JPH10259277A - Inflation film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject film capable of manifesting good transparency by using a high-molecular weight olefin (co)polymer, having a narrow composition distribution and prepared by using a specific catalyst. SOLUTION: This inflation film comprises (W) an olefin (co)polymer having 0.855-0.940g/cm<3> density and 0.1-200g/10min melt flow rate. The olefin (co)polymer W is composed by (co)polymerizing an olefin or olefins by using a catalyst comprising (A) an M<1> complex having one Cp<1> such as a complex represented by the formula (M<1> , A and J are each a group IV transition metallic atom, a group XVI atom and a group XIV atom of the periodic table; Cp<1> is a group having a cyclopentadiene-type anionic skeleton; X<1> , X<2> , R<1> to R<6> are each H, a halogen, etc.) and (B) an Al compound which is a compound, etc., represented by the formula E<1> a AlZ3-a [E<1> is a hydrocarbon group; Z is H or a halogen; 0<(a)<=3] or (C) a boron compound that is a compound, etc., represented by the formula G<+> (BQ<1> Q<2> Q<3> Q<4> )<-> (Q<1> to Q<4> are each a halogenated hydrocarbon group, etc.; G<+> is a cation) at >=130 deg.C temperature under >=300kg/cm<2> G pressure.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a high-temperature, high-pressure
The present invention relates to an inflation film comprising an olefin (co) polymer produced using an olefin polymerization catalyst comprising a transition metal complex. In the present invention, the olefin (co) polymer refers to a homopolymer of olefin or a copolymer of two or more olefins.

[0002]

2. Description of the Related Art At present, the following two methods have been practiced as industrial methods for producing olefin (co) polymers at high temperatures using olefin polymerization catalysts. The first method is a method in which an olefin is polymerized under a condition in which a polymer is melted using a solvent such as cyclohexane, which is generally called a high-temperature solution method.
For example, the polymerization is performed under the conditions of 5 to 50 kg / cm ² . The second method is generally called a high pressure ionic polymerization method,
This 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 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 solid catalysts and vanadium catalysts conventionally used as olefin polymerization catalysts,
An olefin polymerization catalyst using a transition metal compound represented by a metallocene complex as a transition metal catalyst component has attracted attention. Use of a metallocene complex has the advantage that an olefin (co) polymer having a narrow molecular weight distribution or composition distribution can be efficiently obtained, and a film produced using the same has no sticky feeling. However, there is a problem that the control of the density and the polymerization activity in the polymerization reaction, particularly the polymerization activity at a reaction temperature that is efficient for industrial production, are still insufficient. Further, the transparency of a film produced using the same is 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 is insufficient, and the transparency of the film produced using the polymer is also low. It was not satisfactory.

In Japanese Patent Application Laid-Open No. 7-157508, diphenylmethylene (cyclopentadienyl)
Using a catalyst consisting of (fluorenyl) zirconium dichloride, triisobutylaluminum, and N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate for high-pressure ionic polymerization, an olefin (co)
A method for making a polymer is disclosed. However, even in this polymerization method, the molecular weight of the ethylene-α-olefin copolymer was still insufficient for processing a film, even though the polymerization pressure was 900 kg / cm ² or more.

In US Pat. No. 5,408,017, dimethylsilylbis (4,5,6,7-tetrahydro-indenyl) zirconium dimethyl and N,
A method for producing an olefin (co) polymer by using a catalyst comprising N-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 for film processing.

[0007]

In view of such circumstances, the problem to be solved by the present invention, that is, an object of the present invention, is to use a highly active catalyst comprising a novel metallocene complex to increase the temperature of the catalyst. It is an object of the present invention to efficiently produce an olefin (co) polymer having a narrow composition distribution and a high molecular weight under a high pressure condition, and to provide an inflation film produced by using the olefin (co) polymer with improved transparency.

[0008]

Means for Solving the Problems In order to achieve the above object, the present inventors have intensively studied a highly transparent blown film made of an olefin (co) polymer, and have completed the present invention. .

