JP3465348B2 - Novel transition metal compound, olefin polymerization catalyst component comprising the transition metal compound, olefin polymerization catalyst containing the olefin polymerization catalyst component, and olefin polymerization method - Google Patents

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.

As transition metal compounds for producing isotactic polyolefin, ethylenebis (indenyl) zirconium dichloride and ethylenebis (4,5,6,7-
Tetrahydroindenyl) zirconium dichloride (JP-A-61-130314) is known. However, polyolefins produced using such catalysts usually have low stereoregularity and low molecular weight. 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 (Journal of Molecular Cat.
alysis, 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-1-301704 and Polymer Preprint.
s, Japan vol.39, No. 6p. 1614-1616 (1990) and the like, but there is a problem that high polymerization activity, high stereoregularity 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 as a catalyst capable of producing a high molecular weight polyolefin. The molecular weight of the obtained polyolefin is not yet sufficient.

[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.) The molecular weight of the polyolefin obtained by this catalyst is high, and it is industrially satisfactory, but at the same time, the melting point of stereoregular polyolefin such as polypropylene is also high. Since it becomes high, it is suitable for the production of stereoregular polyolefin having a high melting point. However, it is disadvantageous in the production of stereoregular polyolefin having a high molecular weight and a low melting point, especially a copolymer, and the quality of the obtained polymer is not satisfactory.

Further, EP 0537686 discloses an olefin polymerization catalyst comprising a metallocene compound represented by the following formula and an aluminoxane.

[0011]

[Chemical 11]

(In the formula, R ¹ and R ² represent a methyl group or hydrogen, and X represents a Si (CH ₃ ) ₂ group or an ethylene group.) However, the molecular weight of the polyolefin obtained by this catalyst is low and practical. Not on level.

Under these circumstances, it is desired to develop a catalyst for olefin polymerization and a method for polymerizing olefins, which have excellent olefin polymerization activity and excellent properties of the obtained polyolefin, and are used for such catalysts. It is desired to develop a new transition metal compound that can be used as a catalyst component for olefin polymerization, and further as a catalyst component for olefin polymerization.

[0014]

OBJECT OF THE INVENTION It is an object of the present invention to provide a novel transition metal compound which can be an olefin polymerization catalyst component having excellent olefin polymerization activity.
It is an object of the present invention to provide a catalyst component for olefin polymerization composed of 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.

[0015]

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].

[0016]

[Chemical 12]

(In the formula, M represents a transition metal of Groups 4, 5 and 6 of the Periodic Table, and R ¹ and R ² represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a carbon atom. Number 1
20 halogenated hydrocarbon groups, silicon-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups or phosphorus-containing groups
(However, R ¹ is other than a hydrogen atom and R ² is a hydrogen atom.
Except for. ) , R ³ represents an alkyl group having 2 to 20 carbon atoms, and R ⁴ represents an alkyl group having 1 to 20 carbon atoms.

X ¹ and X ² are hydrogen atom, halogen atom,
Hydrocarbon group having 1 to 20 carbon atoms, 1 to 20 carbon atoms
Represents a halogenated hydrocarbon group, an oxygen-containing group or a sulfur-containing group, 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,
Divalent tin-containing group, -O-, -CO-, -S-, -SO
_{-, - SO 2 -, -} NR 5 -, - P (R 5) -, - P
^{(O) (R 5) -} , - BR 5 - or -AlR ⁵ - [however, R ⁵ is a hydrogen atom, a halogen atom, 1 to carbon atoms
20 hydrocarbon groups and halogenated hydrocarbon groups having 1 to 20 carbon atoms]. ) In the catalyst component for olefin polymerization according to the present invention, in the above general formula [I] , M is titania.
, Zirconium or hafnium, and Y is divalent
It is characterized by comprising a transition metal compound which is a silicon-containing group .

The first olefin polymerization catalyst according to the present invention comprises: [A] In the above general formula [I] , M is titanium or di
Ruconium or hafnium, Y is divalent silicon
Selected from the group consisting of a transition metal compound which is a containing group , [B] (B-1) an organoaluminum oxy compound, and (B-2) a compound which reacts with the transition metal compound [A] to form an ion pair. It is characterized by comprising at least one kind of compound.

The second catalyst for olefin polymerization according to the present invention is [A] in the above general formula [I] , M is titanium,
Ruconium or hafnium, Y is divalent silicon
Selected from the group consisting of a transition metal compound which is a containing group , [B] (B-1) an organoaluminum oxy compound, and (B-2) a compound which reacts with the transition metal compound [A] to form an ion pair. And a [C] organoaluminum compound.

The third catalyst for olefin polymerization according to the present invention comprises a fine particle carrier, [A] in the above general formula [I] , M is titanium, and
Ruconium or hafnium, Y is divalent silicon
Selected from the group consisting of a transition metal compound which is a containing group , [B] (B-1) an organoaluminum oxy compound, and (B-2) a compound which reacts with the transition metal compound [A] to form an ion pair. And at least one compound that is carried.

The fourth olefin polymerization catalyst according to the present invention comprises a fine particle carrier, [A] in the above general formula [I] , M is titanium, and
Ruconium or hafnium, Y is divalent silicon
Selected from the group consisting of a transition metal compound which is a containing group , [B] (B-1) an organoaluminum oxy compound, and (B-2) a compound which reacts with the transition metal compound [A] to form an ion pair. It is characterized in that it comprises a solid catalyst component carrying at least one kind of compound described above and [C] an organoaluminum compound.

The fifth olefin polymerization catalyst according to the present invention comprises a fine particle carrier, [A] in the above general formula [I] , M is titanium and
Ruconium or hafnium, Y is divalent silicon
Selected from the group consisting of a transition metal compound which is a containing group , [B] (B-1) an organoaluminum oxy compound, and (B-2) a compound which reacts with the transition metal compound [A] to form an ion pair. It is characterized in that it comprises at least one kind of compound described above and an olefin polymer produced by prepolymerization.

The sixth olefin polymerization catalyst according to the present invention comprises a fine particle carrier, [A] in the above general formula [I] , M is titanium, and
Ruconium or hafnium, Y is divalent silicon
Selected from the group consisting of a transition metal compound which is a containing group , [B] (B-1) an organoaluminum oxy compound, and (B-2) a compound which reacts with the transition metal compound [A] to form an ion pair. It is characterized by comprising at least one kind of compound, an organoaluminum compound [C], and an olefin polymer produced by prepolymerization.

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.

[0026]

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].

[0028]

[Chemical 13]

In the formula, M represents a transition metal of Groups 4, 5 and 6 of the Periodic Table, specifically, titanium, zirconium,
Hafnium, vanadium, niobium, tantalum, chromium,
Molybdenum and tungsten are preferable, titanium, zirconium and hafnium are preferable, and zirconium is particularly preferable.

R ¹ and R ² are a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a carbon atom having 1 to 20 carbon atoms.
20 halogenated hydrocarbon groups, silicon-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups or phosphorus-containing groups, specifically, halogen atoms such as fluorine, chlorine, bromine, iodine; methyl, ethyl , Propyl, butyl, hexyl, cyclohexyl, octyl, nonyl, dodecyl,
Alkyl groups such as eicosyl, norbornyl and adamantyl, alkenyl groups such as vinyl, propenyl and cyclohexenyl, arylalkyl groups such as benzyl, phenylethyl and phenylpropyl, phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl and propylphenyl, A hydrocarbon group having 1 to 20 carbon atoms such as an aryl group such as biphenyl, naphthyl, methylnaphthyl, anthracenyl, and phenanthryl; a halogenated hydrocarbon group in which the hydrocarbon group is substituted with a halogen atom; a monosilyl group such as methylsilyl and phenylsilyl. Dihydrocarbon-substituted silyl such as hydrocarbon-substituted silyl, dimethylsilyl, diphenylsilyl, trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl Trihydrocarbyl-substituted silyl such as dimethylphenylphenyl, methyldiphenylsilyl, tritolylsilyl, and trinaphthylsilyl, silyl ether of hydrocarbon-substituted silyl such as trimethylsilyl ether, silicon-substituted alkyl group such as trimethylsilylmethyl, trimethylphenyl, etc. A silicon-substituted aryl group,
Silicon-containing groups such as; hydroxy groups, alkoxy groups such as methoxy, ethoxy, propoxy, butoxy, allyloxy groups such as phenoxy, methylphenoxy, dimethylphenoxy, naphthoxy, and oxygen-containing groups such as arylalkoxy groups such as phenylmethoxy and phenylethoxy. A sulfur-containing group in which oxygen of the oxygen-containing compound is substituted with sulfur; an amino group, an alkylamino group such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, dicyclohexylamino, phenylamino, diphenylamino, ditolylamino, Nitrogen-containing groups such as arylamino groups such as dinaphthylamino and methylphenylamino or alkylarylamino groups; phosphino groups such as dimethylphosphino and diphenylphosphino Which is a phosphorus-containing group.

Of these, R ¹ is preferably a hydrocarbon group, and particularly preferably a methyl, ethyl or propyl hydrocarbon group having 1 to 3 carbon atoms. Also R ²
Is preferably a hydrogen atom or a hydrocarbon group, and particularly preferably a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms such as methyl, ethyl or propyl.

