JP2002308893A - Transition metal compound, olefin polymerization catalyst, olefin polymer and its preparation process - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transition metal compound useful as a component of an olefin polymerization catalyst, and an olefin polymerization catalyst using this compound. SOLUTION: The transition metal compound is represented by formula (I) or (II) [wherein M is a metal element of group 3-10 or lanthanoids series in the periodic table; X is a σ bonding ligand bound to M; Y is a Lewis base; A is a bridging group containing an element of group 14 in the periodic table; p is an integer of 1-10; q is an integer of 1-5 [(valency of M)-2]; r is an integer of 0-3; and R<1> to R<10> are each a hydrogen atom, a 1-20C hydrocarbon group, a silicon-containing group or a hetero atom-containing group]. The olefin polymerization catalyst contains this transition metal compound and an activated promoter as essential components.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a transition metal compound, a catalyst for olefin polymerization, an olefin polymer using the catalyst, and a method for producing the same. More specifically, the present invention relates to a transition metal compound useful as a component of an olefin polymerization catalyst, an olefin that efficiently provides an olefin homopolymer or copolymer containing the transition metal compound and having a high molecular weight and a narrow molecular weight distribution. The present invention relates to a polymerization catalyst, the olefin polymer, and a method for efficiently producing the olefin polymer.

[0002]

2. Description of the Related Art Heretofore, as a highly active soluble olefin polymerization catalyst, a catalyst comprising a combination of a transition metal compound and an aluminoxane has been known (Japanese Patent Application Laid-Open No. 58-193).
09, JP-A-60-217209). Further, transition metal compounds in which π ligands are bonded to each other (crosslinked) are also known. However, there are few examples of the synthesis of multiple crosslinked (double crosslinked) transition metal compounds,
International Patent Publication No. 93-20113 and "Organom
et allics, "Vol. 12, p. 1931 (19
1993), Organometallics, No. 13
Vol. 3868 (1994 and Organo
Metallics, "Vol. 17, p. 5528 (1
998). Further, the behavior as a polymerization catalyst is described in International Patent Publication No. 93-20113, but its activity and molecular weight were not satisfactory. Japanese Patent Application Laid-Open No. 2000-256411 discloses a double-bridged transition metal compound having a racemic structure, but its olefin polymerization activity, particularly ethylene polymerization activity, was not satisfactory.

[0003]

SUMMARY OF THE INVENTION The present invention provides a novel meso-like double-bridged transition metal compound useful as a component of a catalyst for olefin polymerization under such circumstances, and having a high molecular weight and a narrow molecular weight distribution. An object of the present invention is to provide a highly active polymerization catalyst that gives an olefin polymer, and an olefin polymer or copolymer having a high molecular weight and a narrow molecular weight distribution obtained by using the polymerization catalyst. is there.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that a novel transition metal compound having a specific structure is useful as a component of a catalyst for olefin polymerization. It has been found that a polymerization catalyst containing the transition metal compound and an activating co-catalyst efficiently gives an olefin polymer or copolymer having high activity and a high molecular weight and a narrow molecular weight distribution. The present invention has been completed based on such findings. That is, the present invention relates to (1) general formula (I) or (II)

[0005]

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[Wherein, M represents a metal element belonging to Groups 3 to 10 of the periodic table or a lanthanoid series, X represents a σ-binding ligand bonded to M, and when there are a plurality of X, a plurality of X are They may be the same or different, and may be crosslinked with an indenyl ring or Y. Y represents a Lewis base, and when there are a plurality of Ys, the plurality of Ys may be the same or different, and may be cross-linked to an indenyl ring or X. A is the first of the periodic table
Represents a crosslinking group containing a group 4 element, p is an integer of 1 to 10, q
Is an integer of 1 to 5 [(valency of M) -2], and r is 0 to 3
Indicates an integer. R ¹ to R ¹⁰ are independently a hydrogen atom, a hydrocarbon group, a silicon-containing group or a heteroatom-containing group having 1 to 20 carbon atoms, to which may be the same with or different from each other, adjacent groups and the ring May be formed. (2) (A) a transition metal compound represented by the above general formula (I)
Or a catalyst for olefin polymerization characterized by containing a transition metal compound represented by (II) and an activating cocatalyst as main components; and (3) a catalyst obtained by using the olefin polymerization catalyst. And (4) homopolymerizing olefins or copolymerizing olefins with other olefins and / or other monomers in the presence of the olefin polymerization catalyst. A method for producing an olefin-based polymer.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The transition metal compound of the present invention has the general formula (I) or (II)

[0008]

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A novel meso-like double-bridged transition metal compound having a structure represented by the following formula: General formula (I) or (II)
In the above, R ^{1 to} R ¹⁰ represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group or a hetero atom-containing group. R
^{3 to} R ¹⁰ may each form a ring with an adjacent group.
Here, examples of the hydrocarbon group having 1 to 20 carbon atoms include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclohexyl group, and an octyl group.
Vinyl group, propenyl group, alkenyl group such as cyclohexenyl group, benzyl group, phenylethyl group, arylalkyl group such as phenylpropyl group, phenyl group, tolyl group, dimethylphenyl group, trimethylphenyl group,
Examples include an aryl group such as an ethylphenyl group, a propylphenyl group, a biphenyl group, a naphthyl group, a methylnaphthyl group, an anthracenyl group, and a phenanthonyl group.

As the silicon-containing group, a silicon-containing group having 1 to 20 carbon atoms is preferable, and specific examples thereof include monohydrocarbon-substituted silyl groups such as methylsilyl group and phenylsilyl group; and di-silyl groups such as dimethylsilyl group and diphenylsilyl group. Hydrocarbon-substituted silyl group; trimethylsilyl group, triethylsilyl group,
Trihydrocarbon-substituted silyls such as tripropylsilyl, dimethyl (t-butyl) silyl, tricyclohexylsilyl, triphenylsilyl, dimethylphenylsilyl, methyldiphenylsilyl, tolylsilyl, and trinaphthylsilyl A hydrocarbon substituted silyl ether group such as a trimethylsilyl ether group; a trimethylsilylmethyl group, a bis (trimethylsilyl) methyl group,
A silicon-substituted alkyl group such as a phenyldimethylsilylethyl group; a silicon-substituted aryl group such as a trimethylsilylphenyl group; a dimethylhydrosilyl group; a methyldihydrosilyl group; Among these, a silicon-substituted alkyl group is preferable, and a trimethylsilylmethyl group, a phenyldimethylsilylethyl group and the like are particularly preferable.
Examples of the hetero atom-containing group include a hetero atom-containing hydrocarbon group. Examples of the hetero atom-containing hydrocarbon group include a p-fluorophenyl group, a 3,5-difluorophenyl group, a pentachlorophenyl group, a 3,4,5-trifluorophenyl group, a pentafluorophenyl group, a 3,5
-Bis (trifluoromethyl) phenyl group, bis (trimethylsilyl) methyl group and the like. A represents a cross-linking group containing a Group 14 element of the periodic table, and when there are two or more A, they may be the same or different.
As elements of Group 14 of the periodic table, carbon, silicon, germanium, and tin are preferable. Examples of the group having an element of Group 14 of the periodic table include compounds represented by general formula

[0011]