That is, the present invention provides at least 300 k
At a pressure of at least g / cm ² G and at least a temperature of at least 130 ° C., the following (A), the following (B) and / or (C)
Is an olefin (co) polymer obtained by homopolymerizing an olefin or copolymerizing two or more olefins using an olefin polymerization catalyst comprising: and having a density of 0.855 to 0.940 g. / Cm ³ , 190 ° C,
2. Melt flow rate under a 16 kg load is 0.1 to 2
An inflation film comprising an olefin (co) polymer of 00 g / 10 min. (A): Group 4 transition metal complex of the periodic table of an element having one group having a cyclopentadiene-type anion skeleton (B): 1 selected from the following general formulas (B1) to (B3)
Seed or more aluminum compounds (B1) formula E ¹ _a AlZ organoaluminum compound represented by the _3-a (B2) general formula {-Al (E ²⁾ -O-} cyclic aluminoxane having a structure represented by _b ( B3) the general formula ^{E 3 {-Al (E 3)} -O-} c AlE 3
Linear aluminoxane having a structure represented by ₂ , wherein E ¹ , E ² and E ³ are each a hydrocarbon group, and all E ¹ , all E ² and all E ³ are the same; Z represents a hydrogen atom or a halogen atom, all Z may be the same or different, a is a number satisfying 0 <a ≦ 3, and b is 2 or more. An integer and c represents an integer of 1 or more.) (C): a boron compound represented by any of the following general formulas (C1) to (C3) (C1) a boron compound represented by the general formula BQ ¹ Q ² Q ³ (C2) a boron compound represented by the general formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- , (C3) a boron compound represented by the general formula (LH) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- It is the boron compound (wherein, B is a boron atom in the trivalent valence state, Q ¹ to Q ⁴ are a halogen atom, a hydrocarbon group, c Gen hydrocarbon group, substituted silyl group, an alkoxy group or a disubstituted amino group, they may be different even in the same. G ⁺ is an inorganic or organic cation, L is a neutral Lewis base And (LH) ⁺ is a Bronsted acid.) The present invention will be described in detail below.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION

[Transition metal complex] [Compound (A)] This is a transition metal complex of Group 4 of the periodic table of an element having one group having a cyclopentadiene-type anion skeleton, and specifically described in a) to c) below. The compound of. a) Complex compound represented by the following general formula [II] Cp ¹ YM ¹ X ¹ X ² [II] b) Complex compound described in JP-A-3-1630088 Examples of the specific compound of the above b) include: (Tert
-Butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediylzirconium dichloride, (tert-butylamide) (tetramethyl-
eta ⁵ - cyclopentadienyl) -1,2-ethanediyl titanium dichloride, (methylamide) (tetramethyl-eta ⁵ - cyclopentadienyl) -1,2-ethanediyl zirconium dichloride, (methylamide)
(Tetramethyl-η ⁵ -cyclopentadienyl) -1,
2-ethanediyltitanium dichloride, (tert
-Butylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silanezirconium dichloride,
(Tert-butylamido) dimethyl (tetramethyl-
η ⁵ -cyclopentadienyl) silanetitanium dichloride. c) Complex compound represented by general formula [I] (In the above formulas [I] and [II], M ¹ represents a transition metal atom of Group 4 of the periodic table of the element, A represents an atom of Group 16 of the periodic table of the element, and J represents an element of the element. It represents an atom belonging to Group 14 of the periodic table, wherein Cp ¹ is a group having a cyclopentadiene-type anion skeleton, and X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are Each independently represents a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an aryl group, a substituted silyl group,
It represents an alkoxy group, an aralkyloxy group, an aryloxy group or a disubstituted amino group. R ¹ , R ² , R ³ , R ⁴ , R
⁵ and R ⁶ may be optionally combined to form a ring. Y
Is a ligand containing up to 20 non-hydrogen atoms, including nitrogen, phosphorus, oxygen or sulfur. In particular, among the above a) to c), c) is preferable from the viewpoint of the molecular weight necessary for processing the blown film and the transparency of the blown film.

