JP2000072811A - Catalyst for polymerizing olefin and polymerization of olefin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an olefin polymerization catalyst giving a polymer in a high polymerization activity, when an olefin is polymerized in an aliphatic hydrocarbon solvent or an alicyclic hydrocarbon solvent, and to provide a method for polymerizing the olefin in the presence of the catalyst. SOLUTION: This catalyst for polymerizing an olefin comprises (A) a group 4 transition metal compound containing a ligand having a cyclopentadienyl skeleton, and (B) an organic aluminum oxy compound wherein hydrocarbon groups bonded to the aluminum atom comprises (1) methyl group and (2) at least one long chain alkyl group selected from alkyl groups containing 4-20 carbon atoms in the main chains in (methyl group + long chain alkyl group + other alkyl groups)/aluminum atom molar ratio of 1.5-2.5 and a methyl group/(methyl group + long chain alkyl group + other alkyl groups) molar ratio of 0.70-0.95.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an olefin polymerization catalyst and an olefin polymerization method using the catalyst. More specifically, the present invention relates to an olefin polymerization catalyst containing a specific organic aluminum oxy compound as a catalyst component, and an olefin polymerization catalyst. It relates to a method of polymerizing or copolymerizing an olefin in the presence.

[0002]

BACKGROUND OF THE INVENTION When an olefin is subjected to solution polymerization or suspension polymerization using a catalyst comprising a transition metal compound such as zirconocene and an organoaluminum oxy compound, the organoaluminum oxy compound is usually an aromatic carbon such as toluene. Used as a hydrogen solution. The produced polymer is obtained in a state containing an aromatic hydrocarbon, and is dried by heating and / or reduced pressure. However, it is difficult to completely remove the aromatic hydrocarbon. For this reason, the polymer has an odor peculiar to an aromatic hydrocarbon and cannot be used for food use, medical use and the like. In addition, aromatic hydrocarbons have been pointed out as having problems in occupational safety and health.

On the other hand, when only an aliphatic hydrocarbon or an alicyclic hydrocarbon is used as a polymerization medium, there is a problem that the polymerization activity is reduced. Therefore, when solution polymerization or suspension polymerization of an olefin is performed in an aliphatic hydrocarbon medium or an alicyclic hydrocarbon medium that does not contain an aromatic hydrocarbon,
There is a demand for a catalyst for olefin polymerization and a method for polymerizing olefins, which is capable of (co) polymerizing olefins with high activity.

The present inventors have conducted studies in view of the problems in the prior art as described above. As a result, they have used an organic aluminum oxy compound in which a specific alkyl group is bonded to an aluminum atom at a specific ratio. The present inventors have found that the polymerization activity is excellent when solution polymerization or suspension polymerization of an olefin is performed in an aliphatic hydrocarbon medium or an alicyclic hydrocarbon medium, and the present invention has been completed.

[0005]

An object of the present invention is to provide a method for polymerizing or copolymerizing olefins with high polymerization activity when solution polymerization or suspension polymerization of olefins is carried out in an aliphatic hydrocarbon medium or an alicyclic hydrocarbon medium. It is an object of the present invention to provide an olefin polymerization catalyst that can be used and a method for polymerizing an olefin using the catalyst.

[0006]

SUMMARY OF THE INVENTION The olefin polymerization catalyst 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 hydrocarbon group bonded to an aluminum atom is a methyl group, and the main chain has 4 carbon atoms. And at least one kind of long-chain alkyl group selected from the group consisting of a chain alkyl group of 20 to 20 and a (methyl group + long-chain alkyl group + other alkyl group) / aluminum atom (molar ratio) of 1.5 to 2. Methyl group / (methyl group + long-chain alkyl group + other alkyl group)
(Molar ratio) in the range of 0.70 to 0.95.

In the present invention, the long-chain alkyl group bonded to the aluminum atom of the (B) organoaluminum oxy compound is preferably a chain, particularly a straight-chain alkyl group having 6 to 15 carbon atoms. The (A) organic aluminum oxy compound is (methyl group + long-chain alkyl group + other alkyl group) / aluminum atom (molar ratio).
Is in the range of 1.7 to 2.0, and the methyl group / (methyl group + long-chain alkyl group + other alkyl group) (molar ratio) is preferably in the range of 0.75 to 0.95.

[0008] The olefin polymerization method according to the present invention is characterized in that olefin is polymerized or copolymerized in the presence of the olefin polymerization catalyst. In the present invention, the (B) organic aluminum oxy compound is preferably added to the polymerization system as a solution of an aliphatic hydrocarbon or an alicyclic hydrocarbon, and the (B) organic aluminum oxy compound is preferably a trialkylaluminum. 0.01 to 10 of aluminum atoms in the organic aluminum oxy compound
It is also preferable to add a double-fold molar solution of an aliphatic hydrocarbon or an alicyclic hydrocarbon to 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 this specification, the term "polymerization" may be used to mean not only homopolymerization but also copolymerization, and the term "polymer" means not only homopolymer but also copolymer. It is sometimes used in a sense that also includes coalescence.

The olefin polymerization catalyst according to the present invention comprises:
It is formed from (A) a transition metal compound of Group 4 of the periodic table containing a ligand having a cyclopentadienyl skeleton, and (B) a specific organic aluminum oxy compound. First,
Each component forming the olefin polymerization catalyst according to the present invention will be described.

(A) Transition metal compound (A) The transition metal compound of Group 4 of the periodic table containing a ligand having a cyclopentadienyl skeleton is a transition metal compound represented by the following general formula (I). .

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, preferably zirconium. .

[0013] x is a number satisfying the 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,
At least one L ¹ is a ligand having a cyclopentadienyl skeleton, and L ¹ other than the ligand having a cyclopentadienyl skeleton is a hydrocarbon group having 1 to 20 carbon atoms, It is a halogenated hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a silicon-containing group, a halogen atom or a hydrogen atom of the formulas 1 to 20.

The ligand having a cyclopentadienyl skeleton includes, for example, cyclopentadienyl group, methylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, tetramethylcyclopentadienyl. 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 or an indenyl group, a 4,5,6,7-tetrahydroindenyl group, and a fluorenyl group. These groups may be substituted with 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 the like.

