JP2001348389A - Transition metal compound, catalyst for polymerizing olefins, and method for producing olefinic polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transition metal compound usable as a metallocene olefin polymerization catalyst capable of controlling the stereospecificity in a wide range even in an α-olefin except ethylene. SOLUTION: This transition metal compound is represented by general formula (I) wherein, M is a group 3-10 metal element in the periodic table; E1 is a cyclopentadienyl group, a substituted cyclopentadienyl group or the like; E2 is an aromatic group having a hetero atom in the ring; E1 and E2 form a cross-linking structure through A1; X is a σ-bondable ligand; A1 is a divalent cross-linking group bonding to mutually same or different two ligands, and a 1-20C hydrocarbon group or the like; and q is an integer of 1-5, and is a value of [(the valence of M)-1]).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel transition metal compound used for a metallocene catalyst, a metallocene olefin polymerization catalyst using the transition metal compound, and a method for producing an olefin polymer using the catalyst.

[0002]

2. Description of the Related Art In recent years, metallocene catalysts have attracted attention as olefin polymerization catalysts. More recently, a new type of metallocene catalyst using a transition metal compound having one cyclopentadienyl ring as a kind of metallocene catalyst (Japanese Patent Application Laid-Open Nos. 10-101607 and 3-1)
39504). These catalysts show high activity in the polymerization of ethylene, and have attracted attention as an inexpensive and high-performance ethylene polymerization catalyst that can replace conventional metallocene catalysts. However, these catalysts have high activity in ethylene polymerization, but have low activity in homopolymerization of propylene, and it is difficult to control the stereoregularity of the obtained polypropylene,
At present, there is a drawback that only low-ordered syndiotactic polypropylene has been obtained (Org
nanometallics Vol. 16, p. 2879 (19
1997)). In these metallocene catalysts, even in the polymerization of α-olefins other than ethylene, stereoregularity can be controlled in a wide range so that an isotactic polymer or an atactic polymer can be easily produced. In particular, development of a catalyst capable of producing an olefin polymer having high isotacticity has been desired.

[0003]

SUMMARY OF THE INVENTION The present invention is directed to a metallocene which can control stereoregularity in a wide range even for α-olefins other than ethylene, and particularly can produce an olefin polymer having high isotacticity. It is an object of the present invention to provide a transition metal compound used for an olefin polymerization catalyst, an olefin polymerization catalyst comprising the transition metal compound, and a method for producing an olefin polymer using the catalyst.

[0004]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and as a result of intensive studies by the present inventors, a transition metal compound having a specific ligand; It has been found that this object can be achieved by an olefin polymerization catalyst comprising: and the present invention has been completed based on this. That is, the present invention provides the following transition metal compound, an olefin polymerization catalyst comprising the transition metal compound, and a method for producing an olefin polymer using the catalyst.

[1] (A) General formula (I)

[0006]

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[Wherein, M is a member of Groups 3 to 10 of the periodic table or La
E represents a tanthanoid metal element ¹Is cyclopenta
Dienyl group, substituted cyclopentadienyl group, indenyl
Group, substituted indenyl group, fluorenyl group or substituted fluoro group
A enyl group;^TwoIs a ring containing a heteroatom
Represents an aromatic group;¹And E^TwoIs A¹Cross-linked through
Forming the structure. X represents a σ-binding ligand;
When there are two or more, even if a plurality of X are the same or different
It may be cross-linked with other ligands. A¹Is two
A divalent cross-linking group that binds a ligand, and has 1 to 2 carbon atoms
0 hydrocarbon group, halogen-containing hydrocarbon having 1 to 20 carbon atoms
Element group, silicon-containing group, germanium-containing group, tin-containing group,-
O-, -CO-, -S-, SO_Two-, Se-, -NR
-, -PR-, -P (O) R-, -BR- or -AlR
Represents-, R is a hydrogen atom, a halogen atom, carbon number 1-2.
0 hydrocarbon group or halogen-containing carbon having 1 to 20 carbon atoms
Denote hydride groups, which are the same or different
Is also good. q is an integer of 1 to 5 [(valence of M) -1]
Show. ] The transition metal compound represented by these.

[2] The transition metal compound according to the above [1], wherein E ¹ is an indenyl group or a substituted indenyl group. [3] The transition metal compound according to the above [1] or [2], wherein the hetero atom in E ² is a nitrogen atom.

[4] The transition metal compound according to any one of [1] to [3], wherein E ² is a pyrrole group, a substituted pyrrole group, an indole group, a substituted indole group, a carbazole group or a substituted carbazole group.

[5] The transition metal compound according to any one of the above [1] to [4], wherein M is a transition metal element belonging to Group 4 of the periodic table. [6] (A) Reaction with any of the transition metal compounds described in [1] to [5] above, and (B) (B-1) a reaction with the transition metal compound of the component (A) or a derivative thereof. An olefin polymerization catalyst comprising a compound capable of forming an ionic complex, and a component selected from (B-2) aluminoxane and (B-3) a Lewis acid.

[7] A method for producing an olefin polymer in which olefins are polymerized in the presence of the catalyst for olefin polymerization described in [6]. [8] In addition to the component (A) and the component (B) described in the above item [6], in addition to the olefin polymerization catalyst (C) containing an organoaluminum compound, an olefin-based polymer is prepared. Production method.

