JP3346256B2 - Method for producing olefin (co) polymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing an olefin (co) polymer using an olefin polymerization catalyst containing a transition metal complex as one of the catalyst components. More specifically, the present invention relates to a method for producing an olefin (co) polymer using an olefin polymerization catalyst containing a transition metal complex at high temperature and high pressure. In the present invention, the olefin (co) polymer refers to an olefin homopolymer or a copolymer of two or more olefins.

[0002]

2. Description of the Related Art At present, the following two methods are widely used as industrial methods for producing olefin (co) polymers at high temperatures using olefin polymerization catalysts. The first method is generally referred to as a high-temperature solution method and is a method in which an olefin is polymerized under a condition in which the polymer is melted using a solvent such as cyclohexane.
For example, the polymerization is carried out under the conditions of 5 ° C. and 5 kg / cm ² . The second method is generally called a high-pressure ionic polymerization method, which is a method in which an olefin (co) polymer formed into an olefin in a supercritical fluid state under a high temperature and a high pressure without a solvent is polymerized in a molten state. These high-temperature solution polymerization methods and high-pressure ion polymerization methods have advantages such as a compact reactor and easy switching of monomers.

On the other hand, in addition to the solid catalysts conventionally used as olefin polymerization catalysts, olefin polymerization catalysts comprising a transition metal complex represented by a metallocene complex as a transition metal catalyst component have recently attracted attention. One of the features of using a metallocene complex is that an olefin (co) polymer having a narrow molecular weight distribution or composition distribution can be obtained, but it is necessary to control the density and the polymerization activity, especially at a reaction temperature that is efficient for industrial production. However, there is a problem that the polymerization activity is still insufficient.

Some reports have already been made on a method for producing an olefin (co) polymer using a metallocene complex by a high-pressure ionic polymerization method. For example,
JP-A-503788 discloses a method for producing an olefin (co) polymer using a catalyst comprising bis (n-butyl) cyclopentadienyl zirconium dichloride and methylaluminoxane in a high-pressure ionic polymerization method. However, despite the extremely high polymerization pressure of 1000 bar or more, the molecular weight of the resulting ethylene-α-olefin (co) polymer was insufficient.

In Japanese Patent Application Laid-Open No. 7-157508, diphenylmethylene (cyclopentadienyl)
A method for producing an olefin (co) polymer using a catalyst comprising (fluorenyl) zirconium dichloride, triisobutylaluminum, and N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate in a high-pressure ionic polymerization method is disclosed. Have been. However, even in this polymerization method, the polymerization pressure is 900 kg /
Despite being at least cm ² , the molecular weight of the ethylene-α-olefin copolymer was still insufficient.

In US Pat. No. 5,408,017, dimethylsilylbis (4,5,6,7-tetrahydroindenyl) zirconium dimethyl and N, N
A method for producing an olefin (co) polymer by using a catalyst comprising dimethylanilinium tetrakis (pentafluorophenyl) borate in a high-pressure ionic polymerization method is disclosed. However, even in this polymerization method, the polymerization pressure was as high as 1300 bar, but the molecular weight of the ethylene-α-olefin copolymer was still insufficient.

[0007]

In view of such circumstances, an object of the present invention, that is, an object of the present invention, is to use a highly active catalyst using a novel metallocene complex. An object of the present invention is to provide a method for efficiently producing an olefin (co) polymer having an arbitrary density having a narrow composition distribution and a high molecular weight under high temperature and high pressure conditions.

[0008]

SUMMARY OF THE INVENTION The present inventors have achieved the above object.
For producing an olefin (co) polymer in order to achieve
We have continued our intensive research and have completed the present invention.
Was. That is, the present invention provides at least 300 kg / cm^TwoG and below
At the above pressure and a temperature of at least 130 ° C.,
(A) and the following (B) and / or (C)
The olefin polymerization catalyst
Homopolymerization or copolymerization of two or more olefins
According to the method for producing an olefin (co) polymer.
You. (A): a transition metal complex represented by the following general formula [I](Where M¹Is the transition metal atom of Group 4 of the Periodic Table of the Elements
A represents an atom of Group 16 of the Periodic Table of the Elements,
J represents an atom belonging to Group 14 of the periodic table of the elements. Cp¹Is
A group having a cyclopentadiene-type anion skeleton is shown.
X¹, X^Two, R¹, R ^Two, R^Three, R^Four, R^FiveAnd R⁶Each
Independently, a hydrogen atom, a halogen atom, an alkyl group,
Alkyl group, aryl group, substituted silyl group, alkoxy group,
An aralkyloxy group, an aryloxy group or a disubstituted
Shows a mino group. R¹, R^Two, R^Three, R^Four, R^FiveAnd R⁶Is any
They may be bonded at will to form a ring. (B): at least one selected from the following (B1) to (B3)
(B1) General formula E¹ _aAlZ_3-aOrganic aluminum indicated by
Compound (B2) General formula ｛-Al (E^Two) -O-｝_bIndicated by
Cyclic aluminoxane having a structure (B3) General formula E^Three｛-Al (E^Three) -O-｝_cAlE^Three
_TwoLinear aluminoxane having a structure represented by the following formula (provided that E¹, E^TwoAnd E^ThreeIs a hydrocarbon group
Yes, all E¹, All E^TwoAnd all E^ThreeIs the same
May be different. Z is a hydrogen atom or halo
Gen atom, all Z are the same or different
May be. a is a number satisfying 0 <a ≦ 3, b is 2 or more
And c represents an integer of 1 or more. (C): Boration of any of the following (C1) to (C3)
Compound (C1) General formula BQ¹Q^TwoQ^ThreeBoron compound represented by
Object, (C2) general formula G⁺(BQ¹Q^TwoQ^ThreeQ^Four)^-Represented by
Boron compound, (C3) general formula (LH)⁺(BQ¹
Q^TwoQ^ThreeQ^Four)^-(Where B is trivalent)
Is a boron atom in the valence state of¹~ Q^FourIs halogen
Atom, hydrocarbon group, halogenated hydrocarbon group, substituted silyl
Group, alkoxy group or disubstituted amino group,
May be the same or different. G⁺Is inorganic or
Is an organic cation, L is a neutral Lewis base,
(LH)⁺Is a Bronsted acid. )

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. (A) Transition metal complex In the general formula [I], the transition metal atom represented by M ¹ represents a transition metal element belonging to Group 4 of the Periodic Table of the Elements (IUPAC revised edition of inorganic chemical nomenclature 1989), For example, a titanium atom, a zirconium atom, a hafnium atom and the like can be mentioned. Preferably it is a titanium atom or a zirconium atom.

Examples of the atoms of Group 16 of the periodic table of the element represented by A in the general formula [I] include an oxygen atom, a sulfur atom, a selenium atom and the like, and an oxygen atom is preferred.

Examples of atoms belonging to Group 14 of the periodic table of the element represented by J in the general formula [I] include a carbon atom, a silicon atom, and a germanium atom, and are preferably a carbon atom or a silicon atom. .

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.

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

The substituents X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R
The alkyl group for ⁵ or R ⁶ has 1 carbon atom
~ 20 alkyl groups are preferred, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, amyl, n -Hexyl group,
n-octyl group, n-decyl group, n-dodecyl group, n-
Examples thereof include a pentadecyl group and an n-eicosyl group, and more preferably a methyl group, an ethyl group, an isopropyl group, and a t-group.
tert-butyl or amyl.

[0015] 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 group, iodomethyl group, diiodomethyl group, triiodomethyl group, fluoroethyl group, difluoroethyl group, trifluoroethyl group, tetrafluoroethyl group, pentafluoroethyl group, chloroethyl group, dichloroethyl group, trichloroethyl group , 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 substituents X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R
The aralkyl group for ⁵ or R ⁶ is preferably an aralkyl group having 7 to 20 carbon atoms, for example, 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, (4,6
-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)
Methyl group, (n-dodecylphenyl) methyl group, (n-
Tetradecylphenyl) methyl group, naphthylmethyl group,
Examples include an anthracenylmethyl group, and more preferably a benzyl group. All of these aralkyl 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 substituents X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R
The aryl group for ⁵ or R ⁶ has 6 carbon atoms.
To 20 aryl groups, for example, a phenyl group, 2
-Tolyl group, 3-tolyl group, 4-tolyl group, 2,3-xylyl group, 2,4-xylyl group, 2,5-xylyl group,
2,6-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, Examples include an anthracenyl group, and more preferably a phenyl group. All of these aryl groups are a fluorine atom, a chlorine atom, a bromine atom, a halogen atom such as an iodine atom, a methoxy group, an alkoxy group such as an ethoxy group,
It may be partially substituted with an aryloxy group such as a phenoxy group or an aralkyloxy group such as a benzyloxy group.