When the compound represented by the above general formula (I) contains two or more ligands having a cyclopentadienyl skeleton, two of the ligands having a cyclopentadienyl skeleton are mutually linked. , (Substituted) alkylene group, (substituted) silylene group and the like. The two ligands having a cyclopentadienyl skeleton may be the same or different from each other. Examples of such a transition metal compound in which a ligand having two cyclopentadienyl skeletons are bonded through a divalent bonding group include a transition metal compound represented by the following general formula (Ib). 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, an aryl group, and the like; more specifically, an alkyl group such as methyl, ethyl, propyl, butyl, hexyl, octyl, nonyl, dodecyl, and eicosyl; a cycloalkyl such as cyclopentyl, cyclohexyl, norbornyl, and adamantyl Alkenyl groups such as vinyl, propenyl and cyclohexenyl; arylalkyl groups such as benzyl, phenylethyl and phenylpropyl; phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, naphthyl, methylnaphthyl,
And aryl groups such as anthryl and phenanthryl.

Examples of the halogenated hydrocarbon group having 1 to 20 carbon atoms include groups in which the hydrocarbon group having 1 to 20 carbon atoms is substituted with halogen. A hydroxy group as the oxygen-containing group; methoxy, ethoxy, propoxy,
Alkoxy groups such as butoxy; aryloxy groups such as phenoxy, methylphenoxy, dimethylphenoxy and naphthoxy; and arylalkoxy groups such as phenylmethoxy and phenylethoxy.

The sulfur-containing group includes a substituent in which oxygen of the above-mentioned oxygen-containing group is substituted by sulfur, and methylsulfonate, trifluoromethanesulfonate, phenylsulfonate, benzylsulfonate and p-toluenesulfonate. , Trimethylbenzenesulfonate,
Sulfonate groups such as triisobutylbenzenesulfonate, p-chlorobenzenesulfonate and pentafluorobenzenesulfonate; methylsulfinate, phenylsulfinate, benzylsulfinate, p-toluenesulfinate, trimethylbenzene Sulfinate groups such as sulfinate and pentafluorobenzene sulfinate.

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

[0020] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Such a transition metal compound, for example, when the valence of the transition metal is 4, is specifically represented by the following general formula (Ia).

R ¹ R ² R ³ R ⁴ M ¹ (Ia) In the formula, M ¹ represents a transition metal atom selected from the same periodic group 4 as in the general formula (I), and is preferably zirconium. is there.

R ¹ represents a group (ligand) having a cyclopentadienyl skeleton, and R ² , R ³ and R ⁴ may be the same or different from each other and represent a group having a cyclopentadienyl skeleton. (Ligand) represents 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.

In the present invention, the compound represented by the general formula (Ia) is used.
In the transition metal compound, R^Two, R ^ThreeAnd R^FourOut of
At least one group having a cyclopentadienyl skeleton
(Ligand), for example R¹And R^TwoBut
Is a group (ligand) having a clopentadienyl skeleton
Compounds are preferably used. Also, R¹And R^TwoBut
If it is a group (ligand) having a clopentadienyl skeleton
If R^ThreeAnd R^FourHas a cyclopentadienyl skeleton
Groups, alkyl groups, cycloalkyl groups, alkenyl groups,
Arylalkyl group, aryl group, alkoxy group, ant
-Roxy group, trialkylsilyl group, sulfonate
Preferably a group, a halogen atom or a hydrogen atom
No.

Hereinafter, the compound represented by the general formula (Ia)
Specific examples of the transition metal compound in which ¹ is zirconium are illustrated. Bis (indenyl) zirconium dichloride, bis (indenyl) zirconium dibromide, bis (indenyl) zirconium bis (p-toluenesulfonate), bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, bis (fluorenyl) )
Zirconium dichloride, bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dibromide, bis (cyclopentadienyl) methyl zirconium monochloride, bis (cyclopentadienyl) ethyl zirconium monochloride,
Bis (cyclopentadienyl) cyclohexyl zirconium monochloride, bis (cyclopentadienyl) phenyl zirconium monochloride, bis (cyclopentadienyl) benzyl zirconium monochloride, bis (cyclopentadienyl) zirconium monochloride monohydride, bis (Cyclopentadienyl) methylzirconium monohydride, bis (cyclopentadienyl) dimethylzirconium, bis (cyclopentadienyl) diphenylzirconium, bis (cyclopentadienyl) dibenzylzirconium, bis (cyclopentadienyl) zirconium Methoxy chloride, bis (cyclopentadienyl) zirconium ethoxycyclolide, bis (cyclopentadienyl) zirconium bis (methanesulfonate), Bis (cyclopentadienyl) zirconium bis (p-toluenesulfonate), bis (cyclopentadienyl) zirconium bis (trifluoromethanesulfonate), bis (methylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclo (Pentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium ethoxycyclolide, bis (dimethylcyclopentadienyl) zirconium bis (trifluoromethanesulfonate), bis (ethylcyclopentadienyl) zirconium dichloride, bis ( Methylethylcyclopentadienyl) zirconium dichloride, bis (propylcyclopentadienyl) zirconium dichloride, bis (methylpropylcyclopentadienyl) zirconiumdichloride Chloride, bis (butylcyclopentadienyl) zirconium dichloride, bis (methylbutylcyclopentadienyl) zirconium dichloride, bis (methylbutylcyclopentadienyl) zirconium bis (methanesulfonate),
Bis (trimethylcyclopentadienyl) zirconium dichloride, bis (tetramethylcyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (hexylcyclopentadienyl) zirconium dichloride, bis (trimethylsilylcyclo (Pentadienyl) zirconium dichloride and the like.

In the above examples, disubstituted cyclopentadienyl ring includes 1,2- and 1,3-substituted, and tri-substituted is 1,2,3- and 1,2,4 -Including substitutions. Alkyl groups such as propyl and butyl are n-, i-, sec-, tert
-Including isomers.

In the above-mentioned zirconium compounds, there can also be mentioned compounds in which zirconium is replaced by titanium or hafnium. Examples of the transition metal compound in which a ligand having two cyclopentadienyl skeletons are bonded via a divalent bonding group include, for example, a compound represented by the following general formula (Ib).

[0027]

Embedded image

In the formula, M ¹ represents a transition metal atom selected from the same periodic group 4 as in the above general formula (I), and is preferably zirconium. R ⁵ , R ⁶ , R ⁷ and R
⁸ may be the same or different from each other, 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, It represents a nitrogen-containing group, a phosphorus-containing group, a halogen atom or a hydrogen atom. Among the groups represented by R ⁵ , R ⁶ , R ⁷ and R ⁸ , some of the groups adjacent to each other may be bonded to form a ring together with the carbon atoms to which those groups are bonded. Although R ⁵ , R ⁶ , R ⁷ and R ⁸ are each shown at two places, for example, R ⁵ and R ⁵ may be the same group or different groups. Among the groups represented by R, those denoted by the same reference numerals indicate a preferable combination in the case where they are joined to form a ring.

