JPH10298219A - New transition metal compound and olefin polymerization catalyst component made from this compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an olefin polymerization catalyst component which gives a polyolefin having narrow molecular weight distribution and composition distribution with high molecular weight, and excellent in heat resistance and mechanical strength and which is excellent in polymerization activity by selecting a specified organic transition metal compound. SOLUTION: The transition metal compound used is represented by the formula [M is an atom of any one of groups 4 to 6 transition metals; X<1> and X<2> are each H, halogeno a 1-20C (halogenated) hydrocarbon group, an O-containing group or an S-containing group; R<1> and R<2> are each X<1> , an Si-containing group, an N-containing group or a P-containing group; R<3> and R<5> are each a 1-20C (halogenated) hydrocarbon group; R<4> and R<6> are each H or R<3> ; Y is a divalent 1-20C (halogenated) hydrocarbon group, a divalent Si-containing group, a divalent Ge-containing group, a divalent Sn-containing group, -O-, -CO-, -S-, -SO-, -SO2 -, -N(R<7> )-, -P(R<7> )-, -P(O)(R<7> )-, -B(R<7> )-, or Al(R<7> )-; and R<7> is H, halogeno or R3].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel transition metal compound and a catalyst component for olefin polymerization comprising the transition metal compound.

[0002]

BACKGROUND OF THE INVENTION As a homogeneous catalyst system for olefin polymerization, a so-called Kaminski catalyst is well known. This catalyst is characterized in that the polymerization activity is very high and a polymer having a narrow molecular weight distribution can be obtained.

[0003] Transition metal compounds for producing isotactic polyolefins include ethylenebis (indenyl) zirconium dichloride and ethylenebis (4,5,6,7-).
(Tetrahydroindenyl) zirconium dichloride (JP-A-61-130314) is known. However, polyolefins produced using such catalysts usually have low stereoregularity and low molecular weight. When the polymer is produced at a low temperature, a highly stereoregular body and a high molecular weight body can be obtained, but there are problems such as low polymerization activity.

It is known that a high molecular weight product can be produced by using a hafnium compound instead of a zirconium compound (Journal of Molecular Cat.).
alysis, 56 (1989) pp. 237-247), and this method has a problem that the polymerization activity is low. Further, dimethylsilylbis-substituted cyclopentadienyl zirconium dichloride and the like are disclosed in JP-A-1-301704, Polymer Preprint.
s, Japan vol. 39, No. 6 p. 1614-1616 (1990), but there is a problem that high polymerization activity, high stereoregularity, and high molecular weight are not simultaneously satisfied.

Further, Japanese Patent Application Laid-Open No. 4-268307 describes an olefin polymerization catalyst comprising a metallocene compound represented by the following formula and an aluminoxane.

[0006]

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Further, JP-A-6-184176 describes an olefin polymerization catalyst comprising a metallocene compound represented by the following formula and an aluminoxane.

[0008]

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However, polyolefins obtained with these catalysts have not always been satisfactory in stereoregularity, molecular weight and the like. Under such circumstances, it is desired to develop a catalyst component for olefin polymerization which is more excellent in olefin polymerization activity and excellent in properties of the obtained polyolefin, and a new transition metal compound which can be used as such a catalyst component for olefin polymerization. It is rare.

[0010]

An object of the present invention is to provide a novel transition metal compound which can be a catalyst component for olefin polymerization having excellent olefin polymerization activity.
It is an object of the present invention to provide an olefin polymerization catalyst component comprising the transition metal compound.

[0011]

SUMMARY OF THE INVENTION The novel transition metal compounds according to the present invention are:
A transition metal compound represented by the following general formula (I).

[0012]

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(In the formula, M represents a transition metal atom belonging to Groups 4 to 6 of the periodic table, and R ¹ and R ² may be the same or different from each other and have a hydrogen atom, a halogen atom, and a carbon atom of 1 A hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group, wherein R ³ and R ⁵ are May be the same or different from each other, and may be a hydrocarbon group having 1 to 20 carbon atoms or 1 to 20 carbon atoms.
Wherein R ⁴ and R ⁶ may be the same or different from each other, and represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having 1 to 20 carbon atoms.
R ³ and R ⁴ may be bonded to each other to form a ring together with the carbon atom to which they are bonded, and R ⁵ and R ⁶ may be bonded to each other to form a ring X ¹ and X ² may be a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon having 1 to 20 carbon atoms. Y represents a group having 1 to 20 divalent carbon atoms.
A divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a divalent silicon-containing group, a divalent germanium-containing group, a divalent tin-containing group, -O-, -CO- , -S
-, - SO -, - SO 2 -, - N (R 7) -, - P
(R ⁷ )-, -P (O) (R ⁷ )-, -B (R ⁷ )-or -Al (R ⁷ )-wherein R ⁷ is a hydrogen atom, a halogen atom, a carbon atom number of 1 to 20 hydrocarbon groups and halogenated hydrocarbon groups having 1 to 20 carbon atoms]. The catalyst component for olefin polymerization according to the present invention is characterized by comprising the transition metal compound represented by the general formula (I).

[0014]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the novel transition metal compound according to the present invention and the catalyst component for olefin polymerization comprising the transition metal compound will be described in detail.

The novel transition metal compound according to the present invention is a transition metal compound represented by the following general formula (I).

[0016]

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In the formula, M represents a transition metal atom belonging to Groups 4 to 6 of the periodic table, specifically, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, or tungsten, and preferably titanium. , Zirconium and hafnium, and particularly preferably zirconium.

R ¹ and R ² may be the same or different and each represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms. , A silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group, specifically, a halogen atom such as fluorine, chlorine, bromine or iodine;
Methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, octyl, nonyl, dodecyl, eicosyl,
Alkyl groups such as norbornyl and adamantyl; alkenyl groups such as vinyl, propenyl and cyclohexenyl; arylalkyl groups such as benzyl, phenylethyl and phenylpropyl; phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, Naphthyl, methyl naphthyl,
A hydrocarbon group having 1 to 20 carbon atoms such as an aryl group such as anthryl and phenanthryl; a halogenated hydrocarbon group in which a halogen atom is substituted for the hydrocarbon group; a monohydrocarbon-substituted silyl such as methylsilyl and phenylsilyl;
Dihydrocarbon-substituted silyls such as dimethylsilyl and diphenylsilyl; trihydrocarbons such as trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, dimethylphenylsilyl, methyldiphenylsilyl, tritolylsilyl, and trinaphthylsilyl Substituted silyl; silyl ether of hydrocarbon-substituted silyl such as trimethylsilyl ether; silicon-substituted alkyl group such as trimethylsilylmethyl; silicon-containing group such as silicon-substituted aryl group such as trimethylphenyl; hydroxy group; methoxy, ethoxy, propoxy, butoxy and the like Alkoxy group; Allyloxy group such as phenoxy, methylphenoxy, dimethylphenoxy and naphthoxy; Aryl alcohol such as phenylmethoxy and phenylethoxy An oxygen-containing group such as a sulfur group; a sulfur-containing group such as a substituent in which the oxygen of the oxygen-containing compound is substituted by sulfur; an amino group; an alkyl such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, dicyclohexylamino, and the like. An amino group; a nitrogen-containing group such as an arylamino group such as phenylamino, diphenylamino, ditolylamino, dinaphthylamino, and methylphenylamino or an alkylarylamino group;
And phosphorus-containing groups such as phosphino groups such as dimethylphosphino and diphenylphosphino.

Among them, R ¹ and R ² are preferably a hydrocarbon group, particularly preferably a hydrocarbon group having 1 to 4 carbon atoms such as methyl, ethyl, propyl and butyl.

R ³ and R ⁵ may be the same or different and each represents a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms. Examples of the hydrocarbon group having 1 to 20 carbon atoms and the halogenated hydrocarbon having 1 to 20 carbon atoms include the same groups as described above.

