JP2003306510A - Olefin polymerization catalyst and polymerization method of olefin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an olefin polymerization catalyst having an excellent polymerization activity and a polymerization method of an olefin using the catalyst. <P>SOLUTION: The olefin polymerization catalyst comprises either (A) a transition metal compound of the group IV of the periodic table, containing a ligand having a cyclopentadienyl skeleton, (B) a contactant with a compound forming an ion pair reacting with (A) the transition metal compound and (C) an organometallic compound, or (A) the transition metal compound of the group IV of the periodic table, containing a ligand having a cyclopentadienyl skeleton, (C) the contactant with the organometallic compound and (B) the compound forming an ion pair reacting with (A) the transition metal compound. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an olefin polymerization catalyst and a method for polymerizing olefins, and more specifically,
The present invention relates to an olefin polymerization catalyst excellent in polymerization activity and a method for olefin polymerization using such a catalyst.

[0002]

BACKGROUND OF THE INVENTION Conventional olefin polymers such as polyethylene, polypropylene, poly-4-methyl-1-pentene, ethylene / propylene copolymer, ethylene / styrene copolymer and ethylene / propylene / butene terpolymer. As a catalyst for producing a coalescence, a titanium-based catalyst composed of a titanium compound and an organoaluminum compound, and a vanadium-based catalyst composed of a vanadium compound and an organoaluminum compound are known.

Further, as a catalyst capable of producing an olefin polymer with high polymerization activity, a metallocene compound such as zirconocene and a boron-based compound such as an organoaluminumoxy compound (aluminoxane) or tris (pentafluorophenyl) borane. A metallocene catalyst consisting of is known. By the way, olefin polymers are generally used in various fields such as for various molded products because of their excellent mechanical properties, but in recent years, the demand for physical properties of olefin polymers has been diversified, and various properties have been reported. Polymers are desired and productivity is also desired to be improved.

Under such circumstances, the advent of an olefin polymerization catalyst and an olefin polymerization method which are excellent in polymerization activity is desired.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and an object thereof is to provide an olefin polymerization catalyst excellent in polymerization activity and a method for olefin polymerization.

[0006]

SUMMARY OF THE INVENTION Olefin polymerization catalyst according to the present invention (1)
Is a contact between (A) a transition metal compound of Group 4 of the periodic table containing a ligand having a cyclopentadienyl skeleton, and (B) a compound that reacts with the transition metal compound (A) to form an ion pair. It is characterized in that it comprises the compounds (i) and (C) organometallic compounds.

The olefin polymerization catalyst (2) according to the present invention comprises (A) a transition metal compound of Group 4 of the periodic table containing a ligand having a cyclopentadienyl skeleton, and (C) an organometallic compound. (2) and (B) the transition metal compound (A) which reacts with the transition metal compound (A) to form an ion pair.

The olefin polymerization method according to the present invention comprises:
(A) a transition metal compound of Group 4 of the periodic table containing a ligand having a cyclopentadienyl skeleton, (B) a transition metal compound (A) and a compound forming an ion pair, and (C) an organometal When polymerizing an olefin in the presence of an olefin polymerization catalyst composed of a compound, the transition metal compound (A) reacts with the transition metal compound (A) to form an ion pair compound (B) or organometallic compound (C). ) Is contacted with the outside of the polymerization system and then supplied into the polymerization system.

[0009]

DETAILED DESCRIPTION OF THE INVENTION The olefin polymerization catalyst and the olefin polymerization method according to the present invention will be specifically described below. In the present specification, the term "polymerization" means
The term "polymer" may be used to include not only homopolymerization but also copolymerization, and the term "polymer" may be used to include not only homopolymer but also copolymer.

Olefin Polymerization Catalyst The olefin polymerization catalyst (1) according to the present invention contains (A) a ligand having a cyclopentadienyl skeleton, Periodic Table 4
(I) and (C) organometals of group B transition metal compound and (B) transition metal compound (A) and a compound that forms an ion pair (hereinafter referred to as “ionized ionic compound”) The olefin polymerization catalyst (2) of the present invention comprises a compound (A) a transition metal compound of Group 4 of the periodic table containing a ligand having a cyclopentadienyl skeleton, and (C) an organometallic compound. The contact substance (ii) and (B) consist of ionized ionic compounds.

First, each component forming the olefin polymerization catalysts (1) and (2) according to the present invention will be described. ((A) Transition metal compound of Group 4 of the periodic table containing a ligand having a cyclopentadienyl skeleton) Transition of Group 4 of the periodic table containing a ligand having a cyclopentadienyl skeleton used in the present invention Examples of the metal compound (A) include transition metal compounds represented by any of the following general formulas (I) to (III).

First, the compound represented by formula (I) will be described. M ¹ L ¹ _x (I) In the formula, M ¹ represents a transition metal atom selected from Group 4 of the periodic table, specifically zirconium, titanium or hafnium. x is a number satisfying a valence of the transition metal atom M ^1, illustrating a coordinated number of ligands L ¹ to the transition metal atom M ^1.

L ¹ represents a ligand coordinated to a transition metal atom, and at least one L ¹ is a ligand having a cyclopentadienyl skeleton, and other than a ligand having a cyclopentadienyl skeleton. L ¹ is a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group, a halogen atom or a hydrogen atom.

Examples of the ligand having a cyclopentadienyl skeleton include cyclopentadienyl group, methylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, tetramethylcyclopentadienyl group. Group, pentamethylcyclopentadienyl group, ethylcyclopentadienyl group, methylethylcyclopentadienyl group, propylcyclopentadienyl group, methylpropylcyclopentadienyl group, butylcyclopentadienyl group, methylbutylcyclo Examples thereof include an alkyl-substituted cyclopentadienyl group such as a pentadienyl group and a hexylcyclopentadienyl group, an indenyl group, a 4,5,6,7-tetrahydroindenyl group, and a fluorenyl group. These groups may be substituted with (halogenated) hydrocarbon groups having 1 to 20 carbon atoms, oxygen-containing groups, sulfur-containing groups, silicon-containing groups, halogen atoms and the like.

When the compound represented by the above general formula (I) contains two or more ligands having a cyclopentadienyl skeleton, the ligands having two cyclopentadienyl skeletons among them are , A (substituted) alkylene group, a (substituted) silylene group and the like may be bonded via a divalent bonding group. The transition metal compound represented by the general formula (II) described below is a transition metal compound in which such a ligand having two cyclopentadienyl skeletons is bound via a divalent linking group. Is mentioned.

Specific examples of the ligand L ¹ other than the ligand having a cyclopentadienyl skeleton include the following. Examples of the hydrocarbon group having 1 to 20 carbon atoms include an alkyl group, a cycloalkyl group, an alkenyl group, an arylalkyl group and an aryl group, and more specifically, methyl, ethyl, propyl, butyl, hexyl, Alkyl groups such as octyl, nonyl, dodecyl, eicosyl; cycloalkyl groups such as cyclopentyl, cyclohexyl, norbornyl, adamantyl; vinyl,
Alkenyl groups such as propenyl and cyclohexenyl; arylalkyl groups such as benzyl, phenylethyl, phenylpropyl; phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenylyl, naphthyl, methylnaphthyl, anthryl, phenanthryl, etc. An aryl group is mentioned.

Examples of the halogenated hydrocarbon group having 1 to 20 carbon atoms include a group obtained by substituting the above hydrocarbon group having 1 to 20 carbon atoms with halogen. Examples of the oxygen-containing group include a hydroxy group; an alkoxy group such as methoxy, ethoxy, propoxy and butoxy; an aryloxy group such as phenoxy, methylphenoxy, dimethylphenoxy and naphthoxy; an arylalkoxy group such as phenylmethoxy and phenylethoxy.

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

Examples of the silicon-containing group include monohydrocarbon-substituted silyl such as methylsilyl and phenylsilyl; dihydrocarbon-substituted silyl such as dimethylsilyl and diphenylsilyl;
Trihydrocarbon-substituted silyl such as trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, dimethylphenylsilyl, methyldiphenylsilyl, tritolylsilyl, and trinaphthylsilyl; silyl of hydrocarbon-substituted silyl such as trimethylsilyl ether Ether; silicon-substituted alkyl groups such as trimethylsilylmethyl; silicon-substituted aryl groups such as trimethylphenyl.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. When such a transition metal compound has a valence of 4, the transition metal compound is more specifically represented by the following general formula (I ′). R ¹² R ¹³ R ¹⁴ R ¹⁵ M ¹ (I ′) In the formula, M ¹ represents a transition metal atom selected from Group 4 of the periodic table as described above.

R ¹² represents a group (ligand) having a cyclopentadienyl skeleton, and R ¹³ , R ¹⁴ and R ¹⁵ may be the same or different from each other and are groups having a cyclopentadienyl skeleton. (Ligand), a (halogenated) hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group, a halogen atom or a hydrogen atom.

[0022] In the transition metal compound represented by the above general formula in the present invention (I '), at least one group having a cyclopentadienyl skeleton of R ^13, R ^{1 4} and R ¹⁵ (ligand) Certain compounds, for example, compounds in which R ¹² and R ¹³ are groups (ligands) having a cyclopentadienyl skeleton are preferably used. When R ¹² and R ¹³ are a group (ligand) having a cyclopentadienyl skeleton, R ¹⁴ and R ¹⁵ are a group having a cyclopentadienyl skeleton, an alkyl group, a cycloalkyl group, an alkenyl group,
It is preferably an arylalkyl group, an aryl group, an alkoxy group, an aryloxy group, a trialkylsilyl group, a sulfonate group, a halogen atom or a hydrogen atom.

