylindenyl)} zirconium dichloride, rac-diphenylsilylene-bis {1- (2,7-dimethyl-
4-i-propylindenyl)} zirconium dichloride,
rac-diphenylsilylene-bis {1- (2,7-dimethyl-4-ethylindenyl)} zirconium dichloride, rac-di (p-tolyl) silylene-bis {1- (2,7-dimethyl-4-i -Propylindenyl)} zirconium dichloride, rac-di (p-chlorophenyl) silylene-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1 -(2-Methyl-4-i-propyl-7-ethylindenyl)} zirconium dibromide rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-
Ethylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-n-propylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2, 3,7-Trimethyl-4-i-propylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-n-butylindenyl)} zirconium dichloride, rac- Dimethylsilylene-bis {1- (2,3,7-trimethyl-4-sec-butylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-t- Butylindenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2,3,7-trimethyl-4-n-pentylindenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2,3,7-trimethyl-4-n-hexylindenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2,3,7-trimethyl-4-cyclohexylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-methylcyclohexylindenyl)} Zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-trimethylsilylmethylindenyl)} zirconium dichloride,
rac-Dimethylsilylene-bis {1- (2,3,7-trimethyl-4-
Trimethylsiloxymethylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-
Trimethyl-4-phenylethylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,
3,7-Trimethyl-4-phenyldichloromethylindenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2,3,7-trimethyl-4-chloromethylindenyl)} zirconium dichloride, rac-diethylsilylene
-Bis {1- (2,3,7-trimethyl-4-i-propylindenyl)} zirconium dichloride, rac-di (i-propyl)
Silylene-bis {1- (2,3,7-trimethyl-4-i-propylindenyl)} zirconium dichloride, rac-di (n-butyl) silylene-bis {1- (2,3,7-trimethyl- 4-i-Propylindenyl)} zirconium dichloride, rac-di (cyclohexyl) silylene-bis {1- (2,3,7-trimethyl-
4-i-propylindenyl)} zirconium dichloride,
rac-Methylphenylsilylene-bis {1- (2,3,7-trimethyl-4-i-propylindenyl)} zirconium dichloride, rac-methylphenylsilylene-bis {1- (2,3,7-
Trimethyl-4-t-butylindenyl)} zirconium dichloride, rac-diphenylsilylene-bis {1- (2,3,7-
Trimethyl-4-t-butylindenyl)} zirconium dichloride, rac-diphenylsilylene-bis {1- (2,3,7-
Trimethyl-4-i-propylindenyl)} zirconium dichloride, rac-diphenylsilylene-bis {1- (2,3,7
-Trimethyl-4-ethylindenyl)} zirconium dichloride, rac-di (p-tolyl) silylene-bis {1- (2,3,7
-Trimethyl-4-i-propylindenyl)} zirconium dichloride, rac-di (p-chlorophenyl) silylene-bis {1- (2,3,7-trimethyl-4-i-propylindenyl)} zirconium dichloride, rac-dimethyl silylene
-Bis {1- (2-methyl-4-i-propyl-7-methylindenyl)} zirconium dimethyl, rac-dimethylsilylene-
Bis {1- (2-methyl-4-i-propyl-7-methylindenyl)} zirconium methyl chloride, rac-dimethylsilylene-bis {1- (2-methyl-4-i-propyl-7-methylindene Nyl)} zirconium-bis (methanesulfonate), rac-dimethylsilylene-bis {1- (2-methyl-4-i-
Propyl-7-methylindenyl)} zirconium-bis (p-phenylsulfinato), rac-dimethylsilylene-
Bis {1- (2-methyl-3-methyl-4-i-propyl-7-methylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4,6-di-i -Propylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4-i-propyl-7-methylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2 -Phenyl-4-i-propyl-7-methylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methylindenyl)} zirconium dichloride, rac-ethylene-bis {1- (2, 4,7-Trimethylindenyl)} zirconium dichloride, rac-isopropylidene-bis {1- (2,4,7-trimethylindenyl)} zirconium dichloride and the like.