[0012]

[9] The method for producing an olefin polymer according to the above [7] or [8], wherein the olefin is propylene.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the transition metal compound of the present invention,
The catalyst for olefin polymerization and the method for producing the olefin polymer will be described in detail. [Transition metal compound] The transition metal compound of the present invention comprises (A)
General formula (I)

[0014]

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[Wherein M is a group 3 to 10 of the periodic table or La
E represents a tanthanoid metal element ¹Is cyclopenta
Dienyl group, substituted cyclopentadienyl group, indenyl
Group, substituted indenyl group, fluorenyl group or substituted fluoro group
A enyl group;^TwoIs a ring containing a heteroatom
Represents an aromatic group;¹And E^TwoIs A¹Cross-linked through
Forming the structure. X represents a σ-binding ligand;
When there are two or more, even if a plurality of X are the same or different
It may be cross-linked with other ligands. A¹Is two
A divalent cross-linking group that binds a ligand, and has 1 to 2 carbon atoms
0 hydrocarbon group, halogen-containing hydrocarbon having 1 to 20 carbon atoms
Element group, silicon-containing group, germanium-containing group, tin-containing group,-
O-, -CO-, -S-, SO_Two-, Se-, -NR
-, -PR-, -P (O) R-, -BR- or -AlR
Represents-, R is a hydrogen atom, a halogen atom, carbon number 1-2.
0 hydrocarbon group or halogen-containing carbon having 1 to 20 carbon atoms
Denote hydride groups, which are the same or different
Is also good. q is an integer of 1 to 5 [(valence of M) -1]
Show. ] Is represented.

In the formula, M represents a metal element belonging to Groups 3 to 10 of the periodic table or a lanthanoid series. Preferably, it is a metal element of Group 4 of the periodic table. Examples of the metal element of Group 4 of the periodic table include titanium, hafnium, and zirconium. Of these, titanium is preferred.

E ¹ represents a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a fluorenyl group or a substituted fluorenyl group. Preferably, they are an indenyl group and a substituted indenyl group.
Examples of the substituent in these groups include an alkyl group such as a methyl group, an ethyl group and an isopropyl group, and a 2-methyl-
And a phenyl group such as a 5,6-benzo group. Among them, an indenyl group as E ^1, 2-methylindenyl group, 2,4,7-trimethyl indenyl group, a 2-methyl-5,6-benzoindenyl group.

E ² represents an aromatic group containing a hetero atom in the ring. As a hetero atom, a nitrogen atom, an oxygen atom,
A sulfur atom is mentioned, and among them, a nitrogen atom is preferable. The aromatic group is not particularly limited, but usually includes an aromatic group composed of a cyclic unsaturated hydrocarbon compound having 4 or more carbon atoms. The E ^2, a pyrrole group, a substituted pyrrole group, an indole group, a substituted indole group, a carbazole group or a substituted carbazole group are preferred. Examples of the substituent in these groups include a methyl group, an ethyl group, and an isopropyl group. Among them, as the E ² 2,4-dimethyl pyrrole group, an indole group, carbazole group.
E ¹ and E ² each form a crosslinked structure via A ¹ .

X represents a σ-binding ligand. When there are a plurality of Xs, the plurality of Xs may be the same or different, and may be cross-linked with another ligand. X represents a halogen 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, an amide group having 1 to 20 carbon atoms, and a 1 to 20 carbon atoms. A sulfide group having 1 to 20 carbon atoms, a sulfide group having 1 to 20 carbon atoms, a sulfoxide group having 1 to 20 carbon atoms, or 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 , Methyl naphthyl group,
And aryl groups such as 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. 1-20 carbon atoms
Examples of the amide group include dimethylamide group, diethylamide group, dipropylamide group, dibutylamide group, dicyclohexylamide group, alkylamide group such as methylethylamide group, divinylamide group, dipropenylamide group, dicyclohexenylamide An alkenylamide group such as a group; a dibenzylamide group, a phenylethylamide group,
An arylalkylamide group such as a phenylpropylamide group; and an arylamide group such as a diphenylamide group and a dinaphthylamide group. 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 Group; hydrocarbon-substituted silyl ether group such as trimethylsilyl ether group; silicon-substituted alkyl group such as trimethylsilylmethyl group; silicon-substituted aryl group such as trimethylsilylphenyl group; dimethylhydrosilyl group; methyldihydrosilyl group; Among them, a trimethylsilylmethyl group, a phenyldimethylsilylethyl group and the like are preferable. Examples of the sulfide group having 1 to 20 carbon atoms include alkyl sulfide groups such as methyl sulfide group, ethyl sulfide group, propyl sulfide group, butyl sulfide group, hexyl sulfide group, cyclohexyl sulfide group, octyl sulfide group, vinyl sulfide group, and propenyl group. Alkenyl sulfide groups such as sulfide groups and cyclohexenyl sulfide groups;
Benzyl sulfide group, phenylethyl sulfide group,
Arylalkyl sulfide groups such as phenylpropyl sulfide group; phenyl sulfide group, tolyl sulfide group, dimethyl phenyl sulfide group, trimethyl phenyl sulfide group, ethyl phenyl sulfide group, propyl phenyl sulfide group, biphenyl sulfide group,
Naphthyl sulfide group, methyl naphthyl sulfide group,
And aryl sulfide groups such as anthracenyl sulfide group and phenanthyl sulfide group. Examples of the sulfoxide group having 1 to 20 carbon atoms include a methylsulfoxide group, an ethylsulfoxide group, a propylsulfoxide group, a butylsulfoxide group, a hexylsulfoxide group,
Alkylsulfoxide groups such as cyclohexylsulfoxide group and octylsulfoxide group; alkenylsulfoxide groups such as vinylsulfoxide group, propenylsulfoxide group and cyclohexenylsulfoxide group; arylalkylsulfoxide groups such as benzylsulfoxide group, phenylethylsulfoxide group and phenylpropylsulfoxide group. Groups: phenylsulfoxide, tolylsulfoxide, dimethylphenylsulfoxide, trimethylphenylsulfoxide, ethylphenylsulfoxide, propylphenylsulfoxide, biphenylsulfoxide, naphthylsulfoxide, methylnaphthylsulfoxide, anthracenylsulfoxide,
And arylsulfoxide groups such as 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, Cinnamoyl group, naphthoyl group, arylacyl group such as phthaloyl group, oxalic acid,
Examples thereof include an oxalyl group, a malonyl group, and a succinyl group derived from dicarboxylic acids such as malonic acid and succinic acid. X is preferably an alkyl group such as a methyl group, an ethyl group, or a propyl group, or an aryl group such as a phenyl group.

