JPH08301914A - New transition metal compound and olefin polymerization catalyst component comprising the compound - Google Patents

Abstract

PURPOSE: To produce a catalyst which can give a high-molecular-weight polyolefin having a narrow molecular weight distribution and a narrow compositional distribution by using a specified transition metal compound as the effective component. CONSTITUTION: An olefin polymerization catalyst is obtained by using a catalyst component comprising a transition metal compound of the formula (wherein M is a group IVb, Vb or VIb transition metal atom; R<1> to R<6> are each H, halogeno, a 1-20C hydrocarbon group or a 1-20C halohydrocarbon group, provided that any of the two adjoining groups of them may be combined with each other to form an aromatic or alicyclic ring containing the atoms to which they are bonded; X<1> and X<2> are each H, halogeno, a 1-20C hydrocarbon group, a 1-20C halohydrocarbon group or an O- or S-containing group; and Y is a 1-20C bivalent saturated hydrocarbon group, a 1-20C bivalent saturated halohydrocarbon group or a bivalent Si-, Ge- or Sn-containing group). This catalyst can give a high-molecular-weight polyolefin having a narrow molecular weight distribution and a narrow compositional distribution.

Description

Detailed Description of the Invention

[0001]

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

[0002]

BACKGROUND OF THE INVENTION So-called Kaminsky catalysts are well known as homogeneous catalyst systems for olefin polymerization. This catalyst has a feature that a polymer having a very high polymerization activity and a narrow molecular weight distribution can be obtained.

As a transition metal compound used in such a Kaminsky catalyst, for example, bis (cyclopentadienyl) zirconium dichloride (JP-A-58-1)
9309) and ethylene bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride (JP-A-61).
JP-A-130314) and the like are known.

It is also known that when the transition metal compound used for polymerization is different, the olefin polymerization activity and the properties of the obtained polyolefin are greatly different. Polyolefins are used in various fields such as for various molded products because of their excellent mechanical properties, etc., but in recent years the demands for physical properties of polyolefins have diversified, and polyolefins with various properties are desired. . Further, improvement in productivity is also desired.

Therefore, it is desired to develop a catalyst component for olefin polymerization which is further excellent in olefin polymerization activity and is excellent in the properties of the obtained polyolefin, and a new transition metal which can be such a catalyst component for olefin polymerization. The advent of compounds is desired.

[0006]

It is an object of the present invention to provide a novel transition metal compound which can be an olefin polymerization catalyst component having excellent olefin polymerization activity, and to provide an olefin polymerization catalyst component comprising this transition metal compound. The purpose is to do.

[0007]

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

[0008]

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(Where M is IVb, Vb, VIb of the periodic table)
R ^{1 to} R ⁶ may be the same as or different from each other, and are 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. Two groups represented by R ^{1 to} R ⁶ may be adjacent to each other to form an aromatic ring or an aliphatic ring together with the atom to which they are bonded, and X ¹ and X ² are ,
They may be the same as or different from each other, and are a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or 1 to 20 carbon atoms.
Represents a halogenated hydrocarbon group, an oxygen-containing group or a sulfur-containing group, Y is a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated saturated hydrocarbon group having 1 to 20 carbon atoms, A divalent silicon-containing group, a divalent germanium-containing group,
A divalent tin-containing group is shown. ) The catalyst component for olefin polymerization according to the present invention is characterized by comprising a transition metal compound represented by the above general formula (I).

The olefin polymerization catalyst component according to the present invention is, for example, (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. When combined, it can be used as a catalyst for olefin polymerization.

[0011]

DETAILED DESCRIPTION OF THE INVENTION The novel transition metal compound and the olefin polymerization catalyst component comprising the transition metal compound according to the present invention will be specifically described below.

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

[0013]

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In the formula, M represents a transition metal atom of group IVb, Vb, VIb of the periodic table, specifically titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, or tungsten, Titanium, zirconium and hafnium are preferable, and zirconium is particularly preferable.

R ^{1 to} R ^{6, which} may be the same or different, 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. Specifically, halogen atoms such as fluorine, chlorine, bromine and iodine; alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, octyl, nonyl, dodecyl, eicosyl, norbornyl and adamantyl, vinyl, propenyl, cyclohexenyl. Such as alkenyl groups, benzyl, phenylethyl, phenylpropyl and other arylalkyl groups, phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, naphthyl, methylnaphthyl, anthracenyl, phenanthryl and other aryl groups, etc. carbon 1-20 hydrocarbon group; a halogen atom and a halogenated hydrocarbon group having 1 to 20 carbon atoms which is substituted with a hydrocarbon group having 1 to 20 carbon atoms.

Two adjacent groups among the groups represented by R ^{1 to} R ⁶ may form an aromatic ring or an aliphatic ring together with the atom to which they are bonded. Of these, a hydrocarbon group or a hydrogen atom is preferable, and R ^{1 to} R ⁶ are preferable.
It is more preferable that two of the groups represented by are hydrocarbon groups and the other are hydrogen atoms. In this case, the hydrocarbon group is preferably a hydrocarbon group having 1 to 4 carbon atoms such as methyl, ethyl, propyl and butyl.

X ¹ and X ² may be the same or different from each other, and are a hydrogen atom, a halogen atom, or a carbon number of 1 to 2.
0 represents a hydrocarbon group, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group or a sulfur-containing group, and specifically, the same halogen atom as R ^{1 to} R ⁶ described above and ¹ to 10 carbon atoms.
Examples thereof include 20 hydrocarbon groups and halogenated hydrocarbon groups having 1 to 20 carbon atoms.

Examples of the oxygen-containing group include a hydroxy group, an alkoxy group such as methoxy, ethoxy, propoxy and butoxy, an allyloxy group such as phenoxy, methylphenoxy, dimethylphenoxy and naphthoxy, and an arylalkoxy group such as phenylmethoxy and phenylethoxy. it can.

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

Of these, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms is preferable. Y is a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and 1 to 20 carbon atoms.
The divalent halogenated saturated hydrocarbon group, the divalent silicon-containing group, the divalent germanium-containing group and the divalent tin-containing group, specifically, methylene, dimethylmethylene, 1,2-ethylene, Dimethyl-1,2-ethylene, 1,3-trimethylene,
A divalent saturated hydrocarbon group having 1 to 20 carbon atoms such as 1,4-tetramethylene, 1,2-cyclohexylene and 1,4-cyclohexylene; a divalent saturated hydrocarbon group having 1 to 20 carbon atoms such as chloromethylene Halogenated saturated hydrocarbon group obtained by halogenating a saturated hydrocarbon group; methylsilylene, dimethylsilylene, diethylsilylene, di (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, methylphenylsilylene, Alkyl silylene groups such as diphenyl silylene, di (p-tolyl) silylene, and di (p-chlorophenyl) silylene, alkylaryl silylene groups, diaryl silylene groups, tetramethyl-1,2-disilylene,
Divalent silicon-containing groups such as tetraphenyl-1,2-disilylene and other alkyldisilirene groups, alkylaryldisilirene groups, diaryldisililen groups; divalent silicon-containing groups in which silicon is replaced with germanium And a divalent tin-containing group substituent obtained by substituting tin for silicon in the divalent silicon-containing group.