R ⁴ and R ⁶ may be the same or different and represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms. Examples of the hydrocarbon group having 1 to 20 carbon atoms and the halogenated hydrocarbon having 1 to 20 carbon atoms include the same groups as described above.

R ³ and R ⁴ may be bonded to each other to form a ring together with the carbon atoms to which they are bonded, and R ⁵ and R ⁶ may be bonded to each other to form a ring together with the carbon atoms to which each is bonded. It may be formed. For example, even if R ³ and R ⁴ form a tetramethylene group (—CH ₂ CH ₂ CH ₂ CH ₂ —) together with each other to form a 6-membered ring together with the carbon atom to which they are bonded. Good.

X ¹ and X ² may be the same or different, and each represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms. , An oxygen-containing group or a sulfur-containing group, and specifically, halogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, halogenated hydrocarbon groups having 1 to 20 carbon atoms, oxygen Examples of the group include.

As the sulfur-containing group, the same groups as described above,
And methylsulfonate, trifluoromethanesulfonate, phenylsulfonate, benzylsulfonate, p-toluenesulfonate, trimethylbenzenesulfonate, triisobutylbenzenesulfonate, p-chlorobenzenesulfonate, pentafluoro Sulfonate groups such as benzenesulfonate; and sulfinate groups such as methylsulfinate, phenylsulfinate, benzenesulfinate, p-toluenesulfinate, trimethylbenzenesulfinate, and pentafluorobenzenesulfinate. .

Of these, a halogen atom and a hydrocarbon group having 1 to 20 carbon atoms are preferable. Y is
Divalent hydrocarbon group having 1 to 20 carbon atoms, divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, divalent silicon-containing group, divalent germanium-containing group, divalent tin Containing group, -O-, -CO-, -S-, -SO-, -SO
^{_{2 -, - N (R 7}} ) -, - P (R 7) -, - P (O)
^{(R 7) -, - B} (R 7) - or -Al (R ⁷⁾ - [however, R ⁷ is a hydrogen atom, a halogen atom, carbon atoms 1
Hydrocarbon group having 1 to 20 carbon atoms], specifically, methylene, dimethylmethylene, 1,2-ethylene, dimethyl-1,2-ethylene,
Alkylene groups such as 1,3-trimethylene, 1,4-tetramethylene, 1,2-cyclohexylene, 1,4-cyclohexylene,
2 having 1 to 20 carbon atoms, such as an arylalkylene group such as diphenylmethylene and diphenyl-1,2-ethylene.
A halogenated hydrocarbon group obtained by halogenating a divalent hydrocarbon group having 1 to 20 carbon atoms such as chloromethylene; methylsilylene, dimethylsilylene;
Diethylsilylene, di (n-propyl) silylene, di (i-
Propyl) silylene, di (cyclohexyl) silylene,
Methylphenylsilylene, diphenylsilylene, di (p-
Alkylsilylenes such as (tril) silylene and di (p-chlorophenyl) silylene; alkylarylsilylenes; arylsilylene groups; alkyldisilylenes such as tetramethyl-1,2-disilylene and tetraphenyl-1,2-disilylene; A divalent silicon-containing group such as a silylene or arylsilylene group; a divalent germanium-containing group in which silicon of the divalent silicon-containing group is substituted with germanium; a divalent silicon-containing group in which silicon of the divalent silicon-containing group is substituted with tin And valent tin-containing groups.

R ⁷ is the same halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms as in the above R ¹ and R ² . 2 of these
It is preferably a divalent silicon-containing group, a divalent germanium-containing group, or a divalent tin-containing group, more preferably a divalent silicon-containing group, and an alkylsilylene, an alkylarylsilylene, or an arylsilylene. Is particularly preferred.

Specific examples of the transition metal compound represented by the general formula (I) are shown below. In Table 1 below, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , Y, X ¹ ,
X ² and M are each represented by the general formula (I):
^{R 1, R 2, R 3} , R 4, R 5, R 6, Y, X 1, X 2
And M.

[0028]

[Table 1]

In the present invention, a transition metal compound in which zirconium metal, titanium metal, and hafnium metal are replaced with vanadium metal, niobium metal, tantalum metal, chromium metal, molybdenum metal, and tungsten metal in the above compounds may also be used. it can.

The ligand of the novel indene derivative of the transition metal compound according to the present invention can be synthesized, for example, by the following reaction route using a conventional organic synthesis technique.

[0031]

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The transition metal compound according to the present invention can be prepared from these indene derivatives by a known method, for example, as described in JP-A-4-268.
No. 307 can be synthesized.

The novel transition metal compound according to the present invention can be used as a catalyst component for olefin polymerization in combination with an organic aluminum oxy compound or the like. In this case, the transition metal compound is usually used as a catalyst component for olefin polymerization as a racemate,
Molds can also be used.

Next, an olefin polymerization catalyst containing the above-mentioned novel transition metal compound as a catalyst component will be described. In this specification, the term "polymerization" may be used to mean not only homopolymerization but also copolymerization, and the term "polymer" means not only homopolymer but also copolymer. It is sometimes used in a sense that also includes coalescence.

Examples of the olefin polymerization catalyst containing the transition metal compound catalyst component of the present invention include (A) a transition metal compound represented by the above general formula (I) (component (A));
(B) (B-1) an organic aluminum oxy compound (component (B-
1)) and / or (B-2) the transition metal compound (A)
That forms an ion pair by reacting with the compound (Component (B-2))
And, if necessary, a catalyst formed from (C) an organoaluminum compound (component (C)).

Hereinafter, each catalyst component will be described. (B-1) The organoaluminum oxy compound may be a conventionally known aluminoxane, and JP-A-2-7868.
It may be a benzene-insoluble organic aluminum oxy compound as exemplified in JP-A-7.

A conventionally known aluminoxane can be produced, for example, by the following method. (1) Compounds containing adsorbed water or salts containing water of crystallization, for example, magnesium chloride hydrate, copper sulfate hydrate,
An organic aluminum compound such as trialkylaluminum is added to a hydrocarbon medium suspension such as aluminum sulfate hydrate, nickel sulfate hydrate or cerous chloride hydrate, and adsorbed water or water of crystallization is added to the organic aluminum. A method of reacting with a compound. (2) A method in which water, ice or water vapor is allowed to directly act on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran. (3) A method of reacting an organoaluminum compound such as trialkylaluminum with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene or toluene.

The aluminoxane is usually obtained as a solution of aluminoxane by the above method. In addition,
The aluminoxane solution may contain a small amount of an organometallic component. Alternatively, the solvent or unreacted organoaluminum compound may be removed from the recovered aluminoxane solution by distillation, and then redissolved in the solvent.

Specific examples of the organoaluminum compound used for preparing the aluminoxane include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, trin-butylaluminum, triisobutylaluminum, trisec-butylaluminum. Trialkyl aluminum such as aluminum, tri-tert-butyl aluminum, tripentyl aluminum, trihexyl aluminum, trioctyl aluminum, tridecyl aluminum; tricycloalkyl aluminum such as tricyclohexyl aluminum and tricyclooctyl aluminum; dimethyl aluminum chloride, diethyl aluminum Chloride, diethylaluminum bromide, diisobutylaluminum chloride, etc. Alkylaluminum halides; diethylaluminum hydride, dialkylaluminum hydride such as diisobutylaluminum hydride; dimethyl aluminum methoxide, dialkylaluminum alkoxides such as diethylaluminum ethoxide; and dialkylaluminum Ally Loki Sid such as diethyl aluminum phenoxide and the like.

Of these, trialkyl aluminum and tricycloalkyl aluminum are particularly preferred.
Further, as an organoaluminum compound used for preparing aluminoxane, isoprenylaluminum represented by the following general formula (II) can also be mentioned.

(I-C ₄ H ₉ ) _x Al _y (C ₅ H ₁₀ ) _z (II) (where x, y, and z are positive numbers and z ≧ 2x). Aluminum compounds are used alone or in combination of two or more.