The following is represented by the general formula (I) and M ¹
Specific examples of the transition metal compound in which zirconium is zirconium will be illustrated. Bis (cyclopentadienyl) zirconium monochloride monohydride, bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dibromide, bis (cyclopentadienyl) methylzirconium monochloride, bis (cyclopenta Dienyl) zirconium phenoxymonochloride, bis (methylcyclopentadienyl) zirconium dichloride, bis (ethylcyclopentadienyl) zirconium dichloride, bis (propylcyclopentadienyl) zirconium dichloride, bis (butylcyclopentadienyl) zirconium Dichloride, bis (hexylcyclopentadienyl) zirconium dichloride, bis (octylcyclopentadienyl)
Zirconium dichloride, bis (indenyl) zirconium dichloride, bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, bis (indenyl) zirconium dibromide, bis (cyclopentadienyl) zirconium dimethyl, bis (cyclopentadiene) (Enyl) zirconium methoxy chloride, bis (cyclopentadienyl) zirconium ethoxy chloride, bis (fluorenyl) zirconium dichloride, bis (cyclopentadienyl) zirconium bis (methanesulfonato), bis (cyclopentadienyl) zirconium bis (p -Toluenesulfonato), bis (cyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (methylcyclopentadienyl) zirconium bis (trifluoromethanesulfonato) Nato), bis (ethylcyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (propylcyclopentadienyl)
Zirconium bis (trifluoromethane sulfonate),
Bis (butylcyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (hexylcyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (dimethylcyclopentadienyl) zirconium bis (trifluoromethanesulfonato) , Bis (methylethylcyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (methylpropylcyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (methylbutylcyclopentadienyl) zirconium bis (trifluoro) Chloromethanesulfonato), bis (dimethylcyclopentadienyl) zirconium dichloride, bis (methylpropylcyclopentadienyl) zirconium dichloride, bis (methyl Tylcyclopentadienyl) zirconium dichloride, bis (methylhexylcyclopentadienyl) zirconium dichloride, bis (ethylbutylcyclopentadienyl) zirconium dichloride, bis (trimethylcyclopentadienyl) zirconium dichloride, bis (tetramethylcyclopenta (Dienyl)
Zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (methylbenzylcyclopentadienyl) zirconium dichloride, bis (ethylhexylcyclopentadienyl) zirconium dichloride, bis (methylcyclohexylcyclopentadienyl) zirconium dichloride, Bis (cyclopentadienyl) ethyl zirconium monochloride, Bis (cyclopentadienyl) cyclohexyl zirconium monochloride, Bis (cyclopentadienyl)
Phenylzirconium monochloride, bis (cyclopentadienyl) benzylzirconium monochloride, bis (cyclopentadienyl) methylzirconium monohydride, bis (cyclopentadienyl) diphenylzirconium, bis (cyclopentadienyl) dibenzylzirconium, Bis (indenyl) zirconium bis (p-toluenesulfonato), bis (dimethylcyclopentadienyl) zirconium ethoxy chloride, bis (methylethylcyclopentadienyl) zirconium dichloride, bis (propylcyclopentadienyl) zirconium dichloride, bis (Methylbutylcyclopentadienyl) zirconium bis (methanesulfonate), bis (trimethylsilylcyclopentadienyl) zirconium dichloride, etc.

In the above examples, the di-substituted cyclopentadienyl ring includes 1,2- and 1,3-substituted products, and the tri-substituted product is 1,2,3- and 1,2,4. -Includes substitutions. Alkyl groups such as propyl and butyl are n-, i-, sec-, tert.
-Including isomers such as. In addition, in the zirconium compound as described above, a compound in which zirconium is replaced with titanium or hafnium can be given.

Examples of the transition metal compound in which two ligands having a cyclopentadienyl skeleton are bound via a divalent linking group include compounds represented by the following general formula (II). .

[0026]

[Chemical 1]

In the formula, M ¹ represents a transition metal atom selected from Group 4 of the periodic table, specifically zirconium, titanium or hafnium. R ¹⁶ , R ¹⁷ , R ¹⁸ and R ^{19, which} may be the same or different, are each a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, The oxygen-containing group, sulfur-containing group, nitrogen-containing group, phosphorus-containing group, hydrogen atom or halogen atom is shown.

Of the groups represented by R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ , some of the groups adjacent to each other may be bonded to each other to form a ring with the carbon atom to which those groups are bonded.
Although R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ are shown in two places, R ¹⁶ and R ¹⁶ may be the same group or different groups. Among the groups represented by R, those denoted by the same reference numeral show preferred combinations in the case where they are joined to form a ring.

As the hydrocarbon group having 1 to 20 carbon atoms, alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, octyl, nonyl, dodecyl and eicosyl;
Cycloalkyl groups such as cyclopentyl, cyclohexyl, norbornyl, adamantyl; alkenyl groups such as vinyl, propenyl, cyclohexenyl; benzyl,
Arylalkyl groups such as phenylethyl and phenylpropyl; phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenylyl, naphthyl, methylnaphthyl, anthryl,
Examples thereof include aryl groups such as phenanthryl.

The ring formed by combining these hydrocarbon groups is a benzene ring, a naphthalene ring, an acenaphthene ring,
Examples thereof include a condensed ring group such as an indene ring, and a group in which a hydrogen atom on the condensed ring group is substituted with an alkyl group such as methyl, ethyl, propyl and butyl. Examples of the halogenated hydrocarbon group having 1 to 20 carbon atoms include the above-mentioned 1 to 2 carbon atoms.
A group in which a hydrocarbon group of 0 is substituted with halogen can be mentioned.

As the silicon-containing group, monohydrocarbon-substituted silyl such as methylsilyl and phenylsilyl; dihydrocarbon-substituted silyl such as dimethylsilyl and diphenylsilyl;
Trihydrocarbon-substituted silyl such as trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, dimethylphenylsilyl, methyldiphenylsilyl, tritolylsilyl, and trinaphthylsilyl; silyl of hydrocarbon-substituted silyl such as trimethylsilyl ether Ethers; silicon-substituted alkyl groups such as trimethylsilylmethyl; silicon-substituted aryl groups such as trimethylsilylphenyl.

Examples of the oxygen-containing group include a hydroxy group; an alkoxy group such as methoxy, ethoxy, propoxy and butoxy; an aryloxy group such as phenoxy, methylphenoxy, dimethylphenoxy and naphthoxy; an arylalkoxy group such as phenylmethoxy and phenylethoxy. To be Examples of the sulfur-containing group include a substituent in which oxygen of the oxygen-containing group is replaced with sulfur.

As the nitrogen-containing group, an amino group; an alkylamino group such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, dicyclohexylamino; phenylamino, diphenylamino,
Examples thereof include arylamino groups such as ditolylamino, dinaphthylamino and methylphenylamino, and alkylarylamino groups.

Examples of the phosphorus-containing group include phosphino groups such as dimethylphosphino and diphenylphosphino. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Of these, a hydrocarbon group having 1 to 20 carbon atoms is preferable, and a hydrocarbon group having 1 to 4 carbon atoms such as methyl, ethyl, propyl, and butyl, and benzene formed by combining the hydrocarbon groups are particularly preferable. The hydrogen atom on the benzene ring formed by combining the ring and the hydrocarbon group is methyl, ethyl, n-propyl, iso-
A group substituted with an alkyl group such as propyl, n-butyl, iso-butyl, tert-butyl is preferable.

X ¹ and X ² may be the same or different from each other, and are a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group. , A silicon-containing group, a hydrogen atom or a halogen atom. Examples of the hydrocarbon group having 1 to 20 carbon atoms, the halogenated hydrocarbon group having 1 to 20 carbon atoms, the oxygen-containing group and the halogen atom include the same groups and atoms as those of R ^{16 to} R ¹⁹ .

Examples of the sulfur-containing group include the same groups as those described above for R ^{16 to} R ¹⁹ , as well as methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, p-toluene sulfonate and trimethyl. Sulfonate groups such as benzene sulphonate, triisobutylbenzene sulphonate, p-chlorobenzene sulphonate, pentafluorobenzene sulphonate; methylsulfinate, phenylsulfinate, benzenesulfinate, p-toluenes Examples thereof include sulfinate groups such as ruffinate, trimethylbenzene sulfinate, and pentafluorobenzene sulfinate.

Examples of the silicon-containing group include the same silicon-substituted alkyl group and silicon-substituted aryl group as those described above for R ^{16 to} R ¹⁹ . Of these, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a sulfonate group is preferable. Y ¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a divalent silicon-containing group, a divalent germanium-containing group, or a divalent Tin-containing groups, -O-, -CO-, -S-,-
_{SO -, - SO 2 -,} - Ge -, - Sn -, - NR
^{20 -, - P (R 20} ) -, - P (O) (R 20) -, - BR 20 - or -AlR ²⁰ - (where, R ²⁰ may be the same or different from each other, the number of carbon atoms 1-20 hydrocarbon groups, halogenated hydrocarbon groups having 1-20 carbon atoms, hydrogen atoms or halogen atoms).

Specific examples of the divalent hydrocarbon group having 1 to 20 carbon atoms include methylene, dimethylmethylene, 1,2-ethylene, dimethyl-1,2-ethylene, 1,3-trimethylene,
Examples include alkylene groups such as 1,4-tetramethylene, 1,2-cyclohexylene, and 1,4-cyclohexylene; arylalkylene groups such as diphenylmethylene and diphenyl-1,2-ethylene.

Specific examples of the divalent halogenated hydrocarbon group having 1 to 20 carbon atoms include a group obtained by halogenating the above divalent hydrocarbon group having 1 to 20 carbon atoms such as chloromethylene. To be As the divalent silicon-containing group,
Silylene, methylsilylene, dimethylsilylene, diethylsilylene, di (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, methylphenylsilylene, diphenylsilylene, di (p-tolyl) silylene, di ( Alkylsilylylene group such as p-chlorophenyl) silylene; Alkylarylsilylene group; Arylsilylene group; Alkyldisilylene group such as tetramethyl-1,2-disilylene and tetraphenyl-1,2-disilylene; Alkylaryldisilylene group; Aryl disililen group etc. are mentioned.

Examples of the divalent germanium-containing group include groups obtained by substituting germanium for silicon in the divalent silicon-containing group. Examples of the divalent tin-containing group include groups obtained by substituting tin for silicon in the divalent silicon-containing group. Of these, substituted silylene groups such as dimethylsilylene, diphenylsilylene, and methylphenylsilylene are particularly preferable.

R ²⁰ is the same halogen atom as R ^{16 to} R ¹⁹ , a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms. less than,
Specific examples of the transition metal compound represented by the general formula (II) are shown below. Ethylene-bis (indenyl) dimethyl zirconium, ethylene-bis (indenyl) zirconium dichloride, ethylene-bis (indenyl) zirconium bis (trifluoromethanesulfonato), ethylene-bis (indenyl) zirconium bis (methanesulfonato), ethylene-bis (Indenyl)
Zirconium bis (p-toluenesulfonato), ethylene
-Bis (indenyl) zirconium bis (p-chlorobenzenesulfonato), ethylene-bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, isopropyl Ridene (cyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride, dimethylsilylene-bis (cyclopentadienyl) zirconium dichloride, dimethylsilylene-
Bis (methylcyclopentadienyl) zirconium dichloride, dimethylsilylene-bis (dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene-bis (trimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene-bis (indenyl) zirconium dichloride, dimethyl Silylene-bis (indenyl) zirconium bis (trifluoromethanesulfonato), dimethylsilylene-bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, diphenyl Silylene-bis (indenyl) zirconium dichloride, methylphenylsilylene-bis (indenyl) zirconium dichloride, r
ac-dimethylsilylene-bis (2,3,5-trimethylcyclopentadienyl) zirconium dichloride, rac-dimethylsilylene-bis (2,4,7-trimethylcyclopentadienyl) zirconium dichloride, rac-dimethylsilylene-
Bis (2-methyl-4-tert-butylcyclopentadienyl)
Zirconium dichloride, isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilylene (3-tert-butylcyclopentadienyl) (indenyl) zirconium dichloride, isopropylidene (4-methylcyclopentadienyl) (3- Methylindenyl) zirconium dichloride, isopropylidene (4-tert-butylcyclopentadienyl) (3-methylindenyl) zirconium dichloride, isopropylidene (4-tert-butylcyclopentadienyl) (3-tert-butylindene Nil) zirconium dichloride, dimethylsilylene (4-methylcyclopentadienyl) (3-methylindenyl) zirconium dichloride, dimethylsilylene (4-te
rt-Butylcyclopentadienyl) (3-methylindenyl) zirconium dichloride, dimethylsilylene (4-te
rt-Butylcyclopentadienyl) (3-tert-butylindenyl) zirconium dichloride, dimethylsilylene (3-
tert-Butylcyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (3-tert-butylcyclopentadienyl) (fluorenyl) zirconium dichloride, etc.