R ³ represents an alkyl group having 2 to 20 carbon atoms, and R ⁴ represents an alkyl group having 1 to 20 carbon atoms.
R ³ is preferably a secondary or tertiary alkyl group. The alkyl group represented by R ³ and R ⁴ may be substituted with a halogen atom or a silicon-containing group. Examples of the halogen atom and the silicon-containing group include the substituents exemplified for R ¹ and R ^2. .

R ⁴ is ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, pentyl, hexyl, cyclohexyl, heptyl,
Chain alkyl groups and cyclic alkyl groups such as octyl, nonyl, dodecyl, eicosyl, norbornyl, adamantyl; arylalkyl groups such as benzyl, phenylethyl, phenylpropyl, tolylmethyl, etc., and these groups are double-bonded. It may be substituted with a group having a triple bond.

Examples of R ³ include the alkyl groups exemplified for methyl and R ⁴ .

X ¹ and X ² are a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, and 1 to 1 carbon atoms.
20 represents a halogenated hydrocarbon group, an oxygen-containing group or a sulfur-containing group, and specifically, the same halogen atom as R ¹ and R ² described above, a hydrocarbon group having 1 to 20 carbon atoms, and 1 carbon atom Examples of the halogenated hydrocarbon group and oxygen-containing group of 20 are possible.

Examples of the sulfur-containing group include the same groups as those for R ¹ and R ² , and methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, p-toluene sulfonate, trimethylbenzene sulfonate. Sulfonate groups such as phonate, triisobutylbenzene sulfonate, p-chlorobenzene sulfonate, pentafluorobenzene sulfonate, methylsulfinate, phenylsulfinate, benzenesulfinate, p-toluenesulfinate Examples thereof include sulfinate groups such as trimethylbenzenesulfinate and pentafluorobenzenesulfinate.

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,
Divalent tin-containing group, -O-, -CO-, -S-, -SO
_{-, - SO 2 -, -} NR 5 -, - P (R 5) -, - P
^{(O) (R 5) -} , - BR 5 - or -AlR ⁵ - [however, R ⁵ is a hydrogen atom, a halogen atom, 1 to carbon atoms
20 hydrocarbon groups, halogenated hydrocarbon groups having 1 to 20 carbon atoms], specifically, methylene, dimethylmethylene, 1,2-ethylene, dimethyl-1,2-ethylene, 1,3-
1 to 20 carbon atoms such as alkylene groups such as trimethylene, 1,4-tetramethylene, 1,2-cyclohexylene and 1,4-cyclohexylene, aryl alkylene groups such as diphenylmethylene and diphenyl-1,2-ethylene A divalent hydrocarbon group having 1 to 2 carbon atoms such as chloromethylene
Halogenated hydrocarbon group obtained by halogenating a divalent hydrocarbon group of 0; methylsilylene, dimethylsilylene, diethylsilylene, di (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, methyl Alkylsilylene such as phenylsilylene, diphenylsilylene, di (p-tolyl) silylene, di (p-chlorophenyl) silylene, alkylarylsilylene, arylsilylene group, tetramethyl-1,2-disilyl, tetraphenyl-1,2- Divalent silicon-containing groups such as alkyldisilyl such as disilyl, alkylaryldisilyl, and arylsilyl groups; Divalent germanium-containing groups obtained by substituting germanium for silicon in the above divalent silicon-containing groups; and the like divalent tin-containing group substituents of the silicon-containing groups is replaced with tin, R ⁵ is Wherein R ^1, R ² the same halogen atom, hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms.

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

Specific examples of the transition metal compound represented by the above general formula [I] are shown below. rac-Dimethylsilyl-bis {1- (2,7-dimethyl-4-ethylindenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2,7-dimethyl-4-n-propylindenyl) } Zirconium dichloride, rac-dimethylsilyl-
Bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1-
(2,7-Dimethyl-4-n-butylindenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2,7-dimethyl-4-sec-butylindenyl)} zirconium dichloride, rac-dimethyl Silyl-bis {1- (2,7-dimethyl-4-t-
Butylindenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2,7-dimethyl-4-n-pentylindenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2,7- Dimethyl-4-n-hexylindenyl)} zirconium dichloride, rac-dimethylsilyl-
Bis {1- (2,7-dimethyl-4-cyclohexylindenyl)} zirconium dichloride, rac-dimethylsilyl-
Bis {1- (2,7-dimethyl-4-methylcyclohexylindenyl)} zirconium dichloride, rac-dimethylsilyl
-Bis {1- (2,7-dimethyl-4-phenylethylindenyl)} zirconium dichloride, rac-dimethylsilyl-
Bis {1- (2,7-dimethyl-4-phenyldichloromethylindenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2,7-dimethyl-4-chloromethylindenyl)} zirconium dichloride , Rac-dimethylsilyl-
Bis {1- (2,7-dimethyl-4-trimethylsilylmethylindenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2,7-dimethyl-4-trimethylsiloxymethylindenyl)} zirconium dichloride, rac-Diethylsilyl-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride, rac-di (i-propyl) silylbis {1- (2,7-dimethyl-4-i -Propylindenyl)} zirconium dichloride, rac-di (n-butyl)
Silylbis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride, rac-di (cyclohexyl) silylbis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium Dichloride, rac-methylphenylsilylbis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride, rac-methylphenylsilylbis {1- (2,7-dimethyl-4-t- Butylindenyl)}
Zirconium dichloride, rac-diphenylsilylbis {1- (2,7-dimethyl-4-t-butylindenyl)} zirconium dichloride, rac-diphenylsilylbis {1- (2,7-
Dimethyl-4-i-propylindenyl)} zirconium dichloride, rac-diphenylsilylbis {1- (2,7-dimethyl-4-ethylindenyl)} zirconium dichloride, r
ac-di (p-tolyl) silylbis {1- (2,7-dimethyl-4-i-
Propylindenyl)} zirconium dichloride, rac-
Di (p-chlorophenyl) silylbis {1- (2,7-dimethyl-
4-i-propylindenyl)} zirconium dichloride,
rac-Dimethylsilylbis {1- (2-methyl-4-i-propyl-7
-Ethylindenyl)} zirconium dibromide rac-dimethylsilylbis {1- (2,3,7-trimethyl-4-ethylindenyl)} zirconium dichloride, rac-dimethylsilylbis {1- (2,3,7 -Trimethyl-4-n-propylindenyl)} zirconium dichloride, rac-dimethylsilylbis {1- (2,3,7-trimethyl-4-i-propylindenyl)} zirconium dichloride, rac-dimethylsilylbis { 1- (2,3,7-trimethyl-4-n-butylindenyl)} zirconium dichloride, rac-dimethylsilylbis {1-
(2,3,7-Trimethyl-4-sec-butylindenyl)} zirconium dichloride, rac-dimethylsilylbis {1- (2,3,7
-Trimethyl-4-t-butylindenyl)} zirconium dichloride, rac-dimethylsilylbis {1- (2,3,7-trimethyl-4-n-pentylindenyl)} zirconium dichloride, rac-dimethylsilylbis { 1- (2,3,7-trimethyl-
4-n-hexylindenyl)} zirconium dichloride,
rac-Dimethylsilylbis {1- (2,3,7-trimethyl-4-cyclohexylindenyl)} zirconium dichloride, ra
c-Dimethylsilylbis {1- (2,3,7-trimethyl-4-methylcyclohexylindenyl)} zirconium dichloride, rac-dimethylsilylbis {1- (2,3,7-trimethyl-4-
Trimethylsilylmethylindenyl)} zirconium dichloride, rac-dimethylsilylbis {1- (2,3,7-trimethyl-4-trimethylsiloxymethylindenyl)} zirconium dichloride, rac-dimethylsilylbis {1- (2,
3,7-Trimethyl-4-phenylethylindenyl)} zirconium dichloride, rac-dimethylsilylbis {1- (2,
3,7-Trimethyl-4-phenyldichloromethylindenyl)} zirconium dichloride, rac-dimethylsilylbis {1- (2,3,7-trimethyl-4-chloromethylindenyl)} zirconium dichloride, rac-diethyl Silylbis {1- (2,3,7-trimethyl-4-i-propylindenyl)}
Zirconium dichloride, rac-di (i-propyl) silylbis {1- (2,3,7-trimethyl-4-i-propylindenyl)} zirconium dichloride, rac-di (n-butyl) silylbis {1- (2 , 3,7-Trimethyl-4-i-propylindenyl)} zirconium dichloride, rac-di (cyclohexyl) silylbis {1- (2,3,7-trimethyl-4-i-propylindenyl)} zirconium dichloride, rac-Methylphenylsilylbis {1- (2,3,7-trimethyl-4-i-propylindenyl)} zirconium dichloride, rac-methylphenylsilylbis {1- (2,3,7-trimethyl-4- t-Butylindenyl)} zirconium dichloride, rac-diphenylsilylbis {1- (2,3,7-trimethyl-4-t-butylindenyl)} zirconium dichloride, rac-diphenylsilylbis {1- (2, 3,7-Trimethyl-4-i-propylindenyl)} zirconium di Chloride, rac-diphenylsilylbis {1- (2,3,7-trimethyl-4-ethylindenyl)} zirconium dichloride, rac-di (p-tolyl) silylbis {1- (2,3,7-trimethyl- 4-i-Propylindenyl)} zirconium dichloride, rac-di (p-chlorophenyl) silylbis {1- (2,3,7-trimethyl-4-i-propylindenyl)} zirconium dichloride, rac-dimethylsilyl-
Bis {1- (2-methyl-4-i-propyl-7-methylindenyl)} zirconium dimethyl, rac-dimethylsilyl-bis {1- (2-methyl-4-i-propyl-7-methylindenyl) )} Zirconium methyl chloride, rac-dimethylsilyl-bis {1- (2-methyl-4-i-propyl-7-methylindenyl)} zirconium-bis (methanesulfonato), rac
-Dimethylsilyl-bis {1- (2-methyl-4-i-propyl-7-
Methylindenyl)} zirconium-bis (p-phenylsulfinato), rac-dimethylsilyl-bis {1- (2-methyl-3-methyl-4-i-propyl-7-methylindenyl)}
Zirconium dichloride, rac-dimethylsilyl-bis {1
-(2-Ethyl-4-i-propyl-7-methylindenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1-
(2-Phenyl-4-i-propyl-7-methylindenyl)}
Zirconium dichloride, rac-dimethylsilyl-bis {1
-(2-Methyl-4-i-propyl-7-methylindenyl)} titanium dichloride, rac-dimethylsilyl-bis {1- (2-
Methyl-4-i-propyl-7-methylindenyl)} hafnium dichloride and the like.