Solvents used for the preparation of aluminoxanes include aromatic hydrocarbons such as benzene, toluene, xylene, cumene and cymene; and aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane. Alicyclic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane and methylcyclopentane; petroleum fractions such as gasoline, kerosene and light oil; halides of the aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons Among them, hydrocarbon solvents such as chlorinated products and brominated products are exemplified. In addition, ethers such as ethyl ether and tetrahydrofuran can also be used. Among these solvents, aromatic hydrocarbons are particularly preferred.

These organic aluminum oxy compounds are used alone or in combination of two or more. (B-2) Examples of the compound which reacts with the transition metal compound (A) to form an ion pair include JP-A-1-501950, JP-A-1-502036, and JP-A-3-179.
No. 005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, US Pat. No. 5,321,106, etc., Lewis acids, ionic compounds and carborane compounds. it can.

As the Lewis acid, triphenylboron,
Tris (4-fluorophenyl) boron, tris (p-tolyl) boron, tris (o-tolyl) boron, tris (3,5-
Dimethylphenyl) boron, tris (pentafluorophenyl) _{boron, MgCl 2, Al 2 O 3} , SiO 2 -Al 2
O ₃ can be exemplified.

Examples of the ionic compound include triphenylcarbenium tetrakis (pentafluorophenyl) borate, tri-n-butylammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, and ferrocarbon. Cenium tetra (pentafluorophenyl) borate can be exemplified.

Examples of the carborane compound include dodecaborane, 1-carboundecaborane, bis-n-butylammonium (1-carbedodeca) borate, tri-n-butylammonium (7,8-dicarboundeca) borate, and tri-n-butylammonium (Trideca hydride-7-carboundeca) borate and the like can be exemplified.

The compound (B-2) which forms an ion pair by reacting with the transition metal compound (A) can be used alone or in combination of two or more. As the organoaluminum compound (C) used as required, for example, an organoaluminum compound represented by the following general formula (III) can be exemplified.

[0048] In ^{_{R a n AlX 3-n ...}} (III) ( wherein, R ^a represents a hydrocarbon group having 1 to 12 carbon atoms, X is a halogen atom or a hydrogen atom, n represents 1
3. ) In Formula (III), R ^a is 1 to carbon atoms
12 hydrocarbon groups such as an alkyl group, a cycloalkyl group or an aryl group, specifically, methyl, ethyl, n-propyl, isopropyl, isobutyl, pentyl, hexyl, octyl, cyclopentyl, cyclohexyl, phenyl, tolyl, etc. It is.

Such an organoaluminum compound (C)
Specific examples include the following compounds. Trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, tri (2-ethylhexyl) aluminum; alkenylaluminum such as isoprenylaluminum; dimethylaluminum chloride, diethylaluminumchloride, diisopropylaluminumchloride Dialkyl aluminum sesquichlorides such as methyl aluminum sesquichloride, ethyl aluminum sesquichloride, isopropyl aluminum sesquichloride, butyl aluminum sesquichloride and ethyl aluminum sesquibromide; Chill aluminum dichloride, ethyl aluminum dichloride, alkyl aluminum dihalides such as isopropyl aluminum dichloride, ethyl aluminum dibromide; diethylaluminum hydride, and alkyl aluminum hydride such as diisobutyl aluminum hydride.

The organic aluminum compound (C)
It is also possible to use a compound represented by the following general formula (IV).
it can. R^a _nAll_3-n ... (IV) (wherein, R^aRepresents the same group as described above, and Y represents -OR
^bGroup, -OSiR^c _ThreeGroup, -OAlR^d _TwoGroup, -NR^e _Two
Group, -SiR^f _ThreeGroup or -N (R^g) AlR^h _TwoShow the group
And n is 1-2, R^b, R^c, R^dAnd R^hIs
Methyl, ethyl, isopropyl, isobutyl, cyclohexane
Xyl, phenyl, etc.^eIs a hydrogen atom,
, Ethyl, isopropyl, phenyl, trimethylsilyl
And R ^fAnd R^gIs methyl, ethyl, etc.
is there. ) Specific examples of such an organoaluminum compound include:
The following compounds are used. (1) R^a _nAl (OR^b)_3-nCompound represented by
For example, dimethyl aluminum methoxide, diethyl aluminum
Ethoxide, diisobutylaluminum methoxy
(2) R^a _nAl (OSiR^c _Three)_3-nCompound represented by
Object, eg Et_TwoAl (OSiMe_Three), (Iso-Bu)
_TwoAl (OSiMe_Three), (Iso-Bu)_TwoAl (OSiE
t_Three) Etc .; (3) R^a _nAl (OALR)^d _Two)_3-nCompound represented by
Object, eg Et_TwoAlOAlEt_Two, (Iso-Bu)_TwoA
IOAl (iso-Bu)_Two(4) R^a _nAl (NR^e _Two)_3-nCompound represented by
For example, Me_TwoAlNEt_Two, Et_TwoAlNHMe, Me_Two
AlNHEt, Et_TwoAlN (SiMe_Three)_Two, (Iso-
Bu)_TwoAlN (SiMe_Three)_Two(5) R^a _nAl (SiR^f _Three)_3-nA compound represented by
For example (iso-Bu)_TwoAlSiMe_Three(6) R^a _nAl (N (R^g) AlR^h _Two)_3-nRepresented by
Compounds, such as Et_TwoAlN (Me) AlEt_Two,
(Iso-Bu)_TwoAlN (Et) Al (iso-Bu)_TwoWhat
And so on.

Among the organoaluminum compounds represented by the general formula (III) or (IV), those represented by the general formula R ^a ₃ A
1, R ^a _n Al (OR ^b ) _3-n , R ^a _n Al (OAl
R ^d ₂ ) A compound represented by _3-n is preferred, and a compound in which ^Ra is an isoalkyl group and n = 2 is particularly preferred.

Such an organoaluminum compound (C)
Can be used alone or in combination of two or more. In preparing the olefin polymerization catalyst, water may be used as a catalyst component in addition to the component (A), the component (B-1), the component (B-2) and the component (C). Examples of such water include water dissolved in a polymerization solvent as described below, or adsorbed water or water of crystallization contained in a compound or salt used for producing the component (B-1).

The catalyst for olefin polymerization is prepared by mixing component (A), component (B-1) (or component (B-2)), and optionally component (C), and water as a catalyst component in an inert hydrocarbon solvent. Alternatively, it can be prepared by mixing in an olefin solvent.

The order of mixing the components at this time is arbitrary, but the component (B-1) (or component (B-2)) and water are mixed.
Next, it is preferable to mix the component (A). When the component (C) is used and the component (B-1) is used as the component (B), it is preferable to mix the component (B-1) and the component (C), and then to mix the component (A). . Using component (C),
When the component (B-2) is used as the component (B), it is preferable to mix the component (C) and the component (A), and then to mix the component (B-2).

FIG. 1 shows a process for preparing an olefin polymerization catalyst containing the transition metal compound according to the present invention as a catalyst component. Upon mixing the above components, the atomic ratio (A) of aluminum in component (B-1) to the transition metal in component (A)
1 / transition metal) is usually 10 to 10000, preferably 20 to 5000, and the concentration of the component (A) is about 10 ^-8.
10 ^-1 mol / l (solvent), preferably 10 ^-7 mol / l
The range is 5 × 10 ^-2 mol / liter (solvent).

When component (B-2) is used, the molar ratio of component (A) to component (B-2) ((A) / (B-2)) is usually 0.0
The concentration of the component (A) is about 10 ^-8 to 10 ^-1 mol / liter (solvent), preferably 10 ^{-7 to} 5 × 10 ^-2. It is in the range of mol / liter (solvent).

When component (C) is used, component (C)
Aluminum atom (Al _C) and the atomic ratio of component (B-1) aluminum atom in (Al _B-1) in (Al _C / Al
_B-1 ) is usually 0.02 to 20, preferably 0.2 to 1
It is in the range of 0.