Further, a) and c) will be described in detail. In the general formulas [I] and [II], 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). Atom, zirconium atom, hafnium atom and the like. Preferably it is a titanium atom or a zirconium 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. Specifically, η^Five-Cyclopentadienyl group, η^Five−
Methylcyclopentadienyl group, η^Five-Dimethylcyclo
Pentadienyl group, η^Five-Trimethylcyclopentadie
Nil group, η^FiveA tetramethylcyclopentadienyl group,
η^Five-Ethylcyclopentadienyl group, η^Five-N-propi
Rucyclopentadienyl group, η^Five-Isopropylcyclo
Pentadienyl group, η^Five-N-butylcyclopentadie
Nil group, η^Five-Sec-butylcyclopentadienyl
Group, η^Five-Tert-butylcyclopentadienyl group,
η^Five-N-pentylcyclopentadienyl group, η^Five-Neo
Pentylcyclopentadienyl group, η^Five-N-hexyl
Cyclopentadienyl group, η^Five-N-octylcyclo}
Antadienyl group, η^Five-Phenylcyclopentadienyl
Group, η^Five-Naphthylcyclopentadienyl group, η^Five-Bird
Methylsilylcyclopentadienyl group, η^Five− Triet
Lucylylcyclopentadienyl group, η^Five-Tert-b
Tyldimethylsilylcyclopentadienyl group, η^Five-B
Ndenyl group, η^Five-Methylindenyl group, η^Five-Dimethyl
Indenyl group, η^Five-Ethylindenyl group, η^Five-N-pu
Ropylindenyl group, η^Five-Isopropylindenyl
Group, η^Five-N-butylindenyl group, η^Five-Sec-buchi
Ruindenyl group, η^Five-Tert-butylindenyl
Group, η^Five-N-pentylindenyl group, η^Five-Neo pliers
Ruindenyl group, η^Five-N-hexylindenyl group, η ^Five
-N-octylindenyl group, η^Five-N-decylindene
Nil group, η^Five-Phenylindenyl group, η^Five-Methylfe
Nylindenyl group, η^Five-Naphthylindenyl group, η^Five−
Trimethylsilylindenyl group, η^Five-Triethylsili
Ruindenyl group, η^Five-Tert-butyldimethylsilyl
Ruindenyl group, η^FiveA tetrahydroindenyl group, η^Five
A fluorenyl group, η^Five-Methylfluorenyl group, η^Five−
Dimethylfluorenyl group, η^Five-Ethylfluorenyl
Group, η^Five-Diethylfluorenyl group, η ^Five-N-propyl
Fluorenyl group, η^Five-Di-n-propylfluorenyl
Group, η^Five-Isopropylfluorenyl group, η^Five-Diisop
Ropylfluorenyl group, η^Five-N-butylfluorenyl
Group, η^Five-Sec-butylfluorenyl group, η^Five−ter
t-butylfluorenyl group, η^Five-Di-n-butyl full
Olenyl group, η^Five-Di-sec-butylfluorenyl
Group, η^Five-Di-tert-butylfluorenyl group, η^Five−
n-pentylfluorenyl group, η^Five-Neopentyl full
Olenyl group, η^Five-N-hexylfluorenyl group, η^Five−
n-octylfluorenyl group, η^Five-N-decylfluoro
Renyl group, η^Five-N-dodecylfluorenyl group, η^Five−
Phenylfluorenyl group, η^Five-Di-phenylfluorenyl
Group, η^Five-Methylphenylfluorenyl group, η^Five-Nuff
Tylfluorenyl group, η^Five-Trimethylsilyl fluore
Nil group, η^Five-Bis-trimethylsilylfluorenyl
Group, η^FiveA triethylsilylfluorenyl group, η^Five−te
rt-butyldimethylsilylfluorenyl group and the like.
And preferably η^Five-Cyclopentadienyl group, η^Five−
Methylcyclopentadienyl group, η^Five-Tert-buty
Rucyclopentadienyl group, η^Five-Tetramethylcyclo
Pentadienyl group, η^Five-An indenyl group, or η^Five−
A fluorenyl group.

In the general formula [II], Y is nitrogen,
Ligands containing phosphorus, oxygen or sulfur and having up to 20 non-hydrogen atoms.

In the general formula [I], examples of the atom of Group 16 of the periodic table of the element represented by A include an oxygen atom, a sulfur atom, and a selenium atom, and an oxygen atom is preferable.