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(Wherein E represents carbon, silicon, tin or germanium, and R ¹¹ and R ¹² are each a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, An aryloxy group having 6 to 20 carbon atoms or 1 to
20 represents a silicon-containing group, which may be the same as or different from each other, or may be bonded to each other to form a ring; )). R ¹¹ and R
A hydrocarbon group having 1 to 20 carbon atoms and ^{12 to 12} carbon atoms in ¹²
Examples of the silicon-containing group of 0 include the same ones as exemplified in the description of R ^{1 to} R ¹⁰ . Further, an alkoxy group having 1 to 20 carbon atoms and 6 to 20 carbon atoms.
Examples of the aryloxy group include methoxy, ethoxy, various propoxy, various butoxy, various pentoxy, various hexoxy, various octoxy, phenoxy, methylphenoxy, and naphthoxy. As the A, R ¹³ ₂ Si (However, R ¹³ is. Indicating a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms) can be preferably exemplified. p represents an integer of 2 to 10, and specific examples of A include methylene, ethylene, ethylidene, (tetramethyl) ethylene, isopropylidene, cyclohexylidene, 1,2-cyclohexylene,
Dimethylsilylene, diphenyl silylene, tetramethyl silylene, dimethyl gel Mi Ren, dimethyl stannyl Ren, 1,2-phenylene, vinylene, vinylidene, include ethenylidene (CH ₂ = C =), among these, methylene (CH ₂₎ , Isopropylidene [(C
H ₃ ) ₂ C], ethylene (CH ₂ CH ₂ ), (tetramethyl) ethylene [(CH ₃ ) ₂ C (CH ₃ ) ₂ C], dimethylsilylene [(CH ₃ ) ₂ Si], diphenylsilylene [( C ₆ H ₅ ) ₂ Si] is preferred in terms of ease of synthesis and yield of the catalyst.

X represents a sigma-binding ligand bonded to M, and when there are a plurality of Xs, they may be the same or different. X is a halogen atom, having 1 to 2 carbon atoms.
0 hydrocarbon group, C1-C20 alkoxy group, C6-C20 aryloxy group, C1-C20 amide group, C1-C20 silicon-containing group, C1-C20 Examples thereof include a phosphide group, a sulfide group having 1 to 20 carbon atoms, a sulfoxide group having 1 to 20 carbon atoms, and an acyl group having 1 to 20 carbon atoms. Examples of the halogen atom include a chlorine atom, a fluorine atom, a bromine atom, and an iodine atom.
Specific examples of the hydrocarbon group having 1 to 20 carbon atoms include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclohexyl group and an octyl group, a vinyl group, a propenyl group, and a cycloalkyl group. Alkenyl group such as hexenyl group; arylalkyl group such as benzyl group, phenylethyl group, phenylpropyl group; phenyl group, tolyl group, dimethylphenyl group, trimethylphenyl group, ethylphenyl group, propylphenyl group, biphenyl group, naphthyl group And aryl groups such as methylnaphthyl group, anthracenyl group and phenanthonyl group. Examples of the alkoxy group having 1 to 20 carbon atoms include an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group, a phenylmethoxy group and a phenylethoxy group. Examples of the aryloxy group having 6 to 20 carbon atoms include a phenoxy group, a methylphenoxy group, and a dimethylphenoxy group. Examples of the amide group having 1 to 20 carbon atoms include a dimethylamide group, a diethylamide group, a dipropylamide group, a dibutylamide group, a dicyclohexylamide group, and an alkylamide group such as a methylethylamide group;
Alkenylamide groups such as divinylamide group, dipropenylamide group, dicyclohexenylamide group; arylalkylamide groups such as dibenzylamide group, phenylethylamide group and phenylpropylamide group; diphenylamide group, dinaphthylamide group Arylamide group and the like. Examples of the silicon-containing group having 1 to 20 carbon atoms include monohydrocarbon-substituted silyl groups such as methylsilyl group and phenylsilyl group; dihydrocarbon-substituted silyl groups such as dimethylsilyl group and diphenylsilyl group; trimethylsilyl group, triethylsilyl group; Trihydrocarbon-substituted silyls such as tripropylsilyl, dimethyl (t-butyl) silyl, tricyclohexylsilyl, triphenylsilyl, dimethylphenylsilyl, methyldiphenylsilyl, tolylsilyl, and trinaphthylsilyl Groups; hydrocarbon-substituted silyl ether groups such as trimethylsilyl ether group; silicon-substituted alkyl groups such as trimethylsilylmethyl group; silicon-substituted aryl groups such as trimethylsilylphenyl group; dimethylhydrosilyl group and methyldihydrosilyl group. Carbon number 1-20
Examples of the sulfide group include alkyl sulfide groups such as methyl sulfide group, ethyl sulfide group, propyl sulfide group, butyl sulfide group, hexyl sulfide group, cyclohexyl sulfide group, and octyl sulfide group; vinyl sulfide group, propenyl sulfide group, and cyclohexenyl sulfide. An alkenyl sulfide group such as a group; an arylalkyl sulfide group such as a benzyl sulfide group, a phenylethyl sulfide group or a phenylpropyl sulfide group; a phenyl sulfide group, a tolyl sulfide group, a dimethyl phenyl sulfide group, a trimethyl phenyl sulfide group, an ethyl phenyl sulfide group; Propylphenyl sulfide group, biphenyl sulfide group, naphthyl sulfide group, methyl naphthyl sulfide group, anthracene Rusurufido group, an aryl sulfide groups such as phenanthridine Nils sulfide group. Examples of the sulfoxide group having 1 to 20 carbon atoms include an alkyl sulfoxide group such as a methyl sulfoxide group, an ethyl sulfoxide group, a propyl sulfoxide group, a butyl sulfoxide group, a hexyl sulfoxide group, a cyclohexyl sulfoxide group, and an octyl sulfoxide group; a vinyl sulfoxide group and a propenyl sulfoxide. An alkenyl sulfoxide group such as a cyclohexenyl sulfoxide group; an arylalkyl sulfoxide group such as a benzyl sulfoxide group, a phenylethyl sulfoxide group or a phenylpropyl sulfoxide group; a phenyl sulfoxide group;
Tolylsulfoxide group, dimethylphenylsulfoxide group, trimethylphenylsulfoxide group, ethylphenylsulfoxide group, propylphenylsulfoxide group,
Biphenylsulfoxide group, naphthylsulfoxide group,
And arylsulfoxide groups such as methylnaphthylsulfoxide group, anthracenylsulfoxide group, and phenanthonylsulfoxide group. Examples of the acyl group having 1 to 20 carbon atoms include formyl group, acetyl group, propionyl group, butyryl group, valeryl group, palmitoyl group, tearoyl group, alkylacyl group such as oleoyl group, benzoyl group, toluoyl group, salicyloyl group, Examples include an arylacyl group such as a cinnamoyl group, a naphthoyl group, and a phthaloyl group; an oxalyl group, a malonyl group, and a succinyl group each derived from a dicarboxylic acid such as oxalic acid, malonic acid, and succinic acid. X represents a methyl group,
Preferred are an alkyl group such as an ethyl group and a propyl group, and an aryl group such as a phenyl group.