A ¹ is a divalent cross-linking group connecting two ligands, and is a hydrocarbon group having 1 to 20 carbon atoms,
20 halogen-containing hydrocarbon groups, silicon-containing groups, germanium-containing groups, tin-containing groups, -O-, -CO-, -S-, S
O _2- , Se-, -NR-, -PR-, -P (O) R
-, -BR- or -AlR-, wherein R is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or 1 carbon atom;
And represents 20 to 20 halogen-containing hydrocarbon groups, which may be the same or different from each other. Divalent carbon number 1-20
Examples of the hydrocarbon group include a methylene group, an ethylene group, an isopropylidene group, and a tetramethylethylene group. Examples of the divalent halogen-containing hydrocarbon group having 1 to 20 carbon atoms include the above-mentioned halides in the divalent hydrocarbon group having 1 to 20 carbon atoms. Examples of the divalent silicon-containing group include a dimethylsilylene group, a methylphenylsilylene group, a diphenylsilylene group, and the like. Examples of the divalent germanium-containing group include a dimethylgermylene group and a diphenylgermylene group. Examples of the divalent tin-containing group include a dimethylstannylene group and a diphenylstannylene group. R represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different. Examples of the halogen atom for R 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 and a propenyl group. Alkenyl groups such as cyclohexenyl group; benzyl group, phenylethyl group,
Arylalkyl groups such as phenylpropyl group; aryl groups such as phenyl group, tolyl group, dimethylphenyl group, trimethylphenyl group, ethylphenyl group, propylphenyl group, biphenyl group, naphthyl group, methylnaphthyl group, anthracenyl group, phenanthenyl group Is mentioned. Examples of the halogen-containing hydrocarbon group having 1 to 20 carbon atoms include the above-mentioned halides of the hydrocarbon group having 1 to 20 carbon atoms. q is an integer of 1 to 5 and represents ((valence of M) -1).

As an example of the transition metal compound represented by the general formula (I), specifically, titanium of Group 4 of the periodic table, (carbazolyldimethylsilyltetramethylcyclopentadienyl) titanium trichloride , (Pyrrolyldimethylsilyltetramethylcyclopentadienyl) titanium trichloride, (indolyldimethylsilyltetramethylcyclopentadienyl) titanium trichloride, (carbazolyldimethylsilyl-1-indenyl) titanium trichloride, Dimethylsilyl-1-indenyl) titanium trichloride, (indolyldimethylsilyl-1-indenyl) titanium trichloride, (carbazolyldimethylsilyl-2-indenyl) titanium trichloride, (pyrrolyldimethylsilyl-2-indenyl) ) Titanium trichloride, Indolyl dimethylsilyl-2-indenyl) titanium trichloride, (carbazolyl-butyldimethylsilyl-2- (1,3-dimethyl indenyl)) titanium trichloride, (pyrrolyl butyldimethylsilyl-2-
(1,3-dimethylindenyl)) titanium trichloride, (indolyldimethylsilyl-2- (1,3-dimethylindenyl)) titanium trichloride, (2,4-dimethylpyrrolyldimethylsilyl-1-indenyl) ) Titanium trichloride, (2,4-dimethylpyrrolyldimethylsilyl-2-indenyl) titanium trichloride,
4-dimethylpyrrolyldimethylsilyltetramethylcyclopentadienyl) titanium trichloride, (carbazolyldimethylsilyl-1- (2-methylindenyl)) titanium trichloride, (pyrrolyldimethylsilyl-1-)
(2-methylindenyl)) titanium trichloride, (indolyldimethylsilyl-1- (2-methylindenyl)) titanium trichloride, (carbazolyldimethylsilyl-1- (2,4,7-trimethylindenyl) Nyl)) titanium trichloride, (pyrrolyldimethylsilyl-1-
(2,4,7-trimethylindenyl)) titanium trichloride, (indolyldimethylsilyl-1- (2,4,
7-trimethylindenyl)) titanium trichloride,
(Carbazolyldimethylsilyl-1- (2-methyl-
5,6-benzoindenyl)) titanium trichloride,
(Pyrrolyldimethylsilyl-1- (2-methyl-5,6
-Benzoindenyl)) titanium trichloride, (indolyldimethylsilyl-1- (2-methyl-5,6-benzoindenyl)) titanium trichloride, (9- (carbazolyldimethylsilyl) octahydrofluore Nyl) titanium trichloride, (9- (pyrrolyldimethylsilyl)
(Octahydrofluorenyl) titanium trichloride, (9
-(Indolyldimethylsilyl) octahydrofluorenyl) titanium trichloride, ((2-methylindolyl) dimethylsilyltetramethylcyclopentadienyl) titanium trichloride and the like, and titanium in these compounds is converted to zirconium or hafnium. Substituted ones can be mentioned, but of course the present invention is not limited to these. Further, it may be a similar compound of a metal element of another group of the periodic table or a lanthanoid series.