Among these, those having a branched alkyl group such as i-propyl, sec-butyl, tert-butyl group at the 4-position are particularly preferable.

In the present invention, it is also possible to use a transition metal compound in which zirconium metal is replaced with titanium metal, hafnium metal, vanadium metal, niobium metal, tantalum metal, chromium metal, molybdenum metal, or tungsten metal in the above compounds. it can.

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.

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

[0044]

[Chemical 14]

The transition metal compound according to the present invention can be obtained by a known method from these indene derivatives, for example, JP-A-4-26.
It can be synthesized by the method described in Japanese Patent No. 8307.

Next, an olefin polymerization catalyst containing the above-mentioned novel transition metal compound as a catalyst component will be described. In the present invention, the term "polymerization" may be used to mean not only homopolymerization but also copolymerization, and the term "polymer" may refer to not only a homopolymer but also a copolymer. May be used in the inclusive sense.

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 is [A] in the above general formula [I] , M is titanium,
Ruconium or hafnium, Y is divalent silicon
A transition metal compound which is a containing group (hereinafter sometimes referred to as “component [A]”), [B] (B-1) an organoaluminum oxy compound, and (B-2) the transition metal compound [A ] And at least one compound selected from the group consisting of compounds that react with the above to form an ion pair.

A second olefin polymerization catalyst according to the present invention is [A] in the above general formula [I] , M is titanium,
Ruconium or hafnium, Y is divalent silicon
It comprises a transition metal compound [A] which is a containing group , [B] (B-1) an organoaluminum oxy compound, and (B-2) a compound which reacts with the transition metal compound [A] to form an ion pair. It is formed from at least one compound selected from the group and an organic aluminum compound [C].

(B-1) Organoaluminum oxy compound used in the first and second olefin polymerization catalysts according to the present invention (hereinafter sometimes referred to as "component (B-1)").
May be a conventionally known aluminoxane, or may 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, ceric chloride hydrate, etc. A method of adding an organoaluminum compound such as a trialkylaluminum to the hydrocarbon medium suspension, and reacting the organoaluminum compound with adsorbed water or crystallization water. (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.

Specific examples of the organoaluminum compound used when preparing the aluminoxane include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum and 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 particularly preferable.
Further, as the organoaluminum compound used when preparing the aluminoxane, isoprenylaluminum represented by the following general formula [II] can also be used.

[0054] _{(i-C 4 H 9)} x Al y (C 5 H 10) z ... [II] ( wherein, x, y, z are each a positive number, and z ≧ 2x.) Above Such organoaluminum compounds may be used alone or in combination.

As the solvent used in the aluminoxane solution, aromatic hydrocarbons such as benzene, toluene, xylene, cumene and cymene, and aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane. , Cyclopentane, cyclohexane, cyclooctane, methylcyclopentane, and other alicyclic hydrocarbons, petroleum fractions such as gasoline, kerosene, and light oil, or the above aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbon halides Among these, hydrocarbon solvents such as chlorinated compounds and brominated compounds are mentioned. In addition, ethers such as ethyl ether and tetrahydrofuran can also be used. Of these solvents, aromatic hydrocarbons are particularly preferable.

(B-2) Used in the first and second olefin polymerization catalysts of 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 ) ”).), As described in JP-A-1-501950, JP-A-1-502036, JP-A-3-179005, and JP-A-3-179.
Examples thereof include Lewis acids, ionic compounds, borane compounds and carborane compounds described in JP-A No. 006, JP-A-3-207703, JP-A-3-207704, US-547718 and the like.

As the Lewis acid, Mg-containing Lewis acid, Al
Examples thereof include a Lewis acid containing B and a Lewis acid containing B, and among these, a Lewis acid containing B is preferable. Specific examples of the Lewis acid containing a boron atom include compounds represented by the following general formula.

BR ⁶ R ⁷ R ⁸ (In the formula, R ⁶ R ⁷ and R ⁸ are each independently a phenyl group which may have a substituent such as a fluorine atom, a methyl group and a trifluoromethyl group. Or a fluorine atom.) Specific examples of the compound represented by the above general formula include trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, Examples thereof include tris (4-fluoromethylphenyl) boron, tris (pentafluorophenyl) boron, tris (p-tolyl) boron, tris (o-tolyl) boron, and tris (3,5-dimethylphenyl) boron.
Of these, tris (pentafluorophenyl) boron is particularly preferable.

The ionic compound used in the present invention is a salt composed of a cationic compound and an anionic compound. The anion has a function of cationizing the transition metal compound [A] by reacting with the transition metal compound [A] and stabilizing the transition metal cation species by forming an ion pair. Examples of such anions include an organic boron compound anion, an organic arsenic compound anion, and an organic aluminum compound anion, and those which are relatively bulky and stabilize the transition metal cation species are preferable. Examples of the cation include a metal cation, an organometallic cation, a carbonium cation, a tripium cation, an oxonium cation, a sulfonium cation, a phosphonium cation, and an ammonium cation. More specifically, it includes a triphenylcarbenium cation, a tributylammonium cation, an N, N-dimethylammonium cation, and a ferrocenium cation.

Of these, an ionic compound containing a boron compound as an anion is preferable, and specifically,
Examples of the trialkyl-substituted ammonium salt include triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) ammonium tetra (phenyl) boron,
Trimethylammonium tetra (p-tolyl) boron, Trimethylammonium tetra (o-tolyl) boron, Tributylammonium tetra (pentafluorophenyl)
Boron, tripropylammonium tetra (o, p-dimethylphenyl) boron, tributylammonium tetra (m, m-dimethylphenyl) boron, tributylammonium tetra (p-trifluoromethylphenyl) boron,
Examples thereof include tri (n-butyl) ammonium tetra (o-tolyl) boron and tri (n-butyl) ammonium tetra (4-fluorophenyl) boron. Examples of N, N-dialkylanilinium salts include N, N -Dimethylanilinium tetra (phenyl) boron, N, N-diethylanilinium tetra (phenyl) boron, N, N-2,4,6-pentamethylanilinium tetra (phenyl) boron, and the like,
Examples of the dialkyl ammonium salt include di (n-propyl) ammonium tetra (pentafluorophenyl)
Examples thereof include boron and dicyclohexylammonium tetra (phenyl) boron, and triarylphosphonium salts such as triphenylphosphonium tetra (phenyl) boron, tri (methylphenyl) phosphonium tetra (phenyl) boron and tri (dimethyl). Phenyl)
Examples include phosphonium tetra (phenyl) boron.

In the present invention, as an ionic compound containing a boron atom, triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferrocenium tetra (pentafluoro) Mention may also be made of (phenyl) borate.

The following compounds can also be exemplified.
(In the ionic compounds listed below, the counter ion is, but not limited to, tri (n-butyl) ammonium.) Anion salts such as bis [tri (n-butyl) ammonium] nonaborate and bis [tri] (N-Butyl) ammonium] decaborate, bis [tri (n-butyl) ammonium] undecaborate, bis [tri (n-butyl) ammonium] dodecaborate, bis [tri (n-butyl) ammonium] decachlorodecaborate , Bis [tri (n-butyl) ammonium] dodecachlorododecaborate, tri (n-butyl) ammonium-1-
Carbadecaborate, tri (n-butyl) ammonium-1
-Carbaundecaborate, tri (n-butyl) ammonium-1-carbadodecaborate, tri (n-butyl) ammonium-1-trimethylsilyl-1-carbadecaborate,
Examples thereof include tri (n-butyl) ammonium bromo-1-carbadodecaborate; and borane compounds and carborane compounds. These compounds are used as Lewis acids and ionic compounds.