Y represents a Lewis base, and when there are a plurality of Y, they may be the same or different, and may be cross-linked with another Y, cyclopentadienyl group or X. Examples of Y include amines, ethers, esters, phosphines, thioethers, and nitriles. Examples of the amines include amines having 1 to 20 carbon atoms, specifically, methylamine, ethylamine, propylamine, butylamine, cyclohexylamine, methylethylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, Alkylamines such as dicyclohexylamine, methylethylamine, trimethylamine, triethylamine and tri-n-butylamine; alkenylamines such as vinylamine, propenylamine, cyclohexenylamine, divinylamine, dipropenylamine and dicyclohexenylamine; phenylmethylamine and phenyl Ethylamine,
Arylalkylamines such as phenylpropylamine; arylamines such as diphenylamine and dinaphthylamine; or ammonia, aniline, N-methylaniline, diphenylamine, N, N-dimethylaniline,
Methyldiphenylamine, pyridine, p-bromo-N,
N-dimethylaniline and the like can be mentioned. As ethers, aliphatic single ether compounds such as methyl ether, ethyl ether, propyl ether, isopropyl ether, butyl ether, isobutyl ether, n-amyl ether, isoamyl ether; methyl ethyl ether, methyl propyl ether, methyl isopropyl ether, Aliphatic hybrid ether compounds such as methyl-n-amyl ether, methyl isoamyl ether, ethyl propyl ether, ethyl isopropyl ether, ethyl butyl ether, ethyl isobutyl ether, ethyl n-amyl ether, ethyl isoamyl ether; vinyl ether, allyl ether, methyl Aliphatic unsaturated ether compounds such as vinyl ether, methyl allyl ether, ethyl vinyl ether and ethyl allyl ether; anisole Phenetole, phenyl ether, benzyl ether, phenyl benzyl ether, alpha-naphthyl ether, aromatic ether compounds such as β- naphthyl ether,
Examples include cyclic ether compounds such as ethylene oxide, propylene oxide, trimethylene oxide, tetrahydrofuran, tetrahydropyran, and dioxane. Examples of the esters include ethyl benzoate. Examples of the phosphines include phosphines having 1 to 20 carbon atoms.
Specifically, monohydrocarbon-substituted phosphines such as methylphosphine, ethylphosphine, propylphosphine, butylphosphine, hexylphosphine, cyclohexylphosphine, and octylphosphine; dimethylphosphine, diethylphosphine, dipropylphosphine, dibutylphosphine, dihexylphosphine, dicyclohexyl Dihydrocarbon-substituted phosphines such as phosphine and dioctylphosphine; alkyl phosphines such as trihydrocarbon-substituted phosphines such as trimethylphosphine, triethylphosphine, tripropylphosphine, tributylphosphine, trihexylphosphine, tricyclohexylphosphine, and trioctylphosphine; vinylphosphine Monopropane, propenylphosphine, cyclohexenylphosphine, etc. Benzyl phosphine; Luque alkenyl phosphine and a hydrogen atom alkenyl two substituted dialkenyl phosphines phosphine; tri alkenyl phosphine alkenyl hydrogen atom phosphine has three substituents
Arylalkylphosphines such as phenylethylphosphine and phenylpropylphosphine; diarylalkylphosphines or aryldialkylphosphines in which three hydrogen atoms of phosphine are substituted with three aryl or alkenyl; phenylphosphine, tolylphosphine, dimethylphenylphosphine, trimethylphenylphosphine, ethylphenyl Phosphine, propylphenylphosphine, biphenylphosphine, naphthylphosphine,
Methyl naphthyl phosphine, anthracenyl phosphine, phenanthyl phosphine; di (alkylaryl) phosphine in which two alkylaryls are substituted for phosphine hydrogen atoms; tri (alkylaryl) in which three alkylaryls are substituted for phosphine hydrogen atoms Aryl phosphines such as phosphine; Examples of the thioethers include the above-mentioned sulfides. Nitriles include acetonitrile, benzonitrile and the like.

Q is an integer of 1 to 5 [(valence of M)-
2], and r represents an integer of 0 to 3. M represents a metal element of Groups 3 to 10 of the periodic table or a lanthanoid series, and specifically, titanium, zirconium, hafnium,
Examples include yttrium, vanadium, chromium, manganese, nickel, cobalt, palladium, and lanthanoid-based metals. Among them, for polymerization catalysts for olefins, Group 4, element titanium, zirconium and hafnium are preferred. is there.

Specific examples of such a transition metal compound include (1,1′-dimethylsilylene) (2,2′-tetramethyldisilylene) bis (indenyl) zirconium dichloride and (1,1′-dimethylsilylene). ) (2,
2'-tetramethyldisilylene) bis (3-methylindenyl) zirconium dichloride, (1,1'-dimethylsilylene) (2,2'-tetramethyldisilylene) bis (3-trimethylsilylmethylindenyl) zirconium dichloride , (1,1'-dimethylsilylene)
(2,2′-ethylene) bis (indenyl) zirconium dichloride, (1,1′-dimethylsilylene) (2
2′-ethylene) bis (3-methylindenyl) zirconium dichloride, (1,1′-dimethylsilylene)
(2,2′-ethylene) bis (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,1 ′
-Tetramethyldisilylene) (2,2′-dimethylsilylene) bis (indenyl) zirconium dichloride,
(1,1′-tetramethyldisilylene) (2,2′-dimethylsilylene) bis (3-methylindenyl) zirconium dichloride, (1,1′-tetramethyldisilylene) (2,2′-dimethylsilylene ) Bis (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,1′-ethylene) (2,2′-dimethylsilylene) bis (indenyl) zirconium dichloride,
(1,1′-ethylene) (2,2′-dimethylsilylene) bis (3-methylindenyl) zirconium dichloride, (1,1′-ethylene) (2,2′-dimethylsilylene) bis (3-trimethylsilyl) Methylindenyl) zirconium dichloride, (1,1′-dimethylsilylene) (2,2′-dimethylsilylene) bis (indenyl) zirconium dichloride, (1,1′-dimethylsilylene) (2,2′-dimethylsilylene) Screw (3-
Methylindenyl) zirconium dichloride, (1,
1′-dimethylsilylene) (2,2′-dimethylsilylene) bis (3-trimethylsilylindenyl) zirconium dichloride, (1,1′-dimethylsilylene)
(2,2′-dimethylsilylene) bis (3-phenylindenyl) zirconium dichloride, (1,1′-dimethylsilylene) (2,2′-dimethylsilylene) bis (3-benzylindenyl) zirconium dichloride,
(1,1′-dimethylsilylene) (2,2′-dimethylsilylene) bis (3-neopentylindenyl) zirconium dichloride, (1,1′-dimethylsilylene)
Examples thereof include (2,2′-dimethylsilylene) bis (3-phenethylindenyl) zirconium dichloride, and those obtained by substituting zirconium in these compounds with titanium or hafnium, but are not limited thereto. . Further, a transition metal compound similar to the above, in which zirconium is substituted with a transition metal of another group, or a compound similar to the above, in which zirconium is substituted with a lanthanoid-based metal element, may be used.

The transition metal compound is described, for example, in "Journal of Organometallic Chemistry (J. Org).
ganomet.Chem) ", Volume 369, Page 359 (198
9), that is, preferably by the reaction of the corresponding substituted cycloalkenyl anion with the halide of M described above. The catalyst for olefin polymerization of the present invention comprises (A) a transition metal compound represented by the aforementioned general formula (I) or (II),
It contains an activating co-catalyst as a main component. As the activating co-catalyst, (B) it can react with the transition metal compound of the component (A) or a derivative thereof to form an ionic complex. Compounds, clays, clay minerals or ion-exchange compounds, and (C) an organoaluminum compound used as needed can be mentioned.

Among the above-mentioned components (B), the compound which can react with the transition metal compound of the component (A) or a derivative thereof to form an ionic complex includes the transition metal of the component (B-1). An ionic compound which reacts with a metal compound to form an ionic complex, (B-2) aluminoxane or (B-3)
Lewis acids are preferred because they have high polymerization activity and can reduce catalyst cost. As the component (B-1), any ionic compound can be used as long as it reacts with the transition metal compound of the component (A) to form an ionic complex. From the viewpoint that a polymerization active site can be formed, the following general formula (V),
Those represented by (VI) are preferred.