[Olefin polymerization catalyst] The olefin polymerization catalyst of the present invention comprises (A) the above-mentioned transition metal compound,
And (B) (B-1) a compound capable of forming an ionic complex by reacting with the transition metal compound of the component (A) or a derivative thereof (B-2) aluminoxane and (B-3) a Lewis acid It contains a component selected from the group consisting of:

The component (B-1) includes the component (A)
Any ionic compound capable of reacting with the transition metal compound of the component to form an ionic complex can be used, but from the viewpoint that a polymerization active site can be formed particularly efficiently, the following general compounds can be used. Those represented by the formulas (II) and (III) are preferred.

([L ¹ -R ¹ ] ^{h +} ) _a ([Z] ⁻ ) _b ... (II) ([L ² ] ^{h +} ) _a ([Z] ⁻ ) _b. , L ² is ^{M 1, R 2 R 3 M} 2, R 4 3 C or R ⁵ M ^2.) [(II), (III) wherein, L ¹ is a Lewis base,
[Z] ^- is a non-coordinating anion [Z ^{1] -} or [Z ^{2] -,}
Wherein [Z ^{1] -} is more groups bound anions i.e. ^{[M 3 G 1 G 2 ··· G} f ] (here an element, M ³ is the periodic table 5-15 group element, preferably Periodic Table Nos. 13-15
Indicates a group element. G ^{1 to} G ^f each represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a dialkylamino group having 2 to 40 carbon atoms, an alkoxy group having 1 to 20 carbon atoms,
An aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, and a halogen-substituted hydrocarbon group having 1 to 20 carbon atoms , An acyloxy group having 1 to 20 carbon atoms, an organic metalloid group, or a heteroatom-containing hydrocarbon group having 2 to 20 carbon atoms. Two or more of G ^{1 to} G ^f may form a ring. f represents an integer of [(valence of central metal M ³⁾ +1]. ), [Z ^{2] -} is the logarithm of the reciprocal of the acid dissociation constant (pKa) of a combination of -10 or less Bronsted acid alone or Bronsted acid and Lewis acid conjugate base, or a general superacid defined Shows the conjugate base to be used. Further, a Lewis base may be coordinated. R ¹ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group or an arylalkyl group, and R ² and R ³ each represent a cyclopentadienyl group, Cyclopentadienyl group, indenyl group, substituted indenyl group, fluorenyl group or substituted fluorenyl group, R ⁴ is an alkyl group having 1 to 20 carbon atoms,
It represents an aryl group, an alkylaryl group or an arylalkyl group. R ⁵ represents a macrocyclic ligand such as tetraphenylporphyrin and phthalocyanine. h is [L ¹ −
R ¹¹ ] and [L ² ] are ionic valences and are integers from 1 to 3;
The above integer, b = (h × a). M ¹ contains an element from Groups ¹ to 3, 11 to 13, and 17 of the periodic table;
M ² represents an element in Groups 7 to 12 of the periodic table. ] 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.

R¹Specific examples of hydrogen, methyl,
Examples include tyl, benzyl, and trityl groups.
Come, R^Two, R^ThreeAs a specific example of cyclopentadienyl
Group, methylcyclopentadienyl group, ethylcyclopen
Tadienyl group, pentamethylcyclopentadienyl group
And so on. R^FourAs a specific example,
Nyl, p-tolyl, p-methoxyphenyl, etc.
And R ^FiveAs a specific example of
Ruporfin, phthalocyanine, allyl, methallyl, etc.
Can be mentioned. Also, M¹As a specific example,
Li, Na, K, Ag, Cu, Br, I, I_ThreeEtc.
M^TwoAs specific examples of Mn, Fe,
Co, Ni, Zn and the like can be mentioned.

[Z ¹ ] ^- , that is, [M ³ G ¹ G ^2.
··· G ^f ], examples of M ³ include B, Al, S
i, P, As, Sb and the like, preferably B or Al. Specific examples of G ¹ , G ^{2 to} G ^f include dimethylamino and diethylamino as dialkylamino groups, methoxy, ethoxy, n-butoxy, phenoxy and the like as alkoxy or aryloxy groups. Methyl group, ethyl group, n-
Propyl, isopropyl, n-butyl, isobutyl, n-octyl, n-eicosyl, phenyl, p-tolyl, benzyl, 4-t-butylphenyl, 3,5-dimethylphenyl For example, fluorine, chlorine, bromine, iodine as a halogen atom, p-fluorophenyl group, 3,5-difluorophenyl group, pentachlorophenyl group, 3,4,
5-trifluorophenyl group, pentafluorophenyl group, 3,5-bis (trifluoromethyl) phenyl group,
Pentamethylantimony, trimethylsilyl, trimethylgermyl, diphenylarsine, organic metalloid groups such as bis (trimethylsilyl) methyl group,
Examples include 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 having a trifluoromethanesulfonic acid anion (C
F ₃ SO ₃ ) ^- , bis (trifluoromethanesulfonyl)
Methyl anion, bis (trifluoromethanesulfonyl) benzyl anion, bis (trifluoromethanesulfonyl) amide, perchlorate anion (ClO 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 / antimony pentafluoride ^{_{(FSO 3 / SbF 5) -}} , fluorosulfonic acid anion / 5- fluoride Arsenic (FSO ₃ / AsF ₅ )
^-, trifluoromethanesulfonic acid / antimony pentafluoride _{(CF 3 SO 3 / SbF 5} ) - and the like.

Specific examples of the ionic compound which reacts with the transition metal compound of the component (A) to form an ionic complex, ie, 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) ammonium, dimethyldiphenylammonium tetraphenylborate, triphenyl (methyl) ammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, benzylpyridinium tetraphenylborate, methyl 2-phenylopyridinium 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
Dimethylanilinium 5-di (trifluoromethyl) phenyl] 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.

The component (B-1), which is an ionic compound which forms an ionic complex by reacting with the transition metal compound of the component (A), may be used alone or in combination of two or more. May be used.

