JP2000119288A - Transition metal compound, catalyst component for polymerizing olefin and production of olefin polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new compound useful as a highly active catalyst component for polymerizing an olefin at an efficient reactional temperature in an industrial process for polymerizing the olefin, excellent in copolymerizability and capable of providing a high-molecular weight olefin polymer. SOLUTION: This transition metal compound is represented by formula I or II (M1 is a group 4 transition metal of the periodic table; A is a group 16 element of the periodic table; J is a group 14 element of the periodic table; Cp1 is a group having a cyclopentadienyl form anionic skeleton; X1 and R1 to R6 are each H, a halogen or the like; and X2 is a group 16 element of the periodic table), e.g. μ-oxobis dimethylsilylene (η5-tetramethylcyclopentadienyl)(3- tert-butyl-5-methyl-2-phenoxy)titanium methoxide}. The compound is obtained by reacting a transition metal compound such as dimethylsilylene (η5- tetramethylcyclopentadienyl(3-tert-butyl-5-methyl-2-phenoxy)titanium dimethoxide with water in a molar amount of 0.5 or 1 based on the transition metal compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a transition metal compound useful as an olefin polymerization catalyst component, an olefin polymerization catalyst using the transition metal compound, and a highly active olefin polymer using the olefin polymerization catalyst. It relates to a manufacturing method.

[0002]

2. Description of the Related Art There have already been many reports on processes for producing olefin polymers using metallocene complexes. For example, in JP-A-58-19306,
A method for producing an olefin polymer using a metallocene complex and an aluminoxane has been reported. The metallocene complex disclosed therein is a complex having only one transition metal atom in one molecule. JP-A-4-91095, includes two transition metal atoms in one molecule, two eta ⁵ to each transition metal atom - metallocene complex cyclopentadienyl group has a coordination structure Is used as a catalyst component for olefin polymerization. However, when these metallocene complexes having a structure in which two η ⁵ -cyclopentadienyl groups are coordinated to one transition metal atom are used as a catalyst component for olefin polymerization,
There is a problem that the obtained olefin polymer has a low molecular weight and a low copolymerizability, and further improvement in activity has been desired from an industrial viewpoint.

[0003] JP-A-3-163088 and JP-A-3-188092 disclose that one molecule contains two transition metal atoms and each transition metal atom has only one η.
^Although a metallocene complex in which a ⁵ -cyclopentadienyl group is coordinated is disclosed, the complex has a unique structure in which an excess of anionic ligand is bonded to the valence of the transition metal atom, and has a polymerization performance. Has not been confirmed.

JP-A-7-126315 discloses a metallocene complex in which one molecule contains two transition metal atoms and each transition metal atom is coordinated with only one η ⁵ -cyclopentadienyl group. Although disclosed, it is a complex having a structure in which these two η ⁵ -cyclopentadienyl groups are linked, and an olefin polymerization catalyst using the same as a catalyst component has low copolymerizability, and the resulting copolymer However, there is a problem that the melting point is high, and further improvement in activity has been desired from an industrial viewpoint.

[0005]

SUMMARY OF THE INVENTION In view of such circumstances, the present invention provides a transition catalyst which is important from an industrial point of view and is useful as a catalyst component for olefin polymerization which is highly active at an efficient reaction temperature in an industrial process of olefin polymerization. An object of the present invention is to provide a metal compound, and a highly active olefin polymerization catalyst using the transition metal compound, and a method for producing an olefin polymer using the olefin polymerization catalyst. is there.

[0006]

Means for Solving the Problems In order to achieve the above-mentioned object, the present inventors have proposed a metallocene-based transition metal compound, especially a monocyclopentadienyl transition metal compound as one of the catalyst components. The present inventor has continued his intensive research on the production method of the present invention, and has completed the present invention. That is, the present invention provides a transition metal compound represented by the following general formula [I] or [II], an olefin polymerization catalyst component comprising the transition metal compound, the transition metal compound, and the following (B) and / or C) and a method for producing an olefin polymer using the olefin polymerization catalyst. (In the above general formula [I] or [II], M
¹ represents a transition metal atom of Group 4 of the periodic table of the element;
Represents an atom belonging to Group 16 of the periodic table of the element, and J represents an atom belonging to Group 14 of the periodic table of the element. Cp ¹ represents a group having a cyclopentadiene-type anion skeleton. X ¹ , R ¹ ,
R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an aryl group, a substituted silyl group, an alkoxy group, an aralkyloxy group, an aryloxy group or Shows a substituted amino group.
X ² represents an atom of Group 16 of the periodic table of the element. R ¹ , R
² , R ³ , R ⁴ , R ⁵ and R ⁶ may be optionally combined to form a ring. Multiple M ¹ , A, J, Cp ¹ , X ¹ , X ² , R
¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be the same or different. (B): One or more aluminum compounds selected from the following (B1) to (B3) (B1) Organoaluminum compound represented by general formula E ¹ _a AlZ _3-a (B2) General formula ｛-Al (E ²⁾ -O-} cyclic aluminoxane (B3 having the structure represented by _b) the general formula ^{E 3 {-Al (E 3)} -O-} c AlE 3
Linear aluminoxane having a structure represented by ₂ , wherein E ¹ , E ² and E ³ are each a hydrocarbon group, and all E ¹ , all E ² and all E ³ are the same; Z represents a hydrogen atom or a halogen atom, all Z may be the same or different, a is a number satisfying 0 <a ≦ 3, and b is 2 or more. An integer, and c represents an integer of 1 or more.) (C): a boron compound of any of the following (C1) to (C3) (C1) a boron compound represented by the general formula BQ ¹ Q ² Q ³ , C2) a boron compound represented by the general formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- , (C3) a boron compound represented by the general formula (LH) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- boron compounds (wherein, B is a boron atom in the trivalent valence state, Q ¹ to Q ⁴ are a halogen atom, a hydrocarbon group, a halo Emissions hydrocarbon group, substituted silyl group, an alkoxy group or a di-substituted amino group, they may be different even in the same .G ⁺ is an inorganic or organic cation, L is a neutral Lewis base And (LH) ⁺ is a Bronsted acid.)

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. (A) Transition metal compound In the general formula [I] or [II], the transition metal atom represented by M ¹ is a transition metal belonging to Group 4 of the periodic table of elements (IUPAC revised edition of inorganic chemical nomenclature 1989). Represents an element, such as a titanium atom, a zirconium atom, or a hafnium atom. Preferably it is a titanium atom or a zirconium atom.

The atom of Group 16 of the periodic table of the element represented by A in the general formula [I] or [II] includes:
For example, an oxygen atom, a sulfur atom, a selenium atom and the like can be mentioned, and an oxygen atom is preferable.

In the general formula [I] or [II], as an atom belonging to Group 14 of the periodic table of the element represented by J,
For example, a carbon atom, a silicon atom, a germanium atom and the like can be mentioned, and a carbon atom or a silicon atom is preferable.