Examples of the hydrocarbon group having 1 to 20 carbon atoms, the same alkyl group and the L ^1, a cycloalkyl group,
Examples include an alkenyl group, an arylalkyl group, and an aryl group.

The ring formed by combining these hydrocarbon groups includes a benzene ring, a naphthalene ring, an acenaphthene ring,
Examples 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 groups in which the aforementioned hydrocarbon group having 1 to 20 carbon atoms is substituted with halogen. Examples of the oxygen-containing group include a hydroxy group and the same alkoxy group, aryloxy group and arylalkoxy group as those described above for L ¹ .

Examples of the sulfur-containing group include substituents in which oxygen of the oxygen-containing group has been replaced by sulfur. Examples of the silicon-containing group, wherein L ¹ and similar mono hydrocarbon-substituted silyl, di-hydrocarbon-substituted silyl, tri hydrocarbon-substituted silyl, include silyl ethers of hydrocarbon-substituted silyl, a silicon-substituted alkyl groups, such as silicon-substituted aryl groups Can be

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

Examples of the phosphorus-containing group include phosphino groups such as dimethylphosphino and diphenylphosphino. The halogen atom include the same as the L ^1.

Of these, a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom is preferable, and in particular, hydrocarbon groups having 1 to 4 carbon atoms, such as methyl, ethyl, propyl and butyl, and hydrocarbon groups are preferable. A benzene ring formed by bonding, a hydrogen atom on the benzene ring formed by bonding a hydrocarbon group is methyl, ethyl, n-propyl, iso-propyl,
It is preferably a group substituted with an alkyl group such as n-butyl, iso-butyl and tert-butyl.

X ¹ and X ² may be the same or different from each other and represent a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group,
It represents 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 same alkyl group and the L ^1, a cycloalkyl group,
Examples include an alkenyl group, an arylalkyl group, and an aryl group.

Examples of the halogenated hydrocarbon group having 1 to 20 carbon atoms include groups in which the aforementioned hydrocarbon group having 1 to 20 carbon atoms is substituted with halogen. Hydroxy group as the oxygen-containing groups and the L ¹ and similar alkoxy groups,
Examples include an aryloxy group and an arylalkoxy group.

Examples of the sulfur-containing group, a substituent oxygen is replaced with sulfur in the oxygen-containing groups, and the L ¹ and similar sulfonate groups, such as sulfinate group. Examples of the silicon-containing group, wherein L ¹ similar silicon-substituted alkyl groups include silicon-substituted aryl group.

Examples of the halogen atom include the same groups and atoms as those described above for L ¹ . Among these, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a sulfonate group is preferable.

Y¹Is a divalent carbon having 1 to 20 carbon atoms
Hydrogenated group, divalent halogenated carbon having 1 to 20 carbon atoms
Hydride group, divalent silicon-containing group, divalent germanium-containing
Group, divalent tin-containing group, -O-, -CO-, -S-,
-SO-, -SO_Two-, -Ge-, -Sn-, -NR⁹
-, -P (R⁹)-, -P (O) (R⁹)-, -BR ⁹
-Or -AlR⁹-[However, R⁹Are identical to each other
May also be different, and hydrocarbons having 1 to 20 carbon atoms
Elemental group, a halogenated hydrocarbon group having 1 to 20 carbon atoms,
A hydrogen atom or a halogen atom].

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, 1,4-tetramethylene, 1,2-cyclohexylene, 1,4-
Alkylene groups such as 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 groups obtained by halogenating the above divalent hydrocarbon group having 1 to 20 carbon atoms such as chloromethylene. Is mentioned.

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 (p- Alkylsilylene groups such as chlorophenyl) silylene; alkylarylsilylene groups; arylsilylene groups; alkyldisilylene groups such as tetramethyl-1,2-disilylene and tetraphenyl-1,2-disilylene; alkylaryldisilylene groups; And a silylene group.

Examples of the divalent germanium-containing group include groups in which silicon of the above-mentioned divalent silicon-containing group is substituted with germanium. Examples of the divalent tin-containing group include a group in which silicon of the divalent silicon-containing group is substituted with tin.

R ⁹ is a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms or a halogen atom as in L ¹ . Of these, substituted silylene groups such as dimethylsilylene, diphenylsilylene, and methylphenylsilylene are particularly preferred.

In the following, the compound represented by the general formula (Ib)
Specific examples of the transition metal compound in which ¹ is zirconium are illustrated. Ethylene-bis (indenyl) dimethyl zirconium, ethylene-bis (indenyl) zirconium dichloride, ethylene-bis (indenyl)
Zirconium bis (trifluoromethanesulfonate), ethylene-bis (indenyl) zirconium bis (methanesulfonate), ethylene-bis (indenyl) zirconiumbis (p-toluenesulfonate),
Ethylene-bis (indenyl) zirconium bis (p-chlorobenzenesulfonate), ethylene-bis (4,5,
6,7-tetrahydroindenyl) zirconium dichloride, isopropylidene-bis (cyclopentadienyl)
(Fluorenyl) zirconium dichloride, isopropylidene-bis (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, dimethylsilylene-bis (indenyl) zirconiumbis (trifluoromethanesulfonate ), Dimethylsilylene-bis (4,5,6,7-tetrahydroindenyl)
Zirconium dichloride, dimethylsilylene-bis (cyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylsilylene-bis (indenyl) zirconium dichloride, methylphenylsilylene-bis (indenyl) zirconium dichloride, rac-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-te
rt-butylcyclopentadienyl) (3-methylindenyl) zirconium dichloride, isopropylidene- (4-te
rt-butylcyclopentadienyl) (3-tert-butylindenyl) zirconium dichloride, dimethylsilylene- (4-
Methylcyclopentadienyl) (3-methylindenyl) zirconium dichloride, dimethylsilylene- (4-tert-butylcyclopentadienyl) (3-methylindenyl) zirconium dichloride, dimethylsilylene- (4-tert-butylcyclo Pentadienyl) (3-tert-butylindenyl)
Zirconium dichloride, dimethylsilylene- (3-tert-
Butylcyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene- (3-tert-butylcyclopentadienyl) (fluorenyl) zirconium dichloride and the like.