([L¹-R¹⁴]^{h +})_a([Z]^-)_b ... (V) ([L^Two]^{h +})_a([Z]^-)_b ... (VI) (However, L^TwoIs M¹, R¹⁵R¹⁶M^Two, R¹⁷ _ThreeC or R
¹⁸M^TwoIt is. [(V), (VI) where L¹Is a Lewis base, [Z]
^-Is a non-coordinating anion [Z ¹]^-Or [Z^Two]^-This
Here [Z¹]^-Is an anion in which two or more groups are bonded to an element.
That is, [M^ThreeG¹G^Two... G^f] (Where M^ThreeIs lap
Group 5 to 15 elements of the Periodic Table, preferably Periodic Tables 13 to
Shows Group 15 elements. G¹~ G^fAre hydrogen and ha, respectively.
Rogen atom, alkyl group having 1 to 20 carbon atoms, 2 to 2 carbon atoms
40 dialkylamino groups, alkoxy having 1 to 20 carbon atoms
Si group, aryl group having 6 to 20 carbon atoms, 6 to 20 carbon atoms
Aryloxy group, alkylaryl having 7 to 40 carbon atoms
Group, an arylalkyl group having 7 to 40 carbon atoms,
20 halogen-substituted hydrocarbon groups, 1 to 20 carbon atoms
Roxy group, organic metalloid group, or C2-20
A heteroatom-containing hydrocarbon group is shown. G¹~ G^f2 out of
One or more may form a ring. f is [(center metal M
^ThreeValence) +1]. [Z^Two]^-Is the acid digestion
The log of the reciprocal of the separation constant (pKa) is -10 or less.
Ted acid alone or in combination with Bronsted and Lewis acids
Conjugated base, or generally defined as a superacid
Shows a conjugate base. Also, a Lewis base may be coordinated.
No. Also, R ¹⁴Is hydrogen atom, alkyl having 1 to 20 carbon atoms
Group, aryl group having 6 to 20 carbon atoms, alkylaryl group
Or an arylalkyl group;¹⁵And R¹⁶Each
Cyclopentadienyl group, substituted cyclopentadienyl
Group, indenyl group, substituted indenyl group, fluorenyl group
Or a substituted fluorenyl group, R¹⁷Is an alkyl having 1 to 20 carbon atoms
Kill group, aryl group, alkylaryl group or aryl
Shows an alkyl group. R¹⁸Is tetraphenylporphyri
And macrocyclic ligands such as phthalocyanine. h is
[L¹-R¹⁴], [L^Two1 to 3
The number a is an integer of 1 or more, and b = (h × a). M
¹Includes elements of Groups 1 to 3, 11 to 13, and 17 of the periodic table.
M^TwoIndicates an element in Groups 7 to 12 of the periodic table
You. ] Can be suitably used.

Here, specific examples of L ¹ include ammonia, methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine,
Amines such as N, N-dimethylaniline, trimethylamine, triethylamine, tri-n-butylamine, methyldiphenylamine, pyridine, p-bromo-N, N-dimethylaniline, p-nitro-N, N-dimethylaniline, and triethylphosphine Phosphines such as triphenylphosphine and diphenylphosphine; thioethers such as tetrahydrothiophene; esters such as ethyl benzoate; and nitriles such as acetonitrile and benzonitrile. Specific examples of R ¹⁴ include hydrogen, methyl group, ethyl group, benzyl group and trityl group. Specific examples of R ¹⁵ and R ¹⁶ include cyclopentadienyl group, methylcyclopentadienyl group , Ethylcyclopentadienyl group,
A pentamethylcyclopentadienyl group and the like can be mentioned. Specific examples of R ¹⁷ include a phenyl group, a p-tolyl group, and a p-methoxyphenyl group. Specific examples of R ¹⁸ include tetraphenylporphine,
Examples include phthalocyanine, allyl, and methallyl. Specific examples of M ¹ include Li, Na,
K, Ag, Cu, Br, I, and the like can be illustrated. I _3, specific examples of M ² are, Mn, Fe, Co, Ni ,
Zn and the like can be mentioned.

[Z ¹ ] ⁻ , that is, [M ³ G ¹ G
² ... G ^f ], B and A are specific examples of M ^3.
l, Si, P, As, Sb, etc., preferably B or Al
Is mentioned. Specific examples of G ¹ , G ^{2 to} G ^f include dimethylamino and diethylamino as dialkylamino groups, and methoxy, ethoxy, n-butoxy groups as alkoxy or aryloxy groups.
Methyl, ethyl, n-propyl, isopropyl, n-butyl, hydrocarbon groups such as phenoxy group, etc.
Fluorine, chlorine, bromine and the like as halogen atoms such as isobutyl group, n-octyl group, n-eicosyl group, phenyl group, p-tolyl group, benzyl group, 4-t-butylphenyl group and 3,5-dimethylphenyl group. Iodine, p-fluorophenyl group as a hetero atom-containing hydrocarbon group, 3,5
-Difluorophenyl group, pentachlorophenyl group,
Organic metalloid groups such as 3,4,5-trifluorophenyl group, pentafluorophenyl group, 3,5-bis (trifluoromethyl) phenyl group and bis (trimethylsilyl) methyl group, as pentamethylantimony group, trimethylsilyl group, trimethyl Examples thereof include a germyl group, a diphenylarsine group, a dicyclohexylantimony group, and diphenylboron.

Further, a non-coordinating anion, ie, pKa
Specific examples of the conjugated base [Z ² ] ⁻ , which is a Brönsted acid alone or a combination of a Brönsted acid and a Lewis acid with -10 or less, include trifluoromethanesulfonic acid anion (CF ₃ SO ₃ ) ⁻ , bis (trifluoromethanesulfonyl) ) Methyl anion, bis (trifluoromethanesulfonyl) benzyl anion, bis (trifluoromethanesulfonyl) amide, perchlorate anion (Cl
O ₄ ) ^- , trifluoroacetic acid anion (CF ₃ CO ₂ )
-, Hexafluoroantimony anion (SbF ₆ )-
, Fluorosulfonic acid anion (FSO ₃ ) ⁻ , chlorosulfonic acid anion (ClSO ₃ ) ⁻ , fluorosulfonic acid anion / 5-antimony fluoride (FSO ₃ / S
bF ₅₎ ^-, fluorosulfonic acid anion / 5- fluoride arsenic ^{_{(FSO 3 / AsF 5) -}} , trifluoromethanesulfonic acid / antimony pentafluoride (CF ₃ SO ₃ / Sb
F ₅₎ ^-, and the like.

Specific examples of the ionic compound which forms an ionic complex by reacting with the transition metal compound of the component (A), that is, the compound of the component (B-1) include:
Triethylammonium tetraphenylborate, tri-n-butylammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, methyl (tri-n-butyl) ammonium tetraphenylborate, benzyltetraphenylborate (tri-n-butyl) Butyl) ammonium, dimethyldiphenylammonium tetraphenylborate, triphenyl (methyl) ammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, benzylpyridinium tetraphenylborate, methyltetraphenylborate (2-cyanopyridinium) Triethylammonium, tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate ) Tri-n-butylammonium borate, triphenylammonium tetrakis (pentafluorophenyl) borate, tetra-n-butylammonium tetrakis (pentafluorophenyl) borate, tetraethylammonium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) Benzyl (tri-n-butyl) ammonium borate, methyldiphenylammonium tetrakis (pentafluorophenyl) borate, triphenyl (methyl) ammonium tetrakis (pentafluorophenyl) borate, methylanilinium tetrakis (pentafluorophenyl) borate, tetrakis (pentane) Dimethylanilinium fluorophenyl) borate, trimethylanilinium tetrakis (pentafluorophenyl) borate, tetrakis Methylpyridinium pentafluorophenyl) borate, benzylpyridinium tetrakis (pentafluorophenyl) borate, methyl (2-cyanopyridinium) tetrakis (pentafluorophenyl) borate, benzyl (2-cyanopyridinium) tetrakis (pentafluorophenyl) borate, tetrakis ( Methyl pentafluorophenyl) borate (4-cyanopyridinium), triphenylphosphonium tetrakis (pentafluorophenyl) borate, tetrakis [3
5-Di (trifluoromethyl) phenyl] dimethylanilinium borate, ferrocenium tetraphenylborate, silver tetraphenylborate, trityl tetraphenylborate, tetraphenylporphyrin manganese tetraphenylborate, ferrocenium tetrakis (pentafluorophenyl) borate, tetrakis (pentane) Fluorophenyl) borate (1,1′-dimethylferrocenium), decamethylferrocenium tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate,
Trityl tetrakis (pentafluorophenyl) borate,
Lithium tetrakis (pentafluorophenyl) borate,
Sodium tetrakis (pentafluorophenyl) borate, tetraphenylporphyrin manganese tetrakis (pentafluorophenyl) borate, silver tetrafluoroborate, silver hexafluorophosphate, silver hexafluoroarsenate,
Silver perchlorate, silver trifluoroacetate, silver trifluoromethanesulfonate and the like can be mentioned.