In addition, compounds in which zirconium in the above compounds is replaced by titanium or hafnium can also be mentioned. Among these, i-propyl and sec- in the 4th position
Those having a branched alkyl group such as a butyl or tert-butyl group are particularly preferable.

In the present invention, the racemate of the transition metal compound represented by the general formula (VIII) is usually used as the catalyst component, but R type or S type can also be used. The transition metal compound represented by the general formula (VIII) as described above is
A known method from an indene derivative, for example, JP-A-4-26
It can be synthesized by the method described in Japanese Patent No. 8307.

Further, in the present invention, a compound represented by the following formula (IX) can be used as the transition metal compound (B). L ² M ⁴ X ³ ₂ (IX) In the formula, M ⁴ represents a transition metal atom of Group IV of the periodic table.

L ² is a derivative of a delocalized π-bonding group and imparts a constrained geometry to the metal M ⁴ active site, and X ^{3 s} may be the same or different from each other. A hydrocarbon group, a silyl group or a germyl group containing a halogen atom or 20 or less carbon atoms, a silicon atom or a germanium atom.

Among the compounds represented by the general formula (IX), the compound represented by the following formula (IX ′) is preferable.

[0104]

Embedded image

In the formula, M ⁴ represents a transition metal atom of Group IV of the periodic table, specifically zirconium, titanium or hafnium, preferably zirconium. Cp
Represents a substituted cyclopentadienyl group or a derivative thereof which is π-bonded to M ⁴ and has a substituent Z.

Z is an oxygen atom, a sulfur atom or a boron atom
Or a ligand containing an element of Group IVA of the Periodic Table
For example -Si (R⁴¹ _Two)-, -C (R⁴¹ _Two)-, -Si
(R⁴¹ _Two) Si (R⁴¹ _Two)-, -C (R⁴¹ _Two) C (R⁴¹ _Two)
-, -C (R⁴¹ _Two) C (R⁴¹ _Two) C (R⁴¹ _Two)-, -C
(R⁴¹) = C (R⁴¹)-, -C (R⁴¹ _Two) Si (R⁴¹ _Two)
-, -Ge (R⁴¹ _Two)-.

Y ² represents a ligand containing a nitrogen atom, a phosphorus atom, an oxygen atom or a sulfur atom, for example, --N (R
⁴² )-, -O-, ^-S- , -P ( ^R42 )-and the like.
Further, Z and Y ² may form a condensed ring.

R ⁴¹ is a hydrogen atom or a group selected from an alkyl group having up to 20 non-hydrogen atoms, an aryl group, a silyl group, a halogenated alkyl group, a halogenated aryl group or a combination thereof, and R ⁴² is a carbon atom. Alkyl having 1 to 10 atoms, aryl group having 6 to 10 carbon atoms or aralkyl group having 7 to 10 carbon atoms, or condensation of one or more R ⁴¹ and up to 30 non-hydrogen atoms. It may form a ring system.

Specific examples of the transition metal compound represented by the above general formula (IX ') are shown below. (Tert-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) -1,2-
Ethanediylzirconium dichloride, (tert-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl)-
1,2-ethanediyl titanium dichloride, (methyl amide)
(Tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediylzirconium dichloride, (methylamide)
(Tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediyltitanium dichloride, (ethylamide) (tetramethyl-η ⁵ -cyclopentadienyl) -methylenetitanium dichloride, (tert-butylamido) dimethyl (tetra Methyl-η ⁵ -cyclopentadienyl) silanetitanium dichloride, (tert-butylamido) dimethyl (tetramethyl-
η ⁵ -cyclopentadienyl) silane zirconium dichloride, (benzylamido) dimethyl- (tetramethyl-η
⁵ -cyclopentadienyl) silane titanium dichloride,
(Phenyl phosphide) dimethyl (tetramethyl-η ^5-
Cyclopentadienyl) silane zirconium dibenzyl and the like.