On the other hand, examples of the aluminoxane as the component (B-2) include a chain aluminoxane represented by the following general formula (IV) and a cyclic aluminoxane represented by the following general formula (V).

[0032]

Embedded image

(Wherein, R ⁶ is a group having 1 to 2 carbon atoms.
It represents 0, preferably 1-8 alkyl groups, which may be the same or different. Also, m is 2 <m ≦
40 and n are integers satisfying 1 <n ≦ 50. Specific examples include aluminoxanes such as methylaluminoxane, ethylaluminoxane and isobutylaluminoxane.

Examples of the method for producing the aluminoxane include a method in which an alkylaluminum is brought into contact with a condensing agent such as water. The means is not particularly limited, and the reaction may be carried out 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 initially during polymerization and adding water later, water of crystallization contained in a metal salt and 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 and the like 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 such as aluminum oxide and aluminum chloride; and boron compounds such as triphenylboron and tris (pentafluorophenyl) boron. Tris [3,5-bis (trifluoromethyl) phenyl] boron, tris [(4-fluoromethyl) phenyl] boron, trimethylboron, triethylboron, tri-n-butylboron, tris (fluoromethyl)
Boron, tris (pentafluoroethyl) boron, tris (nonafluorobutyl) boron, tris (2,4,6-trifluorophenyl) boron, tris (3,5-difluoro) boron, tris [3,5-bis ( Trifluoromethyl) phenyl] boron, bis (pentafluorophenyl)
Fluoroboron, diphenylfluoroboron, bis (pentafluorophenyl) chloroboron, dimethylfluoroboron, diethylfluoroboron, di-n-butylfluoroboron, pentafluorophenyldifluoroboron, phenyldifluoroboron, pentafluorophenyldichloroboron, methyldifluoro Boron, ethyldifluoroboron, n
-Butyldifluoroboron and the like. One of these Lewis acids may be used, or two or more may be used in combination.

In the polymerization catalyst of the present invention, the use ratio of the catalyst component (A) to the catalyst component (B) 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
If the ratio is outside the above range, the catalyst cost per unit mass polymer becomes high,
Not practical. When the compound (B-2) is used, the molar ratio is preferably from 1: 1 to 1: 1,000,000.
0, more preferably in the range of 1:10 to 1: 10,000. If the ratio is outside this range, the cost of the catalyst per unit mass of the polymer increases, which is not practical.

The use ratio of the catalyst component (A) to the catalyst component (B-3) is preferably 10: 1 to 1:
2,000, more preferably 5: 1 to 1: 1,000,
More preferably, the ratio is in the range of 2: 1 to 1: 500. If the ratio deviates from this range, the catalyst cost per unit mass polymer increases, which is not practical. The catalyst component (B) includes (B-1), (B-2) and (B-3).
Etc. 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). ) An organic aluminum compound may be contained as a main component.

Here, the organoaluminum compound as the component (C) is represented by the following general formula (VI): R ⁷ _v AlQ _3-v (VI) (wherein R ⁷ is an alkyl group having 1 to 10 carbon atoms) , Q is a hydrogen atom, an alkoxy group having 1 to 20 carbon atoms, 6 to 20 carbon atoms.
And v is a real number of 1 to 3).

Specific examples of the compound represented by the general formula (VI) include trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, dimethylaluminum chloride,
Examples include diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum fluoride, diisobutylaluminum hydride, diethylaluminum hydride, ethylaluminum sesquichloride and the like.

These organoaluminum compounds may be used alone or in combination of two or more. The molar ratio of the catalyst component (A) to the catalyst component (C) is preferably 1: 1 to 1: 10000, more preferably 1: 5 to 1: 2000, and still more preferably 1:10 to 1: 1. : A range of 1000 is desirable. By using the catalyst component (C), the polymerization activity per transition metal can be improved. However, when the amount is too large, especially when it is out of the above range, the organoaluminum compound is wasted and the polymer is not contained in the polymer. If the amount is large and the amount is small, sufficient catalytic activity cannot be obtained, which may be undesirable.

In the present invention, when each component is contacted,
Or after contact, polyethylene, polypropylene, etc.
Polymer, silica, coexist with inorganic oxides such as alumina or
You may contact. When supported on a carrier,
Preferably, the carrier polymer is supported on a polymer.
-, The particle size is 1 to 300 μm, preferably 1 to 300 μm.
0 to 200 μm, more preferably 20 to 100 μm
You. If the particle size is smaller than 1 μm, fine powder in the polymer
If it exceeds 300 μm, coarseness in the polymer
Large particles increase, bulk density decreases and hopper in manufacturing process
That is the cause. The specific surface area of the carrier in this case is 1
~ 1,000m^Two/ G, preferably 50 to 500 m^Two/ G
And the pore volume is 0.1 to 5 m^Three/ G, preferably
0.3-3m ^Three/ G. Contact with an inert gas such as nitrogen
Pentane, hexane, heptane, toluene, xy
It may be performed in a hydrocarbon such as ren. Until each component is added
Or the contact can be carried out at the polymerization temperature.
Of course, the boiling point of each solvent from -30 ° C to the boiling point of each solvent, especially from room temperature
It is preferably performed between points.

[Production Method of Olefin Polymer] The production method of the olefin polymer of the present invention comprises, if necessary, olefins in the presence of the aforementioned olefin polymerization catalyst containing an organoaluminum compound (C). A method for producing a polymer, characterized by homopolymerization or copolymerization. As the organoaluminum compound (C), a compound represented by the general formula (VI) is used, and a trialkylaluminum compound is preferable. Among them, trimethylaluminum and triisobutylaluminum are preferable. 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 added to the reactor. May be charged and used in contact with the component (A) and the component (B). The amount of the component (C) is the same as in the olefin polymerization catalyst. 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, olefins Copolymerization of olefins with other monomers or copolymerization of different olefins with other monomers).