As the component (B-1), one kind of the ionic compound which reacts with the transition metal compound of the component (A) to form an ionic complex may be used alone, or two or more kinds thereof may be used. May be used in combination. On the other hand, examples of the aluminoxane of the component (B-2) include a chain aluminoxane represented by the following general formula (VII) and a cyclic aluminoxane represented by the general formula (VIII).

[0025]

Embedded image

(Wherein, R ¹⁹ is a group having 1 to 2 carbon atoms, respectively)
It represents 0, preferably 1 to 8 alkyl groups, which may be the same or different. Also, w is 2 ≦ w ≦
40 and s are integers satisfying 1 <s ≦ 50. Specific examples include aluminoxanes such as methylaluminoxane, ethylaluminoxane and isobutylaluminoxane. As a method for producing the aluminoxane,
A method of contacting an alkylaluminum with a condensing agent such as water may be mentioned, but there is no particular limitation on the means, and the reaction may be performed according to a known method. For example, a method of dissolving an organic aluminum compound in an organic solvent and bringing it into contact with water, a method of adding an organic aluminum compound at the beginning during polymerization, and then adding water, a crystal water contained in a metal salt or the like, There are a method of reacting water adsorbed on an inorganic or organic substance with an organoaluminum compound, a method of reacting a trialkylaluminum with a tetraalkyldialuminoxane, and further reacting water. In addition,
The aluminoxane may be toluene-insoluble. These aluminoxanes may be used alone or in a combination of two or more.

The Lewis acid as the component (B-3) is not particularly limited, and may be an organic compound or a solid inorganic compound. Organic compounds include boron compounds and aluminum compounds, and inorganic compounds include magnesium compounds,
Aluminum compounds are preferably used because they can form active sites efficiently. Examples of the aluminum compound include bis (2,6-di-t-butyl-4-methylphenoxy) aluminum methyl, (1,1-bi-2-
Naphthoxy) aluminum methyl and the like; magnesium compounds such as magnesium chloride and diethoxymagnesium; aluminum compounds as aluminum oxide and aluminum chloride; boron compounds as triphenylboron and tris (pentafluorophenyl) boron; Tris [3,5-bis (trifluoromethyl) phenyl] boron, tris [(4-fluoromethyl) phenyl] boron, trimethylboron, triethylboron, tri-n-butyl-boron, tris (fluoromethyl) boron, tris (Pentafluoroethyl) boron, tris (nonafluorobutyl) boron, tris (2,4,6-
Trifluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris [3,5-bis (trifluoromethyl) phenyl] boron, bis (pentafluorophenyl) fluoroboron, diphenylfluoroboron, bis (pentafluoro Phenyl) chloroboron, dimethylfluoroboron, diethylfluoroboron, di-n-butylfluoroboron, pentafluorophenyldifluoroboron, phenyldifluoroboron, pentafluorophenyldichloroboron, methyldifluoroboron, ethyldifluoroboron, n-butyldifluoroboron And the like. One of these Lewis acids may be used, or two or more may be used in combination.

On the other hand, in the component (B) (B-4) clay, clay mineral or ion-exchange compound, the clay is an aggregate of fine hydrated silicate minerals, and is mixed with an appropriate amount of water. A substance that produces plasticity when twisted, shows rigidity when dried, and sinters when baked at high temperatures.
Clay minerals are hydrated silicates that are the main component of clay.
For the preparation of the olefin polymerization catalyst component, any of clay and clay mineral may be used, and these may be natural products or artificially synthesized products. The ion-exchangeable layered compound is a compound having a crystal structure in which surfaces formed by ionic bonds and the like are stacked in parallel with weak bonding force to each other, and the ions contained therein can be exchanged. Some clay minerals are ion-exchangeable layered compounds.

Specific examples of the component (B-4) include, for example, phyllosilicates as clay minerals. The phyllosilicic acids include phyllosilicic acid and phyllosilicates. The phyllosilicates include, as natural products, montmorillonite belonging to smectite group, saponite, hectorite, illite belonging to mica group, sericite and mixed layer minerals of smectite group and mica group or mica group and vermiculite group. Can be.
In addition, as synthetic products, tetrasilicon mica, laponite,
Smecton and the like can be mentioned. In addition, α-Zr
(HPO ₄ ) ₂ , γ-Zr (HPO ₄ ) ₂ , α-Ti
Ionic crystalline compounds having a layered crystal structure that are not clay minerals, such as (HPO ₄ ) ₂ and γ-Ti (HPO ₄ ) _2, can be used. In addition, as clays and clay minerals that do not belong to the ion-exchange layered compound, clays called bentonite because of low montmorillonite content, Kibushi clay, montmorillonite containing many other components in montmorillonite, sepiolite in fibrous form , Palygorskite, and amorphous or low-crystalline allophane, imogolite, and the like.

Further, as the component (B-4), particles having a volume average particle diameter of 10 μm or less are preferable, and particles having a volume average particle diameter of 3 μm or less are more preferable. Generally, the particle shape of the particles has a particle size distribution, but (B
-4) The component preferably has a particle size distribution in which the volume average particle diameter is 10 μm or less, and the content ratio of the volume average particle diameter of 3.0 μm or less is 10% by weight or more. Is more preferably 10 μm or less, and more preferably has a particle size distribution in which the content ratio of the volume average particle diameter of 1.5 μm or less is 10% by weight or more. As a method for measuring the volume average particle diameter and the content ratio, for example, an apparatus for measuring the particle diameter by light transmittance by laser light (GALA)
I Production Ltd. CIS-1)
Is used. Further, the component (B-4) may be an acid-treated, alkali-treated, salt-treated, or organic-treated component. Among them, those pretreated with an organosilicon compound or an organoaluminum compound,
It is preferable because the polymerization activity is improved. Among these (B-4) components, quaternary ammonium salts (with no particular limitation, quaternary alkyl ammonium salts, quaternary aryl ammonium salts,
Those having a high ability to adsorb quaternary arylalkylammonium salt, quaternary benzylammonium salt, heteroaromatic ammonium salt or the like and react with clay or the like to form an interlayer compound (also referred to as intercalation) are preferable. For example, clay or clay mineral is preferable, specifically, phyllosilicates are preferable, and smectite is more preferable,
Particularly preferred is montmorillonite. As the synthetic product, tetrasilicic mica is preferable.

The use ratio of the catalyst component (A) to the catalyst component (B) in the polymerization catalyst of the present invention is preferably a molar ratio when the compound (B-1) is used as the catalyst component (B). Is from 10: 1 to 1: 100, more preferably from 2: 1 to
A ratio of 1:10 is desirable, and if the ratio is outside the above range, the catalyst cost per unit weight polymer becomes high,
Impractical. When the compound (B-2) is used, the molar ratio is preferably 1: 1 to 1: 1,000,000,
More preferably, the range is from 1:10 to 1: 10,000. If the ratio is outside this range, the cost of the catalyst per unit weight of polymer increases, which is not practical. (A)
The use ratio of the catalyst component to the (B-3) catalyst component is preferably 10: 1 to 1: 2,000, more preferably 5: 1 to 1: 1,000, and still more preferably 2: 1, in a molar ratio. 1 to
A ratio of 1: 500 is desirable. If the ratio deviates from this range, the catalyst cost per unit weight polymer increases, which is not practical. The ratio of the component (A) to the component (B-4) is as follows:
(B-4) With respect to the unit weight [g] of the component clay, etc.,
The transition metal complex of the component (A) is in the range of 0.1 to 1.00 micromol, preferably 1 to 100 micromol.