Further, there may be mentioned a compound in which zirconium in the above-mentioned zirconium compound is replaced with titanium or hafnium. In the present invention, more specifically, as a transition metal compound in which a ligand having two cyclopentadienyl skeletons represented by the formula (Ib) is bonded via a divalent bonding group, The general formula (I
The transition metal compound represented by c) is mentioned.

[0049]

Embedded image

In the formula, M ¹ represents a transition metal atom selected from the same periodic group 4 as in the general formula (I), and is preferably zirconium. R ^{11 s} may be the same or different, and represent a hydrocarbon group having 1 to 6 carbon atoms, and specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec- Alkyl groups such as butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl and cyclohexyl; and alkenyl groups such as vinyl and propenyl.

Of these, a primary alkyl group having carbon atoms bonded to the indenyl group is preferable, an alkyl group having 1 to 4 carbon atoms is more preferable, and a methyl group or an ethyl group is particularly preferable.

R ¹² , R ¹⁴ , R ¹⁵ and R ¹⁶ may be the same or different and each represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 6 carbon atoms similar to R ¹¹ . R ¹³ may be the same or different, and represent an aryl group having 6 to 16 carbon atoms. Specifically, phenyl, α-naphthyl, β-naphthyl, anthryl, phenanthryl, pyrenyl, acenaphthyl, phenalenyl ,
Aceanthrenyl, tetrahydronaphthyl, indanyl, biphenylyl and the like. Of these, phenyl, naphthyl, anthryl and phenanthryl are preferred.

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 and phenylpropyl; phenyl, tolyl, dimethylphenyl, trimethylphenyl and ethylphenyl , Propylphenyl, biphenyl,
α- or β-naphthyl, methylnaphthyl, anthryl, phenanthryl, benzylphenyl, pyrenyl, acenaphthyl, phenalenyl, aceanthrenyl, tetrahydronaphthyl, indanyl, biphenylyl and other hydrocarbon groups having 1 to 20 carbon atoms. It may be substituted by an organic silyl group such as trimethylsilyl, triethylsilyl and triphenylsilyl.

X ¹ and X ² may be the same or different from each other, and are the same as X ¹ and X ^{2 in} formula (Ib). Among these, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms is preferable.

[0055] Y ¹ is the same as Y ¹ in the general formula (Ib). Of these, a divalent silicon-containing group, a divalent germanium-containing group is preferable, and a divalent silicon-containing group is more preferable.
More preferably, it is an alkylarylsilylene or an arylsilylene.

Hereinafter, the compound represented by the general formula (Ic)
Specific examples of the transition metal compound in which ¹ is zirconium are illustrated. rac-dimethylsilylene-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, ra
c-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, ra
c-dimethylsilylene-bis {1- (2-methyl-4- (p-chlorophenyl) indenyl)} zirconium dichloride, ra
c-dimethylsilylene-bis {1- (2-methyl-4- (m-chlorophenyl) indenyl)} zirconium dichloride, ra
c-dimethylsilylene-bis {1- (2-methyl-4- (o-chlorophenyl) indenyl)} zirconium dichloride, ra
c-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, ra
c-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, rac-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, ra
c-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-dimethylsilylene-bis ｛1- (2-methyl-
4-phenylindenyl) zirconium dibromide, ra
c-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-phenyl-indenyl)} zirconium dichloride, rac- dimethylsilylene - bis {1- (2-ethyl-4- (alpha-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
-(2-ethyl-4- (o-chlorophenyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1-
(2-ethyl-4- (m-chlorophenyl) indenyl) zirconium dichloride, rac-dimethylsilylene-bis
(2-ethyl-4- (p-chlorophenyl) indenyl) デ 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-dimethylsilylene-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-dimethylsilylene-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, rac-dimethylsilylene-bis ｛1
-(2-n-pentyl-4- (α-naphthyl) indenyl)｝ zirconium dichloride, rac-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, rac-methylphenylsilylene-bis ｛1
-(2-ethyl-4- (α-naphthyl) indenyl) {zirconium dichloride, rac-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, r
ac-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, compounds in which zirconium in the zirconium compound as described above is replaced with titanium or hafnium can also be mentioned. In the present invention, a racemate of the transition metal compound represented by the general formula (Ic) is generally used as a catalyst component, but an R-type or S-type may also be used.

The transition metal compound represented by the general formula (Ic) is described in Journal of Organometallic Chem.
985), pp. 63-67, European Patent Application 0,320,76.
It can be manufactured according to the description of No. 2 and Examples.

Further, in the present invention, a compound represented by the following general formula (II) can also be used as (A) a transition metal compound of Group 4 of the periodic table containing a ligand having a cyclopentadienyl skeleton.

[0060] _{^{L 2 M 1 X 3 2 ...}} (II) wherein, M ¹ is, a transition metal atom selected from the same period of Group 4 in the general formula (I).

L ² is a derivative of a delocalized π-bonded group, which imparts a constrained geometry to the metal M ¹ active site. X ^{3, which} may be the same or different, is a hydrogen atom, It is a halogen atom or a hydrocarbon group containing not more than 20 carbon atoms, silicon atoms or germanium atoms, a silyl group or a germyl group.

Among the transition metal compounds represented by the general formula (II), compounds represented by the following general formula (IIa) are preferable.

[0063]

Embedded image

In the formula, M ¹ represents a transition metal atom selected from the same group as periodic group 4 as in the general formula (I), and is preferably zirconium. Cp is a substituted cyclopentadienyl group having a π bond to M ¹ and having a substituent Z or a derivative thereof.

Z¹Means oxygen atom, sulfur atom, boron atom
Or a ligand containing an element of Group 14 of the periodic table;
For example, -Si (R¹⁸ _Two)-, -C (R¹⁸ _Two)-, -Si
(R¹⁸ _Two) Si (R¹⁸ _Two)-, -C (R¹⁸ _Two) C (R¹⁸ _Two)
-, -C (R¹⁸ _Two) C (R¹⁸ _Two) C (R¹⁸ _Two)-, -C
(R¹⁸) = C (R¹⁸)-, -C (R¹⁸ _Two) Si (R¹⁸ _Two)
-, -Ge (R¹⁸ _Two)-.