Of these, a divalent saturated hydrocarbon group having 1 to 20 carbon atoms is preferable. Below, the above general formula (I)
Specific examples of the transition metal compound represented by are shown below, but the invention is not limited thereto.

1,2-ethylenebis-7,7- (2,4-dimethylindenyl) zirconium dichloride, 1,3-trimethylenebis-7,7- (2,4-dimethylindenyl) zirconium dichloride, 1,3-trimethylenebis-7,7- (2,4-dimethylindenyl) titanium dichloride, 1,3-trimethylenebis-7,7- (2,4-dimethylindenyl) hafnium dichloride, 1, 3-trimethylenebis-7,7- (2,4-dimethylindenyl) zirconium dimethyl, methyl-1,2-ethylenebis-7,7- (3-methyl-4-phenylindenyl) zirconium dichloride, dimethyl Silylenebis-7,7- (1-ethyl-5-n-propylindenyl) zirconium bis (trifluoromethanesulfonate), dimethylgermylenebis-7,7- (4-chloro-6-naphthylindenyl) Zirconium Dimethoxide In the present invention, in the compound as described above, A transition metal compound in which the ruconium metal is replaced with a titanium metal, a hafnium metal, a vanadium metal, a niobium metal, a tantalum metal, a chromium metal, a molybdenum metal, or a tungsten metal can be used. Alternatively, a transition metal compound in which vanadium metal, niobium metal, tantalum metal, chromium metal, molybdenum metal, or tungsten metal is replaced can be used. Further, the above compound usually has two kinds of isomers, a meso form and a racemic form, but either one or a mixture of both can be used for the polymerization of ethylene, and an olefin having 3 or more carbon atoms can be used. When producing an isotactic polymer in the polymerization, it is desirable to use the racemate.

The novel transition metal compound according to the present invention can be produced, for example, as follows. In the following manufacturing process, M in the general formula (I) is zirconium, and R ¹ , R ³ , R ⁵ and R ^{6 are used.}
Is hydrogen and X ¹ and X ² are chlorine, to produce a transition metal compound.

[0024]

[Chemical 4]

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 Figure 1,
The preparation process of the olefin polymerization catalyst using the transition metal compound according to the present invention will be described.

Next, an olefin polymerization catalyst containing the above-mentioned novel transition metal compound as a catalyst component will be described. In the present 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 copolymerization. It may be used in the sense of including coalescence.

The catalyst component for olefin polymerization according to the present invention can be used in the following modes. (A) a transition metal compound represented by the general formula (I), (B) an organoaluminum oxy compound (B-1) and / or (B-2) an ion by reacting with the transition metal compound (A) An olefin polymerization catalyst formed from a compound forming a pair and, if necessary, (C) an organoaluminum compound.

(B-1) The organoaluminum oxy compound is
It may be a conventionally known aluminoxane or a benzene-insoluble organoaluminum oxy compound as exemplified in JP-A-2-78687.

The conventionally known aluminoxane can be produced, for example, by the following method. (1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, cerium chloride hydrate, etc. The method of adding an organoaluminum compound such as trialkylaluminum to the suspension of a hydrocarbon medium, and reacting the adsorbed water or crystal water with the organoaluminum 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 may contain a small amount of organometallic component. Further, the solvent or the unreacted organoaluminum compound may be removed by distillation from the recovered solution of the aluminoxane, and then redissolved in the solvent or suspended in the poor solvent of the aluminoxane.

Specific examples of the organoaluminum compound used in preparing the aluminoxane include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, trisec-butyl. Aluminum, tri-tert-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum and other trialkylaluminums; tricyclohexylaluminum, tricyclooctylaluminum and other tricycloalkylaluminums; dimethylaluminum chloride, diethylaluminum Chloride, diethyl aluminum bromide, diisobutyl aluminum 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, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum is particularly preferable. Further, as the organoaluminum compound used when preparing the aluminoxane, isoprenylaluminum represented by the following general formula (II) can also be used.

(I-C ₄ H ₉ ) _x Al _y (C ₅ H ₁₀ ) _z (II) (In the formula, x, y, and z are positive numbers, and z ≧ 2x). Such organoaluminum compounds may be used alone or in combination.

Solvents used for the aluminoxane solution 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. , Cyclopentane, cyclohexane, cyclooctane, methylcyclopentane, and other alicyclic hydrocarbons, petroleum fractions such as gasoline, kerosene, and light oil, or the above aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbon halides Among these, hydrocarbon solvents such as chlorinated compounds and brominated compounds are mentioned. In addition, ethers such as ethyl ether and tetrahydrofuran can also be used. Of these solvents, aromatic hydrocarbons are particularly preferable.

(B-2) As a compound which reacts with the transition metal compound (A) to form an ion pair (hereinafter sometimes referred to as "ionized ionic compound"), JP-A-1-50.
No. 1950, No. 1-502036, No. 3-179005, No. 3-179006, No. 3-207703, No. 3-20
Examples thereof include Lewis acids, ionic compounds and carborane compounds described in JP-A-7704, US-547718 and the like.

Examples of the Lewis acid include magnesium-containing Lewis acid, aluminum-containing Lewis acid, boron-containing Lewis acid and the like, among which boron-containing Lewis acid is preferable.

Specific examples of the boron-containing Lewis acid include compounds represented by the following general formula. BR ^a R ^b R ^c (In the formula, R ^a , R ^b and R ^c may be the same or different from each other, and may have a substituent such as a fluorine atom, a methyl group and a trifluoromethyl group. Phenyl group,
Alternatively, it represents a fluorine atom. ) Specific examples of the compound represented by the above general formula include trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl). ) Boron, tris (pentafluorophenyl) boron, tris (p-tolyl) boron, tris (o-tolyl) boron, tris (3,5-dimethylphenyl) boron and the like.
Of these, tris (pentafluorophenyl) boron is particularly preferable.

The ionic compound is a salt composed of a cation part and an anion part. The cation portion has a function of cationizing the transition metal compound (A) by reacting with the transition metal compound (A) and stabilizing the transition metal cation species by forming an ion pair with the anion portion.

Examples of such cations include metal cations, organometallic cations, carbonium cations, tripium cations, oxonium cations, sulfonium cations, phosphonium cations and ammonium cations. More specifically, triphenylcarbenium cation, tributylammonium cation, N,
Examples thereof include N-dimethylammonium cation and ferrocenium cation.

The anions include an organic boron compound anion, an organic arsenic compound anion and an organic aluminum compound anion, and those which are relatively bulky and stabilize the transition metal cation species are preferable.