(C) Organoaluminum Compound As the organoaluminum compound, for example, an organoaluminum compound represented by the following formula (X) can be exemplified.

[0111] In ^{_{R a n AlX 3-n ...}} (X) formula, R ^a represents a hydrocarbon group, for example an alkyl group, a cycloalkyl group or an aryl group having 1 to 12 carbon atoms, specifically, Examples include methyl, ethyl, n-propyl, isopropyl, isobutyl, pentyl, hexyl, octyl, cyclopentyl, cyclohexyl, phenyl and tolyl.

X represents a halogen atom or a hydrogen atom,
n is 1 to 3. Specific examples of such an organoaluminum compound include the following compounds.

Trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, trioctyl aluminum, tri 2-
Trialkylaluminums such as ethylhexylaluminum and tridecylaluminum; Alkenylaluminums such as isoprenylaluminum; Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, dimethylaluminum bromide; Methylaluminum sesquichloride, Ethyl aluminum sesquichloride,
Alkyl aluminum sesquihalides such as isopropyl aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesquibromide; alkyl aluminum dihalides such as methyl aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride, ethyl aluminum dibromide; diethyl aluminum hydride, diisobutyl aluminum Alkyl aluminum hydride such as hydride.

Further, as the organoaluminum compound, a compound represented by the following general formula (XI) can also be used. R ^a _n AlY _{3 −n} (XI) (In the formula, R ^a is the same as above, Y is an —OR ^b group,
OSiR ^c ₃ group, -OAlR ^d ₂ group, -NR ^e ₂ group, -S
a iR ^f ₃ group or -N (R ^g) AlR ^h ₂ group, n is ^{1~2, R b, R c,} R d and R ^h are each methyl, ethyl, isopropyl, isobutyl, A cyclohexyl group, a phenyl group, etc., wherein ^Re is a hydrogen atom,
Examples include a methyl group, an ethyl group, an isopropyl group, a phenyl group, and a trimethylsilyl group, and R ^f and R ^g are a methyl group, an ethyl group, and the like. ) As such an organoaluminum compound, the following compounds are specifically used. (I) compounds represented by R ^a _n Al (OR ^b ) _3-n , such as dimethylaluminum methoxide, diethylaluminum ethoxide, diisobutylaluminum methoxide, and (ii) R ^a _n Al (OSiR ^c ₃ ) ₃ a compound represented by _-n , for example, Et ₂ Al (OSiMe ₃ ), (is
o-Bu) ₂ Al (OSiMe ₃ ), (iso-Bu) ₂ Al
(OSiEt ₃ ), etc. (iii) R ^a _n Al (OAl
Compounds represented by R ^d ₂ ) _3-n , such as Et ₂ AlOA
lEt ₂ , (iso-Bu) ₂ AlOAl (iso-Bu) _2, etc., a compound represented by (iv) R ^a _n Al (NR ^e ₂ ) _3-n , for example, Me ₂ AlNEt ₂ , Et ₂ AlNHM.
e, Me ₂ AlNHEt, Et ₂ AlN (SiM
e ₃ ) ₂ , (iso-Bu) ₂ AlN (SiMe ₃ ) _2, etc.,
(V) ^a compound represented by R ^a _n Al (SiR ^f ₃ ) _3-n ,
For example, (iso-Bu) ₂ AlSiMe _3, etc., (vi) R
^a _n Al [N (R ^g ) AlR ^h ₂ ] _3-n , for example, Et ₂ AlN (Me) AlEt ₂ , (iso-
Bu) ₂ AlN (Et) Al (iso-Bu) _{2 and the} like.

Among the organoaluminum compounds represented by the above general formulas (X) and (XI), the general formula R ^a ₃ Al,
R ^a _n Al (OR ^b ) _3-n , R ^a _n Al (OAlR ^d ₂ )
_A preferred example is an organoaluminum compound represented by _3-n , wherein R ^a is an isoalkyl group,
Particularly preferably, n = 2. These organoaluminum compounds can be used as a mixture of two or more kinds.