When water is used as the catalyst component, the molar ratio (Al _B-1 / H ₂ O) of aluminum atom (Al _B-1 ) to water (H ₂ O) in component (B-1) is used. O) is 0.5-5
0, preferably in the range of 1 to 40.

The above catalyst components may be mixed in a polymerization vessel, or may be mixed in advance and added to the polymerization vessel.
The mixing temperature when mixing in advance is usually -50 to 150 ° C,
Preferably, it is -20 to 120 ° C, and the contact time is 1 to 1
000 minutes, preferably 5 to 600 minutes. Also,
During the mixing contact, the mixing temperature may be changed.

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

The catalyst for olefin polymerization containing the transition metal compound as a catalyst component according to the present invention comprises the components (A) to
At least one component of (C) may be a solid catalyst supported on a fine particle carrier. Such a solid catalyst includes, for example, (A) a compound represented by the above general formula (I) on a fine particle carrier. And (B) (B-1) an organoaluminum oxy compound and / or (B-2) a compound that reacts with the transition metal compound (A) to form an ion pair. (A) a transition metal compound represented by the general formula (I), (B) (B)
-1) Organoaluminum oxy compound and / or (B-
2) a solid catalyst component carrying a compound that forms an ion pair by reacting with the transition metal compound (A);
(C) a catalyst formed from an organoaluminum compound;

The fine particle carrier used for the solid catalyst includes:
An inorganic or organic compound having a particle size of 10 to 300
μm, preferably 20 to 200 μm, in the form of granules or fine particles.

Among them, a porous oxide is used as the inorganic carrier.
Preferably, specifically, SiO 2_Two, Al_TwoO_Three, MgO,
ZrO_Two, TiO_Two, B_TwoO_Three, CaO, ZnO, Ba
O, ThO_TwoOr a mixture thereof, such as Si
O_Two-MgO, SiO_Two-Al_TwoO_Three , SiO_Two-TiO_Two, S
iO_Two-V_TwoO_Five, SiO_Two-Cr_TwoO_Three, SiO_Two-TiO_Two-
MgO and the like can be exemplified. Among them, Si
O_TwoAnd Al_TwoO_ThreeAt least selected from the group consisting of
It is also preferable that the main component is one component.

The above inorganic oxide contains a small amount of Na ₂ C
O ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO
₄ , Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg
(NO ₃ ) ₂ , Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, Li
_It may contain carbonate, sulfate, nitrate and oxide components such as ₂ O.

Although the properties of such a fine particle carrier differ depending on the kind and the production method, the fine particle carrier preferably used in the present invention has a specific surface area of 50 to 1000 m ² / m ² .
g, preferably 100 to 700 m ² / g, and the pore volume is desirably 0.3 to 2.5 cm ³ / g.
Such a particulate carrier may be used in an amount of 100 to 10 as required.
It is used by firing at a temperature of 00 ° C, preferably 150 to 700 ° C.

Further, as the particulate carrier, a particle size of 1
Granular or particulate solids of organic compounds having a size of 0 to 300 μm can be mentioned. These organic compounds include ethylene, propylene, 1-butene, 4-methyl-1-
Examples thereof include (co) polymers mainly composed of α-olefins having 2 to 14 carbon atoms such as pentene and polymers or copolymers mainly composed of vinylcyclohexane and styrene. .

Such a particulate carrier may contain surface hydroxyl groups or water. In that case, it is desirable that the ratio of the surface hydroxyl groups is 1.0% by weight or more, preferably 1.5 to 4.0% by weight, particularly preferably 2.0 to 3.5% by weight, and water is 1. It is desirable that the proportion is 0% by weight or more, preferably 1.2 to 20% by weight, more preferably 1.4 to 15% by weight. In addition, the water contained in the particulate carrier refers to water adsorbed on the surface of the particulate carrier.

Here, the amount of adsorbed water (% by weight) and the amount of surface hydroxyl groups (% by weight) of the particulate carrier can be determined as follows. [Amount of adsorbed water] at a temperature of 200 ° C. under normal pressure and nitrogen flow
The weight loss when dried for a period of time is defined as the amount of adsorbed water and is shown as a percentage of the weight before drying. [Amount of surface hydroxyl groups] The weight of a carrier obtained by drying at a temperature of 200 ° C. under a normal pressure under a nitrogen stream for 4 hours is defined as X (g),
Further, the weight of the calcined product from which the surface hydroxyl groups disappeared obtained by calcining the carrier at 1000 ° C. for 20 hours is defined as Y (g),
It is calculated by the following formula.

Surface hydroxyl group amount (% by weight) = {(XY) / X} × 100 When such a specific amount of adsorbed water and a particulate carrier having a surface hydroxyl group are used, high polymerization activity and excellent particle properties are obtained. An olefin polymerization catalyst capable of producing an olefin polymer can be obtained.

In the above solid catalyst, water as described above may be used as a catalyst component. The solid catalyst (component)
It is prepared by mixing and contacting the finely divided carrier, component (A), component (B-1) (or component (B-2)), and, if desired, water in an inert hydrocarbon solvent or an olefin medium. be able to. When the components are brought into mixed contact, the component (C) can be further added.
The mixing order at this time is arbitrarily selected, but preferably, the particulate carrier and the component (B-1) (or the component (B-2)) are mixed and contacted, and then the component (A) is mixed and contacted. If desired, water is mixed and contacted, or component (B-1) (or component
(B-2) a mixture of the component (A) and the particulate carrier is mixed and contacted, and then, if desired, water is mixed and contacted, or the particulate carrier and the component (B-1) (or component (B
-2)) is mixed-contacted with water and then mixed-contacted with component (A).

In mixing each of the above components, the component (A) is used in an amount of usually 10 ^{-6 to} 5 × per gram of the fine particle carrier.
It is used in an amount of 10 ⁻³ mol, preferably 3 × 10 ⁻⁶ to 10 ⁻³ mol, and the concentration of the component (A) is about 5 × 10 ⁻⁶ to 2 × 1.
0 ^-2 mol / l (solvent), preferably 10 ^-5 to 10
^-2 mol / liter (solvent). The atomic ratio (Al / transition metal) of aluminum (Al) in the component (B-1) to the transition metal in the component (A) is usually 10 to 3000,
Preferably it is 20-2000. When component (B-2) is used, the molar ratio of component (A) to component (B-2) (component (A)
/ Component (B-2)) is generally in the range of 0.01 to 10, preferably 0.1 to 5.

When water is used as the catalyst component, the molar ratio (Al _B-1 / H ₂ O) of aluminum atom (Al _B-1 ) to water (H ₂ O) in component (B-1) is used. O) is 0.5 ~
50, preferably in the range of 1 to 40.

The mixing temperature for mixing the above components is usually -50 to 150 ° C, preferably -20 to 120 ° C, and the contact time is 1 to 1000 minutes, preferably 5 to 60 minutes.
0 minutes. Further, the mixing temperature may be changed during the mixing contact.

The olefin polymerization catalyst may be formed from the above solid catalyst (component) and (C) an organoaluminum compound. In this case, the component (C) is desirably used in an amount of 500 mol or less, preferably 5 to 200 mol per gram atom of the transition metal atom in the component (A) contained in the solid catalyst (component).

The olefin polymerization catalyst containing a transition metal compound as a catalyst component according to the present invention comprises the above-mentioned component (A), component (B) and, if necessary, component (C), and an olefin polymer produced by preliminary polymerization. And a prepolymerization catalyst comprising: Examples of such a prepolymerization catalyst include a particulate carrier, (A) a transition metal compound represented by the above general formula (I), (B) an organic aluminum oxy compound (B-1) and / or (B-1). -2) a catalyst and a particulate carrier formed from a compound that forms an ion pair by reacting with the transition metal compound (A) and an olefin polymer formed by prepolymerization; (B) (B-1) an organoaluminum oxy compound and / or (B-2) a compound which reacts with the transition metal compound (A) to form an ion pair;
(C) A catalyst formed from an organoaluminum compound and an olefin polymer produced by prepolymerization. In such a prepolymerized catalyst, water as described above may be used as a catalyst component.