The substituent Cp¹Cyclopenta shown as
Examples of the group having a diene-type anion skeleton include η^Five
-(Substituted) cyclopentadienyl group, η^Five-(Replacement) a
Ndenyl group, η^Five-(Substituted) fluorenyl group, etc.
You. To give a concrete example, for example, η^Five-Cyclopentadi
Enyl group, η^Five-Methylcyclopentadienyl group, η^Five−
Dimethylcyclopentadienyl group, η^Five-Trimethylsi
Clopentadienyl group, η^Five-Tetramethylcyclopen
Tadienyl group, η^Five-Ethylcyclopentadienyl group,
η^Five-N-propylcyclopentadienyl group, η^Five-Iso
Propylcyclopentadienyl group, η^Five-N-butyl
Clopentadienyl group, η^Five-Sec-butylcyclope
Antadienyl group, η^Five-Tert-butylcyclopenta
Dienyl group, η^Five-N-pentylcyclopentadienyl
Group, η^Five-Neopentylcyclopentadienyl group, η^Five−
n-hexylcyclopentadienyl group, η^Five-N-oct
Tylcyclopentadienyl group, η^Five-Phenylcyclo ぺ
Antadienyl group, η^Five-Naphthylcyclopentadienyl
Group, η^Five-A trimethylsilylcyclopentadienyl group,
η^Five-Triethylsilylcyclopentadienyl group, η^Five−
tert-butyldimethylsilylcyclopentadienyl
Group, η^Five-Indenyl group, η^Five-Methylindenyl group, η
^Five-Dimethylindenyl group, η^Five-Ethylindenyl group,
η^Five-N-propylindenyl group, η^Five-Isopropyl
Ndenyl group, η^Five-N-butylindenyl group, η^Five-Se
c-butylindenyl group, η^Five-Tert-butylin
Denenyl group, η^Five-N-pentylindenyl group, η^Five-Neo
Pentylindenyl group, η^Five-N-hexylindenyl
Group, η^Five-N-octylindenyl group, η^Five-N-decyl
Indenyl group, η^Five-Phenylindenyl group, η^Five−
Ruphenylindenyl group, η^Five-Naphthylindenyl
Group, η^FiveA trimethylsilylindenyl group, η^Five-Trie
Tylsilylindenyl group, η^Five-Tert-butyldim
Tylsilylindenyl group, η^Five-Tetrahydroindeni
Group, η^FiveA fluorenyl group, η^Five-Methylfluorenyl
Group, η^Five-Dimethylfluorenyl group, η^Five-Ethylfluor
Renyl group, η^Five-Diethylfluorenyl group, η^Five-N-pu
Ropylfluorenyl group, η^Five-Di-n-propylfluoro
Renyl group, η^Five-Isopropylfluorenyl group, η^Five−
Isopropylfluorenyl group, η^Five-N-butylfluor
Renyl group, η^Five-Sec-butylfluorenyl group, η^Five−
tert-butylfluorenyl group, η^Five-Di-n-buty
Lufluorenyl group, η^Five-Di-sec-butyl fluor
Nil group, η^Five-Di-tert-butylfluorenyl group,
η^Five-N-pentylfluorenyl group, η^Five-Neopentyl
Fluorenyl group, η^Five-N-hexylfluorenyl group,
η^Five-N-octylfluorenyl group, η ^Five-N-decylph
Fluorenyl group, η^Five-N-dodecylfluorenyl group, η^Five
A phenylfluorenyl group, η^Five-Di-phenylfluoro
Renyl group, η^Five-Methylphenylfluorenyl group, η^Five−
Naphthylfluorenyl group, η^Five-Trimethylsilylfur
Olenyl group, η^Five-Bis-trimethylsilylfluorenyl
Group, η^FiveA triethylsilylfluorenyl group, η^Five-T
tert-butyldimethylsilylfluorenyl group and the like.
And preferably η^Five-Cyclopentadienyl group, η^Five
-Methylcyclopentadienyl group, η^Five-Tert-b
Tylcyclopentadienyl group, η^Five-Tetramethylsic
Lopentadienyl group, η^Five-An indenyl group, or η^Five−
It is a fluorenyl group.

Examples of the halogen atom for the substituents X ¹ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ or R ⁶ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. It is an atom or a bromine atom, more preferably a chlorine atom.

The alkyl group for the substituents X ¹ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ or R ⁶ has 1 to 2 carbon atoms.
An alkyl group of 0 is preferable, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group,
sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, amyl group, n-hexyl group, n-
Octyl group, n-decyl group, n-dodecyl group, n-pentadecyl group, n-eicosyl group and the like, more preferably methyl group, ethyl group, isopropyl group, ter
It is a t-butyl group or an amyl group.

Any of these alkyl groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the alkyl group having 1 to 20 carbon atoms substituted with a halogen atom include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a chloromethyl group, a dichloromethyl group, a trichloromethyl group, a bromomethyl group and a dibromomethyl group. , Tribromomethyl, iodomethyl, diiodomethyl, triiodomethyl, fluoroethyl, difluoroethyl, trifluoroethyl, tetrafluoroethyl, pentafluoroethyl, chloroethyl, dichloroethyl, trichloroethyl , Tetrachloroethyl group, pentachloroethyl group, bromoethyl group, dibromoethyl group, tribromoethyl group, tetrabromoethyl group, pentabromoethyl group, perfluoropropyl group,
Perfluorobutyl, perfluoropentyl, perfluorohexyl, perfluorooctyl, perfluorododecyl, perfluoropentadecyl, perfluoroeicosyl, perchloropropyl, perchlorobutyl, perchloropentyl Group, perchlorohexyl group, perchlorooctyl group, perchlorododecyl group,
Perchloropentadecyl group, perchloroeicosyl group,
Perbromopropyl, perbromobutyl, perbromopentyl, perbromohexyl, perbromooctyl, perbromododecyl, perbromopentadecyl, perbromoeicosyl and the like. All of these alkyl groups may be partially substituted with an alkoxy group such as a methoxy group or an ethoxy group, an aryloxy group such as a phenoxy group, or an aralkyloxy group such as a benzyloxy group.

The aralkyl group for the substituents X ¹ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ or R ⁶ has 7 to 7 carbon atoms.
20 aralkyl groups are preferred, for example a benzyl group,
(2-methylphenyl) methyl group, (3-methylphenyl) methyl group, (4-methylphenyl) methyl group,
(2,3-dimethylphenyl) methyl group, (2,4-dimethylphenyl) methyl group, (2,5-dimethylphenyl) methyl group, (2,6-dimethylphenyl) methyl group, (3,4-dimethyl Phenyl) methyl group, (3,5
-Dimethylphenyl) methyl group, (2,3,4-trimethylphenyl) methyl group, (2,3,5-trimethylphenyl) methyl group, (2,3,6-trimethylphenyl) methyl group, (3,4 , 5-trimethylphenyl) methyl group, (2,4,6-trimethylphenyl) methyl group, (2,3,4,5-tetramethylphenyl) methyl group, (2,3,4,6-tetramethylphenyl) ) Methyl, (2,3,5,6-tetramethylphenyl) methyl, (pentamethylphenyl) methyl, (ethylphenyl) methyl, (n-propylphenyl) methyl,
(Isopropylphenyl) methyl group, (n-butylphenyl) methyl group, (sec-butylphenyl) methyl group, (tert-butylphenyl) methyl group, (n-pentylphenyl) methyl group, (neopentylphenyl)
Methyl group, (n-hexylphenyl) methyl group, (n-
Octylphenyl) methyl group, (n-decylphenyl)
Examples include a methyl group, a (n-tetradecylphenyl) methyl group, a naphthylmethyl group, an anthracenylmethyl group, and more preferably a benzyl group. All of these aralkyl groups are a fluorine atom, a chlorine atom, a bromine atom,
It may be partially substituted with a halogen atom such as an iodine atom, an alkoxy group such as a methoxy group or an ethoxy group, an aryloxy group such as a phenoxy group, or an aralkyloxy group such as a benzyloxy group.

The aryl group represented by the substituents X ¹ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ or R ⁶ has ^{6 to 2} carbon atoms.
And an aryl group of 0 is preferable, for example, a phenyl group, a 2-tolyl group, a 3-tolyl group, a 4-tolyl group, a 2,3-xylyl group, a 2,4-xylyl group, a 2,5-xylyl group,
6-xylyl group, 3,4-xylyl group, 3,5-xylyl group, 2,3,4-trimethylphenyl group, 2,3,5
-Trimethylphenyl group, 2,3,6-trimethylphenyl group, 2,4,6-trimethylphenyl group, 3,4
5-trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, 2,3,4,6-tetramethylphenyl group, 2,3,5,6-tetramethylphenyl group, pentamethylphenyl group, Ethylphenyl group, n-propylphenyl group, isopropylphenyl group, n-butylphenyl group, sec-butylphenyl group, tert-butylphenyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n -Octylphenyl group, n-decylphenyl group, n-dodecylphenyl group, n-tetradecylphenyl group, naphthyl group, anthracenyl group and the like, and more preferably a phenyl group. All of these aryl groups are a fluorine atom,
Halogen atoms such as chlorine atom, bromine atom and iodine atom,
It may be partially substituted with an alkoxy group such as a methoxy group or an ethoxy group, an aryloxy group such as a phenoxy group, or an aralkyloxy group such as a benzyloxy group.