Of these, an ionic compound containing a boron compound as an anion is preferable. Specific examples will be given below. As the trialkyl-substituted ammonium salt,
For example, triethylammonium tetra (phenyl) borate, tripropylammonium tetra (phenyl) borate, tri (n-butyl) ammonium tetra (phenyl) borate, trimethylammonium tetra (p-tolyl) borate, trimethylammonium tetra (o-tolyl) borate , Tributylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (o, p-dimethylphenyl) borate,
Tributylammonium tetrakis (m, m-dimethylphenyl) borate, tributylammonium tetrakis (p-trifluoromethylphenyl) borate, tri (n-
Butyl) ammonium tetra (o-tolyl) borate, tri (n-butyl) ammonium tetrakis (4-fluorophenyl) borate, etc .; Examples of N, N-dialkylanilinium salts include N, N-dimethylanilinium tetra (phenyl) ) Borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetra (phenyl) borate, N, N-2,
4,6-Pentamethylanilinium tetra (phenyl) borate, etc .; Examples of the dialkylammonium salt include di (n-propyl) ammonium tetra (pentafluorophenyl) borate, dicyclohexylammonium tetra (phenyl) borate, etc .; Triarylphosphoric acid Examples of the aluminum salt include triphenylphosphonium tetra (phenyl) borate, tri (methylphenyl)
Phosphonium tetra (phenyl) borate, tri (dimethylphenyl) phosphonium tetra (phenyl) borate and the like; further, as the carbenium salt, for example, triphenylcarbenium tetrakis (pentafluorophenyl) borate, and as the ferrocene compound,
For example, ferrocenium tetrakis (pentafluorophenyl) borate and the like can be mentioned.

The following compounds can be exemplified as the carborane compound. Decaborane, dodecaborane, 1-carbaundecaborane, 7,8-dicarbaundecaborane, 2,
7-Dicarbound Decaborane, Undeca Hydride-7,8
-Dimethyl-7,8-dicarbaundecaborane, dodecahydride-11-methyl-2,7-dicarbaundecaborane, tri (n-butyl) ammonium 6-carbadecaborate, tri (n-butyl) ammonium 6- Carbadecaborate, tri (n-butyl) ammonium 7-carbaundecaborate,
Tri (n-butyl) ammonium 7,8-dicarbaundecaborate, tri (n-butyl) ammonium 2,9-dicarbaundecaborate, tri (n-butyl) ammonium dodecahydride-8-methyl 7,9-dical Boundecaborate, tri (n-butyl) ammonium undecahydride 8-Ethyl-7,9-dicarbaundecaborate, tri (n-
Butyl) ammonium undeca hydride-8-butyl-
7,9-Dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-allyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-9-trimethylsilyl-7, 8-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-4,6-dibromo-7-carbaundecaborate, 4-carbanonaborane, 1,3-dicarbanonaborane, 6,
9-dicarbadecaborane, dodecahydride-1-phenyl-1,3-dicarbanonaborane, dodecahydride-1-methyl-1,3-dicarbanonaborane, undecahydride-
Compounds (B-2), such as 1,3-dimethyl-1,3-dicarbanonaborane, which react with the above transition metal compound (A) to form an ion pair are mixed in two or more kinds. Can be used.

Examples of the organoaluminum compound (C) used as necessary include the organoaluminum compounds represented by the following general formula (III). R ^d _n AlX _3-n (III) (In the formula, R ^d represents a hydrocarbon group having 1 to 12 carbon atoms;
Represents a halogen atom or a hydrogen atom, and n is 1 to 3. ) In the above general formula (III), R ^d is a hydrocarbon group having 1 to 12 carbon atoms, for example, an alkyl group, a cycloalkyl group or an aryl group, and specifically, a methyl group, an ethyl group, n-propyl Group, isopropyl group, isobutyl group, pentyl group, hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group, tolyl group and the like.

Such an organoaluminum compound (C)
Specifically, the following compounds may be mentioned. Trialkyl aluminum such as trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, trioctyl aluminum, tri (2-ethylhexyl) aluminum; alkenyl aluminum such as isoprenyl aluminum; dimethyl aluminum chloride, diethyl aluminum chloride, diisopropyl aluminum chloride. , Dialkyl aluminum halides such as diisobutyl aluminum chloride and dimethyl aluminum bromide; alkyl aluminum sesquihalides 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.

As the organoaluminum compound (C), compounds represented by the following general formula (IV) can be used. During ^{_{R d n AlL 3-n ...}} (IV) ( wherein, R ^d are as defined above, L is -OR ^e group, -
OSiR ^f ₃ group, -OAlR ^g ₂ group, -NR ^h ₂ group, -S
iR ⁱ ₃ group or —NR ^j AlR ^k ₂ group, and n is 1
To 2 and R ^e , R ^f , R ^g and R ^k are methyl groups,
It is an ethyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, a phenyl group, etc., R ^h is a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, a phenyl group, a trimethylsilyl group, etc., and R ⁱ and R ^j are methyl groups. ,
For example, an ethyl group. ) As such an organoaluminum compound, the following compounds are specifically used. (1) a compound represented by R ^d _n Al (OR ^e ) _3-n ,
For example, dimethyl aluminum methoxide, diethyl aluminum ethoxide, diisobutyl aluminum methoxide, etc. (2) A compound represented by R ^d _n Al (OSiR ^f ₃ ) _3-n , such as Et ₂ Al (OSiMe ₃ ), (iso- Bu)
₂ Al (OSiMe ₃ ), (iso-Bu) ₂ Al (OSi
Et ₃ ), etc .; (3) A compound represented by R ^d _n Al (OAlR ^g ₂ ) _3-n , for example, Et ₂ AlOAlEt ₂ , (iso-Bu) ₂ A
such _{lOAl (iso-Bu) 2;} (4) R d n Al (NR h 2) a compound represented by _3-n, e.g., _{Me 2 AlNEt 2, Et 2 AlNHMe} , Me 2
AlNHEt, Et ₂ AlN (SiMe ₃ ) ₂ , (iso-
Bu) ₂ AlN (SiMe ₃ ) _{2 and the} like; (5) Compounds represented by R ^d _n Al (SiR ⁱ ₃ ) _3-n , such as (iso-Bu) ₂ AlSiMe _{3 and the} like; (6) R ^d _n Al A compound represented by (N (R ^j ) AlR ^k ₂ ) _3-n , for example, Et ₂ AlN (Me) AlEt ₂ ,
(Iso-Bu) ₂ AlN (Et) Al (iso-Bu) _{2 and the} like.

Among the organoaluminum compounds represented by the above general formulas (III) and (IV), the general formula R ^d ₃ A
1, R ^d _n Al (OR ^e ) _3-n , R ^d _n Al (OAlR ^g ₂
) A compound represented by _3-n is preferable, and a compound in which R ^d is an isoalkyl group and n = 2 is particularly preferable.