The prepolymerized catalyst is prepared by mixing the above-mentioned fine particle carrier, component (A), component (B-1) (or component (B-2)) and, if desired, water with an inert hydrocarbon solvent or an olefin medium. Can be prepared by pre-polymerizing a small amount of an olefin to the solid catalyst component obtained by mixing and contacting the above. In addition, at the time of mixing contact, the component (C) can be further added.

At this time, the order of mixing the components is arbitrarily selected. Preferably, the particulate carrier and the component (B-1) (or the component (B-2)) are mixed and contacted, and then the component (A) And then, if desired, water, or the mixture of component (B-1) (or component (B-2)) and component (A) and the particulate carrier are mixed and contacted. If desired, water may be mixed and contacted, or the particulate carrier and the component (B
-1) (or component (B-2)) and water are mixed and contacted, and then component (A) is mixed and contacted.

The mixing contact is desirably performed with stirring. When mixing the above components, component (A)
Usually 10 ^{-6 to} 5 × 10 ^-3 mol per 1 g of the fine particle carrier,
It is preferably used in an amount of 3 × 10 ^-6 to 10 ^-3 mol, and the concentration of the component (A) is about 5 × 10 ^-6 to 2 × 10 ^-2 mol / l (solvent), preferably 10 ^-5 to It is in the range of 10 ^-2 mol / l (solvent). The atomic ratio (Al / transition metal) of aluminum in the component (B-1) to the transition metal in the component (A) is usually 10 to 3000, preferably 20 to 200.
0. When component (B-2) is used, component (A) and component
The molar ratio to (B-2) (component (A) / component (B-2)) is generally in the range of 0.01 to 10, preferably 0.1 to 5.

When water is used as the catalyst component, the aluminum atom (Al _B-1 ) in the component (B-1)
Water (H ₂ O) and the molar ratio of _{(Al B-1 / H 2} O) is 0.5
50, preferably in the range of 1 to 40.

The mixing temperature for mixing the above components is usually -50 to 150 ° C, preferably -20 to 120 ° C, and the contact time is 1 to 1000 minutes, preferably 5 to 60 minutes.
0 minutes. Further, the mixing temperature may be changed during the mixing contact.

The prepolymerization catalyst can be prepared by prepolymerizing an olefin in the presence of each of the above components. The prepolymerization can be carried out by introducing an olefin into an inert hydrocarbon solvent in the presence of each of the above components or, if necessary, in the presence of the component (C).

In the prepolymerization, the prepolymerization temperature was -2.
The temperature is 0 to 80C, preferably 0 to 50C, and the prepolymerization time is 0.5 to 100 hours, preferably about 1 to 50 hours. The olefin used for the prepolymerization is selected from olefins used for the polymerization,
Preferably, it is the same monomer as the polymerization or a mixture of the same monomer and the α-olefin as the polymerization.

The prepolymerized catalyst obtained as described above contains the transition metal compound (A) in an amount of about 10 ^-6 to 10 ^-3 gram atoms, preferably 2 ×, in terms of transition metal atoms per gram of the particulate carrier. The organoaluminum oxy compound (B) is supported in an amount of 10 ^{-6 to} 3 × 10 ^-4 gram atoms, and the organic aluminum oxy compound (B) is converted to aluminum atoms in an amount of about 10 ^-3 to 10 ^-1 gram atoms, preferably 2 × 10 ^-3 gram atoms. Preferably, it is carried in an amount of 5 × 10 ^-2 gram atoms. Component (B-2) is replaced by component (B-
2) 10 g / g of particulate carrier
^{-7 to} 0.1 gram atoms, preferably 2 × 10 ^{-7 to} 3 × 1
^Preferably, it is carried in an amount of 0 ^-2 gram atoms.
Further, the amount of the polymer produced by the prepolymerization is about 0.1 to 500 g, preferably 0.3 g / g of the fine particle carrier.
It is desirably in the range of ３００300 g, particularly preferably 1-100 g.

The olefin polymerization catalyst may be formed from the prepolymerization catalyst and (C) an organoaluminum compound. In this case, (C) the organoaluminum compound is used in an amount of 500 mol or less, preferably 5 to 5 mol per gram atom of the transition metal atom in the component (A) contained in the prepolymerization catalyst.
It is desirable to use it in an amount of 200 moles.

The olefin polymerization catalyst containing the transition metal compound according to the present invention as a catalyst component may contain other components useful for olefin polymerization in addition to the above components.

The polyolefin obtained by the olefin polymerization catalyst containing the transition metal compound according to the present invention as a catalyst component has a narrow molecular weight distribution and composition distribution, a high molecular weight, and a high polymerization activity. When an olefin having 3 or more carbon atoms is polymerized, a polyolefin having excellent stereoregularity can be obtained.

Next, a method for polymerizing olefins using the olefin polymerization catalyst as described above will be described. When performing olefin polymerization in the presence of the above-mentioned olefin polymerization catalyst, the polymerization can be carried out by either a liquid phase polymerization method such as suspension polymerization or a gas phase polymerization method. In the liquid phase polymerization method, the same inert hydrocarbon solvent as used in the above catalyst preparation can be used, and the olefin itself can be used as the solvent.

When olefin polymerization is carried out using the olefin polymerization catalyst of the present invention, the above-mentioned catalyst is usually used in a concentration of 10 ⁻⁸ to 10 ⁻ as a transition metal atom concentration in the component (A) in the polymerization system. ³ gram atoms / liter, preferably 1
Desirably, it is used in an amount of 0 ^-7 to 10 ^-4 gram atoms / liter.

When a solid catalyst or a prepolymerized catalyst is used, an organoaluminum compound or aluminoxane not supported on a fine particle carrier may be used, if necessary. As the organoaluminum compound used at this time, the same compound as the component (C) described above can be used. The amount used is preferably in the range of 0 to 500 mol per gram atom of transition metal atom contained in the transition metal compound (A).

The polymerization temperature of the olefin is usually in the range of -50 to 100 ° C., preferably 0 to 90 ° C. when performing the slurry polymerization method, and is preferably in the range of 0 to 90 ° C. when performing the liquid phase polymerization method. , Usually 0 to 250 ° C, preferably 20 to
It is desirable to be in the range of 200 ° C. When carrying out the gas phase polymerization method, the polymerization temperature is preferably in the range of usually 0 to 120 ° C, preferably 20 to 100 ° C.
The polymerization pressure is usually atmospheric pressure to 100 kg / cm ^2, preferably under conditions of normal pressure to 50 kg / cm ^2. The polymerization reaction can be performed in any of a batch system, a semi-continuous system, and a continuous system, and the polymerization can be performed in two or more stages under different reaction conditions.

The molecular weight of the obtained olefin polymer can be adjusted by allowing hydrogen to be present in the polymerization system or by changing the polymerization temperature. Examples of the olefin that can be polymerized by the olefin polymerization catalyst according to the present invention include α-olefins having 2 to 20 carbon atoms, such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, and 4-methyl. -1-pentene, 1-octene, 1
-Decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene;
20 cyclic olefins such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl 1,4,5,8-dimethano
-1,2,3,4,4a, 5,8,8a-octahydronaphthalene and the like. Further, styrene, vinylcyclohexane, diene and the like can be used.

[0092]

The novel transition metal compound according to the present invention is:
It can be used as a catalyst component for olefin polymerization.