Y ² represents a ligand containing a nitrogen atom, a phosphorus atom, an oxygen atom or a sulfur atom, for example, —N (R
^{19) -, - O -,} - S -, - P (R 19) - and the like.
Z ¹ and Y ² may form a condensed ring.

R ¹⁸ is a hydrogen atom or a group selected from alkyl, aryl, silyl, halogenated alkyl, halogenated aryl groups having up to 20 non-hydrogen atoms and combinations thereof, and R ¹⁹ is a carbon atom. An alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms or an aralkyl group having 7 to 10 carbon atoms, or 1
One or more R ¹⁸ may form a fused ring system of up to 30 non-hydrogen atoms.

In the following, M ¹ is represented by the general formula (IIa).
Specific examples of the transition metal compound in which is zirconium are shown. (tert-butylamide) (tetramethyl
-η ⁵ -cyclopentadienyl) -1,2-ethanediylzirconium dichloride, (tert-butylamide) (tetramethyl
-η ⁵ -cyclopentadienyl) -1,2-ethanediyltitanium dichloride, (methylamide) (tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediylzirconium dichloride, (methylamide) (tetramethyl -η ⁵ -cyclopentadienyl) -1,2-ethanediyltitanium dichloride,
(Ethylamide) (tetramethyl-η ⁵ -cyclopentadienyl) -methylene titanium dichloride, (tert-butylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silanetitanium dichloride, (tert-butylamido) dimethyl (tetra Methyl-η ⁵ -cyclopentadienyl) silane zirconium dichloride, (benzylamido) dimethyl- (tetramethyl-η ⁵ -cyclopentadienyl) silane titanium dichloride, (phenylphosphido) dimethyl (tetramethyl-η ⁵ -cyclo (Pentadienyl) silane zirconium dibenzyl and the like.

Among such transition metal compounds,
The compound represented by the general formula (Ic) is preferable. the above
(A) The transition metal compound is applied to a particulate carrier as described below.
It can also be used by carrying. As a particulate carrier,
An inorganic or organic compound having a particle size of 10 to 300
μm, preferably 20 to 200 μm
Particulate solids are used. Of these, as inorganic compounds
Is preferably a porous oxide, specifically, SiO 2_Two, Al
_TwoO_Three, MgO, ZrO, TiO_Two, B_TwoO_Three, CaO,
ZnO, BaO, ThO_TwoOr a mixture containing these
Compound, for example SiO_Two-MgO, SiO_Two-Al_TwoO_Three,
SiO_Two-TiO_Two, SiO_Two-V_TwoO_Five, SiO_Two-Cr _Two
O_Three, SiO_Two-TiO_Two-MgO etc. can be exemplified
Wear. Of these, SiO_TwoAnd Al_TwoO_ThreeConsists of
The main component is at least one component selected from the group
Is preferred.

The above inorganic oxide contains a small amount of Na._TwoC
O_Three, K_TwoCO_Three, CaCO_Three, MgCO_Three, Na_TwoSO
_Four, Al_Two(SO_Four)_Three, BaSO_Four, KNO_Three, Mg (N
O_Three)_Two , Al (NO_Three)_Three, Na_TwoO, K_TwoO, Li_TwoO etc.
Contains carbonate, sulfate, nitrate and oxide components
I don't mind.

The properties of such fine-grained carriers differ depending on the kind and the production method, but the finely-grained carriers preferably used have a specific surface area of 50 to 1000 m ² / g, preferably 100 to 700 m ² / g. It is desirable that the pore volume is in the range of 0.3 to 2.5 cm ³ / g. The fine particle carrier may be 100 to 1000 as needed.
C., preferably at 150 to 700.degree.

Further, examples of the particulate carrier that can be used in the present invention include a granular or particulate solid of an organic compound having a particle size in the range of 10 to 300 μm. As these organic compounds, ethylene, propylene, 1-butene, 4-methyl-1-pentene and other (co) polymers mainly composed of α-olefins having 2 to 14 carbon atoms or vinylcyclohexane, A polymer or copolymer formed mainly with styrene can be exemplified.

(B) Organoaluminum Oxy Compound Usually, an organoaluminum oxy compound mainly comprises an alkylaluminum oxy compound represented by the following general formula (i) or (ii), and a small amount of an organoaluminum oxy compound such as trialkylaluminum. It is thought to contain.

[0074]

Embedded image

(In the formula, m is an integer of 2 or more, usually 2 to 50, and R represents a hydrocarbon group.) (B) The organoaluminum oxy compound is such that the hydrocarbon group bonded to the aluminum atom is methyl. An organic aluminum oxy compound comprising a group and at least one long-chain alkyl group selected from chain alkyl groups having 4 to 20 carbon atoms in the main chain, wherein (methyl group + long-chain alkyl group +
Other alkyl groups) / Aluminum atom (molar ratio)
(Hereinafter sometimes referred to as “R / Al ratio”) is 1.5 to
2.5, preferably in the range of 1.7 to 2.0, and a methyl group / (methyl group + long-chain alkyl group + other alkyl group) (molar ratio) (hereinafter referred to as “Me / R ratio”) Is 0.70 to 0.95, preferably 0.75 to 0.95.
It is in the range of 0.95.

Here, the chain alkyl group having 4 to 20 carbon atoms in the main chain includes carbon atoms such as n-butyl, n-hexyl, n-octyl, n-nonyl, n-dodecyl and n-tetradecyl. A linear alkyl group having 4 to 20 atoms; i-pentyl,
Examples include branched alkyl groups having 4 to 20 carbon atoms in the main chain, such as i-hexyl and i-hexadecyl. Among these, a linear alkyl group is preferable, and a linear alkyl group having 6 to 16 carbon atoms is particularly preferable. Other alkyl groups include an ethyl group, a propyl group, a chain alkyl group having more than 20 carbon atoms, and
To 20 cycloalkyl groups.

(B) The organic aluminum oxy compound is
R / Al in one molecule of alkyl aluminum oxy compound
The ratio and the Me / R ratio may be in the above range, and the R / Al ratio and the Me / R ratio of the mixture containing two or more alkylaluminum oxy compounds may be in the above range.

(B) The organoaluminum oxy compound is
When used for solution polymerization or suspension polymerization of olefins, dissolved in an aliphatic hydrocarbon or an alicyclic hydrocarbon,
It is added to the polymerization system as a solution of an aliphatic hydrocarbon or a solution of an alicyclic hydrocarbon. An organoaluminum oxy compound having an R / Al ratio and a Me / R ratio within the above ranges is represented by
Compared to an organoaluminum oxy compound having a / Al ratio or Me / R ratio outside the above range, it has excellent solubility in aliphatic hydrocarbons and alicyclic hydrocarbons, and is well dispersed in a polymerization system. When such an organoaluminum oxy compound is used as a catalyst component, it is considered to be excellent in olefin polymerization activity.