The olefin polymerization catalyst using the transition metal compound of the present invention as a catalyst component includes the above-mentioned (A) transition metal compound, (B-1) organoaluminum oxy compound, (B-2) ionized ionic compound and (C ) Water may be used as a catalyst component other than the organoaluminum compound. Examples of such water include water dissolved in a polymerization solvent as described below, or (B-1) adsorbed water containing a compound or salt used in producing an organoaluminum oxy compound, crystal water. You can

The olefin polymerization catalyst includes (A) a transition metal compound, (B-1) an organoaluminum oxy compound (or
(B-2) Ionized ionic compound) and optionally water as a catalyst component can be prepared by mixing them in an inert hydrocarbon solvent or an olefin solvent.

In this case, the order of mixing the respective components is arbitrary, but (B-1) organoaluminum oxy compound (or (B-
2) It is preferable to mix (ionized ionic compound) and water, and then mix the transition metal compound (A).

The olefin polymerization catalyst includes (A) a transition metal compound, (B-1) an organoaluminum oxy compound (or (B-2) an ionized ionic compound), (C) an organoaluminum compound and, if desired, a catalyst component. It can be prepared by mixing water as a solvent in an inert hydrocarbon solvent or an olefin solvent.

In this case, the order of mixing the respective components is arbitrary, but when the (B-1) organoaluminum oxy compound is used, the (B-1) organoaluminum oxy compound and the (C) organoaluminum compound are mixed. It is preferable to mix and then mix the transition metal compound (A).

When the (B-2) ionized ionic compound is used, (C) the organoaluminum compound and (A) the transition metal compound are mixed, and then (B-2) the ionized ionic compound is mixed. Preferably.

When mixing the above components, (B-1)
Aluminum atom in organic aluminum oxy compound,
(A) Atomic ratio with the transition metal atom in the transition metal compound (A
(l / transition metal) is usually 10 to 10,000, preferably
20 to 5000, and the concentration of (A) transition metal compound
Is about 10^-8-10^-1Mol / l, preferably 10
^-7~ 5 × 10^-2It is in the range of mol / liter.

(B-2) When using an ionized ionic compound
(A) transition metal compound and (B-2) ionization ionization
The molar ratio with the compound ((A) / (B-2)) is usually 0.01 to
10, preferably in the range of 0.1 to 5, (A) transition
The concentration of the metal compound is about 10 ^-8-10^-1Mol / lit
Le, preferably 10^-7~ 5 × 10^-2Mol / liter
It is a fence.

In addition, (C) an aluminum atom (Al _C ) in the organoaluminum compound, which is used as necessary,
(B-1) The atomic ratio (Al _C / Al _B-1 ) to the aluminum atom (Al _B-1 ) in the organoaluminum oxy compound is usually 0.02 to 20, preferably 0.2 to 10. Is.

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

The above catalyst components may be mixed in the 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,
It is preferably -20 to 120 ° C, and the contact time is 1 to 1
000 minutes, preferably 5 to 600 minutes. Also,
The mixing temperature may be changed during the mixing contact.

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 and cyclohexane. , Alicyclic hydrocarbons such as methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, xylene; ethylene chloride, chlorobenzene,
Examples thereof include halogenated hydrocarbons such as dichloromethane and mixtures thereof.

The transition metal compound which is the catalyst component for olefin polymerization according to the present invention is (A) a transition metal compound, (B-1)
It can also be used as a supported catalyst in which at least one component selected from the organoaluminum oxy compound, the (B-2) ionized ionic compound and the (C) organoaluminum compound is supported on a carrier.

Specific examples of such a catalyst include (A) a transition metal compound represented by the general formula (I), (B) an organoaluminum oxy compound and // Alternatively, (B-2) a solid catalyst on which an ionized ionic compound is supported, and a fine particle carrier, (A) a transition metal compound represented by the general formula (I), and (B) (B- 1) A catalyst comprising a solid catalyst component carrying an organoaluminum oxy compound and / or (B-2) an ionizable ionic compound and (C) an organoaluminum compound.

The fine particle carrier used in such a supported catalyst is an inorganic or organic compound, and is a granular or fine particle solid having a particle size of 10 to 300 μm, preferably 20 to 200 μm.

Among these, porous oxides are used as the inorganic carrier.
Preferably, specifically, SiO₂, Al₂O₃, MgO, Z
rO₂, TiO₂, B₂O₃, CaO, ZnO, BaO,
ThO₂Or a mixture thereof, such as SiO₂-
MgO, SiO₂-Al₂O₃, SiO₂-TiO₂, Si
O₂-V₂O_Five, SiO₂-Cr₂O₃, SiO₂-TiO₂-M
Examples thereof include gO. Among these SiO
₂And / or Al ₂O₃At least one selected from
Those having a seed component as a main component are preferable.

The 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 )
_It does not matter if it contains a carbonate, a sulfate, a nitrate or an oxide component such as ₂ , Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O and Li ₂ O. The properties of such a fine particle carrier vary depending on the type and production method, but the specific surface area is 50 to 10
00 m ² / g, preferably 100 to 700 m ² / g, and the pore volume is preferably 0.3 to 2.5 cm ³ / g. The particulate carrier is 100 to 1 if necessary.
It is used by firing at a temperature of 000 ° C, preferably 150 to 700 ° C.

Further, the fine particle carrier has a particle size of 1
A granular or fine particle solid of an organic compound having a particle size of 0 to 300 μm can be mentioned. As these organic compounds, ethylene, propylene, 1-butene, 4-methyl-1-
Examples thereof include a (co) polymer produced mainly from an α-olefin having 2 to 14 carbon atoms such as pentene, or a polymer produced from vinylcyclohexane or styrene as a main component.

Such a fine particle carrier may contain surface hydroxyl groups or water. In that case, it is desirable that the amount of 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. 0% by weight or more, preferably 1.
It is desirable that the amount is 2 to 20% by weight, more preferably 1.4 to 15% by weight. The water contained in the fine particle carrier means water adsorbed on the surface of the fine particle carrier.

Here, the amount of adsorbed water (% by weight) and the amount of surface hydroxyl groups (% by weight) of the particulate carrier are determined as follows. [Amount of adsorbed water] 4 at normal temperature and nitrogen flow at a temperature of 200 ° C
The weight loss when dried for an hour is defined as the amount of adsorbed water. [Amount of surface hydroxyl groups] X (g) is the weight of the carrier obtained by drying at a temperature of 200 ° C under normal pressure and nitrogen flow for 4 hours.
Furthermore, the weight of the calcined product obtained by calcining the carrier at 1000 ° C. for 20 hours in which the surface hydroxyl groups have disappeared is Y (g),
Calculate by the following formula.