Borane and carborane complex compounds and salts of carborane anions, such as decaborane (14), 7,
8-dicarbaundecaborane (13), 2,7-dicarbaundecaborane (13), undecahydride-7,8-dimethyl-7,8-dicarbaundecaborane, dodecahydride-11-methyl-2, 7-Dicarbaundecaborane, tri (n-
Butyl) ammonium 6-carbadecaborate (14),
Tri (n-butyl) ammonium 6-carbadecaborate (12), tri (n-butyl) ammonium 7-carbaundecaborate (13), tri (n-butyl) ammonium
7,8-dicarbaundecaborate (12), tri (n-butyl) ammonium 2,9-dicarbaundecaborate (1)
2), tri (n-butyl) ammonium dodecahydride-8-methyl 7,9-dicarbaundecaborate, tri (n-
Butyl) ammonium undeca hydride 8-ethyl-
7,9-Dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-butyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-allyl-7, 9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-9-trimethylsilyl-7,8-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-4,6-dibromo-7- Carbalane and carborane salts, such as 4-carbanonaborane (14), 1,3-dicarbanonaborane (13), 6,9-dicarbadecaborane (14), dodecahydride-1-phenyl -1,3-Dicarbano Naborane, Dodeca Hydride-
The following compounds can also be exemplified, such as 1-methyl-1,3-dicarbanonaborane and undecahydride-1,3-dimethyl-1,3-dicarbanonaborane. (In the ionic compounds listed below, the counter ion is, but not limited to, tri (n-butyl) ammonium.) A salt of metal carborane and a metal borane anion such as tri (n-butyl) ammonium bis (nona). Hydride-
1,3-Dicarbanonaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) ferrate (ferrate) (III), tri (n-) Butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate)
Cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) nickelate (III), tri (n-butyl) ammonium bis (undecahydride-7,8- Dicarbaundecaborate) cubrate (cuprate) (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) aurate (metal salt) (III), tri (n-) Butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarbaundecaborate) ferrate (III), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8- Dicarbaundecaborate) Chromate (Chromate) (II
I), tri (n-butyl) ammonium bis (tribromooctahydride-7,8-dicarbaundecaborate)
Cobaltate (III), tri (n-butyl) ammonium bis (dodeca hydride dicarbadodecaborate) Cobaltate (III), bis [tri (n-butyl) ammonium] bis (dodeca hydride dodecaborate) nickelate (III), Tris [Tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) chromate (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) Manganate (IV), Bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) Cobaltate (II
I), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate) nickelate (IV) and the like.

The compound (B-2) which reacts with the above transition metal compound [A] to form an ion pair can be used as a mixture of two or more kinds. The [C] organoaluminum compound used in the second olefin polymerization catalyst according to the present invention (hereinafter sometimes referred to as "component [C]").
For example, an organoaluminum compound represented by the following general formula [III] can be exemplified.

R ⁹ _n AlX _3-n ... [III] (wherein, R ⁹ is a hydrocarbon group having 1 to 12 carbon atoms, X is a halogen atom or a hydrogen atom, and n is 1 to 1).
It is 3. ) In the above general formula [III], R ⁹ has 1 to 1 carbon atoms.
2 hydrocarbon groups such as an alkyl group, a cycloalkyl group or an aryl group, specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an isobutyl group,
Examples include a pentyl group, a hexyl group, an octyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group and a tolyl group.

Such an organoaluminum compound [C]
Specifically, the following compounds may be mentioned. Trialkyl aluminum such as trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, trioctyl aluminum, tri (2-ethylhexyl) aluminum; alkenyl aluminum such as isoprenyl aluminum; dimethyl aluminum chloride, diethyl aluminum chloride, diisopropyl aluminum chloride. , Diisobutylaluminum chloride, dimethylaluminum bromide and other dialkylaluminum halides; methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide and other alkylaluminum sesquihalides; methyl Alkylaluminum dihalides such as aluminum aluminum dichloride, ethylaluminum dichloride, isopropylaluminum dichloride and ethylaluminum dibromide; alkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride.

As the organoaluminum compound [C], a compound represented by the following general formula [IV] can also be used. R ⁹ _n AlL _3-n ... [IV] (In the formula, R ⁹ is the same as above, L is a —OR ¹⁰ group,
OSiR ¹¹ ₃ group, -OAlR ¹² ₂ group, -NR ¹³ ₂ group, -Si
R ¹⁴ ₃ group or —N (R ¹⁵ ) AlR ¹⁶ ₂ group, n is 1 to
2, R ¹⁰ , R ¹¹ , R ¹² and R ¹⁶ are a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, a phenyl group and the like, and R ¹³ is a hydrogen atom, a methyl group, an ethyl group, isopropyl group. Group, phenyl group, trimethylsilyl group and the like, R ¹⁴ and R ¹⁵ are methyl groups,
For example, an ethyl group. ) As such an organoaluminum compound, the following compounds are specifically used. (1) A compound represented by R ⁹ _n Al (OR ¹⁰ ) _3-n , for example, dimethyl aluminum methoxide, diethyl aluminum ethoxide, diisobutyl aluminum methoxide, etc. (2) R ⁹ _n Al (OSiR ¹¹ ₃ ) ₃ a compound represented by _-n , for example, Et ₂ Al (OSi Me ₃ ), (iso-Bu) ₂ Al (OSiM
e ₃ ), (iso-Bu) ₂ Al (OSiEt ₃ ), etc .; (3) Compounds represented by R ⁹ _n Al (OAlR ¹² ₂ ) _3-n , for example, Et ₂ AlOAiLet ₂ , (iso-Bu) ₂ AlOAl (iso-B
u) _{2 and the} like; (4) compounds represented by R ⁹ _n Al (NR ¹³ ₂ ) _3-n , such as Me ₂ AlNEt ₂ , Et ₂ AlNHMe, Me ₂ AlNHEt,
_{Et 2 AlN (SiMe 3) 2} , (iso-Bu) 2 AlN (SiMe 3) 2
(5) A compound represented by R ⁹ _n Al (SiR ¹⁴ ₃ ) _3-n , such as (iso-Bu) ₂ AlSi Me ₃ ; (6) R ⁹ _n Al (N (R ¹⁵ ) AlR ¹⁶ ₂ ) _3-n , such as Et ₂ AlN (Me) AlEt ₂ , (iso-Bu) ₂ AlN
(Et) Al (iso-Bu) ₂ etc.

Among the organoaluminum compounds represented by the above general formulas [III] and [IV], the general formula R ⁹ ₃ Al,
The compounds represented by R ⁹ _n Al (OR ¹⁰ ) _3-n and R ⁹ _n Al (OAlR ¹² ₂ ) _3-n are preferable, and the compound in which R ⁹ is an isoalkyl group and n = 2 is particularly preferable.

In the present invention, the above component [A] and the component (B-
In addition to 1), component (B-2) and component [C], water may be used as a catalyst component. The water used in the present invention may be exemplified by water dissolved in a polymerization solvent as described below, or adsorbed water containing a compound or salt used in producing the component (B-1), and crystal water. it can.

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.

In this case, 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 comprises a component [A] and a component (B
-1) (or component (B-2)), component [C] and optionally water as a catalyst component can be prepared by mixing them in an inert hydrocarbon solvent or an olefin solvent.

In this case, the order of mixing the 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 using the component (B-2), the component [C]
It is preferable to mix the component (A) with the component [A], and then mix the component (B-2). FIG. 1 shows steps for preparing the first and second olefin polymerization catalysts according to the present invention.

When mixing the above components, the components (B-
The atomic ratio (Al / transition metal) between aluminum in 1) and the transition metal in component [A] is usually 10 to 10,000, preferably 20 to 5,000, and the concentration of component [A] is
About 10 ^-8 to 10 ^-1 mol / liter, preferably 10 ^-7 to
It is in the range of 5 × 10 ^-2 mol / liter.

When the component (B-2) is used, it is mixed with the component [A].
The molar ratio with the component (B-2) (component [A] / component (B-2)) is usually
The range is 0.01 to 10, preferably 0.1 to 5,
The concentration of minute [A] is about 10^-8-10^-1Mol / liter,
Preferably 10^-7~ 5 x 10 ^-2In the mole / liter range
is there.

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

When water is used as the catalyst component, the molar ratio of 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 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 according to 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. The third catalyst for olefin polymerization according to the present invention comprises: [A] in the above general formula [I] , M is titanium,
Ruconium or hafnium, Y is divalent silicon
Selected from the group consisting of a transition metal compound which is a containing group , [B] (B-1) an organoaluminum oxy compound, and (B-2) a compound which reacts with the transition metal compound [A] to form an ion pair. And at least one compound that is carried.

The fourth catalyst for olefin polymerization according to the present invention comprises a fine particle carrier, [A] in the above general formula [I] , M is titanium and di
Ruconium or hafnium, Y is divalent silicon
Selected from the group consisting of a transition metal compound which is a containing group , [B] (B-1) an organoaluminum oxy compound, and (B-2) a compound which reacts with the transition metal compound [A] to form an ion pair. And a solid catalyst component carrying at least one compound described above, 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 above-mentioned 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 is the component (B) used in the above-mentioned first and second olefin polymerization catalysts. The same organoaluminum oxy compound as described in -1) can be exemplified.

Examples of the compound (B-2) used in the third and fourth olefin polymerization catalysts according to 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.

Further, as the [C] organoaluminum compound used in the fourth olefin polymerization catalyst according to the present invention, the same organoaluminum compound as the 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, porous oxides are used as the inorganic carrier.
Preferably, specifically, SiO₂, Al₂O₃, MgO, Z
rO₂, TiO₂, B₂O₃, CaO, ZnO, BaO, T
hO ₂Or a mixture thereof, such as SiO₂-M
gO, SiO₂-Al₂O₃, SiO₂-TiO₂, SiO₂-
V₂O_Five, SiO₂-Cr₂O₃, SiO₂-TiO₂-MgO
What can be illustrated. Among these SiO₂And
And Al₂O₃At least one selected from the group consisting of
Those containing minutes as the main component are preferable.