The substituted silyl group in the substituents X ¹ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ or R ⁶ is a silyl group substituted by a hydrocarbon group, wherein the hydrocarbon group is Is a carbon such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, n-pentyl, n-hexyl, cyclohexyl, etc. Examples thereof include an alkyl group having 1 to 10 atoms and an aryl group such as a phenyl group. Examples of the substituted silyl group having 1 to 20 carbon atoms include mono-substituted silyl groups having 1 to 20 carbon atoms such as methylsilyl group, ethylsilyl group and phenylsilyl group.
Disubstituted silyl group having 2 to 20 carbon atoms such as dimethylsilyl group, diethylsilyl group, diphenylsilyl group, trimethylsilyl group, triethylsilyl group, tri-n-propylsilyl group, triisopropylsilyl group, tri-n-
Butylsilyl group, tri-sec-butylsilyl group, tri-tert-butylsilyl group, tri-isobutylsilyl group, tert-butyl-dimethylsilyl group, tri-n-
A pentylsilyl group, a tri-n-hexylsilyl group, a tricyclohexylsilyl group, a trisubstituted silyl group having 3 to 20 carbon atoms such as a triphenylsilyl group, and the like;
Preferably, they are a trimethylsilyl group, a tert-butyldimethylsilyl group, or a triphenylsilyl group. All of these substituted silyl groups have a hydrocarbon group such as a fluorine atom, a chlorine atom, a bromine atom, a halogen atom such as an iodine atom, an alkoxy group such as a methoxy group or an ethoxy group, an aryloxy group such as a phenoxy group, or a benzyloxy group. May be partially substituted with an aralkyloxy group such as a group.

The alkoxy group in the substituents X ¹ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ or R ⁶ has 1 to 1 carbon atoms.
Preferred are 20 alkoxy groups, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-
Butoxy group, sec-butoxy group, tert-butoxy group, n-pentoxy group, neopentoxy group, n-hexoxy group, n-octoxy group, n-dodecoxy group, n-pentadeoxy group, n-icosoxy group, and the like. More preferably, a methoxy group, an ethoxy group, or tert
-A butoxy group. All of these alkoxy groups include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkoxy group such as a methoxy group and an ethoxy group, an aryloxy group such as a phenoxy group and an aralkyloxy group such as a benzyloxy group. May be partially substituted.

The aralkyloxy group for the substituents X ¹ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ or R ⁶ is preferably an aralkyloxy group having 7 to 20 carbon atoms, for example, a benzyloxy group. A (2-methylphenyl) methoxy group,
(3-methylphenyl) methoxy group, (4-methylphenyl) methoxy group, (2,3-dimethylphenyl) methoxy group, (2,4-dimethylphenyl) methoxy group,
(2,5-dimethylphenyl) methoxy group, (2,6-
(Dimethylphenyl) methoxy group, (3,4-dimethylphenyl) methoxy group, (3,5-dimethylphenyl) methoxy group, (2,3,4-trimethylphenyl) methoxy group, (2,3,5-trimethylphenyl) A) methoxy group, a (2,3,6-trimethylphenyl) methoxy group,
(2,4,5-trimethylphenyl) methoxy group,
A (2,4,6-trimethylphenyl) methoxy group,
(3,4,5-trimethylphenyl) methoxy group,
(2,3,4,5-tetramethylphenyl) methoxy, (2,3,4,6-tetramethylphenyl) methoxy, (2,3,5,6-tetramethylphenyl) methoxy, (penta (Methylphenyl) methoxy group, (ethylphenyl) methoxy group, (n-propylphenyl) methoxy group, (isopropylphenyl) methoxy group, (n
-Butylphenyl) methoxy group, (sec-butylphenyl) methoxy group, (tert-butylphenyl) methoxy group, (n-hexylphenyl) methoxy group, (n-
Examples thereof include a (decylphenyl) methoxy group, a (n-tetradecylphenyl) methoxy group, a naphthylmethoxy group, and an anthracenylmethoxy group, and more preferably a benzyloxy group. All of these aralkyloxy groups include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkoxy group such as a methoxy group and an ethoxy group, an aryloxy group such as a phenoxy group, and an aralkyloxy group such as a benzyloxy group. It may be partially substituted with a group or the like.

As the aryloxy group for the substituents X ¹ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ or R ^6, an aryloxy group having 6 to 20 carbon atoms is preferable. -Methylphenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, 2,3-dimethylphenoxy group, 2,4-dimethylphenoxy group, 2,5-dimethylphenoxy group, 2,6-dimethylphenoxy group,
3,4-dimethylphenoxy group, 3,5-dimethylphenoxy group, 2,3,4-trimethylphenoxy group, 2,
3,5-trimethylphenoxy group, 2,3,6-trimethylphenoxy group, 2,4,5-trimethylphenoxy group, 2,4,6-trimethylphenoxy group, 3,4,5
-Trimethylphenoxy group, 2,3,4,5-tetramethylphenoxy group, 2,3,4,6-tetramethylphenoxy group, 2,3,5,6-tetramethylphenoxy group, pentamethylphenoxy group, ethyl Phenoxy group,
n-propylphenoxy group, isopropylphenoxy group, n-butylphenoxy group, sec-butylphenoxy group, tert-butylphenoxy group, n-hexylphenoxy group, n-octylphenoxy group, n-decylphenoxy group, n-tetradecyl Examples include a phenoxy group, a naphthoxy group, and an anthracenoxy group. All of these aryloxy groups are a fluorine atom, a chlorine atom,
A halogen atom such as a bromine atom or an iodine atom, an alkoxy group such as a methoxy group or an ethoxy group, an aryloxy group such as a phenoxy group, or an aralkyloxy group such as a benzyloxy group may be partially substituted.

The disubstituted amino group in the substituents X ¹ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ or R ⁶ is an amino group substituted by two hydrocarbon groups, wherein Examples of the hydrogen group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group,
1 to 10 carbon atoms such as t-butyl group, isobutyl group, n-pentyl group, n-hexyl group and cyclohexyl group
And an aryl group having 6 to 10 carbon atoms such as an alkyl group and a phenyl group, and an aralkyl group having 7 to 10 carbon atoms. Examples of such a disubstituted amino group substituted with a hydrocarbon group having 1 to 10 carbon atoms include a dimethylamino group, a diethylamino group, a di-n-propylamino group, a diisopropylamino group, a di-n-butylamino group, Di-sec-butylamino group, di-tert-butylamino group, di-isobutylamino group, tert-butylisopropylamino group, di-n-hexylamino group,
Di-n-octylamino group, di-n-decylamino group,
Diphenylamino group, bistrimethylsilylamino group,
Examples thereof include a bis-tert-butyldimethylsilylamino group, and a dimethylamino group or a diethylamino group is preferable. Each of these disubstituted amino groups is
Partially substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, an alkoxy group such as a methoxy group or an ethoxy group, an aryloxy group such as a phenoxy group, or an aralkyloxy group such as a benzyloxy group. You may.

The substituents R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶
May be arbitrarily bonded to form a ring.

Preferably, R ¹ is each independently an alkyl group, an aralkyl group, an aryl group or a substituted silyl group. Preferably, X ¹ is each independently a halogen atom,
It is an alkyl group, an aralkyl group, an alkoxy group, an aryloxy group or a disubstituted amino group, more preferably an alkoxy group.