Olefin Polymerization Catalyst The olefin polymerization catalyst used in the present invention is a catalyst comprising the polymer particles (A), a transition metal compound (B), and optionally (C) an organoaluminum compound. A solid catalyst in which the transition metal compound (B) and / or the organoaluminum compound (C) are supported on the polymer particles (A) may be used, and the catalyst and the olefin in the presence of the catalyst may be used. It may be a prepolymerization catalyst which is a prepolymerized polyolefin obtained by prepolymerizing.

The solid catalyst (component) can be prepared, for example, by mixing and contacting the above components in an inert solvent. The prepolymerization catalyst can be obtained by introducing an olefin into an inert hydrocarbon solvent in the presence of each of the above components, preferably in the presence of the solid catalyst (component).

Specific examples of the inert hydrocarbon medium used for preparing the olefin polymerization catalyst include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene; cyclopentane, Examples thereof include alicyclic hydrocarbons such as cyclohexane and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, and mixtures thereof.

Polymer particles (A), transition metal compound (B)
When the mixture and the organoaluminum compound (C) are mixed and contacted, the concentration of the transition metal compound (B) is about 10 ⁻⁴ to 2
× 10 ^-2 mol / liter (solvent), preferably 2 × 10
It is in the range of ^-4 to 10 ^-2 mol / liter (solvent).

The polymer particles (A) are the same as the polymer particles (A).
The atomic ratio ((B) / (A)) of the boron atom in the compound to the transition metal in the transition metal compound (B) is usually 0.01 to 10,
It is preferably used in an amount so as to be in the range of 0.5 to 5.

The organoaluminum compound (C) has an atomic ratio (Al / transition metal) of aluminum in the organoaluminum compound to the transition metal in the transition metal compound (B),
It is usually used in an amount of 10 to 500, preferably 20 to 200.

The mixing temperature at the time of mixing and contacting each component is usually -50 to 150 ° C, preferably -20 to 120 ° C, and the contact time is 1 minute to 50 hours, preferably 10 minutes to 2 ° C.
5 hours.

The olefin polymerization catalyst in which the transition metal compound (B) and the organoaluminum compound (C) obtained as described above are supported on the polymer particles (A) is used per 1 g of the polymer particles (A). The transition metal compound (B) is 5 × 10 ⁻⁶ to 5 in terms of the transition metal atom in the transition metal compound.
It is supported in an amount of x10 ^-4 gram atom, preferably 10 ^-5 to 2 x 10 ^-4 gram atom, and the organoaluminum compound (C) is 10 ^-3 to 10 in terms of aluminum atom in the organoaluminum compound. It is desirable that it is supported in an amount of 5 × 10 ⁻² gram atom, preferably 2 × 10 ⁻³ to 2 × 10 ⁻² gram atom.

The olefin polymerization catalyst may be a prepolymerization catalyst obtained by prepolymerizing an olefin in the presence of the polymer particles (A), the transition metal compound (B) and the organoaluminum compound (C). The prepolymerization can be carried out by introducing an olefin into an inert hydrocarbon solvent in the presence of the polymer particles (A), the transition metal compound (B) and the organoaluminum compound (C) as described above.

In the prepolymerization, the above transition metal compound (B) is usually used in an amount of 10 ⁻⁶ to 2 × 10 ⁻² mol / liter (solvent), preferably 5 × 10 ⁻⁵ to 10 ⁻² mol / liter. It is used in the amount of (solvent).

The polymer particles (A) are the same as the polymer particles (A).
The atomic ratio ((B) / (A)) of the boron atom in the compound to the transition metal in the transition metal compound (B) is usually 0.01 to 10,
It is preferably used in an amount so as to be in the range of 0.5 to 5.

The organoaluminum compound (C) generally has an atomic ratio (Al / transition metal) of aluminum in the organoaluminum compound to the transition metal in the transition metal compound of 1
It is used in an amount of 0 to 500, preferably 20 to 200.