The above inorganic oxide contains a small amount of Na ₂ C.
O ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO ₄ ,
Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO ₃ ) ₂ ,
Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, Li ₂ O and other carbonates, sulfates, nitrates and oxides may be contained.

The properties of such a fine particle carrier vary depending on the type and production method, but the fine particle carrier preferably used in the present invention has a specific surface area of 50 to 1000 m ² /
g, preferably 100 to 700 m ² / g, and the pore volume is preferably 0.3 to 2.5 cm ³ / g. The fine particle carrier is used by firing at a temperature of 100 to 1000 ° C., preferably 150 to 700 ° C., if necessary.

Further, as the fine particle carrier which can be used in the present invention, a granular or fine particle solid of an organic compound having a particle diameter of 10 to 300 μm can be mentioned. Examples of these organic compounds include (co) polymers produced mainly from α-olefins having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, and 4-methyl-1-pentene, or vinylcyclohexane, styrene. The polymer or copolymer produced by using as a main component can be exemplified.

Such a fine particle carrier may contain surface hydroxyl groups or water. In that case, it is desirable that the amount of surface hydroxyl groups is 1.0% by weight or more, preferably 1.5 to 4.0% by weight, particularly preferably 2.0 to 3.5% by weight, and water is 1.0% by weight. 0% by weight or more, preferably 1.2 to
The amount is preferably 20% by weight, more preferably 1.4 to 15% by weight. The water contained in the fine particle carrier means water adsorbed on the surface of the fine particle carrier.

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

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

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 a 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 component (B-1) (or component (B-2)), and optionally water, in an inert hydrocarbon solvent or in 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 particulate carrier and the component (B-1) (or the component (B-2)).
And are brought into mixed contact, and then the component [A] is brought into mixed contact,
If desired, water may be mixed and contacted, or component (B-1)
(Or component (B-2)) and component [A] are mixed and contacted with a fine particle carrier, and then water is optionally mixed and contacted, or alternatively, the fine particle carrier and component (B-1) are contacted.
(Or component (B-2)) and water are mixed and contacted, and then component [A] is mixed and contacted.

FIG. 1 shows the steps for preparing the third and fourth olefin polymerization catalysts according to the present invention. When mixing the above-mentioned components, the component [A] is usually 10 ^{−6 to} 5 × 10 ⁻³ mol, preferably 3 × 10 3, per 1 g of the particulate carrier.
Used in an amount of ^-6 to 10 ^-3 mol, the concentration of the component [A] is
The range is about 5 × 10 ^{−6 to} 2 × 10 ⁻² mol / liter, preferably 2 × 10 ⁻⁵ to 10 ⁻² mol / liter. component
The atomic ratio (Al / transition metal) between the aluminum in (B-1) and the transition metal in the component [A] is usually 10 to 3000,
It is preferably 20 to 2000. When the component (B-2) is used, the molar ratio of the component [A] and the component (B-2) (the component [A]
/ Component (B-2)) is usually 0.01 to 10, preferably 0.1.
It is in the range of 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 of the present invention will be described. The fifth catalyst for olefin polymerization according to the present invention comprises a fine particle carrier, [A] in the above general formula [I] , M is titanium, and
Ruconium or hafnium, Y is divalent silicon
Selected from the group consisting of a transition metal compound which is a containing group , [B] (B-1) an organoaluminum oxy compound, and (B-2) a compound which reacts with the transition metal compound [A] to form an ion pair. At least one compound described above and an olefin polymer produced by prepolymerization.

A sixth olefin polymerization catalyst according to the present invention comprises a fine particle support, [A] in the above general formula [I] , M is titanium and di
Ruconium or hafnium, Y is divalent silicon
Selected from the group consisting of a transition metal compound which is a containing group , [B] (B-1) an organoaluminum oxy compound, and (B-2) a compound which reacts with the transition metal compound [A] to form an ion pair. At least one compound, a [C] organoaluminum compound, 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 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) used in the above-mentioned first and second olefin polymerization catalysts. The same organoaluminum oxy compound as described in -1) can be exemplified.

Examples of the compound (B-2) used in the fifth and sixth olefin polymerization catalysts of the present invention to react with the transition metal compound [A] to form an ion pair are:
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 comprises the above-mentioned fine particle carrier, the component [A], the component (B-1) (or the component (B-2)) and optionally water and an inert carbon. It can be prepared by prepolymerizing a small amount of olefin to a solid catalyst component obtained by mixing and contacting with a hydrogen fluoride solvent or an olefin medium. Further, the component [C] can be further added at the time of mixing and contacting.

At this time, the order of mixing the respective components is arbitrarily selected, but preferably the fine particle carrier and the component (B-1) (or the component (B-2)) are mixed and brought into contact with each other, and then the component [A]. Are mixed and contacted with water if desired, or a mixture of the component (B-1) (or component (B-2)) and the component [A] is mixed and contacted with a fine particle carrier, and then, If desired, water may be mixed and contacted, or fine particle carrier and components
It is selected that (B-1) (or component (B-2)) and water are mixed and contacted, and then component [A] is mixed and contacted.

It is desirable to carry out the mixing contact with stirring. FIG. 3 shows steps of preparing the fifth and sixth olefin polymerization catalysts according to the present invention.

When mixing the above components,
[A] is usually 10 per 1 g of the particulate carrier.^-6~ 5 x 1
0^-3Mol, preferably 3 × 10^-6-10^-3For use in molar amounts
The concentration of ingredient [A] is approximately 5 x 10^-6~ 2 x 10^-2
Mol / l, preferably 10 ^-Five-10^-2Mol / li
It is in the Torr range. Aluminum in component (B-1)
Atomic ratio with transition metal in minute [A] (Al / transition metal)
Is usually 10 to 3000, preferably 20 to 2000
is there. When using component (B-2), component [A] and component (B-2)
The molar ratio (component [A] / component (B-2)) is usually 0.01
The range is from 10 to 10, preferably from 0.1 to 5.

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 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 an olefin in the presence of each of the above components. Preliminary polymerization can be carried out by introducing an olefin into an inert hydrocarbon solvent in the presence of the above-mentioned components or, if necessary, in the coexistence of the component [C].

In the prepolymerization, the component [A] is usually 10 ^-5 to 2 × 10 ^-2 mol / liter, preferably 5 × 1.
It is used in an amount of 0 ^-5 to 10 ^-2 mol / liter, and the prepolymerization temperature is -20 to 80 ° C, preferably 0 to 50 ° C.
The prepolymerization time is 0.5 to 100 hours, preferably 1
It is about 50 hours.

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

[0119] 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. In addition, the component (B-2) is a borax derived from the component (B-2).
5 × 10 as elementary atoms ^-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 preferably 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 catalyst for olefin polymerization according to the present invention may contain other components useful for olefin polymerization in addition to the above 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 polyolefin obtained by such an olefin polymerization catalyst according to the present invention has a narrow molecular weight distribution and composition distribution, a high molecular weight, and a high polymerization activity.
When an olefin having 3 or more carbon atoms is polymerized, a polyolefin having excellent stereoregularity can be obtained.

Next, 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 the olefin polymerization using the first or second olefin polymerization catalyst of the present invention, the above-mentioned catalyst usually has a concentration of transition metal atoms derived from the component [A] in the polymerization system of 10 ^{− 8-10 -3} gram atom / liter,
It is preferably used in an amount of 10 ⁻⁷ to 10 ⁻⁴ gram atom / liter.

Third or Fourth Olefin Polymerization of the Present Invention
When carrying out the polymerization of olefins using a catalyst for use
The catalysts such as the above are transitions derived from the component [A] in the polymerization system.
The concentration of metal atoms is usually 10^-8-10^-3Gram atom
/ Liter, preferably 10 ^-7-10^-FourGram atom / Li
It is preferably used in the amount of tottle. At this time, desired
Therefore, aluminoxane may be used.

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, an organoaluminum compound or aluminoxane may be used if desired. Examples of the organoaluminum compound used at this time include the same compounds as the above-mentioned component [C]. As the usage amount,
It is desirable that the range is 0 to 500 mol per gram atom of the transition metal atom.

The olefin polymerization temperature is usually in the range of -50 to 100 ° C., preferably 0 to 90 ° C. when carrying out the slurry polymerization method, and when carrying out the liquid phase polymerization method. , Usually 0 to 250 ° C., preferably 20 to
It is preferably in the range of 200 ° C. Further, when carrying out the gas phase polymerization method, the polymerization temperature is usually 0 to 120 ° C., preferably 20 to 100 ° C.
The polymerization pressure is usually from atmospheric pressure to 100 kg / cm ² , preferably from atmospheric pressure to 50 kg / cm ² , and the polymerization reaction may be carried out by any of batch, semi-continuous and continuous methods. You can In addition, polymerization is performed under different reaction conditions 2
It is also possible to divide into more than one step.

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. The olefins that can be polymerized by the olefin polymerization catalyst according to the present invention include ethylene and 3 to 2 carbon atoms.
0 α-olefins such as propylene, 1-butene, 1-
Pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene; 3 to 20 carbon atoms Cyclic olefins such as cyclopentene,
Cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, etc. Can be mentioned. Further, styrene, vinylcyclohexane, diene and the like can be used.