Surface hydroxyl group amount (wt%) = {(X−Y) / X} × 100 When such a particulate carrier having a specific amount of adsorbed water and a surface hydroxyl group is used, high polymerization activity and excellent particle properties are obtained. It is possible to obtain an olefin polymerization catalyst capable of producing an olefin polymer.

The solid catalyst (component) includes the fine particle carrier, (A) transition metal compound, (B-1) organoaluminum oxy compound (or (B-2) ionized ionic compound),
And optionally water with mixed contact in an inert hydrocarbon solvent or in an olefin medium. Further, when the respective components are mixed and brought into contact with each other, (C) an organoaluminum compound can be further added.

The mixing order at this time is arbitrarily selected, but preferably the fine particle carrier and the (B-1) organoaluminum oxy compound (or (B-2) ionized ionic compound) are mixed and contacted, and then ( A) a transition metal compound is mixed and brought into contact with water if desired, or (B-1) an organoaluminum oxy compound (or (B-2) an ionized ionic compound) and (A) a transition metal compound A mixture,
The particulate carrier is mixed and contacted, and then water is optionally mixed and contacted, or the particulate carrier, (B-1) organoaluminum oxy compound (or (B-2) ionized ionic compound) and water are mixed. It is selected to carry out mixed contact and then (A) transition metal compound.

When the above components are mixed, the amount of the transition metal compound (A) is usually 10 ⁻⁶ to 1 g of the particulate carrier in terms of the transition metal atom in the transition metal compound (A).
It is used in an amount of 5 × 10 ⁻³ mol, preferably 3 × 10 ⁻⁶ to 10 ⁻³ mol, and the concentration of the (A) transition metal compound is converted to the transition metal atom in the (A) transition metal compound. About 5
× 10 ^{-6 to} 2 × 10 ^-2 mol / liter, preferably 10
It is in the range of ^-5 to 10 ^-2 mol / liter. (B-1) an aluminum atom in the organoaluminum oxy compound,
(A) Atomic ratio with the transition metal atom in the transition metal compound (A
1 / transition metal) is usually 10 to 3000, preferably 2
0 to 2000. When the (B-2) ionized ionic compound is used, the molar ratio ((A) / (B-2)) of the (A) transition metal compound to the (B-2) ionized ionic compound is usually 0.01. It is in the range of -10, preferably 0.1-5.

When water is used as the catalyst component,
Is the aluminum in the (B-1) organoaluminum oxy compound.
Um atom (Al_B-1) And water (H₂O) molar ratio (Al
_B-1/ H ₂O) is 0.5 to 50, preferably 1 to 40
It is a range.

The mixing temperature at the time of 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.

When the solid catalyst (component) is used, it is preferable to use (C) an organoaluminum compound in combination. The (C) organoaluminum compound is 500 per gram atom of the transition metal atom in the (A) transition metal compound.
It is desirable to use it in an amount of not more than mol, preferably 5 to 200 mol.

The transition metal compound which is the catalyst component for olefin polymerization according to the present invention includes (A) a transition metal compound and (B-
1) Organoaluminum oxy compound and / or (B-2)
It can also be used as a prepolymerization catalyst obtained by prepolymerizing an olefin in the presence of an ionized ionic compound and, if necessary, in the presence of an organoaluminum compound (C).

Examples of such a catalyst include a fine particle carrier, (A) a transition metal compound represented by the general formula (I), and (B) (B-1) an organoaluminum oxy compound and / or (B). -2) a catalyst formed from an ionized ionic compound and an olefin polymer produced by prepolymerization, and a fine particle carrier, (A) a transition metal compound represented by the general formula (I), A catalyst formed from (B) (B-1) an organoaluminum oxy compound and / or (B-2) an ionizable ionic compound, (C) an organoaluminum compound, and an olefin polymer produced by prepolymerization, etc. Is mentioned.

Such a prepolymerization catalyst includes a fine particle carrier, (A) a transition metal compound, (B-1) an organoaluminum oxy compound (or (B-2) an ionizable ionic compound), and optionally (C) an organic compound. Although it can be prepared by prepolymerizing a small amount of olefin in the presence of an aluminum compound, it is desirable to prepare by prepolymerizing a small amount of olefin to the above solid catalyst (component). In this case, together with the solid catalyst (component),
(C) Organoaluminum compound can also be used.

In prepolymerization, solid catalyst (component)
Is usually 10 ⁻⁵ to 2 × 10 ⁻² in terms of the transition metal in the (A) transition metal compound contained in the solid catalyst (component).
Mol / liter, preferably 5 × 10 ^-5 to 10 ^-2 mol /
It is used in an amount of liters and has a prepolymerization temperature of -20 to 80.
C., preferably 0 to 50.degree. C., and the prepolymerization time is 0.5 to 100 hours, preferably about 1 to 50 hours.

The olefin used in the prepolymerization is selected from the olefins used in the polymerization,
Preferably, it is the same monomer as the polymerization or a mixture of the same monomer as the polymerization and an α-olefin.

The olefin polymerization catalyst obtained as described above has a transition of about 10 ^-6 to 10 ^-3 gram atom, preferably 2 × 10 ^{-6 to} 3 × 10 ^-4 gram atom per 1 g of the particulate carrier. It is desirable to carry metal atoms, preferably about 10 ⁻³ to 10 ⁻¹ gram atom, preferably 2 × 10 ^{−3 to} 5 × 10 ⁻² gram atom of aluminum atom. The (B-2) ionized ionic compound has a boron atom in the (B-2) ionized ionic compound of 10 ^{−7 to} 0.1 gram atom, preferably 2 × 10 ^{−7 to} 3 × 10 ⁻² g. It is desirable that they are supported in the amount of atoms.

Further, the amount of the polymer produced by the prepolymerization is about 0.1 to 500 g, preferably 0.3 to 300 g, particularly preferably 1 to 100 g, per 1 g of the fine particle carrier.
Is desirably within the range.

When the prepolymerization catalyst (component) is used, it is preferable to use the organoaluminum compound (C) in combination. (C) The organoaluminum compound is 500 per gram atom of the transition metal atom in the (A) transition metal compound.
It is desirable to use it in an amount of not more than mol, preferably 5 to 200 mol.

The olefin polymerization catalyst may contain other components useful for olefin polymerization in addition to the above components. The polyolefin obtained by such an olefin polymerization catalyst has a narrow molecular weight distribution and composition distribution, a high molecular weight, and high polymerization activity.

Next, the olefin polymerization method using the above olefin polymerization catalyst will be described. When the olefin polymerization is carried out in the presence of the 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-mentioned catalyst preparation can be used, and the olefin itself can also be used as a solvent.
When the olefin polymerization catalyst is used to polymerize an olefin, the above-mentioned catalyst usually has a concentration of the transition metal atom in the (A) transition metal compound in the polymerization system of 10 or less.
^-8 to 10 ^-3 gram atom / liter, preferably 10 ^-7 to
It is preferably used in an amount of 10 ⁻⁴ gram atom / liter.