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

The substituents X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R
^{As the} halogen atom for ⁵ or R ⁶ , a fluorine atom,
Examples thereof include a chlorine atom, a bromine atom and an iodine atom, preferably a chlorine atom or a bromine atom, and 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.

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. Further, 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, (3,5
-Dimethylphenyl) methyl group, (2,3,4-trimethylphenyl) methyl group, (2,3,5-trimethylphenyl) methyl group, (2,3,6-trimethylphenyl) methyl group, (3,4 , 5-trimethylphenyl) methyl group, (2,4,6-trimethylphenyl) methyl group, (2,3,4,5-tetramethylphenyl) methyl group, (2,3,4,6-tetramethylphenyl) ) Methyl, (2,3,5,6-tetramethylphenyl) methyl, (pentamethylphenyl) methyl, (ethylphenyl) methyl, (n-propylphenyl) methyl,
(Isopropylphenyl) methyl group, (n-butylphenyl) methyl group, (sec-butylphenyl) methyl group, (tert-butylphenyl) methyl group, (n-pentylphenyl) methyl group, (neopentylphenyl)
Methyl group, (n-hexylphenyl) methyl group, (n-
Octylphenyl) methyl group, (n-decylphenyl)
Methyl group, (n-decylphenyl) methyl group, (n-dodecylphenyl) methyl group, (n-tetradecylphenyl) methyl group, naphthylmethyl group, anthracenylmethyl group, etc., and more preferably benzyl group It is. 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 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 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 group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, 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.

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 t- Butoxy group, n-pentoxy group, neopentoxy group, n-hexoxy group, n-octoxy group, n-dodecoxy group, n-
A pentadeoxy group, an n-icosoxy group, and the like,
More preferably, they are a methoxy group, an ethoxy group, or a t-butoxy group. All of these alkoxy groups include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkoxy group such as a methoxy group and an ethoxy group, an aryloxy group such as a phenoxy group, and an aralkyloxy group such as a benzyloxy group. May be partially substituted.

The 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 are 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 aryloxy group for ⁵ or R ⁶ is preferably an aryloxy group having 6 to 20 carbon atoms, for example, a phenoxy group, 2-methylphenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, 2,3- Dimethylphenoxy group, 2,4-dimethylphenoxy group, 2,5
-Dimethylphenoxy group, 2,6-dimethylphenoxy group, 3,4-dimethylphenoxy group, 3,5-dimethylphenoxy group, 2,3,4-trimethylphenoxy group,
2,3,5-trimethylphenoxy group, 2,3,6-trimethylphenoxy group, 2,4,5-trimethylphenoxy group, 2,4,6-trimethylphenoxy group, 3,
4,5-trimethylphenoxy group, 2,3,4,5-tetramethylphenoxy group, 2,3,4,6-tetramethylphenoxy group, 2,3,5,6-tetramethylphenoxy group, pentamethylphenoxy Group, 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.

The substituents X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R
^The disubstituted amino group for 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;
More preferably, it is a halogen atom.

Specific examples of the compound (A) represented by the formula [I] include, for example, methylene (cyclopentadienyl)
(3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-t
tert-butyl-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-ter
t-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, dichloride is dibromide, diiodide, bis (dimethylamide), bis (diethylamide), di-n-butoxide,
Alternatively, a transition metal complex in which J in the general formula [I] is an atom of Group 14 of the periodic table of an element other than a carbon atom, such as a compound converted to isopropoxide, may be mentioned.

The transition metal complex represented by the general formula [I] can be synthesized, for example, by the following method. That is, first, an alkoxybenzene compound having a halogenated ortho position and a cyclopentadiene compound substituted with a halogenated Group 14 atom are reacted in the presence of an organic alkali metal or metallic magnesium to form a cycloalkyl compound. 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.