The substituents X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R
The substituted silyl group in ⁵ or R ⁶ is a silyl group substituted with a hydrocarbon group, wherein the hydrocarbon group includes
For example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-
Examples thereof include an alkyl group having 1 to 10 carbon atoms such as a butyl group, an isobutyl group, an n-pentyl group, an n-hexyl group and a cyclohexyl group, 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 substituents X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R
^{As the} alkoxy group for ⁵ or R ^6, an alkoxy group having 1 to 20 carbon atoms is preferable. For example, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, a tert-
Butoxy group, n-pentoxy group, neopentoxy group, n
-Hexoxy group, n-octoxy group, n-dodesoxy group, n-pentadeoxy group, n-icosoxy group and the like, and more preferably methoxy group, ethoxy group or tert-butoxy group. Each of these alkoxy groups is 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 substituents X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R
The aralkyloxy group for ⁵ or R ⁶ is preferably an aralkyloxy group having 7 to 20 carbon atoms, such as a benzyloxy group, a (2-methylphenyl) methoxy group, a (3-methylphenyl) methoxy group, or a (4-methylphenyl) methoxy group. 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)
A methoxy group, a (2,3,5-trimethylphenyl) methoxy group, a (2,3,6-trimethylphenyl) methoxy group, a (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 (octylphenyl) methoxy, (n-decylphenyl) methoxy, (n-tetradecylphenyl) methoxy, naphthylmethoxy, and anthracenylmethoxy, and more preferably benzyloxy. 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.

The substituents X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R
^The aryloxy group for ⁵ or R ⁶ is preferably an aryloxy group having 6 to 20 carbon atoms, for example, a phenoxy group, a 2-methylphenoxy group, a 3-methylphenoxy group, a 4-methylphenoxy group, a 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 Group, ethylphenoxy 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-tetradecylphenoxy group, naphthoxy group, anthracenoxy group and the like. All of these aryloxy groups are 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. It may be partially substituted with a group or the like.

Substituents X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R
^The disubstituted amino group in ⁵ or R ⁶ is an amino group substituted with two hydrocarbon groups, and examples of the hydrocarbon group include a methyl group, an ethyl group, an n-propyl group,
Isopropyl group, n-butyl group, sec-butyl group, t
tert-butyl group, isobutyl group, n-pentyl group, n
A hexyl group, a cyclohexyl group or the like having 1 to 1 carbon atoms
10 to 6 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 include a bis-tert-butyldimethylsilylamino group, and a dimethylamino group or a diethylamino group is preferable.

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

Preferably, R ¹ is an alkyl, aralkyl, aryl or substituted silyl group. Preferably, X ¹ and X ² are each independently a halogen atom, an alkyl group, an aralkyl group, an alkoxy group, an aryloxy group or a disubstituted amino group, and more preferably a halogen atom.

Examples of the transition metal complex (A) include methylene (cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride and methylene (cyclopentadienyl) (3-tert-butyl-
2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-tert-butyl-5
-Methyl-2-phenoxy) titanium dichloride,
Methylene (cyclopentadienyl) (3-phenyl-2
-Phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-trimethylsilyl-5-methyl-2 -Phenoxy) titanium dichloride, methylene (cyclopentadienyl)
(3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-tert-butyl-5-chloro-2-
Phenoxy) titanium dichloride,

Methylene (methylcyclopentadienyl)
(3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl)
(3-tert-butyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3 -Phenyl-2-phenoxy)
Titanium dichloride, methylene (methylcyclopentadienyl) (3-tert-butyldimethylsilyl-
5-methyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-tert-butyl- 5-methoxy-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-tert-butyl-5-
Chloro-2-phenoxy) titanium dichloride,

Methylene (tert-butylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride , Methylene (tert
-Butylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene (tert) -Butylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-
Methyl-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3
-Trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadiene) Enil) (3
-Tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Methylene (tetramethylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-tert-butyl-2-phenoxy)
Titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride , Methylene (tetramethylcyclopentadienyl) (3-ter
t-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-trimethylsilyl-5-
Methyl-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-t
tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-chloro-
2-phenoxy) titanium dichloride,

Methylene (trimethylsilylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, methylene (trimethylsilyl) Cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) ) (3-tert-butyldimethylsilyl-5-
Methyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3
-Trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3
-Tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Methylene (fluorenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-tert-butyl- 5-methyl-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-ter
t-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-tert-butyl-5- Methoxy-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Isopropylidene (cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, isopropylidene ( Cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) ) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl)
(3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-tert
-Butyl-5-chloro-2-phenoxy) titanium dichloride,

Isopropylidene (methylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, isopropylidene Riden (methylcyclopentadienyl) (3-tert-butyl-5
-Methyl-2-phenoxy) titanium dichloride,
Isopropylidene (methylcyclopentadienyl) (3
-Phenyl-2-phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl)
(3-tert-butyldimethylsilyl-5-methyl-
2-phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl) (3-tert-butyl-5- Methoxy-2-
Phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Isopropylidene (tert-butylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (te
rt-butylcyclopentadienyl) (3-tert-
Butyl-2-phenoxy) titanium dichloride, isopropylidene (tert-butylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (t
tert-butylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (tert-butylcyclopentadienyl)
(3-tert-butyldimethylsilyl-5-methyl-
2-phenoxy) titanium dichloride, isopropylidene (tert-butylcyclopentadienyl) (3
-Trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (tert-
Butylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, isopropylidene (tert-butylcyclopentadienyl) (3-tert-butyl-5-chloro-2)
-Phenoxy) titanium dichloride,

Isopropylidene (tetramethylcyclopentadienyl) (3,5-dimethyl-2-phenoxy)
Titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-tert-butyl-
2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-t
tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3- tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-trimethylsilyl-5-
Methyl-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl)
(3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Isopropylidene (trimethylsilylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3-tert-
Butyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3-phenyl- 2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl)
(3-tert-butyldimethylsilyl-5-methyl-
2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3
-Trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-chloro-2
-Phenoxy) titanium dichloride,

Isopropylidene (fluorenyl) (3,
5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-tert
-Butyl-2-phenoxy) titanium dichloride,
Isopropylidene (fluorenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-tert- Butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl)
(3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-tert-butyl-5-methoxy-2
-Phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Diphenylmethylene (cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, diphenylmethylene ( Cyclopentadienyl) (3-tert-butyl-5-methyl-2
-Phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3-phenyl-2-
Phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3-trimethylsilyl-5-methyl- 2-
Phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl)
(3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Diphenylmethylene (methylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, diphenyl Methylene (methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, diphenylmethylene ( Methylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-
Methyl-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3
-Trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3
-Tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Diphenylmethylene (tert-butylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3-te
rt-butyl-2-phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3-tert-butyl-5-methyl-2)
-Phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3
-Phenyl-2-phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3-tert-butyldimethylsilyl-
5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2
-Phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3
-Tert-butyl-5-methoxy-2-phenoxy)
Titanium dichloride, diphenylmethylene (ter
t-butylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Diphenylmethylene (tetramethylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride , Diphenylmethylene (tetramethylcyclopentadienyl)
(3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3-phenyl-2
-Phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3-t
tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopenta Dienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl)
(3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Diphenylmethylene (trimethylsilylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) (3-te
rt-butyl-2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-methyl-2)
-Phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) (3
-Phenyl-2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) (3-tert-butyldimethylsilyl-
5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2
-Phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) (3
-Tert-butyl-5-methoxy-2-phenoxy)
Titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Diphenylmethylene (fluorenyl)
(3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-
tert-butyl-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-t
tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-phenyl-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-
tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-tert-butyl- 5-methoxy-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-te
rt-butyl-5-chloro-2-phenoxy) titanium dichloride and the like, compounds obtained by changing titanium to zirconium or hafnium, dibromide to dichloride, diiodide, bis (dimethylamide), bis (diethylamide), -A compound changed to n-butoxide or diisopropoxide,
(Cyclopentadienyl) is replaced by (dimethylcyclopentadienyl), (trimethylcyclopentadienyl), (n
-Butylcyclopentadienyl), (tert-butyldimethylsilylcyclopentadienyl) or a compound modified to (indenyl), (3,5-dimethyl-2-
Phenoxy) to (2-phenoxy), (3-methyl-2)
-Phenoxy), (3,5-di-tert-butyl-2)
-Phenoxy), (3-phenyl-5-methyl-2-phenoxy), (3-tert-butyldimethylsilyl-
2-phenoxy) or (3-trimethylsilyl-2)
A transition metal complex wherein J in the general formula [I] is a carbon atom, such as a compound changed to -phenoxy);