Further, a compound in which zirconium in the above compound is replaced by titanium or hafnium can also be mentioned. Another specific example of the transition metal compound represented by the general formula (II) is a transition metal compound represented by the following general formula (II ′) or (II ″).

[0043]

[Chemical 2]

In the formula, M ¹ represents a transition metal atom selected from Group 4 of the periodic table, specifically titanium, zirconium or hafnium. R ²¹ may be the same or different and each represents a hydrocarbon group having 1 to 6 carbon atoms, specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, Alkyl groups such as tert-butyl, n-pentyl, neopentyl, n-hexyl and cyclohexyl; alkenyl groups such as vinyl and propenyl.

Of these, an alkyl group having a primary carbon atom bonded to an indenyl group is preferable, an alkyl group having 1 to 4 carbon atoms is more preferable, and a methyl group and an ethyl group are particularly preferable. R ²² , R ²⁴ , R ²⁵ and R ^{26, which} may be the same or different, each represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 6 carbon atoms similar to R ²¹ .

R ^{23, which} may be the same or different, each represents a hydrogen atom or an aryl group having 6 to 16 carbon atoms, specifically, phenyl, α-naphthyl, β-naphthyl, anthryl, phenanthryl, Pyrenyl, acenaphthyl, phenalenyl, aceanthrylenyl, tetrahydronaphthyl, indanyl, biphenylyl and the like can be mentioned. Of these, phenyl, naphthyl, anthryl, and phenanthryl are preferable.

These aryl groups include halogen atoms such as fluorine, chlorine, bromine and iodine; methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, octyl,
Alkyl groups such as nonyl, dodecyl, eicosyl, norbornyl and adamantyl; alkenyl groups such as vinyl, propenyl and cyclohexenyl; arylalkyl groups such as benzyl, phenylethyl, phenylpropyl; phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl , Propylphenyl, biphenyl,
α- or β-naphthyl, methylnaphthyl, anthryl,
C1-C20 hydrocarbon groups such as aryl groups such as phenanthryl, benzylphenyl, pyrenyl, acenaphthyl, phenalenyl, aceanthrylenyl, tetrahydronaphthyl, indanyl and biphenylyl; organic silyl groups such as trimethylsilyl, triethylsilyl and triphenylsilyl. It may be substituted with a group.

[0048] X ¹ and X ² may be the same or different from each other, it is the same as X ¹ and X ² in the general formula (II). Of these, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms is preferable. Y ¹
Is the same as Y ¹ in the general formula (II). Of these, a divalent silicon-containing group, a divalent germanium-containing group are preferable, a divalent silicon-containing group is more preferable, and an alkylsilylene, alkylarylsilylene or arylsilylene is more preferable. preferable.

Specific examples of the transition metal compound represented by the above general formula (II ') are shown below. rac-dimethyl silylene
-Bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2
-Methyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- (β-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis { 1- (2-methyl-
4- (1-anthryl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- (2
-Anthryl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- (9-
Anthryl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (9-phenanthryl) indenyl)} zirconium dichloride,
rac-Dimethylsilylene-bis {1- (2-methyl-4- (p-fluorophenyl) indenyl)} zirconium dichloride, rac-Dimethylsilylene-bis {1- (2-methyl-4- (pentafluorophenyl) indenyl) )} Zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-
4- (p-chlorophenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-
4- (m-chlorophenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-
4- (o-chlorophenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-
4- (o, p-dichlorophenyl) phenylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1
-(2-Methyl-4- (p-bromophenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1
-(2-Methyl-4- (p-tolyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- (m-tolyl) indenyl)} zirconium dichloride, rac-dimethylsilylene -Bis {1- (2-methyl-4- (o
-Tolyl) indenyl)} zirconium dichloride, rac
-Dimethylsilylene-bis {1- (2-methyl-4- (o, o'-dimethylphenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- (p -
Ethylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- (pi
-Propylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4-)
(p-benzylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-
4- (p-biphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- (m
-Biphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- (p-
Trimethylsilylenephenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-
Methyl-4- (m-trimethylsilylenephenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-phenyl-4-phenylindenyl)} zirconium dichloride, rac-diethylsilylene-bis {1-
(2-Methyl-4-phenylindenyl)} zirconium dichloride, rac-di- (i-propyl) silylene-bis {1- (2
-Methyl-4-phenylindenyl)} zirconium dichloride, rac-di- (n-butyl) silylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-dicyclohexylsilylene-bis { 1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-methylphenylsilylene-bis {1- (2-methyl-
4-phenylindenyl)} zirconium dichloride, ra
c-diphenylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-di (p-tolyl) silylene-bis {1- (2-methyl-4-phenylindenyl)} Zirconium dichloride, rac-di (p-chlorophenyl) silylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-methylene-bis {1- (2-methyl-4-phenylindenyl) )} Zirconium dichloride, rac-ethylene-bis {1- (2-methyl-4-)
Phenylindenyl)} zirconium dichloride, rac-
Dimethylgermylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-Dimethylstannylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac- Dimethyl silylene
-Bis {1- (2-methyl-4-phenylindenyl)} zirconium dibromide, rac-dimethylsilylene-bis {1- (2
-Methyl-4-phenylindenyl)} zirconium dimethyl, rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium methyl chloride, rac-
Dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium chloride SO ₂ Me, rac-Dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium chloride OSO ₂ Me, rac-dimethylsilylene-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-ethyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-ethyl-4- (β-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-ethyl-4- (2-methyl-1-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4- (5-acenaphthyl) indenyl) } Zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4- (9-anthryl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-ethyl-4- (9-phenanthryl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-ethyl-4- (o-methylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-ethyl-4- (m-methylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-ethyl-4- (p-methylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-ethyl-4- (2,3-dimethylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4- (2,4-dimethylphenyl))
Indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4- (2,5-dimethylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl- 4- (2,4,6-trimethylphenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (o-chlorophenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (m-chlorophenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (p-chlorophenyl) indenyl)} zirconium dichloride,
rac-Dimethylsilylene-bis {1- (2-ethyl-4- (2,3-dichlorophenyl) indenyl)} zirconium dichloride, rac-Dimethylsilylene-bis {1- (2-ethyl-4- (2,6
-Dichlorophenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4-
(3,5-Dichlorophenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl
-4- (2-Bromophenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl)
-4- (3-Bromophenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl)
-4- (4-Bromophenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl)
-4- (4-Biphenylyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4)
-(4-Trimethylsilylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1-
(2-n-Propyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-n-propyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene -Bis {1- (2-n-propyl-4- (β-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-n-propyl)
-4- (2-Methyl-1-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-n-propyl-4- (5-acenaphthyl) indenyl)} zirconium dichloride, rac-dimethyl Silylene-bis {1- (2-n-
Propyl-4- (9-anthryl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-n-
Propyl-4- (9-phenanthryl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1-
(2-i-Propyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-i-propyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene -Bis {1- (2-i-propyl-4- (β-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-i-propyl)
-4- (8-Methyl-9-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-i-propyl-4- (5-acenaphthyl) indenyl)} zirconium dichloride, rac-dimethyl Silylene-bis {1- (2-i-
Propyl-4- (9-anthryl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-i-
Propyl-4- (9-phenanthryl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1-
(2-s-Butyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-s-butyl
-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-s-butyl-4-
(Β-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-s-butyl-4- (2
-Methyl-1-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-s-butyl-
4- (5-acenaphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-s-butyl-4)
-(9-Anthryl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-s-butyl-4-
(9-phenanthryl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-n-pentyl)
-4-Phenylindenyl)} zirconium dichloride, r
ac-Dimethylsilylene-bis {1- (2-n-pentyl-4- (α-
Naphthyl) indenyl)} zirconium dichloride, ra
c-Dimethylsilylene-bis {1- (2-n-butyl-4-phenylindenyl)} zirconium dichloride, rac-Dimethylsilylene-bis {1- (2-n-butyl-4- (α-naphthyl) indenyl) )} Zirconium dichloride, rac-dimethylsilylene-bis {1- (2-n-butyl-4- (β-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-n-butyl-4- (2-methyl-1-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-n-butyl-4- (5- Acenaphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-n-butyl-4- (9-anthryl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-n -Butyl-4- (9-phenanthryl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-i-butyl-4-phenylindenyl)}
Zirconium dichloride, rac-dimethylsilylene-bis {1- (2-i-butyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1
-(2-i-Butyl-4- (β-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-
i-Butyl-4- (2-methyl-1-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1
-(2-i-Butyl-4- (5-acenaphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1
-(2-i-Butyl-4- (9-anthryl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1-
(2-i-Butyl-4- (9-phenanthryl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1
-(2-Neopentyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-neopentyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis { 1- (2-n-
Hexyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-n-hexyl
-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-methylphenylsilylene-bis {1- (2-ethyl
-4-Phenylindenyl)} zirconium dichloride, r
ac-Methylphenylsilylene-bis {1- (2-ethyl-4- (α
-Naphthyl) indenyl)} zirconium dichloride, r
ac-methylphenylsilylene-bis {1- (2-ethyl-4- (9-
Anthryl) indenyl)} zirconium dichloride,
rac-Methylphenylsilylene-bis {1- (2-ethyl-4- (9
-Phenanthryl) indenyl)} zirconium dichloride, rac-diphenylsilylene-bis {1- (2-ethyl-4-
Phenylindenyl)} zirconium dichloride, rac-
Diphenylsilylene-bis {1- (2-ethyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-diphenylsilylene-bis {1- (2-ethyl-4- (9-anthryl) indenyl)} zirconium Dichloride, rac-diphenylsilylene-bis {1- (2-ethyl-4- (9-phenanthryl) indenyl)} zirconium dichloride, rac-diphenylsilylene-bis {1- (2-ethyl-4- (4-biphenylyl)) Indenyl)} zirconium dichloride, rac-methylene-bis {1- (2-ethyl-4-phenylindenyl)}
Zirconium dichloride, rac-methylene-bis {1- (2-ethyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-ethylene-bis {1- (2-ethyl-4-phenylindenyl)} zirconium Dichloride, rac-ethylene-bis {1- (2-ethyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-ethylene-bis {1
-(2-n-Propyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-dimethylgermyl-bis {1-
(2-Ethyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylgermyl-bis {1- (2-ethyl-4-
(Α-Naphthyl) indenyl)} zirconium dichloride, rac-dimethylgermyl-bis {1- (2-n-propyl-4-
Phenylindenyl)} zirconium dichloride and the like.

Further, a compound in which zirconium in the above compound is replaced by titanium or hafnium can also be mentioned. Next, the transition metal compound represented by the general formula (II ″) will be described.