The atom of Group 16 of the periodic table of the element represented by X ² in the general formula [I] or [II] includes, for example, an oxygen atom, a sulfur atom, a selenium atom and the like, preferably an oxygen atom It is.

Examples of the transition metal compound [I] include μ-oxobis {isopropylidene (η ⁵ -cyclopentadienyl) (2-phenoxy) titanium chloride} and μ-oxobis {isopropylidene (η ⁵ -cyclopentane). Dienyl) (2-phenoxy) titanium methoxide {, μ-oxobis} isopropylidene (η ⁵
-Cyclopentadienyl) (3-tert-butyl-5
-Methyl-2-phenoxy) titanium chloride｝,
μ-oxobis {isopropylidene (η ⁵ -cyclopentadienyl) (3-tert-butyl-5-methyl-2
-Phenoxy) titanium methoxide {, μ-oxobis {isopropylidene (η ⁵ -methylcyclopentadienyl) (2-phenoxy) titanium chloride}, μ
- Okisobisu {isopropylidene (eta ⁵ - cyclopentadienyl) (2-phenoxy) titanium methoxide}, .mu. Okisobisu {isopropylidene (eta ⁵ - cyclopentadienyl) (3-tert-butyl -
5-methyl-2-phenoxy) titanium chloride}, .mu. Okisobisu {isopropylidene (eta ⁵ - cyclopentadienyl) (3-tert-butyl-5
-Methyl-2-phenoxy) titanium methoxide
μ-oxobis {isopropylidene (η ⁵ -tetramethylcyclopentadienyl) (2-phenoxy) titanium chloride}, μ-oxobis {isopropylidene (η ⁵ -tetramethylcyclopentadienyl) (2-phenoxy) titanium methoxy De, μ-oxobis {isopropylidene (η ⁵ -tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-
Phenoxy) titanium chloride}, .mu. Okisobisu {isopropylidene (eta ⁵ - tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-
Phenoxy) titanium methoxide

Μ-oxobis ｛dimethylsilylene (η ⁵
-Cyclopentadienyl) (2-phenoxy) titanium chloride, μ-oxobis {dimethylsilylene (η ⁵ -cyclopentadienyl) (2-phenoxy) titanium methoxide}, μ-oxobisdimethylsilylene (η ⁵ − Cyclopentadienyl) (3-tert-
Butyl-5-methyl-2-phenoxy) titanium chloride {, μ-oxobis} dimethylsilylene (η ⁵ −
Cyclopentadienyl) (3-tert-butyl-5-
Methyl-2-phenoxy) titanium methoxide {, μ
- Okisobisu {dimethylsilylene (eta ⁵ - cyclopentadienyl) (2-phenoxy) titanium chloride}, .mu. Okisobisu {dimethylsilylene (eta ⁵ - cyclopentadienyl) (2-phenoxy) titanium methoxide}, μ-oxobis ｛dimethylsilylene (η ⁵ -methylcyclopentadienyl) (3-tert
-Butyl-5-methyl-2-phenoxy) titanium chloride {, μ-oxobis} dimethylsilylene (η ⁵
-Methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium methoxide {, μ-oxobis} dimethylsilylene (η ⁵ -tetramethylcyclopentadienyl) (2-phenoxy) titanium Chloride｝, μ-oxobis ｛dimethylsilylene (η ⁵ -tetramethylcyclopentadienyl) (2
-Phenoxy) titanium methoxide {, μ-oxobis} dimethylsilylene (η ⁵ -tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2
-Phenoxy) titanium chloride｝, μ-oxobis ｛dimethylsilylene (η ⁵ -tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2
-Phenoxy) titanium methoxide, and the like.

Examples of the transition metal compound [II] include di-μ-oxobis {isopropylidene (η ⁵ -cyclopentadienyl) (2-phenoxy) titanium} and di-μ-oxobis {isopropylidene (η ^5). −
Cyclopentadienyl) (3-tert-butyl-5-
Methyl-2-phenoxy) titanium {, di-μ-oxobis {isopropylidene (η ⁵ -methylcyclopentadienyl) (2-phenoxy) titanium}, di-μ-
Oxobis {isopropylidene (η ⁵ -methylcyclopentadienyl) (3-tert-butyl-5-methyl-
2-phenoxy) titanium {, di-μ-oxobis {isopropylidene (η ⁵ -tetramethylcyclopentadienyl) (2-phenoxy) titanium}, di-μ-
Okisobisu {isopropylidene (eta ⁵ - tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium}, di -μ- Okisobisu {dimethylsilylene (eta ⁵ - cyclopentadienyl) (2-phenoxy) titanium｝,

Di-μ-oxobis {dimethylsilylene (η ⁵ -cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium}, di-
μ-oxobis {dimethylsilylene (η ⁵ -methylcyclopentadienyl) (2-phenoxy) titanium},
Di-μ-oxobis ｛dimethylsilylene (η ⁵ -methylcyclopentadienyl) (3-tert-butyl-5-
Methyl-2-phenoxy) titanium, di-μ-oxobis {dimethylsilylene (η ⁵ -tetramethylcyclopentadienyl) (2-phenoxy) titanium}, di-μ-oxobis {dimethylsilylene (η ⁵ -tetramethyl) Cyclopentadienyl) (3-tert-butyl-
5-methyl-2-phenoxy) titanium}, and the like.

The transition metal compound represented by the general formula [I] or [II] is, for example, a transition metal compound obtained by the method described in WO 97/03992.
It is produced by reacting with 0.5 or 1 molar amount of water. At that time, a method of directly reacting a transition metal compound with a required amount of water, a method of charging a transition metal compound into a solvent such as a hydrocarbon containing a required amount of water, and a method of adding a transition metal to a solvent such as a dried hydrocarbon. A method in which a compound is charged and an inert gas containing a necessary amount of water and the like are allowed to flow can be adopted.

(B) Aluminum Compound The aluminum compound (B) used in the present invention is at least one aluminum compound selected from the following (B1) to (B3). (B1) Organoaluminum compound represented by the general formula E ¹ _a AlZ _3-a (B2) Cyclic aluminoxane having a structure represented by the general formula ｛-Al (E ² ) -O-｝ _b (B3) General formula E ³ ｛-Al (E ³ ) -O-｝ _c AlE ³
Linear aluminoxane having a structure represented by ₂ (provided that E ¹ , E ² , and E ³ are each a hydrocarbon group, and all E ¹ , all E ^2, and all E ³ are the same; Z represents a hydrogen atom or a halogen atom, all Z may be the same or different, a is a number satisfying 0 <a ≦ 3, and b is 2 or more. And c represents an integer of 1 or more.) As the hydrocarbon group for E ¹ , E ² or E ³ , a hydrocarbon group having 1 to 8 carbon atoms is preferable, and an alkyl group is more preferable.

[0030] As specific examples of the general formula E ¹ _a AlZ organoaluminum compound represented by the _3-a (B1), trimethyl aluminum, triethyl aluminum, tripropyl aluminum, triisobutyl aluminum, trialkyl aluminum such as tri-hexyl aluminum; Dialkylaluminum chlorides such as dimethylaluminum chloride, diethylaluminum chloride, dipropylaluminum chloride, diisobutylaluminum chloride and dihexylaluminum chloride; alkylaluminum dichlorides such as methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride and hexylaluminum dichloride Dimethylal Examples thereof include dialkylaluminum hydrides such as minium hydride, diethylaluminum hydride, dipropylaluminum hydride, diisobutylaluminum hydride, and dihexylaluminum hydride. Preferably, it is a trialkylaluminum, and more preferably, triethylaluminum or triisobutylaluminum.

[0031] In the general formula {-Al (E ²⁾ -O-} cyclic aluminoxane having the structure represented by _b (B2), the general formula ^{E 3 {-Al (E 3)} -O-} c AlE 3 2 In a linear aluminoxane (B3) having the structure shown,
Specific examples of E ² and E ³ include a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group,
Examples thereof include an alkyl group such as an isobutyl group, a normal pentyl group, and a neopentyl group. b is an integer of 2 or more, and c is an integer of 1 or more. Preferably, E ²
And E ³ is a methyl group or an isobutyl group, and b
Is 2 to 40 and c is 1 to 40.

The above aluminoxane is made by various methods. The method is not particularly limited, and may be made according to a known method. For example, a solution prepared by dissolving a trialkylaluminum (for example, trimethylaluminum) in a suitable organic solvent (benzene, aliphatic hydrocarbon, or the like) is brought into contact with water. In addition, a method in which a trialkylaluminum (for example, trimethylaluminum or the like) is brought into contact with a metal salt (for example, copper sulfate hydrate or the like) containing water of crystallization can be exemplified.

(C) Boron Compound In the present invention, the boron compound (C) includes (C1)
A boron compound represented by the general formula BQ ¹ Q ² Q ³ , (C
2) a boron compound represented by the general formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^— , (C3) a general formula (LH) ⁺ (BQ ¹ Q ² Q ³ Q)
^{4) -} one of boron compound represented by can be used.

In the boron compound (C1) represented by the general formula BQ ¹ Q ² Q ³ , B is a trivalent boron atom, and Q ^{1 to} Q ³ are a halogen atom, a hydrocarbon group or a halogen atom. A substituted hydrocarbon group, a substituted silyl group, an alkoxy group or a disubstituted amino group, which may be the same or different. Q ^{1 to} Q ³ are preferably a halogen atom, a hydrocarbon group containing 1 to 20 carbon atoms, 1 to 20
A halogenated hydrocarbon group containing 1 to 20 carbon atoms, a substituted silyl group containing 1 to 20 carbon atoms, an alkoxy group containing 1 to 20 carbon atoms or an amino group containing 2 to 20 carbon atoms. Q ^{1 to} Q ³ are more preferably a halogen atom, a hydrocarbon group containing 1 to 20 carbon atoms, or 1
Halogenated hydrocarbon groups containing up to 20 carbon atoms. More preferably, Q ^{1 to} Q ⁴ are each a fluorinated hydrocarbon group having 1 to 20 carbon atoms containing at least one fluorine atom, and particularly preferably, Q ^{1 to} Q ⁴ each have at least one fluorine atom. 6 to 2 carbon atoms including atoms
0 is a fluorinated aryl group.

Specific examples of the compound (C1) include tris (pentafluorophenyl) borane, tris (2,3,
5,6-tetrafluorophenyl) borane, tris (2,3,4,5-tetrafluorophenyl) borane,
Tris (3,4,5-trifluorophenyl) borane,
Tris (2,3,4-trifluorophenyl) borane,
Phenylbis (pentafluorophenyl) borane and the like can be mentioned, and most preferred is tris (pentafluorophenyl) borane.

In the boron compound (C2) represented by the general formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- , G ⁺ is an inorganic or organic cation, and B is boron in a trivalent valence state. And Q ^{1 to} Q ⁴ are Q ^{1 to} Q ³ in the above (C1).
Is the same as

The general formula ^{G + (BQ 1 Q 2 Q} 3 Q 4) - Examples of G ⁺ as an inorganic cation in the compound represented by, ferrocenium cation, alkyl-substituted ferrocenium cation, silver Examples of G ^{+ in} which a cation or the like is an organic cation include a triphenylmethyl cation. G ⁺ is preferably a carbenium cation, and particularly preferably a triphenylmethyl cation. ^{(BQ 1 Q 2 Q 3 Q} 4) - as the tetrakis (pentafluorophenyl) borate, tetrakis (2,3,5,6-tetrafluorophenyl) borate, tetrakis (2,3,4,5-tetrafluoro Phenyl) borate, tetrakis (3,4,5-trifluorophenyl) borate, tetrakis (2,3,4-trifluorophenyl) borate, phenyltris (pentafluorophenyl) borate, tetrakis (3,5-bistriborate) Fluoromethylphenyl) borate and the like.

Specific combinations of these include ferrocenium tetrakis (pentafluorophenyl) borate, 1,1'-dimethylferrocenium tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate, Phenylmethyltetrakis (pentafluorophenyl) borate,
Triphenylmethyltetrakis (3,5-bistrifluoromethylphenyl) borate and the like can be mentioned, and most preferred is triphenylmethyltetrakis (pentafluorophenyl) borate.

The general formula (LH) ⁺ (BQ ¹ Q ² Q ³ Q
^{4) -} In the boron compound represented (C3), L is a neutral Lewis base, (L-H) ⁺ is a Bronsted acid, B is boron atom in the trivalent valence state ,
Q ¹ to Q ⁴ are the same as Q ¹ to Q ³ in the above Lewis acid (C1).

The general formula ^{(L-H) + (BQ} 1 Q 2 Q 3 Q 4) - is a Brønsted acid in the compound represented by (L-
Specific examples of H) ⁺ include trialkyl-substituted ammonium, N, N-dialkylanilinium, dialkylammonium, triarylphosphonium, and the like.
As (BQ ¹ Q ² Q ³ Q ⁴ ) ^{−, the same} as those described above can be mentioned.

As specific combinations of these, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, tri ( n-butyl) ammonium tetrakis (3,5-bistrifluoromethylphenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N N-2,4,6-pentamethylanilinium tetrakis (pentafluorophenyl) borate, N, N
-Dimethylanilinium tetrakis (3,5-bistrifluoromethylphenyl) borate, diisopropylammonium tetrakis (pentafluorophenyl) borate, dicyclohexylammonium tetrakis (pentafluorophenyl) borate, triphenylphosphonium tetrakis (pentafluorophenyl) borate,
Tri (methylphenyl) phosphonium tetrakis (pentafluorophenyl) borate, tri (dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate and the like can be mentioned. Most preferably, tri (n-butyl) ammonium tetrakis (pentafluoro) is used. Phenyl) borate or N, N-
Dimethylanilinium tetrakis (pentafluorophenyl) borate.

[Polymerization of olefin] In the present invention,
The transition metal compound (A) represented by the general formula [I] and / or [II], and the above (B) and / or the above (C)
Is used. When using an olefin polymerization catalyst comprising the transition metal compounds (A) and (B), the cyclic aluminoxane (B2) and / or the linear aluminoxane (B3) are preferred as (B). Other preferred embodiments of the olefin polymerization catalyst include transition metal compounds (A) and (B).
And a catalyst for olefin polymerization using (C). In this case, (B1) is easily used as (B).

In the present invention, general formulas [I] and / or
Alternatively, the transition metal compounds (A) and (B) represented by [II] or (C) can be added and used in an arbitrary order during polymerization, and a combination of these arbitrary compounds can be used. May be used in advance to obtain a reaction product.

The amount of each component used is usually such that the molar ratio of (B) / transition metal compound (A) is 0.1 to 10000, preferably 5 to 2000, and the molar ratio of (C) / transition metal compound (A) It is desirable to use each component such that the ratio is between 0.01 and 100, preferably between 0.5 and 10.

The concentration when each component is used in the form of a solution or suspended or slurried in a solvent is appropriately selected depending on conditions such as the performance of an apparatus for supplying each component to the polymerization reactor. The transition metal compound (A) is usually 0.001 to 200 mmol / L, more preferably 0.001 to 100 mmol / L, still more preferably 0.05 to 50 mmol / L, and (B) the equivalent of Al atom. In general, 0.01 to 5000 mmol / L, more preferably 0.1 to 2500 mmol / L, still more preferably 0.1 to 2000 mmol / L, (C)
It is desirable to use each component so as to be usually in the range of 0.001 to 500 mmol / L, more preferably 0.01 to 250 mmol / L, and still more preferably 0.05 to 100 mmol / L.

The olefin applicable to the polymerization in the present invention includes olefins having 2 to 20 carbon atoms, particularly ethylene, α-olefins having 3 to 20 carbon atoms, and diolefins having 4 to 20 carbon atoms. And the like, and two or more types of monomers can be used at the same time. Specific examples of the olefin include linear olefins such as ethylene, propylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1, nonene-1, and decene-1, and 3-methylbutene-. Examples thereof include branched olefins such as 1,3-methylpentene-1, 4-methylpentene-1, and 5-methyl-hexene-1, and vinylcyclohexane, but the present invention is not limited to the above compounds. Absent. Specific examples of the combination of monomers when performing the copolymerization, ethylene and propylene,
Examples include ethylene and butene-1, ethylene and hexene-1, ethylene and octene-1, and propylene and butene-1, but the present invention should not be limited to these combinations.

The present invention is particularly applicable to the production of copolymers of ethylene with other α-olefins, especially propylene, butene-1, 4-methylpentene-1, hexene-1, octene-1 and other α-olefins. Can be applied effectively.

The polymerization method is not particularly limited either. For example, aliphatic hydrocarbons such as butane, pentane, hexane, heptane and octane, aromatic hydrocarbons such as benzene and toluene, and methylene dichloride and the like can be used. Solvent polymerization using a halogenated hydrocarbon as a solvent, or slurry polymerization, or a method called high-pressure ionic polymerization, in which the olefin polymer formed into an olefin in a supercritical fluid state under high temperature and pressure without solvent is melted. The polymerization can be carried out in a state in which the polymerization has been carried out, and furthermore, a gas phase polymerization in a gaseous monomer or the like is possible, and both continuous polymerization and batch polymerization are possible.

The polymerization temperature can range from -50 ° C to 350 ° C, preferably from 0 ° C to 300 ° C, particularly preferably from 50 ° C to 300 ° C. Polymerization pressure is normal pressure ~
Although it can be in the range of 350 MPa, it is preferably normal pressure to 3 MPa.
00 MPa, particularly preferably normal pressure to 200 MPa.

In general, the polymerization time is appropriately determined depending on the kind of the intended polymer and the reaction apparatus, and there is no particular restriction, but it can be in the range of 1 minute to 20 hours. In the present invention, a chain transfer agent such as hydrogen may be added to adjust the molecular weight of the copolymer.

The process for producing the olefin polymer of the present invention comprises:
Particularly, it is preferably carried out by a high-pressure ion polymerization method. Specifically, it is preferably carried out at a pressure of 30 MPa or more and a temperature of 300 ° C. or more. More preferably, the pressure is between 35 and
The operation is performed at 350 MPa and at a temperature of 135 to 350 ° C.
In this case, the polymerization system may be either a batch system or a continuous system, but it is preferable to carry out the system in a continuous system. Generally, a stirred tank reactor or a tubular reactor can be used as the reactor. The polymerization may be carried out in a single reaction zone, but may be carried out by dividing one reactor into a plurality of reaction zones, or by connecting a plurality of reactors in series or in parallel. When a plurality of reactors are used, any combination of tank type-tank type or tank type-tube type may be used. In the method of polymerizing in a plurality of reaction zones or a plurality of reactors, it is possible to produce olefin polymers having different properties by changing the temperature, pressure, and gas composition for each nuclear reaction zone.

[0052]

The present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples. The properties of the polymers in the examples were measured by the following methods.

(1) The melt index (MFR) is
According to the method specified in JIS K-6760, 190
Measured at ° C. Unit: g / 10 minutes

(2) The density was determined according to JIS K-6760. However, the density value described as density (without annealing) is a value measured without annealing treatment in JIS K-6760, and the density value described as density (with annealing) is a measured value after annealing treatment. It is. Unit: g / cm ³

(3) Melting point of copolymer: Perkin-E
It was determined under the following conditions using DSC7 manufactured by Imer. Heating: Heating up to 150 ° C, holding until the change in calorie becomes stable Cooling: 150 ° C to 10 ° C (5 ° C / min), Holding for 10 minutes Measurement: 10 ° C to 160 ° C (5 ° C / min)

(4) α-olefin content: Determined from the characteristic absorption of ethylene and α-olefin using an infrared spectrophotometer (FT-IR7300 manufactured by JASCO Corporation).
Expressed as the number of short chain branches per 000 carbons (SCB).

(5) Molecular weight and molecular weight distribution: Determined using gel permeation chromatograph (150, C, manufactured by Waters) under the following conditions. Column: TSK gel GMH-HT Measurement temperature: 145 ° C Setting Measurement concentration: 10 mg / 10 ml-ortho-dichlorobenzene The weight average molecular weight may be abbreviated as Mw. The molecular weight distribution is represented by the ratio M between the weight average molecular weight Mw and the number average molecular weight Mn.
w / Mn.

(6) Intrinsic viscosity [η]: 100 mg of the obtained copolymer was dissolved in 50 ml of tetralin at 135 ° C., and an Ubbelohde viscometer set in a water bath maintained at 135 ° C. was used. And the falling speed of the tetralin solution in which the sample was dissolved.

Reference Example 1 (Transition metal compound: dimethylsilylene (η ⁵ -tetramethylcyclopentadienyl) (3-tert-butyl-
Example of synthesis of 5-methyl-2-phenoxy) titanium dimethoxide 0.131 g (4.1 mmol) of methanol was dissolved in 10 ml of anhydrous ether in a Schlenk tube, and -78 ° C.
An ether solution of methyl lithium (3.9 ml, 4.1 mmol) having a concentration of 1.05 mol / L was added dropwise. 20
Temperature to ℃ and confirm the end of gas generation,
The formation of lithium methoxide was confirmed, and the mixture was cooled again to -78 ° C. It prepared in advance to another Schlenk tube, dimethylsilylene (eta ⁵ - tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride 0.919 g (2.0 mm
ol) in 20 ml of anhydrous ether was transferred to the previous reaction solution, and then gradually heated to room temperature. After concentrating the reaction solution, 20 ml of toluene was added, and insolubles were filtered off.
The filtrate was concentrated, dimethylsilylene (eta ⁵ - tetramethylcyclopentadienyl) (3-tert-butyl-5-
Methyl-2-phenoxy) titanium dimethoxide was obtained as yellow crystals. (0.86 g, 95%) ¹ H NMR (270 MHz, C ₆ D ₆ ) δ7.26
(M, 2H), 4.13 (s, 6H), 2.33 (s,
3H), 1.97 (s, 6H), 1.89 (s, 6
H), 1.59 (s, 9H), 0.55 (s, 6H)

Reference Example 2 (Transition metal compound: μ-oxobis @ dimethylsilylene (η ⁵ -tetramethylcyclopentadienyl) (3-t
Synthesis Example of tert-butyl-5-methyl-2-phenoxy) titanium methoxide (Compound 1) Dimethylsilylene (η ⁵ -tetramethylcyclopentadienyl) (3-tert-butyl-5) under a nitrogen atmosphere
10.00 g of methyl-2-phenoxy) titanium dimethoxide (a compound obtained in the same manner as in Reference Example 1) was dissolved in 50 ml of heptane, 0.30 g of distilled water was added, and the mixture was stirred at the same temperature for 12 hours. The resulting solid was collected by filtration, washed with 5.0 ml of heptane, and dried under reduced pressure to give μ-oxobis {dimethylsilylene (η ⁵ -tetramethylcyclopentadienyl) (3-tert-butyl-5- Methyl-2-phenoxy) titanium methoxide was obtained as a yellow solid (5.51 g, 56%). Mass spectrum (m / e) 855 Calculated: 855 ¹ H-NMR (C ₆ D ₆ ) δ 7.25 (d, J = 2.0)
Hz, 2H), 7.16 (d, J = 2.0 Hz, 2
H), 3.99 (s, 6H), 2.32 (s, 6H),
2.30 (s, 6H), 2.06 (s, 6H), 1.8
6 (s, 6H), 1.71 (s, 6H), 1.27
(S, 18H), 0.83 (s, 6H), 0.63
(S, 6H)

Reference Example 3 (Transition metal compound: di-μ-oxobis @ dimethylsilylene (η ⁵ -tetramethylcyclopentadienyl) (3
-Tert- butyl-5-methyl-2-phenoxy) titanium} (Synthesis Example of Compound 2)) in a Schlenk tube, dimethylsilylene toluene 20 ml (eta ⁵ - tetramethylcyclopentadienyl) (3-t
1.50 g (3.3 mmol) of tert-butyl-5-methyl-2-phenoxy) titanium dimethoxide was dissolved, 10 ml of water was added, and the mixture was stirred at 70 ° C. for 1 hour.
The organic layer obtained by liquid separation was concentrated and then recrystallized from 10 ml of heptane to obtain di-μ-oxobis {dimethylsilylene (η ⁵ -tetramethylcyclopentadienyl) (3-t
tert-butyl-5-methyl-2-phenoxy) titanium} was obtained as yellow crystals (0.40 g, 33
%). Mass spectrum (m / e) 808 Calculated 808 ¹ H NMR (270 MHz, C ₆ D ₆ ) δ 7.28
(M, 4H), 2.32 (s, 12H), 1.97
(S, 6H), 1.78 (s, 6H), 1.59 (s,
6H), 1.53 (s, 18H), 0.78 (s, 6
H), 0.58 (s, 6H)

Example 1 Ethylene and hexene-1 were continuously fed into a reactor using an autoclave-type reactor equipped with a stirring blade having an internal volume of 1 liter to carry out polymerization. The polymerization conditions were set to a total pressure of 80 MPa.
Hexene-to the sum of ethylene and hexene-1
One concentration was set to 28.8 mol%. μ-oxobis ｛dimethylsilylene (η ⁵ -tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-
Heptane solution (phenoxy) titanium methoxide (compound 1) and triisobutylaluminum mixed (concentration of compound 1 is 0.185 μmol / g, concentration of triisobutylaluminum is 18.5 μmol / g,
The molar ratio between Al atoms and Ti atoms was adjusted to 50. )
And a toluene solution of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate (0.90
μmol / g) were separately prepared in separate containers, and each was continuously supplied to the reactor at a supply rate of 100 g / hour and 140 g / hour. When the polymerization reaction temperature reaches 222 ° C,
The ratio of boron atoms to Ti atoms was set to 3.4.
As a result, the MFR was 8.39, the density (without annealing) was 0.883, the SCB was 36.0, and the molecular weight (Mw) was 62.
Ethylene-hexene-1 copolymer having a molecular weight distribution (Mw / Mn) of 1.9 at 2.72K per hour.
g, 74 ton per mole of Ti atom.

COMPARATIVE EXAMPLE 1 Ethylene and hexene-1 were continuously fed into a reactor using an autoclave-type reactor equipped with stirring blades having an internal volume of 1 liter to carry out polymerization. The polymerization conditions were set to 80 MPa
Hexene-to the sum of ethylene and hexene-1
One concentration was set to 34 mol%. Dimethylsilylene (eta ⁵ - tetramethylcyclopentadienyl) (3-t
tert-butyl-5-methyl-2-phenoxy) titanium dichloride in hexane (0.7 μmol /
g), a heptane solution of triisobutylaluminum (33 μmol / g) and a toluene solution of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate (1.2 μmol / g) were prepared in separate containers. 290 g / hour, 350 g each
/ Hr, and at a feed rate of 580 g / hr. When the polymerization reaction temperature reaches 215 ° C, Al
The molar ratio of atoms to Ti atoms was 57, and the ratio of boron atoms to Ti atoms was 3.3. As a result, the MFR was 4.2, the density (without annealing) was 0.881, and the melting point was 6
7.3 ° C, SCB 40.4, molecular weight (Mw) 660
Ethylene-hexene-1 copolymer having a molecular weight distribution (Mw / Mn) of 1.8 was converted to 2.84 K per hour.
g, 14 ton per mole of Ti atom.

Example 2 An autoclave type reactor equipped with a stirring blade having an inner volume of 0.4 liter was purged with argon, and then 185 ml of cyclohexane as a solvent and 1 part of hexene-1 as an α-olefin.
After charging 5 ml, the reactor was heated to 180 ° C. After the temperature was raised, the ethylene pressure was adjusted to 2.5 Mpa and the mixture was fed. After the system was stabilized, 0.2 mmol of triisobutylaluminum was added to μ-oxobis ｛dimethylsilylene (η ⁵ -tetramethylcyclopentadienyl) ( 3-t
tert-butyl-5-methyl-2-phenoxy) titanium methoxide (compound 1) and triisobutylaluminum in a heptane solution (compound 1 has a concentration of 1
The concentration of μmol / ml and triisobutylaluminum was 50 μmol / ml, and the molar ratio between Al atoms and Ti atoms was adjusted to 25. ) In 0.5 ml (ie, 0.5 μmol of compound 1 and 25 μl of triisobutylaluminum).
mol), followed by N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate 1.5
μmol was supplied as a liquid (slurry concentration, 1 μmol / ml) slurried in heptane. Polymerization was performed for 2 minutes. As a result of polymerization, [η] was 0.85 and SCB was 3
1.43, 2.53 g of ethylene-hexene-1 copolymer having a melting point of 78.6 ° C. and 90.8 ° C. was obtained. Ti atom 1
The polymerization activity per mole was 2.53 × 10
⁶ g / Timol.

Example 3 After replacing an autoclave type reactor equipped with a stirring blade having an inner volume of 0.4 liter with argon, 185 ml of cyclohexane was used as a solvent, and hexene-1 was used as an α-olefin.
After charging 5 ml, the reactor was heated to 180 ° C. After the temperature was raised, the ethylene pressure was adjusted to 2.5 Mpa and the mixture was fed. After the system was stabilized, 0.2 mmol of triisobutylaluminum was added to μ-oxobis ｛dimethylsilylene (η ⁵ -tetramethylcyclopentadienyl) ( 3-t
tert-butyl-5-methyl-2-phenoxy) titanium methoxide (compound 1) and triisobutylaluminum in a heptane solution (compound 1 has a concentration of 1
The concentration of μmol / ml and triisobutylaluminum was 50 μmol / ml, and the molar ratio between Al atoms and Ti atoms was adjusted to 25. ) In 0.5 ml (ie, 0.5 μmol of compound 1 and 25 μl of triisobutylaluminum).
mol), followed by N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate 3 μm
ol in heptane (slurry concentration, 1
μmol / ml). Polymerization was performed for 2 minutes. As a result of polymerization, [η] was 0.67 and SCB was 35.
5.33 g of an ethylene-hexene-1 copolymer having a melting point of 74.2 ° C., 88.6 ° C., a molecular weight (Mw) of 43,000, and a molecular weight distribution (Mw / Mn) of 2.7 was obtained. T
The polymerization activity per mole of i atom is 5.3 per 2 minutes.
It was 3 × 10 ⁶ g / Timol.

Example 4 An autoclave type reactor equipped with a stirring blade having an inner volume of 0.4 liter was purged with argon, 185 ml of cyclohexane was used as a solvent, and hexene-1 was used as an α-olefin.
After charging 5 ml, the reactor was heated to 180 ° C. After the temperature was raised, the ethylene pressure was adjusted to 2.5 Mpa and the mixture was fed. After the inside of the system was stabilized, 0.2 mmol of triisobutylaluminum was added to di-μ-oxobis ｛dimethylsilylene (η ⁵ -tetramethylcyclopentadienyl). ) (3-
Heptane solution in which tert-butyl-5-methyl-2-phenoxy) titanium (compound 2) and triisobutylaluminum were mixed (the concentration of compound 2 was 1 μmol /
ml, the concentration of triisobutylaluminum is 50 μmo
At 1 / ml, the molar ratio between Al atoms and Ti atoms was adjusted to 25. ) In 0.5 ml (ie, 0.5 μm
l, triisobutylaluminum (25 μmol) was charged, and subsequently, a liquid in which 1.5 μmol of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate was slurried in heptane (slurry concentration: 1 μmo)
1 / ml). Polymerization was performed for 2 minutes. As a result of the polymerization, ethylene-hexene-1 having [η] of 0.84, SCB of 30.7, and melting points of 80.2 ° C. and 93.0 ° C.
2.55 g of a copolymer was obtained. The polymerization activity per mole of Ti atom is 2.55 × 10 ⁶ g / Timo per 2 minutes.
l.

Example 5 An autoclave type reactor equipped with a stirring blade having an inner volume of 0.4 liter was purged with argon, 185 ml of cyclohexane was used as a solvent, and hexene-1 was used as an α-olefin.
After charging 5 ml, the reactor was heated to 180 ° C. After the temperature was raised, the ethylene pressure was adjusted to 2.5 Mpa and the mixture was fed. After the inside of the system was stabilized, 0.2 mmol of triisobutylaluminum was added to di-μ-oxobis ｛dimethylsilylene (η ⁵ -tetramethylcyclopentadienyl). ) (3-
Heptane solution in which tert-butyl-5-methyl-2-phenoxy) titanium (compound 2) and triisobutylaluminum were mixed (the concentration of compound 2 was 1 μmol /
ml, the concentration of triisobutylaluminum is 50 μmo
At 1 / ml, the molar ratio of Al atoms to Ti atoms was adjusted to 25. ) In 0.5 ml (i.e., 0.5 μm
ol, triisobutylaluminum (25 μmol), and then a solution in which 3 μmol of N, N-dimethylaniliniumtetrakis (pentafluorophenyl) borate was slurried in heptane (slurry concentration: 1 μmol /
ml). Polymerization was performed for 2 minutes. As a result of polymerization, [η] was 0.73, SCB was 33.0, and melting point was 7
8.9 ° C., 91.5 ° C., molecular weight (Mw) 48,000,
3.92 g of an ethylene-hexene-1 copolymer having a molecular weight distribution (Mw / Mn) of 2.5 was obtained. The polymerization activity per mole of Ti atom was 3.92 × 10 ⁶ g per 2 minutes.
/ Timol.

[0068]

As described in detail above, according to the present invention,
A transition metal compound useful as a catalyst component for highly active olefin polymerization at an efficient reaction temperature in an industrial process of olefin polymerization, and a highly active catalyst for olefin polymerization using the transition metal compound, and A method for producing an olefin polymer using a catalyst is provided. Further, the transition metal compound of the present invention is excellent in copolymerizability and is also effective as a catalyst component for olefin polymerization that gives a high-molecular-weight olefin polymer, and its utility value is extremely large.

[Brief description of the drawings]

FIG. 1 is a flowchart for helping the understanding of the present invention. The flowchart is a representative example of the embodiment of the present invention, and the present invention is not limited to this.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Hiroaki Katayama 5-1, Anesaki Beach, Ichihara-shi, Chiba Sumitomo Chemical Co., Ltd. (72) Inventor Takeshi Watanabe 5-1, Anesaki Beach, Ichihara-shi, Chiba Sumitomo Chemical Industry Co., Ltd.

Claims (15)

[Claims] 1. A transition metal compound represented by the following general formula [I] or [II]. (In the above general formula [I] or [II], M
¹ represents a transition metal atom of Group 4 of the periodic table of the element;
Represents an atom belonging to Group 16 of the periodic table of the element, and J represents an atom belonging to Group 14 of the periodic table of the element. Cp ¹ represents a group having a cyclopentadiene-type anion skeleton. X ¹ , R ¹ ,
R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an aryl group, a substituted silyl group, an alkoxy group, an aralkyloxy group, an aryloxy group or Shows a substituted amino group.
X ² represents an atom of Group 16 of the periodic table of the element. R ¹ , R
² , R ³ , R ⁴ , R ⁵ and R ⁶ may be optionally combined to form a ring. Multiple M ¹ , A, J, Cp ¹ , X ¹ , X ² , R
¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be the same or different. ) 2. A in the general formula [I] or [II] is:
The transition metal compound according to claim 1, which is an oxygen atom. 3. X in the general formula [I] or [II]
^3. The transition metal compound according to claim 1, wherein ² is an oxygen atom. 4. A compound represented by the formula (I) or (II):
4. The transition metal compound according to claim ¹ , wherein ¹ is independently an alkyl group, an aralkyl group, an aryl group, or a substituted silyl group. 5. The method according to claim 1, wherein X ¹ in the general formula [I] is independently a halogen atom, an alkyl group, an aralkyl group, an alkoxy group, an aryloxy group or a disubstituted amino group. The transition metal compound according to any one of the above. 6. A catalyst component for olefin polymerization, comprising the transition metal compound according to any one of claims 1 to 5. 7. An olefin polymerization catalyst comprising the transition metal compound according to claim 1 and the following (B) and / or (C). (B): one or more aluminum compounds selected from the following (B1) to (B3) (B1) an organoaluminum compound represented by the general formula E ¹ _a AlZ _3-a (B2) a general formula ｛-Al (E ² ) -O-} cyclic aluminoxane having the structure represented by _b (B3) formula ^{E 3 {-Al (E 3)} -O-} c AlE 3
Linear aluminoxane having a structure represented by ₂ , wherein E ¹ , E ² and E ³ are each a hydrocarbon group, and all E ¹ , all E ² and all E ³ are the same; Z represents a hydrogen atom or a halogen atom, all Z may be the same or different, a is a number satisfying 0 <a ≦ 3, and b is 2 or more. An integer, and c represents an integer of 1 or more.) (C): a boron compound of any of the following (C1) to (C3) (C1) a boron compound represented by the general formula BQ ¹ Q ² Q ³ , C2) a boron compound represented by the general formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- , (C3) a boron compound represented by the general formula (LH) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- boron compounds (wherein, B is a boron atom in the trivalent valence state, Q ¹ to Q ⁴ are a halogen atom, a hydrocarbon group, a halo Emissions hydrocarbon group, substituted silyl group, an alkoxy group or a di-substituted amino group, they may be different even in the same .G ⁺ is an inorganic or organic cation, L is a neutral Lewis base And (LH) ⁺ is a Bronsted acid.) 8. The catalyst for olefin polymerization according to claim 7, wherein (B) is triethylaluminum, triisobutylaluminum or methylaluminoxane. 9. The catalyst for olefin polymerization according to claim 7, wherein (C) is dimethylanilinium tetrakis (pentafluorophenyl) borate or triphenylmethyltetrakis (pentafluorophenyl) borate. 10. The olefin polymerization catalyst according to claim 1, wherein
A catalyst for olefin polymerization, comprising using the transition metal compound according to any one of (1) to (B) and (C) according to claim 7. 11. The olefin polymerization catalyst according to claim 1, wherein
A catalyst for olefin polymerization, comprising using the transition metal compound according to any one of the above, and (B2) according to claim 7 and / or (B3) according to claim 7. 12. A process for producing an olefin polymer, comprising using the catalyst for olefin polymerization according to any one of claims 7 to 11. 13. The method according to claim 1, wherein the olefin polymer is a copolymer of ethylene and an α-olefin.
3. The method for producing an olefin polymer according to item 2. 14. The method for producing an olefin polymer according to claim 12, which is carried out by a high pressure ionic polymerization method. 15. The method for producing an olefin polymer according to claim 12, which is carried out at a pressure of 30 MPa or more and a temperature of 130 ° C. or more.