As the catalyst component (B), (B-
1), (B-2), (B-3) and (B-4) can be used alone or in combination of two or more. The polymerization catalyst of the present invention may contain the above components (A) and (B) as main components, or may contain the components (A), (B) and (C) organoaluminum. It may contain a compound as a main component. here,
As the organoaluminum compound as the component (C), a compound represented by the following general formula (IX): R ²⁰ _v AlQ _3-v (IX) (wherein, R ²⁰ is an alkyl group having 1 to 10 carbon atoms, Q is a hydrogen atom, C1-C20 alkoxyl group, C6-C2
0 represents an aryl group or a halogen atom, and v is a real number of 1 to 3).

Specific examples of the compound represented by the general formula (IX) include trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum Examples include aluminum fluoride, diisobutylaluminum hydride, diethylaluminum hydride, and ethylaluminum sesquichloride. As the organoaluminum compound, a trialkylaluminum compound is preferable, and among them, trimethylaluminum and triisobutylaluminum are preferable. These organoaluminum compounds may be used alone or in combination of two or more.

The use ratio of the catalyst component (A) to the catalyst component (C) is preferably 1: 1 to 1: 1,00 by molar ratio.
0, more preferably 1: 5 to 1: 2,000, further preferably 1:10 to 1: 1,000.
By using the catalyst component (C), the polymerization activity per transition metal can be improved. However, if the amount is too large, especially if it exceeds the above range, the organoaluminum compound will be wasted and the polymer Left in large quantities,
On the other hand, if the amount is small, sufficient catalytic activity cannot be obtained, which may be undesirable. In the present invention, a polymer such as polyethylene or polypropylene, or an inorganic oxide such as silica or alumina may coexist or be brought into contact with or after each component is contacted. When loading on a carrier,
It is preferable to support the polymer on a polymer, and the particle size of such a carrier polymer is usually 1 to 300 μm, preferably 10 to 200 μm, more preferably 20 to 10 μm.
0 μm. When the particle size is smaller than 1 μm, fine particles in the polymer increase, and when the particle size is larger than 300 μm, coarse particles in the polymer increase, resulting in a decrease in bulk density and clogging of a hopper in a manufacturing process. Become. The specific surface area of the support in this case is from 1 to 1,000 m ² / g, preferably 50 m ² / g.
５００500 m ² / g, and the pore volume is 0.1-5 m ³ / g.
g, preferably 0.3 to ³ m ³ / g.

The contact of each component is performed in an inert gas such as nitrogen,
It may be carried out in a hydrocarbon such as pentane, hexane, heptane, toluene and xylene. Of course, addition or contact of each component can be performed at the polymerization temperature,
It is preferably carried out at a temperature of from -30 ° C to the boiling point of each solvent, particularly from room temperature to the boiling point of the solvent. The olefin polymer of the present invention is obtained using the above-mentioned olefin polymerization catalyst, and homopolymerizes olefins or olefins and other olefins and / or olefins in the presence of the olefin polymerization catalyst. Alternatively, it can be produced by copolymerizing with another monomer. In the method for producing an olefin polymer of the present invention, the organoaluminum compound (C) may be used in contact with the component (A) and / or the component (B) in advance, or the component (C) may be placed in a reactor. It may be charged and brought into contact with the component (A) and the component (B) before use. The amount of the component (C) used is the same as in the olefin polymerization catalyst described above. According to the method for producing an olefin polymer of the present invention, using the polymerization catalyst described above, homopolymerization of olefins,
Or copolymerization of olefins with other olefins and / or other monomers (that is, copolymerization with different olefins, copolymerization of olefins with other monomers, or different olefins) Copolymerization with each other and other monomers) can be suitably performed.

The olefin is not particularly limited, but ethylene or an α-olefin having 3 to 20 carbon atoms is preferable. Examples of the α-olefin include propylene, 1-butene, 1-pentene, 1-hexene,
Heptene, 1-octene, 1-nonene, 1-decene, 4
-Phenyl-1-butene, 6-phenyl-1-hexene, 3-methyl-1-butene, 4-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-hexene, 5-methyl -1-hexene, 3,3-dimethyl-
1-pentene, 3,4-dimethyl-1-pentene, 4,
Α-olefins such as 4-dimethyl-1-pentene and vinylcyclohexane, dienes such as 1,3-butadiene, 1,4-pentadiene and 1,5-hexadiene, hexafluoropropene, tetrafluoroethylene and 2-fluoro Halogen-substituted α-olefins such as propene, fluoroethylene, 1,1-difluoroethylene, 3-fluoropropene, trifluoroethylene, and 3,4-dichloro-1-butene; cyclopentene; cyclohexene; norbornene; 5-methylnorbornene; Cyclic olefins such as -ethylnorbornene, 5-propylnorbornene, 5,6-dimethylnorbornene, and 5-benzylnorbornene; and styrenes such as styrene, p-methylstyrene, p-ethylstyrene, p-propylstyrene, and p- Isopropyl Styrene, p-butylstyrene,
p-tert-butylstyrene, p-phenylstyrene, o-methylstyrene, o-ethylstyrene, o-propylstyrene, o-isopropylstyrene, m-methylstyrene, m-ethylstyrene, m-isopropylstyrene, m-butyl Styrene, mesityl styrene, 2,
4-dimethylstyrene, 2,5-dimethylstyrene,
Alkylstyrenes such as 3,5-dimethylstyrene, p
-Methoxystyrene, o-methoxystyrene, alkoxystyrenes such as m-methoxystyrene, p-chlorostyrene, m-chlorostyrene, o-chlorostyrene, p
Halogenated styrenes such as -bromostyrene, m-bromostyrene, o-bromostyrene, p-fluorostyrene, m-fluorostyrene, o-fluorostyrene, o-methyl-p-fluorostyrene, furthermore, trimethylsilylstyrene and vinylbenzoate Acid esters, divinylbenzene and the like. Further, the other olefins described above may be appropriately selected from the olefins described above.

In the present invention, the above olefins may be used alone or in combination of two or more. When copolymerizing two or more olefins, the above olefins can be arbitrarily combined. Further, in the present invention, the above-mentioned olefins and other monomers may be copolymerized.
For example, chain diolefins such as butadiene, isoprene, 1,4-pentadiene, and 1,5-hexadiene;
Norbornene, 1,4,5,8-dimethano-1,2,2
Polycyclic olefins such as 3,4,4a, 5,8,8a-octahydronaphthalene and 2-norbornene, cyclic diolefins such as norbornadiene, 5-ethylidene norbornene, 5-vinylnorbornene and dicyclopentadiene, and acrylic acid Examples thereof include unsaturated esters such as ethyl and methyl methacrylate. In the present invention, propylene is particularly preferred as the olefin.

The method for polymerizing olefins in the present invention is not particularly limited, and any polymerization method such as a slurry polymerization method, a solution polymerization method, a gas phase polymerization method, a bulk polymerization method, and a suspension polymerization method may be employed. Can be. When a polymerization solvent is used, examples of the solvent include hydrocarbons such as benzene, toluene, xylene, n-hexane, n-heptane, cyclohexane, methylene chloride, chloroform, 1,2-dichloroethane, and chlorobenzene, and halogenated solvents. Hydrocarbons and the like. These may be used alone.
Two or more kinds may be used in combination. Further, a monomer used for polymerization may be used depending on the kind thereof. The amount of the catalyst used in the polymerization reaction is selected so that the amount of the component (A) is usually in the range of 0.5 to 100 micromol, preferably 2 to 25 micromol, per liter of the solvent. This is advantageous in terms of reactor efficiency.