[0051]

[Chemical 3]

In the formula, M ¹ represents a transition metal atom selected from Group 4 of the periodic table, specifically titanium, zirconium or hafnium. R ³¹ and R ³² may be the same or different from each other, and are a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group, and a sulfur-containing group. It represents a group, a nitrogen-containing group, a phosphorus-containing group, a hydrogen atom or a halogen atom, and specific examples thereof include the same atoms or groups as those of R ^{16 to} R ¹⁹ .

Of these, R ³¹ has 1 to 20 carbon atoms.
Is preferred, and a hydrocarbon group having 1 to 3 carbon atoms such as methyl, ethyl and propyl is particularly preferred. R ³² is a hydrogen atom or a carbon atom of 1 to
20 hydrocarbon groups are preferred, and particularly hydrogen atom or methyl, ethyl, propyl having 1 to 3 carbon atoms.
It is preferable that the hydrocarbon group is

R ³³ and R ^{34, which} may be the same or different, each represents an alkyl group having 1 to 20 carbon atoms, specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl. , Sec-butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, cyclohexyl, octyl, nonyl, dodecyl, eicosyl, norbornyl, adamantyl and the like.

Of these, R ³³ is preferably a secondary or tertiary alkyl group. X ¹ and X ² may be the same or different from each other, are the same as X ¹ and X ² in the general formula (II). Y ¹ is represented by the general formula (I
It is the same as Y ¹ in I). The general formula (I
Specific examples of the transition metal compound represented by I ″) are shown below.

Rac-Dimethylsilylene-bis {1- (2,7-dimethyl-4-ethylindenyl)} zirconium dichloride, rac-Dimethylsilylene-bis {1- (2,7-dimethyl-4-)
n-propylindenyl)} zirconium dichloride, ra
c-Dimethylsilylene-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-n-butylindene) Nil)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-sec-butylindenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2,7-dimethyl-4-tert-butylindenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2,7-dimethyl-4-n-pentylindenyl)}
Zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-n-hexylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1-
(2,7-Dimethyl-4-cyclohexylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1-
(2,7-Dimethyl-4-methylcyclohexylindenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2,7-dimethyl-4-phenylethylindenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2,7-dimethyl-4-phenyldichloromethylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-chloromethylindenyl)} zirconium dichloride , Rac-Dimethylsilylene-bis {1- (2,7-dimethyl-4-trimethylsilylmethylindenyl)} zirconium dichloride, rac-Dimethylsilylene-bis {1- (2,7-dimethyl-4-trimethylsiloxymethylindene) Nil)} Zirconium dichloride, rac-
Diethylsilylene-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride, rac-di (i-
Propyl) silylene-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride, rac-di (n-butyl) silylene-bis {1- (2,7-dimethyl-4- i-Propylindenyl)} zirconium dichloride, rac-di (cyclohexyl) silylene-bis {1- (2,7-dimethyl-
4-i-propylindenyl)} zirconium dichloride,
rac-Methylphenylsilylene-bis {1- (2,7-dimethyl-
4-i-propylindenyl)} zirconium dichloride,
rac-Methylphenylsilylene-bis {1- (2,7-dimethyl-
4-tert-Butylindenyl)} zirconium dichloride, rac-diphenylsilylene-bis {1- (2,7-dimethyl-
4-tert-Butylindenyl)} zirconium dichloride, rac-diphenylsilylene-bis {1- (2,7-dimethyl-
4-i-propylindenyl)} zirconium dichloride,
rac-diphenylsilylene-bis {1- (2,7-dimethyl-4-ethylindenyl)} zirconium dichloride, rac-di (p-tolyl) silylene-bis {1- (2,7-dimethyl-4-i -Propylindenyl)} zirconium dichloride, rac-di (p-chlorophenyl) silylene-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1 -(2-Methyl-4-i-propyl-7-ethylindenyl)} zirconium dibromide, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-ethylindenyl)} zirconium dichloride , R
ac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-n
-Propylindenyl)} zirconium dichloride, rac
-Dimethylsilylene-bis {1- (2,3,7-trimethyl-4-i-
Propylindenyl)} zirconium dichloride, rac-
Dimethylsilylene-bis {1- (2,3,7-trimethyl-4-n-butylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-sec- Butylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-tert-butylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2, 3,7-Trimethyl-4-n-pentylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-n-hexylindenyl)} zirconium dichloride, rac- Dimethylsilylene-bis {1- (2,3,7-trimethyl-4-cyclohexylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-methylcyclohexylindenyl) )} Zirconium dichloride, rac-
Dimethylsilylene-bis {1- (2,3,7-trimethyl-4-trimethylsilylmethylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-trimethylsiloxymethyl) Indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1-
(2,3,7-Trimethyl-4-phenylethylindenyl)}
Zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-phenyldichloromethylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl -4-chloromethylindenyl)} zirconium dichloride, rac-diethylsilylene-bis {1- (2,3,7-trimethyl-4-i-propylindenyl)} zirconium dichloride, rac-di (i-propyl) Silylene-bis {1- (2,3,7-trimethyl-4-i-propylindenyl)} zirconium dichloride, rac-di (n-
Butyl) silylene-bis {1- (2,3,7-trimethyl-4-i-propylindenyl)} zirconium dichloride, rac-di (cyclohexyl) silylene-bis {1- (2,3,7-trimethyl- 4-i-Propylindenyl)} zirconium dichloride, rac-methylphenylsilylene-bis {1- (2,3,7-
Trimethyl-4-i-propylindenyl)} zirconium dichloride, rac-methylphenylsilylene-bis {1-
(2,3,7-Trimethyl-4-tert-butylindenyl)} zirconium dichloride, rac-diphenylsilylene-bis {1
-(2,3,7-Trimethyl-4-tert-butylindenyl)} zirconium dichloride, rac-diphenylsilylene-bis {1- (2,3,7-trimethyl-4-i-propylindenyl)}
Zirconium dichloride, rac-diphenylsilylene-bis {1- (2,3,7-trimethyl-4-ethylindenyl)} zirconium dichloride, rac-di (p-tolyl) silylene-
Bis {1- (2,3,7-trimethyl-4-i-propylindenyl)} zirconium dichloride, rac-di (p-chlorophenyl) silylene-bis {1- (2,3,7-trimethyl-4- i-Propylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4-i-propyl-7-methylindenyl)} zirconium dimethyl, rac-dimethylsilylene-bis {1- ( 2-Methyl-4-i-propyl-7-methylindenyl)} zirconium methyl chloride, rac-dimethylsilylene-bis {1- (2-methyl-4-i-propyl-7-
Methylindenyl)} zirconium-bis (methanesulfonato), rac-dimethylsilylene-bis {1- (2-methyl-)
4-i-Propyl-7-methylindenyl)} zirconium-bis (p-phenylsulfinato), rac-dimethylsilylene
-Bis {1- (2-methyl-3-methyl-4-i-propyl-7-methylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4,6-di- i-Propylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4-i-propyl-7-methylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- ( 2-phenyl-4-i-propyl-7-methylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methylindenyl)} zirconium dichloride, rac-ethylene-bis {1- (2 , 4,7-Trimethylindenyl)} zirconium dichloride, rac-isopropylidene-bis {1- (2,4,7-trimethylindenyl)} zirconium dichloride and the like.

Further, a compound in which zirconium in the above compound is replaced by titanium or hafnium can also be mentioned. In the present invention, a compound represented by the following general formula (III) can be used as the transition metal compound. L ² M ² X ³ ₂ (III) In the formula, M ² represents a transition metal atom of Group 4 of the periodic table.

L ² is a derivative of a delocalized π-bonding group, which imparts a constrained geometric shape to the metal M ² active site, and X ^{3 s} may be the same or different from each other. A halogen atom, a hydrocarbon group containing 20 or less carbon atoms, a silyl group containing 20 or less silicon atoms, or a germyl group containing 20 or less germanium atoms.

Among the compounds represented by the general formula (III), the compound represented by the following general formula (III ') is preferable.

[0060]

[Chemical 4]

In the formula, M ² represents a transition metal atom selected from Group 4 of the periodic table, specifically zirconium, titanium or hafnium. X ³ may be the same or different from each other is the same as X ³ in the general formula (III). Cp represents a substituted cyclopentadienyl group or a derivative thereof that is π-bonded to M ² .

Z is an oxygen atom, a sulfur atom or a boron atom
Or showing a ligand containing an atom of Group 14 of the periodic table, for example
If -Si (R³⁵ ₂)-, -C (R³⁵ ₂)-, -Si (R³⁵ ₂) S
i (R ³⁵ ₂)-, -C (R³⁵ ₂) C (R³⁵ ₂)-, -C (R³⁵ ₂) C
(R³⁵ ₂) C (R³⁵ ₂)-, -C (R ³⁵) = C (R³⁵)-, -C
(R³⁵ ₂) Si (R³⁵ ₂)-, -Ge (R³⁵ ₂)-And so on.
Y²Is a nitrogen atom, phosphorus atom, oxygen atom or sulfur atom.
A ligand containing a child, for example, -N (R³⁶)-, -O-,
-S-, -P (R³⁶)-And so on.

Further, Z and Y ² may form a condensed ring. R ³⁵ is a hydrogen atom or a group selected from an alkyl group having up to 20 non-hydrogen atoms, an aryl group, a silyl group, a halogenated alkyl group, a halogenated aryl group and a combination thereof, and R ³⁶ is a carbon atom. An alkyl of 1 to 10 atoms, an aryl group of 6 to 10 carbon atoms or an aralkyl group of 7 to 10 carbon atoms, or the condensation of one or more R ³⁵ with up to 30 non-hydrogen atoms. It may form a ring system.

Specific examples of the transition metal compound represented by the above general formula (III) are shown below. (Tert-butylamide)
(Tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediylzirconium dichloride, (tert-butylamide)
(Tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediyl titanium dichloride, (methylamide) (Tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediyl zirconium dichloride, (methylamide) (Tetramethyl-
η ⁵ -Cyclopentadienyl) -1,2-ethanediyl titanium dichloride, (ethylamido) (tetramethyl-η ⁵ -Cyclopentadienyl) -methylene titanium dichloride, [dimethyl (tert-butylamide) (tetramethyl-η ⁵ -Cyclopentadienyl) silane] titanium dichloride, [dimethyl (tert-butylamido) (tetramethyl-η ⁵ -cyclopentadienyl) silane] zirconium dichloride, (benzylamido) dimethyl- (tetramethyl-η ⁵ -cyclo Pentadienyl) silane titanium dichloride, (phenylphosphide) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silane zirconium dibenzyl and the like.

Further, the following compounds can be used as the transition metal compound. Dihydrocarbon substituted bis (cyclopentadienyl) zirconium compounds, such as bis (cyclopentadienyl) zirconium dimethyl, bis (cyclopentadienyl) zirconium diethyl, bis (cyclopentadienyl) zirconium dipropyl, bis (cyclopentadiene Dienyl) zirconium dibutyl, bis (cyclopentadienyl) zirconium diphenyl,
Bis (cyclopentadienyl) zirconium dineopentyl, bis (cyclopentadienyl) zirconium di (m-tolyl), bis (cyclopentadienyl) zirconium di (p-tolyl), etc.