The olefin polymerization catalyst containing the transition metal compound according to the present invention as a catalyst component is highly active, and can produce a polyolefin having a narrow molecular weight distribution and a narrow composition distribution and a high molecular weight. Polyolefins obtained by polymerizing olefins having 3 or more carbon atoms have high stereoregularity and are excellent in heat resistance and rigidity. When a copolymer elastomer containing ethylene or propylene as a main component is produced using the olefin polymerization catalyst according to the present invention, a copolymer having a high molecular weight distribution can be obtained. Such a copolymer elastomer has high strength, and when used as a modifier, is excellent in the effect of modifying the impact strength and hardness of polyolefin. Furthermore, when used for the production of a block copolymer of propylene, the molecular weight of the copolymerized elastomer can be increased, so that excellent heat resistance, rigidity or transparency, and an excellent balance in impact strength are obtained. . Even when used in the production of polyethylene, a high molecular weight product can be obtained, so that a polyethylene having excellent mechanical strength such as impact strength, tensile strength, and bending strength can be obtained.

[0094]

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

In this example, the intrinsic viscosity [η] of the obtained polymer was measured in decalin at 135 ° C., and the melting point was determined by a differential scanning calorimeter (DSC).

[0096]

Example 1 [rac-dimethylsilylenebis [1- (2,7-dimethyl-4,5-
Synthesis of benzo) indenyl] zirconium dichloride] Synthesis of 2,7-dimethyl-4,5-benzo-1-indanone 20 g (0.141 mol) of 2-methylnaphthalene in a 1-liter 3-necked reactor sufficiently purged with nitrogen. And 2-bromo-2-
38.8 g (0.169 mol) of methyl propionate bromide and 320 ml of methylene chloride were charged, and 46.8 g (0.352) of powdered aluminum chloride was added thereto at room temperature.
Mol) was added in small portions over about 1 hour. After completion of the addition, the reaction was further performed at room temperature for 0.5 hour. The obtained reaction mixture was poured into ice water to decompose it, separated into oil and water, and then the aqueous phase was further extracted twice with 50 ml of methylene chloride. An equal amount of ether was added to the combined organic phases, and the mixture was washed until neutral with saturated aqueous sodium hydrogen carbonate and saturated brine, and then dried over anhydrous Na ₂ SO _4.
And dried. The solvent was concentrated under reduced pressure, and the obtained black-brown liquid was separated and purified by silica gel column chromatography (developed with hexane / ethyl acetate) to obtain 18.0 g of the target substance as a yellow-brown liquid (yield; 61%). The physical properties of the obtained product are shown below.

FD-MS: 210 (M ⁺ ) IR (Neat): 1702 cm ⁻¹ (ν _{c = 0} ) NMR (CDCl ₃ , 90 MHz): σ = 1.36 (d,
_{J = 7.6Hz, 3H, CH 3} ); 2.51 (s, 3H,
_{CH 3); 2.61~3.08 (m,} 2H); 3.64 (d
d, J = 7.6 Hz, 17.8 Hz, 1H); 7.13-
7.94 (m, 5H); Synthesis of 2,7-dimethyl-4,5-benzo-1-indanol Under a nitrogen atmosphere, 2,7-dimethyl-4,5-benzo-1-in a 200 ml three-necked flask. 18 g (85.7 mmol) of indanone, 36 ml of tetrahydrofuran and 9 parts of ethanol
0 ml and powdered NaBH ₄ at room temperature 9.73 (2
(57.1 mmol) was added in small portions. After the addition,
The mixture was heated under reflux (internal temperature 66 ° C.) for 3 hours. The obtained reaction mixture was concentrated under reduced pressure, and 150 ml of water and 300 ml of ether were added.
1 was added and extracted. After separating the organic phase, the aqueous phase was further extracted with 150 ml of ether. The combined organic phases were washed with brine and dried over anhydrous Na ₂ SO ₄ . The solvent was distilled off under reduced pressure to obtain 22 g of the target substance as a pale yellow-white solid. This crude alcohol was used for the next reaction without further purification. The physical properties of the obtained product are shown below. FD-MS: 212 (M ⁺ ) IR (KBr disk): 3328 cm ⁻¹ (ν _OH )

Synthesis of 2,7-dimethyl-4,5-benzoindene 22.0 g of the above-obtained crude alcohol was added to a 100 ml eggplant-shaped flask, and reacted under an atmosphere of nitrogen at an oil bath temperature of 195 ° C. for 15 minutes. After cooling, it was dissolved in methylene chloride, separated into oil and water, and the organic phase was dried over anhydrous Na ₂ SO ₄ . The solvent was distilled off under reduced pressure to obtain 17 g of a tan solid. Next, the product was separated and purified by silica gel column chromatography using hexane as a developing solvent to obtain 12.8 g of the target substance (a mixture of two isomers) as a white solid (total yield from indanone;
77%). The physical properties of the obtained product are shown below.

FD-MS: 194 (M ⁺ ) NMR (CDCl ₃ , 90 MHz): σ = 2.23 (m,
_{3H, CH 3); 2.49 (} s, 3H, CH 3); 3.4
0, 3.55 (s, respectively, 2H in total); 6.51,
7.01 (bs each, 1H in total);
7.99 (m, 5H); dimethylsilylenebis [1- (2,7-dimethyl-4,5-ben
Zo) Indene] 2,7-into a 200 ml 3-neck round bottom flask (with stirrer chip, Dimroth condenser, dropping funnel, thermometer)
Dimethyl-4,5-benzoindene (5.0 g, 25.8 mmol), copper thiocyanate (85 mg, 0.70 mmol), and anhydrous ether (70 ml) were added. 17.7 ml (28.3 mmol) of a hexane solution of n-butyllithium was slowly added dropwise. After completion of the dropwise addition, the temperature was raised to room temperature, and the reaction was further performed for 3 hours. Next, 1.72 ml of dimethyldichlorosilane (1
(4.2 mmol) in 4.3 ml of anhydrous ether was slowly added dropwise. After dropping, add another 1
The reaction was performed for 2 hours. 30 ml of methylene chloride was added to the reaction mixture.
And 30 ml of ether, and then poured into 50 ml of saturated aqueous sodium hydrogen carbonate and 150 ml of water to decompose. Oil-water separation was performed, and the aqueous phase was further extracted with methylene chloride. The combined organic phase was filtered through celite, washed with saturated saline until neutral, and dried over anhydrous Na ₂ SO ₄ . The solvent was distilled off under reduced pressure, and the obtained pale yellowish white solid residue was dissolved by heating in 10 ml of methylene chloride and cooled in a dry ice-acetone bath. Next, 200 ml of acetone was added for crystallization to obtain 4.0 g of the target substance as a white solid (yield: 70%). The physical properties of the obtained product are shown below.

FD-MS: 444 (M ⁺ ) NMR (CDCl ₃ , 90 MHz): σ = −0.38, −
0.36, -0.28 (each _{s, 6H, Si-CH 3} )
2.32,2.37 (each _{bs, 6H, CH 3);} 2.
53 (s, 6H); 3.94 (s, 2H, -CH-S
i); 7.11 to 7.77 (m, 10H); 7.97
(D, J = 8.9 Hz, 2H); rac-dimethylsilylenebis [1- (2,7-dimethyl-4,5-beta)
Synthesis of [ zo]) indenyl] zirconium dichloride Dimethylsilylenebis [1-
(2,7-dimethyl-4,5-benzo) indene] 2.0 g
(4.5 mmol) and 30 ml of anhydrous ether were added.
5.77 ml of a hexane solution of butyllithium (9.23
Mmol) was slowly added dropwise. After the dropwise addition, the ice bath was removed, the temperature was returned to room temperature, and the reaction was further performed for 3 hours. Next, the obtained reaction solution was cooled in an ice bath, and ZrCl ₄ powder 1.05
g (4.5 mmol) was added slowly. After the addition,
The ice bath was removed, the temperature was returned to room temperature, and the mixture was further reacted for 1 hour, and then heated and refluxed for 1 hour (internal temperature 36 ° C.). After cooling to room temperature, the resulting brown reaction slurry was filtered and the residue was washed 5 times with 10 ml of anhydrous ether. The residue was further reslurried and washed with 20 ml of anhydrous methylene chloride and then with a mixture of 20 ml of anhydrous methylene chloride and 10 ml of anhydrous ether.
Next, 240 ml of anhydrous methylene chloride was added to the residue, and the insoluble material was filtered. The obtained filtrate was concentrated to dryness at room temperature, 20 ml of anhydrous ether and 100 ml of anhydrous methylene chloride were added thereto, and the mixture was reslurried and dried to obtain 1.0 g of the target substance as a yellow powder.
(Yield; 37%). The physical properties of the obtained product are shown below.