Dimethylsilyl (cyclopentadienyl)
(2-phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, Dimethylsilyl (cyclopentadienyl) (3-tert-butyl-2
-Phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (3-tert-butyl-
5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (3,5
-Di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (3-tert -Butyldimethylsilyl-5
-Methyl-2-phenoxy) titanium dichloride,
Dimethylsilyl (cyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, Dimethylsilyl (cyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (3,5-diamyl-2-phenoxy) titanium dichloride,

Dimethylsilyl (methylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (3,5-
Dimethyl-2-phenoxy) titanium dichloride,
Dimethylsilyl (methylcyclopentadienyl) (3-
tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (3 5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) ( 3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethyi Silyl (cyclopentadienyl) (3-tert-butyl-5-methoxy-2-
Phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl)
(3,5-diamyl-2-phenoxy) titanium dichloride,

Dimethylsilyl (n-butylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilyl (n-butylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (n- Butylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilyl (n-butylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (n- Butylcyclopentadienyl) (3-tert-butyl-
5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (n-butylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (n-butylcyclopentadienyl) ) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilyl (n-butylcyclopentadienyl) (3-t
tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (n
-Butylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilyl (n-butylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium Dichloride, dimethylsilyl (n
-Butylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilyl (n-butylcyclopentadienyl) (3,5-diamyl-2-phenoxy) titanium dichloride,

Dimethylsilyl (tert-butylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (tert-butyl) Butylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilyl (te
rt-butylcyclopentadienyl) (3-tert-
Butyl-2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (te
rt-butylcyclopentadienyl) (3,5-di-t
tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilyl (ter
t-butylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2- Phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-
Phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (3-te
rt-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (3,5-diamyl-2-phenoxy) titanium dichloride,

Dimethylsilyl (tetramethylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopenta Dienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) ) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium Chloride, dimethylsilyl (tetramethylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl)
(3-tert-butyldimethylsilyl-5-methyl-
2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl- 5-methoxy-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (3-
tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (3,5-diamyl-2-phenoxy) titanium dichloride,

Dimethylsilyl (trimethylsilylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3-tert-
Butyl-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3,5- Di-t
tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3-tert- Butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) ( 3-tert-butyl-5-methoxy-2-
Phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3-te
rt-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3,5-diamyl-2-phenoxy) titanium dichloride,

Dimethylsilyl (indenyl) (2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (3,5
-Dimethyl-2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (3-tert-butyl-5
-Methyl-2-phenoxy) titanium dichloride,
Dimethylsilyl (indenyl) (3,5-di-tert
-Butyl-2-phenoxy) titanium dichloride,
Dimethylsilyl (indenyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) ) (5-Methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (3
-Tert-butyl-5-methoxy-2-phenoxy)
Titanium dichloride, dimethylsilyl (indenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (3,5-diamyl-2-phenoxy) titanium dichloride,

Dimethylsilyl (fluorenyl) (2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl)
(3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (3-te
rt-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (3-tert-
Butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (3,5-
Di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (3-te
rt-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (5-methyl-3-trimethylsilyl-2-
Phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (3-tert-butyl-5
-Chloro-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (3,5-diamyl-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl))
(1-Naphthoxy-2-yl) titanium dichloride and the like, and (cyclopentadienyl) of these compounds are replaced with (dimethylcyclopentadienyl), (trimethylcyclopentadienyl), (ethylcyclopentadienyl),
(N-propylcyclopentadienyl), (isopropylcyclopentadienyl), (sec-butylcyclopentadienyl), (isobutylcyclopentadienyl), (tert-butyldimethylsilylcyclopentadienyl), (phenyl Compounds in which (cyclopentadienyl), (methylindenyl), or (phenylindenyl) has been changed, (2-phenoxy) is converted to (3-phenyl2
-Phenoxy), (3-trimethylsilyl-2-phenoxy), or a compound obtained by changing (3-tert-butyldimethylsilyl-2-phenoxy), a compound obtained by changing dimethylsilyl to diethylsilyl, diphenylsilyl, or dimethoxysilyl; A compound in which titanium is changed to zirconium or hafnium, dibromide is dibromide, diiodide, bis (dimethylamide), bis (diethylamide), di-n-butoxide,
Or a transition metal complex in which J in the general formula [I] is an atom other than a carbon atom, ie, a group 14 atom of the periodic table, such as a compound converted to diisopropoxide.

The transition metal complex represented by the above general formula [I] can be synthesized, for example, by the following method. That is, first, by reacting an alkoxybenzene compound having a halogenated ortho position with a cyclopentadiene compound substituted with a halogenated Group 14 atom in the presence of an organic alkali metal or magnesium metal, A compound having a structure in which a group having a pentadiene skeleton and a group having an alkoxybenzene skeleton are connected by a Group 14 atom is obtained. Then, after treating the compound with a base, the compound is reacted with a halide, hydrocarbon, or hydrocarbon oxy compound of a transition metal to synthesize a transition metal complex represented by the general formula [I]. it can.

(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, and 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.

[0053] 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.

[0054] 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 are methyl group or isobutyl group,, b is 2 to 40, c is 1 to 40.

The above aluminoxanes are 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.

As specific examples of the compound (C1), 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

[0060] 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 examples of these combinations 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 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 compound represented by the general formula (LH) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^— is a Bronsted acid (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, and most preferably, tri (n-butyl) ammonium tetrakis (pentafluoro) Phenyl) borate or N, N-
Dimethylanilinium tetrakis (pentafluorophenyl) borate.

[Polymerization of olefin] In the present invention,
An olefin polymerization catalyst comprising the transition metal complex (A) represented by the general formula [I] and the above (B) and / or the above (C) is used. When an olefin polymerization catalyst comprising two components (A) and (B) is used, the cyclic aluminoxane (B2) and / or the linear aluminoxane (B3) are preferred as (B). As another preferred embodiment of the olefin polymerization catalyst, an olefin polymerization catalyst using the above (A), (B) and (C) is exemplified. ) Easy to use.

The amount of each component used is usually such that the molar ratio of (B) / (A) is 0.1 to 10,000, preferably 5 to 200.
It is desirable to use each component so that the molar ratio of 0, (C) / (A) is in the range of 0.01 to 100, preferably in the range of 0.5 to 10. When each component is used in a solution state or a suspension state in a solvent, the concentration is appropriately selected depending on conditions such as the performance of an apparatus for supplying each component to the polymerization reactor. .01-500 μmol
/ G, more preferably 0.05 to 100 μmol /
g, more preferably 0.05 to 50 μmol / g,
(B) is usually 0.01 to 10,000 in terms of Al atom.
μmol / g, more preferably 0.1-5000 μm
mol / g, more preferably 0.1 to 2000 μm
ol / g, (C) is usually 0.01 to 500 μmol /
g, more preferably 0.05 to 200 μmol /
g, more preferably 0.05 to 100 μmol / g
It is desirable to use each component so as to fall within the range.

The olefins applicable to the polymerization in the present invention include 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 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-2-pentene-1, and vinylcyclohexane, but the present invention should be limited to the above compounds. Not something. Specific examples of the combination of monomers when performing the copolymerization include ethylene and propylene, ethylene and butene-1, ethylene and hexene-1,
Examples include 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. It can be applied effectively and has good density controllability.