When a supported catalyst or a prepolymerization catalyst is used, an organoaluminum oxy compound which is not supported on a carrier can be used at any stage of the reaction, if desired.

The polymerization temperature of the olefin is usually in the range of -100 to 100 ° C., preferably -50 to 90 ° C. when carrying out the slurry polymerization method, and when carrying out the liquid phase polymerization method. Is usually in the range of -100 to 250 ° C, preferably -50 to 200 ° C.
Further, when carrying out the gas phase polymerization method, the polymerization temperature is usually −
It is desirable that the temperature is in the range of 47 to 120 ° C, preferably -40 to 100 ° C.

The polymerization pressure is usually from atmospheric pressure to 100 kg / c.
The m ² condition is preferably atmospheric pressure to 50 kg / cm ² , and the polymerization reaction can be carried out by any of a batch system, a semi-continuous system and a continuous system. It is also possible to carry out the polymerization 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 olefins that can be polymerized by the olefin polymerization catalyst include ethylene and α-olefins having 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 1-
Hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-
Octadecene, 1-eicosene; cyclic olefins having 3 to 20 carbon atoms, such as cyclopentene, cycloheptene,
Norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl 1,4,5,8-dimethano-1,2,3,4,4a, 5,
Examples thereof include 8,8a-octahydronaphthalene. Further, styrene, vinylcyclohexane, diene and the like can be used.

[0089]

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 according to the present invention has a novel structure and can produce a polyolefin having a narrow molecular weight distribution and compositional distribution and a high molecular weight.

[0091]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited to these examples.

In this example, the intrinsic viscosity [η] is
It was measured in decalin at 135 ° C.

[0093]

Example 1 Synthesis of 1,2-ethylenebis-7,7- (2,4-dimethylindenyl) zirconium dichloride [Synthesis of 1,2-bis (4-methylphenyl) ethane] 100
ml-three-necked flask (with thermometer, Dimroth condenser, dropping funnel) 0.944 g of magnesium (38.8)
4 mmol) and put in an argon atmosphere, and ether 3
5 ml was added and stirred. A solution prepared by dissolving 10 g (54 mmol) of 4-methylbenzyl bromide in 5 ml of ether was slowly added dropwise from the dropping funnel. After confirming the generation of heat, the mixture was added dropwise at a rate such that the ether was gently refluxed, and after completion of the addition, the mixture was refluxed for 3 hours. After cooling with ice, 20 ml of water was slowly added dropwise to quench the reaction solution, 20 ml of 2 mol / l hydrochloric acid was further added, and the mixture was stirred for a while to completely crush excess magnesium.
After adding 50 ml of ether, the reaction solution was transferred to a separating funnel, the aqueous layer was separated, and the organic layer was washed 3 times with 20 ml of water. After drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and the obtained crude product was recrystallized from ethanol to obtain 5.13 g of the desired product as a white solid (GC purity 97.6%) ( Yield 88%).

The physical properties of the obtained product are shown below. FD-MS: 210 (M ⁺ ) NMR (CDCl ₃ , 90 MHz): δ = 2.32 (s, 6H); 2.86 (s, 4H);
7.12 (s, 8H) [1,2-ethylenebis-7,7- (2,4-dimethylindanone)]
Synthesis] 200 ml-Three-necked flask (with thermometer, Dimroth condenser, dropping funnel), nitrobenzene 30 m
1 l was added, the atmosphere was changed to an argon atmosphere, and 13.08 g (98.1 mmol) of aluminum chloride was added with stirring to give a yellow uniform solution. 9 ml of methacrylic acid chloride here
(82.9 mmol) was added and the mixture was stirred for a while, and 4.97 g (23.06 mmol) of 1,2-bis (4-methylphenyl) ethane obtained in the above reaction was added to nitrobenzene 9
The solution dissolved in ml was added dropwise over 50 minutes. The reaction liquid changed from yellow to reddish black, and the internal temperature rose from 20 ° C to 24 ° C. After completion of the dropping, the mixture was stirred at room temperature for 21 hours, cooled with ice, and then 50 ml of water was added dropwise to quench the reaction solution. 50 ml of ether was added and the mixture was filtered through Celite, and the filter cake was washed with 50 ml of ether. The filtrate was transferred to a separating funnel to separate oil and water, and the aqueous layer was extracted twice with 20 ml of ether. The organic layers were combined and washed twice with 20 ml of dilute hydrochloric acid and then four times with 30 ml of saturated saline. After drying over anhydrous sodium sulfate, the solvent was evaporated under reduced pressure, and 3.17 g of the obtained crude product was purified by column chromatography (silica gel 60 g, hexane-ethyl acetate mixed system). The target indanone is 2.0 as a mixture of isomers.
75 g (GC purity 90.1%) was obtained (yield 23
%).

The physical properties of the obtained product are shown below. FD-MS: 346 (M ⁺ ) IR (Neat): 1705 cm ^-1 (νc = o) [Synthesis of 1,2-ethylenebis-7,7- (2,4-dimethylindene)] 100 ml eggplant type flask 1,2-ethylenebis-7,7- (2,4-dimethylindanone) obtained by the above reaction
2.0077 g (5.22 mmol) and ethanol 10
ml, and with stirring, sodium borohydride 0.
2 g (4.76 mmol) was added. After heating in an oil bath and refluxing for 4 hours, 1.5 ml of acetone was dropped to crush excess sodium borohydride. After the solvent was distilled off under reduced pressure, 30 ml of dilute hydrochloric acid and 70 m of ethyl acetate were used.
1 was added and stirred, the insoluble matter was filtered, the filtrate was transferred to a separating funnel, and oil-water separation was performed. The organic layer was washed twice with 20 ml of saturated saline and dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure to obtain 1.22 g of crude dihydroxy compound.

This crude dihydroxy compound was dissolved in 5 ml of toluene, and 3.3 mg of p-toluenesulfonic acid monohydrate was obtained.
(0.017 mmol) was added and the mixture was refluxed for 1 hour. After cooling, the reaction solution was directly purified by column chromatography (silica gel 20 g, toluene) to obtain 0.78 g (GC purity 97.2%) of the target product as a beige powder (yield 46%).

The physical properties of the obtained product are shown below. FD-MS: 314 (M ⁺ ) NMR (CDCl ₃ , 90 MHz): δ = 2.17 (s, 6H); 2.38 (s, 6H);
2.92 (s, 4H); 3.20 (s, 4H); 6.5
8 (q, J = 1.5 Hz, 2H); 6.94 (m, 4
H) [1,2-ethylenebis-7,7- (2,4-dimethylindenyl)]
Synthesis of Zirconium Dichloride (Compound 1)] 50 ml
-To a three-necked flask (with a thermometer and a dropping funnel), 0.78 g (2.41 mmol) of 1,2-ethylenebis-7,7- (2,4-dimethylindene) obtained in the above reaction was added. Get in,
Argon atmosphere, tetrahydrofuran (THF) 2
0 ml was added and the mixture was stirred under ice cooling. n-Butyl lithium 3
ml (4.89 mmol) was added dropwise over 20 minutes, and the mixture was further stirred for 1 hour after completion of the addition. The reaction solution changed from a yellow homogeneous solution to a gray slurry. Remove the ice bath at room temperature 1
After stirring for 7 hours, the solvent was distilled off under reduced pressure and the residue was dried to give a dark beige dilithium salt. The reaction vessel was cooled to -78 ° C with a dry ice-acetone bath, and 20 ml of dichloromethane at -78 ° C was added thereto. After stirring for a while, 0.559 g of zirconium tetrachloride (2.4 mmo
1) was added little by little as a powder. The temperature was slowly raised to room temperature over 17 hours with vigorous stirring to obtain a dark orange slurry. This slurry was filtered through a G4 glass filter under an argon atmosphere to remove lithium chloride, and the filtrate was concentrated and dried. 10 ml of ether was added and stirred, insoluble matter was filtered off with a G4 filter, and the filtrate was concentrated again.
Dried up. Ether (2 ml) was added and the mixture was stirred for a while, and the precipitated yellow solid was filtered with a G4 filter, washed with ether (1 ml), and vacuum dried to obtain 0.06 g of the desired compound (yield 5%).

The physical properties of the obtained product are shown below. FD-MS: 472-476 (M ⁺ ) NMR (CDCl ₃ , 90 MHz): δ = 2.10 (s, 6H); 2.56 (s, 6H);
2.9-3.5 (m, 4H); 4.14 (d, J = 3H
z, 2H); 6.46 (d, J = 3Hz, 2H); 7.
02 (m, 4H)

[0099]

Example 2 Synthesis of 1,3-trimethylenebis-7,7- (2,4-dimethylindenyl) zirconium dichloride [Synthesis of 1,3-bis (4-methylphenyl) propane] 20
0ml-3 neck flask (thermometer, Dimroth condenser,
(With dropping funnel), 1,3-dibromopropane 10.445
g (51.56 mmol), cuprous bromide 0.9 g (6.
27 mmol) and 10 ml of hexamethylphosphoric triamide were added, and the mixture was stirred under heating in an oil bath at 85 ° C. under an argon atmosphere. 120 ml (1 mol / l) of a THF solution of p-tolylmagnesium bromide prepared from p-bromotoluene and magnesium (1
20 mmol) was added dropwise over 1.5 hours. After completion of the dropping, stirring was continued for another 2 hours, the mixture was cooled in an ice bath, and then 50 ml of 2 mol / liter hydrochloric acid was slowly added dropwise to quench. The organic layer was separated, the solvent was distilled off under reduced pressure, 100 ml of ether was added, and the deposited precipitate was removed by filtration through Celite. The mixture was transferred to a separating funnel, washed twice with 20 ml of water, dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and the obtained crude product (13.6 g) was purified by column chromatography (340 g of silica gel, Hexane-ethyl acetate mixed system). 9.93 g of the target compound
(GC purity 98.8%) was obtained (yield 85%).

The physical properties of the obtained product are shown below. FD-MS: 224 (M ⁺ ) NMR (CDCl ₃ , 90 MHz): δ = 1.96 (m, 2H); 2.34 (s, 6H);
2.64 (t, J = 8 Hz, 4H); 7.14 (s, 8
H) [Synthesis of 1,3-trimethylenebis-7,7- (2,4-dimethylindanone)] Nitrobenzene 60 in a 200 ml three-necked flask (with thermometer, Dimroth condenser, dropping funnel)
2 ml (177 mmol) of aluminum chloride was added thereto with stirring to make an argon atmosphere, and a yellow uniform solution was obtained. 18 ml of methacrylic acid chloride here
(165.8 mmol) was added and the mixture was stirred for a while, and a solution of 9.93 g (43.73 mmol) of 1,3-bis (4-methylphenyl) propane obtained in the above reaction in 10 ml of nitrobenzene was taken for 2 hours. Was dropped. The reaction liquid changes from yellow to reddish black, and the internal temperature is 20 ° C to 24 ° C.
Rose to. After the dropping, stir at room temperature for another 4 hours,
After cooling with ice, 100 ml of water was added dropwise to quench the reaction solution. 50 ml of ether was added and the mixture was filtered through Celite, and the filter cake was washed with 50 ml of ether. The filtrate was transferred to a separating funnel to separate oil and water, and the aqueous layer was washed with 20 ml of ether to 3 times.
Extracted times. The organic layers were combined and washed twice with 20 ml of dilute hydrochloric acid and then three times with 20 ml of saturated saline. After drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and 22 g of the crude product obtained was purified by column chromatography (silica gel 200 g, hexane-ethyl acetate mixed system). The target indanone is 5.2 as a mixture of isomers.
53 g (GC purity 89.8%) was obtained (yield 30
%).

The physical properties of the obtained product are shown below. FD-MS: 360 (M ⁺ ) IR (Neat): 1704 cm ^-1 (νc = o) [Synthesis of 1,3-trimethylenebis-7,7- (2,4-dimethylindene)] 100 ml eggplant type flask 5.253 g (13.08 mmol) of 1,3-trimethylene bis-7,7- (2,4-dimethylindanone) obtained in the above reaction and 20 ml of ethanol were added to and sodium borohydride was added with stirring. 0.7 g (16.65 mmol) was added. After heating in an oil bath and refluxing for 1 hour, acetone 5m
Excess sodium borohydride was crushed by adding 1 liter dropwise. After the solvent was distilled off under reduced pressure, 30 ml of dilute hydrochloric acid and 120 ml of ethyl acetate were added and stirred, the insoluble matter was filtered, the filtrate was transferred to a separatory funnel, and oily water was separated. The organic layer was washed twice with 20 ml of saturated saline and dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure to give crude dihydroxy compound 5.063.
g was obtained.

20 ml of this crude dihydroxy compound was added to toluene.
Dissolve in p-toluenesulfonic acid monohydrate 10.4 mg
(0.055 mmol) was added and the mixture was refluxed for 1 hour. After cooling, the reaction solution was directly purified by column chromatography (silica gel 100 g, toluene) to obtain 3.343 g (GC purity 93.5%) of pale ocher sticky solid (yield 73%). This became a dry powder by washing with an ether-hexane mixed solvent.

The physical properties of the obtained product are shown below. FD-MS: 328 (M ⁺ ) NMR (CDCl ₃ , 90 MHz): δ = 1.8 to 2.3 (m, 2H); 2.16 (s, 6).
H); 2.38 (s, 6H); 2.70 (t, J = 8H
z, 4H); 3.16 (s, 4H); 6.58 (q, J
= 1.5 Hz, 2H); 6.92 (m, 4H) [Synthesis of 1,3-trimethylenebis-7,7- (2,4-dimethylindenyl) zirconium dichloride] 50 ml-three neck flask ( 0.946 g (2.81 mmol) of 1,3-trimethylene bis-7,7- (2,4-dimethylindene) obtained in the above reaction was put in a thermometer and a dropping funnel, and the atmosphere was changed to argon. , THF (20 ml) were added, and the mixture was stirred under ice cooling. 3.6 ml of n-butyllithium (5.87 mmo
1) was added dropwise over 30 minutes, and after completion of the addition, the mixture was stirred for 30 minutes. The reaction solution changed from a yellow homogeneous solution to a dark brown slurry. After removing the ice bath and stirring at room temperature for 18 hours, the solvent was distilled off under reduced pressure and the residue was evaporated to dryness to obtain a dark beige dilithium salt. The reaction vessel was cooled to -78 ° C with a dry ice-acetone bath, and 20 ml of dichloromethane at -78 ° C was added thereto. After stirring for a while, 0.65 g (2.79 mmol) of zirconium tetrachloride was added little by little as a powder. The temperature was slowly raised to room temperature over 18 hours with vigorous stirring to obtain an orange slurry. This slurry was filtered through a G4 glass filter under an argon atmosphere to remove lithium chloride, and the filtrate was concentrated and dried. 20 ml of ether was added and stirred, the insoluble matter was filtered off with a G4 filter, and the filtrate was concentrated and dried again. Ether 4
ml was added and the mixture was stirred for a while, and the precipitated yellow solid was filtered through a G4 filter, washed with 1 ml of ether, and then vacuum dried to obtain 0.12 g of the desired compound (yield 9%).

The physical properties of the obtained product are shown below. ^{FD-MS: 486~490 (M +} ) NMR (CDCl 3, 90MHz): δ = 2.0~2.3 (m, 2H); 2.22 (s, 6
H); 2.46 (s, 6H); 2.82 (t, J = 7H
z, 4H); 4.74 (d, J = 3Hz, 2H);
54 (d, J = 3 Hz, 2H); 7.02 (m, 4H)

[0105]

Example 3 [Polymerization] 400 ml of purified toluene was placed in a glass flask having an internal volume of 500 ml that had been sufficiently replaced with nitrogen, and ethylene was passed at 100 liters / hr at 75 ° C.
After maintaining for 10 minutes, 0.6 mmol of triisobutylaluminum was added and stirred. Next, methylaluminoxane (methylaluminoxane manufactured by Schering Co., dried and redissolved in toluene) 0.035 mmol
(Aluminum atom equivalent) and 1,2-ethylenebis-7,7-
A solution in which 0.002 mmol of (2,4-dimethylindenyl) zirconium dichloride was mixed well with stirring was added to the flask to initiate polymerization. After polymerization was carried out at 75 ° C. for 3 minutes, a small amount of isopropanol was added to stop the polymerization.

To the obtained polymer suspension, 1.5 liters of methanol containing a small amount of hydrochloric acid was added to precipitate a polymer, which was filtered through a glass filter to remove the solvent and washed with methanol, and then at 80 ° C. It was dried under reduced pressure for 10 hours. The amount of polyethylene obtained was 0.23 g, and the polymerization activity was 46.
It was 00 g / mmol-Zr · hr.

[0107]

Example 4 [Polymerization] 400 ml of purified toluene was placed in a glass flask having an internal volume of 500 ml that had been sufficiently replaced with nitrogen, and ethylene was passed at 100 liters / hr at 75 ° C.
After maintaining for 10 minutes, 0.6 mmol of triisobutylaluminum was added and stirred. Next, methylaluminoxane (methylaluminoxane manufactured by Schering Co., Ltd., dried and redissolved in toluene) 0.07 mmol
(Aluminum atom equivalent) and 1,3-trimethylenebis-
A solution in which 0.007 mmol of 7,7- (2,4-dimethylindenyl) zirconium dichloride was thoroughly stirred and mixed was added to the flask to initiate polymerization. After carrying out the polymerization at 75 ° C. for 1 hour, the polymerization was stopped by adding a small amount of isopropanol.

To the obtained polymer suspension, 1.5 liters of methanol containing a small amount of hydrochloric acid was added to precipitate a polymer, which was filtered through a glass filter to remove the solvent and washed with methanol, and then at 80 ° C. It was dried under reduced pressure for 10 hours. The amount of polyethylene obtained was 0.75 g, and the polymerization activity was 37.
It was 5 g / mmol-Zr · hr.

[0109]

Example 5 [Polymerization] Purified toluene (500 ml) was placed in a glass flask having an internal volume of 1 liter, which had been sufficiently purged with nitrogen, and propylene was flowed at 100 liter / hr for 50 times.
After keeping the temperature at 10 ° C. for 10 minutes, 1.52 mmol of triisobutylaluminum was added and stirred. Next, 4.0 mmol of methylaluminoxane (methylaluminoxane manufactured by Schering Co., Ltd., dried and redissolved in toluene)
(Aluminum atom equivalent) and 1,3-trimethylenebis-
A solution in which 0.017 mmol of 7,7- (2,4-dimethylindenyl) zirconium dichloride was well stirred and mixed was added to the flask to initiate polymerization. After carrying out the polymerization at 50 ° C. for 4 hours, the polymerization was stopped by adding a small amount of isopropanol.

The polymerization reaction liquid was transferred to a separating funnel and water 250
The mixture was washed with hydrochloric acid water obtained by adding 10 ml of concentrated hydrochloric acid to ml, and then with 250 ml of water three times. It was concentrated with a rotary evaporator and further dried under reduced pressure at 130 ° C. for 10 hours. The atactic polypropylene obtained is 0.9
and the polymerization activity is 14.8 g / mmol-Zr · h.
The intrinsic viscosity [η] was 0.09 dl / g.

[Brief description of drawings]

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

Claims (2)

[Claims] 1. A novel transition metal compound represented by the following general formula (I): (In the formula, M represents a transition metal atom of Group IVb, Vb or VIb of the Periodic Table, R ^{1 to} R ⁶ may be the same or different from each other, and may be a hydrogen atom, a halogen atom, or a carbon number of 1 to 20. Hydrocarbon groups of,
A halogenated hydrocarbon group having 1 to 20 carbon atoms is shown, and R ¹ to
Two adjacent groups of the group represented by R ⁶ may form an aromatic ring or an aliphatic ring together with the atom to which they are bonded, and X ¹ and X ² are the same or different from each other. May also represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group or a sulfur-containing group, and Y represents C 1 to 20 A divalent saturated hydrocarbon group, a divalent halogenated saturated hydrocarbon group having 1 to 20 carbon atoms, a divalent silicon-containing group, a divalent germanium-containing group and a divalent tin-containing group are shown. ) 2. A catalyst component for olefin polymerization, comprising a transition metal compound represented by the general formula (I) according to claim 1.