[Compound (B)]
As the luminium compound (B), a known organic aluminum
Compounds can be used. (B1) General formula E¹ _aAl
Z_3-aAn organoaluminum compound represented by the formula (B2):
General formula ｛-Al (E^Two) -O-｝_bHas the structure shown by
Cyclic aluminoxane, and (B3) a general formula E
^Three｛-Al (E^Three) -O-｝_cAlE^Three _TwoThe structure shown by
Linear aluminoxane (provided that E¹, E ^TwoAnd E
^ThreeAre each a hydrocarbon group, and all E¹, All E
^TwoAnd all E ^ThreeMay be the same or different.
Z represents a hydrogen atom or a halogen atom, and all Z are the same
Or different. a satisfies 0 <a ≦ 3
B represents an integer of 2 or more, and c represents an integer of 1 or more.
You. At least one aluminum compound selected from
You. , E¹, E^TwoOr E^ThreeAs a hydrocarbon group in
Is preferably a hydrocarbon group having 1 to 8 carbon atoms, and an alkyl group
Is more preferred.

[0057] 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, dihexylaluminum chloride; alkylaluminum dichlorides such as methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride, 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.

[0058] 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 a methyl group and an isobutyl group, and b is 2 to 4
0 and c are 1 to 40.

The above aluminoxane can be 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. From the viewpoint of high-temperature activity, and more preferably is an organoaluminum compound represented by (B1) the general formula E ¹ _a AlZ _3-a.

[Compound (C)] In the present invention, the boron compound (C) includes (C1) a boron compound represented by the general formula BQ ¹ Q ² Q ³ and (C2) a boron compound represented by the general formula G ⁺ (BQ ¹ Q
² Q ³ Q ^{4) -} boron compound represented by, (C3) the general formula
Any of the boron compounds represented by (LH) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ 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, 1
Hydrocarbon groups containing 1-20 carbon atoms, halogenated hydrocarbon groups containing 1-20 carbon atoms, substituted silyl groups containing 1-20 carbon atoms, alkoxy containing 1-20 carbon atoms Group or an amino group containing 2 to 20 carbon atoms, more preferably Q ^{1 to} Q ³ are a halogen atom,
A hydrocarbon group containing -20 carbon atoms, or 1-20
Halogenated hydrocarbon group containing carbon atoms.

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

[0064] 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, 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.

As specific combinations of these, 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.
Examples of (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ include the same as described above.

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

[Olefin polymerization] In the present invention,
An olefin polymerization catalyst comprising the compound (A) and the compound (B) and / or the compound (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 (B) may be used as (B).
3) is preferred. 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 catalyst component used is generally the same as that of compound (B)
And the molar ratio of the compound (A) is from 0.1 to 10,000, preferably from 5 to 2,000, and the molar ratio of the compound (C) / the compound (A) is from 0.01 to 100, preferably from 0.5 to 10. It is desirable to use each component as falling within the range. The concentration when each catalyst component is used in a solution state or a suspension state in a solvent is appropriately selected depending on conditions such as the performance of a device for supplying each catalyst component to the polymerization reactor. , Usually 0.01 to 500 μmol / g,
More preferably, 0.05 to 100 μmol / g, still more preferably 0.05 to 50 μmol / g, the compound (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, compound (C) is usually 0.01 to 500 μm
ol / g, more preferably 0.05 to 200 μmo
1 / g, more preferably 0.05 to 100 μmol
/ G of each component is desirably used.

In the present invention, olefins applicable to polymerization include olefins having 2 to 20 carbon atoms,
In particular, ethylene, C3-20α-olefins, C4-20 diolefins and the like can be used, and two or more olefins 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-. 1,3-methylpentene-1,4-methylpentene-1,5-methyl-
Branched α-olefins such as 2-pentene-1, diolefins such as butadiene, isoprene, 1,4-pentadiene, 1,5-hexadiene, 1,7-octadiene and 1,9-decadiene, styrene and vinylcyclohexane And the like, but the present invention should not be limited to the above compounds. Examples of the combination of monomers used in the copolymerization include ethylene and propylene, ethylene and butene-1, ethylene and pentene-1, and ethylene and hexene.
1, ethylene and heptene-1, ethylene and octene
1, ethylene and α-olefins such as ethylene and decene-1, and propylene and butene-1 are exemplified, but the present invention should not be limited to these combinations. In particular, as the α-olefin content of the copolymer,
Preferably it is 4 to 60 mol%, more preferably 5 to 55 mol%, most preferably 6 to 50 mol%.

The present invention particularly relates to ethylene and α-olefin (propylene, butene-1,4-methylpentene-1,
Hexene-1, octene-1) can be effectively applied to the production of a copolymer with hexene-1 and octene-1), and the density controllability is good.