[0130]

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 of the present invention is highly active and can produce a polyolefin having a narrow molecular weight distribution and narrow composition distribution. When used for the polymerization of α-olefins having 3 or more carbon atoms, a polymer having an equivalent molecular weight and a low melting point is obtained as compared with a polymer using a conventional metallocene catalyst.

By using such a catalyst, a copolymer having a low melting point can be obtained with a small amount of comonomer. Further, since the amount of the solvent-soluble polymer is small, the yield is high, and the obtained copolymer has excellent qualities such as transparency, heat sealability and blocking resistance. Furthermore, the number of reaction steps in the synthesis is small and it is economical as compared with the conventional metallocene-based catalysts that can obtain polypropylene having an equivalent molecular weight.

Many different kinds of bonds are present in the polyolefin molecule obtained by polymerizing an α-olefin having 3 or more carbon atoms with the olefin polymerization catalyst according to the present invention. In addition to the usual 1,2-insertion, 2,1-insertion and 1,3-insertion are available in the insertion form of α-olefin in the case of polymerizing α-olefin having 3 or more carbon atoms with a chiral metallocene catalyst. It is known that heterogeneous bonds such as head-to-head bonds are formed in polyolefin molecules as a result (for example, K. Soga, T. Shiono, S. Takemura and W. Kaminsky, Makr).
Omol. Chem ,. Rapid Commun., 8, 305 (1987)). It is also known that the melting point of a polyolefin when the heterogeneous bond is present in the polyolefin molecule is low for its stereoregularity (T.Tsutsui, N. Ishimura, A. Mizuno, A. Toyo).
taand N. Kashiwa, Polymer, 30, 1350 (1989)).

The polyolefin obtained by polymerizing an α-olefin having 3 or more carbon atoms with the olefin polymerization catalyst according to the present invention has many different kinds of bonds. Therefore, it is the same as that obtained by using a conventional catalyst. It is considered that the melting point is lower than that of the polyolefin having the above molecular weight.

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. Furthermore, when used in the production of a block copolymer of propylene, the molecular weight of the copolymer elastomer can be increased, so that an excellent balance between heat resistance, rigidity or transparency and impact strength can be 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.

[0136]

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 the present invention, the intrinsic viscosity [η], molecular weight distribution (Mw / Mn), stereoregularity (mmmm), heterogeneous bond, and melting point (Tm) are measured as follows. [Intrinsic viscosity [η]] measured in decalin at 135 ° C, dl
/ G.

[Molecular Weight Distribution (Mw / Mn)] The molecular weight distribution (Mw / Mn) was measured as follows using GPC-150C manufactured by Millipore.

The separation column was TSK GNH HT, the column size was 72 mm in diameter and 600 mm in length, the column temperature was 140 ° C., the mobile phase was o-dichlorobenzene (Wako Pure Chemical Industries) and an antioxidant. As BH
Using T (Takeda Yakuhin) 0.025% by weight, the sample was moved at 1.0 ml / min, the sample concentration was 0.1% by weight, the sample injection amount was 500 microliters, and a differential refractometer was used as a detector. . Standard polystyrene has a molecular weight of Mw <10
00 and Mw> 4 × 10 ⁶ were manufactured by Tosoh Corporation, and 1000 <Mw <4 × 10 ⁶ were manufactured by Pressure Chemicals.

[Stereoregularity (fraction of mmmm pentad)] The stereoregularity is about 50 mg of a sample in a mixed solvent of 0.5 ml of o-dichlorobenzene (or hexachlorobutadiene) and 0.1 ml of deuterated benzene and 5 mmφ. After completely dissolving in an NMR sample tube at about 120 ° C., it was measured by JEOL GX500 type NMR (measured nuclide; ¹³ C,
Measurement mode; complete decoupling of protons, measurement temperature;
120 ° C).

The peak that resonates at the lowest magnetic field on the ¹³ C-NMR spectrum (21.8 ppm in the literature, A. Zambell
i, P.Locatelli, G.Bajo, and FABovey, Macromolecul
es, 8, 687, (1975)) was divided by the total peak area of the methyl group to give a value of mmmm pentad fraction.

[Heterogeneous Bond] Present in the propylene chain
The amount of 2,1-insertion and heterologous bond based on 1,3-insertion was determined by ¹³ C-NMR spectrum in the same manner as the measurement of stereoregularity. The frequency of 2,1-insertion and 1,3-insertion can be calculated by the following formula.

[0143]

[Equation 1]

Here, Iαα is the αα carbon peak (42.
Resonance around 0 ppm and 46.2 ppm), Iαβ is the αβ carbon peak (30.2 ppm and 3
Resonating around 5.6 ppm), Iαδ is αδ
It is the area of the carbon peak (which resonates near 37.1 ppm). The names of peaks such as αα follow Carman's classification (CJ Carman and CEWilkes, Rubber Chem.Techn.
ol., 44, 781 (1971)).

[Melting point (Tm)] About 5 mg of a sample was packed in an aluminum pan, heated to 200 ° C. at 10 ° C./minute, kept at 200 ° C. for 5 minutes, then cooled to room temperature at 20 ° C./minute, and then 10 ° C. It was determined from the endothermic curve when the temperature was raised in / min. For the measurement, a Perkin Elmer DSC-7 type device was used.

[0146]

[Example 1] [Rac-Dimethylsilyl-bis {1- (4-isopropyl-2,7-
Dimethylindenyl)} zirconium dichloride
Formed](4-isopropyl-2,7-dimethyl) indene (compound
) Synthesis Add aluminum chloride to a 1 liter reactor that has been thoroughly purged with nitrogen.
90 g of um (0.67 mol) and 150 ml of carbon disulfide
Charge, p-cymene 47ml (0.30mol) into this
Add 33 ml (0.3 mol) of methacryloyl chloride.
A solution mixed with 30 ml of carbon sulfide is added dropwise at 20 to 25 ° C.
did. After reacting for 12 hours at room temperature, add to 1 kg of ice,
Extraction was performed with ether. Saturate the resulting ether solution
After washing with sodium bicarbonate water, wash the ether layer further with water.
The tell layer was concentrated to obtain 68 g of oil. this
Silica gel column chromatography (developing solution)
When purified with a medium: n-hexane, 2,4-dimethyl-7-
Propyl-1-indanone and 2,7-dimethyl-4-isopropyl
42 g of a mixture (mixture) with 1-indanone was obtained.
(Yield: 67%).

To a 1 liter reactor which had been sufficiently purged with nitrogen was charged 2.82 g (0.075 mol) of lithium aluminum hydride and 200 ml of ether, and 36.5 g (0.18 mol) of the mixture and 150 ml of ether were charged therein. The mixture was added dropwise under ice cooling. After completion of the dropping, the mixture was stirred at room temperature for 30 minutes and then refluxed for 1 hour. After completion of the reaction, usual post-treatment was carried out and ether extraction was carried out. The obtained ether solution was washed with saturated aqueous sodium hydrogen carbonate and water, dried over anhydrous sodium sulfate, and the ether layer was concentrated to give 36 g of a solid. This solid was reslurried with 100 ml of n-hexane to obtain 30 g of a mixture (mixture) of 2,4-dimethyl-7-isopropyl-1-indanol and 2,7-dimethyl-4-isopropyl-1-indanol. (Yield: 82%) The mixture was placed in a 1 liter reactor which had been thoroughly purged with nitrogen.
Charge 5 g (0.12 mol) and 500 ml of benzene,
50 mg of paratoluenesulfonic acid monohydrate
(0.55 mmol) was added and the mixture was refluxed for 1 hour. After completion of the reaction, the mixture was poured into 300 ml of saturated aqueous sodium hydrogen carbonate, washed with an ether layer and water, and dried over anhydrous sodium sulfate. The ether layer was concentrated, and the obtained oil was distilled (bp .: 9
(0 ° C / 1 mmHg), 20 g of the target compound was obtained (yield: 90%).

1,1′-dimethylsilyl-bis (4-isopro
Synthesis of pill-2,7-dimethylindene) (compound) Add the compound to a 200 ml reactor with sufficient nitrogen substitution.
9.5 g (51 mmol), tetramethylethylenediamine 7.7 ml (51 mmol), diethyl ether 6
0 ml was charged and cooled to -10 ° C. N- in this solution
A hexane solution of butyllithium (51 mmol) was added. After warming to room temperature, it was cooled again to -10 ° C and 3.1 ml (25.5 mmol) of dimethyldichlorosilane.
Was dropped for 30 minutes, and the reaction was performed for 1 hour. After completion of the reaction, the mixture was added to 40 ml of saturated aqueous ammonium chloride solution, extracted with n-hexane, washed with water, and dried over magnesium sulfate.
The salt was removed, and the yellow oil obtained by concentrating the organic layer under reduced pressure was purified by silica gel column chromatography (developing solvent: n-hexane) to obtain 5.4 g of the compound as a colorless amorphous (yield : 50%).

Rac-dimethylsilyl-bis {1- (4-isopro
Pyr-2,7-dimethylindenyl)} zirconium dichloride
Synthesis of Lido (Compound)
5.4 g (12.6 mmol), tetrahydrofuran 1
00 ml was charged, cooled to -78 ° C, and stirred. 16 ml of n-butyllithium (n-hexane solution, 1.
(58 N, 25.2 mmol) was added dropwise over 20 minutes, and the mixture was stirred for 1 hour while maintaining the temperature to prepare an anion solution. Then, the temperature was slowly raised to room temperature.