(Monohydrocarbon-substituted cyclopentadienyl) zirconium compounds such as (methylcyclopentadienyl) (cyclopentadienyl) zirconium dimethyl, bis (methylcyclopentadienyl) zirconium dimethyl, (ethylcyclopentadienyl) ) (Cyclopentadienyl) zirconium dimethyl, bis (ethylcyclopentadienyl) zirconium dimethyl, (propylcyclopentadienyl) (cyclopentadienyl) zirconium dimethyl, bis (propylcyclopentadienyl) zirconium dimethyl, (n -Butylcyclopentadienyl) (cyclopentadienyl) zirconium dimethyl, bis (n-butylcyclopentadienyl) zirconium dimethyl, (tert-butylcyclopentadienyl) (cyclopentadienyl) zirconium Dimethyl, bis (te
rt-Butylcyclopentadienyl) zirconium dimethyl, (cyclohexylmethylcyclopentadienyl) (cyclopentadienyl) zirconium dimethyl, bis (cyclohexylmethylcyclopentadienyl) zirconium dimethyl, (benzylcyclopentadienyl) (cyclopenta Dienyl) zirconium dimethyl, bis (benzylcyclopentadienyl) zirconium dimethyl, (diphenylmethylcyclopentadienyl) (cyclopentadienyl) zirconium dimethyl, bis (diphenylmethylcyclopentadienyl) zirconium dimethyl, (methylcyclopenta Dienyl) (cyclopentadienyl) zirconium dihydride, bis (methylcyclopentadienyl) zirconium dihydride, (ethylcyclopentadienyl) (cycl Lopentadienyl) zirconium dihydride, bis (ethylcyclopentadienyl) zirconium dihydride, (propylcyclopentadienyl) (cyclopentadienyl) zirconium dihydride, bis (propylcyclopentadienyl)
Zirconium dihydride, (n-butylcyclopentadienyl) (cyclopentadienyl) zirconium dihydride, bis (n-butylcyclopentadienyl) zirconium dihydride, (tert-butylcyclopentadienyl) (cyclopentadienyl) (Enyl) zirconium dihydride, bis (tert-butylcyclopentadienyl)
Zirconium dihydride, (cyclohexylmethylcyclopentadienyl) (cyclopentadienyl) zirconium dihydride, bis (cyclohexylmethylcyclopentadienyl) zirconium dihydride,
(Benzylcyclopentadienyl) (cyclopentadienyl) zirconium dihydride, bis (benzylcyclopentadienyl) zirconium dihydride, (diphenylmethylcyclopentadienyl) (cyclopentadienyl) zirconium dihydride Bis (diphenylmethyl) Cyclopentadienyl) zirconium dihydride, etc.

(Polyhydrocarbon-substituted cyclopentadienyl) zirconium compounds such as (dimethylcyclopentadienyl) (cyclopentadienyl) zirconium dimethyl, bis (dimethylcyclopentadienyl) zirconium dimethyl, (trimethylcyclopentadienyl) ) (Cyclopentadienyl) zirconium dimethyl, bis (trimethylcyclopentadienyl) zirconium dimethyl, (tetramethylcyclopentadienyl) (cyclopentadienyl) zirconium dimethyl, bis (tetramethylcyclopentadienyl) zirconium dimethyl, (Permethylcyclopentadienyl) (cyclopentadienyl) zirconium dimethyl, bis (permethylcyclopentadienyl) zirconium dimethyl, (ethyltetramethylcyclopentadienyl) ) (Cyclopentadienyl)
Zirconium dimethyl, bis (ethyltetramethylcyclopentadienyl) zirconium dimethyl, (indenyl) (cyclopentadienyl) zirconium dimethyl, bis (indenyl) zirconium dimethyl, (dimethylcyclopentadienyl) (cyclopentadienyl) zirconium di Hydride, bis (dimethylcyclopentadienyl) zirconium dihydride, (trimethylcyclopentadienyl) (cyclopentadienyl) zirconium dihydride, bis (trimethylcyclopentadienyl) zirconium dihydride, (tetramethylcyclopentadienyl) ) (Cyclopentadienyl) zirconium dihydride, bis (tetramethylcyclopentadienyl) zirconium dihydride, (permethylcyclopentadienyl) ) (Cyclopentadienyl) zirconium dihydride, bis (permethylcyclopentadienyl) zirconium dihydride, (ethyltetramethylcyclopentadienyl) (cyclopentadienyl) zirconium dihydride, bis (ethyltetramethylcyclopenta) Dienyl) zirconium dihydride, (indenyl) (cyclopentadienyl) zirconium dihydride, bis (indenyl) zirconium dihydride and the like.

(Metallic hydrocarbon-substituted cyclopentadienyl) zirconium compounds such as (trimethylsilylcyclopentadienyl) (cyclopentadienyl) zirconium dimethyl, bis (trimethylsilylcyclopentadienyl) zirconium dimethyl, (trimethylgermylcyclopenta) Dienyl) (cyclopentadienyl) zirconium dimethyl, bis (trimethylgermylcyclopentadienyl) zirconium dimethyl, (trimethylstannylcyclopentadienyl) (cyclopentadienyl)
Zirconium dimethyl, bis (trimethylstannylcyclopentadienyl) zirconium dimethyl, (trimethylplumbylcyclopentadienyl) (cyclopentadienyl) zirconium dimethyl, bis (trimethylplumbylcyclopentadienyl) zirconium dimethyl,
(Trimethylsilylcyclopentadienyl) (cyclopentadienyl) zirconium dihydride, bis (trimethylsilylcyclopentadienyl) zirconium dihydride, (trimethylgermylcyclopentadienyl) (cyclopentadienyl) zirconium dihydride, bis ( Trimethylgermyl cyclopentadienyl)
Zirconium dihydride, (trimethylstannylcyclopentadienyl) (cyclopentadienyl) zirconium dihydride, bis (trimethylstannylcyclopentadienyl) zirconium dihydride,
(Trimethylplumbylcyclopentadienyl) (cyclopentadienyl) zirconium dihydride, bis (trimethylplumbylcyclopentadienyl) zirconium dihydride and the like.

(Halogen-substituted cyclopentadienyl) zirconium compounds such as (trifluoromethylcyclopentadienyl) (cyclopentadienyl) zirconium dimethyl, bis (trifluoromethylcyclopentadienyl) zirconium dimethyl, (trifluoromethyl Cyclopentadienyl) (cyclopentadienyl) zirconium dihydride, bis (trifluoromethylcyclopentadienyl) zirconium dihydride, etc.

Silyl-substituted bis (cyclopentadienyl)
Zirconium compounds such as bis (cyclopentadienyl) (trimethylsilyl) (methyl) zirconium, bis (cyclopentadienyl) (triphenylsilyl) (methyl) zirconium, bis (cyclopentadienyl) [tris (dimethylsilyl) silyl ] (Methyl) zirconium, bis (cyclopentadienyl) [bis (mesityl)
Silyl] (methyl) zirconium, bis (cyclopentadienyl) (trimethylsilyl) (trimethylsilylmethyl) zirconium, bis (cyclopentadienyl) (trimethylsilylbenzyl) zirconium and the like.

(Bridged cyclopentadienyl) zirconium compounds such as methylenebis (cyclopentadienyl) zirconium dimethyl, ethylenebis (cyclopentadienyl) zirconium dimethyl, dimethylsilylbis (cyclopentadienyl) zirconium dimethyl, methylenebis (cyclo) Pentadienyl) zirconium dihydride, ethylenebis (cyclopentadienyl) zirconium dihydride, dimethylsilylbis (cyclopentadienyl) zirconium dihydride, and the like.

Zirconacycles such as bis (pentamethylcyclopentadienyl) zirconacyclobutane, bis (pentamethylcyclopentadienyl) zirconacyclopentane, bis (cyclopentadienyl) zirconindane. Olefin, diolefin or allyne ligand-substituted bis (cyclopentadienyl) zirconium compounds, such as bis (cyclopentadienyl) (1,3-butadiene) zirconium, bis (cyclopentadienyl) (2,3-dimethyl) -1,3-butadiene) zirconium, bis (pentamethylcyclopentadienyl) (benzine) zirconium, etc.

(Hydrocarbon) (hydride) bis (cyclopentadienyl) zirconium compounds such as bis (pentamethylcyclopentadienyl) zirconium (phenyl) (hydride), bis (pentamethylcyclopentadienyl) (methyl) (Hydride) etc. A bis (cyclopentadienyl) zirconium compound in which a substituent on the cyclopentadienyl group is bound to a metal, for example, (pentamethylcyclopentadienyl) (tetramethylcyclopentadienylmethylene) zirconium hydride,
(Pentamethylcyclopentadienyl) (tetramethylcyclopentadienylmethylene) zirconium phenyl and the like.

In addition, compounds in which zirconium in the above compounds is replaced with titanium or hafnium can also be mentioned. ((B) Ionizable Ionic Compound) The ionizable ionic compound (B) used in the present invention is a compound that reacts with the above transition metal compound to form an ion pair. -501950, Japanese Patent Laid-Open No. 1-502036, Japanese Patent Laid-Open No. 3-179005.
Japanese Patent Laid-Open No. 3-179006, Japanese Patent Laid-Open No. 3-2900
No. 07703, JP-A-3-207704, U
Lewis acids, ionic compounds, borane compounds and carborane compounds described in SP-5321106 and the like can be mentioned.

Specifically, the Lewis acid is BR
₃ (R is a phenyl group which may have a substituent such as fluorine, a methyl group, a trifluoromethyl group or fluorine), and examples thereof include trifluoroboron, triphenylboron, Tris (4-fluorophenyl) boron, Tris (3,5-difluorophenyl) boron, Tris (4-fluoromethylphenyl) boron, Tris (pentafluorophenyl) boron, Tris (p-tolyl) boron, Tris (o- Trily) boron, tris (3,5-dimethylphenyl) boron and the like.

Examples of the ionic compound include compounds represented by the following general formula (IV).

[0077]

[Chemical 5]

In the formula, R ¹⁹ includes H ⁺ , carbonium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, and ferrocenium cation having a transition metal. R ²⁰ to R ²³ may be the same or different from each other, an organic group, preferably an aryl group or a substituted aryl group.

Specific examples of the carbonium cation include triphenylcarbonium cation, tri (methylphenyl) carbonium cation, tri (dimethylphenyl) carbonium cation, and other trisubstituted carbonium cations. Specifically as the ammonium cation, trimethyl ammonium cation,
Trialkylammonium cations such as triethylammonium cation, tripropylammonium cation, tributylammonium cation, tri (n-butyl) ammonium cation; N, N-dimethylanilinium cation, N, N-diethylanilinium cation, N, N- 2,4,
Examples include N, N-dialkylanilinium cations such as 6-pentamethylanilinium cation; dialkylammonium cations such as di (isopropyl) ammonium cation and dicyclohexylammonium cation.

Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation and tri (dimethylphenyl) phosphonium cation. R ¹⁹ is preferably a carbonium cation, an ammonium cation or the like, and particularly preferably a triphenylcarbonium cation, an N, N-dimethylanilinium cation or an N, N-diethylanilinium cation.

As the ionic compound, trialkyl-substituted ammonium salt, N, N-dialkylanilinium salt,
A dialkyl ammonium salt, a triaryl phosphonium salt, etc. can also be mentioned. Specific examples of the trialkyl-substituted ammonium salt include, for example, triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) ammonium tetra (phenyl) boron, trimethylammonium tetra (p-tolyl). Boron, trimethylammonium tetra (o-tolyl) boron, tri (n-butyl) ammonium tetra (pentafluorophenyl) boron,
Tripropylammonium tetra (o, p-dimethylphenyl) boron, tri (n-butyl) ammonium tetra (m,
m-Dimethylphenyl) boron, tri (n-butyl) ammonium tetra (p-trifluoromethylphenyl) boron, tri (n-butyl) ammonium tetra (3,5-ditrifluoromethylphenyl) boron, tri (n-butyl) ) Ammonium tetra (o-tolyl) boron and the like.

Specific examples of the N, N-dialkylanilinium salt include, for example, N, N-dimethylanilinium tetra (phenyl) boron, N, N-diethylanilinium tetra (phenyl) boron, N, N-2, Examples include 4,6-pentamethylanilinium tetra (phenyl) boron. Specific examples of the dialkylammonium salt include di (1-propyl) ammonium tetra (pentafluorophenyl) boron and dicyclohexylammonium tetra (phenyl) boron.

Further, as an ionic compound, triphenylcarbenium tetrakis (pentafluorophenyl)
Borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferrocenium tetra (pentafluorophenyl) borate, triphenylcarbenium pentaphenylcyclopentadienyl complex,
Other examples include N, N-diethylanilinium pentaphenylcyclopentadienyl complex, a boron compound represented by the following formula (V) or (VI), and the like.

[0084]

[Chemical 6]

(In the formula, Et represents an ethyl group.)

[0086]

[Chemical 7]

Specific examples of the borane compound include decaborane (14); bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate, bis [tri (n-butyl) ammonium]. ] Anions such as undecaborate, bis [tri (n-butyl) ammonium] dodecaborate, bis [tri (n-butyl) ammonium] decachlorodecaborate, bis [tri (n-butyl) ammonium] dodecachlorododecaborate Salts of tris (n-butyl) ammonium bis (dodecahydride dodecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (dodecahydridododecaborate) nickelate (III), etc. Examples thereof include salts of borane anion.

Specific examples of the carborane compound include 4-carbanonaborane (14), 1,3-dicarbanonaborane (13), 6,9-dicarbadecaborane (14) and dodecahydride-1-phenyl- 1,3-dicarbanonaborane, dodecahydride-1-methyl-1,3-dicarbanonaborane,
Undeca hydride-1,3-Dimethyl-1,3-dicarbano naborane, 7,8-dicarbaundecaborane (13), 2,7-dicarbaundecaborane (13), undeca hydride
-7,8-Dimethyl-7,8-dicarbaundecaborane, dodecahydride-11-methyl-2,7-dicarbaundecaborane,
Tri (n-butyl) ammonium 1-carbadecaborate,
Tri (n-butyl) ammonium 1-carbaundecaborate, tri (n-butyl) ammonium 1-carbadodecaborate, tri (n-butyl) ammonium 1-trimethylsilyl-1-carbadecaborate, tri (n-butyl) Ammonium bromo-1-carbadodecaborate, tri (n-butyl) ammonium 6-carbadecaborate (14), tri (n-butyl) ammonium 6-carbadecaborate (1
2), tri (n-butyl) ammonium 7-carbaundecaborate (13), tri (n-butyl) ammonium 7,8-
Dicarbaundecaborate (12), tri (n-butyl)
Ammonium 2,9-dicarbaundecaborate (12),
Tri (n-butyl) ammonium dodeca hydride-8-
Methyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-ethyl-7,9-
Dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-butyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-allyl-7,9-dicarbaun Decaborate, tri (n-butyl) ammonium undecahydride-9-trimethylsilyl-7,8-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-4,6-dibromo-7-carbaundecaborate Salts of anions such as; tri (n-butyl) ammonium bis (nonahydride-1,3-dicarbanonaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8 -Dicarbaundecaborate) ferrate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) co Belt salt (III), tri (n- butyl) ammonium bis (undecapeptide 7,8-dicarbaundecaborate deca borate)
Nickelate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) cuprate (III), tri (n-butyl) ammonium bis (undecahydride-7) , 8-Dicarbaundecaborate) aurate (III), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarbaundecaborate) ferrate (III), tri (N-Butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarbaundecaborate) chromate (III), tri (n-
Butyl) ammonium bis (tribromooctahydride-7,8-dicarbaundecaborate) cobaltate (I
II), tris [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate)
Chromate (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) manganate (IV), bis [tri (n-butyl)]
Ammonium] bis (undecahydride-7-carbaundecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) nickelate (IV ) And other salts of metal carborane anions.

The above-mentioned (B-3) ionized ionic compound may be used alone or in combination of two or more kinds. ((C) Organometallic Compound) Specific examples of the (C) organometallic compound used in the present invention include the following organometallic compounds of Groups 1, 2 and 12 and 13 of the periodic table.

(C-1a) General formula R ^a _m Al (OR ^b ) _n H _p X _q (In the formula, R ^a and R ^b may be the same or different from each other, and have 1 to 15 carbon atoms, Preferably, 1 to 4 hydrocarbon groups are shown, X is a halogen atom, and m is 0 <m ≦.
3, n is 0 ≦ n <3, p is 0 ≦ p <3, and q is 0 ≦ q <3
And m + n + p + q = 3. ) An organoaluminum compound represented by.

(C-1b) General formula M ² AlR ^a ₄ (In the formula, M ² represents Li, Na or K, and R ^a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms. A complex alkylated product of a Group 1 metal and aluminum represented by the formula (1). (C-1c) Formula R ^a R ^b M ³ (In the formula, R ^a and R ^b may be the same or different from each other, and may be a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms. Shown, M ³ is Mg, Zn or Cd.)
A dialkyl compound of a Group 2 or Group 12 metal represented by:

Examples of the organoaluminum compound belonging to the above (C-1a) include the following compounds. In the general formula _{^{R a m Al (OR b)}} 3-m ( wherein, R ^a and R ^b may be the same or different, from 1 to 15 carbon atoms, preferably 1-4 hydrocarbon group indicates, m is preferably a number 1.5 ≦ m ≦ 3. the organic aluminum compound represented by), the general formula R ^a _m AlX _3-m (wherein, R ^a is from 1 to 15 carbon atoms, Preferably 1-4
Is a hydrocarbon group, X is a halogen atom, and m is preferably 0 <m <3. ), An organoaluminum compound represented by the general formula R ^a _m AlH _{3 -m} (wherein R ^a has 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms).
Of the hydrocarbon group, and m is preferably 2 ≦ m <3. ), An organoaluminum compound represented by the formula: R ^a _m Al (OR ^b ) _n X _q (wherein R ^a and R ^b may be the same or different from each other, and preferably have 1 to 15 carbon atoms. Represents a hydrocarbon group of 1 to 4, X represents a halogen atom, and m represents 0 <m ≦.
3, n is 0 ≦ n <3, q is a number 0 ≦ q <3, and m + n + q = 3. ) An organoaluminum compound represented by.

Specific examples of the organoaluminum compound belonging to (C-1a) include trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum. Such as tri-n-alkyl aluminum; triisopropyl aluminum, triisobutyl aluminum, tri sec-butyl aluminum, tri tert-
Butyl aluminum, tri 2-methylbutyl aluminum, tri 3-methylbutyl aluminum, tri 2-methylpentyl aluminum, tri 3-methylpentyl aluminum, tri 4-methylpentyl aluminum, tri 2-methylhexyl aluminum, tri 3-methylhexyl Aluminum, tri-branched alkyl aluminum such as tri-2-ethylhexyl aluminum; tricycloalkyl aluminum such as tricyclohexyl aluminum and tricyclooctyl aluminum; triaryl aluminum such as triphenyl aluminum and tritolyl aluminum; (i-C ₄ H _{9 ) x Al y (C 5 H} 10) z ( wherein, x, y, z are each a positive number, and z ≧ 2x) tri alkenyl aluminum such as tri-isoprenyl aluminum represented by like;. isobutanol Alkyl aluminum alkoxides such as chill aluminum methoxide, isobutyl aluminum ethoxide and isobutyl aluminum isopropoxide; Dialkyl aluminum alkoxides such as dimethyl aluminum methoxide, diethyl aluminum ethoxide and dibutyl aluminum butoxide; Ethyl aluminum sesquiethoxide, butyl aluminum sesquibutoxide Alkyl aluminum sesquialkoxides such as; Partially alkoxylated alkyl aluminums having an average composition represented by R ^a _2.5 Al (OR ^b ) _0.5 ; diethyl aluminum phenoxide, diethyl aluminum (2,6-di-tert- Butyl-4-methylphenoxide), ethyl aluminum bis (2,6-di-tert-butyl-4)
-Methylphenoxide), diisobutylaluminum (2,6-di-tert-butyl-4-methylphenoxide), isobutylaluminum bis (2,6-di-tert-butyl-4-methylphenoxide) and other dialkylaluminum aryloxides Dialkyl aluminum hydrides such as diethyl aluminum hydride, dibutyl aluminum hydride, diisobutyl aluminum hydride; Other partially hydrogenated alkyl aluminums such as ethyl aluminum dihydride, propyl aluminum dihydride and other alkyl aluminum dihydrides; dimethyl aluminum chloride; Diethyl aluminum chloride, dibutyl aluminum chloride, diethyl aluminum bromide, diisobutyl aluminum chloride, etc. Alkylaluminum sesquihalide such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquichloride bromide; Kill halides;
Partially halogenated alkyl aluminum such as alkyl aluminum dihalide such as ethyl aluminum dichloride, propyl aluminum dichloride and butyl aluminum dibromide; ethyl aluminum ethoxy chloride, butyl aluminum butoxycyclolide,
Partially alkoxylated and halogenated alkyl aluminum such as ethyl aluminum ethoxy bromide and the like can be mentioned.

A compound similar to (C-1a) can also be used, and examples thereof include an organoaluminum compound in which two or more aluminum compounds are bonded via a nitrogen atom. Specific examples of such a compound include (C ₂ H ₅ ) ₂ A
such _{lN (C 2 H 5) Al} (C 2 H 5) 2 and the like. The above
Examples of the compound belonging to (C-1b) include LiAl (C ₂ H ₅ ) ₄ LiAl (C ₇ H ₁₅ ) ₄ .