As for the polymerization conditions, the pressure is usually selected from the range of normal pressure to 200 MPa · G. The reaction temperature is usually in the range of -50C to 250C. Examples of the method for controlling the molecular weight of the polymer include the type and amount of each catalyst component, selection of the polymerization temperature, and introduction of hydrogen. Further, at the time of polymerization of the olefin in the present invention,
Prepolymerization can be performed using the above catalyst. This prepolymerization can be carried out by bringing a small amount of olefin into contact with the catalyst. In this case, the reaction temperature is −20 to 100 ° C.,
Preferably -10 to 70 ° C, particularly preferably 0 to 50 ° C
It is. As a solvent used in the prepolymerization, an inert hydrocarbon, an aliphatic hydrocarbon, an aromatic hydrocarbon, or a monomer is used, and an aliphatic hydrocarbon is particularly preferable. This prepolymerization can be carried out without a solvent. The prepolymerized product has an intrinsic viscosity [η] (135
(Measured in decalin) at 0.2 deciliters / g, preferably 0.5 deciliters / g or more, and the amount of the prepolymerized product per 1 mmol of transition metal component in the catalyst is reduced. 1 to 10,000 g, preferably 10
It is preferable to adjust the conditions so that the weight becomes １1,000 g. According to this production method, in particular, a copolymer of polypropylene, polyethylene or propylene with ethylene and / or an α-olefin having 4 to 20 carbon atoms has a high molecular weight and a high polymerization activity. As the olefin polymer of the present invention, specifically, polypropylene, polyethylene or propylene with ethylene and / or carbon number of 4 to 20
And α-olefins, which have a narrow molecular weight distribution. Molecular weight distribution (Mw / M
n) is usually 5 or less, preferably 4 or less.

[0040]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples. Example 1 (1,1′-SiMe ₂ ) (2,2′-SiMe ₂ Si
Synthesis of Me ₂ ) bis (indenyl) zirconium dichloride (1) Under a nitrogen stream, 2.5 g of magnesium and 10 parts of tetrahydrofuran (THF) were placed in a 300 ml three-necked flask.
0 ml was added, and a piece of iodine (about 5 mg) was added. To this, 5.0 g (25.6 mmol) of 2-bromoindene dissolved in 40 ml of THF was added dropwise from a dropping funnel. After the addition, the mixture was further stirred at room temperature for 2 hours.
1.33 g of 1,2-dichlorotetramethyldisilane (7.1
Mmol) was added dropwise. After stirring overnight at room temperature, the solvent was distilled off, and the residue was extracted with 50 ml of hexane to obtain 2.03 g (82% yield) of 1,2-bis (indenyl) tetramethyldisilane as a pale yellow oil. Was.
This was dissolved in 30 ml of ether, and a solution of n-butyllithium (n-BuLi) in n-hexane (1.52 mol / l, 7.8 ml) was added at -78 ° C. After stirring at room temperature overnight, the supernatant was filtered off, and the obtained white solid was washed with hexane and dried under reduced pressure to obtain a dilithium salt. This salt was dissolved in THF (20 ml), and dichlorodimethylsilane (0.3 ml) was added dropwise. After stirring at room temperature for 3 hours, the solvent was removed and the residue was extracted with 30 ml of hexane. After filtration, the solvent was distilled off to obtain (1,1′-SiMe ₂ ) (2,
2′-SiMe ₂ SiMe ₂ ) bis (indene) is 1.2
6 g were obtained. This was dissolved in 20 ml of ether, and a solution of n-BuLi in n-hexane (1.5
2 mol / l, 3.3 ml) was added dropwise. After stirring at room temperature overnight, the supernatant was filtered off and the obtained white precipitate was dried under reduced pressure to obtain 0.99 g of a dilithium salt. This salt was suspended in 10 ml of toluene,
0.47 g (2.0 mmol) of zirconium tetrachloride suspended in 10 ml of toluene at 78 ° C. was added. After stirring at room temperature overnight, the supernatant was filtered off, concentrated to 1/3, cooled to -20 ° C and stored, whereby a yellow powder precipitated (yield 25%). ¹ H NMR (90 MHz, CDCl ₃ ): δ-0.5
3, 0.76, 0.82, 1.02 (s, -SiMe _2- , 1
8H); 6.47 (s, CH, 2H); 7.0-7.8 (m,
ArH, 8H)

Example 2 (1,1′-SiMe ₂ SiMe ₂ ) (2,2′-Si
Synthesis of Me ₂ ) bis (indenyl) zirconium dichloride (2) 2.5 g of magnesium and tetrahydrofuran (THF) 10 were placed in a 300 ml three-necked flask under a nitrogen stream.
0 ml was added, and a piece of iodine (about 5 mg) was added. To this, 5.0 g (25.6 mmol) of 2-bromoindene dissolved in 40 ml of THF was added dropwise from a dropping funnel. After completion of the dropwise addition, the mixture was further stirred at room temperature for 2 hours, and then 1.5 ml (12.4 mmol) of dichlorodimethylsilane was added dropwise. After dropping, the mixture was stirred at room temperature overnight,
The solvent was distilled off, and the residue was extracted with 50 ml of hexane to obtain 2.68 g (yield 73%) of bis (indenyl) dimethylsilane as a pale yellow oil. This was dissolved in 30 ml of ether, and a solution of n-butyllithium (n-BuLi) in n-hexane (1.5 ml) was added at -78 ° C.
2 mol / l, 12.2 ml). After stirring at room temperature overnight, the supernatant was filtered off, and the obtained white solid was washed with hexane and dried under reduced pressure to obtain a dilithium salt. This salt was dissolved in 30 ml of THF, and 1,2-dichlorotetramethyldisilane 1.1 was dissolved.
Milliliter was added dropwise. After stirring at room temperature for 3 hours, the solvent was removed and the residue was extracted with 30 ml of hexane. After filtration, the solvent is distilled off to give (1,1′-SiMe ₂ S
iMe ₂ ) (2,2′-SiMe ₂ ) bis (indene)
Was obtained in an amount of 2.42 g. This was dissolved in 30 ml of ether, and a solution of n-BuLi in n-hexane (1.52 mol / l, 7.9 ml) was added dropwise at -78 ° C. After stirring overnight at room temperature, the supernatant was filtered off and the resulting white precipitate was dried under reduced pressure to remove dilithium salt to 2.0.
1 g was obtained. This salt was suspended in 10 ml of toluene, and 0.96 g (4.1 mmol) of zirconium tetrachloride suspended in 10 ml of toluene at -78 ° C was added. After stirring overnight at room temperature, the supernatant was filtered off, concentrated to 1/3, cooled to -20 ° C and stored, whereupon a yellow powder precipitated (yield 23%).