At the same time, 100 ml of tetrahydrofuran was charged into a 300 ml reactor which had been sufficiently replaced with nitrogen, and -7
It was cooled to 8 ° C. and stirred. After slowly adding 2.94 g (12.6 mmol) of zirconium tetrachloride,
The temperature was raised to room temperature. Add the above-mentioned anion solution 3
The mixture was added dropwise over 0 minutes and stirred at room temperature for 12 hours. After completion of the reaction, the mixture was concentrated under reduced pressure and the precipitated solid was washed 3 times with 300 ml of hexane to remove insoluble matter. The obtained hexane solution was concentrated to about 50 ml and cooled at 6 ° C for 12 hours. When the obtained solid was analyzed by ¹ H-NMR, it was 1.78 g of a mixture of racemate and meso body (4: 1) (yield: 24%). 100 ml of hexane was added to this mixture and recrystallization was carried out again to obtain yellow columnar crystals of the compound of 0.
22 g was obtained (yield: 3%). The result of FD mass spectrometry of the compound was 588 (M ⁺ ).

[0151]

Example 2 [rac-diphenylsilyl-bis {1- (4-isopropyl-2,
Synthesis of 7-dimethylindenyl)} zirconium dichloride] 1,1′-diphenylsilyl-bis (4-isopropyl-2,7-di
Synthesis of Methylindene (Compound) Copper cyanide 1 instead of tetramethylethylenediamine
An experiment was conducted in the same manner as in the synthesis of the compound except that 20 mg and 5.7 ml of diphenyldichlorosilane were used instead of dimethyldichlorosilane.

7.2 Compound as colorless amorphous
g was obtained (yield: 49%). rac-diphenylsilyl-bis {1- (4-isopropyl-2,7-
Dimethylindenyl)} zirconium dichloride (Compound
In place of the compound, 7.1 g (12.9 mmol) of the compound, 16.0 ml of n-butyllithium were used instead of 16.0 ml of the compound.
An experiment was conducted in the same manner as in the synthesis of the compound, except that 6.3 ml and 3.01 g were used instead of 2.94 g of zirconium tetrachloride.

1.10 g of the compound was obtained as yellow columnar crystals (yield: 12%). The result of FD mass spectrometry of the compound was 712 (M ⁺ ).

[0154]

[Table 1]

[0155]

Example 3 500 g of propylene was charged into a 2 liter autoclave which had been sufficiently replaced with nitrogen, and the temperature was raised to 40 ° C. to obtain 0.2 mmol of triisobutylaluminum, 0.2 mmol of methylaluminoxane, rac-dimethylsilyl-.
Bis {1- (2,7-dimethyl-4-isopropylindenyl)} zirconium dichloride was added in an amount of 0.001 mmol in terms of Zr atom, and polymerization was carried out at 50 ° C. for 1 hour. After polymerization, degas to remove propylene and remove polymer
It dried at 10 degreeC.

The amount of the polymer obtained was 158 g, and the polymerization activity was 158 kg PP / mmol Zr, [η] = 4.5.
5 dl / g, Mw / Mn = 2.2, mmmm = 95.5
%, 2,1-insertion = 0.90%, Tm = 147 ° C.

[0157]

Example 4 500 g of propylene was charged into a 2 liter autoclave that had been sufficiently replaced with nitrogen, and the temperature was raised to 40 ° C. to obtain 0.2 mmol of triethylaluminum, rac-diphenylsilyl-bis {1- (2,7-dimethyl). -4-Isopropylindenyl)} zirconium dichloride was converted to 0.001 mmol in terms of Zr atoms and tris (pentafluorophenyl) boron was converted to 0.002 mmol in terms of B atoms, and polymerization was carried out at 50 ° C. for 1 hour. It was After the polymerization, degassing was performed to remove propylene, and the polymer was dried at 80 ° C. for 10 hours.

The amount of the polymer obtained was 94 g, and the polymerization activity was 94 kg PP / mmol Zr, [η] = 4.75 d.
1 / g, Mw / Mn = 2.3, mmmm = 96.4%, 2,
1-insertion = 0.80%, Tm = 148 ° C.

[0159]

[Comparative Example 1] 500 g of propylene was charged into a 2 liter autoclave, which had been sufficiently purged with nitrogen, and the temperature was raised to 40 ° C., 0.2 mmol of triisobutylaluminum, 0.2 mmol of methylaluminoxane, rac-dimethylsilyl-.
Bis {1- (2-methyl-4-isopropylindenyl)} zirconium dichloride converted to Zr atom and 0.001
Mmol and added, polymerization was carried out at 50 ° C. for 1 hour. After polymerization,
The polymer was degassed to remove propylene and the polymer was dried at 80 ° C. for 10 hours.

The amount of the polymer obtained was 125 g, and the polymerization activity was 125 kg PP / mmol Zr, [η] = 3.4.
7 dl / g, Mw / Mn = 2.1, mmmm = 96.2
%, 2,1-insertion = 0.40%, Tm = 152 ° C.

[0161]

Example 5 500 ml of toluene was added to a 1 liter glass reactor which had been sufficiently replaced with nitrogen, and propylene was added to 10 ml.
Flow at 0 liter / hr, raise the temperature to 50 ° C., 3.5 mmol of methylaluminoxane, rac-dimethylsilyl-bis {1- (2,7-dimethyl-4-isopropylindenyl)} zirconium dichloride to Zr atom. A solution prepared by preliminarily contacting 0.01 mmol of toluene in toluene was added,
Polymerization was performed at 20 ° C. for 20 minutes. After the polymerization, the solution was poured into a methanol-hydrochloric acid solution, the polymer was filtered with a filter,
It was dried at 80 ° C. for 10 hours.

The amount of the polymer obtained was 32.6 g, the polymerization activity was 8.2 kg PP / mmol Zr, and [η] = 1.
It was 37 dl / g, Mw / Mn = 2.2, and Tm = 148 ° C.

[0163]

Comparative Example 2 rac-Dimethylsilyl-bis {1- (2,7-dimethyl-4-isopropylindenyl)} zirconium dichloride instead of rac-ethylenebis {1- (2,4,7-trimethylindenyl) )} The experiment was conducted in the same manner as in Example 5 except that zirconium dichloride was used.

The amount of the polymer obtained was 23.1 g, the polymerization activity was 5.8 kg PP / mmol Zr, and [η] = 0.4.
It was 4 dl / g, Mw / Mn = 2.3, Tm = 150 ° C., and the molecular weight was much lower than that obtained in Example 5.

[0165]

[Example 6] [Preparation of solid catalyst component (a)] Fully nitrogen-substituted 50
Silica (F-9, manufactured by Fuji Devison Co., Ltd., in a 0 ml reactor)
48) dried at 200 ° C. for 6 hours under nitrogen flow 25
g, and 310 ml of toluene were charged, and the system was cooled to 0 with stirring.
℃ was made. To this, 90 ml of an organoaluminum oxy compound (methyl aluminoxane manufactured by Schering, diluted with toluene, 2.1 mol / liter) was added dropwise under a nitrogen atmosphere for 60 minutes. Then at this temperature for 30 minutes, 9
The reaction was carried out at 0 ° C for 4 hours. The reaction system was allowed to cool, and when the temperature reached 60 ° C., the supernatant solution was removed by decantation, and subsequently, it was washed 3 times with 150 ml of toluene at room temperature. As a result, a solid catalyst component (a) having 6.8 mmol of Al per 1 g of silica was obtained.

[Preparation of solid catalyst component (b)] A 200 ml reactor which had been sufficiently replaced with nitrogen was charged with 50 ml of n-hexane, and the solid catalyst component (a) obtained above was converted to Al atoms to be 10.5. Mmol, rac-dimethylsilyl-bis {1-
(2,7-Dimethyl-4-isopropylindenyl)} zirconium dichloride was converted to Zr atoms and 0.03 mmol was added, and the mixture was stirred for 20 minutes. After adding 100 ml of n-hexane and then 0.9 mmol of triisobutylaluminum and stirring for 10 minutes, propylene gas (2.2
Liter / hr) was passed for 4 hours at 20 ° C. to preliminarily polymerize propylene. The supernatant solution was removed by decantation and washed 3 times with 150 ml of decane. As a result, a solid catalyst component (b) carrying Zr; 0.011 mmol and Al; 4.48 mmol per 1 g of the solid catalyst was obtained.

750 m of purified n-hexane was placed in a 2-liter stainless steel autoclave which had been sufficiently replaced with nitrogen.
1 was added, and the mixture was placed in a propylene / ethylene mixed gas (ethylene 3.6 mol%) atmosphere and stirred at 25 ° C. for 20 minutes. 1.0 mmol of triisobutylaluminum was added to the reaction system, and the solid catalyst component (b) was converted to Zr atom and 0.00
Add 2 mmol, raise the temperature to 50 ° C and total pressure 2 kg / cm ² -G
Was polymerized for 1 hour. After the polymerization, the solvent was removed by filtration, washed with hexane, and then dried at 80 ° C. for 10 hours.

The obtained polymer (powder) was 75 g,
The polymer content (SP) dissolved in the solvent was 1.9 g (2.5
wt%), the polymerization activity is 38.5 kg copolymer / mmol Zr, powder MFR = 6.0 dg / min,
Mw / Mn = 2.6, ethylene content 2.9 mol%, Tm
= 126 ° C.