NMR (CDCl ₃ , 90 MHz): σ =
1.33 (s, 6H, Si- CH 3) 2.34 (s, 6
_{H, CH 3); 2.47 (} s, 6H, CH 3); 7.08~
7.66 (m, 10H); 7.80 (d, J = 8.9H)
z, 2H);

[0102]

EXAMPLE 2 400 ml of purified toluene was placed in a 1-liter glass flask whose internal volume had been sufficiently replaced with nitrogen, and propylene was kept at 50 ° C. for 15 minutes while flowing propylene at a rate of 100 liter / hr. Subsequently, 0.90 mmol of triisobutylaluminum was added, and methylaluminoxane (methylaluminoxane manufactured by Schering Co., Ltd., which was dried and redissolved in toluene) was obtained with 1.75 mg atom in terms of aluminum atom in Example 1 while stirring. Rac-dimethylsilylenebis [1- (2,7-dimethyl-4,5-
Benzo) indenyl] zirconium dichloride 0.00
A solution in which 5 mmol was well mixed at room temperature in advance was added to the flask, and polymerization was started. After conducting the polymerization at 50 ° C. for 3 minutes, the polymerization was stopped by adding a small amount of isobutanol. The polymerization suspension was added to 3 liters of methanol, sufficiently stirred, and filtered with a glass filter. The polymer is washed with a large amount of methanol, and
It dried under reduced pressure for 0 hours. 24.38 g of polymer obtained
And the polymerization activity is 97.5 kg-PP / mmol-Z
r · hr. The intrinsic viscosity [η] is 1.14 dl /
g, melting point was 148.6 ° C.

[0103]

Example 3 400 ml of purified toluene was placed in a 1-liter glass flask whose inside had been sufficiently purged with nitrogen.
The system was sufficiently purged with nitrogen while blowing nitrogen at 5 ° C.
Next, methylaluminoxane (Methylaluminoxane manufactured by Schering Co., Ltd., which was dried and redissolved in toluene) was 1.30 milligram atoms in terms of aluminum atoms, and rac-dimethylsilylenebis [1- (2 , 7-Dimethyl-4,5-benzo) indenyl] zirconium dichloride (0.002 mmol) was added to the flask at room temperature. Polymerization was performed at 75 ° C. for 3 minutes while stopping blowing of nitrogen and flowing ethylene at a rate of 100 liter / hr. The polymerization was then stopped by adding a small amount of isobutanol. The polymerization suspension was added to 3 liters of methanol, sufficiently stirred, and filtered with a glass filter. The polymer was washed with a large amount of methanol and dried under reduced pressure at 80 ° C. for 10 hours. The obtained polymer was 18 g and the polymerization activity was 180 kg-PE / m
It corresponds to mol-Zr · hr. 3. The intrinsic viscosity [η] is 4.
It was 29 dl / g.

[0104]

Example 4 [rac-dimethylsilylenebis [1- (7-isopropyl-2-
Synthesis of methyl-4,5-benzo) indenyl] zirconium dichloride] of 7-isopropyl-2-methyl-4,5-benzo-1-indanone
Synthesis In a 1-liter three-necked reactor sufficiently purged with nitrogen, 20 g (0.110 mol) of 2-isopropylnaphthalene and 30.4 g of 2-bromo-2-methylpropionic bromide (0.1
33 mol) and 320 ml of methylene chloride, and 36.8 g of powdered aluminum chloride (0.3 g) was added thereto at room temperature.
276 mol) was added in small portions over about one hour. After completion of the addition, the reaction was further performed at room temperature for 40 minutes. The obtained reaction mixture was poured into 300 ml of ice water to decompose it, separated into oil and water, and then the aqueous phase was further extracted twice with 50 ml of ethanol. The combined organic phase was washed three times with 100 ml of a saturated saline solution, and then dried over anhydrous Na ₂ SO ₄ . The solvent was concentrated under reduced pressure, and the obtained yellow-brown viscous liquid was separated and purified by silica gel column chromatography (developed with hexane / ethyl acetate) to obtain 11.0 g of a light yellow-orange liquid as a target substance. Rate; 39%). The physical properties of the obtained product are shown below.

FD-MS: 238 (M ⁺ ) IR (KBr disk): 1692 cm
^-1 (ν _{c = 0} ) NMR (CDCl ₃ , 90 MHz): σ = 1.37 (d,
_{J = 6.4Hz, 6H, CH 3} ); 1.38 (d, J = 7.
6 Hz, 3 H, CH ₃ ); 2.71 to 3.28 (m, 2
H); 3.70 (dd, J = 7.6 Hz, 17.8 Hz,
1H); 7.34 to 8.08 (m, 5H); 7-isopropyl-2-methyl-4,5-benzo-1-indanol
In a 200 ml three-necked flask, 11 g of 7-isopropyl-2-methyl-4,5-benzo-1-indanone (4
6.2 mmol), 22 ml of tetrahydrofuran,
55 ml of ethanol was added, and at room temperature, 5.26 (139 mmol) of NaBH ₄ powder was added little by little. After completion of the addition, the mixture was heated under reflux (internal temperature: 71 ° C.) for 4 hours. The reaction mixture was concentrated under reduced pressure.
1 was added and extracted. The organic phase was washed with saturated saline and dried over anhydrous Na ₂ SO ₄ . The solvent was distilled off under reduced pressure to obtain 11.9 g of the target substance as a white solid. This crude alcohol was used for the next reaction without further purification. The physical properties of the obtained product are shown below.

FD-MS: 240 (M ⁺ ) IR (KBr disk): 3360 cm ⁻¹ (ν _OH ) NMR (CDCl ₃ , 90 MHz): σ = 1.07-1.
_{58 (m, 9H, CH 3} ); 2.23~3.74 (m, 4
_{H, CH 3); 4.69~5.31 (} m, 1H, -CH-
O-); 7.23 to 7.99 (m, 5H); Synthesis of 7-isopropyl-2-methyl-4,5-benzoindene The crude 7-isopropyl-2- obtained above in a 50 ml eggplant flask. Methyl-4,5-benzo-1-indanol 11.0 g
Was added, and reacted under an atmosphere of nitrogen at an oil bath temperature of 255 ° C. for 30 minutes. After cooling, the mixture was dissolved in 150 ml of ether, separated into oil and water, and the organic phase was dried over anhydrous Na ₂ SO ₄ . The solvent was distilled off under reduced pressure, and the obtained residue was separated and purified by silica gel column chromatography using hexane / ethyl acetate (100 / 0.1 = v / v) as a developing solvent to give the target compound as a yellow-white solid (2 types). Isomer mixture) (7.39 g, total yield from indanone; 28%). The physical properties of the obtained product are shown below.