In the present invention, the polymerization is carried out for at least 30
0 kg / cm ² , preferably 350 to 3500 kg / c
m ² pressure, at least 130 ° C., preferably 135-135 ° C.
It is performed at a temperature of 350 ° C. As a polymerization system, either a batch system or a continuous system is possible, but a continuous system is preferred. Generally, a stirred tank reactor or a tubular reactor can be used as the reactor. The polymerization may be carried out in a single reaction zone, but may be carried out by dividing one reactor into a plurality of reaction zones or by connecting a plurality of reactors in series or in parallel. When a plurality of reactors are used, any combination of tank type-tank type or tank type-tube type may be used. In the method of polymerizing in a plurality of reaction zones or a plurality of reactors, it is also possible to produce polymers having different characteristics by changing the temperature, pressure, and gas composition for each reaction zone. From the viewpoint of molecular weight, it is preferable to carry out polymerization in a solvent-free state.

Each catalyst component 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, the catalyst is injected into the high-pressure part by a pump, so that the catalyst is in a liquid state, 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 of 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 oils, 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 atmosphere of an inert gas such as nitrogen or argon so as not to come into contact with water and air.

In the present invention, the compound (A) and the compound (B) and / or the compound (C) may be mixed in advance and then injected into the reactor, or each may be independently injected into another reactor. A method of injecting from a tube and mixing in a reactor may be used. 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.

The density of the olefin (co) polymer used in the present invention is 0.855 to 0.940 g / cm ³ , preferably 0.880 to 0.935 g / cm ³ , more preferably 0.900 to 0. 0.935 g / cm ³ . If the density is too low, it will result in a highly adhesive blown film,
If the density is too high, the effect of transparency is lost. Melt flow rate of olefin (co) polymer used in the present invention (JIS K-6760, 190 ° C, 2.16 kg
Load) is 0.1 to 200 g / 10 min, preferably 0.1 g / min.
2 to 20 g / 10 min. If the melt flow rate is too low, the load during processing of the blown film is large, and if the melt flow rate is too high, the strength of the blown film becomes low. The inflation film of the present invention can be produced by a known inflation method. The processing temperature is equal to or higher than the melting point of the resin and equal to or lower than the temperature at which the resin is deteriorated by heat. In the form of a multilayer film or sheet having two or more layers with another material, it can be produced by a known method such as a coextrusion method, a dry lamination method, and a sandwich lamination method. As other materials, known materials such as paper, paperboard, aluminum thin film, cellophane, nylon, PET, PP, polyvinylidene chloride, EVOH, and various adhesive resins can be used.

The blown film of the present invention contains, if necessary, known additives such as an antioxidant, a weathering agent, a lubricant, an antiblocking agent, an antistatic agent, an antifogging agent, a dripless agent, a pigment and a filler. be able to. In addition, to the olefin (co) polymer, radical polymerization method low density polyethylene, high density polyethylene, linear low density polyethylene,
Known polymer substances such as an ethylene-α-olefin copolymer elastomer and polypropylene may be blended. The blown film of the present invention can be subjected to known post-treatments such as corona discharge treatment, plasma treatment, ozone treatment, ultraviolet irradiation, and electron beam irradiation.

[0080]

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 polymer in the examples were measured by the following methods. (1) Melt flow rate (MFR) is JIS K-
190 ° C., 2.16 according to the method specified in 6760
It was measured with a kg load. (2) The density was determined according to JIS K-6760. (3) Melting point of copolymer: determined by using DSC7 manufactured by Perkin-Elmer under the following conditions. Heating: Heating up to 150 ° C, holding until the change in heat 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), and expressed as a number of short chain branches per 1000 carbons (SCB). did.

(5) Molecular Weight and Molecular Weight Distribution: Gel Permeation Chromatograph (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 (6) Film forming 1 to Placo EX-50 type inflation molding machine
A die with 25 mmφ and a lip interval of 2 mm was attached, processing temperature was 160 ° C., blow-up ratio was 1.8, and extrusion amount was
Inflation film processing was performed under the conditions of kg / hr to produce films having a thickness of 30 μm and 80 μm. (7) Haze of film The haze was measured by a method specified in ASTM D1003.