The olefin is not particularly limited, but is preferably an α-olefin having 2 to 20 carbon atoms. Examples of the α-olefin include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-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,
Α- such as 5-methyl-1-hexene, 3,3-dimethyl-1-pentene, 3,4-dimethyl-1-pentene, 4,4-dimethyl-1-pentene and vinylcyclohexane;
Olefins, dienes such as 1,3-butadiene, 1,4-pentadiene, 1,5-hexadiene, hexafluoropropene, tetrafluoroethylene, 2-fluoropropene, fluoroethylene, 1,1-difluoroethylene, 3- Fluoropropene, trifluoroethylene,
Halogen-substituted α-olefins such as 3,4-dichloro-1-butene, cyclopentene, cyclohexene, norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-propylnorbornene, 5,6-dimethylnorbornene, 5-benzylnorbornene and the like Cyclic olefins, styrenes such as styrene, p-methylstyrene, p-ethylstyrene, p-propylstyrene, p-
-Isopropylstyrene, p-butylstyrene, pt
tert-butylstyrene, p-phenylstyrene, o-
Methylstyrene, o-ethylstyrene, o-propylstyrene, o-isopropylstyrene, m-methylstyrene, m-ethylstyrene, m-isopropylstyrene,
Alkyl styrenes such as m-butylstyrene, mesitylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,5-dimethylstyrene, p-methoxystyrene, o-methoxystyrene, m-methoxystyrene, etc. Alkoxystyrenes, p-chlorostyrene, m
-Chlorostyrene, o-chlorostyrene, p-bromostyrene, m-bromostyrene, o-bromostyrene, p
Halogenated styrenes such as -fluorostyrene, m-fluorostyrene, o-fluorostyrene and o-methyl-p-fluorostyrene; further, trimethylsilylstyrene, vinyl benzoate, divinylbenzene and the like. The other olefins described above may be appropriately selected from the olefins.

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.

In the present invention, the above-mentioned olefins and other monomers may be copolymerized. Examples of other monomers used in this case include butadiene, isoprene and 1,4-pentadiene. , 1,5-hexadiene and other chain diolefins, norbornene, 1,4,5,8
Polycyclic olefins such as dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene and 2-norbornene, norbornadiene, 5-ethylidene norbornene, 5-vinylnorbornene and dicyclopentadiene; Examples include cyclic diolefins, unsaturated esters such as ethyl acrylate and methyl methacrylate.

In the present invention, propylene is particularly preferred as the olefin. The method for polymerizing olefins 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 can be employed.

When a polymerization solvent is used, the solvent may be benzene, toluene, xylene, n-hexane,
Examples include hydrocarbons such as n-heptane, cyclohexane, methylene chloride, chloroform, 1,2-dichloroethane, chlorobenzene, halogenated hydrocarbons, and the like.
These may be used alone or in combination of two or more. Further, the monomers used for the polymerization may be used depending on the type.

The amount of the catalyst used in the polymerization reaction is as follows:
The component [A] is usually 0.5 to 1 per liter of the solvent.
It is advantageous from the viewpoints of polymerization activity and reactor efficiency to select from 00 micromol, preferably from 2 to 25 micromol.

Regarding 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, the selection of the polymerization temperature, and the introduction of hydrogen.

Further, at the time of polymerization of the olefins in the present invention, preliminary polymerization can be carried out using the above catalyst. This prepolymerization can be carried out by bringing a small amount of olefins into contact with the solid catalyst component. 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 also be performed without a solvent. The prepolymerized product has an intrinsic viscosity [η] (measured at 135 ° C. in decalin) of 0.2.
Deciliter / g, preferably 0.5 deciliter / g
The amount of the prepolymerized product per 1 mmol of the transition metal component in the catalyst is preferably 1 to 10,
It is preferable to adjust the conditions so as to be 000 g, preferably 10 to 1,000 g.

[0052]