The prepolymerization temperature is -20 to 80 ° C, preferably 0 to 60 ° C, and the prepolymerization time is 0.5 to 10 ° C.
It is 0 hours, preferably about 1 to 50 hours. The olefin polymer produced by the preliminary polymerization is 1 g of polymer particles (A).
0.1 to 500 g, preferably 0.2 to 300 g,
More preferably, the amount is 0.5 to 200 g. Further, 1 g of polymer particles (A) is used as the prepolymerization catalyst.
The transition metal compound (B) is about 5 × as a transition metal atom.
10 ^{−6 to} 5 × 10 ⁻⁴ gram atom, preferably 10 ⁻⁵ to 2
The organoaluminum compound is supported in an amount of × 10 ⁻⁴ gram atom, and the organoaluminum compound has a molar ratio (Al / M) of aluminum in the organoaluminum compound to transition metal atom (M) in the transition metal compound of 5 to 200. , Preferably 10-1
It is desirable that the carrier be loaded in an amount such that the range is 50.

The prepolymerization can be carried out batchwise or continuously, and can be carried out under reduced pressure, normal pressure or under pressure. Polymerization Method In the present invention, the olefin polymerization is carried out in the gas phase or in the liquid phase in the form of a slurry. In slurry polymerization, an inert hydrocarbon may be used as a solvent, or an olefin itself may be used as a solvent.

Specific examples of the inert hydrocarbon solvent used in the slurry polymerization include butane, isobutane, pentane, hexane, octane, decane, dodecane, hexadecane, octadecane and other aliphatic hydrocarbons; cyclopentane, methylcyclopentane. , Cyclohexane,
Alicyclic hydrocarbons such as cyclooctane; aromatic hydrocarbons such as benzene, toluene and xylene; gasoline;
Examples include petroleum fractions such as kerosene and light oil. Among these inert hydrocarbon media, aliphatic hydrocarbons, alicyclic hydrocarbons, petroleum fractions and the like are preferred.

During the polymerization, the (B) transition metal compound is
The amount of the transition metal atom in the transition metal compound (B) in the polymerization system is 10 ^-8 to 10 ^-3 gram atom, preferably 10 ^-7 to 10 ^-4 gram atom per liter of the polymerization volume. Used in.

The polymer particles (A) have a molar ratio of the transition metal compound (B) to the polymer particles (A) [(B) / (A)].
Is used in an amount of 0.01 to 10, preferably 0.5 to 5.

In the organoaluminum compound (C), the atomic ratio (Al / transition metal) between the aluminum atom (Al) in the (C) organoaluminum compound and the transition metal in the (B) transition metal compound is usually It is used in an amount such that it is in the range of 5 to 10,000, preferably 10 to 5,000.

When a solid catalyst or a prepolymerization catalyst is used for the polymerization, an organoaluminum compound similar to the organoaluminum compound (C) may be added. At this time, the atomic ratio (Al / M) of the aluminum atom (Al) derived from the organoaluminum compound and the transition metal atom (M) in the (B) transition metal compound is 5 to 300, preferably 10 to 200. , And more preferably in the range of 15 to 150.

The olefin which can be polymerized by the olefin polymerization catalyst of the present invention has 2 carbon atoms.
Α-20 olefins such as ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene,
1-octene, 1-decene, 1-dodecene, 1-tetradecene,
1-hexadecene, 1-octadecene, 1-eicosene; a cyclic olefin having 3 to 20 carbon atoms, for example, cyclopentene, cycloheptene, norbornene, 5-methyl-2-
Norbornene, tetracyclododecene, 2-methyl-1,4,
5,8-Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene and the like can be mentioned. Further, styrene, vinylcyclohexane, diene and the like can be mentioned.

In the present invention, when carrying out the polymerization, the polymerization temperature is usually in the range of 0 to 100 ° C., and the polymerization pressure is usually from normal pressure to 100 kg / cm ² , preferably 2
It is a pressurized condition of ˜50 kg / cm ² .