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-necked port 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 100 ml of 10% diluted hydrochloric acid was added each time, followed by washing 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) was added and stirring 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 1-bromo-3-tert-butyl- as a pale yellow oil was obtained.
13.8 g of 2-methoxy-5-methylbenzene (5
3.7 mmol). The yield was 94%.

(3) Synthesis of (3-tert-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 heated to room temperature over 2 hours, and further stirred at room temperature for 12 hours. The solvent and excess dichlorodimethylsilane were distilled off from the reaction mixture under reduced pressure, and hexane-soluble components were extracted from the residue with hexane. (3-t
tert-butyl-2-methoxy-5-methylphenyl)
41.9 g of chlorodimethylsilane were obtained. The yield is 8
4%.

(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. 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
-Methylphenyl) dimethyl (tetramethylcyclopentadienyl) silane 6.69 g was 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 to give orange columnar crystals of dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5-butyl-5 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 pressure was set to 900 kg /
Hexene-1 concentration was set to 23 mol% and hydrogen 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).
g) and a toluene solution of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate (1.2 μmol / g) were prepared in separate containers, and were continuously supplied to the reactor. Polymerization reaction temperature is 231
At ° C, the molar ratio of Al atoms to Ti atoms was 64, and the ratio of boron atoms to Ti atoms was 3.9. As a result, the MFR was 1.7 g / 10 min, and the density was 0.901 g /
cm ^3, a melting point of 94.6 ° C., SCB is 25.0, the molecular weight (Mw) of 79000, a molecular weight distribution (Mw / Mn) of ethylene is 1.8 - per hour hexene-1 copolymer, Ti 18 tons were produced per mole of atom. To 100 parts by weight of the above copolymer, an antioxidant Sumilizer B was added.
0.10 parts by weight of P76 (manufactured by Sumitomo Chemical Co., Ltd.), antioxidant Sandstarve P-EPQ (manufactured by Sand Japan)
0.10 parts by weight and 0.05 parts by weight of hydrotalcite DHT-4A (manufactured by Kyowa Chemical Co., Ltd.) were mixed using a single screw extruder, and an inflation film was produced using the mixture. Table 1 shows the physical properties of the obtained copolymer and the evaluation results of the blown film.

Comparative Example 1 A commercially available ethylene-butene-1 copolymer produced by solution polymerization in the presence of a vanadium-based catalyst (Sumitomo Chemical Co., Ltd.)
An inflation film was produced in the same manner as in Example 1 using Esplen SPO N0352 manufactured by Co., Ltd.). Table 1 shows the results.

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 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 prepared in separate containers, and were continuously supplied to the reactor. Polymerization reaction temperature is 229
At ° C, the molar ratio of Al atoms to Ti atoms was 56, and the ratio of boron atoms to Ti atoms was 3.0. As a result, the MFR was 1.5 g / 10 min, and the density was 0.913 g /
cm ^3, a melting point of 108 ° C., SCB is 15.5, the molecular weight (Mw) of 81000, a molecular weight distribution (Mw / Mn) of ethylene is 1.8 - per hour hexene-1 copolymer, Ti atom 1 15 tons were produced per mole. Next, using the obtained copolymer, a blown film was produced in the same manner as in Example 1. Table 1 shows the results.

Comparative Example 2 Ethylene and hexene-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 /
The hexene-1 concentration was set to 66.0 mol% in cm ² G. As a transition metal complex, bis (n) manufactured by Witco
-Butylcyclopentadienyl) zirconium dichloride in toluene solution (0.1 μmol / g) was mixed with a triisobutylaluminum in heptane solution (9.05 μmo).
1 / g) and a toluene solution of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate (0.45 μmol / g) were prepared in separate containers, and were continuously supplied to the reactor. Polymerization reaction temperature is 20
At 0 ° C., the molar ratio of Al atoms to Zr atoms was 63, and the ratio of boron atoms to Ti atoms was 4.4. Table 1 shows the results of the polymerization. The obtained copolymer had a very high MFR and could not produce a film.