EXAMPLES The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to the following examples. Example 1 Preparation of Catalyst Synthesis of (carbazolyldimethylsilyltetramethylcyclopentadienyl) titanium trichloride Under a nitrogen stream, 100 ml of hexane and 5.75 g of tetramethylcyclopentadiene (47 in a 200 ml three-necked flask) .1 mmol). Here, a hexane solution (1.50 M) of n-butyllithium was added to 3
1.4 ml (47.1 mmol) are added dropwise. After stirring at room temperature for 10 hours, the supernatant is removed to obtain a white powder. This white powder is dissolved in 50 ml of THF, and 16.8 ml of dimethyldichlorosilane is added dropwise at room temperature. After 8 hours of reaction, the solvent is distilled off and the residue is extracted with 100 ml of hexane. The solvent of the extract was distilled off under reduced pressure to obtain 7.05 g of chlorodimethylsilyltetramethylcyclopentadiene as a pale yellow oil. Next, 5.5 g (32.8 g) of carbazole was placed in a Schlenk bottle.
Mmol) and 30 ml of THF. When 21.9 ml of n-butyllithium (1.50 M) is added at 0 ° C., the mixture becomes cloudy brownish white. After stirring overnight at room temperature, the solvent is distilled off and the residue is washed with 20 ml of ether to obtain a white powder. 50 mL of THF is added thereto, and 7.05 g (32.8 mmol) of chlorodimethylsilyltetramethylcyclopentadiene is added. After stirring for 12 hours, the solvent was distilled off, and the residue was extracted with 50 ml of hexane to give carbazolyldimethylsilyltetramethylcyclopentadiene as a yellow-white solid.
18 g were obtained. ¹ H-NMR (90 MHz, CDCl ₃ ) δ 0.56
_{(S, 6H, -SiCH 3)} , 1.57 (s, 6H, C
_{H 3), 1.81 (s,} 6H, CH 3), 3.63 (b
r, 1H, CH), 7.10-8.15 (m, 8H, A
rH) Then, 1.19 g (3.40 mmol) of carbazolyldimethylsilyltetramethylcyclopentadiene was dissolved in 40 mL of THF, and 2.2 mL of n-butyllithium (1.60 M) was added dropwise at room temperature. After stirring for an hour, the solution was added to TiCl ₄ (THF) ₂ 1.1.
g to a solution of 60 ml of THF. The solution turns dark green. After reacting at room temperature for 10 hours, the solvent is distilled off, and the remaining blue residue is washed with 20 ml of hexane and extracted with 40 ml of dichloromethane. The solvent was distilled off to obtain 0.59 g (1.2 mmol) of (carbazolyldimethylsilyltetramethylcyclopentadienyl) titanium trichloride. (Yield 3
5%) ¹ H-NMR (90 MHz, CDCl ₃ ) δ 0.80,
_{0.88 (s, 6H, -SiCH 3} ), 1.63,1.
_{82 (s, 12H, -CH 3} ), 7.05-8.20
(M, 8H, ArH) Ethylene Polymerization In a stainless steel autoclave having an inner volume of 1 liter, 400 ml of heptane, 0.5 mmol of triisobutylaluminum, and 10 mmol of methylaluminoxane (manufactured by Albemarle Co.) were prepared as described above in terms of aluminum. Then, 10 μmol of (carbazolyldimethylsilyltetramethylcyclopentadienyl) titanium trichloride was charged, the temperature was raised to 50 ° C., and propylene gas was introduced to a total pressure of 0.5 MPa · G. During the polymerization, propylene gas was supplied by a pressure regulator so that the pressure became constant. After 60 minutes, the content was taken out and dried under reduced pressure to obtain 4.1 g of polyethylene. Polymerization of Propylene 400 ml of heptane, 0.5 mmol of triisobutylaluminum and 10 mmol of methylaluminoxane (manufactured by Albemarle Co., Ltd.) were prepared in a stainless steel autoclave having an internal volume of 1 liter in the above manner to give 10 mmol in terms of aluminum (carbazolyldimethylsilyl). 10 μmol of tetramethylcyclopentadienyl) titanium trichloride was charged, the temperature was raised to 50 ° C., and propylene gas was introduced to a total pressure of 0.8 MPa · G. During the polymerization, propylene gas was supplied by a pressure regulator so that the pressure became constant. After 60 minutes, the content was taken out and dried under reduced pressure to obtain 1.2 g of polypropylene.
In addition, as a result of evaluating polypropylene by the measurement method described below, the pentad meso fraction [mmmm] was 7
%, Which was atactic polypropylene. (Method of evaluating resin properties) Pentad meso fraction [mmm
m] is 19 to 22 p of ¹³ C-NMR of the polymer.
The ratio of the area occupied by the 21.8 ppm signal attributed to pentad meso in the total area of the nine signals appearing in pm was measured using the following apparatus and conditions. Apparatus: JNM-EX400 NMR apparatus manufactured by JEOL Ltd. Observation nucleus: ¹³ C (100.4 MHz) Method: ¹ H complete decoupling method Concentration: about 200 mg / 3 ml (6.7 × ¹⁰ k)
g / m ³ ) (10φ sample tube) Solvent: 90:10 (volume ratio) mixed solvent of 1,2,4-trichlorobenzene and heavy benzene Temperature: 130 ° C. Pulse width: 45 ° Pulse repetition time: 4 seconds Integration: 10,000 times [Example 2] Preparation of catalyst Synthesis of (carbazolyldimethylsilyl-1-indenyl) titanium trichloride Under a nitrogen stream, 100 ml of hexane and 10 ml of indene (85.7) were placed in a 200 ml three-necked flask. Mmol). Here, 53.6 ml (85.7 mmol) of a hexane solution of n-butyl lithium (1.60 M) is added dropwise. After stirring at room temperature for 10 hours, the supernatant is removed to obtain a yellowish white powder. This white powder is dissolved in 60 ml of THF, and 10.4 ml of dimethyldichlorosilane is added dropwise at room temperature. After 8 hours of reaction, the solvent is distilled off and the residue is extracted with 100 ml of hexane. The solvent of the extract was distilled off under reduced pressure to obtain chlorodimethylsilylindene as a pale yellow oil.