R / Al of organic aluminum oxy compound
The value of the ratio and the value of the Me / R ratio are measured as follows. [R / Al ratio, Me / R ratio] A prescribed amount of a solution of an organoaluminum oxy compound is charged into a device capable of quantifying the generated gas replaced with an inert gas. Here, the solution used is different from the compound generated by hydrolysis of the organic aluminum oxy compound. Next, excess water is added to hydrolyze the organic aluminum oxy compound. At this time, acidic or alkaline is preferable. The R / Al ratio and the Me / R ratio are determined from the gas generation amount, the gas layer composition, and the liquid composition after the charging is completed.

The organoaluminum oxy compound having such R / Al ratio and Me / R ratio in a specific range can be prepared, for example, by the following method. (1) Compounds containing water of adsorption or salts containing water of crystallization such as hydrated magnesium chloride, hydrated copper sulfate, hydrated aluminum sulfate, hydrated nickel sulfate, hydrated cerium chloride A method of adding an organoaluminum compound such as a trialkylaluminum to a suspension of a hydrocarbon medium of the above, and reacting the water of adsorption or water of crystallization with the organoaluminum compound. (2) A method in which water, ice, steam or a humidified inert gas is allowed to act directly 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 organic aluminum oxy compound is
It may contain a small amount of an organometallic component. The solvent or unreacted organic aluminum compound may be removed from the recovered solution of the organic aluminum oxy compound by distillation, and then redissolved in a solvent or suspended in a poor solvent for the organic aluminum oxy compound.

Specific examples of the organoaluminum compound used for preparing the organoaluminum oxy compound include trimethylaluminum and tri (long-chain alkyl) aluminum having a chain alkyl group having 4 to 20 carbon atoms in the main chain. Is mentioned.

In preparing the organoaluminum oxy compound, the following organoaluminum compounds other than trimethylaluminum and tri (long-chain alkyl) aluminum may be used in combination.

[0084] The organoaluminum compound represented by the following general formula (a), in _{^{R a m Al (OR b)}} 3-m ... (a) ( wherein, R ^a and R ^b, be the same as or different from each other It often represents a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms, and m is preferably a number satisfying 1.5 ≦ m ≦ 3.) An organic compound represented by the following general formula (b) aluminum compounds, in _{^{R a m AlX 3-m ...}} (b) ( wherein, R ^a is the number of 1 to 20 carbon atoms, preferably a hydrocarbon group of 1 or 5 to 16, X is a halogen atom, m is preferably 0 <m <3.) an organoaluminum compound represented by the following general formula (c), in _{^{R a m AlH 3-m ...}} (c) ( wherein, R ^a is the number of carbon atoms 1 -20, preferably 1 or 5-16 hydrocarbon groups, and m is preferably 2 ≦
m <3. ) Following general formula organoaluminum compound (d) represented by, in _{^{R a m Al (OR b)}} n X q ... (d) ( wherein, R ^a and R ^b may be the same or different from each other, X represents a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms, X represents a halogen atom, and m represents 0 <
m ≦ 3, n is a number of 0 ≦ n <3, q is a number of 0 ≦ q <3,
And m + n + q = 3. More specifically, such organoaluminum compounds are tri-n-alkylaluminums such as triethylaluminum and tri-n-butylaluminum; triisopropylaluminum, triisobutylaluminum, trisec-
Butyl aluminum, tri-tert-butyl aluminum,
Tri-2-methylbutylaluminum, tri3-methylbutylaluminum, tri2-methylpentylaluminum, tri3-methylpentylaluminum, tri4-methylpentylaluminum, tri2-methylhexylaluminum,
Tribranched alkyl aluminum such as tri-3-methylhexyl aluminum and tri-2-ethylhexyl aluminum; tricycloalkyl aluminum such as tricyclohexyl aluminum; triaryl aluminum such as triphenyl aluminum and tritolyl aluminum; dialkyl aluminum such as diisobutyl aluminum hydride Hydride; trialkenyl aluminum such as triisoprenyl aluminum; alkyl aluminum alkoxide such as isobutyl aluminum methoxide, isobutyl aluminum ethoxide and isobutyl aluminum isopropoxide; dialkyl aluminum alkoxide such as diethyl aluminum ethoxide and dibutyl aluminum butoxide; ethyl aluminum sesqui D Alkyl aluminum sesquialkoxides such as toxide and butyl aluminum sesquibutoxide; partially alkoxylated alkyl aluminum having an average composition represented by ^Ra _2.5 Al (OR ^b ) _0.5 ; diethyl aluminum (2,6-di- t-butyl-
4-methylphenoxide), ethyl aluminum bis (2,
6-di-t-butyl-4-methylphenoxide), diisobutylaluminum (2,6-di-t-butyl-4-methylphenoxide), isobutylaluminum bis (2,6-di-t-butyl-
Alkyl aluminum aryloxides such as 4-methylphenoxide); dialkyl aluminum halides such as diethyl aluminum chloride, dibutyl aluminum chloride and diethyl aluminum bromide; alkyl aluminum sesquihalides such as ethyl aluminum sesquichloride, butyl aluminum sesquichloride and ethyl aluminum sesquibromide Partially aluminum halides such as alkylaluminum dihalides such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide; dialkylaluminum hydrides such as diethylaluminum hydride, dibutylaluminum hydride; ethylaluminum dihydride, propyl Aluminum dihydride Other partially hydrogenated alkylaluminums such as any alkylaluminum dihydride; partially alkoxylated and halogenated alkylaluminums such as ethylaluminum ethoxychloride, butylaluminum butoxycyclolide, ethylaluminum ethoxybromide, etc. Can be.

Solvents used for preparing the organic aluminum oxy compound include aromatic hydrocarbons such as benzene, toluene, xylene, cumene and cymene, pentane,
Aliphatic hydrocarbons such as hexane, heptane, octane, decane, dodecane, hexadecane, and octadecane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane, and methylcyclopentane; petroleum fractions such as gasoline, kerosene, and gas oil; or Examples of the above-mentioned aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons include hydrocarbon solvents such as halides, especially chlorinated compounds and brominated compounds. Further, ethers such as ethyl ether and tetrahydrofuran can also be used. Among these solvents, aromatic hydrocarbons and aliphatic hydrocarbons are particularly preferred.