[0169]

[Example 7] [Preparation of solid catalyst component (c)]
50 ml of n-hexane was charged into a 0 ml reactor, and the solid catalyst component (a) obtained above was converted into Al atoms to be 10.5.
Mmol, rac-diphenylsilyl-bis {1- (2,7-dimethyl-4-isopropylindenyl)} zirconium dichloride converted to Zr atom, and added 0.03 mmol 2
Stir for 0 minutes. 100 ml of n-hexane was added, followed by 0.9 mmol of triisobutylaluminum and 1
After stirring for 0 minutes, propylene gas (2.2 liter /
was circulated for 4 hours at 20 ° C. to preliminarily polymerize propylene. The supernatant solution was removed by decantation and washed 3 times with 150 ml of decane. As a result, Zr per 0.01 g of the solid catalyst: 0.011 mmol, A
1; solid catalyst component (c) carrying 4.55 mmol
Got

[Polymerization] 750 ml of purified n-hexane was placed in a 2 liter stainless steel autoclave which had been sufficiently replaced with nitrogen, and the mixture was placed in a propylene / ethylene mixed gas (ethylene 3.6 mol%) atmosphere for 20 minutes at 25 ° C. It was stirred. Triisobutylaluminum 1.0 in the reaction system
Mmol, the solid catalyst component (c) was converted to Zr atom and added to 0.002 mmol, and the temperature was raised to 50 ° C. and the total pressure was 2 kg /
Polymerization was carried out for 1 hour at cm ² -G. After the polymerization, the solvent was removed by filtration, washed with hexane, and then dried at 80 ° C. for 10 hours.

The obtained polymer (powder) was 59 g,
The polymer content (SP) dissolved in the solvent was 2.5 g (4.0
wt%), the polymerization activity is 30.7 kg copolymer / mmol Zr, powder MFR = 5.8 dg / min,
Mw / Mn = 2.6, ethylene content 2.9 mol%, Tm
= 127 ° C.

[0172]

[Comparative Example 3] [Preparation of solid catalyst component (d)]
50 ml of n-hexane was charged into a 0 ml reactor, and the solid catalyst component (a) obtained above was converted into Al atoms to be 10.5.
Mmol, rac-dimethylsilyl-bis {1- (2-methyl-4-
Isopropylindenyl)} zirconium dichloride was converted into Zr atoms and 0.03 mmol was added, and the mixture was stirred for 20 minutes. 100 ml of n-hexane was added, 0.09 mmol of triisobutylaluminum was added, and the mixture was stirred for 10 minutes, and then propylene gas (2.2 liter / hr) was added.
Was circulated for 4 hours at 20 ° C. to preliminarily polymerize propylene. The supernatant solution was removed by decantation and washed 3 times with 150 ml of decane. As a result, Zr: 0.011 mmol per 1 g of the solid catalyst, Al: 4.3
A solid catalyst component (d) carrying 5 mmol was obtained.

[Polymerization] 750 ml of purified n-hexane was placed in a 2 liter stainless steel autoclave, which had been sufficiently purged with nitrogen, and the mixture was placed in a propylene / ethylene mixed gas (ethylene 5.2 mol%) atmosphere for 20 minutes at 25 ° C. It was stirred. Triisobutylaluminum 1.0 in the reaction system
Mmol, the solid catalyst component (d) was converted to Zr atoms and added to 0.002 mmol, and the temperature was raised to 50 ° C. and the total pressure was 2 kg /
Polymerization was carried out for 1 hour at cm ² -G. After the polymerization, the solvent was removed by filtration, washed with hexane, and then dried at 80 ° C. for 10 hours.

In the obtained solid polymer, in addition to the powder (67 g), a small amount of wall-adhering polymer was recognized on the wall of the autoclave. Polymer content (SP) dissolved in the solvent was 9.0 g (12.0 wt%), polymerization activity was 38 kg copolymer / mmol Zr, powder MFR.
= 12 dg / min, Mw / Mn = 2.5, ethylene content 5.0 mol%, and Tm = 127 ° C.

When the amount of SP is too large, not only the powder yield is lowered but also the heat transfer efficiency due to the wall-adhering polymer and the viscosity of the solvent are increased, which makes the operation extremely difficult in industrial level production. is expected.

[Brief description of drawings]

FIG. 1 is an explanatory view showing a preparation process of first and second olefin polymerization catalysts according to the present invention.

FIG. 2 is an explanatory view showing a process for preparing third and fourth olefin polymerization catalysts according to the present invention.

FIG. 3 is an explanatory view showing a preparation process of fifth and sixth olefin polymerization catalysts according to the present invention.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yoshihisa Kiso 6-1-2 Waki, Waki-cho, Kuga-gun, Yamaguchi Mitsui Petrochemical Industry Co., Ltd. (56) Reference JP-A-8-12715 (JP , A) JP-A-6-206890 (JP, A) JP-A-6-25343 (JP, A) JP-A-5-306304 (JP, A) JP-A-4-312538 (JP, A) (58) Fields surveyed (Int.Cl. ⁷ , DB name) C07F 17/00-17/02 C08F 4/64-4/658 CA (STN)

Claims (10)

(57) [Claims] 1. A novel transition metal compound represented by the following general formula [I]: (In the formula, M represents a transition metal of Groups 4, 5, and 6 of the Periodic Table, R ¹ and R ² represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or 1 to 1 carbon atoms. 20 halogenated hydrocarbon groups, silicon-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups or phosphorus-containing groups (provided that R ¹ is
Except when R ² is a hydrogen atom other than a hydrogen atom,
Ku. ) , R ³ represents an alkyl group having 2 to 20 carbon atoms, and R ⁴ represents an alkyl group having 1 to 20 carbon atoms. X ¹ and X ² are hydrogen atom, halogen atom, carbon atom 1
To 20 hydrocarbon groups, halogenated hydrocarbon groups having 1 to 20 carbon atoms, oxygen-containing groups or sulfur-containing groups, Y represents a divalent hydrocarbon group having 1 to 20 carbon atoms, or the number of carbon atoms. 1 to 20 divalent halogenated hydrocarbon group, divalent silicon-containing group, divalent germanium-containing group, divalent tin-containing group, -O-, -CO-, -S-, -SO-, -SO ₂
^{-, - NR 5 -, -} P (R 5) -, - P (O) (R 5)
—, —BR ⁵ — or —AlR ⁵ — [wherein R ⁵ represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms]. ) 2. In the general formula [I] according to claim 1,
M is titanium, zirconium or hafnium
A catalyst component for olefin polymerization , wherein Y is a transition metal compound in which Y is a divalent silicon-containing group . 3. A compound represented by the general formula [I] according to claim 1.
And M is titanium, zirconium or hafnium
And a transition metal compound in which Y is a divalent silicon-containing group , [B] (B-1) an organoaluminum oxy compound, and (B-2) the transition metal compound [A] are reacted to form an ion pair. An olefin polymerization catalyst comprising at least one compound selected from the group consisting of compounds forming 4. A compound represented by the general formula [I] according to claim 1.
And M is titanium, zirconium or hafnium
And a transition metal compound in which Y is a divalent silicon-containing group , [B] (B-1) an organoaluminum oxy compound, and (B-2) the transition metal compound [A] are reacted to form an ion pair. A catalyst for olefin polymerization, comprising at least one compound selected from the group consisting of compounds which form (C) and [C] an organoaluminum compound. 5. In the general formula [I] according to claim 1, wherein M is a fine particle carrier,
Thallium, zirconium or hafnium, where Y is
An olefin polymerization catalyst comprising a transition metal compound, which is a divalent silicon-containing group, and [B] an organoaluminumoxy compound supported on the catalyst. 6. A fine particle-shaped carrier, wherein [A] is M in the general formula [I] according to claim 1.
Thallium, zirconium or hafnium, where Y is
From a transition metal compound that is a divalent silicon-containing group , [B] (B-1) an organoaluminum oxy compound, and (B-2) a compound that reacts with the transition metal compound [A] to form an ion pair An olefin polymerization catalyst comprising a solid catalyst component carrying at least one compound selected from the group consisting of: and [C] an organoaluminum compound. 7. A fine particle carrier, and [A] in the general formula [I] according to claim 1, M is
Thallium, zirconium or hafnium, where Y is
From a transition metal compound that is a divalent silicon-containing group , [B] (B-1) an organoaluminum oxy compound, and (B-2) a compound that reacts with the transition metal compound [A] to form an ion pair An olefin polymerization catalyst comprising at least one compound selected from the group consisting of: and an olefin polymer produced by prepolymerization. 8. A fine particle carrier, and [A] in the general formula [I] of claim 1, M is
Thallium, zirconium or hafnium, where Y is
From a transition metal compound that is a divalent silicon-containing group , [B] (B-1) an organoaluminum oxy compound, and (B-2) a compound that reacts with the transition metal compound [A] to form an ion pair An olefin polymerization catalyst comprising at least one compound selected from the group consisting of: [C] an organoaluminum compound; and an olefin polymer produced by prepolymerization. 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 any one of claims 3 to 8. 10. A catalyst for olefin polymerization according to claim 7 or 8, polymerization of olefins characterized by the presence polymerizing or copolymerizing an olefin of an organic aluminum compound.