Next, carbazole 1.8 was placed in a Schlenk bottle.
g (10.8 mmol) and 20 ml of THF are added. 5. At 0 ° C., add n-butyllithium (1.60 M) to 6.
When 8 ml is added, it becomes brownish white. After stirring overnight at room temperature, the solvent is distilled off and the residue is washed with 20 ml of ether to obtain a white powder. To this was added 50 ml of THF, and 2.3 g of chlorodimethylsilylindene (1 g).
1.0 mmol). After stirring for 12 hours, the solvent is distilled off, and the residue is extracted with 50 ml of hexane to obtain carbazolyldimethylsilyl-1-indene as a yellowish white solid. ¹ H-NMR (90 MHz, CDCl ₃ ) δ 1.23
_{(S, 6H, -SiCH 3)} , 3.40 (br, 1H,
CH), 6.53, 6.90 (m, 2H, CH = CH)
7.03-8.13 (m, 8H, ArH) 0.34 g (1.0 mmol) of this was dissolved in 20 ml of THF, and n-butyllithium (1.60 M) was dissolved.
Was added dropwise and stirred at room temperature for 4 hours.
This solution was mixed with 0.33 g of TiCl ₄ (THF) _{2 in} THF ₂
Add to 0 ml solution. The solution turns dark green. After reacting at room temperature for 10 hours, the solvent is distilled off, and the remaining blue residue is washed with 20 ml of hexane and extracted with 40 ml of dichloromethane. The solvent was distilled off to obtain 0.1 g of (carbazolyldimethylsilyl-1-indenyl) titanium trichloride. Polymerization of Propylene In a stainless steel autoclave having an inner volume of 1 liter, 400 ml of heptane and 40 mmol of methylaluminoxane (manufactured by Albemarle Co.) were prepared as described above in terms of aluminum (carbazolyldimethylsilyl-1-).
Indenyl) titanium trichloride (60 μmol) was charged, the temperature was raised to 50 ° C., and the total pressure was 8.0 MPa · G.
Up to this, propylene gas was introduced. During the polymerization, propylene gas was supplied by a pressure regulator so that the pressure became constant.
After one minute, the content was taken out, deashed, and dried under reduced pressure to obtain 1 g of polypropylene. As a result of evaluation in the same manner as in Example 1, the pentad meso fraction [mmmm] was 14%, and it was an isotactic polypropylene. Comparative Example 1 400 ml of heptane, 0.5 mmol of triisobutylaluminum, and 2 micromol of dimethylanilinium (bentafluoropheel) borate were placed in a stainless steel autoclave having an internal volume of 1 liter and disclosed in JP-A-3-16388. (Tertiary butylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silanetitanium dichloride (1 μmol) prepared in the same manner as in Example 1 was preliminarily contacted in toluene for 5 minutes, and a catalyst component was charged. Here, hydrogen 0.03
After introducing MPa (gauge), 0.8MP at full pressure
A propylene gas was introduced up to a (gauge), and propylene was supplied by a pressure regulator so that the pressure during polymerization was constant. After performing polymerization at a polymerization temperature of 70 ° C. for 1 hour, the content was taken out and dried under reduced pressure to obtain a propylene homopolymer. As a result of evaluation in the same manner as in Example 1,
The pentad meso fraction [mmmm] was 2%, and it was a syndiotactic polypropylene.

[0054]

According to the present invention, there is provided a novel transition metal compound used for a metallocene catalyst. A metallocene catalyst using the compound can produce an olefin polymer with controlled stereoregularity.

 ──────────────────────────────────────────────────の Continued on the front page F-term (reference) 4H049 VN01 VN05 VP01 VP02 VQ60 VR21 VR24 VR33 VU14 VW01 4H050 AA01 AA03 AB40 4J028 AA01A AB00A AB01A AC01A AC02A AC03A AC06A AC22A AC31A AC41A AC45A BA00BBAB00A01B BC17B BC18B BC24B BC25A CA35A CB55A CB84A CB86A CB94A CB97A EA01 EB02 EB04 EB05 EB07 EB08 EB09 EB10 EB11 EB13 EB17 EB18 EB21 EB22 EB24 FA01 FA02 FA03 FA04 GA13

Claims (9)

[Claims] (A) General formula (I)[Wherein, M is a group 3 to 10 of the periodic table or a lanthanoid type
Indicates the metal element of the column, E ¹Is a cyclopentadienyl group,
Substituted cyclopentadienyl group, indenyl group, substituted in
Represents a enyl, fluorenyl or substituted fluorenyl group
Then E^TwoRepresents an aromatic group containing a hetero atom in the ring
Then E¹And E^TwoIs A¹Forms a crosslinked structure via
are doing. X represents a σ-binding ligand, and there are a plurality of Xs
In this case, a plurality of Xs may be the same or different, and
It may be crosslinked with a ligand. A¹Connects two ligands
A divalent cross-linking group that is combined with a hydrocarbon having 1 to 20 carbon atoms
Element group, halogen-containing hydrocarbon group having 1 to 20 carbon atoms, silicon
Containing group, germanium containing group, tin containing group, -O-, -C
O-, -S-, SO_Two-, Se-, -NR-, -PR
-, -P (O) R-, -BR- or -AlR-,
R is a hydrogen atom, a halogen atom, a hydrocarbon having 1 to 20 carbon atoms
A hydrogen atom-containing hydrocarbon group having 1 to 20 carbon atoms.
However, they may be the same or different from each other. q is
[(Valence of M) -1] is represented by an integer of 1 to 5. ]
Transition metal compound. 2. The transition metal compound according to claim 1, wherein E ¹ is an indenyl group or a substituted indenyl group. 3. The transition metal compound according to claim 1, wherein the hetero atom in E ² is a nitrogen atom. Wherein E ² is a pyrrole group, a substituted pyrrole group,
The transition metal compound according to any one of claims 1 to 3, which is an indole group, a substituted indole group, a carbazole group, or a substituted carbazole group. 5. The transition metal compound according to claim 1, wherein M is a transition metal element belonging to Group 4 of the periodic table. 6. An ion formed by reacting with (A) the transition metal compound according to any one of claims 1 to 5, and (B) (B-1) a transition metal compound of the component (A) or a derivative thereof. An olefin polymerization catalyst containing a compound capable of forming an acidic complex and a component selected from (B-2) aluminoxane and (B-3) a Lewis acid. 7. A method for producing an olefin polymer in which an olefin is polymerized in the presence of the catalyst for olefin polymerization according to claim 6. 8. An olefin polymer in which olefins are polymerized in the presence of an olefin polymerization catalyst containing (C) an organoaluminum compound in addition to the components (A) and (B) according to claim 6. Manufacturing method. 9. The method for producing an olefin polymer according to claim 7, wherein the olefin is propylene.