R / Al of organic aluminum oxy compound
The ratio is controlled by adjusting the ratio of the amount of the organoaluminum compound used in the preparation to the amount of oxygen source such as water of crystallization, water, and organotin oxide.

The organic aluminum oxy compound Me
The / R ratio is controlled by adjusting the ratio of the amount of trimethylaluminum and the amount of tri-long-chain alkylaluminum used in the preparation.

Polymerization Method In the present invention, (A) a transition metal compound as described above,
(B) An olefin is polymerized or copolymerized in the presence of a catalyst comprising an organic aluminum oxy compound. In the present invention, the olefin can be polymerized in a gas phase or a liquid phase, but the olefin is polymerized or copolymerized in an aliphatic hydrocarbon medium or an alicyclic hydrocarbon medium by a solution polymerization method or a suspension polymerization method. Polymerization is preferred. At the time of polymerization, (B) the organoaluminum oxy compound is dissolved in an aliphatic hydrocarbon or an alicyclic hydrocarbon and added to the polymerization system as a solution of an aliphatic hydrocarbon or a solution of an alicyclic hydrocarbon.

Specific examples of the aliphatic hydrocarbon include butane, isobutane, pentane, 3-methylpentane, hexane, octane, decane, dodecane, hexadecane, and octadecane. Specific examples of the alicyclic hydrocarbon include: Include cyclopentane, cyclohexane, methylcyclopentane, cyclooctane and the like. Of these, hexane and decane are preferred.

The organic aluminum oxy compound (B) may be an aliphatic hydrocarbon containing a trialkylaluminum in an amount of 0.01 to 10 times, preferably 0.1 to 5 times, the mole of an aluminum atom in the organic aluminum oxy compound. It can also be added to the polymerization system as a solution of an alicyclic hydrocarbon.

When such an aliphatic hydrocarbon or an alicyclic hydrocarbon is used as a polymerization medium and (B) an organoaluminum oxy compound is added to the polymerization system as a solution of an aliphatic hydrocarbon or a solution of an alicyclic hydrocarbon, A polymer having high polymerization activity and no aromatic hydrocarbon odor can be obtained. Also,
In the gas phase polymerization, when the (A) organoaluminum oxy compound is added to the polymerization system as a solution of an aliphatic hydrocarbon or a solution of an alicyclic hydrocarbon, a polymer having no aromatic hydrocarbon odor is obtained.

(B) An organic aluminum oxy compound is
When a solution of an aliphatic hydrocarbon or an alicyclic hydrocarbon containing a specific amount of trialkylaluminum is added to the polymerization system, the decrease in polymerization activity is further reduced.

The olefin used for the polymerization in the present invention includes ethylene, propylene, 1-butene, 1-pentene,
1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl- 1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-
Α-olefins having 2 to 20 carbon atoms such as hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene; styrene, dimethylstyrenes, allyl Aromatic vinyl compounds such as benzene, allyltoluenes, vinylnaphthalenes, and allylnaphthalenes; alicyclic vinyl compounds such as vinylcyclohexane, vinylcyclopentane, vinylcycloheptane, and allylnorbornane; cyclopentene, cycloheptene, norbornene, and 5-methyl 2-norbornene, tetracyclododecene, 2-methyl-1,4,5,8-
Cyclic olefins such as dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene; 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,5,9 A chain polyene having 4 to 20 carbon atoms such as -decatriene; and a cyclic polyene such as 5-ethylidene norbornene and dicyclopentadiene.

These olefins can be used alone or
It can be used in combination of more than one kind. In the present invention,
1 selected from α-olefins having 2 to 20 carbon atoms
It is preferable to polymerize at least one kind of α-olefin or to copolymerize propylene with at least one kind of α-olefin selected from α-olefins having 4 to 20 carbon atoms.

In the polymerization of olefin, the transition metal compound (A) is usually added in an amount of 10 ^-8 to 1 per liter of reaction volume.
0 ^-3 mol, used in an amount such preferably 10 ^-7 to 10 ^-4 mol.

(B) The organoaluminum oxy compound is
The molar ratio of the aluminum atom (Al) in (B) to the transition metal atom (M) in the transition metal compound (A) [(Al)
/ M] is usually 10 to 5000, preferably 20 to 20
It is used in such an amount as to give 00.

The polymerization temperature is usually from -50 to 200.
° C, preferably in the range of 0 to 170 ° C. The polymerization pressure is usually from normal pressure to 100 kg / cm ² , preferably from normal pressure to
Under a condition of 50 kg / cm ² , the polymerization reaction can be carried out by any of a batch system, a semi-continuous system, and a continuous system. Further, the polymerization can be performed in two or more stages having different reaction conditions.

The molecular weight of the obtained olefin polymer can be adjusted by adding hydrogen to the polymerization system or changing the polymerization temperature. After the polymerization, the produced polymer is separated from the polymerization medium by a conventionally known method,
By collecting and drying, a solid polymer can be obtained.

[0099]

The catalyst for olefin polymerization according to the present invention comprises:
In an aliphatic or alicyclic hydrocarbon medium,
When solution polymerization or suspension polymerization is performed, olefins can be polymerized or copolymerized with high activity.

The olefin polymerization method according to the present invention can polymerize or copolymerize an olefin with high activity,
And it has excellent safety and health. Further, the obtained polymer does not contain aromatic hydrocarbons and has no aromatic hydrocarbon odor, and thus can be used for food applications, medical applications, and the like.

[0101]

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.

[0102]

Example 1 Into a 2 liter stainless steel (SUS) autoclave at 23 ° C. sufficiently purged with nitrogen, 930 ml of hexane and 40 g of butene from which impurities had been removed were charged, and 1 mmol of triisobutylaluminum was added. Heat to 70 ° C, 70 ° C
Was applied, pressure was applied with propylene so that the total pressure became 7 kg / cm ² -G.

On the other hand, 0.01 mmol of rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride and methyl Hexane solution of n-hexyl group-containing methylalumoxane [Al content = 2.34 mol / l, molar ratio of methyl group to methyl group and n-hexyl group (methyl group / (Methyl group + n-hexyl group) = 0.76, and the molar ratio of methyl group / n-hexyl group to aluminum atom (methyl group + n-hexyl group / aluminum atom) = 1.93] is calculated as 3 in terms of Al atom.
and stirred with a rotator at 23 ° C. for 20 minutes. Note that MMAO does not substantially contain an alkyl group other than a methyl group and an n-hexyl group.