In the present invention, the polymerization is carried out for at least 30
0 kg / cm ² or more, preferably 350 to 3500 kg
/ Cm ^{2 at} a pressure of at least 130 ° C. or higher, preferably 135 to 350 ° C. As the polymerization type, either a batch type or a continuous type is possible,
It is preferable to carry out in a continuous manner. In general, 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 multiple reaction zones or multiple reactors, the temperature, pressure,
By changing the gas composition, it is also possible to produce polymers with different properties.

Each component used for the catalyst is usually supplied to the reactor by a high-pressure pump as a solution dissolved in a suitable inert solvent or a suspension in the inert solvent. In the polymerization under high pressure as in the present invention, since the catalyst is injected into the high pressure part by a pump, the catalyst is in a liquid state, or is uniformly dissolved in an inert solvent, or is a solid insoluble in the solvent, Those having a small particle size and good dispersibility in a solvent are preferred. In this case, it is preferable that the maximum particle size is usually 50 μm or less. In order to control the particle diameter of the boron compound (C) or the like, a method such as pulverization or a method in which a solution dissolved in toluene or the like is dropped into an aliphatic hydrocarbon solvent such as heptane to precipitate it can be applied.

Suitable inert solvents include, for example, white spirit hydrocarbon oil, pentane, hexane, cyclohexane, heptane, octane, toluene, kerosene components,
Oligomers such as higher branched saturated aliphatic hydrocarbons, isobutene oligomers, 1-butene oligomers, and mixtures thereof are mentioned. The catalyst solution is usually handled under an inert gas atmosphere such as nitrogen or argon so as not to come into contact with water and air.

In the present invention, the above (A) and (B)
And / or (C) may be mixed in advance and then injected into the reactor, or each may be independently injected from another injection tube and mixed in the reactor. In the case of the multiple reaction zone method, the reaction may be injected into the first reaction zone at once, or may be split into other reaction zones and injected.

The polymerization time is generally appropriately determined depending on the kind of the target polymer and the reaction apparatus, and there are no particular restrictions. In the present invention, a chain transfer agent such as hydrogen may be added to adjust the molecular weight of the copolymer.

[0074]

The present invention will be described in more detail with reference to the following Examples and Comparative Examples, but the present invention is not limited thereto. 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 40 ° C (5 ° C / min), Holding for 2 minutes Measurement: 10 ° C to 150 ° 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: gel permeation chromatograph (manufactured by Waters)
150, C) under the following conditions. Column: TSK gel GMH-HT Measurement temperature: 145 ° C Setting Measurement concentration: 10 mg / 10 ml-ortho-dichlorobenzene

Reference Example (Transition metal complex: dimethylsilyl (tetramethylcyclopentadienyl) (3-tert
Synthesis of -butyl-5-methyl-2-phenoxy) titanium dichloride) (1) Synthesis of 1-bromo-3-tert-butyl-5-methyl-2-phenol Under a nitrogen atmosphere, a 500 ml four-hole equipped with a stirrer In a flask, 20.1 g (123 mmol) of 2-tert-butyl-4-methylphenol was dissolved in 150 ml of toluene, followed by 25.9 ml of tert-butylamine.
(18.0 g, 246 mmol) was added. The solution was cooled to -70 ° C and 10.5 ml of bromine (32.6
g, 204 mmol). This solution was kept at -70 ° C and stirred for 2 hours. Thereafter, the temperature was raised to room temperature, and each time, 100 ml of 10% diluted hydrochloric acid was added, and the mixture was washed three times. The organic layer obtained after washing is dried using anhydrous sodium sulfate, the solvent is removed using an evaporator, and then purified using a silica gel column, and 1-bromo-3-tert-butyl as a colorless oil is obtained. 18.4 g (75.7 mmol) of -5-methyl-2-phenol was obtained. The yield was 62%.

(2) Synthesis of 1-bromo-3-tert-butyl-2-methoxy-5-methylbenzene In a 100 ml four-necked flask equipped with a stirrer under a nitrogen atmosphere, 1 -Bromo-3-ter
13.9 g of t-butyl-5-methyl-2-phenol
(57.2 mmol) was dissolved in 40 ml of acetonitrile, followed by 3.8 g (67.9 mmol) of potassium hydroxide.
l) was added. Further, 17.8 ml of methyl iodide (4
0.6 g, 286 mmol) and stirring was continued for 12 hours. Thereafter, the solvent was removed by an evaporator, and 40 ml of hexane was added to the residue to extract hexane-soluble components.
The extraction was repeated three times. The solvent was removed from the extract, and a pale yellow oil, 1-bromo-3-tert-butyl-
13.8 g of 2-methoxy-5-methylbenzene (5
3.7 mmol). The yield was 94%.

(3) Synthesis of (3-tret-butyl-2-methoxy-5-methylphenyl) chlorodimethylsilane Tetrahydrofuran (31.5 ml), hexane (13
9 ml) and 1-bromo-3-t synthesized in (2) above.
To a solution of tert-butyl-2-methoxy-5-methylbenzene (45 g) was added at −40 ° C. a 1.6 mol / l hexane solution of n-butyllithium (115
ml) was added dropwise over 20 minutes. The obtained mixture was -4
After incubating at 0 ° C for 1 hour, tetrahydrofuran (3
1.5 ml) was added dropwise. Dichlorodimethylsilane (1
31 g) and hexane (306 ml) at −40 ° C., the mixture obtained above was added dropwise. The resulting mixture was allowed to warm to room temperature over 2 hours and then at room temperature for 1 hour.
Stir for 2 hours. The solvent and excess dichlorodimethylsilane were distilled off from the reaction mixture under reduced pressure, hexane-soluble components were extracted from the residue using hexane, and the solvent was distilled off from the resulting hexane solution to give a pale yellow oil. (3-te
41.9 g of rt-butyl-2-methoxy-5-methylphenyl) chlorodimethylsilane were obtained. The yield is 84
%Met.

(4) Synthesis of (3-tert-butyl-2-methoxy-5-methylphenyl) dimethyl (tetramethylcyclopentadienyl) silane (3-tert-butyl-2-silane synthesized in the above (3)) (Methoxy-5-methylphenyl) chlorodimethylsilane (5.24 g) and tetrahydrofuran (50 ml) were added to a solution of lithium tetramethylcyclopentadienyl (2.73 g) at -35 ° C at -35 ° C for 2 hours. Then, the mixture was heated to room temperature, and further stirred at room temperature for 10 hours. The solvent was distilled off from the obtained reaction mixture under reduced pressure, and the hexane-soluble component was extracted from the residue with hexane.The solvent was distilled off from the obtained hexane solution under reduced pressure to give a yellow oil. (3-tert-butyl-2-methoxy-5
6.69 g of -methylphenyl) dimethyl (tetramethylcyclopentadienyl) silane were obtained. The yield is 97
%Met.

(5) Synthesis of dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride (3-tert-butyl-2) synthesized in the above (4) -Methoxy-5-methylphenyl) dimethyl (tetramethylcyclopentadienyl) silane (10.04 g), toluene (100 ml), and triethylamine (6.30 g)
A solution of 1.63 mol / l of n-butyllithium in hexane (19.0 m
l) was added dropwise, and then the temperature was raised to room temperature over 2 hours.
Further, the temperature was kept at room temperature for 12 hours. At 0 ° C under nitrogen atmosphere,
A solution of titanium tetrachloride (4.82 g) in toluene (50
ml), the mixture obtained above was added dropwise, and the mixture was heated to room temperature over 1 hour, and then heated and refluxed for 10 hours.
The reaction mixture was filtered, the solvent was distilled off from the filtrate, and the residue was recrystallized from a mixed solvent of toluene and hexane. 3.46 g of methyl-2-phenoxy) titanium dichloride were obtained. The yield was 27%. The spectrum data was as follows. ¹ H-NMR (CDCl ₃ ) δ 0.57 (s, 6
H), 1.41 (s, 9H), 2.15 (s, 6H),
2.34 (s, 6H), 2.38 (s, 3H), 7.1
5 (s, 1H), 7.18 (s, 1H) 13 C-NMR (CDCl 3) δ 1.25,14.4
8, 16.28, 22.47, 31.25, 36.2
9, 120.23, 130.62, 131.47, 13
3.86, 135.50, 137.37, 140.8
2, 142.28, 167.74 Mass spectrum (CI, m / e) 458

Example 1 Ethylene and hexene-1 were continuously supplied into a reactor by 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 800 kg /
The hexene-1 concentration was set to 34 mol% in cm ² G. Hexane solution of dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride (0.7
μmol / g), a solution of triisobutylaluminum in heptane (33 μmol / g), and N, N-dimethylanilinium tetrakis (pentafluorophenyl).
A borate toluene solution (1.2 μmol / g) was prepared in a separate container, and each was prepared at 290 g / hour.
At a feed rate of 350 g / hr, and 580 g / hr,
The reactor was continuously fed. Polymerization reaction temperature is 215 ° C
In addition, the molar ratio between Al atoms and Ti atoms was 57, and the ratio between boron atoms and Ti atoms was 3.3. as a result,
Ethylene having an MFR of 4.2, a density (without annealing) of 0.881, a melting point of 67.3 ° C., an SCB of 40.4, a molecular weight (Mw) of 66,000, and a molecular weight distribution (Mw / Mn) of 1.8 Hexene-1 copolymer per hour
14 tons were produced per mole of atom.

Example 2 Ethylene and hexene-1 were continuously supplied into a reactor by 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 a total pressure of 800 kg /
The hexene-1 concentration was set to 30 mol% in cm ² G. Hexane solution of dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride (0.7
μmol / g), a solution of triisobutylaluminum in heptane (33 μmol / g), and N, N-dimethylanilinium tetrakis (pentafluorophenyl).
A borate toluene solution (1.2 μmol / g) was prepared in a separate container, and each was prepared at 290 g / hour.
At a feed rate of 355 g / hr, and 565 g / hr,
The reactor was continuously fed. Polymerization reaction temperature is 223 ° C
In addition, the molar ratio between Al atoms and Ti atoms was 57, and the ratio between boron atoms and Ti atoms was 3.2. as a result,
Ethylene having an MFR of 3.3, a density (without annealing) of 0.887, a melting point of 73.5 ° C., an SCB of 36.6, a molecular weight (Mw) of 70000, and a molecular weight distribution (Mw / Mn) of 1.9. Hexene-1 copolymer per hour
15 tons were produced per mole of atom.

Example 3 Ethylene and hexene-1 were continuously supplied 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 800 kg /
The hexene-1 concentration was set to 27 mol% in cm ² G. Hexane solution of dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride (0.7
μmol / g), a solution of triisobutylaluminum in heptane (33 μmol / g), and N, N-dimethylanilinium tetrakis (pentafluorophenyl).
A borate toluene solution (1.2 μmol / g) was prepared in a separate container, and each was prepared at 240 g / hour.
At a feed rate of 290 g / hr, and 550 g / hr,
The reactor was continuously fed. Polymerization reaction temperature is 230 ° C
The molar ratio of Al atoms to Ti atoms was 55, and the ratio of boron atoms to Ti atoms was 3.6. as a result,
Ethylene having MFR of 2.5, density (without annealing) of 0.892, melting point of 80.6 ° C., SCB of 29.8, molecular weight (Mw) of 76,000, and molecular weight distribution (Mw / Mn) of 1.8 Hexene-1 copolymer per hour
17 tons were produced per mole of atom.

Example 4 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 pressure was set to 900 kg /
The hexene-1 concentration was set to 23 mol% and the hydrogen concentration was set to 0.05 mol% in cm ² G. A hexane solution (0.7 μmol / g) of dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride was added to a heptane solution of triisobutylaluminum (33 μmol).
/ G) and a toluene solution of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate (1.2 μmol / g) were further prepared in separate containers, each of which was 210 g / h, 270 g / h, and At a feed rate of 488 g / hr. The polymerization reaction temperature was 231 ° C., the molar ratio between Al atoms and Ti atoms was 64, and the ratio between boron atoms and Ti atoms was 3.
It was set to 9. As a result, the MFR was 1.7, the density (without annealing) was 0.897, the density (with annealing) was 0.901, the melting point was 94.6 ° C., the SCB was 25.0, the molecular weight (Mw) was 79000, and the molecular weight was Distribution (Mw / Mn)
Was 1.8 tons per hour per mole of Ti atom to produce an ethylene-hexene-1 copolymer having a ratio of 1.8.

Example 5 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 pressure was set to 900 kg /
The hexene-1 concentration was set to 33 mol% in cm ² G. Hexane solution of dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride (0.7
μmol / g), a solution of triisobutylaluminum in heptane (33 μmol / g), and N, N-dimethylanilinium tetrakis (pentafluorophenyl).
A borate toluene solution (1.2 μmol / g) was prepared in a separate container, and each was prepared at 106 g / hour.
At a feed rate of 195 g / h and 420 g / h,
The reactor was continuously fed. Polymerization reaction temperature is 202 ° C
In addition, the molar ratio between Al atoms and Ti atoms was adjusted to 85, and the ratio between boron atoms and Ti atoms was adjusted to 6.7. as a result,
MFR 2.8, density (without annealing) 0.880, S
An ethylene-hexene-1 copolymer having a CB of 38.7, a molecular weight (Mw) of 77000, and a molecular weight distribution (Mw / Mn) of 1.9 was converted into 2 parts per one hour per mole of Ti atom.
8 tons manufactured.

Example 6 Ethylene and hexene-1 were continuously supplied 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 pressure was set to 900 kg /
The hexene-1 concentration was set to 32 mol% in cm ² G. Hexane solution of dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride (0.7
μmol / g), a solution of triisobutylaluminum in heptane (33 μmol / g), and N, N-dimethylanilinium tetrakis (pentafluorophenyl).
A toluene solution of borate (1.2 μmol / g) was prepared in a separate container, and each was prepared at 60 g / hour, 1 g.
The reactor was continuously fed at a feed rate of 10 g / hr and 260 g / hr. When the polymerization temperature reaches 195 ° C,
The molar ratio of Al atoms to Ti atoms is 84, and boron atoms and T
The ratio of i atoms was adjusted to 6.7. As a result, MF
R: 2.3, density (without annealing): 0.879, SCB
-Hexene-1 having a molecular weight (Mw) of 82,000 and a molecular weight distribution (Mw / Mn) of 1.8
43 hours per mole of Ti atom per hour
on.

Example 7 Ethylene and hexene-1 were continuously supplied into a reactor by using an autoclave type reactor equipped with a stirring blade having an internal volume of 1 liter to carry out polymerization. The polymerization pressure was set to 900 kg /
The hexene-1 concentration was set to 14 mol% and the hydrogen concentration was set to 0.20 mol% in cm ² G. A hexane solution (0.7 μmol / g) of dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride was added to a heptane solution of triisobutylaluminum (33 μmol).
/ G) and a toluene solution of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate (1.2 μmol / g) were further prepared in separate containers, respectively, at 200 g / h, 240 g / h, and The reactor was continuously fed at a feed rate of 365 g / hr. The polymerization reaction temperature was 229 ° C., the molar ratio between Al atoms and Ti atoms was 56, and the ratio between boron atoms and Ti atoms was 3.
It was set to 0. As a result, the MFR was 1.5, the density (without annealing) was 0.908, the density (with annealing) was 0.913, the melting point was 108 ° C., the SCB was 15.5, the molecular weight (Mw) was 81,000, and the molecular weight distribution ( An ethylene-hexene-1 copolymer having a ratio (Mw / Mn) of 1.8 was produced at a rate of 15 tons per mole of Ti atom per hour.

Example 8 Ethylene and hexene-1 were continuously supplied into a reactor by 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 800 kg /
The hexene-1 concentration was set to 37 mol% in cm ² G. Hexane solution of dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride (0.2
μmol / g), a solution of triisobutylaluminum in heptane (10 μmol / g) and N, N-dimethylanilinium tetrakis (pentafluorophenyl)
A toluene solution of borate (0.9 μmol / g) was prepared in a separate container, and 80 g / hour, 8 g
The reactor was continuously fed at a feed rate of 0 g / hr and 110 g / hr. When the polymerization reaction temperature reaches 190 ° C, A
The molar ratio of l atom to Ti atom is 50, and boron atom and Ti atom
The atomic ratio was adjusted to 6.0. As a result, MFR
5.6, density (without annealing) 0.866, melting point 5
7.1 ° C., SCB 52.0, molecular weight (Mw) 700
And an ethylene-hexene-1 copolymer having a molecular weight distribution (Mw / Mn) of 1.8
110 tons were produced per mole.

Example 9 Ethylene and hexene-1 were continuously supplied 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 a total pressure of 800 kg /
The hexene-1 concentration was set to 34 mol% in cm ² G. Hexane solution of dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride (0.2
μmol / g), a solution of triisobutylaluminum in heptane (10 μmol / g) and N, N-dimethylanilinium tetrakis (pentafluorophenyl)
The borate toluene solutions (0.45 μmol / g) were each prepared in separate vessels and each was continuously fed to the reactor at a feed rate of 120 g / hr, 130 g / hr, and 170 g / hr. Polymerization reaction temperature is 190
At ° C, the molar ratio of Al atoms to Ti atoms was 55, and the ratio of boron atoms to Ti atoms was 3.5. As a result, the MFR was 4.2 and the density (without annealing) was 0.86.
9, melting point 58.0 ° C, SCB 49.7, molecular weight (M
w) is 72,000, and the molecular weight distribution (Mw / Mn) is 1.8.
Was produced at a rate of 70 tons per mole of Ti atom per hour.

Example 10 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 a total pressure of 800 kg /
The hexene-1 concentration was set to 33 mol% in cm ² G. Hexane solution of dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride (0.4
μmol / g), a solution of triisobutylaluminum in heptane (20 μmol / g) and N, N-dimethylanilinium tetrakis (pentafluorophenyl)
A borate toluene solution (0.9 μmol / g) was prepared in a separate container, and each was 680 g / hour,
The reactor was continuously fed at a feed rate of 740 g / hr and 1000 g / hr. Polymerization reaction temperature is 224
At ° C, the molar ratio of Al atoms to Ti atoms was 55, and the ratio of boron atoms to Ti atoms was 3.3. As a result, the MFR was 5.8 and the density (without annealing) was 0.88.
2, melting point 64.3 ° C, SCB 40.0, molecular weight (M
w) is 65,000 and the molecular weight distribution (Mw / Mn) is 1.8.
Was produced in an amount of 11 ton per mole of Ti atom per hour.

Example 11 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 a total pressure of 800 kg /
The hexene-1 concentration was set to 24 mol% and the hydrogen concentration was set to 0.11 mol% in cm ² G. A hexane solution (0.4 μmol / g) of dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride was added to a heptane solution of triisobutylaluminum (20 μmol).
/ G) and a toluene solution of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate (0.9 μmol / g) were further prepared in separate containers, each of which was 470 g / h, 530 g / h, and The reactor was continuously fed at a feed rate of 530 g / hr. The polymerization reaction temperature was 231 ° C., the molar ratio of Al atoms to Ti atoms was 55, and the ratio of boron atoms to Ti atoms was 2.
It was set to 6. As a result, MFR was 7.8, density (without annealing) was 0.897, melting point was 92.8 ° C., SC
Ethylene-hexene having a B of 28.4, a molecular weight (Mw) of 58,000, and a molecular weight distribution (Mw / Mn) of 1.9
1 copolymer is added per hour to 13 moles per mole of Ti atom.
Ton manufactured.

Example 12 Ethylene and octene-1 were continuously supplied into a reactor by using an autoclave type reactor equipped with a stirring blade having an inner volume of 1 liter to carry out polymerization. The polymerization conditions were set to a total pressure of 800 kg /
The octene-1 concentration was set to 20 mol% in cm ² G. Hexane solution of dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride (0.7
μmol / g), a heptane solution of triisobutylaluminum (114 μmol / g) and a toluene solution of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate (0.9 μmol / g) in separate containers. Prepared and each was continuously fed to the reactor at a feed rate of 180 g / hr, 180 g / hr, and 440 g / hr. Polymerization reaction temperature is 234
At ° C, the molar ratio of Al atoms to Ti atoms was set to 150, and the ratio of boron atoms to Ti atoms was set to 3.0. As a result, the MFR was 4.7 and the density (without annealing) was 0.89.
1, melting point 91.9 ° C, SCB 26.7, molecular weight (M
w) is 71,000 and the molecular weight distribution (Mw / Mn) is 1.8.
Was produced in an amount of 22 ton per mole of Ti atom per hour.

Example 13 Ethylene and octene-1 were continuously supplied into a reactor by using an autoclave type reactor equipped with a stirring blade having an inner volume of 1 liter to carry out polymerization. The polymerization conditions were set to a total pressure of 800 kg /
The octene-1 concentration was set to 33 mol% in cm ² G. Hexane solution of dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride (0.7
μmol / g), a heptane solution of triisobutylaluminum (150 μmol / g), and a toluene solution of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate (0.9 μmol / g) in separate containers. Prepared and each was continuously fed to the reactor at a feed rate of 80 g / hr, 90 g / hr, and 380 g / hr. Polymerization reaction temperature is 185
At ° C, the molar ratio of Al atoms to Ti atoms was set to 280, and the ratio of boron atoms to Ti atoms was set to 8.0. As a result, the MFR was 5.1 and the density (without annealing) was 0.86.
9, melting point 60.2 ° C, SCB 39.8, molecular weight (M
w) is 72,000, and the molecular weight distribution (Mw / Mn) is 1.7.
Was produced in an amount of 33 ton per mole of Ti atom per hour.

Example 14 Ethylene and butene-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 a total pressure of 800 kg / c.
The butene-1 concentration was set to 46 mol% at m ² G.
Dimethylsilyl (tetramethylcyclopentadienyl)
Hexane solution of (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride (0.2 μm
mol / g), a heptane solution of triisobutylaluminum (35 μmol / g), and a toluene solution of N, N-dimethylaniliniumtetrakis (pentafluorophenyl) borate (0.45 μmol / g) in separate containers. Prepare, 70 g / h each, 9
The reactor was continuously fed at a feed rate of 0 g / hr and 130 g / hr. When the polymerization reaction temperature reaches 194 ° C, A
The molar ratio of l atom to Ti atom is 200, and boron atom and T atom
The ratio of i atoms was set to 4.0. As a result, MF
R is 2.8, density (without annealing) is 0.869, melting point is 56.7 ° C., SCB is 58.0, and molecular weight (Mw) is 80.
Ethylene-butene-1 copolymer having a molecular weight distribution (Mw / Mn) of 1.7
110 tons were produced per mole.

Example 15 Ethylene and butene-1 were continuously supplied into a reactor by 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 a total pressure of 800 kg / c.
The butene-1 concentration was set to 46 mol% at m ² G.
Dimethylsilyl (tetramethylcyclopentadienyl)
Hexane solution of (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride (0.2 μm
mol / g), a heptane solution of triisobutylaluminum (10 μmol / g), and a toluene solution of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate (0.45 μmol / g) in separate containers. Prepare, 90g / hour each, 1
The reactor was continuously fed at a feed rate of 10 g / hour and 170 g / hour. When the polymerization reaction temperature reaches 205 ° C,
The molar ratio of Al atom to Ti atom is 60, boron atom and T atom
The ratio of i atoms was set to 4.0. As a result, MF
R is 5.2, density (without annealing) is 0.868, melting point is 56.7 ° C., SCB is 61.1, and molecular weight (Mw) is 66.
Ethylene-butene-1 copolymer having a molecular weight distribution (Mw / Mn) of 1.8
90 tons were produced per mole.

Example 16 Ethylene and butene-1 were continuously fed into a reactor using an autoclave-type reactor equipped with stirring blades having a volume of 1 liter to carry out polymerization. The polymerization conditions were set to a total pressure of 800 kg / c.
In m ² G, the butene-1 concentration was set to 29 mol% and the hydrogen concentration was set to 0.06 mol%. A hexane solution (0.7 μmol / g) of dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride was added to a heptane solution of triisobutylaluminum (35 μmol / g).
g), and a toluene solution of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate (0.9 μmol / g) was further prepared in separate containers, each of which was 230 g / h, 280 g / h, and The reactor was continuously fed at a feed rate of 670 g / hr. The polymerization reaction temperature was 230 ° C., the molar ratio of Al atoms to Ti atoms was 60, and the ratio of boron atoms to Ti atoms was 3.
It was set to 5. As a result, MFR was 1.8, density (without annealing) was 0.897, melting point was 90.7 ° C., SC
Ethylene-butene-1 having a B of 30.4, a molecular weight (Mw) of 82,000, and a molecular weight distribution (Mw / Mn) of 1.9
10 hours per mole of Ti atom per hour
on.

Example 17 Ethylene and butene-1 were continuously supplied into a reactor by using an autoclave type reactor equipped with a stirring blade having an inner volume of 1 liter to carry out polymerization. The polymerization conditions were set to a total pressure of 800 kg / c.
In m ² G, the butene-1 concentration was set to 29 mol% and the hydrogen concentration was set to 0.13 mol%. A hexane solution (0.7 μmol / g) of dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride was added to a heptane solution of triisobutylaluminum (35 μmol / g).
g), a toluene solution of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate (0.9 μmol / g) was prepared in separate containers, and each was prepared at 300 g / h, 380 g / h, and The reactor was continuously fed at a feed rate of 700 g / hr. The polymerization reaction temperature was 230 ° C., the molar ratio of Al atoms to Ti atoms was 60, and the ratio of boron atoms to Ti atoms was 3.
It was set to 0. As a result, MFR was 4.6, density (without annealing) was 0.899, melting point was 92.5 ° C., SC
Ethylene-butene-1 having a B of 30.0, a molecular weight (Mw) of 65,000 and a molecular weight distribution (Mw / Mn) of 1.8
10 hours per mole of Ti atom per hour
on.

Example 18 Ethylene and butene-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 a total pressure of 800 kg / c.
In m ² G, the butene-1 concentration was set to 29 mol% and the hydrogen concentration was set to 0.12 mol%. A hexane solution (0.7 μmol / g) of dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride was added to a heptane solution of triisobutylaluminum (35 μmol / g).
g) with heptane and liquid paraffin (Esso Petroleum)
N, N- dispersed in a mixed solution of Christol 202 (manufactured by K.K.) (heptane: liquid paraffin = 1: 4 by volume).
Dimethylanilinium tetrakis (pentafluorophenyl) borate (finely divided by a solvent precipitation method using toluene and heptane. The particle diameter is 2 to 3 μm, and no particles of 10 μm or more are observed.
mol / g) in separate containers, each containing 300 g / hr, 360 g / hr, and 750 g / hr.
The reactor was continuously fed at an hourly feed rate. When the polymerization reaction temperature is 230 ° C. and the molar ratio of Al atoms to Ti atoms is 6
At 0, the ratio of boron atoms to Ti atoms was set to 4.4. As a result, an ethylene-butene-1 copolymer having a melting point of 90.6 ° C., a molecular weight (Mw) of 64000, and a molecular weight distribution (Mw / Mn) of 1.7 was produced at a rate of 10 tons per hour and per mole of Ti atom. did.

Example 19 Ethylene and butene-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 a total pressure of 800 kg / c.
m to ² G, was set butene-1 concentration in 45.9mol%. Dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5) was mixed in a mixed solution (heptane: liquid paraffin = 1: 4 by volume) of heptane and liquid paraffin (Cristol 202, manufactured by Esso Petroleum Co., Ltd.). -Methyl-2-phenoxy) titanium dichloride was dissolved (0.066 μmol / g), and N, N-dimethylaniliniumtetrakis (pentafluorophenyl) borate (solvent precipitation using toluene and heptane) was added to the solution. (Particles having a particle size of 2 to 3 μm and particles of 10 μm or more are not observed) are dispersed (0.4 μmol / g) so that the ratio of boron atoms to Ti atoms becomes 6.0. It was adjusted. This mixed suspension and a solution of triisobutylaluminum in heptane (5.47)
μmol / g) were separately prepared in separate containers, and each was continuously supplied to the reactor at a supply rate of 323 g / hour and 240 g / hour. Polymerization reaction temperature is 20
At 5 ° C., the molar ratio of Al atoms to Ti atoms was adjusted to 61.7. As a result, the density (without annealing) was 0.87
3. Production of ethylene-butene-1 copolymer having an MFR of 6.8, a molecular weight (Mw) of 72,000, and a molecular weight distribution (Mw / Mn) of 1.7 per hour and 98.4 tons per mole of Ti atom did.

Example 20 Ethylene and butene-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 a total pressure of 800 kg / c.
m to ² G, was set butene-1 concentration in 47.0mol%. Dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5) was mixed in a mixed solution (heptane: liquid paraffin = 1: 4 by volume) of heptane and liquid paraffin (Cristol 202, manufactured by Esso Petroleum Co., Ltd.). -Methyl-2-phenoxy) titanium dichloride was dissolved (0.066 μmol / g), and N, N-dimethylaniliniumtetrakis (pentafluorophenyl) borate (solvent precipitation using toluene and heptane) was added to the solution. (Particles having a particle size of 2 to 3 μm and particles of 10 μm or more are not observed) are dispersed (0.4 μmol / g) so that the ratio of boron atoms to Ti atoms becomes 6.0. It was adjusted. This mixed suspension and a solution of triisobutylaluminum in heptane (5.47)
μmol / g) were separately prepared in separate containers, and each was continuously supplied to the reactor at a supply rate of 373 g / hour and 283 g / hour. Polymerization reaction temperature is 20
At 6 ° C., the molar ratio of Al atoms to Ti atoms was adjusted to 63.3. As a result, the density (without annealing) was 0.86.
7. An ethylene-butene-1 copolymer having a melting point of 42.6 ° C. and an MFR of 11.8 was produced in an amount of 106.3 tons per hour per mole of Ti atom.

Example 21 Polymerization was carried out by continuously feeding ethylene and butene-1 into a reactor by using an autoclave type reactor equipped with a stirring blade having an inner volume of 1 liter. The polymerization conditions were set to a total pressure of 800 kg / c.
m to ² G, was set butene-1 concentration in 43.9mol%. Dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5) was mixed in a mixed solution (heptane: liquid paraffin = 1: 4 by volume) of heptane and liquid paraffin (Cristol 202, manufactured by Esso Petroleum Co., Ltd.). -Methyl-2-phenoxy) titanium dichloride was dissolved (0.066 μmol / g), and N, N-dimethylaniliniumtetrakis (pentafluorophenyl) borate (solvent precipitation using toluene and heptane) was added to the solution. (Particles having a particle size of 2 to 3 μm and particles of 10 μm or more are not observed) are dispersed (0.4 μmol / g) so that the ratio of boron atoms to Ti atoms becomes 6.0. It was adjusted. This mixed suspension and a solution of triisobutylaluminum in heptane (5.47)
μmol / g) were separately prepared in separate containers, and each was continuously supplied to the reactor at a supply rate of 290 g / hour and 270 g / hour. Polymerization reaction temperature is 20
At 5 ° C., the molar ratio of Al atoms to Ti atoms was adjusted to 77.2. As a result, an ethylene-butene-1 copolymer having an MFR of 13.3 was produced at a rate of 104.5 tons per mole of Ti atom per hour.

Example 22 Ethylene and hexene-1 were continuously supplied into a reactor by using an autoclave type reactor equipped with stirring blades having an internal volume of 1 liter to carry out polymerization. The polymerization conditions were such that the total pressure was 796 kg /
The hexene-1 concentration was set to 30.8 mol% in cm ² G. Heptane solution in which dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride and triisobutylaluminum are mixed (the concentration of the complex and triisobutylaluminum is Respectively,
0.37 μmol / g and 18.5 μmol / g
And Al / Ti = 50 mol / mol), and a toluene solution of triphenylmethyltetrakis (pentafluorophenyl) borate (1.85 μmol / g).
Are prepared in separate containers, and 260 g /
The reactor was continuously fed at time and at a feed rate of 425 g / hr. The polymerization reaction temperature was adjusted to 200 ° C., and the ratio of boron atoms to Ti atoms was adjusted to 8.2. As a result, the MFR was 3.0 and the density (without annealing) was 0.88.
7. An ethylene-hexene-1 copolymer having a melting point of 63.9 ° C. and an SCB of 34.8 was treated with 1 Ti atom per hour.
19.2 tons were produced per mole.

Example 23 Ethylene and hexene-1 were continuously fed into a reactor by using an autoclave type reactor equipped with stirring blades having an inner volume of 1 liter to carry out polymerization. The polymerization conditions were such that the total pressure was 796 kg /
The hexene-1 concentration was set to 29.7 mol% in cm ² G. Heptane solution in which dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride and triisobutylaluminum are mixed (the concentration of the complex and triisobutylaluminum is Respectively,
0.37 μmol / g and 18.5 μmol / g
And the molar ratio of Al atoms to Ti atoms is 50)
Further, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate (maximum particle size: 20 μm or less) heptane / liquid paraffin (Christol 202 manufactured by Esso Petroleum Co., Ltd.) mixed liquid (volume ratio) finely divided by wet pulverization. A suspension (0.71 μmol / g) in heptane: liquid paraffin = 1: 4) was prepared in a separate container, and each was continuously supplied to the reactor at a feed rate of 246 g / hr and 484 g / hr. Supplied. The polymerization reaction temperature was adjusted to 210 ° C., and the ratio of boron atoms to Ti atoms was adjusted to 3.6. As a result, ethylene-hexene-1 having an MFR of 3.8 and a density (without annealing) of 0.889 was obtained.
28 hours per mole of Ti atom per hour
on.

Example 24 Ethylene and hexene-1 were continuously supplied into a reactor by using an autoclave type reactor equipped with stirring blades having an internal volume of 1 liter to carry out polymerization. The polymerization conditions were such that the total pressure was 796 kg /
The hexene-1 concentration was set to 31.6 mol% in cm ² G. Heptane solution in which dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride and triisobutylaluminum are mixed (the concentration of the complex and triisobutylaluminum is 2 respectively
μmol / g and 200 μmol / g, and the molar ratio of Al atoms to Ti atoms is 100), and N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate (maximum particles) Liquid paraffin having a diameter of 20 μm or less (Christol 202 manufactured by Esso Oil Co., Ltd .: IP Solvent 2 manufactured by Idemitsu Petrochemical Co., Ltd.)
028 = 60: 40 (vol%) mixture) suspension (7.
0 μmol / g) were prepared in separate containers, each of which was continuously fed to the reactor at a feed rate of 90 g / hr and 195 g / hr. Polymerization reaction temperature 220
At ℃, the ratio of boron atoms to Ti atoms was adjusted to 7.6. As a result, MFR was 5.8 and density (without annealing)
Is 0.888, the melting point is 69.8 ° C., and the SCB is 32.6.
11 tons were produced per mole of Ti atom.

Example 25 Ethylene and hexene-1 were continuously supplied 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 such that the total pressure was 796 kg /
The hexene-1 concentration was set to 31.1 mol% in cm ² G. Heptane solution in which dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride and triisobutylaluminum are mixed (the concentration of the complex and triisobutylaluminum is Respectively,
0.37 μmol / g and 18.5 μmol / g
And the molar ratio of Al atoms to Ti atoms is 50)
Further, liquid paraffin of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate (maximum particle diameter of 20 μm or less) finely divided by wet pulverization (Christol 202, manufactured by Esso Oil Co., Ltd .: IP Solvent 2028, manufactured by Idemitsu Petrochemical Co., Ltd.) A 60:40 (vol%) mixture) suspension (1.39 μmol / g) was prepared in separate containers, each containing 745 g / hour and 1235 g.
/ Hour feed rate to the reactor. The polymerization reaction temperature was set to 247 ° C., and the ratio of boron atoms to Ti atoms was set to 6.22. As a result, the MFR is 55,
An ethylene-hexene-1 copolymer having a density (without annealing) of 0.886 was produced in an amount of 13 tons per mole of Ti atom per hour.

[0110]

As described in detail above, according to the present invention,
By using a highly active catalyst containing a novel metallocene complex, under high-temperature and high-pressure conditions, an olefin (co) polymer having an arbitrary density having a narrow composition distribution and a high molecular weight,
In particular, a method for efficiently producing a linear low-density polyethylene is provided.

[Brief description of the drawings]

FIG. 1 is a flowchart for assisting 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.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-9-87313 (JP, A) JP-A-10-158442 (JP, A) JP-A-7-157508 (JP, A) 503788 (JP, A) WO 94/29356 (WO, A1) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 4/60-4/70

Claims (11)

(57) [Claims] At least 300 kg / cm^TwoPressure above G
At a force and at least a temperature of at least 130 ° C., the following (A)
And (B) and / or (C) below.
Olefin polymerization using an olefin polymerization catalyst
Or copolymerization of two or more olefins
A method for producing a characteristic olefin (co) polymer. (A): a transition metal complex represented by the following general formula [I](Where M¹Is the transition metal atom of Group 4 of the Periodic Table of the Elements
A represents an atom of Group 16 of the Periodic Table of the Elements,
J represents an atom belonging to Group 14 of the periodic table of the elements. Cp¹Is
A group having a cyclopentadiene-type anion skeleton is shown.
X¹, X^Two, R¹, R ^Two, R^Three, R^Four, R^FiveAnd R⁶Each
Independently, a hydrogen atom, a halogen atom, an alkyl group,
Alkyl group, aryl group, substituted silyl group, alkoxy group,
An aralkyloxy group, an aryloxy group or a disubstituted
Shows a mino group. R¹, R^Two, R^Three, R^Four, R^FiveAnd R⁶Is any
They may be bonded at will to form a ring. (B): at least one selected from the following (B1) to (B3)
(B1) General formula E¹ _aAlZ_3-aOrganic aluminum indicated by
Compound (B2) General formula ｛-Al (E^Two) -O-｝_bIndicated by
Cyclic aluminoxane having a structure (B3) General formula E^Three｛-Al (E^Three) -O-｝_cAlE^Three
_TwoLinear aluminoxane having a structure represented by the following formula (provided that E¹, E^TwoAnd E^ThreeIs a hydrocarbon group
Yes, all E¹, All E^TwoAnd all E^ThreeIs the same
May be different. Z is a hydrogen atom or halo
Gen atom, all Z are the same or different
May be. a is a number satisfying 0 <a ≦ 3, b is 2 or more
And c represents an integer of 1 or more. (C): Boration of any of the following (C1) to (C3)
Compound (C1) General formula BQ¹Q^TwoQ^ThreeBoron compound represented by
Object, (C2) general formula G⁺(BQ¹Q^TwoQ^ThreeQ^Four)^-Represented by
Boron compound, (C3) general formula (LH)⁺(BQ¹
Q^TwoQ^ThreeQ^Four)^-(Where B is trivalent)
Is a boron atom in the valence state of¹~ Q^FourIs halogen
Atom, hydrocarbon group, halogenated hydrocarbon group, substituted silyl
Group, alkoxy group or disubstituted amino group,
May be the same or different. G⁺Is inorganic or
Is an organic cation, L is a neutral Lewis base,
(LH)⁺Is a Bronsted acid. ) 2. The pressure is 350 to 3500 kg / cm ² G.
The method for producing an olefin (co) polymer according to claim 1, wherein 3. The method according to claim 1, wherein the temperature is 135 to 350 ° C.
Or the process for producing an olefin (co) polymer according to 2 above. 4. The process for producing an olefin (co) polymer according to claim 1, wherein A in the general formula [I] is an oxygen atom. 5. The process for producing an olefin (co) polymer according to claim 1, wherein R ¹ in the general formula [I] is an alkyl group, an aralkyl group, an aryl group or a substituted silyl group. 6. The compound according to claim 1, wherein X ¹ and X ² in the general formula [I] are each independently a halogen atom, an alkyl group, an aralkyl group, an alkoxy group, an aryloxy group or a disubstituted amino group. Or a method for producing an olefin (co) polymer. 7. The process for producing an olefin (co) polymer according to claim 1, wherein the compound (B) is triethylaluminum, triisobutylaluminum or methylaluminoxane. 8. The olefin (co) poly according to any one of claims 1 to 7, wherein the compound (C) is dimethylanilinium tetrakis (pentafluorophenyl) borate or triphenylmethyltetrakis (pentafluorophenyl) borate. Manufacturing method of coalescence. 9. The olefin polymerization catalyst according to any one of claims 1 to 7, wherein the olefin polymerization catalyst is a catalyst for olefin polymerization using (A), (B2) and / or (B3). A method for producing an olefin (co) polymer. 10. The olefin (co) according to any one of claims 1 to 8, wherein the catalyst for olefin polymerization is a catalyst for olefin polymerization using (A), (B) and (C). A method for producing a polymer. 11. The method for producing an olefin (co) polymer according to claim 1, wherein the olefin (co) polymer is a copolymer of ethylene and an α-olefin.