[0092]

[Table 1]

[0093]

As described in detail above, according to the present invention,
Efficient production of olefin (co) polymer with narrow composition distribution and high molecular weight under high-temperature and high-pressure conditions using a highly active catalyst using a novel metallocene complex and produced using it An inflation film with improved transparency can be provided.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI // C08F 10/02 C08F 10/02 B29K 23:00 B29L 7:00 (72) Inventor Hiroaki Katayama Anesaki Beach, Ichihara-shi, Chiba 5-1 In Sumitomo Chemical Co., Ltd. (72) Inventor Waki Wakamatsu In 5-1 Anesaki Beach, Ichihara City, Chiba Prefecture In Sumitomo Chemical Co., Ltd.

Claims (9)

[Claims] At least at a pressure of at least 300 kg / cm ² G and a temperature of at least 130 ° C., the following (A)
And an olefin (co) polymer obtained by homopolymerizing an olefin or copolymerizing two or more olefins using an olefin polymerization catalyst comprising the following (B) and / or (C). And the density is 0.855 ~
An inflation film comprising an olefin (co) polymer having a melt flow rate of 0.1 to 200 g / 10 min at 0.940 g / cm ³ , 190 ° C. and a load of 2.16 kg. (A): Group 4 transition metal complex of the periodic table of an element having one group having a cyclopentadiene-type anion skeleton (B): 1 selected from the following general formulas (B1) to (B3)
Seed or more aluminum compounds (B1) formula E ¹ _a AlZ organoaluminum compound represented by the _3-a (B2) general formula {-Al (E ²⁾ -O-} cyclic aluminoxane having a structure represented by _b ( B3) the general formula ^{E 3 {-Al (E 3)} -O-} c AlE 3
Linear aluminoxane having a structure represented by ₂ , wherein E ¹ , E ² and E ³ are each a hydrocarbon group, and all E ¹ , all E ² and all E ³ are the same; Z represents a hydrogen atom or a halogen atom, all Z may be the same or different, a is a number satisfying 0 <a ≦ 3, and b is 2 or more. An integer and c represents an integer of 1 or more.) (C): a boron compound represented by any of the following general formulas (C1) to (C3) (C1) a boron compound represented by the general formula BQ ¹ Q ² Q ³ (C2) a boron compound represented by the general formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- , (C3) a boron compound represented by the general formula (LH) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- It is the boron compound (wherein, B is a boron atom in the trivalent valence state, Q ¹ to Q ⁴ are a halogen atom, a hydrocarbon group, c Gen hydrocarbon group, substituted silyl group, an alkoxy group or a disubstituted amino group, they may be different even in the same. G ⁺ is an inorganic or organic cation, L is a neutral Lewis base And (LH) ⁺ is a Bronsted acid.) 2. The blown film according to claim 1, wherein (A) is a transition metal complex represented by the following general formula [I]. (Wherein, M ¹ represents a transition metal atom of Group 4 of the periodic table of the element, A represents an atom of Group 16 of the periodic table of the element,
J represents an atom belonging to Group 14 of the periodic table of the elements. Cp ¹ represents a group having a cyclopentadiene-type anion skeleton.
X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an aryl group, a substituted silyl group, an alkoxy group,
It represents an aralkyloxy group, an aryloxy group or a disubstituted amino group. R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be arbitrarily combined to form a ring. ) (B) wherein (B) is (B1) a general formula E ¹ _a AlZ _3-a
The blown film according to claim 1, which is an organoaluminum compound represented by the formula: (However, E ¹ is a hydrocarbon group. Z represents a hydrogen atom or a halogen atom. A represents a number of 0 to 3.) 4. The blown film according to claim 1, wherein the olefin (co) polymer is produced in a solvent-free state. 5. The blown film according to claim 1, wherein (B) is triethylaluminum or triisobutylaluminum. 6. The blown film according to claim 1, wherein (C) is dimethylanilinium tetrakispentafluorophenyl borate or triphenylmethyltetrakispentafluorophenyl borate. 7. A polymerization pressure of 350 to 3500 kg / cm ²
The blown film according to any one of claims 1 to 6, which is G. 8. The blown film according to claim 1, wherein the polymerization temperature is 135 to 350 ° C. 9. An olefin (co) polymer comprising ethylene-α
-The blown film according to any one of claims 1 to 8, which is an olefin copolymer.