In addition, as the organometallic compound (C), methyl lithium, ethyl lithium, propyl lithium, butyl lithium, methyl magnesium bromide, methyl magnesium chloride, ethyl magnesium bromide, ethyl magnesium chloride, propyl magnesium bromide, propyl It is also possible to use magnesium chloride, butyl magnesium bromide, butyl magnesium chloride, dimethyl magnesium, diethyl magnesium, dibutyl magnesium, butyl ethyl magnesium and the like.

It is also possible to use a compound capable of forming the above-mentioned organoaluminum compound in the polymerization system, for example, a combination of aluminum halide and alkyllithium, or a combination of aluminum halide and alkylmagnesium. Furthermore, as the organometallic compound, the following organoaluminum oxy compounds can be used.

The organoaluminum oxy compound may be a conventionally known aluminoxane, and is also described in JP-A 2-7.
It may be a benzene-insoluble organoaluminum oxy compound as exemplified in 8687. The conventionally known aluminoxane can be produced, for example, by the following method, and is usually obtained as a solution of a hydrocarbon solvent. (1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate,
An organoaluminum compound such as trialkylaluminum is added to a hydrocarbon medium suspension such as aluminum sulfate hydrate, nickel sulfate hydrate, and ceric chloride hydrate to obtain adsorbed water or crystal water and organoaluminum. A method of reacting with a compound. (2) A method in which water, ice or water vapor is allowed to directly act on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran. (3) A method of reacting an organoaluminum compound such as trialkylaluminum with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene or toluene.

The aluminoxane may contain a small amount of an organometallic component. Further, the solvent or unreacted organoaluminum compound may be removed by distillation from the recovered solution of the aluminoxane, and then redissolved in the solvent or suspended in a poor solvent for the aluminoxane. Specific examples of the organoaluminum compound used when preparing the aluminoxane include the same organoaluminum compounds as those exemplified as the organoaluminum compound belonging to (C-1a) above.

Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum is particularly preferable. The above organoaluminum compounds may be used alone or in combination of two or more. As the solvent used for the preparation of aluminoxane, aromatic hydrocarbons such as benzene, toluene, xylene, cumene and cymene, pentane, hexane, heptane, octane, decane, dodecane, hexadecane, octadecane and other aliphatic hydrocarbons, cyclopentane , Cyclohexane, cyclooctane, alicyclic hydrocarbons such as methylcyclopentane, petroleum fractions such as gasoline, kerosene, and light oil, or the above aromatic hydrocarbons, aliphatic hydrocarbons, halides of alicyclic hydrocarbons, especially chlorine And hydrocarbon solvents such as bromine and bromide. Further, ethers such as ethyl ether and tetrahydrofuran can also be used. Of these solvents, aromatic hydrocarbons or aliphatic hydrocarbons are particularly preferable.

In the benzene-insoluble organoaluminum oxy compound, the Al component dissolved in benzene at 60 ° C. is usually 10% or less, preferably 5% or less in terms of Al atom.
It is particularly preferably 2% or less and insoluble or hardly soluble in benzene. Examples of the organoaluminum oxy compound also include boron-containing organoaluminum oxy compounds represented by the following general formula (VII).

[0101]

[Chemical 8]

In the formula, R ¹⁷ represents a hydrocarbon group having 1 to 10 carbon atoms. R ^{18 s} may be the same or different and each represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 10 carbon atoms. The organoaluminum oxy compound containing boron represented by the general formula (VII) includes an alkylboronic acid represented by the following general formula (VIII) and R ¹⁷ —B— (OH) ₂ (VIII) (wherein , R ¹⁷ represents the same groups as described above.) It can be produced by reacting an organoaluminum compound in an inert solvent in an inert solvent at a temperature of −80 ° C. to room temperature for 1 minute to 24 hours.

Specific examples of the alkylboronic acid represented by the general formula (VIII) include methylboronic acid, ethylboronic acid, isopropylboronic acid, n-propylboronic acid, n-butylboronic acid, isobutylboronic acid, n. -Hexylboronic acid, cyclohexylboronic acid, phenylboronic acid, 3,5-difluoroboronic acid, pentafluorophenylboronic acid, 3,5-bis (trifluoromethyl) phenylboronic acid and the like. Of these, methylboronic acid, n-butylboronic acid, isobutylboronic acid, 3,5-difluorophenylboronic acid, and pentafluorophenylboronic acid are preferable. These may be used alone or in combination of two or more.

Specific examples of the organoaluminum compound to be reacted with the alkylboronic acid include the above-mentioned (C-1a)
The same organoaluminum compounds as those exemplified as the organoaluminum compounds belonging to 1) can be mentioned. Among these, trialkyl aluminum and tricycloalkyl aluminum are preferable, and trimethyl aluminum, triethyl aluminum and triisobutyl aluminum are particularly preferable. These may be used alone or in combination of two or more.

Among the organometallic compounds (C), organoaluminum compounds are preferred. The organometallic compound (C) as described above may be used alone or in combination of two or more. (Olefin Polymerization Catalyst (1)) The olefin polymerization catalyst according to the present invention comprises a contact product (i) of the transition metal compound (A) and the ionized ionic compound (B), and an organometallic compound (C). Become.

The contact product (i) of the transition metal compound (A) and the ionized ionic compound (B) can be prepared as follows. (1) A method in which the transition metal compound (A) and the ionized ionic compound (B) are mixed and brought into contact with each other, and (2) the transition metal compound (A) and an organic solvent solution of the ionized ionic compound (B) are mixed. Method of contacting, (3) Method of mixing and contacting the organic solvent solution of the transition metal compound (A) and the ionized ionic compound (B), (4) Organic solvent solution of the transition metal compound (A), and ionized ion Method of mixing and contacting the organic compound solution (B) with an organic solvent solution, (5) transition metal compound (A) and ionized ionic compound (B)
And a method of mixing and contacting with and in an organic solvent.

Specific examples of the organic solvent used here include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene; and fats such as cyclopentane, cyclohexane and methylcyclopentane. Examples thereof include aromatic hydrocarbons; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, and mixtures thereof.

When the transition metal compound (A) is contacted with the ionized ionic compound (B), the ionized ionic compound (B) is added to 1 mol of the transition metal compound (A).
Is 0.01 to 10000 mol, preferably 0.05 to
It is desirable to bring them into contact at a ratio of 2000 mol. The temperature at which the transition metal compound (A) and the ionized ionic compound (B) are mixed and contacted is usually 0 to 40.
C., preferably in the range of 5-35.degree.

The contact product (i) of the transition metal compound (A) and the ionized ionic compound (B) is usually used as a solution or slurry of an organic solvent. (1) to (5) above
The contact product (i) obtained by the method (1) can be diluted with an organic solvent. The contact product (i) of the transition metal compound (A) and the ionized ionic compound (B) is prepared by contacting the transition metal compound (A) with the ionized ionic compound (B) in a preparation container or the like. Alternatively, it can be prepared by bringing the transition metal compound (A) and the ionized ionic compound (B) into contact with each other in a supply line when the transition metal compound (A) and the ionized ionic compound (B) are supplied to the polymerization system.

When the contact product (i) of the transition metal compound (A) thus prepared and the ionized ionic compound (B) is a solution or a slurry, the concentration of the transition metal compound (A) is , Usually 5 × 10 ^{-2 to} 5 × 10
^-5 mol / liter, preferably 1 × 10 ^-2 to 1 × 10 ^-4
It is preferably mol / liter. In the olefin polymerization catalyst (1), the molar ratio [(C) / M] of the organometallic compound (C) and the transition metal atom (M) derived from the transition metal compound (A) in the contact product (i). Is usually 10
Is in the range of up to 50,000, preferably 20 to 20,000.

(Olefin Polymerization Catalyst (2)) The olefin polymerization catalyst according to the present invention comprises a contact product (ii) of the transition metal compound (A) and the organometallic compound (C), and an ionized ionic compound (B). ) And. The contact product (ii) of the transition metal compound (A) and the organometallic compound (C) can be prepared as follows. (1) Transition metal compound (A) and organometallic compound (C)
(2) transition metal compound (A)
And a method of mixing and contacting an organic solvent solution of the organometallic compound (C) with each other, (3) a method of mixing and contacting an organic solvent solution of the transition metal compound (A) with the organometallic compound (C),
(4) A method of mixing and contacting an organic solvent solution of a transition metal compound (A) and an organic solvent solution of an organometallic compound (C), (5) a transition metal compound (A), and an organometallic compound (C) And a method of bringing them into contact with each other in an organic solvent.

Specific examples of the organic solvent used here include those mentioned above. When bringing the transition metal compound (A) and the organometallic compound (C) into contact with each other,
The organometallic compound (C) is 10 to 50,000 mol, preferably 20 to 2 with respect to 1 mol of the transition metal compound (A).
It is desirable to bring them into contact with each other at a rate of 0000 mol.

The temperature at which the transition metal compound (A) and the organometallic compound (C) are mixed and contacted is usually 0 to 40.
C., preferably in the range of 5-35.degree. The contact product (ii) of the transition metal compound (A) and the organometallic compound (C) is
It is usually used as a solution or slurry of an organic solvent. The contact product (ii) obtained by the above method (1) to (5) is
It can be diluted with an organic solvent.

The contact product (ii) of the transition metal compound (A) and the organometallic compound (C) is prepared by bringing the transition metal compound (A) and the organometallic compound (C) into contact with each other in a preparation container or the like. Alternatively, it can be prepared by bringing the transition metal compound (A) and the organometallic compound (C) into contact with each other in a supply line when the transition metal compound (A) and the organometallic compound (C) are supplied to the polymerization system.

When the contact product (ii) of the transition metal compound (A) thus prepared with the organometallic compound (C) is a solution or a slurry, the transition metal compound (A)
The concentration of is usually 5 × 10 ^{−2 to} 5 × 10 ⁻⁵ mol / liter, preferably 1 × 10 ⁻² to 1 × 10 ⁻⁴ mol / liter. In the olefin polymerization catalyst (2), the molar ratio of the ionized ionic compound (B) to the transition metal atom (M) derived from the transition metal compound (A) in the contact product (ii) [(B) / ( M)] is 0.01 to
It is in the range of 10,000, preferably 0.05 to 2000.

Method for Polymerizing Olefin The method for polymerizing an olefin according to the present invention is a method for polymerizing an olefin in the presence of an olefin polymerization catalyst comprising (A) the above transition metal compound, (B) an ionizable ionic compound and (C) an organometallic compound. Upon polymerization, the transition metal compound (A) is brought into contact with the ionized ionic compound (B) or the organometallic compound (C) outside the polymerization system and then supplied into the polymerization system.

The contact between the transition metal compound (A) and the ionized ionic compound (B) or the contact between the transition metal compound (A) and the organometallic compound (C) is carried out in the same manner as above. Then, a contact product of the transition metal compound (A) and the ionized ionic compound (B) and an organometallic compound (C)
Or is supplied to the polymerization system, or the contact product of the transition metal compound (A) and the organometallic compound (C) and the ionized ionic compound (B) are supplied to the polymerization system.