Example 3 Synthesis of (1,1′-SiMe ₂ ) (2,2′-SiMe ₂ ) bis (indenyl) zirconium dichloride (3) Magnesium was placed in a 500 ml three-necked flask under a nitrogen stream. 0 g and tetrahydrofuran (THF) 2
One hundred milliliters were charged and one piece of iodine (about 5 mg) was added. Here, 2-dissolved in 100 ml of THF
20.6 g (105.6 mmol) of bromoindene was added dropwise from the dropping funnel. After completion of the dropwise addition, the mixture was further stirred at room temperature for 2 hours, and then 5.8 ml of dichlorodimethylsilane (47.
8 mmol) was added dropwise. After completion of the dropwise addition, the mixture was stirred at room temperature overnight, the solvent was distilled off, and the residue was extracted with 100 ml of hexane to obtain 12.89 g (yield: 85%) of bis (indenyl) disilane as a pale yellow oil.
This was dissolved in 30 ml of ether, and a solution of n-butyllithium (n-BuLi) in n-hexane (1.59 mol / l, 56.2 ml) was added at -78 ° C. After stirring at room temperature overnight, the supernatant was filtered off, and the obtained yellow-white solid was washed with hexane and dried under reduced pressure to obtain 15.15 g of a dilithium salt. This salt is
It was dissolved in 40 ml of HF, and 4.1 ml of dichlorodimethylsilane was added dropwise. After stirring at room temperature for 3 hours, the solvent was removed and the residue was extracted with 50 ml of hexane. After filtration, the yellow solution was concentrated and refrigerated at −20 ° C. (1,1′-SiMe ₂ SiMe ₂ )
2.67 g of (2,2′-SiMe ₂ ) bis (indene) were obtained as a cream-colored powder. This is ether 50
Dissolved in milliliter and n-BuLi n-
A hexane solution (1.59 mol / L, 9.7 mL) was added dropwise. After stirring at room temperature overnight, the supernatant was filtered off and the resulting white precipitate was dried under reduced pressure to obtain a dilithium salt. 0.61 g of this salt was suspended in 10 ml of toluene, and 0.33 g (2.0 mmol) of zirconium tetrachloride suspended in 10 ml of toluene at -78 ° C was added. After stirring at room temperature overnight, the solvent was distilled off, and the obtained yellow solid was washed with 40 ml of hexane. Further extraction with 40 ml of dichloromethane and concentration of the yellow solution gave (1,1′-Si
Me ₂ ) (2,2′-SiMe ₂ ) bis (indenyl)
Zirconium dichloride was obtained as a yellow powder (15% yield). ¹ H NMR (90 MHz, CDCl ₃ ): δ-0.7
₂ , 1.01, 1.05, 1.17 (s, -SiMe _2- , 1,
2H); 6.95 (s, CH, 2H); 7.1-7.8 (m,
ArH, 8H)

Example 4 Assembly of Ethylene To a heated and dried 1 liter autoclave, 400 ml of heptane and 1 mmol of MMAO (manufactured by Tosoh Akzo Co., Ltd.) as methylaluminoxane were added at room temperature under a nitrogen atmosphere, and ethylene was added at 0.2 MPa · G. Introduced. After the temperature was raised to 60 ° C. with stirring, the (1,1′-SiMe ₂ ) (2,2′-SiMe ₂ Si) obtained in Example 1 was obtained.
1 μmol of (Me ₂ ) bis (indenyl) zirconium dichloride (1) was added and polymerized for 60 minutes. After completion of the polymerization reaction, the reaction product was dried under reduced pressure to obtain 22 g of polyethylene. The catalytic activity is 241 kg / g
-It was Zr. The intrinsic viscosity [η] of the obtained polyethylene was 2.04 deciliter / g, and the weight average molecular weight (M
w) was 284,000, and the weight average molecular weight / number average molecular weight ratio (Mw / Mn) was 2.4. The intrinsic viscosity [η] was determined using an automatic viscometer VMR-053 manufactured by Rigo Co., Ltd.
Measured in decalin at 35 ° C. Molecular weight and molecular weight distribution were as follows: Apparatus: Waters ALC / GPC 150C Column: Tosoh, GMHHR + H (S) HT × 2 Temperature: 145 ° C. Solvent: 1,2,4-trichlorobenzene Flow rate: 1 ml / min. Under the conditions described above, the measurement was carried out in terms of polyethylene by gel permeation chromatography (GPC).

Example 5 In the case of ethylene To a heated and dried 1 liter autoclave, 400 ml of heptane and 1 mmol of MMAO (manufactured by Tosoh Akzo) as methylaluminoxane were added at room temperature under a nitrogen atmosphere, and ethylene was added at 0.2 MPa · G. Introduced. After the temperature was raised to 60 ° C. with stirring, (1,1′-SiMe ₂ ) (2,2′-SiMe ₂ ) bis (indenyl) zirconium dichloride (3) obtained in Example 3 was added to 1
Micromol was added and polymerization was carried out for 60 minutes. After completion of the polymerization reaction, the reaction product was dried under reduced pressure to obtain 7 g of polyethylene. The catalyst activity was 77 kg / g · Zr. The intrinsic viscosity [η] of the obtained polyethylene was 17 deciliter / g.

Comparative Example 1 Polymerization of Ethylene Bis (cyclopentadienyl) zirconium dichloride (Cp ₂ ZrCl ₂ ) instead of (1,1′-SiMe ₂ ) (2,2′-SiMe ₂ ) bis (indenyl) zirconium dichloride ) Was performed in the same manner as in Example 4 except that 3.9 g of polyethylene was obtained. The catalyst activity was 43 kg / g · Zr. The intrinsic viscosity [η] of the obtained polyethylene was 3.73 deciliter / g, the weight average molecular weight (Mw) was 523,000, and the weight average molecular weight / number average molecular weight ratio (Mw / Mn) was 2.5.

[0046]

The transition metal compound of the present invention is useful as a catalyst component for olefin polymerization, and a high-molecular-weight polyolefin can be obtained with high activity by using an olefin polymerization catalyst containing the same.

 ──────────────────────────────────────────────────の Continued on the front page F-term (reference) 4H049 VN01 VN06 VP01 VU14 4H050 AA01 AA03 AB40 WB11 4J028 AA01A AB01A AC01A AC02A AC09A AC22A AC28A AC31A AC41A AC45A AC49A BA01B BB01B BC12B BC14BBCBC BCBC BCBC BCBC BC BC BC BC BC BC BC BC BC BC BC EA01 EA02 EB01 EB02 FA01 FA02 FA03 FA04 GA01 GA04 GA06 GB07 4J128 AA01 AB01 AC01 AC02 AC09 AC22 AC28 AC31 AC41 AC45 AC49 AD00 BA01B BB01B BC12B BC14B BC15B BC16B BC17B BC27B BC32B BC33A BC42B BC43ABC01 FA03 FA01 FA02 GA04 GA06 GB07

Claims (6)

[Claims] 1. A compound of the general formula (I) or (II) [Wherein, M represents a metal element belonging to Groups 3 to 10 of the periodic table or a lanthanoid series, X represents a σ-binding ligand bonded to M, and when there are a plurality of Xs, a plurality of Xs are the same or different. And it may be crosslinked with an indenyl ring or Y. Y represents a Lewis base, and when there are a plurality of Ys, the plurality of Ys may be the same or different, and may be cross-linked to an indenyl ring or X. A represents a crosslinking group containing a Group 14 element of the periodic table, p is an integer of 1 to 10, q is an integer of 1 to 5 [(valency of M) -2], and r is an integer of 0 to 3 Is shown. R ^{1 to} R ¹⁰ each represent a hydrogen atom, a carbon number of 1 to 20;
A hydrocarbon group, a silicon-containing group or a heteroatom-containing group, which may be the same or different,
It may form a ring with an adjacent group. ] The transition metal compound represented by these. 2. An olefin polymerization catalyst comprising (A) the transition metal compound according to claim 1 and an activating co-catalyst as main components. 3. A compound capable of forming an ionic complex by reacting the activating cocatalyst with the transition metal compound (B) or (A) or a derivative thereof, or a clay, a clay mineral or an ion-exchangeable compound. The olefin polymerization catalyst according to claim 2, which is 4. A compound capable of forming an ionic complex by reacting the activating cocatalyst with the transition metal compound (B) or (A) or a derivative thereof, or a clay, a clay mineral or an ion-exchangeable compound. 3. The olefin polymerization catalyst according to claim 2, which is a combination of (C) and an organoaluminum compound. 5. An olefin polymer obtained by using the olefin polymerization catalyst according to claim 2. Description: 6. An olefin is homopolymerized or an olefin is copolymerized with another olefin and / or another monomer in the presence of the olefin polymerization catalyst according to claim 2. Description: A method for producing an olefin polymer, comprising: