JPH07286005A - New transition metal compound, olefin polymerization catalyst component comprising the same, olefin polymerization catalyst containing this component and polymerization of olefin - Google Patents

Abstract

PURPOSE:To provide a new transition metal compound, an olefin polymerization catalyst containing a catalyst component containing this compound and the polymerization process. CONSTITUTION:An olefin (co)polymerization catalyst is obtained by pretreating, by prepolymerization of an olefin, a solid catalyst component prepared by impregnating a fine particulate support with a transition metal compound (A) such as represented by the formula [wherein M is IVa, Va or VIa transition metal; R<1> is a 2-6C hydrocarbon group; R<2> is a 6-16C aryl group; X<1> and X<2> are each H, halogen, a 1-20C hydrocarbon group, a 1-20C halohydrocarbon group, an oxygenous group or a sulfur group; Y is a 1-20C bivalent hydrocarbon group; a 1-20C halohydrocarbon group; a bivalent siliciferous group, a germanous group, -O-, -CO-, -S-, -SO-, -NR<3>-,-P(R<3>), AIR<3> (wherein R<3> is H, halogen or the like)], an organoaluminumoxy compound and at least one compound selected from compounds capable of forming an ionic pair by reaction with component A and an organoaluminumoxy compound.

Description

Detailed Description of the Invention

[0001]

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

[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.

Among the transition metal compound catalyst components used in the Kaminsky catalyst, the catalyst components for producing isotactic polyolefin include ethylenebis (indenyl) zirconium dichloride and ethylenebis (4,5,6,
7-Tetrahydroindenyl) zirconium dichloride (Japanese Patent Laid-Open No. 61-130314) is known.
However, polyolefins produced using such catalyst components usually have low stereoregularity and low molecular weight.
Further, when it is produced at a low temperature, a highly stereoregular substance and a high molecular weight substance can be obtained, but there are problems such as low polymerization activity.

It is known that a high molecular weight compound can be produced by using a hafnium compound instead of a zirconium compound as a transition metal compound catalyst component (Journal of Molecular Catalysis, 56 (1989) p. 237 ~
247), 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-1-3017.
04 publication, Polymer Preprints, Japan vol.39, No.6 p.1
614 to 1616 (1990) and the like, but there is a problem that high polymerization activity, high stereoregularity, high regioregularity and high molecular weight are not simultaneously satisfied.

Further, JP-A-4-268307 discloses an olefin polymerization catalyst comprising a metallocene compound represented by the following formula and an aluminoxane.

[0006]

[Chemical 9]

Further, EP 0 530 648 A1 describes a catalyst for olefin polymerization comprising a metallocene compound represented by the following formula and an aluminoxane.

[0008]

[Chemical 10]

(In the formula, A is a lower alkyl group.) However, even the polyolefins obtained by these catalysts are not always satisfactory in stereoregularity, regioregularity and molecular weight.

Further, in the metallocene compound represented by the chemical formula 10, the catalyst component in which A is a phenyl group or a naphthyl group is 40 YEARS ZIEGLER CATALYSTS IN HONOR OF
Published by Hoechst in the KARL ZIEGER AND WORKSHOP (SEP.1 ~ 3,1993). However, the polyolefins obtained by these catalysts have a problem that they have low stereoregularity and regioregularity.

As a result of intensive studies in view of such conventional techniques, the present inventors have found that the catalyst component composed of the transition metal compound represented by the above chemical formulas 9 and 10 has a kind of substituent group which is substituted on the indenyl group. It was found that the polymerization activity and the stereoregularity and regioregularity of the obtained polyolefin are greatly different from each other, and the present invention has been completed.

[0012]

An object of the present invention is to provide a novel transition metal compound which can be used as a catalyst component for olefin polymerization to obtain a polyolefin having excellent olefin polymerization activity and excellent stereoregularity and regioregularity. In addition to the above, it is an object to provide a catalyst component for olefin polymerization which comprises this transition metal compound. Further, it is an object to provide an olefin polymerization catalyst containing the olefin polymerization catalyst component, and to provide an olefin polymerization method using the olefin polymerization catalyst.

[0013]

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].

[0014]

[Chemical 11]

(Where M is IVa, Va, VIa of the periodic table)
Group ¹ represents a transition metal, R ¹ represents a hydrocarbon group having 2 to 6 carbon atoms, R ² represents an aryl group having 6 to 16 carbon atoms, and the aryl group is a halogen atom or 1 to 1 carbon atoms. 20
It may be substituted with a hydrocarbon group of.

X ¹ and X ² 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 , A divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a divalent silicon-containing group, a divalent germanium-containing group, -O-, -CO
-, - S -, - SO -, - SO 2 -, - NR 3 -, - P
^{(R 3) -, - P} (O) (R 3) -, - BR 3 - or -AlR ³ - [however, R ³ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, carbon atoms 1-20 halogenated hydrocarbon groups]. ) 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 first olefin polymerization catalyst according to the present invention comprises: [A] a transition metal compound represented by the above general formula [I], [B] (B-1) an organoaluminum oxy compound, and (B)
-2) It is characterized by comprising at least one compound selected from the group consisting of compounds which react with the transition metal compound [A] to form an ion pair.

The second olefin polymerization catalyst according to the present invention comprises [A] a transition metal compound represented by the above general formula [I], [B] (B-1) an organoaluminum oxy compound, and (B)
-2) At least one compound selected from the group consisting of compounds that react with the transition metal compound [A] to form an ion pair, and [C] an organoaluminum compound.

The third olefin polymerization catalyst according to the present invention comprises: [A] a transition metal compound represented by the above general formula [I] and [B] (B-1) an organoaluminum oxygenated catalyst on a fine particle carrier. Compound, and (B
-2) It is characterized in that at least one compound selected from the group consisting of compounds that react with the transition metal compound [A] to form an ion pair is supported.

A fourth olefin polymerization catalyst according to the present invention comprises: [A] a transition metal compound represented by the above general formula [I] and [B] (B-1) an organoaluminum oxy on a particulate carrier. Compound, and (B
-2) From a solid catalyst component carrying at least one compound selected from the group consisting of compounds that react with the transition metal compound [A] to form an ion pair, and [C] an organoaluminum compound It is characterized by becoming.

The fifth olefin polymerization catalyst according to the present invention comprises a fine particle carrier, [A] a transition metal compound represented by the above general formula [I], and [B] (B-1) organoaluminum oxy. Compound, and (B
-2) It is characterized by comprising at least one compound selected from the group consisting of compounds that react with the transition metal compound [A] to form an ion pair, and an olefin polymer produced by prepolymerization.

The sixth olefin polymerization catalyst according to the present invention comprises a fine particle carrier, [A] a transition metal compound represented by the above general formula [I], and [B] (B-1) organoaluminum oxy Compound, and (B
-2) From at least one compound selected from the group consisting of compounds that react with the transition metal compound [A] to form an ion pair, [C] an organoaluminum compound, and an olefin polymer formed by prepolymerization It is characterized by becoming.

The olefin polymerization method according to the present invention is carried out in the presence of the above-mentioned first to sixth olefin polymerization catalysts or in the presence of the fifth or sixth olefin polymerization catalyst and an organoaluminum compound. It is characterized by polymerizing or copolymerizing an olefin.

[0024]

DETAILED DESCRIPTION OF THE INVENTION A novel transition metal compound according to the present invention, an olefin polymerization catalyst component comprising the transition metal compound, an olefin polymerization catalyst containing the olefin polymerization catalyst component, and an olefin polymerization catalyst are described below. The olefin polymerization method used will be specifically described.

First, the novel transition metal compound according to the present invention will be described. The novel transition metal compound according to the present invention is a transition metal compound represented by the following general formula [I].

[0026]

[Chemical 12]

In the formula, M represents a transition metal atom of Group IVa, Va or VIa 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 represents a hydrocarbon group having 2 to 6 carbon atoms, specifically, ethyl, n-propyl, isopropyl,
n-butyl, isobutyl, sec-butyl, tert-butyl, n-
Examples thereof include alkyl groups such as pentyl, neopentyl, n-hexyl and cyclohexyl, and hydrocarbon groups having 2 to 6 carbon atoms such as alkenyl groups such as vinyl and propenyl.

Of these, an alkyl group having a primary carbon atom bonded to an indenyl group is preferable, an alkyl group having 2 to 4 carbon atoms is more preferable, and an ethyl group is particularly preferable. R
² represents an aryl group having 6 to 16 carbon atoms, specifically, phenyl, α-naphthyl, β-naphthyl, anthracenyl, phenanthryl, pyrenyl, acenaphthyl, phenalenyl, aceanthrylenyl, tetrahydronaphthyl, indanyl, biphenylyl, etc. Is. Of these, phenyl, naphthyl, anthracenyl and phenanthryl are preferable.

These aryl groups include halogen atoms such as fluorine, chlorine, bromine and iodine; methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, octyl,
Alkyl groups such as nonyl, dodecyl, eicosyl, norbornyl and adamantyl, alkenyl groups such as vinyl, propenyl and cyclohexenyl, arylalkyl groups such as benzyl, phenylethyl and phenylpropyl, phenyl, tolyl, dimethylphenyl, trimethylphenyl and ethylphenyl. , Propylphenyl, biphenyl,
It may be substituted with a hydrocarbon group having 1 to 20 carbon atoms such as an aryl group such as naphthyl, methylnaphthyl, anthracenyl and phenanthryl; an organic silyl group such as trimethylsilyl, triethylsilyl and triphenylsilyl.

X ¹ and X ² 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. Examples of the halogen atom and the hydrocarbon group having 1 to 20 carbon atoms include the same atoms and groups as described above. Moreover, as a C1-C20 halogenated hydrocarbon group, the group which the said C1-C20 hydrocarbon group substituted by the halogen atom can be illustrated.

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. Can be mentioned.

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

Of these, halogen atoms and carbon atoms of 1 to 1
It is preferably 20 hydrocarbon groups. Y is a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a divalent silicon-containing group, a divalent germanium-containing group, -O-,-. CO-, -S-, -SO
_{-, - SO 2 -, -} NR 3 -, - P (R 3) -, - P
^{(O) (R 3) -} , - BR 3 - or -AlR ³ - [however, R ³ is a hydrogen atom, a halogen atom, having from 1 to 20 carbon atoms
And a halogenated hydrocarbon group having 1 to 20 carbon atoms], specifically, methylene, dimethylmethylene, 1,2-ethylene, dimethyl-1,2-ethylene, 1,3-trimethylene, Divalent C1-C20 such as alkylene groups such as 1,4-tetramethylene, 1,2-cyclohexylene and 1,4-cyclohexylene, aryl alkylene groups such as diphenylmethylene and diphenyl-1,2-ethylene Hydrocarbon group; halogenated hydrocarbon group obtained by halogenating the above divalent hydrocarbon group having 1 to 20 carbon atoms such as chloromethylene; methylsilylene, dimethylsilylene, diethylsilylene,
Alkylsilylene such as di (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, methylphenylsilylene, diphenylsilylene, di (p-tolyl) silylene, di (p-chlorophenyl) silylene, alkyl Arylsilylene, arylsilylene group, tetramethyl-1,2-disilyl, tetraphenyl-1,2-
A divalent silicon-containing group such as an alkyldisilyl such as disilyl, an alkylaryldisilyl, an aryldisilyl group; a divalent germanium-containing group obtained by substituting germanium for silicon in the above divalent silicon-containing group, R
³ 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 described above.

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

Specific examples of the transition metal compound represented by the above general formula [I] are shown below. rac-Dimethylsilyl-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-ethyl-4- (α-naphthyl) indenyl)} zirconium dichloride , Rac-dimethylsilyl-
Bis {1- (2-ethyl-4- (β-naphthyl) indenyl)}
Zirconium dichloride, rac-dimethylsilyl-bis {1
-(2-Ethyl-4- (2-methyl-1-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-
Bis {1- (2-ethyl-4- (5-acenaphthyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-
Bis {1- (2-ethyl-4- (9-anthracenyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-
Bis {1- (2-ethyl-4- (9-phenanthryl) indenyl)} zirconium dichloride, rac-dimethylsilyl-
Bis {1- (2-ethyl-4- (o-methylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-
Bis {1- (2-ethyl-4- (m-methylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-
Bis {1- (2-ethyl-4- (p-methylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-
Bis {1- (2-ethyl-4- (2,3-dimethylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-ethyl-4- (2,4-dimethylphenyl) indenyl) )} Zirconium dichloride, rac-dimethylsilyl-bis {1- (2-ethyl-4- (2,5-dimethylphenyl))
Indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-ethyl-4- (2,4,6-trimethylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2- Ethyl-4- (o-chlorophenyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-ethyl-4- (m-chlorophenyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1 -(2-Ethyl-4- (p-chlorophenyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-ethyl-4- (2,3-dichlorophenyl) indenyl)} zirconium dichloride, rac- Dimethylsilyl-bis {1- (2-ethyl-4- (2,6-dichlorophenyl) indenyl)} zirconium dichloride, rac-
Dimethylsilyl-bis {1- (2-ethyl-4- (3,5-dichlorophenyl) indenyl)} zirconium dichloride, ra
c-Dimethylsilyl-bis {1- (2-ethyl-4- (2-bromophenyl) indenyl)} zirconium dichloride, rac-
Dimethylsilyl-bis {1- (2-ethyl-4- (3-bromophenyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-ethyl-4- (4-bromophenyl) indenyl) } Zirconium dichloride, rac-dimethylsilyl-bis {1- (2-ethyl-4- (4-biphenylyl))
Indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-ethyl-4- (4-trimethylsilylphenyl) indenyl)} zirconium dichloride, rac-
Dimethylsilyl-bis {1- (2-n-propyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-n-propyl-4- (α-naphthyl) indenyl)} Zirconium dichloride, rac-dimethylsilyl
-Bis {1- (2-n-propyl-4- (β-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-
Bis {1- (2-n-propyl-4- (2-methyl-1-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-n-propyl-4- (5-acenaphthyl) ) Indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-n-propyl-4- (9-anthracenyl)
Indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-n-propyl-4- (9-phenanthryl) indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-i-propyl) -4-Phenylindenyl)} zirconium dichloride, rac-dimethylsilyl
-Bis {1- (2-i-propyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-
Bis {1- (2-i-propyl-4- (β-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-
Bis {1- (2-i-propyl-4- (8-methyl-9-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-i-propyl-4- (5-acenaphthyl) ) Indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-i-propyl-4- (9-anthracenyl))
Indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-i-propyl-4- (9-phenanthryl) indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-s-butyl) -4-Phenylindenyl)} zirconium dichloride, rac-dimethylsilyl-
Bis {1- (2-s-butyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-
Bis {1- (2-s-butyl-4- (β-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-
Bis {1- (2-s-butyl-4- (2-methyl-1-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-s-butyl-4- (5-acenaphthyl) ) Indenyl)} zirconium dichloride, rac-dimethylsilyl
-Bis {1- (2-s-butyl-4- (9-anthracenyl) indenyl)} zirconium dichloride, rac-dimethylsilyl
-Bis {1- (2-s-butyl-4- (9-phenanthryl) indenyl)} zirconium dichloride, rac-dimethylsilyl
-Bis {1- (2-n-pentyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1-
(2-n-pentyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-
n-Butyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-n-butyl-4-
(Α-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-n-butyl-4- (β-
Naphthyl) indenyl)} zirconium dichloride, ra
c-Dimethylsilyl-bis {1- (2-n-butyl-4- (2-methyl-
1-naphthyl) indenyl)} zirconium dichloride,
rac-Dimethylsilyl-bis {1- (2-n-butyl-4- (5-acenaphthyl) indenyl)} zirconium dichloride, ra
c-Dimethylsilyl-bis {1- (2-n-butyl-4- (9-anthracenyl) indenyl)} zirconium dichloride, ra
c-Dimethylsilyl-bis {1- (2-n-butyl-4- (9-phenanthryl) indenyl)} zirconium dichloride, ra
c-Dimethylsilyl-bis {1- (2-i-butyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-i-butyl-4- (α-naphthyl) indenyl) )} Zirconium dichloride, rac-dimethylsilyl-
Bis {1- (2-i-butyl-4- (β-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-
Bis {1- (2-i-butyl-4- (2-methyl-1-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-i-butyl-4- (5-acenaphthyl) ) Indenyl)} zirconium dichloride, rac-dimethylsilyl
-Bis {1- (2-i-butyl-4- (9-anthracenyl) indenyl)} zirconium dichloride, rac-dimethylsilyl
-Bis {1- (2-i-butyl-4- (9-phenanthryl) indenyl)} zirconium dichloride, rac-dimethylsilyl
-Bis {1- (2-neopentyl-4-phenylindenyl)}
Zirconium dichloride, rac-dimethylsilyl-bis {1
-(2-Neopentyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1-
(2-n-hexyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-n-hexyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-methylphenyl Silyl-bis {1- (2-ethyl
-4-Phenylindenyl)} zirconium dichloride, r
ac-methylphenylsilyl-bis {1- (2-ethyl-4- (α-
Naphthyl) indenyl)} zirconium dichloride, ra
c-Methylphenylsilyl-bis {1- (2-ethyl-4- (9-anthracenyl) indenyl)} zirconium dichloride, rac-methylphenylsilyl-bis {1- (2-ethyl-4-
(9-phenanthryl) indenyl)} zirconium dichloride, rac-diphenylsilyl-bis {1- (2-ethyl-4-
Phenylindenyl)} zirconium dichloride, rac-
Diphenylsilyl-bis {1- (2-ethyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-diphenylsilyl-bis {1- (2-ethyl-4- (9-anthracenyl) indenyl)} zirconium Dichloride, rac-diphenylsilyl-bis {1- (2-ethyl-4- (9-phenanthryl) indenyl)} zirconium dichloride, rac-diphenylsilyl-bis {1- (2-ethyl-4- (4-biphenylyl)) Indenyl)} zirconium dichloride, rac-methylene-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride, rac-methylene-bis {1- (2-ethyl-4- (α-naphthyl) indenyl )} Zirconium dichloride, rac-ethylene-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride, rac-ethylene
-Bis {1- (2-ethyl-4- (α-naphthyl) indenyl)}
Zirconium dichloride, rac-ethylene-bis {1- (2-n-
Propyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-dimethylgermyl-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylgermyl-bis {1- (2-ethyl-4- (α-
Naphthyl) indenyl)} zirconium dichloride, ra
c-dimethylgermyl-bis {1- (2-n-propyl-4-phenylindenyl)} zirconium dichloride and the like.

In the present invention, in the above compound, zirconium metal is replaced with titanium metal, hafnium metal,
A transition metal compound in which vanadium metal, niobium metal, tantalum metal, chromium metal, molybdenum metal or tungsten metal is substituted can also be used.

Such a novel transition metal compound according to the present invention is described in Journal of Organometallic Chem. 288 (1985),
It can be manufactured according to the description of European Patent Application Publication No. 0,320,762 and Examples on pages 63 to 67, for example, as follows.

[0039]

[Chemical 13]

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. The transition metal compound is usually used as a racemate as a catalyst component for olefin polymerization, but R type or S type can also be used.

Next, an olefin polymerization catalyst containing the above-mentioned novel transition metal compound as a catalyst component will be described. FIG. 1 shows a process for preparing an olefin polymerization catalyst according to the present invention.

In the present invention, the term "polymerization" may be used in the sense of including not only homopolymerization but also copolymerization, and the term "polymer" may refer to not only homopolymer but also homopolymer. It may be used to include a polymer.

First, the first and second olefin polymerization catalysts according to the present invention will be described. The first olefin polymerization catalyst according to the present invention comprises [A] a transition metal compound represented by the general formula [I] (hereinafter sometimes referred to as "component [A]"), and [B]. At least one selected from the group consisting of (B-1) an organoaluminum oxy compound, and (B-2) a compound that reacts with the transition metal compound [A] to form an ion pair.
It is formed from a seed compound.

The second olefin polymerization catalyst according to the present invention is [A] a transition metal compound [A] represented by the general formula [I], and [B] (B-1) an organoaluminum oxy compound. And (B-2) at least one selected from the group consisting of compounds that react with the transition metal compound [A] to form an ion pair.
And a [C] organoaluminum compound.

The (B-1) organoaluminum oxy compound (hereinafter sometimes referred to as "component (B-1)") used in the first and second olefin polymerization catalysts according to the present invention has been conventionally used. It may be a known aluminoxane,
It may also be 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. A method in which an organoaluminum compound such as trialkylaluminum is added to the hydrocarbon medium suspension and reacted. (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 when preparing the aluminoxane include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, trisec-butyl. Aluminum, trialkyl aluminum such as tri-tert-butyl aluminum, tripentyl aluminum, trihexyl aluminum, trioctyl aluminum, and tridecyl aluminum; tricycloalkyl aluminum such as tricyclohexyl aluminum and tricyclooctyl aluminum; dimethyl aluminum chloride, diethyl aluminum 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. For example, trimethylaluminum and triisobutylaluminum are used in combination.

The solvent used for the preparation of the aluminoxane includes 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 or aliphatic hydrocarbons are particularly preferable.

(B-2) Used in the first and second olefin polymerization catalysts according to the present invention (B-2) A compound that reacts with the transition metal compound [A] to form an ion pair (hereinafter referred to as "component (B-2 ) ”.)), Which is described in Japanese Patent Publication No. 1-501950, Japanese Patent Publication No. 1-502036, Japanese Patent Laid-Open No. 3-179005, and Japanese Patent Laid-Open No. 3-17.
Examples thereof include Lewis acids, ionic compounds and carborane compounds described in JP-A-9006, JP-A-3-207703, JP-A-3-207704, US-547718 and the like.

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
Examples include O _{3 and the} like.

As the ionic compound, triphenylcarbenium tetrakis (pentafluorophenyl) borate, tri-n-butylammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferroferrite Examples include cerium tetra (pentafluorophenyl) borate.

Examples of the carborane compound are dodecaborane, 1-carbaundecaborane, bis-n-butylammonium (1-carbedodeca) borate, tri-n-butylammonium (7,8-dicarbaundeca) borate, tri-n-butylammonium (Trideca hydride-7-carbaundeca) borate etc. can be illustrated.

The compound (B-2) which forms an ion pair by reacting with the above transition metal compound [A] can be used as a mixture of two or more kinds. The [C] organoaluminum compound (hereinafter sometimes referred to as “component [C]”) used in the second olefin polymerization catalyst according to the present invention is represented by the following general formula [III]. An organic aluminum compound can be illustrated.

R ⁷ _n AlX _3-n ... [III] (In the formula, R ⁷ represents a hydrocarbon group having 1 to 12 carbon atoms, and X
Represents a halogen atom or a hydrogen atom, and n is 1 to 3. In the above general formula [III], R ⁷ is a hydrocarbon group having 1 to 12 carbon atoms, such as an alkyl group, a cycloalkyl group or an aryl group, and specifically, a methyl group, an ethyl group, an n-propyl group. , Isopropyl group, isobutyl group, pentyl group, hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group and tolyl group.

Such an organoaluminum compound [C]
Specifically, the following compounds may be mentioned. Trialkyl aluminums such as trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, trioctyl aluminum, tri (2-ethylhexyl) aluminum and tridecyl aluminum; alkenyl aluminums such as isoprenyl aluminum; dimethyl aluminum chloride, diethyl aluminum chloride. Dialkyl aluminum halides such as diisopropyl aluminum chloride, diisobutyl aluminum chloride and dimethyl aluminum bromide; Ummesquihalide; methyl aluminum dichloride, ethyl aluminum dichloride,
Alkyl aluminum dihalides such as isopropyl aluminum dichloride and ethyl aluminum dibromide; Alkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride.

As the organoaluminum compound [C], a compound represented by the following general formula [IV] can also be used. R ⁷ _n AlL _3-n ... [IV] (In the formula, R ⁷ is the same as above, L is an —OR ⁸ group,
OSiR ⁹ ₃ group, -OAlR ¹⁰ ₂ group, -NR ¹¹ ₂ group, -Si
R ¹² ₃ group or —N (R ¹³ ) AlR ¹⁴ ₂ group, and n is 1
To R 2, R ⁸ , R ⁹ , R ¹⁰ and R ¹⁴ are a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, a phenyl group and the like, and R ¹¹ is a hydrogen atom, a methyl group, an ethyl group, Isopropyl group, phenyl group, trimethylsilyl group and the like, R ¹² and R ¹³ are methyl groups,
For example, an ethyl group. ) Among such organoaluminum compounds, R ⁷ _n A
a compound represented by 1 (OAlR ¹⁰ ₂ ) _3-n , for example Et ₂
AlOAlEt ₂ , (iso-Bu) ₂ AlOAl (iso-B
u) _{2 and the} like are preferable.

[0060] Among the above general formula [III] and an organoaluminum compound represented by the [IV], formula R ⁷ compound represented by ₃ Al are preferred, especially those wherein R ⁷ is an isoalkyl group.

In the present invention, the above component [A] and component (B-
In addition to 1), component (B-2) and component [C], water may be used as a catalyst component. Water used in the present invention is water dissolved in a polymerization solvent as described below, or a component (B-
The adsorbed water and water of crystallization contained in the compound or salt used in the production of 1) can be exemplified.

The first olefin polymerization catalyst according to the present invention comprises a component [A], a component (B-1) (or a component (B-2)), and optionally water as a catalyst component, an inert hydrocarbon. It can be prepared by mixing in a solvent or an olefin solvent.

At this time, the order of mixing the respective components is arbitrary, but it is preferable to mix the component (B-1) (or the component (B-2)) with water and then mix the component [A]. . The second olefin polymerization catalyst according to the present invention is a component [A],
It can be prepared by mixing component (B-1) (or component (B-2)), component [C] and optionally water as a catalyst component in an inert hydrocarbon solvent or an olefin solvent. .

In this case, the order of mixing the components is arbitrary, but when the component (B-1) is used, the component (B-1) and the component [C] are mixed, and then the component [A]. Are preferably mixed.

When the component (B-2) is used, the component [C]
It is preferable to mix the component (A) with the component [A], and then mix the component (B-2). When mixing the above components, 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 100.
00, preferably 20 to 5000, and the concentration of the component [A] is about 10 ⁻⁸ to 10 ⁻¹ mol / liter (solvent), preferably 10 ^{−7 to} 5 × 10 ⁻² mol / liter (solvent). Is the range.

When the component (B-2) is used, the molar ratio of the component [A] and the component (B-2) (component [A] / component (B-2))
Is usually in the range of 0.01 to 10, preferably 0.1 to 5, and the concentration of the component [A] is about 10 ^-8 to 10 ^-1 mol / liter (solvent), preferably 10 ^-7 to 10. 5 × 10 ^-2 mol /
It is in the liter (solvent) range.

The aluminum atom (Al _C ) in the component [C] and the aluminum atom (A in the component (B-1) used in the second catalyst for olefin polymerization according to the present invention.
l _{B- 1)} and the atomic ratio of _{(Al C / Al B-1} ) is usually 0.02
-20, preferably 0.2-10.

When water is used as the catalyst component, the molar ratio of the aluminum atom (Al _B-1 ) in the component ( _B-1 ) to water (H ₂ O) (Al _B-1 / H ₂ O) is 0.5-5
The range is 0, preferably 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 of the present invention include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene. ;
Alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, and mixtures thereof. it can.

Next, the third and fourth olefin polymerization catalysts according to the present invention will be described. A third olefin polymerization catalyst according to the present invention comprises: [A] a transition metal compound represented by the above general formula [I], [B] (B-1) an organoaluminum oxy compound, and (B-2) At least one selected from the group consisting of compounds that react with the transition metal compound [A] to form an ion pair
Loaded with the compound of the species.

The fourth catalyst for olefin polymerization according to the present invention comprises: [A] a transition metal compound represented by the above general formula [I] and [B] (B-1) an organoaluminum oxygenated catalyst on a particulate carrier. At least one selected from the group consisting of a compound, and (B-2) a compound which reacts with the transition metal compound [A] to form an ion pair.
It is formed of a solid catalyst component carrying a seed compound and [C] an organoaluminum compound.

The [A] transition metal compound used in the third and fourth olefin polymerization catalysts according to the present invention is the same as the component [A] used in the first and second olefin polymerization catalysts. And a transition metal compound represented by the above general formula [I].

The (B-1) organoaluminum oxy compound used in the third and fourth olefin polymerization catalysts according to the present invention includes the components (B) used in the first and second olefin polymerization catalysts described above. The same organoaluminum oxy compounds as those described in -1) can be exemplified.

Examples of the compound (B-2) used in the third and fourth olefin polymerization catalysts of the present invention to react with the transition metal compound [A] to form an ion pair include:
Examples thereof include the same compounds as the component (B-2) used in the above-mentioned first and second olefin polymerization catalysts.

As the [C] organoaluminum compound used in the fourth olefin polymerization catalyst according to the present invention, the same organoaluminum compound as the above-mentioned component [C] used in the second olefin polymerization catalyst can be used. It can be illustrated.

The fine particle carrier used in the third and fourth olefin polymerization catalysts of the present invention is an inorganic or organic compound and has a particle size of 10 to 300 μm, preferably 20 to 200 μm. It is a solid in the form of fine particles.

Of these, the inorganic carrier is preferably a porous oxide, and examples thereof include SiO ₂ and Al ₂ O ₃ . Examples of the granular or fine particle solid of the organic compound include polymers or copolymers produced mainly from α-olefin such as ethylene, propylene, 1-butene, or styrene.

Further, in the third and fourth olefin polymerization catalysts according to the present invention, water as described in the above first and second olefin polymerization catalysts may be used as the catalyst component.

The third catalyst for olefin polymerization (solid catalyst component) according to the present invention is the above-mentioned particulate carrier, component [A],
It can be prepared by mixing and contacting the component (B-1) (or the component (B-2)) and optionally water in an inert hydrocarbon solvent or an olefin medium. Further, when the components are mixed and brought into contact with each other, the component [C] can be further added.

The mixing order at this time is arbitrarily selected, but preferably the fine particle carrier and the component (B-1) (or the component (B-
2)) is mixed and contacted, then component [A] is mixed and contacted, and further water is optionally mixed or contacted, or component (B-1) (or component (B-2)) and component [A] are mixed and contacted. The mixture of (1) and the particulate carrier are mixed and contacted, and then water is optionally mixed and contacted, or the particulate carrier and the component (B-1) (or the component (B-2)) and water are mixed and contacted. Let
Then, mixing and contacting the component [A] is selected.

When the above components are mixed, the component [A] is usually 10 ^{−6 to} 5 × 10 ⁻³ per 1 g of the particulate carrier in terms of the transition metal atom derived from the component [A].
It is used in a molar amount, preferably 3 × 10 ⁻⁶ to 10 ⁻³ mol, and the concentration of the component [A] is about 5 × 10 ⁻⁶ to the transition metal atom derived from the component [A]. It is in the range of 2 × 10 ^-2 mol / liter (solvent), preferably 10 ^-5 to 10 ^-2 mol / liter (solvent). The atomic ratio of the aluminum in component (B-1) to the transition metal in component [A] (Al / transition metal) is usually 10 to 3000, preferably 20 to 2
It is 000. When using the component (B-2), the component [A]
To component (B-2) molar ratio (component [A] / component (B-2))
Is usually in the range of 0.01 to 10, preferably 0.1 to 5.

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

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.

The fourth olefin polymerization catalyst according to the present invention is the third olefin polymerization catalyst (solid catalyst component).
And [C] organoaluminum compound. 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].

The olefin polymerization catalyst of the present invention is
In addition to the above components, other components useful for olefin polymerization may be included. As the inert hydrocarbon medium used for the preparation of the third and fourth olefin polymerization catalysts according to the present invention, the same inert hydrocarbon medium as that used for the first and second olefin polymerization catalysts can be used. Can be mentioned.

Next, the fifth and sixth olefin polymerization catalysts according to the present invention will be described. A fifth olefin polymerization catalyst according to the present invention is a particulate carrier, [A] a transition metal compound represented by the above general formula [I], [B] (B-1) an organoaluminum oxy compound, and (B-2) At least one selected from the group consisting of compounds that react with the transition metal compound [A] to form an ion pair
It is formed from a seed compound and an olefin polymer produced by prepolymerization.

The sixth olefin polymerization catalyst according to the present invention comprises a fine particle carrier, [A] a transition metal compound represented by the above general formula [I], and [B] (B-1) organoaluminum oxy. At least one selected from the group consisting of a compound, and (B-2) a compound which reacts with the transition metal compound [A] to form an ion pair.
It is formed from a seed compound, an organoaluminum compound [C], and an olefin polymer produced by prepolymerization.

Examples of the fine particle carrier used in the fifth and sixth olefin polymerization catalysts of the present invention are the same as the above-mentioned fine particle carriers used in the third and fourth olefin polymerization catalysts. it can.

The [A] transition metal compound used in the fifth and sixth olefin polymerization catalysts according to the present invention is the same as the component [A] used in the above-mentioned first and second olefin polymerization catalysts. And a transition metal compound represented by the above general formula [I].

The (B-1) organoaluminum oxy compound used in the fifth and sixth olefin polymerization catalysts according to the present invention includes the components (B-1) used in the above-mentioned first and second olefin polymerization catalysts. The same organoaluminum oxy compounds as those described in -1) can be exemplified.

Examples of the compound (B-2) which is used in the fifth and sixth olefin polymerization catalysts of the present invention and which reacts with the transition metal compound [A] to form an ion pair include:
Examples thereof include the same compounds as the component (B-2) used in the above-mentioned first and second olefin polymerization catalysts.

As the [C] organoaluminum compound used in the sixth olefin polymerization catalyst according to the present invention, the same organoaluminum compound as the above-mentioned component [C] used in the second olefin polymerization catalyst can be used. It can be illustrated.

Further, in the fifth and sixth olefin polymerization catalysts according to the present invention, water as described in the above first and second olefin polymerization catalysts may be used as a catalyst component.

The fifth catalyst for olefin polymerization according to the present invention is the above-mentioned particulate carrier, component [A], component (B-1).
(Or component (B-2)) and, optionally, water in mixed contact with an inert hydrocarbon solvent or in an olefin medium, to obtain a solid catalyst component, which can be prepared by prepolymerizing a small amount of olefin. it can. Further, the component [C] can be further added at the time of mixing and contacting.

The mixing order of the respective components in preparing the solid catalyst component is arbitrarily selected, but it is preferable that the fine particle carrier and the component (B-1) (or the component (B-2)) are mixed and brought into contact with each other. ,
Then, the component [A] is mixed and brought into contact with water, and if desired, water is mixed and brought into contact with the component [B-1] (or the component (B-
2)) and the component [A] are mixed and contacted with the particulate carrier, and then water is optionally mixed and contacted, or
Alternatively, the particulate carrier and the component (B-1) (or the component (B
-2)) and water are mixed and contacted, and then the component [A] is mixed and contacted.

It is desirable to carry out the mixing contact with stirring. In mixing the above components, the component [A] is
The components [A] fine particle carrier 1g per normal 10 ^-6 ~5 × 10 ^-3 mol in terms of transition metal atom derived from, preferably used in an amount of 3 × 10 ^-6 ~10 ^-3 mol, The concentration of the component [A] is about 5 × 10 ⁻⁶ to 2 × 10 ⁻² mol / liter (solvent), preferably 10 ⁻⁵ to 10 ⁻ , in terms of the transition metal atom derived from the component [A]. It is in the range of ² mol / liter (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.
It is 0. When the component (B-2) is used, the molar ratio of the component [A] and the component (B-2) (component [A] / component (B-2)) is
It is usually 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),
The molar ratio with water (H ₂ O) (Al _B-1 / H ₂ O) is 0.5-5.
The range is 0, preferably 1 to 40.

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.

The fifth catalyst for olefin polymerization according to the present invention can be prepared by prepolymerizing olefin in the presence of the above solid catalyst component. The prepolymerization can be carried out by introducing an olefin into an inert hydrocarbon solvent in the presence of the above solid catalyst component or, if necessary, in the coexistence of the component [C].

In the prepolymerization, the solid catalyst component is usually 10 ⁻⁵ to 2 × 10 ⁻² mol / liter (solvent), preferably in terms of the transition metal atom derived from the component [A] in the solid catalyst component. Is used in an amount of 5 × 10 ⁻⁵ to 10 ⁻² mol / liter (solvent), and the prepolymerization temperature is −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,
Olefins preferably similar to those used for polymerization,
Or it is a mixture of the same olefins used in the polymerization.

According to the present invention obtained as described above,
The catalyst for reffin polymerization is about 10 per 1 g of the particulate carrier.
^-6-10^-3Gram atom, preferably 2 × 10^-6~ 3 x 1
0^-FourGram atom of transition metal atom is supported, and about 10^-3~
10^-1Gram atom, preferably 2 × 10^-3~ 5 x 10^-2
The aluminum atom of gram atom is supported
desirable. The component (B-2) is derived from the component (B-2).
10 as a boron atom ^-7~ 0.1 gram atom, preferably
Is 2 × 10^-7~ 3 x 10^-2Supported in the amount of grams atom
Is desirable.

Further, the amount of the polymer produced by the prepolymerization is about 0.1 to 500 g, preferably 0.3 to 300 g, and particularly preferably 1 to 100 g per 1 g of the fine particle carrier.
It is desirable that the range is.

A sixth olefin polymerization catalyst according to the present invention comprises the above-mentioned fifth olefin polymerization catalyst (component),
[C] An organoaluminum compound.
The organoaluminum compound [C] is used in an amount of 500 mol or less, preferably 5 to 200 mol, per 1 gram atom of the transition metal atom in the component [A].

The olefin polymerization catalyst according to the present invention may contain other components useful for olefin polymerization in addition to the above-mentioned components. As the inert hydrocarbon solvent used in the preparation of the fifth and sixth olefin polymerization catalysts according to the present invention, the same inert carbon solvents as those used in the preparation of the above-mentioned first and second olefin polymerization catalysts can be used. A hydrogen fluoride solvent may be used.

The olefin polymerization catalyst according to the present invention as described above can obtain a polyolefin having a narrow molecular weight distribution and composition distribution and a high molecular weight with high polymerization activity. When an olefin having 3 or more carbon atoms is polymerized, a polyolefin having excellent stereoregularity can be obtained.

Next, the olefin polymerization method according to the present invention will be described. In the present invention, olefin polymerization is carried out in the presence of the above 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 also be used as the solvent.
When carrying out olefin polymerization using the first or second olefin polymerization catalyst of the present invention, the above-mentioned catalyst usually has a concentration of the transition metal atom derived from the component [A] in the polymerization system of 10 ⁻ It is desirable to use it in an amount of ⁸ to 10 ^-3 gram atom / liter (solvent), preferably 10 ^-7 to 10 ^-4 gram atom / liter (solvent).

When the olefin polymerization is carried out by using the third or fourth olefin polymerization catalyst of the present invention, the above-mentioned catalyst has a concentration of transition metal atoms derived from the component [A] in the polymerization system. It is desirable that it is used in an amount of usually 10 ⁻⁸ to 10 ⁻³ g atom / liter (solvent), preferably 10 ⁻⁷ to 10 ⁻⁴ g atom / liter (solvent). At this time, if desired, an unsupported organoaluminum oxy compound may be used in addition to the organoaluminum oxy compound (B-1) supported on the particulate carrier.

When the olefin polymerization is carried out using the olefin polymerization catalyst in which the olefin is prepolymerized like the fifth or sixth olefin polymerization catalyst according to the present invention, the above-mentioned catalyst is The concentration of transition metal atoms derived from the component [A] in the polymerization system is usually 10
^-8 to 10 ^-3 gram atom / liter, preferably 10 ^-7 to
It is preferably used in an amount of 10 ⁻⁴ gram atom / liter. At this time, in addition to the organoaluminum oxy compound (B-1) optionally supported on the particulate carrier,
An unsupported organoaluminum oxy compound may be used.

The olefin polymerization temperature 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.
It is under conditions of kg / cm ² , preferably atmospheric pressure to 50 kg / cm ² , and the polymerization reaction can be carried out by any of batch, semi-continuous and continuous methods. 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 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,
For example ethylene, 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 -1,2,3,4,4
Examples include a, 5,8,8a-octahydronaphthalene. Further, styrene, vinylcyclohexane, diene and the like can be used.

The olefin polymerization catalyst according to the present invention is a homopolymerization of propylene or a copolymerization of propylene with at least one α-olefin selected from the group consisting of ethylene and α-olefins having 4 to 20 carbon atoms. It is particularly preferably used for.

When the polyolefin thus obtained is a copolymer of propylene and ethylene containing, for example, 50 mol% or more of propylene units, the Mw is usually Mw.
The value of / Mn is in the range of 1.5 to 3.5, the triad tacticity (mm fraction) is 98.0% or more,
The proportion of positional disordered units based on 2,1-insertion of propylene monomer was 0.20% or less, and the proportion of positional disordered unit based on 1,3-insertion of propylene monomer was 0.03.
% Or less.

When the obtained polyolefin is a propylene homopolymer, the value of Mw / Mn is usually 1.5.
In the range of up to 3.5, the triad tacticity (m
m fraction) is 99.0% or more, and the proportion of regio-irregular units based on the 2,1-insertion of the propylene monomer is 0.50.
%, And the proportion of regio-irregular units based on the 1,3-insertion of propylene monomer is 0.03% or less.

In the present invention, the molecular weight distribution (Mw /
Mn), triad tacticity (mm fraction), proportion of regio irregular units based on 2,1-insertion of propylene monomer and proportion of regio irregular units based on 1,3-insertion of propylene monomer are as follows. Be measured.

[Molecular weight distribution (Mw / Mn)] Water
s company gel permeation chromatography (GP
C) From the chromatograph measured using (150-ALC / GPC), the number average molecular weight (Mn) and the weight average of polypropylene conversion (however, polystyrene conversion when the comonomer amount is 10 mol% or more) by the universal method. The molecular weight (Mw) was calculated and Mw / Mn was calculated.
The measurement is made by Toyo Soda GMH-HT and GMH-HL.
Using a T type column, o-dichlorobenzene was used as a solvent at 140 ° C.

[Triad Tacticity (mm Fraction)] The triad tacticity (mm fraction) of the propylene-based copolymer is defined by the planar zigzag pattern of any three head-to-tail propylene unit chains in the polymer chain. When expressed by a structure, it was defined as a ratio in which the directions of the methyl branches were the same, and it was determined from the ¹³ C-NMR spectrum by the following formula.

[0120]

[Equation 1]

¹³ C-NMR spectrum is obtained by NMR analysis of the sample.
Hexachlorobutadiene in a sample tube (5 mmφ),
About 0.5 ml of o-dichlorobenzene or 1,2,4-trichlorobenzene and about 0.05 ml of deuterated benzene, which is a lock solvent, were completely dissolved in a solvent.
It was measured by the complete proton decoupling method at 0 ° C. The measurement conditions are: flip angle 45 °, pulse interval 3.4T
₁ (T ₁ is the longest value of the spin lattice relaxation time of the methyl group) or more is selected. In polypropylene, the spin-lattice relaxation time of the methyl group is longer than the spin-lattice relaxation time of the methylene group and the methine group, so under this condition, the magnetization recovery of all carbons in the sample is 99% or more. The chemical shift was set to 21.593 ppm for the methyl group in the third unit of the propylene unit 5 chain having head-to-tail bonds, and the chemical shifts of other carbon peaks were based on this.

The peak area is the first area (21.1 to 21.
9 ppm), the second region (20.3 to 21.0 ppm) and the third region (19.5 to 20.3 ppm). In the first region, the methyl group of the second unit in the propylene unit 3 chain represented by PPP (mm) resonates.

In the second region, a methyl group at the second unit of the propylene unit 3 chain represented by PPP (mr) and
A methyl group (PPE-methyl group) of a propylene unit in which adjacent units are a propylene unit and an ethylene unit resonates.

In the third region, a methyl group at the second unit of the propylene unit 3 chain represented by PPP (rr) and
The methyl group (EPE-methyl group) of the propylene unit in which all the adjacent units are ethylene units resonates.

Here, the propylene-based copolymer has the following structure (i) as a partial structure containing a position disorder unit:
It has (ii) and (iii).

[0126]

[Chemical 14]

Among the peaks derived from the structures (i), (ii) and (iii), carbon A and carbon B resonate at 17.3 ppm and 17.0 ppm, respectively.
And the peak based on carbon B does not appear in the first to third regions. Furthermore, carbon A and carbon B do not need to be considered in the triad tacticity calculation, since neither carbon A nor carbon B participate in the propylene 3 chain based on head-to-tail bonds.

Further, a peak based on carbon C, a D peak based on carbon and a peak based on carbon D ′ appear in the second region, and a peak based on carbon E and a peak based on carbon E ′ appear in the third region.

Therefore, among the peaks appearing in the first to third regions, the peaks not based on the head-to-tail bonded propylene unit 3 chain are the PPE-methyl group (resonance near 20.7 ppm) and the EPE-methyl group (19). Resonance around 0.8 ppm), carbon C, carbon D, carbon D ′, carbon E and carbon E ′.

The peak area based on the PPE-methyl group is
It can be determined from the peak area of PPE-methine group (resonance near 30.6 ppm), and the peak area based on EPE-methyl group can be determined from the peak area of EPE-methine group (resonance near 32.9 ppm). it can. Further, the peak area based on carbon C can be obtained from the peak areas of adjacent methine groups (resonance near 31.3 ppm), and the peak area based on carbon D is based on αβ methylene carbon of the above structure (ii). Peak (34.3p
Resonance at resonance near pm and around 34.5 ppm) can be obtained from 1/2 of the sum of the peak areas of carbon D '
The peak area based on the methine group adjacent to the methyl group of carbon E ′ of the structure (iii) (33.3 pp).
Resonance near m) and the peak area based on carbon E is
It can be obtained from the peak area of (resonance near pm),
The peak area based on carbon E ′ can be obtained from the peak areas of adjacent methine carbons (resonance near 33.3 ppm).

Therefore, when these peak areas are subtracted from the peak areas of the second and third regions, the peak areas of the remaining methyl carbons are all head-to-tail linked propylene unit 3 chains (PPP (mr) and PPP ( rr))
It becomes the peak area derived from.

From the above, PPP (mm) and PPP (m
Since the peak areas of r) and PPP (rr) can be determined, the triad tacticity (mm) of the propylene unit chain part consisting of head-to-tail bonds can be calculated according to the above formula.
Can be calculated.

The triad tacticity (mm fraction) of a propylene homopolymer is the direction of the methyl group when the main chain of any three propylene unit chains in the polymer chain is represented by a plane zigzag structure. Are the same, and
It was defined as the proportion of tail-bound and was measured in the same manner as above ¹³
It was determined from the C-NMR spectrum by the following formula.

[0134]

[Equation 2]

The chemical shift was 21.593 for the methyl group in the third unit of the propylene unit 5 chain having head-to-tail bonds.
It was set as ppm, and the chemical shifts of other carbon peaks were based on this.

According to this standard, the peak based on the methyl group of the second unit in the propylene unit 3 chain represented by PPP (mm) appears in the range of 21.1 to 21.9 ppm, and P
The peak based on the methyl group of the second unit in the propylene unit 3 chain represented by PP (mr) is 20.3 to 21.0 p.
The peak based on the methyl group of the second unit in the propylene unit 3 chain represented by PPP (rr) appears in the range of 19.5 to 20.3 ppm).

Here, the propylene homopolymer is a moiety containing a regio-irregular unit based on 2,1-insertion as shown in the above-mentioned structure (i) in addition to a regular structure in which propylene units are bonded head-to-tail. Has a small amount of structure.

In the disordered structure represented by the above structure (i), carbon A, carbon B and carbon C are the same as the above-mentioned PPP.
Does not meet the definition of (mm). However, carbon A and carbon B resonate in the region of 16.5 to 17.5 ppm, and carbon C resonates in the vicinity of 20.7 ppm (the region of PPP (mr)) (provided that it contains a position disorder unit). It is necessary to confirm the partial structure together with the confirmation of the peaks of the adjacent methylene group and methine group in addition to these methyl groups). Therefore, carbon A, carbon B and carbon C are PP
It is not included in the region of P (mm).

Therefore, the triad tacticity (mm fraction) of the propylene homopolymer can be obtained by the above formula. [Ratio of regio-irregular units based on 2,1-insertion of propylene monomer] During polymerization, propylene monomer is 1,2-inserted (the methylene side is bonded to the catalyst), but rarely 2,1-inserted. There is. Therefore, the propylene-based copolymer has the structure (i), (ii) and (iii) described above.
2,1-Has a positional irregular unit based on insertion. The proportion of the regio-irregular units based on the 2,1-insertion was determined from the following formula using ¹³ C-NMR.

[0140]

[Equation 3]

Here, the peaks were named according to the method of Carman et al. (Rubber Chem. Technol., 44 (1971), 781). In addition, Iαβ and the like indicate peak areas such as αβ peaks. The propylene homopolymer has regio-irregular units based on the 2,1-insertion as shown in the above structure (i).
The proportion of positional irregular units based on this 2,1-insertion is ¹³ C-
It was determined from the following formula using NMR.

[0142]

[Equation 4]

[Ratio of Positional Irregular Units Based on 1,3-Insertion of Propylene Monomer] In the propylene-based copolymer, the amount of three chains based on 1,3-insertion of propylene is at a βγ peak (around 27.4 ppm). Resonance).

In the propylene homopolymer,
The amount of 3 linkages based on 1,3-insertion is due to the αδ peak (37.1 p
Resonance around pm) and βγ peak (resonance around 27.4 ppm).

[0145]

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 is highly active and can produce a polyolefin having a narrow molecular weight distribution and composition distribution and a high molecular weight. A polyolefin obtained by polymerizing an olefin having 3 or more carbon atoms has high stereoregularity and a small proportion of positional irregular units, and is 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 of the present invention, a polymer having a high molecular weight 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 the polyolefin.

Further, when used in the production of a propylene block copolymer, it is possible to increase the molecular weight of the copolymer elastomer, so that it is excellent in the balance between heat resistance, rigidity or transparency and impact strength. Is obtained. Further, even when used in the production of polyethylene, a polyethylene having a high molecular weight can be obtained, and thus polyethylene having excellent mechanical strength such as impact strength, tensile strength and bending strength can be obtained.

[0149]

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]
The copolymer composition was measured as follows. [Intrinsic viscosity [η]] measured in decalin at 135 ° C, dl
/ G.

[Measurement Method of Copolymer Composition] The composition of the propylene copolymer was determined by utilizing ¹³ C-NMR.

[0152]

Example 1 Synthesis of rac-dimethylsilyl-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride [Synthesis of 3- (2-biphenylyl) -2-ethylpropionic acid] 500 ml -4 Potassium in a round neck flask (with stirrer, Dimroth condenser, dropping funnel, thermometer)
13.46 g (120 mmol) of -t-butoxide, 100 ml of toluene and 20 ml of N-methylpyrrolidone were added, and 20.7 g (110 mmol) of diethyl ethylmalonate was added to 50 ml of toluene while heating at 60 ° C in a nitrogen atmosphere.
The solution dissolved in was added dropwise. After the dropping was completed, the reaction was carried out at the same temperature for 1 hour. Next, at the same temperature, 2-phenylbenzyl bromide 2
A solution prepared by dissolving 0.27 g (100 mmol) in 30 ml of toluene was added dropwise. After the dropping was completed, the temperature was raised and the mixture was refluxed for 2 hours. The reaction mixture was poured into 200 ml of water, 2N-HC
1 was added to adjust the pH to 1. The organic phase was separated and the aqueous phase was extracted 3 times more with 100 ml of toluene. The combined organic phases were washed with saturated saline until neutral and dried over anhydrous Na ₂ SO ₄ . The solvent was concentrated under reduced pressure to obtain 36.7 g of a yellow orange liquid concentrate.

1-liter-4 neck round bottom flask (with stirrer, Dimroth condenser, dropping funnel, thermometer)
67.3 g (1.02 mol) of potassium hydroxide and 160 ml of an aqueous methanol solution (methanol / water = 4/1 (= v /
v)) was added. At room temperature, in a nitrogen atmosphere, the above concentrate was added with 50 ml of an aqueous methanol solution (methanol / water = 4/1 (=
The solution dissolved in v / v)) was added dropwise. After the dropping, the temperature was raised and the mixture was refluxed for 4 hours. Then, it cooled to room temperature and filtered the depositing solid. The residue was dissolved in water, acidified with sulfuric acid (pH = 1), and extracted with 100 ml of methylene chloride 5 times. The combined organic phases were dried over anhydrous Na ₂ SO ₄ . The solvent was concentrated under reduced pressure to give a white solid product 24.2
g was obtained.

Next, in a 300 ml-three-necked round bottom flask (with a stirrer tip, Dimroth condenser and thermometer), 24.2 g of the above white solid, 56 ml of acetic acid, and 37 of water were placed.
ml and conc.
Reflux for hours. After completion of the reaction, acetic acid was distilled off under reduced pressure, 50 ml of water was added, and the mixture was extracted 3 times with 50 ml of methylene chloride. The combined organic phase was washed with 50 ml of saturated saline and then dried over anhydrous Na ₂ SO ₄ . The solvent was distilled off under reduced pressure, and the residue was separated and purified by silica gel chromatography (hexane / ethyl acetate = 2/1 → developed by 1/1 volume part) to obtain a white solid 13.7 (yield: 54% ). The physical properties of the obtained product are shown below.

[0155]

[Chemical 15]

[Synthesis of 3- (2-biphenylyl) -2-ethylpropionyl chloride] 100 ml-3- (2-biphenylyl) in a 3-neck round bottom flask (with stirrer chip, Dimroth condenser, thermometer, NaOH trap) -2-
13.3 g (52.4 mmol) of ethyl propionic acid and 25.9 ml (355 mmol) of thionyl chloride were added, and the mixture was heated under reflux in a nitrogen atmosphere for 2.5 hours. After the reaction was completed, unreacted thionyl chloride was distilled under reduced pressure to obtain 15.2 g of a crude product as a yellow-orange liquid. This acid chloride was used for the next reaction without further purification. The physical properties of the obtained product are shown below.

IR (Neat): 1786 cm ⁻¹ (ν _{c = o} ) [Synthesis of 4-ethyl-2-phenyl-1-indanone] 200 m
l-3 necked round bottom flask (with stirrer tip, Dimroth condenser, dropping funnel, thermometer, NaOH trap) 8.04 g (60.3 mmol) of anhydrous aluminum chloride and 50 ml of carbon disulfide were added, and under ice cooling, A solution of 15.2 g (52.4 mmol) of 3- (2-biphenylyl) -2-ethylpropionyl chloride obtained above in 21 ml of carbon disulfide was added dropwise under a nitrogen atmosphere. After the dropping was completed, the internal temperature was raised to room temperature and the reaction was carried out for 1 hour. The reaction solution was poured into 200 ml of ice water to decompose, and 100 ml of ether was added.
It was extracted twice with. The combined organic phases were washed with 100 ml of saturated aqueous NaHCO ₃ solution, then 100 ml of saturated saline solution and dried over anhydrous Na ₂ SO ₄ . The solvent was distilled off under reduced pressure, and the residue was separated and purified by silica gel chromatography (developed with hexane / ethyl acetate = 10/1 by volume) to obtain 10.8 g of the desired product as a yellow solid (yield: 88%). . The physical properties of the obtained product are shown below.

[0158]

[Chemical 16]

[Synthesis of 2-ethyl-1-hydroxy-4-phenylindane] 200 ml-0.85 g of sodium borohydride in a three-necked round bottom flask (with stirrer tip, Dimroth condenser, dropping funnel and thermometer) 22.6
Mmol) and 28 ml of ethanol are added, and 10.6 g of 2-ethyl-4-phenyl-1-indanone at room temperature under a nitrogen atmosphere.
A solution of (45.1 mmol) dissolved in 20 ml of ethanol was added dropwise. After the dropping was completed, the temperature was raised to 50 ° C. and the reaction was further performed for 3.5 hours. After the reaction, the mixture was cooled, and unreacted sodium borohydride was added dropwise with acetone to decompose it.
Then, the reaction mixture was concentrated under reduced pressure, and 50 ml of water and 50 ml of ether were added for extraction. After separating the organic phase, the aqueous phase was extracted twice with 50 ml of ether. The combined organic phase was washed with 100 ml of saturated saline and dried over anhydrous Na ₂ SO ₄ . The solvent was distilled off under reduced pressure to obtain 10.67 g of a viscous pale yellow liquid target product (mixture of two isomers) (yield:
99%). The physical properties of the obtained product are shown below.

[0160]

[Chemical 17]

[Synthesis of 2-ethyl-4-phenylindene]
300 ml-4 neck round bottom flask (stirrer tip,
In a dropping funnel and a thermometer), 9.78 g (41.3 mmol) of 2-ethyl-1-hydroxy-4-phenylindane, 17.2 ml (123.8 mmol) of triethylamine, and 0.25 g of 4-dimethylaminopyridine ( 2.1 mmol) and 98 ml of methylene chloride were added. Under ice cooling, a solution of 6.4 ml (82.5 mmol) of methanesulfonyl chloride in 6.5 ml of methylene chloride was slowly added dropwise under a nitrogen atmosphere. After the dropping was completed, the reaction was continued for another 3.5 hours at the same temperature. After pouring the reaction mixture into 250 ml of ice water,
The organic phase was separated and the aqueous phase was extracted twice more with 50 ml methylene chloride. The combined organic phases are saturated NaHCO ₃ water,
Next, it was washed with saturated saline and dried over anhydrous Na ₂ SO ₄ . The solvent was distilled off under reduced pressure, and the residue was separated and purified by silica gel chromatography (developed with hexane) to give the desired product (mixture of two isomers) as a pale yellow liquid at 6.56.
g was obtained (yield: 73%). The physical properties of the obtained product are shown below.

NMR (CDCl ₃ , 90 MHz): δ = 1.20 (t, J = 7.6 Hz, 3H, CH ₃ );
2.49 (q, J = 7.6 Hz, 2H); 3.41 (s, 2H); 6.61, 6.72 (bs each, 1H in total); 7.09 to 8.01 (m, 8H) [Synthesis of dimethylsilyl-bis (2-ethyl-4-phenylindene)] 2-ethyl-4-phenyl in a 200 ml-three neck round bottom flask (with stirrer tip, Dimroth condenser, dropping funnel, thermometer) Indene 5.0g (2
2.8 mmol), copper thiocyanate 80 mg (0.63 mmol) and anhydrous ether 50 ml were added, and 15.7 ml (25.1 mmol) of a 1.6 M concentration n-butyllithium hexane solution under ice-cooling in a nitrogen atmosphere. ) Was slowly added dropwise. After completion of the dropping, the temperature was raised to room temperature and the reaction was further performed for 1 hour. Next, 1.52 ml of dimethyldichlorosilane
A solution of (12.6 mmol) in 4.5 ml of anhydrous ether was slowly added dropwise. After the dropping was completed, the reaction was continued at room temperature for 12 hours. The reaction mixture was filtered through Celite, and the filtrate was poured into 50 ml of saturated aqueous ammonium chloride solution.
After separating the organic phase, the aqueous phase was extracted with 50 ml of ether.
The combined organic phase was washed with saturated brine and dried over anhydrous Na ₂ SO ₄
Dried in. The solvent was distilled off under reduced pressure, and the residue was separated by silica gel column chromatography (developed with hexane → hexane / methylene chloride = 20/1 by volume) to give a pale yellow solid of the target product (a mixture of two isomers). 4.5 g was obtained (80% yield). The physical properties of the obtained product are shown below.

[0163]

[Chemical 18]

[Rac-dimethylsilyl-bis {1- (2-ethyl
-4-Phenylindenyl)} zirconium-dichloride synthesis] 50 ml-in a three-necked round bottom flask (with stirrer chip, ball condenser, dropping funnel, thermometer) dimethylsilyl-bis (2-ethyl-) under argon atmosphere 4-Phenylindene) (0.84 g, 1.69 mmol) and anhydrous ether (17 ml) were added, and 2.25 ml (3.56 mmol) of a hexane solution of n-butyllithium having a concentration of 1.58 M was slowly added dropwise at room temperature. After the dropping, the reaction was further performed for 13.5 hours. The obtained reaction liquid was cooled to −70 ° C. in a dry ice-acetone bath, and 0.395 g of ZrCl ₄ (1.
69 mmol) of powder was added slowly. After the addition is complete
While stirring was continued, it was left overnight. Then the solvent was distilled off under reduced pressure at room temperature. After adding 30 ml of methylene chloride,
The insoluble matter was filtered off, and the filtrate was concentrated and crystallized at room temperature. The precipitated solid was filtered and then washed twice with 3 ml of anhydrous ether,
It was dried under reduced pressure to give the desired product as an orange-yellow solid 0.17.
g was obtained (yield: 15%). The physical properties of the obtained product are shown below.

NMR (CDCl ₃ , 90 MHz): δ = 1.09 (t, J = 7.3 Hz, 6H, CH ₃ ); 1.34 (s, 6H, Si-CH ₃ ); 2.46 (quin) , J = 7.3 Hz, 2H); 2.73 (quin, J = 7.3 Hz, 2H); 6.96 (s, 2H, 3-H-Ind); 6.99 to 7.88 (m, 16H)

[0166]

Example 2 1.7 liters of toluene was placed in a gas flow type glass polymerization vessel having an internal volume of 2 liters, which had been sufficiently replaced with nitrogen, cooled to -30 ° C., and 100 liters of propylene /
The system was sufficiently saturated with hydrogen and hydrogen at a flow rate of 10 l / hr. Then triisobutylaluminum was added to 4.
25 mmol, 8.5 mmol of methylaluminoxane converted to Al atom, rac-dimethylsilyl-bis {1- (2
-Ethyl-4-phenylindenyl)} zirconium dichloride was added in an amount of 0.017 mmol in terms of Zr atom, and polymerization was carried out for 45 minutes while maintaining the system at -30 ° C. The polymerization was stopped by adding a small amount of methanol. The polymerization suspension was added to 3 liters of methanol to which a small amount of hydrochloric acid was added, and the mixture was sufficiently stirred and filtered. The polymer was washed with a large amount of methanol and dried at 80 ° C. for 10 hours.

The amount of the polymer obtained was 51.3 g, and the polymerization activity was 4.02 kgPP / mmol Zr · hr. [Η] is 3.37 dl / g, Mw / Mn is 2.22, and triad tacticity is 99.7%.
The proportion of regio irregular units based on 2,1-insertion of propylene monomer was 0.10%, and the proportion of regio irregular units based on 1,3-insertion of propylene monomer was less than the lower limit of detection (0. Was less than 03).

[0168]

Example 3 In Example 2, propylene was 100 liters / hr, hydrogen was 2 liters / hr, triisobutylaluminum was 0.65 mmol, methylaluminoxane was converted to Al atoms to be 1.3 mmol, and rac-dimethylsilyl. -Bis {1- (2-ethyl-4-phenylindenyl)}
Zirconium dichloride converted to Zr atom is 0.00
Polymerization was carried out in the same manner as in Example 2 except that 26 mmol was added and the system was kept at 0 ° C. The polymer obtained was 60.
7 g, polymerization activity is 31.1 kg PP / mmol Z
Corresponds to r · hr. [Η] is 3.01 dl / g, Mw / Mn is 2.18, triad tacticity is 99.5%, and the propylene monomer 2,1-
The proportion of positional disordered units based on insertion was 0.15%, and the proportion of positional disordered units based on 1,3-insertion of propylene monomer was below the detection limit (less than 0.03).

[0169]

Comparative Example 1 As a transition metal compound catalyst component, rac-dimethylsilyl-bis {1- (2- (2- (2-ethyl-4-phenylindenyl)) zirconium dichloride was used instead of rac-dimethylsilyl-bis {1- (2- Methyl-4-phenylindenyl)}
Polymerization was performed in the same manner as in Example 3 except that zirconium dichloride was used.

The amount of the polymer obtained was 4.7 g, and the polymerization activity was 2.4 kg PP / mmol Zr · hr. [Η] is 4.05 dl / g and Mw / Mn is 2.
18, the triad tacticity is 98.6%, the proportion of regio-irregular units based on the 2,1-insertion of the propylene monomer is 0.33%, based on the 1,3-insertion of the propylene monomer. The ratio of positional irregular units was below the detection limit (less than 0.03).

[0171]

Example 4 250 ml of toluene was placed in a gas flow type glass polymerization vessel having an internal volume of 500 ml, which had been sufficiently replaced with nitrogen, and cooled to 0 ° C., and 160 liter / h of propylene was added.
r and ethylene were circulated at 40 liters / hr to fully saturate the system. Next, 0.25 mmol of triisobutylaluminum, 0.5 mmol of methylaluminoxane converted into Al atoms, and rac-dimethylsilyl-bis {1
-(2-Ethyl-4-phenylindenyl)} zirconium dichloride was added in an amount of 0.001 mmol in terms of Zr atom, and polymerization was carried out for 10 minutes while keeping the system at 0 ° C. The polymerization was stopped by adding a small amount of methanol. The polymerization suspension was added to 2 liters of methanol containing a small amount of hydrochloric acid, stirred sufficiently, and filtered. The polymer was washed with a large amount of methanol and dried at 80 ° C. for 10 hours.

The amount of the polymer obtained was 5.62 g, and the polymerization activity corresponded to 33.7 kg polymer / mmol Zr · hr. The ethylene content is 3.9 mol% and [η]
Is 1.80 dl / g, Mw / Mn is 2.15, triad tacticity is 99.3%, and the proportion of regiorandom units based on the 2,1-insertion of the propylene monomer is 0. 12%, and the proportion of regio-irregular units based on 1,3-insertion of propylene monomer was below the lower limit of detection (0.
Was less than 03).

[0173]

Example 5 Polymerization was carried out in the same manner as in Example 4 except that propylene was 140 liters / hr and ethylene was 60 liters / hr. The obtained polymerization solution was put into 2 liters of methanol containing a small amount of hydrochloric acid to precipitate a polymer. After sufficiently removing methanol, it was dried at 130 ° C. for 10 hours.

The amount of the polymer obtained was 6.63 g, and the polymerization activity corresponded to 39.8 kg polymer / mmol Zr · hr. Ethylene content is 8.7 mol%, [η]
Is 1.66 dl / g, Mw / Mn is 2.46, triad tacticity is 99.2%, and the proportion of regio-irregular units based on the 2,1-insertion of the propylene monomer is 0. 12%, and the proportion of regio-irregular units based on 1,3-insertion of propylene monomer was below the lower limit of detection (0.
Was less than 03).

[0175]

Example 6 Polymerization was carried out in the same manner as in Example 4 except that propylene was 100 liters / hr and ethylene was 100 liters / hr. The obtained polymerization solution was put into 2 liters of methanol containing a small amount of hydrochloric acid to precipitate a polymer. . After sufficiently removing methanol, it was dried at 130 ° C. for 10 hours.

The amount of the polymer obtained was 8.95 g, and the polymerization activity was equivalent to 53.7 kg polymer / mmol Zr · hr. The ethylene content is 28.9 mol%, [η] is 1.34 dl / g, Mw / Mn is 1.95,
The triad tacticity is 98.5%, the proportion of regio irregular units based on the 2,1-insertion of the propylene monomer is 0.09%, and the regio irregular unit based on the 1,3-insertion of the propylene monomer. Is less than the lower limit of detection (0.03
Was less than).

[0177]

Example 7 Synthesis of rac-dimethylsilyl-bis {1- (2-ethyl-4- (1-naphthyl) indenyl)} zirconium dichloride [of 3- (2-bromophenylyl) -2-ethylpropionic acid Synthesis] 2 liters-a 4-neck round bottom flask (with a stirrer, Dimroth condenser, dropping funnel, and thermometer) was added with potassium-t-butoxide 44.2 g (394 mmol), toluene 392 ml, N-methylpyrrolidone 30 ml, While heating to 60 ° C. in a nitrogen atmosphere, diethyl ethyl malonate 61.2 g (325 mmol) was added to toluene 61 ml.
The solution dissolved in was added dropwise. After the dropping was completed, the reaction was carried out at the same temperature for 1 hour. Next, at the same temperature, 2-bromobenzyl bromide 7
A solution of 5.4 g (302 mmol) in 75 ml of toluene was added dropwise. After the dropping was completed, the temperature was raised and the mixture was refluxed for 5 hours. The reaction mixture was poured into 300 ml of water and a 10% aqueous sulfuric acid solution was added to adjust the pH to 1. The organic phase was separated and the aqueous phase was extracted 3 times more with 100 ml of ether. The combined organic phase was saturated sodium bicarbonate water 200 ml, then saturated saline water 150 m.
It was washed 3 times with 1 L and dried over anhydrous Na ₂ SO ₄ . The solvent was concentrated under reduced pressure to obtain 111.1 g of a yellow liquid concentrate.

2 liter-4 neck round bottom flask (stirrer,
195 g (2.96 mol) of potassium hydroxide and 585 ml of methanol aqueous solution (methanol / water = 4/1 (= v /
v)) was added. The above concentrate was added dropwise at room temperature in a nitrogen atmosphere. After the dropping, the temperature was raised and the mixture was refluxed for 3 hours. afterwards,
It cooled to room temperature and filtered the white solid which precipitated. The filtrate was concentrated and then cooled to obtain a secondary crystal. Further, a tertiary crystal was obtained in the same manner. After slurrying the combined filter cake with hexane,
After drying, 101.5 g of white powder was obtained. The white powder obtained was dissolved in 400 ml of water, and a 50% sulfuric acid aqueous solution was added to make the solution acidic (pH = 1).
Extracted twice. The combined organic phases were dried over anhydrous Na ₂ SO ₄ . The solvent was concentrated under reduced pressure to give 74.2 g of a hard white solid.
Got

Next, 300 ml-3 neck round bottom flask (with stirrer tip, Dimroth condenser, thermometer)
The above white solid was added to, and the oil bath temperature was 200 ° C in a nitrogen atmosphere.
The mixture was heated and reacted for 5 hours. After the reaction, the product was cooled to room temperature to obtain 61.2 as a pale yellowish white solid (yield: 79).
%). The physical properties of the obtained product are shown below.

FD-MS: 256 (M ⁺ ), 2
58 (M ⁺ +2) NMR (CDCl ₃ , 90 MHz): δ = 1.0 (t, J = 7.0 Hz, 3H, CH ₃ ); 1.40 to 1.85 (m, 2H); 2.53 -3.12 (m, 3H); 6.88, 7.66 (m, 3H); [Synthesis of 3- (2-bromophenyl) -2-ethylpropionyl chloride] 300 ml-3 neck round bottom flask (stirrer) Chip, Dimroth condenser, thermometer, NaOH
(With trap), 60.86 g (237 mmol) of 3- (2-bromophenyl) -2-ethylpropionic acid and benzene 4
0 ml and thionyl chloride (120 ml) were added, and the mixture was heated under reflux in a nitrogen atmosphere for 1.5 hours. After completion of the reaction, unreacted thionyl chloride was distilled under reduced pressure to obtain a yellow liquid crude product. This acid chloride was used for the next reaction without further purification.

[Synthesis of 4-bromo-2-ethyl-1-indanone] 1 liter-3 neck round bottom flask (stirrer chip, Dimroth condenser, dropping funnel, thermometer, N
36.3 g of anhydrous aluminum chloride in aOH trap)
(272 mmol) and 280 ml of carbon disulfide were added, and 3- (2-bromophenyl) -2-ethylpropionyl chloride (237 mmol equivalent) obtained above was dissolved in 50 ml of carbon disulfide in a nitrogen atmosphere under ice cooling. The resulting solution was added dropwise. After the dropping was completed, the internal temperature was raised to room temperature and the reaction was carried out for 1 hour. The reaction solution was poured into 1 liter of ice water to decompose, and extracted with 300 ml of ether twice. Saturate the combined organic phases with N
washed with aHCO ₃ water, then saturated brine, dried over anhydrous Na ₂ S
Dry with O ₄ . The solvent was distilled off under reduced pressure to obtain 56.9 g of a reddish brown liquid having a slightly high viscosity. This ketone was used in the next reaction without further purification.

[Synthesis of 4-bromo-2-ethyl-1-trimethylsilyloxyindane] 4.97 g of sodium borohydride in a 500 ml-3 neck round bottom flask (with stirrer chip, Dimroth condenser, dropping funnel and thermometer)
(118 mmol) and 200 ml of ethanol were added,
4-Bromo-2-ethyl-1-indanone 5 at room temperature under nitrogen atmosphere
A solution prepared by dissolving 6.93 g (corresponding to 236 mmol) in 85 ml of ethanol was added dropwise. After completion of dropping, the reaction was continued for 4 hours. After the reaction, the mixture was cooled, and unreacted sodium borohydride was decomposed by dropping 35 ml of acetone.
Next, the reaction mixture was concentrated under reduced pressure, and 300 ml of water and 300 ml of ether were added for extraction. After separating the organic phase, the aqueous phase was extracted 3 times with 100 ml of ether. The combined organic phase was washed 3 times with 150 ml of saturated saline and dried over anhydrous Na ₂ SO.
Dried at ₄ . The solvent was distilled off under reduced pressure to obtain 58.92 g of a skin-colored solid substance (mixture of two isomers).

Next, in a 500 ml-4 neck round bottom flask (with a stirrer chip, a Dimroth condenser, a dropping funnel and a thermometer), 58.91 g (244 mmol equivalent) of the solid matter and 43.3 ml (307 ml) of triethylamine were added.
Mmol) and 280 ml of methylene chloride. Me ₃ SiCl 37.2 ml (29
A solution of 3 mmol) in methylene chloride (15 ml) was slowly added dropwise. After the dropping is completed, the temperature is raised to room temperature and further 3.5
Reacted for hours. After pouring 100 ml of water into the reaction mixture, the organic phase was separated and the aqueous phase was extracted twice more with 100 ml of methylene chloride. The combined organic phases were washed 3 times with 100 ml of water and dried over anhydrous Na ₂ SO ₄ . The solvent was distilled off under reduced pressure, and the residue was distilled under reduced pressure to obtain 69.9 g of the desired product (mixture of two isomers) as a colorless liquid (from 3- (2-bromophenyl) -2-ethylpropionic acid). Total yield of: 95%). The physical properties of the obtained product are shown below.

Mp. 133-135 ° C / 2 mmHg FD-MS: 312 (M ⁺ ), 314 (M ⁺
+2) NMR (CDCl ₃ , 90 Hz): δ = 0.17, 0.24 (s respectively, 9H, S in total)
_{i-CH 3); 0.79~1.12 (} m, 3H); 1.16~3.31 (m, 5H); 4.82,5.10 ( each bd, each J = 6.4
Hz, 1H in total, —CH—O—); 6.91 to 7.46 (m, 3H) [Synthesis of 2-ethyl-4- (1-naphthyl) phenylindene] 300 ml-3 neck round bottom flask ( (With stirrer chip, Dimroth condenser, dropping funnel, thermometer)
4-bromo-2-ethyl-1-trimethylsilyloxyindane 11.4 g (36.4 mmol), PdCl ₂ (see
f) 0.13 g (0.18 mmol) and 35 ml anhydrous ether were added. 0.72M at room temperature under nitrogen atmosphere
101 ml (72.8 mmol) of a concentrated solution of 1-naphthylmagnesium bromide in ether / benzene was slowly added dropwise. After the dropping was completed, the reaction was further performed for 1 hour. Next, the internal temperature was raised to 50 to 51 ° C. and the reaction was carried out for 5 hours. After completion of the reaction, while cooling with ice, 135 ml of a 5N aqueous hydrochloric acid solution was slowly added to decompose excess Grignard reagent, and ether 1 was added.
Extracted twice with 00 ml. The combined organic phases were washed successively with saturated aqueous sodium hydrogen carbonate and saturated brine and dried over anhydrous Na ₂ SO ₄ . The solvent was distilled off under reduced pressure to obtain 20.5 g of a reddish brown liquid.

Next, the reddish brown liquid was diluted with 20 ml of tetrahydrofuran, 5 ml of 12% aqueous hydrochloric acid was added, and the mixture was reacted overnight at room temperature. After completion of the reaction, 100 ml of ether
Was added to separate oil and water. The organic phase was washed with saturated aqueous sodium hydrogen carbonate and saturated brine in this order, and dried over anhydrous Na ₂ SO ₄ . The solvent was distilled off under reduced pressure, and the resulting reddish brown liquid residue was subjected to silica gel chromatography (silica gel 60, 7 manufactured by MERCK).
Separation and purification with 0-230 mesh, hexane → developed with hexane / ethyl acetate = 1/3 volume part) gave 9.0 g of the desired product (mixture of two isomers) as a yellow solid (yield: 98%). ). The physical properties of the obtained product are shown below.

FD-MS: 270 (M ⁺ ) NMR (CDCl ₃ , 90 MHz): δ = 1.20 (t, J = 7.4 Hz, 3H, CH ₃ ); 2.38 (bq, J = 7. 4.02, 2H); 3.02, 3.42 (s respectively, 2H in total); 6.54 (bs, 1H); 6.19 to 8.12 (m, 10H) [dimethylsilyl-bis {1- (Synthesis of 2-ethyl-4- (1-naphthyl) indene)}] 200 ml-3 neck round bottom flask (with stirrer chip, Dimroth condenser, dropping funnel, thermometer), 2-ethyl-4- (1-naphthyl) ) Indene 4.97 g (18.4 mmol), copper cyanide 50 m
g (0.51 mmol) and 53 ml of anhydrous ether were added, 1.58 with cooling to -10 ° C under a nitrogen atmosphere.
M-concentration n-butyllithium hexane solution 12.8 ml
(20.2 mmol) was slowly added dropwise. After completion of the dropping, the temperature was raised to room temperature and the reaction was further continued for 4 hours. Then, a solution of 1.24 ml (10.1 mmol) of dimethyldichlorosilane dissolved in 5 ml of anhydrous ether was slowly added dropwise. After the dropping was completed, the reaction was continued at room temperature for 15 hours. The reaction mixture was poured into 50 ml of saturated aqueous ammonium chloride solution, filtered through Celite, the filtrate was separated into oil and water, and the aqueous phase was extracted with 50 ml of ether. The combined organic phase was washed with saturated brine and dried over anhydrous Na ₂ SO ₄ . The solvent was distilled off under reduced pressure, and the reddish brown viscous liquid residue was separated by silica gel column chromatography (developed with hexane) to obtain 3.2 g of a target product (a mixture of two isomers) as a yellow solid. (Yield: 58%). The physical properties of the obtained product are shown below.

FD-MS: 596 (M ⁺ ) NMR (CDCl ₃ , 90 MHz): δ = −0.20, −0.20 (s respectively, 6 in total)
_{H, Si-CH 3);} 0.82~1.41 (m, 6H, CH 3); 2.23~2.74 (m, 4H); 3.84~4.10 (m, 2H, - 6.20, 6.30 (bd, 2H respectively) 6.98-8.14 (m, 20H) [rac-dimethylsilyl-bis {1- (2-ethyl-4- (1- Synthesis of Naphthyl) indenyl)} Zirconium Dichloride]
2.0 g (3.0 ml) of dimethylsilyl-bis (2-ethyl-4- (1-naphthyl) indene) in an argon atmosphere in a 100-ml 3-neck round bottom flask (with a stirrer tip, a condenser with a ball, a dropping funnel, and a thermometer). (36 mmol) and 40 ml of anhydrous ether were added, and 4.58 ml (7.06 mmol) of a hexane solution of n-butyllithium having a concentration of 1.54 M was slowly added dropwise at room temperature. After the dropping, the reaction was further performed for 17.5 hours. The obtained reaction solution was cooled to −75 ° C. in a dry ice-acetone bath, and 0.83 g (3.5%) of ZrCl _{4 was used.}
6 mmol) of powder was added slowly. After the addition was completed, the mixture was left overnight while continuing stirring.

The red-yellow reaction slurry obtained is filtered,
The residue was washed with 45 ml of anhydrous ether. After adding 60 ml of methylene chloride and 40 ml of anhydrous ether to the residue, the insoluble matter was filtered off, and the filtrate was concentrated to dryness at room temperature. 15 ml of methylene chloride was added to the obtained yellow dry solid to dissolve it, and then about 1
Concentrated to / 3. Next, 2 ml of anhydrous ether was added for crystallization. After filtering the precipitated solid, 2m of anhydrous ether
It was washed with l and dried under reduced pressure to obtain 0.12 g of the desired product as a yellow-orange powder (yield: 5%).

The physical properties of the obtained product are shown below. NMR (CDCl ₃ , 90 MHz): δ = 1.04 (t, J = 7.4 Hz, 6H, CH ₃ ); 1.38 (s, 6H, Si-CH ₃ ); 2.12-3.02 ( m, 4H); 6.53 (s, 2H, 3-H-Ind); 6.86-8.02 (m, 20H)

[0190]

Example 8 As a transition metal compound catalyst component, rac-dimethylsilyl-bis {1- (2-ethyl) was used instead of rac-dimethylsilyl-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride. Example 3 except that 4- (1-naphthyl) indenyl)} zirconium dichloride was used.
Polymerization was carried out in the same manner as in.

The amount of the polymer obtained was 20.2 g, and the polymerization activity was equivalent to 10.4 kg-PP / mmol Zr · hr. [Η] is 3.08 dl / g, and Mw / Mn
Is 2.09 and Triad Tacticity is 99.7
%, The proportion of regio irregular units based on 2,1-insertion of propylene monomer was 0.12%, and the proportion of regio irregular units based on 1,3-insertion of propylene monomer was below the detection limit (0 Was less than 0.03).

[0192]

Example 9 As a transition metal compound catalyst component, rac-dimethylsilyl-bis {1- (2-ethyl) was substituted for rac-dimethylsilyl-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride. Example 5 except that 4- (1-naphthyl) indenyl)} zirconium dichloride was used.
Polymerization was carried out in the same manner as in.

The amount of the polymer obtained was 2.08 g, and the polymerization activity was 12.5 kg-polymer / mmol Zr · hr.
Equivalent to. The ethylene content is 7.9 mol%,
[Η] is 1.39 dl / g and Mw / Mn is 2.33.
And the triad tacticity is 99.2%, the proportion of regio-irregular units based on the 2,1-insertion of the propylene monomer is 0.10%,
The proportion of regio-irregular units based on 1,3-insertion was below the lower limit of detection (<0.03).

[0194]

Example 10 Synthesis of rac-dimethylsilyl-bis {1- (2-n-propyl-4- (1-naphthyl) indenyl)} zirconium dichloride [3- (2-bromophenyl) -2-n-propyl Synthesis of Propionic Acid] 1 liter-a 4-neck round bottom flask (with a stirrer, Dimroth condenser, dropping funnel and thermometer), 37 g (330 mmol) of potassium t-butoxide, 32 ml (334 mmol) of N-methylpyrrolidone, Toluene 4
00 ml was added, and 60.7 g (300 mmol) of diethyl n-propylmalonate was added to toluene 5 while stirring in an ice bath.
A solution dissolved in 0 ml was added dropwise (dropping time: 30 minutes,
Reaction temperature 5-10 ° C). After the completion of dropping, the mixture was stirred at 45 ° C for 30 minutes and further at 65 ° C for 1 hour. The obtained solution became a cream-colored hetero state immediately after the start of heating.

Then, in an ice bath, a solution of 75 g (300 mmol) of 2-bromobenzyl bromide in 50 ml of toluene was added dropwise (dropping time: 30 minutes, reaction temperature 5 to 5).
15 ° C). After the dropping was completed, the reaction was carried out at 65 ° C. for 30 minutes, the temperature was further raised, and the mixture was refluxed for 1 hour. The color of the reaction gradually changed to gray. After allowing to cool, pour the reaction product into 500 ml of water,
The pH was adjusted to 1 by adding a 10% aqueous sulfuric acid solution. The organic phase was separated and the aqueous phase was extracted 5 times more with 100 ml of toluene and the organic phases were combined. The combined organic phase was saturated saline solution 200.
It was washed 4 times with ml and dried over anhydrous MgSO ₄ . The solvent was distilled off to obtain 114 g of a dark brown liquid concentrate.

2 liters-4 neck round bottom flask (with stirrer, Dimroth condenser, dropping funnel, thermometer)
Add the above concentrate and 200 ml of methanol to and stir,
237 g of potassium hydroxide (85% content, 3.59 mol)
Was added to a solution of 520 ml of methanol and 180 ml of water. Then place the flask in a 90 ° C. oil bath,
After refluxing for 5 hours, most of the methanol was distilled off with an evaporator, and 500 ml of water was added to make a uniform solution.
Under ice-cooling, 10% sulfuric acid aqueous solution was added to adjust the pH to 1, and the precipitated white solid was filtered off. Then, the organic phase of the filtrate was separated, the aqueous phase was extracted 6 times with 200 ml of ether, and the organic phases were combined and dried over anhydrous MgSO ₄ . The solvent was distilled off to obtain 94 g of a yellowish white semisolid.

Next, the above semi-solid was placed in a 1-liter round bottom flask and heated at an oil bath temperature of 180 ° C. for 10 minutes. After heating, cool the target product to a brown transparent liquid 7
8.0 g was obtained (yield: 96%). The physical properties of the obtained product are shown below.

FD-MS: 270 (M ⁺ ), 272 (M ⁺ +2) NMR (CDCl ₃ , 90 MHz): δ = 0.95 (t, J = 7.0 Hz, 3H, CH ₃ ); 1.10. -2.00 (m, 4H); 2.60-3.25 (m, 3H); 6.90-7.80 (m, 4H); [3- (Bromophenyl) -2-n-propylpropionyl Chloride synthesis] 500 ml-3 neck round bottom flask (stirrer tip, Dimroth condenser, thermometer, Na
(With OH trap), 277 mmol of 3- (2-bromophenyl) -2-n-propylpropionic acid and 200 thionyl chloride
ml was added, and the mixture was heated under reflux for 2 hours. Next, thionyl chloride is distilled off by simple distillation, and then vacuum distillation is performed to obtain a boiling point of 13
77.4 g of a crude product of a light brown transparent liquid having a temperature of 0 to 135 ° C./1 mmHg was obtained. This acid chloride was used for the next reaction without further purification.

Of 4-bromo-2-n-propyl-1-indanone
Synthesis] 1 liter-4 neck round bottom flask (Starrarch
Up, Dimroth condenser, dripping funnel, thermometer,
Anhydrous aluminum chloride 74.5 with NaOH trap)
g (559 mmol) and 400 ml of carbon disulfide were added,
Under ice cooling, the acid chloride obtained above was treated with 100 carbon disulfide.
The solution dissolved in ml was slowly added dropwise. After the dropping is completed,
The reaction was continued for 3 hours under ice cooling. Next, add the reaction solution to ice.
Pour into 600 ml of water, separate the organic phase and wash the aqueous phase with ether.
200 ml of four extractions and the organic phases were combined. Match
The organic phase was washed 4 times with 300 ml of saturated aqueous sodium hydrogen carbonate and then dried.
MgSO _FourAnd the solvent was distilled off to give a brown liquid 66.
Got 7. This ketone was used in the next reaction without further purification.
Used for.

[Synthesis of 4-bromo-2-n-propyl-1-trimethylsilyloxyindane] 1 liter-4 neck round bottom flask (stirrer tip, Dimroth condenser,
Sodium borohydride on the dropping funnel and thermometer) 4.
96 g (131 mmol) and 300 ml of ethanol were added, and the 4-bromo-2-n-propyl-1-obtained above was cooled under ice cooling.
A solution of indanone dissolved in 200 ml of ethanol was added dropwise. After the dropping was completed, the reaction was continued at room temperature for 3 hours. After the reaction, 200 ml of ice water was added, and most of the methanol was distilled off with an evaporator. The residue is ether 300
Transfer to a separatory funnel using ml and separate the organic phase,
The aqueous phase was extracted 3 times with 200 ml of ether and the organic phases were combined. The combined organic phases were dried over anhydrous MgSO ₄ and the solvent was distilled off to obtain 66.50 g of a yellowish white powder.

Next, in a 1 liter-4 neck round bottom flask
Yellow-white powder obtained above, 200 ml of ether,
Add 47 ml (337 mmol) of triethylamine,
Under ice cooling, 39 ml of trimethylsilyl chloride (307 ml
Limol) dissolved in 50 ml ether slowly
Dropped. After reacting for 7 hours, the reaction product is saturated sodium bicarbonate water 400 m
The organic phase is separated and the aqueous phase is washed with 200 m of ether.
Extracted 3 times with 1 and combined the organic phases. The combined organic phases
Washed with 400 ml of saturated saline solution, anhydrous MgSO _FourDried in
After that, the solvent was distilled off to obtain a yellowish brown liquid. this
Distilled under reduced pressure and boiling point is 120-125 ℃ / 2mmHg
76.00 g of a target substance was obtained as a pale yellowish white transparent liquid.
3- (2-bromophenyl) -2-n-propylpropionic acid
The total yield was 81%.

[Synthesis of 2-n-propyl-4- (1-naphthyl) indene] 300 ml-in a 4-neck round bottom flask (with stirrer tip, dropping funnel, thermometer), 4-bromo-2-n-propyl -1-Trimethylsilyloxyindane 10 g (3
0.5 mmol), 50 ml of anhydrous ether, PdCl ₂
(Dppf) 112 mg (0.153 mmol) was added, and at room temperature, 85 ml (61 mmol) of a 0.72 M concentration solution of 1-naphthylmagnesium bromide in ether / benzene was slowly added dropwise. Next, the internal temperature was raised to 48 ° C., the mixture was refluxed for 4 hours, then the reaction product was poured into 300 ml of a saturated aqueous ammonium chloride solution, and extracted with 200 ml of ether four times. After washing the organic phase with saturated saline, anhydrous MgS
Dry with O ₄ . The solvent was distilled off to obtain 17.83 g of a yellowish brown semisolid.

300 ml-In a three-necked round bottom flask, the above yellow-brown semisolid and 50 ml of ether were placed, and at room temperature,
After 60 ml of 5N hydrochloric acid aqueous solution was added dropwise, the mixture was vigorously stirred. After 2 hours, the mixture was transferred to a separating funnel and extracted three times with 50 ml of ether. The organic phases were combined, washed twice with 100 ml of saturated aqueous sodium hydrogen carbonate, and dried over anhydrous MgSO ₄ . The brown semisolid obtained by distilling off the solvent was subjected to silica gel chromatography (hexane: ethyl acetate = 50: 1-50:
The product was purified in 5) to obtain 8.40 g of yellowish white powder.

Next, a yellow-white powder obtained above and 80 m of anhydrous methylene chloride were placed in a 200 ml-four-necked flask.
1, triethylamine 11.3 ml (81 mmol),
165 ml (1.35 mmol) of 4-dimethylaminopyridine was added, and methanesulfonyl chloride 4.2 was added under ice cooling.
ml (54.3 mmol) to 20 ml of anhydrous methylene chloride
The solution dissolved in was slowly added dropwise. After completion of the dropping, the temperature was raised to room temperature and the reaction was carried out overnight.
It was poured into 100 ml and extracted three times with 100 ml of methylene chloride.
The extracted organic phases were combined, washed 3 times with 100 ml of saturated aqueous sodium hydrogen carbonate, and dried over anhydrous MgSO ₄ . The brown liquid obtained by removing the solvent was subjected to silica gel chromatography (silica gel 200 g, hexane: ethyl acetate = 50:
Purification in 1) yielded 6.51 g of the desired product as a white solid (yield: 75%). The physical properties of the obtained product are shown below.

NMR (CDCl ₃ , 90 MHz): δ = 0.91 (t, J = 7.0 Hz, 3H, CH ₃ ); 1.53 (m, 2H); 2.40 (t, J = 7. 0 Hz, 2H); 3.04, 3.41 (s respectively, 2H in total); 6.60 (s, 1H); 7.00-8.0 (m, 10H) [dimethylsilyl-bis {1- Synthesis of (2-n-propyl-4- (1-naphthyl) indene)}] 200 ml-4 neck round bottom flask (stirrer chip, Dimroth condenser,
To the dropping funnel with a thermometer, 6.27 g (22.0 mmol) of 2-n-propyl-4- (1-naphthyl) indene, 120 ml of anhydrous ether, and 60 mg of copper cyanide were added, and cooled under ice cooling to 1.63M. 15 ml (24.5 mmol) of a hexane solution of n-butyllithium having a concentration was added dropwise. After completion of the dropwise addition, the mixture was refluxed for 30 minutes, and then 1.5 ml (12.4 mmol) of dimethyldichlorosilane was added to anhydrous ether 5 under ice cooling.
The solution dissolved in ml was slowly added dropwise. After the dropping is completed,
The reaction was carried out overnight at room temperature, then the reaction mixture was poured into saturated aqueous ammonium chloride solution. After natural filtration, the organic phase of the filtrate was separated, the aqueous phase was extracted twice with 50 ml of ether, and the organic phases were combined. The combined organic phase is 100 ml of saturated saline.
It was washed twice with and dried over anhydrous MgSO ₄ . The yellow oil obtained by distilling off the solvent was subjected to silica gel chromatography (silica gel 200 g, hexane: ethyl acetate = 5).
0: 1), and the target product as a yellowish white powder.
80 g was obtained (yield: 84%). The physical properties of the obtained product are shown below.

NMR (CDCl₃, 90 MHz): δ = −0.20, −0.17 (s respectively, 6 in total)
H, Si-CH ₃); 0.64 to 2.70 (m, 14H); 3.80 to 4.10 (m, 2H, -CH-Si); 6.25, 6.34 (6d, 2H respectively); 7.20 ~ 8.20 (m, 20H) [rac-dimethylsilyl-bis {1- (2-n-propyl-4- (1-
Naphthyl) indenyl)} zirconium dichloride
100 ml-4 neck round bottom flask (Stirrer chip)
With a ball, condenser with a ball, a dropping funnel, and a thermometer)
Cylsilyl-bis {1- (2-n-propyl-4- (1-naphthyl)
Indene)} 2.5 g (4.00 mmol) and anhydrous ac
Add 50 ml of tell and add 1.63M n-butyrate in water bath.
5.15 ml (8.40 mm) of hexane solution of rulithium
Mol) was slowly added dropwise. After dropping, stir overnight at room temperature
Then at -78 ° C ZrCl_Four1.00 g (4.29 mm
Mol) was added slowly. Overnight after addition
The temperature rose naturally. The obtained orange reaction slurry
Filter and filter the residue with anhydrous ether (40 ml).
It was washed with 40 ml of water. Insoluble matter deposited from the filtrate is filtered
The filtrate obtained here was concentrated to about 1/3 and deposited.
Add 10 ml of methylene chloride to the powder to redissolve it, then
20 ml of anhydrous ether was added for crystallization. Deposited
The solid was filtered, washed with 5 ml of anhydrous ether, and
After drying, 0.09 g of the desired product was obtained as a yellow powder.
Rate: 3%). The physical properties of the obtained product are shown below.

NMR (CDCl ₃ , 90 MHz): δ = 0.80 (t, J = 7.4 Hz, 6H, CH ₃ ); 1.36 (s, 6H, Si—CH ₃ ); 1.10-3 0.000 (m, 8H); 6.53 (s, 2H, 3-H-Ind); 7.00-8.0 (m, 20H)

[0208]

Example 11 Synthesis of rac-dimethylsilyl-bis {1- (2-n-propyl-4- (9-phenanthryl) indenyl)} zirconium dichloride [2-n-propyl-4- (9-phenanthryl) indene Synthesis] of 300 ml-4 neck round bottom flask (with stirrer tip, dropping funnel, thermometer) 10 g (30.5) of 4-bromo-2-n-propyl-1-trimethylsilyloxyindane synthesized in Example 10 above Mmol), anhydrous ether 50
ml, PdCl ₂ (dppf) 112 mg (0.153
Millimolar), and under stirring at room temperature, a 1.45M concentration of 9-
42 ml (61 mmol) of an ether / benzene solution of phenanthryl magnesium bromide was slowly added dropwise. Next, the internal temperature was raised to 42 ° C. and the mixture was refluxed for 10 hours, then the reaction product was poured into 300 ml of a saturated aqueous solution of ammonium chloride, extracted with 200 ml of ether four times, and the organic phases were combined. The combined organic phase was washed with saturated brine and then dried over anhydrous M
It was dried over gSO ₄ . The solvent was distilled off to give a brown liquid 20.
32 g was obtained.

300 ml-Into a 4-neck round bottom flask, the above brown liquid and 50 ml of ether were placed, and 60 ml of 5N hydrochloric acid aqueous solution was added dropwise at room temperature, followed by vigorous stirring. 6.5
After the lapse of time, the mixture was transferred to a separating funnel and extracted 4 times with 50 ml of ether. The organic phases were combined, washed twice with 100 ml of saturated aqueous sodium hydrogen carbonate, and dried over anhydrous MgSO ₄ . The brown semisolid obtained by distilling off the solvent was purified by silica gel chromatography to obtain 10.75 g of a yellow powder.

Next, the yellow powder obtained above and 80 m of anhydrous methylene chloride were placed in a 200 ml-4 neck round bottom flask.
1, triethylamine 12.8 ml (92.0 mmol), 4-dimethylaminopyridine 187 ml (1.53
Then, a solution prepared by dissolving 4.72 ml (61.0 mmol) of methanesulfonyl chloride in 20 ml of anhydrous methylene chloride was slowly added dropwise under ice cooling. After the dropping, the temperature was raised to room temperature and the reaction was carried out for 4 hours. Then, the reaction product was poured into 100 ml of ice water and extracted 3 times with 100 ml of methylene chloride. Combine the extracted organic phases and add 100 ml of saturated aqueous sodium hydrogen carbonate.
After being washed 3 times with, it was dried with anhydrous MgSO ₄ . The reddish brown semisolid obtained by removing the solvent was purified by silica gel chromatography to obtain 7.20 g of the desired product as a yellowish white powder (yield: 71%). The physical properties of the obtained product are shown below.

NMR (CDCl ₃ , 90 MHz): δ = 0.92 (t, J = 7.0 Hz, 3H, CH ₃ ); 1.50 (m, 2H); 2.36 (t, J = 7. 0Hz, 2H); 3.02 (bd, 2H); 6.60 (s, 1H); 7.05 to 9.00 (m, 12H) [dimethylsilyl-bis {1- (2-n-propyl- Synthesis of 4- (9-phenanthryl) indene)}] 300-ml 4-necked round bottom flask (with stirrer tip, Dimroth condenser, dropping funnel, thermometer) 2-n-propyl-4- (9-
6.20 g (18.5 mmol) of phenanthryl) indene, 120 ml of anhydrous ether and 50 mg of copper cyanide were added, and 12.5 ml (20.4 mmol) of a hexane solution of n-butyllithium having a concentration of 1.63 M was added under ice cooling. Dropped. After completion of the dropwise addition, the mixture was refluxed for 1.5 hours, and then a solution of 1.34 ml (11.1 mmol) of dimethyldichlorosilane dissolved in 10 ml of anhydrous ether was slowly added dropwise under ice cooling. After completion of the dropwise addition, the mixture was reacted overnight at room temperature, and then the reaction mixture was poured into 200 ml of a saturated aqueous solution of ammonium chloride. After gravity filtration, the filtrate was extracted 3 times with 100 ml of ether, the organic phase was washed with 200 ml of saturated saline and dried over anhydrous MgSO ₄ . The yellowish white powder obtained by distilling off the solvent is purified by silica gel chromatography,
3.80 g of the target product was obtained as a yellowish white powder (yield:
54%). The physical properties of the obtained product are shown below.

NMR (CDCl₃, 90 MHz): δ = −0.17, −0.15 (s respectively, 6 in total)
H, Si-CH ₃); 0.65-2.75 (m, 14H); 3.86-4.25 (m, 2H, -CH-Si); 6.25, 6.34 (6d, 2H respectively); ~ 9.05 (m, 24H) [rac-dimethylsilyl-bis {1- (2-n-propyl-4- (9-
Phenanthryl) indenyl)} zirconium dichloride
Synthesis of 200 ml-4 neck round bottom flask (stirrer)
-Chip, ball condenser, dropping funnel, thermometer)
Dimethylsilyl-bis {1- (2-n-propyl-4- (9-phen
(Nantryl) indene)} 2.9 g (4.00 mm)
60 ml of anhydrous ether) and 1.63 under ice cooling.
5.15 ml of M-concentration n-butyllithium hexane solution
(8.40 mmol) was slowly added dropwise. End of dripping
After that, stir at room temperature overnight, and then at −78 ° C. with ZrCl 2.
_Four1.00 g (4.29 mmol) was added slowly
It was After the addition was completed, the temperature was raised naturally overnight. Got
The orange reaction slurry is filtered and the residue is filtered over anhydrous methyl chloride.
It was washed with 100 ml of ethylene. The filtrate was concentrated to dryness
After that, 100 ml of anhydrous methylene chloride was added and redissolved,
Next, anhydrous ether was added for crystallization. Precipitated solid
Was filtered, washed with 15 ml of anhydrous ether and dried under reduced pressure.
When dried, 0.10 g of the desired product was obtained as a yellow powder.
Rate: 2.8%). The physical properties of the obtained product are shown below.

NMR (CDCl ₃ , 90 MHz): δ = 0.80 (t, J = 7.4 Hz, 6H, CH ₃ ); 1.39 (s, 6H, Si—CH ₃ ); 1.10-3 6.00 (m, 8H); 6.61 (s, 2H, 3-H-Ind); 7.00-9.10 (m, 24H)

[0214]

Example 12 Synthesis of rac-dimethylsilyl-bis {1- (2-ethyl-4- (9-phenanthryl) indenyl)} zirconium dichloride [2-ethyl-1-hydroxy-4- (9-phenanthryl) indane Synthesis] In a 200 ml-3 neck round bottom flask (with stirrer tip, Dimroth condenser, dropping funnel and thermometer), 11.54 g (36.8 mmol) of 4-bromo-2-ethyl-1-trimethylsilyloxyindane, PdC
l ₂ (dppf) 0.135 g (0.184 mmol)
And 35 ml of anhydrous ether were added, and 51.5 ml of an ether / benzene solution of 9-phenanthrylmagnesium bromide having a concentration of 1.4 M (73.7) was added at room temperature under a nitrogen atmosphere.
(Mmol) was slowly added dropwise. Internal temperature 4 after dropping
The temperature was raised to 2 ° C., and the mixture was heated under reflux for 8 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, 100 ml of water was slowly added to decompose excess Grignard reagent, and 50 ml of ether was added.
Was added to separate oil and water. The organic phase was filtered through Celite, the filtrate was washed with 100 ml of saturated saline and dried over anhydrous Na ₂ SO _4.
Dried in. The solvent was distilled off under reduced pressure to give a dark reddish brown liquid 2
5 g was obtained.

Next, the dark reddish brown liquid and 50 ml of tetrahydrofuran were added to a 200 ml-three-necked round bottom flask (with a stirrer tip, Dimroth condenser, dropping funnel, and thermometer), and 6 ml of 12% hydrochloric acid aqueous solution was added at room temperature under a nitrogen atmosphere. Was added dropwise, and the reaction was continued for 5 hours. After completion of the reaction, 100 ml of ether was added to separate oil and water. The organic phase is 100 ml of saturated aqueous sodium hydrogen carbonate and then 100 m of saturated saline.
It was washed 3 times with 1 and dried over anhydrous Na ₂ SO ₄ . The solvent was distilled off under reduced pressure, and the resulting dark red liquid residue was separated and purified by silica gel column chromatography (developed with hexane → hexane / ethyl acetate = 4/1 volume part) to give the desired product (two isomers). 1) as a viscous reddish brown liquid
2.33 g was obtained (yield: 99%). The physical properties of the obtained product are shown below.

FD-MS: 338 (M ⁺ ) [Synthesis of 2-ethyl-4- (9-phenanthryl) indene]
300 ml-3 neck round bottom flask (stirrer tip,
Dimroth condenser, dropping funnel, with thermometer) 2-
Ethyl-1-hydroxy-4- (9-phenanthryl) indane 12.3 g (36.3 mmol), triethylamine 1
9.7 ml (142 mmol) and methylene chloride 6
1.5 ml was added. Under ice cooling, a solution of 3.3 ml (42.6 mmol) of methanesulfonyl chloride in 5 ml of methylene chloride was slowly added dropwise under a nitrogen atmosphere. After completion of the dropping, the temperature was raised to room temperature and the reaction was further continued for 4 hours. After adding 80 ml of saturated aqueous sodium hydrogen carbonate to the reaction mixture, the organic phase was separated and the aqueous phase was further extracted twice with 50 ml of methylene chloride. The combined organic phase was washed with water, then with saturated saline, and dried over anhydrous Na ₂ SO ₄ . The solvent was distilled off under reduced pressure,
The residue was separated and purified by silica gel column chromatography (developed with hexane → hexane / ethyl acetate = 100/3 by volume) to obtain 9.61 g of the desired product (a mixture of two isomers) as a viscous pale yellowish green liquid. (Yield: 83%).
The physical properties of the obtained product are shown below.

FD-MS: 320 (M ⁺ ) NMR (CDCl ₃ , 90 MHz): δ = 0.86 to 1.44 (m, 3H, CH ₃ ); 2.16 to 2.58 (m, 2H) 4.03, 3.42 (respectively bs, 2H in total); 6.09, 6.55 (respectively bs, 1H in total); 6.95-7.97 (m, 10H); 8.57- 8.93 (m, 2H) [Synthesis of dimethylsilyl-bis {1- (2-ethyl-4- (9-phenanthryl) indene)}] 200 ml-3 neck round bottom flask (stirrer tip, Dimroth condenser, dropping) To the funnel and a thermometer), 5.3 g (16.5 mmol) of 2-ethyl-4- (9-phenanthryl) indene, 45 mg (0.45 mmol) of copper cyanide and 106 ml of anhydrous ether were added, and the mixture was put in a nitrogen atmosphere. 1.54 M n-butyrate while cooling to 10 ° C Lithium in hexane solution 1
1.8 ml (18.2 mmol) was slowly added dropwise.
After the dropping was completed, the temperature was raised to room temperature and the reaction was continued for 5 hours.
Next, while the reaction mixture was cooled with ice, 1.12 ml (9.1 mmol) of dimethyldichlorosilane was added to 5 m of anhydrous ether.
The solution dissolved in 1 was slowly added dropwise. After the completion of the dropping, the temperature was raised to room temperature and the reaction was further performed for 15 hours. After pouring 50 ml of saturated aqueous ammonium chloride into the reaction mixture, the insoluble matter was filtered through Celite, the filtrate was separated into oil and water, and the aqueous phase was washed with ether 50.
Extracted with ml. The combined organic phase is 50 ml of saturated saline.
It was washed 3 times with and dried over anhydrous Na ₂ SO ₄ . The solvent was distilled off under reduced pressure, and the resulting pale ocher viscous liquid residue was separated by silica gel column chromatography (developed with hexane → hexane / ethyl acetate = 1000/7 parts by volume) to give the desired product as a yellow solid. (Stereoisomer mixture) 3.19
g was obtained (yield: 55%). The physical properties of the obtained product are shown below.

[0218]

[Chemical 19]

[Synthesis of rac-dimethylsilyl-bis {1- (2-ethyl-4- (9-phenanthryl) indenyl)} zirconium dichloride] 100 ml-three-neck round bottom flask (stirrer tip, ball-condensing condenser, dropping) Funnel,
Dimethylsilyl-bis {1
-(2-Ethyl-4- (9-phenanthryl) indene)} 0.
60 g (0.86 mmol) and 12 ml of anhydrous ether were added, and 1.18 ml (1.81 mmol) of a hexane solution of n-butyllithium having a concentration of 1.54 M was slowly added dropwise at room temperature. After the dropping was completed, the reaction was further performed for 18.5 hours. The resulting pale yellow-orange reaction mixture was cooled to −70 ° C. with a dry ice-acetone bath and 0.20 g of ZrCl ₄
(0.86 mmol) powder was added slowly. After the addition was completed, the mixture was left overnight while continuing stirring. The resulting orange-yellow reaction slurry was filtered, and the residue was filtered with anhydrous ether (6 m).
After washing with l, it was further washed 5 times with 5 ml of methylene chloride. After adding 55 ml of methylene chloride to the residue, the insoluble matter was filtered off, the filtrate was concentrated to dryness, 2 ml of anhydrous ether was added, and the mixture was reslurried and dried to obtain 80 mg of yellow-orange powder. When this powder was analyzed by NMR, rac / mes
It was a mixture consisting of o = 91/9. Next, 2 ml of methylene chloride and 2 ml of anhydrous ether were added to the powder obtained above.
Was added, and the mixture was washed with reslurry and dried under reduced pressure to obtain 66 mg of the desired product as a yellow-orange powder. (Yield: 9%). The physical properties of the obtained product are shown below.

NMR (CDCl ₃ , 90 MHz): δ = 1.01 (t, J = 7.6 Hz, 6H, CH ₃ ); 1.37 (s, 6H, Si-CH ₃ ); 2.16-2 .91 (m, 4H); 6.55 (s, 2H, 3-H-Ind); 6.78-8.12 (m, 20H) 8.39-8.76 (m, 4H)

[0221]

Example 13 rac-dimethylsilyl-bis {1- (2-i-butyl-4- (1-naphth
[Cyl) indenyl)} zirconium dichloride [Synthesis of diethyl 2-bromobenzylidene malonate] 50
0 ml-3 neck round bottom flask (stirrer tip, di
For Starnak, Dimroth condenser, thermometer)
2-Bromobenzaldehyde 74.0 g (400 mm
), Diethyl malonate 70.48 g (440 mm
), Piperidine 1.6 ml, acetic acid 4.8 ml and
80 ml of water, and under a nitrogen atmosphere, oil bath temperature 110
An azeotropic dehydration reaction was performed at 7 ° C for 7 hours. After the reaction is complete,
After cooling with and adding 300 ml of ether, 100 ml of water
It is washed twice with and the organic phase is dried over anhydrous Na. ₂SO_FourDried in.
The solvent was concentrated under reduced pressure and the orange liquid concentrate was distilled under reduced pressure.
As a result, 117.2 g of the desired product as a yellow liquid was obtained (yield: 90%).
The physical properties of the obtained product are shown below.

Bp. 164 to 171 ° C./0.2 mmHg NMR (CDCl ₃ , 90 MHz): δ = 1.17 (t, J = 7.0 Hz, 3H, CH ₃ ); 1.34 (t, J = 7.0 Hz, 3H) , CH ₃ ); 4.22 (q, J = 7.0 Hz, 2H, -O-CH
_2- ); 4.32 (q, J = 7.0 Hz, 2H, -O-CH
_2- ); 7.06 to 7.80 (m, 3H); 7.97 (s, 1H) IR (Neat): 1725 cm ^-1 (ν _{c = 0} ) mp. : 43.6-45.6 ° C. [Synthesis of diethyl 2-bromobenzylmalonate] 500 m
1-sodium borohydride 13.64 g (360.
8 mmol) and 280 ml of ethanol were added, and 117 g (357.6 mmol) of solid diethyl 2-bromobenzylidene malonate was added little by little under a nitrogen atmosphere under ice cooling. After the addition was completed, the reaction was continued for 1 hour. next,
The white slurry thus obtained was filtered, and the residue was filtered with ethanol 50.
Washed with ml. The combined filtrate was concentrated under reduced pressure and washed with water 20
Extraction was performed by adding 0 ml and 200 ml of ether. After separating the organic phase, the aqueous phase was further extracted with 200 ml of ether.
The combined organic phase was washed twice with 200 ml of saturated saline,
It was dried over anhydrous Na ₂ SO ₄ . The solvent was distilled off under reduced pressure, and the residue was separated and purified by silica gel column chromatography (developed with hexane / ethyl acetate = 6/1 volume part) to obtain 55.4 g of the desired product as a colorless liquid (yield. : 4
7%). The physical properties of the obtained product are shown below.

NMR (CDCl ₃ , 90 MHz): δ = 1.21 (t, J = 7.1 Hz, 6H, CH ₃ ); 3.33 (d, J = 7.6 Hz, 2H); 3.84 ( dd, J = 7.6 Hz, 7.6 Hz, 1
H); 4.13 (q, J = 7.1 Hz, 4H, -O-CH
₂₋ ); 6.87 to 7.36 (m, 3H); 7.51 (dd, J = 2.3 Hz, 7.6 Hz, 1
H); IR (Neat): 1730cm -1, 1750cm -1 (ν
_{c = 0} ) [Synthesis of 3- (2-bromophenyl) -2-i-butylpropionic acid] 1 liter-potassium in a 4-neck round bottom flask (with stirrer, Dimroth condenser, dropping funnel, thermometer) t-Butoxide 20.45 g (182.3 mmol), toluene 180 ml, N-methylpyrrolidone 25 m
1 was added, and a solution of diethyl 2-bromobenzylmalonate (50.0 g, 151.9 mmol) in toluene (40 ml) was added dropwise at room temperature under a nitrogen atmosphere. After completion of the dropping, the temperature was raised and the reaction was carried out at an internal temperature of 60 ° C. for 1 hour. Next, a solution of 24.97 g (182.3 mmol) of i-butyl bromide in 30 ml of toluene was added dropwise at the same temperature.
After the completion of dropping, the temperature was raised and the mixture was refluxed for 18 hours. The obtained reaction mixture was poured into 150 ml of saturated saline and a 12% hydrochloric acid aqueous solution was added to adjust the pH to 3. The organic phases were separated, the aqueous phase was extracted twice more with 100 ml of ether and the organic phases were combined. The combined organic phases were washed with 200 ml of saturated aqueous sodium hydrogen carbonate and then with 150 ml of saturated saline, and dried over anhydrous Na ₂ SO ₄ . The solution was concentrated under reduced pressure to give 64 g of an orange liquid concentrate.

Next, 100 g (1.52 mol) of potassium hydroxide and 300 ml of an aqueous methanol solution (methanol / water = 4) were placed in a 1-liter 4-neck round bottom flask (with a stirrer, Dimroth condenser, dropping funnel, and thermometer). / 1
(V / v)) was added, and the above concentrate was added dropwise at room temperature in a nitrogen atmosphere. After the completion of dropping, the temperature was raised and the mixture was refluxed for 7 hours.
After completion of the reaction, methanol was distilled off under reduced pressure, and water was added to the precipitate to dissolve it. Dilute sulfuric acid was added to this solution, and the pH was 3
And the precipitated solid was filtered. Next, the filter cake was washed with 150 ml of ether, and the combined filtrate was separated into oil and water. The aqueous phase was further extracted twice with 100 ml of ether, and the combined organic phase was washed with 100 ml of saturated saline and then dried over anhydrous Na ₂ S.
Dry with O ₄ . The solvent was concentrated under reduced pressure to obtain 49.7 g of an orange-brown viscous liquid. Next, the above orange-brown viscous liquid was added to a 300 ml eggplant flask (with a stirrer chip and Dimroth condenser), and the oil bath temperature was set to 1 under a nitrogen atmosphere.
Heated at 80 ° C. for 1.5 hours. After completion of heating, the mixture was cooled to room temperature to obtain 42.1 g of the desired product as a dark red viscous liquid (yield: 97%). This carboxylic acid was used in the next reaction without further purification. The physical properties of the obtained product are shown below.

NMR (CDCl ₃ , 90 MHz): δ = 0.90 (d, J = 6.4 Hz, 3H, CH ₃ ); 0.93 (d, J = 6.4 Hz, 3H, CH ₃ ); 1 0.07 to 1.89 (m, 3H); 2.57 to 3.09 (m, 3H); 6.72 to 7.30 (m, 4H); 7.51 (dd, J = 2.0Hz, 7.1 Hz, 1H); [Synthesis of 3- (2-bromophenyl) -2-i-butylpropionyl chloride] 200 ml-3 neck round bottom flask (stirrer chip, Dimroth condenser, thermometer, Na
4 (2g) of 3- (2-bromophenyl) -2-i-butylpropionic acid and 60ml of thionyl chloride were added to (with OH trap), and the mixture was heated under reflux in a nitrogen atmosphere for 1.5 hours. After completion of the reaction, unreacted thionyl chloride was distilled off under reduced pressure, and the residue was distilled under reduced pressure to obtain 40.3 g of the desired product as a light orange liquid (yield:
90%). The physical properties of the obtained product are shown below.

Bp. : 130 to 132 ° C./0.
1 to 0.2 mmHg NMR (CDCl ₃ , 90 MHz): δ = 0.90 (d, J = 6.4 Hz, 3H, CH ₃ ); 0.96 (d, J = 6.4 Hz, 3H, CH ₃ ). 1.13 to 2.06 (m, 3H); 2.71 to 3.53 (m, 3H); 6.88 to 7.40 (m, 3H); 7.50 (d, J = 6. 9 Hz, 1 H); IR (Neat): 1780 cm ^-1 (ν _{c = 0} ) [Synthesis of 4-bromo-2-i-butyl-1-indanone] 500 m
1-A four-necked round bottom flask (with a stirrer, Dimroth condenser, dropping funnel, thermometer, and NaOH trap) was charged with 20.33 g (152.5 mmol) of anhydrous aluminum chloride and 70 ml of carbon disulfide, and nitrogen was added under ice cooling. In an atmosphere, a solution of 40.2 g (132.6 mmol) of 3- (2-bromophenyl) -2-i-butylpropionyl chloride obtained above in 50 ml of carbon disulfide was slowly added dropwise. After the dropping was completed, the internal temperature was raised to room temperature and the reaction was carried out for 1 hour. Then, the reaction solution was poured into 200 ml of ice water to decompose, and extracted with 100 ml of ether three times, and the organic phases were combined. The combined organic phases were washed with 100 ml of saturated aqueous sodium hydrogen carbonate and then with 100 ml of saturated brine, and dried over anhydrous Na ₂ SO ₄ . The solvent was distilled off under reduced pressure to obtain the desired product as an orange liquid 37.4.
Got This ketone was used in the next reaction without further purification. The physical properties of the obtained product are shown below.

NMR (CDCl ₃ , 90 MHz): δ = 0.99 (t, J = 6.4 Hz, 6H, CH ₃ ); 1.02 to 1.55 (m, 1H); 1.59 to 2. 12 (m, 2H); 2.53 to 2.94 (m, 2H); 3.02 to 3.62 (m, 1H); 7.24 (t, J = 7.6Hz, 1H); 7. 66 (d, J = 7.6 Hz, 1H); 7.74 (d, J = 7.6 Hz, 1H); IR (Neat): 1718 cm ^-1 (ν _{c = 0} ) [4-bromo-2-i -Butyl-1-hydroxyindan synthesis]
300 ml-3 neck round bottom flask (stirrer tip,
Dimroth condenser, dropping funnel, with thermometer) 2.51 g (66.3 mmol) of sodium borohydride
And 85 ml of ethanol were added thereto, and 4-bromo-2-i-butyl-1-indanone obtained above was obtained at room temperature under a nitrogen atmosphere 37.
A solution prepared by dissolving 0 g (132.6 mmol) in 55 ml of ethanol was added dropwise. After the dropping was completed, the reaction was further performed for 16 hours. The reaction mixture is then concentrated under reduced pressure and water 1
50 ml and ether 150 ml were added and extracted. After separating the organic phase, the aqueous phase was further extracted with 100 ml of ether and the organic phases were combined. The combined organic phase was saturated saline 1
It was washed twice with 00 ml and dried over anhydrous Na ₂ SO ₄ .
The solvent was distilled off under reduced pressure to obtain 34.4 g of the desired product (mixture of two kinds of isomers) as a pale yellow solid (yield: 96
%). This alcohol was used in the next reaction without further purification. The physical properties of the obtained product are shown below.

[0228]

[Chemical 20]

IR (KBr disk): 3232 cm ^-1 (ν _OH ) [Synthesis of 4-bromo-2-i-butyl-1-trimethylsilyl oxyquinindane] 300 ml-3 neck round bottom flask (stirrer chip, Dimroth condenser, 34.4 g (127.8 mmol) of 4-bromo-2-i-butyl-1-hydroxyindane, 23.1 ml (166.2 mmol) of triethylamine and 118 ml of methylene chloride were added to a dropping funnel and a thermometer, and ice was added. 19.45 ml (153.4 mmol) of trimethylsilyl chloride in a nitrogen atmosphere under cooling
20 ml of methylene chloride solution of was slowly added dropwise. After the dropping was completed, the temperature was raised to room temperature and the reaction was further performed for 1.5 hours.
The reaction mixture was poured into a mixture of 200 ml of ice water / 20 ml of saturated aqueous sodium hydrogen carbonate, the organic phase was separated, and the aqueous phase was further extracted twice with 50 ml of methylene chloride, and the organic phases were combined. The combined organic phase was washed with 100 ml of saturated saline and dried over anhydrous Na.
Dried with ₂ SO ₄ . The solvent was distilled off under reduced pressure, and the residue was distilled under reduced pressure to obtain 41.8 g of the desired product (mixture of two isomers) as a pale yellow liquid (yield: 96%). The physical properties of the obtained product are shown below.

[0230]

[Chemical 21]

[Synthesis of 2-i-butyl-1-hydroxy-4- (1-naphthyl) indene] 200 ml 4-in a 3-neck round bottom flask (with stirrer chip, Dimroth condenser, dropping funnel, thermometer) Bromo-2-i-butyl-1-trimethylsilyloxyindane 5.0 g (14.65 mmol), PdCl ₂ (dppf) 53.6 mg (0.07)
3 mmol) and 15 ml of anhydrous ether were added, and 40.7 ml of an ether / benzene solution of 1-naphthylmagnesium bromide having a concentration of 0.72 M at room temperature under a nitrogen atmosphere.
(29.3 mmol) was slowly added dropwise. After the dropping was completed, the internal temperature was raised to 50 to 51 ° C. and the mixture was refluxed for 18 hours.
After completion of the reaction, the mixture was cooled to room temperature, the reaction mixture was slowly added to a mixture of 100 ml of saturated ammonium chloride aqueous solution and ice to decompose excess Grignard reagent, and 50 ml of ether.
It was extracted twice with. The combined organic phases were washed with saturated aqueous sodium hydrogen carbonate and saturated brine in this order, and dried over anhydrous Na ₂ SO ₄ . The solvent was distilled off under reduced pressure to obtain 12.1 g of a viscous liquid.

Next, the viscous liquid was diluted with 24.2 ml of tetrahydrofuran, 7 ml of 12% hydrochloric acid aqueous solution was added, and the mixture was reacted at room temperature for 3 hours. After completion of the reaction, the reaction mixture was added to 50 ml of saturated aqueous sodium hydrogen carbonate and extracted twice with 50 ml of ether. The organic phases were combined, washed successively with saturated aqueous sodium hydrogen carbonate and saturated brine, and dried over anhydrous Na ₂ SO ₄ . The solvent was distilled off under reduced pressure, the residue was separated and purified by silica gel chromatography (developed with hexane / ethyl acetate = 20/1 by volume), and the target substance (mixture of two isomers) was used as a brown viscous liquid. 54 g was obtained (yield: 98%). The physical properties of the obtained product are shown below.

[0233]

[Chemical formula 22]

[Synthesis of 2-i-butyl-4- (1-naphthyl) indene] 200 ml-3 neck flask (with stirrer chip, Dimroth condenser, dropping funnel, thermometer)
2-i-butyl-1-hydroxy-4- (1-naphthyl) indene 4.54 g (14.4 mmol), triethylamine 5.13 g (50.8 mmol), 4-dimethylaminopyridine 0.10 g (0 0.82 mmol) and 57.7 ml of methylene chloride were added, and under nitrogen cooling with ice, 3.87 ml (33.8 mmol) of methanesulfonyl chloride.
Was dissolved in methylene chloride (7.7 ml) and slowly added dropwise. After the completion of the dropping, the temperature was raised to room temperature and the reaction was further performed for 3 hours. After pouring the reaction mixture into 100 ml of water, the organic phase was separated and the aqueous phase was extracted with 50 ml of methylene chloride.
The extracted organic phases are combined, washed with saturated saline, and dried with anhydrous N 2.
a ₂ SO ₄ dried. The solvent was distilled off under reduced pressure, the residue was separated and purified by silica gel column chromatography (developed with hexane / ethyl acetate = 20/1 by volume), and the target product (mixture of two isomers) was viscous pale yellow. As a liquid, 3.98 g was obtained (yield: 93%). The physical properties of the obtained product are shown below.

NMR (CDCl ₃ , 90 MHz): δ = 0.86 (d, J = 6.4 Hz, 6H, CH ₃ ); 1.13-1.99 (m, 1H); 2.24 (d, J = 6.4 Hz, 2H); 3.01, 3.40 (s respectively, 2H in total); 6.07, 6.55 (s, 1H in total); 6.92 to 7.98 (m 10H) [Synthesis of dimethylsilyl-bis {1- (2-i-butyl-4- (1-naphthyl) indene)}] 100 ml-3 neck round bottom flask (stirrer tip, Dimroth condenser, dropping funnel, temperature) 2-i-butyl-4- (1-naphthyl)
2.37 g (7.95 mmol) of indene, 28 mg (0.22 mmol) of copper thiocyanate, anhydrous ether 24
ml, and in a nitrogen atmosphere at room temperature at a concentration of 1.58 M n-
5.54 ml of hexane solution of butyl lithium (8.75
(Mmol) was slowly added dropwise. 1 more after dropping
The reaction was carried out for 5 hours. Next, dimethyldichlorosilane 0.
53 ml (4.37 mmol) of anhydrous ether 1.6 m
The solution dissolved in 1 was slowly added dropwise. After the dropping was completed, the reaction was continued at room temperature for 27.5 hours. The reaction mixture was filtered through Celite, and 30 ml of water was added to the filtrate to separate oil and water.
After separating the organic phase, the aqueous phase was extracted with 30 ml of ether and the organic phases were combined. The combined organic phase is 30 ml of saturated saline.
It was washed with and dried over anhydrous Na ₂ SO ₄ . The solvent was distilled off under reduced pressure, and the viscous yellow liquid residue obtained was subjected to silica gel column chromatography (hexane / ethyl ether =
The product was separated and purified with 160/1 volume parts) to obtain 1.85 g of the desired product (mixture of two isomers) as a pale yellow solid (yield: 71%). The physical properties of the obtained product are shown below.

[0236]

[Chemical formula 23]

[Synthesis of rac-dimethylsilyl-bis {1- (2-i-butyl-4- (1-naphthyl) indenyl)} zirconium dichloride] 50 ml-3 neck round bottom flask (stirrer tip, condenser with ball) , Dropping funnel, with thermometer) in an argon atmosphere with dimethylsilyl-bis {1- (2-i
-Butyl-4- (1-naphthyl) indene)} 1.0 g (1.
(53 mmol) and 20 ml of anhydrous ether were added, and a hexane solution of n-butyllithium having a concentration of 1.54 M was added at room temperature.
09 ml (3.22 mmol) was slowly added dropwise. After the dropping, the reaction was continued for 15 hours. The obtained bright red reaction solution was cooled to -68 ° C with a dry ice-acetone bath, and Z
A powder of 0.36 g (1.53 mmol) of rCl ₄ was added slowly. After the addition was completed, the mixture was left overnight while continuing stirring. The resulting orange-yellow reaction slurry was filtered, and the residue was washed twice with anhydrous ether. Methylene chloride 2 on the filter cake
After adding 5 ml, the insoluble matter was filtered off, and the filtrate was concentrated to dryness at room temperature. 8 ml of methylene chloride was added to the obtained orange-yellow dry solid.
Was added to dissolve and then concentrated to about 1/2. Next, 1 ml of anhydrous ether was added for crystallization. The precipitated solid was filtered, washed with 1 ml of anhydrous ether, and dried under reduced pressure to obtain 140 mg of orange-yellow powder. When this powder was analyzed by NMR, it was a mixture of rac / meso = 88/12. Next, 3 ml of methylene chloride was added to and dissolved in the powder obtained above, and 6 ml of anhydrous ether was added for crystallization. The precipitated solid is filtered and ether 0.5 ml
After washing with, dry under reduced pressure to give the desired product as a yellow-orange powder.
7 mg was obtained. (Yield: 6%). The physical properties of the obtained product are shown below.

FD-MS: 812 (M ⁺ ) NMR (CDCl ₃ , 90 MHz): δ = 0.71 (d, J = 6.4 Hz, 6H, CH ₃ ); 0.86 (d, J = 6. _{4Hz, 6H, CH 3);} 1.36 (s, 6H, Si-CH 3) 1.78~2.22 (m, 2H) 2.51~2.87 (m, 4H) 6.41 (s 2H, 3-H-Ind); 6.86 to 8.02 (m, 20H)

[0239]

Example 14 As a transition metal compound catalyst component, rac-dimethylsilyl-bis {1- (2-ethyl) was used instead of rac-dimethylsilyl-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride. Polymerization was performed in the same manner as in Example 2 except that -4- (9-phenanthryl) indenyl)} zirconium dichloride was used and the flow rate of hydrogen was 3 liter / hr.

The amount of the polymer obtained was 23.4 g, and the polymerization activity was equivalent to 12.0 kg-PP / mmol Zr · hr. [Η] is 2.92 dl / g, Mw / Mn is 2.22, and triad tacticity is 99.7.
%, The proportion of regio disordered units based on the 2,1-insertion of propylene monomer was 0.14%, and the proportion of regio-irregular units based on the 1,3-insertion of propylene monomer was below the detection limit. (Less than 0.03).

[0241]

Example 15 As a transition metal compound catalyst component, rac-dimethylsilyl-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride was used in place of rac-dimethylsilyl-bis {1- (2-i -Butyl-4- (1-naphthyl) indenyl)} zirconium dichloride with a hydrogen flow rate of 3
Polymerization was carried out in the same manner as in Example 2 except that liter / hr was used.

The amount of the polymer obtained was 24.6 g, and the polymerization activity was equivalent to 12.6 kg-PP / mmol Zr · hr. [Η] is 3.05 dl / g, Mw / Mn is 2.10, and triad tacticity is 99.2.
%, The proportion of regio-irregular units based on 2,1-insertion of propylene monomer was 0.19%, and the proportion of regio-irregular units based on 1,3-insertion of propylene monomer was below the detection limit. (Less than 0.03).

[0243]

Example 16 As a transition metal compound catalyst component, rac-dimethylsilyl-bis {1- (2-n) was used instead of rac-dimethylsilyl-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride. Polymerization was performed in the same manner as in Example 2 except that -propyl-4- (1-naphthyl) indenyl)} zirconium dichloride was used and the flow rate of hydrogen was changed to 3 liter / hr.

The amount of the polymer obtained was 19.9 g, and the polymerization activity was 10.2 kg-PP / mmol Zr · hr. [Η] is 3.13 dl / g, Mw / Mn is 2.19, and triad tacticity is 99.5.
%, The proportion of regio-irregular units based on 2,1-insertion of propylene monomer was 0.19%, and the proportion of regio-irregular units based on 1,3-insertion of propylene monomer was below the detection limit. (Less than 0.03).

[0245]

[Example 17] rac-Dimethylsilyl-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride was replaced by rac-dimethylsilyl-bis {1- (2-n as a transition metal compound catalyst component. -Propyl-4- (9-phenanthryl)
Polymerization was carried out in the same manner as in Example 2 except that indenyl)} zirconium dichloride was used and the flow rate of hydrogen was 3 liter / hr.

The amount of the polymer obtained was 14.5 g, and the polymerization activity was equivalent to 7.4 kg-PP / mmol Zr · hr. [Η] is 3.47 dl / g, Mw / Mn is 2.15, and triad tacticity is 99.7.
%, The proportion of regio-irregular units based on 2,1-insertion of propylene monomer was 0.16%, and the proportion of regio-irregular units based on 1,3-insertion of propylene monomer was below the detection limit. (Less than 0.03).

The above results are shown in Table 1.

[0248]

[Table 1]

[Brief description of drawings]

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

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Junji Saito Waka 6-chome, Waki-cho, Kuga-gun, Yamaguchi Prefecture Mitsui Petrochemical Industries Ltd. (72) Inventor Junichi Imuta, Kazu-gun, Yamaguchi Prefecture 6-1-2 Waki Kimachi Mitsui Petrochemical Industry Co., Ltd. (72) Inventor Terunori Fujita 6-1-2 Waki Town Waki-machi, Kuga-gun, Yamaguchi Mitsui Petrochemical Industry Co., Ltd. (72) Invention Person Masato Futahara 6-1-2 Waki, Waki-cho, Kuga-gun, Yamaguchi Mitsui Petrochemical Industry Co., Ltd. (72) Takashi Ueda 6-1-2 Waki, Waki-cho, Kuma-gun, Yamaguchi Prefecture Mitsui Oil Within Chemical Industry Co., Ltd. (72) Inventor Yoshihisa Kiso 6-1-2, Waki, Kuga-gun, Yamaguchi Prefecture Within Mitsui Petrochemical Industry Co., Ltd. (72) Inventor, Masaru Yasuda Waki-cho, Kuga-gun, Yamaguchi Prefecture 6-chome No. 1 No. 2 Mitsui Petrochemical Industries Co., Ltd. in the tree

Claims (10)

[Claims] 1. A novel transition metal compound represented by the following general formula [I]: (In the formula, M represents a transition metal of Group IVa, Va, or VIa of the Periodic Table, R ¹ represents a hydrocarbon group having 2 to 6 carbon atoms, and R ² represents an aryl group having 6 to 16 carbon atoms. This aryl group may be substituted with a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and X ¹ and X ² are a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Represents a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group or a sulfur-containing group, and Y represents a divalent hydrocarbon group having 1 to 20 carbon atoms, or 1 to carbon atoms.
20 divalent halogenated hydrocarbon groups, divalent silicon-containing groups, divalent germanium-containing groups, -O-, -CO-,-
S -, - SO -, - SO 2 -, - NR 3 -, - P
^{(R 3) -, - P} (O) (R 3) -, - BR 3 - or -AlR ³ - [however, R ³ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, carbon atoms 1-20 halogenated hydrocarbon groups]. ) 2. A catalyst component for olefin polymerization, which comprises a transition metal compound represented by the following general formula [I]; (In the formula, M represents a transition metal of Group IVa, Va, or VIa of the Periodic Table, R ¹ represents a hydrocarbon group having 2 to 6 carbon atoms, and R ² represents an aryl group having 6 to 16 carbon atoms. This aryl group may be substituted with a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and X ¹ and X ² are a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Represents a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group or a sulfur-containing group, and Y represents a divalent hydrocarbon group having 1 to 20 carbon atoms, or 1 to carbon atoms.
20 divalent halogenated hydrocarbon groups, divalent silicon-containing groups, divalent germanium-containing groups, -O-, -CO-,-
S -, - SO -, - SO 2 -, - NR 3 -, - P
^{(R 3) -, - P} (O) (R 3) -, - BR 3 - or -AlR ³ - [however, R ³ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, carbon atoms 1-20 halogenated hydrocarbon groups]. ) 3. A transition metal compound represented by the following general formula [I]: (In the formula, M represents a transition metal of Group IVa, Va, or VIa of the Periodic Table, R ¹ represents a hydrocarbon group having 2 to 6 carbon atoms, and R ² represents an aryl group having 6 to 16 carbon atoms. This aryl group may be substituted with a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and X ¹ and X ² are a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Represents a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group or a sulfur-containing group, and Y represents a divalent hydrocarbon group having 1 to 20 carbon atoms, or 1 to carbon atoms.
20 divalent halogenated hydrocarbon groups, divalent silicon-containing groups, divalent germanium-containing groups, -O-, -CO-,-
S -, - SO -, - SO 2 -, - NR 3 -, - P
^{(R 3) -, - P} (O) (R 3) -, - BR 3 - or -AlR ³ - [however, R ³ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, carbon atoms 1-20 halogenated hydrocarbon groups]. ) [B] (B-1) organoaluminum oxy compound, and (B
-2) An olefin polymerization catalyst comprising at least one compound selected from the group consisting of compounds that react with the transition metal compound [A] to form an ion pair. 4. A transition metal compound represented by the following general formula [I]: (In the formula, M represents a transition metal of Group IVa, Va, or VIa of the Periodic Table, R ¹ represents a hydrocarbon group having 2 to 6 carbon atoms, and R ² represents an aryl group having 6 to 16 carbon atoms. This aryl group may be substituted with a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and X ¹ and X ² are a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Represents a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group or a sulfur-containing group, and Y represents a divalent hydrocarbon group having 1 to 20 carbon atoms, or 1 to carbon atoms.
20 divalent halogenated hydrocarbon groups, divalent silicon-containing groups, divalent germanium-containing groups, -O-, -CO-,-
S -, - SO -, - SO 2 -, - NR 3 -, - P
^{(R 3) -, - P} (O) (R 3) -, - BR 3 - or -AlR ³ - [however, R ³ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, carbon atoms 1-20 halogenated hydrocarbon groups]. ) [B] (B-1) organoaluminum oxy compound, and (B
-2) For olefin polymerization, which comprises at least one compound selected from the group consisting of compounds that react with the transition metal compound [A] to form an ion pair, and [C] an organoaluminum compound. catalyst. 5. A fine particle carrier, [A] a transition metal compound represented by the following general formula [I], and (In the formula, M represents a transition metal of Group IVa, Va, or VIa of the Periodic Table, R ¹ represents a hydrocarbon group having 2 to 6 carbon atoms, and R ² represents an aryl group having 6 to 16 carbon atoms. This aryl group may be substituted with a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and X ¹ and X ² are a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Represents a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group or a sulfur-containing group, and Y represents a divalent hydrocarbon group having 1 to 20 carbon atoms, or 1 to carbon atoms.
20 divalent halogenated hydrocarbon groups, divalent silicon-containing groups, divalent germanium-containing groups, -O-, -CO-,-
S -, - SO -, - SO 2 -, - NR 3 -, - P
^{(R 3) -, - P} (O) (R 3) -, - BR 3 - or -AlR ³ - [however, R ³ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, carbon atoms 1-20 halogenated hydrocarbon groups]. ) [B] (B-1) organoaluminum oxy compound, and (B
-2) An olefin polymerization catalyst, which is loaded with at least one compound selected from the group consisting of compounds that react with the transition metal compound [A] to form an ion pair. 6. A fine particle carrier, [A] a transition metal compound represented by the following general formula [I], and (In the formula, M represents a transition metal of Group IVa, Va, or VIa of the Periodic Table, R ¹ represents a hydrocarbon group having 2 to 6 carbon atoms, and R ² represents an aryl group having 6 to 16 carbon atoms. This aryl group may be substituted with a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and X ¹ and X ² are a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Represents a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group or a sulfur-containing group, and Y represents a divalent hydrocarbon group having 1 to 20 carbon atoms, or 1 to carbon atoms.
20 divalent halogenated hydrocarbon groups, divalent silicon-containing groups, divalent germanium-containing groups, -O-, -CO-,-
S -, - SO -, - SO 2 -, - NR 3 -, - P
^{(R 3) -, - P} (O) (R 3) -, - BR 3 - or -AlR ³ - [however, R ³ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, carbon atoms 1-20 halogenated hydrocarbon groups]. ) [B] (B-1) organoaluminum oxy compound, and (B
-2) A solid catalyst component carrying at least one compound selected from the group consisting of compounds that react with the transition metal compound [A] to form an ion pair, and [C] an organoaluminum compound. And a catalyst for olefin polymerization. 7. A fine particle carrier, [A] a transition metal compound represented by the following general formula [I], and (In the formula, M represents a transition metal of Group IVa, Va, or VIa of the Periodic Table, R ¹ represents a hydrocarbon group having 2 to 6 carbon atoms, and R ² represents an aryl group having 6 to 16 carbon atoms. This aryl group may be substituted with a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and X ¹ and X ² are a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Represents a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group or a sulfur-containing group, and Y represents a divalent hydrocarbon group having 1 to 20 carbon atoms, or 1 to carbon atoms.
20 divalent halogenated hydrocarbon groups, divalent silicon-containing groups, divalent germanium-containing groups, -O-, -CO-,-
S -, - SO -, - SO 2 -, - NR 3 -, - P
^{(R 3) -, - P} (O) (R 3) -, - BR 3 - or -AlR ³ - [however, R ³ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, carbon atoms 1-20 halogenated hydrocarbon groups]. ) [B] (B-1) organoaluminum oxy compound, and (B
-2) An olefin comprising at least one compound selected from the group consisting of compounds that react with the transition metal compound [A] to form an ion pair, and an olefin polymer formed by prepolymerization. Polymerization catalyst. 8. A particulate support, [A] a transition metal compound represented by the following general formula [I], and (In the formula, M represents a transition metal of Group IVa, Va, or VIa of the Periodic Table, R ¹ represents a hydrocarbon group having 2 to 6 carbon atoms, and R ² represents an aryl group having 6 to 16 carbon atoms. This aryl group may be substituted with a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and X ¹ and X ² are a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Represents a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group or a sulfur-containing group, and Y represents a divalent hydrocarbon group having 1 to 20 carbon atoms, or 1 to carbon atoms.
20 divalent halogenated hydrocarbon groups, divalent silicon-containing groups, divalent germanium-containing groups, -O-, -CO-,-
S -, - SO -, - SO 2 -, - NR 3 -, - P
^{(R 3) -, - P} (O) (R 3) -, - BR 3 - or -AlR ³ - [however, R ³ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, carbon atoms 1-20 halogenated hydrocarbon groups]. ) [B] (B-1) organoaluminum oxy compound, and (B
-2) At least one compound selected from the group consisting of compounds that react with the transition metal compound [A] to form an ion pair, [C] an organoaluminum compound, and an olefin polymer formed by prepolymerization. An olefin polymerization catalyst comprising: 9. A method for polymerizing an olefin, which comprises polymerizing or copolymerizing an olefin in the presence of the catalyst for olefin polymerization according to claim 3. 10. A method for polymerizing an olefin, which comprises polymerizing or copolymerizing an olefin in the presence of the catalyst for olefin polymerization according to claim 7 and an organoaluminum compound.