FD-MS: 222 (M ⁺ ) NMR (CDCl ₃ , 90 MHz): σ = 1.34 (d,
J = 6.4 Hz, 6H, CH ₃ ); 2.23 (bs, 3
_{H, CH 3); 2.77~3.22 (} m, 1H); 3.4
2, 3.56 (each s, 2H in total); 6.53;
7.01 (bs each, 1H in total);
8.02 (m, 5H); dimethylsilylenebis [1- (7-isopropyl-2-methyl-
Synthesis of 4,5-benzo) indene 7.08 g of 7-isopropyl-2-methyl-4,5-benzoindene in a 300 ml three-necked round bottom flask (with stirrer chip, Dimroth condenser, dropping funnel, thermometer)
(31.9 mmol) and 105 mg of copper thiocyanate
(0.86 mmol) and 117 ml of anhydrous ether were added thereto, and 21.9 ml (35.1 mmol) of a 1.6 M n-butyllithium hexane solution was slowly added dropwise while cooling with ice in a nitrogen atmosphere. After completion of the dropwise addition, the temperature was raised to room temperature, and the reaction was further performed for 4 hours. Next, a solution of 2.13 ml (17.55 mmol) of dimethyldichlorosilane dissolved in 5.3 ml of anhydrous ether was slowly added dropwise. After the completion of the dropwise addition, the reaction was further performed at room temperature for 12 hours. After adding 60 ml of methylene chloride to the reaction mixture, saturated aqueous sodium bicarbonate 100
The mixture was decomposed by pouring into 200 ml of water and 200 ml of water. Separate oil and water, filter the organic phase through Celite, and add 100 ml of saturated saline.
, And dried over anhydrous Na ₂ SO ₄ . The solvent was distilled off under reduced pressure, and methylene chloride (5 ml) was added to the obtained pale yellowish white solid residue and dissolved by heating.
g (yield; 35%). The physical properties of the obtained product are shown below.

FD-MS: 500 (M ⁺ ) NMR (CDCl ₃ , 90 MHz): σ = −0.51-−
0.23 (m, 6H, Si- CH 3) 1.36 (d, J =
6.4 Hz, 12 H, CH ₃ ); 2.32, 2.37 (bs, 6 H, CH ₃ , respectively); 2.80 to 3.31 (m, 2
H); 3.97 (s, 2H, -CH-Si); 7.18
(Bs, 2H); 7.23-7.74 (m, 8H);
02 (d, J = 8.9 Hz, 2H); rac-dimethylsilylenebis [1- (7-isopropyl-2-me
Tyl-4,5-benzo) indenyl] zirconium dichloride
Schlenk the dimethylsilylenebis de Synthesis 100 ml [1-
(7-isopropyl-2-methyl-4,5-benzo) indene]
2.0 g (4.0 mmol) and 30 ml of anhydrous ether were added, and the mixture was cooled with an ice bath in an argon atmosphere to 1.6 M.
5.1ml hexane solution of n-butyllithium
(8.2 mmol) was slowly added dropwise. After the dropwise addition, the ice bath was removed, the temperature was returned to room temperature, and the reaction was further performed for 4 hours. The obtained reaction solution was cooled in an ice bath, and powder of ZrCl ₄ was added in an amount of 0.9.
3 g (4.0 mmol) were added slowly. After completion of the addition, the ice bath was removed, the temperature was returned to room temperature, and the mixture was further reacted for 1 hour. After cooling to room temperature, the resulting green reaction slurry was filtered, and the residue was washed eight times with 10 ml of anhydrous ether and once with a mixed solution of 2.5 ml of anhydrous methylene chloride and 2.5 ml of anhydrous ether. Next, anhydrous methylene chloride / anhydrous ether = 5/1
After adding 50 ml of a mixture of (v / v), insolubles were filtered. The obtained filtrate was concentrated to dryness at room temperature, added with 10 ml of anhydrous ether, reslurried, and dried to obtain 0.7 g of the target substance as a yellow powder (yield: 26.6%). The physical properties of the obtained product are shown below.

FD-MS: 658 (M ⁺ ) NMR (CDCl ₃ , 90 MHz): σ = 1.27 (d,
J = 6.4 Hz, 12 H, CH ₃ ) 1.34 (s, 6 H,
_{Si-CH 3); 2.34 (} s, 6H, CH 3); 2.82
~ 3.22 (m, 2H); 7.06 to 7.68 (m, 10
H); 7.85 (d, J = 8.9 Hz, 2H);

[0110]

Example 5 400 ml of purified toluene was placed in a 1-liter glass flask whose internal volume had been sufficiently replaced with nitrogen, and propylene was maintained at 50 ° C. for 15 minutes while flowing propylene at a rate of 100 liter / hr. Subsequently, 0.36 mmol of triisobutylaluminum was added, and methylaluminoxane (a product obtained by drying methylaluminoxane manufactured by Schering Co., Ltd. to dryness and re-dissolving in toluene) was obtained in Example 4 with 0.70 mg atom converted to aluminum atom while stirring. Rac-dimethylsilylenebis [1- (7-isopropyl-2-
A solution in which 0.004 mmol of [methyl-4,5-benzo) indenyl] zirconium dichloride was well mixed at room temperature was added to the flask, and polymerization was started. After polymerization at 50 ° C. for 10 minutes, the polymerization was stopped by adding a small amount of isobutanol. The polymerization suspension was added to 3 liters of methanol, sufficiently stirred, and filtered with a glass filter. The polymer was washed with a large amount of methanol and dried under reduced pressure at 80 ° C. for 10 hours. The obtained polymer was 13.68 g, and the polymerization activity was 54.7 kg-PP.
/ Mmol-Zr · hr. The intrinsic viscosity [η] was 1.42 dl / g, and the melting point was 147.6 ° C.

[0111]

EXAMPLE 6 400 ml of purified toluene was placed in a 1-liter glass flask whose internal volume had been sufficiently replaced with nitrogen.
The system was sufficiently purged with nitrogen while blowing nitrogen at 5 ° C.
Next, 1.30 milligram atoms of methylaluminoxane (a product obtained by drying and re-dissolving methylaluminoxane manufactured by Schering Co., Ltd. in toluene) were converted to rac-dimethylsilylenebis [1- (7 -Isopropyl-2-methyl-4,5-benzo) indenyl] zirconium dichloride (0.002 mmol) was added to the flask at room temperature. Polymerization was performed at 75 ° C. for 3 minutes while stopping blowing of nitrogen and flowing ethylene at a rate of 100 liter / hr. The polymerization was then stopped by adding a small amount of isobutanol. The polymerization suspension was added to 3 liters of methanol, sufficiently stirred, and filtered with a glass filter. The polymer was washed with a large amount of methanol and dried under reduced pressure at 80 ° C. for 10 hours. The amount of the obtained polymer was 3.78 g, and the polymerization activity was 37.
Equivalent to 8 kg-PE / mmol-Zr · hr. The intrinsic viscosity [η] was 4.42 dl / g.

[Brief description of the drawings]

FIG. 1 is an explanatory view showing a process for preparing an olefin polymerization catalyst containing a transition metal compound according to the present invention as a catalyst component.

Claims (2)

[Claims] 1. A transition metal compound represented by the following general formula (I): (In the formula, M represents a transition metal atom belonging to Groups 4 to 6 of the periodic table, R ¹ and R ² may be the same or different from each other, and include a hydrogen atom, a halogen atom, and a carbon atom having 1 to 20 carbon atoms. hydrocarbon group, halogenated hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group, R ³ and R ⁵ are also identical to one another Which may be different, represents a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms, and R ⁴ and R ⁶ may be the same or different from each other; A hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms, wherein R ³ and R ⁴ are bonded to each other together with R ⁵ and R ^{5 6} may be bonded to each other to form a ring together with the carbon atoms to which each is bonded; X ¹ and X ^{2 each} represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a carbon atom A halogenated hydrocarbon group, an oxygen-containing group or a sulfur-containing group having 1 to 20 carbon atoms; Y represents a hydrocarbon group having 1 to 20 divalent carbon atoms and 1 to 20 divalent carbon atoms; Halogenated hydrocarbon group, divalent silicon-containing group, divalent germanium-containing group, divalent tin-containing group, -O-, -CO-, -S-, -SO-, -S
O _2- , -N (R ⁷ )-, -P (R ⁷ )-, -P (O)
^{(R 7) -, - B} (R 7) - or -Al (R ⁷⁾ - [however, R ⁷ is a hydrogen atom, a halogen atom, carbon atoms 1
To 20 hydrocarbon groups and halogenated hydrocarbon groups having 1 to 20 carbon atoms]. ) 2. A catalyst component for olefin polymerization, comprising the transition metal compound represented by the general formula (I) according to claim 1.