The ionized ionic compound (B) and the organometallic compound (C) are preferably not brought into contact with each other until they are supplied to the polymerization system. In the present invention, the polymerization is usually carried out by a liquid phase polymerization method such as solution polymerization or suspension polymerization. Specific examples of the inert hydrocarbon medium used in the polymerization include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene;
Alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, or a mixture thereof, and the like. When the olefin used for polymerization is liquid under the polymerization conditions, the olefin itself used for polymerization can also be used as a medium.

In carrying out olefin polymerization using the olefin polymerization catalyst as described above, the component (A) is
Usually 10 ^-8 to 10 ^-2 mol per liter of reaction volume,
It is preferably used in an amount such that it is 10 ⁻⁷ to 10 ⁻³ mol. Component (B) molar ratio of the group 13 atoms and (M _B) with component (A) a transition metal atom in the (M _A) in (B) [M _B / M _A] is usually 0.01 It is used in an amount such that it is from 1 to 10,000, preferably from 0.05 to 2000.

Component (C) has a molar ratio [(C) / M] of component (C) to transition metal atom (M) in component (A) of usually 10 to 50,000, preferably 20 to 20,000. Used in such an amount that The polymerization temperature is usually -50.
The temperature is in the range of to 200 ° C, preferably 0 to 170 ° C. The polymerization pressure is usually atmospheric pressure to 10 MPa, preferably atmospheric pressure to 5
It is under the condition of MPa, and the polymerization reaction can be carried out by any of a batch system, a semi-continuous system and a continuous system. It is also possible to carry out the polymerization in two or more stages under different reaction conditions.

The molecular weight of the obtained olefin polymer can be adjusted by allowing hydrogen to be present in the polymerization system or by changing the polymerization temperature. The olefin used in the present invention, ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4
2 to 20 carbon atoms such as -methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene Linear or branched α-olefin; cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl
Examples thereof include cyclic olefins having 3 to 20 carbon atoms such as 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene.

Further, aromatic vinyl compounds such as styrene and α-methylstyrene; acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride, bicyclo (2,2,1) -5-heptene- Unsaturated fatty acids such as 2,3-dicarboxylic acid; methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate,
N-Butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, etc. It is also possible to copolymerize the unsaturated carboxylic acid ester of diene, triene, tetraene and the like.

Examples of the olefin polymer obtained by the present invention include polyethylene, polypropylene, polybutene, polypentene, polyhexene, poly-4-methyl-
1-pentene, ethylene / propylene copolymer, ethylene / butene copolymer, ethylene / pentene copolymer, ethylene / hexene copolymer, ethylene / 4-methyl-1-pentene copolymer, ethylene / octene copolymer Coalescence, ethylene / propylene / butene / terpolymer, ethylene / butene / hexene / terpolymer, ethylene / butene / octene / terpolymer, propylene / butene copolymer, propylene / pentene copolymer Coalesce, propylene / hexene copolymer, propylene / octene copolymer, ethylene / styrene copolymer, propylene / styrene copolymer, ethylene / propylene / styrene terpolymer, ethylene /
Octene / styrene terpolymer, ethylene / α-olefin / diene terpolymer (diene is butadiene, isoprene, 1,4-hexadiene, dicyclopentadiene, 5-ethylidene-2-norbornene, 7- Methyl-1,6-
Examples include octadiene. ), An ethylene / α-olefin / triene terpolymer (as a triene,
6,10-dimethyl-1,5,9-undecatriene, 5,9-dimethyl
Examples include chain or cyclic trienes such as -1,4,8-decatriene. ), Ethylene / α-olefin / tetraene terpolymer (as tetraene, 6,10,14-trimethyl-1,5,9,13-pentadecatriene, 5,9,13-trimethyl-1,4 , 8,12-Tetradecatriene and the like.)
Are exemplified. As the α-olefin of the terpolymer, propylene, 1-butene, 1-pentene, 1-
Examples include hexene, 1-octene, 1-decene, and the like.

[0124]

The olefin polymerization catalyst and the olefin polymerization method according to the present invention have excellent polymerization activity.

[0125]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited to these examples.

[0126]

Example 1 40 ml of 4,8-dimethyl-1,4,8-decatriene (hereinafter abbreviated as “DMDT”) and heptane were placed at 23 ° C. in a stainless steel autoclave with a stirring blade and a capacity of 2 liters, which had been sufficiently replaced with nitrogen. Charge 860 ml. Propylene 12N-liter was inserted into this autoclave while rotating the stirring blade and cooling with ice. Next, the autoclave is heated to 70 ° C and the total pressure is 8 kg / cm.
Pressurized with ethylene to be ² . When the internal pressure of the autoclave reached 8 kg / cm ² , 1.0 mmol / ml hexane solution of triisobutylaluminum 0.5
ml was purged with nitrogen. Then, prepared in advance,
Triphenylcarbenium (tetrakispentafluorophenyl) borate 0.04 mM, [dimethyl (tert-
Butylamido) (tetramethyl-η ⁵ -cyclopentadienyl) silane] titanium dichloride (3 ml) in a toluene solution containing 0.002 mmol of toluene was introduced into the autoclave with nitrogen to initiate polymerization. Then, for 30 minutes, the temperature of the autoclave was adjusted so that the internal temperature became 70 ° C., and ethylene was directly supplied so that the pressure became 8 kg / cm ² . After 30 minutes from the start of polymerization, 5 ml of methanol was inserted into the autoclave by a pump to stop the polymerization, and the autoclave was depressurized to atmospheric pressure. After the solvent of the obtained polymer solution was distilled off with an evaporator, the polymer was dried at 130 ° C. for 13 hours at 600 torr. The molar ratio of ethylene and propylene was 65/35, and DMDT was contained in an amount of 3.0 mol%. Thus, 31 g of an ethylene / propylene / DMDT copolymer having an intrinsic viscosity [η] of 2.6 dl / g was obtained.

[0127]

Comparative Example 1 In Example 1, triphenylcarbenium (tetrakispentafluorophenyl) borate was added at 0.04 mM and [dimethyl (tert-butylamido) (tetramethyl-η ⁵ -cyclopentadienyl) silane] titanium dichloride was added. Toluene solution 3 containing 002 mmol
Instead of pressurizing ml into the autoclave with nitrogen,
[Dimethyl (tert-butylamido) (tetramethyl-η ⁵ -cyclopentadienyl) silane] Titanium dichloride 0.0
3 ml of a toluene solution containing an amount of 02 mM was pressed into the autoclave with nitrogen, and then triphenylcarbenium (tetrakispentafluorophenyl) borate was added thereto.
Polymerization was performed in the same manner as in Example 1 except that 3 ml of a toluene solution containing 04 mM was sequentially introduced into the autoclave with nitrogen. After distilling off the solvent of the obtained polymer solution with an evaporator, the polymer was heated at 130 ° C. for 13 hours, and
When dried at 00 torr, the ethylene / propylene molar ratio was 69/31, DMDT was contained at 2.7 mol%, and the intrinsic viscosity [η] was 2.3 dl / g. Obtained.

[0128]

Example 2 Inner volume 136 with a stirrer and jacket
Copolymerization was carried out by continuously supplying hexane as a solvent and ethylene and 1-butene as a monomer to a liter (100 liters of gas phase part, 36 liters of liquid phase part) polymerization vessel. Hydrogen is used to control the molecular weight, and the polymerization conditions are temperature 15
The temperature was set to 0 ° C., the pressure was 3.0 MPaG, and the average residence time of the liquid phase was 1 hour.

As the catalyst, [dimethyl (tert-butylamido) (tetramethyl-η ⁵ -cyclopentadienyl) silane] titanium dichloride, triphenylcarbenium tetrakis (pentafluorophenyl) borate,
Three components of triisobutylaluminum were used. The method of supplying the catalyst to the polymerization vessel was as follows. Diluted with hexane [dimethyl (tert-butylamide) (tetramethyl-
26 mol of triisobutylaluminum diluted with hexane was fed to the polymerization reactor while continuously contacting with 1 mol of η ⁵ -cyclopentadienyl) silane] titanium dichloride. Triphenylcarbenium tetrakis (pentafluorophenyl) borate diluted with hexane was used without contact with [dimethyl (tert-butylamido) (tetramethyl-η ⁵ -cyclopentadienyl) silane] titanium dichloride or triisobutylaluminum. It was continuously fed to the polymerization vessel in another line. The concentration of triisobutylaluminum in the polymerization vessel was 0.005 mmol per liter of liquid phase.

At this time, [dimethyl (tert-butylamide)
(Tetramethyl-η ⁵ -cyclopentadienyl) silane] titanium dichloride 50 kg of polymer were continuously obtained per 1 mmol of the polymer.

[0131]

Comparative Example 2 Polymerization was carried out in the same manner as in Example 2 except that the method of supplying the catalyst to the polymerization vessel was as follows. [Dimethyl (tert-butylamido) (tetramethyl-η ⁵ -cyclopentadienyl) silane] titanium dichloride diluted with hexane, triphenylcarbenium tetrakis (pentafluorophenyl) borate diluted with hexane, triisobutyl diluted with hexane Aluminum was continuously fed to the polymerization vessel in a separate line without contacting each other.

At this time, [dimethyl (tert-butylamide)
(Tetramethyl-η ⁵ -cyclopentadienyl) silane] titanium dichloride 29 kg of polymer were continuously obtained per 1 mmol.

Continued front page    (72) Inventor Keiji Okada             580-32 Nagaura, Sodegaura-shi, Chiba Mitsui Chemicals, Inc.             Inside the company F-term (reference) 4J128 AA01 AB00 AB01 AC01 AC10                       AC28 AD02 AD05 AD06 AD07                       AD08 AD11 AD13 AD17 AD19                       BA00A BA02B BB00A BB01B                       BC01B BC05B BC06B BC12B                       BC13B BC15B BC16B BC17B                       BC19B BC24B BC25B BC28B                       BC29B EA01 EB02 EB04                       EB05 EB08 EB10 EB16 EB18                       EB21 EB25 EC01 EC02 EC04                       GA04

Claims (3)

[Claims] 1. A transition metal compound of Group 4 of the periodic table containing (A) a ligand having a cyclopentadienyl skeleton, and (B)
An olefin polymerization catalyst (1), which comprises a contact product (i) with a compound that reacts with a transition metal compound (A) to form an ion pair and (C) an organometallic compound. 2. A transition metal compound of Group 4 of the periodic table containing (A) a ligand having a cyclopentadienyl skeleton, and (C)
An olefin polymerization catalyst (2), which comprises a compound (ii) contacting with an organometallic compound and (B) a compound which reacts with the transition metal compound (A) to form an ion pair. 3. A transition metal compound of Group 4 of the periodic table containing (A) a ligand having a cyclopentadienyl skeleton, (B) a compound which reacts with the transition metal compound (A) to form an ion pair, and (C) When polymerizing an olefin in the presence of an olefin polymerization catalyst composed of an organometallic compound, the transition metal compound (A) reacts with the transition metal compound (A) to form an ion pair (B), or A method for polymerizing an olefin, which comprises bringing the organometallic compound (C) into contact with the outside of the polymerization system and then supplying it into the polymerization system.