The polymerization can be carried out in any of batch system, semi-continuous system and continuous system, and it is also possible to carry out the polymerization in two or more stages under different reaction conditions.

[0138]

The olefin polymerization product according to the present invention has high polymerization activity and is easy to handle. Also, a polyolefin having good particle properties can be obtained.

According to the olefin polymerization method of the present invention, a polyolefin having high polymerization activity and good particle properties can be obtained.

[0140]

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.

[0141]

Example 1 Preparation of Carrier Styrene and para-bromostyrene were radically polymerized in toluene using azobisisobutyronitrile, precipitated in methanol, and the produced polymer was recovered by filtration. Elemental analysis revealed that 35% by weight of para-bromostyrene had been introduced into this polymer.

Preparation of Solid Catalyst In a solution prepared by dissolving the produced polymer in toluene, n-butyllithium was added to bromine (mol) in the polymer in an amount of 1.
A 0-fold amount was added and the mixture was reacted at 60 ° C. for 3 hours. Next, trispentafluorophenylborane was added to this solution in the same amount as the above n-butyllithium and reacted at room temperature for 2 hours to obtain polymer particles.

Polymerization The heptane 1 was added to a 200 ml glass reactor which was replaced with nitrogen.
00 ml was added and the temperature was raised to 40 ° C. After replacing the system with ethylene, 1.0 mmol of triisobutylaluminum, 1 g of the polymer particles obtained above, and 0.05 mmol of bis (cyclopentadienyl) zirconium dichloride were sequentially added to initiate polymerization. After polymerizing with ethylene for 2 hours while maintaining the atmospheric pressure, the reaction liquid was filtered through a glass filter, and the obtained polymer was collected, and 6.5 g of a white solid was obtained. The filtrate was placed in methanol acidified with hydrochloric acid, but no solid was observed.

[0144]

Example 2 Example 1 was repeated except that propylene was used instead of ethylene and ethylene-bis (tetrahydroindenyl) zirconium dichloride was used instead of bis (cyclopentadienyl zirconium dichloride). Polymerization was carried out in the same manner, and the reaction solution was filtered through a glass filter to collect the resulting polymer, whereby 4.3 g of a white solid was obtained.The filtrate was put into methanol acidified with hydrochloric acid. However, solid formation was not observed.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Masaaki Ozawa Akira Maki Petrochemical Industry Co., Ltd. 1-2-6 Waki, Waki-cho, Kuga-gun, Yamaguchi Prefecture

Claims (5)

[Claims] 1. A polymer particle comprising a polymer having (A) a repeating unit represented by the following formula (I) in at least a part thereof: (In the formula, R ^{1 s} may be the same or different from each other and represent an alkyl group having 1 to 5 carbon atoms, a hydrogen atom or a halogen atom, and m is an integer of 0 to 4;
^- indicates the residues of boron compound anion, Z ⁺ represents a metal cation, organometallic cation, carbonium cation, tri pin um cation, oxonium cation, sulfonium cation, an ammonium cation, anilinium cation, a phosphonium cation . ) (B) A catalyst for olefin polymerization, which comprises a transition metal compound of Group IVB of the periodic table containing a ligand having a cyclopentadienyl skeleton. 2. The catalyst for olefin polymerization according to claim 1, wherein the polymer particles (A) are particles of a styrene polymer having at least a part of the repeating unit represented by the formula (I). . 3. The olefin polymerization according to claim 1, further comprising (C) an organoaluminum compound in addition to the (A) polymer particles and (B) transition metal compound. Catalyst. 4. An olefin polymerization catalyst according to claim 1, and a prepolymerized polyolefin obtained by prepolymerizing an olefin in the presence of the olefin polymerization catalyst. Olefin polymerization catalyst. 5. A method for polymerizing an olefin, which comprises polymerizing or copolymerizing an olefin in the presence of the catalyst for olefin polymerization according to any one of claims 1 to 4.