Thereafter, a mixture of rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride and MMAO was added to an autoclave at 70 ° C. and 7 kg / cm ² -G with Zr atoms. 0.002mmo
1 was injected with nitrogen. At this time, the toluene concentration in the polymerization solution was substantially 0 (less than 1 ppm, the same applies hereinafter). After the injection, the autoclave is maintained at 70 ° C. for 30 minutes,
The pressure was maintained just after the injection by propylene pressurization. After the specified time, 3 ml of methanol was injected into the autoclave with nitrogen to terminate the polymerization. As a result, 58 g of a propylene / butene copolymer having a propylene content of 81 mol% and an [η] of 1.8 dl / g were obtained.

[0105]

Comparative Example 1 A toluene solution of methylalumoxane containing no long-chain alkyl group [manufactured by Tosoh Akzo Co., Al content = 0.962 mo] was used in place of MMAO in Example 1.
1 / liter, molar ratio of methyl group to methyl group and long-chain alkyl group (methyl group / methyl group + long-chain alkyl group)
= 1.00, and a molar ratio of methyl group to aluminum atom (methyl group / aluminum atom) = 1.40], except that the same operation as in Example 1 was performed. At this time, the concentration of toluene in the polymerization solution is 620 ppm. As a result, the propylene content was 85 mol%, and [η] was 2.0 d.
42 g of a 1 / g propylene / butene copolymer was obtained.

[0106]

Example 2 A hexane solution of n-hexyl group-containing methylalumoxane [Al content = 2.47 mol] as MMAO
/ Liter, molar ratio of methyl group to methyl group and n-hexyl group (methyl group / methyl group + n-hexyl group) = 0.
83, the same operation as in Example 1 was carried out except that the molar ratio of methyl group and long-chain alkyl group to aluminum atom (methyl group + n-hexyl group / aluminum atom) = 1.90] was used. At this time, the toluene concentration in the polymerization solution was substantially 0. As a result, the propylene content was 85 mo.
Thus, 69 g of a propylene / butene copolymer having 1% and [η] of 1.8 dl / g were obtained.

[0107]

Example 3 A hexane solution of n-decyl group-containing methylalumoxane as MMAO [Al content = 2.56 mol /
Liter, molar ratio of methyl group to methyl group and n-decyl group (methyl group / methyl group + n-decyl group) = 0.84,
Molar ratio of methyl group and n-decyl group to aluminum atom (methyl group + n-decyl group / aluminum atom) = 1.
87], except that Example 87 was used. At this time, the toluene concentration in the polymerization solution was substantially 0. As a result, the propylene content was 85 mol%, [η]
Propylene / butene copolymer 5 whose is 1.8 dl / g
2 g were obtained.

[0108]

Example 4 A hexane solution of n-tetradecyl group-containing methylalumoxane as MMAO [Al content = 2.59 m
ol / liter, the molar ratio of methyl group to methyl group and n-tetradecyl group (methyl group / methyl group + n-tetradecyl group) = 0.85, the molar ratio of methyl group and n-tetradecyl group to aluminum atom (methyl Group + n-tetradecyl group / aluminum atom) = 1.98], and the same operation as in Example 1 was performed. At this time, the toluene concentration in the polymerization solution was substantially 0. As a result, 46 g of a propylene / butene copolymer having a propylene content of 85 mol% and an [η] of 1.9 dl / g was obtained.

[0109]

Example 5 A hexane solution of n-tetradecyl group-containing methylalumoxane as MMAO [Al content = 2.68 m
ol / liter, the molar ratio of methyl group to methyl group and n-tetradecyl group (methyl group / methyl group + n-tetradecyl group) = 0.91, the molar ratio of methyl group and n-tetradecyl group to aluminum atom (methyl Group + n-tetradecyl / aluminum atom) = 1.73], except that the same operation as in Example 1 was performed. At this time, the toluene concentration in the polymerization solution was substantially 0. As a result, 49 g of a propylene / butene copolymer having a propylene content of 83 mol% and an [η] of 1.8 dl / g was obtained.

[0110]

Example 6 A hexane solution of methylalumoxane containing i-hexadecyl group [Al content = 2.71 m
ol / liter, the molar ratio of methyl group to methyl group and i-hexadecyl group (methyl group / methyl group + i-hexadecyl group) = 0.95, the molar ratio of methyl group and long chain alkyl group to aluminum atom (methyl Group + i-hexadecyl group / aluminum atom) = 1.76], and the same operation as in Example 1 was performed. At this time, the toluene concentration in the polymerization solution was substantially 0. As a result, 66 g of a propylene / butene copolymer having a propylene content of 86 mol% and an [η] of 1.9 dl / g were obtained.

[0111]

Comparative Example 2 Instead of MMAO, a hexane solution of propyl group-containing methylalumoxane [Al content = 2.41 mol
1 / liter, molar ratio of methyl group to methyl group and propyl group (methyl group / methyl group + propyl group) = 0.7
0, molar ratio of methyl group and propyl group to aluminum atom (methyl group + propyl group / aluminum atom) =
2.03], except that 2.03] was used. At this time, the toluene concentration in the polymerization solution was substantially 0. As a result, the propylene content was 83 mol%,
27 g of a propylene / butene copolymer having [η] of 2.0 dl / g was obtained.

[0112]

Comparative Example 3 Instead of MMAO, a hexane solution of methylalumoxane containing an i-butyl group [Al content = 2.22 mol
1 / liter, molar ratio of methyl group to methyl group and i-butyl group (methyl group / methyl group + i-butyl group) = 0.7
2. Mole ratio of methyl group and i-butyl group to aluminum atom (methyl group + isobutyl group / aluminum atom)
= 2.01], except that the same operation as in Example 1 was performed. At this time, the concentration of toluene in the polymerization solution was substantially 0.
Met. As a result, the propylene content was 85 mol%,
27 g of a propylene / butene copolymer having [η] of 2.0 dl / g was obtained.

[0113] The propylene obtained in the above Examples 1 to 6
The butene copolymer had no aromatic hydrocarbon odor, whereas the propylene / butene copolymers obtained in Comparative Examples 1 to 3 had an aromatic hydrocarbon odor. Table 1 shows the above results.

[0114]

[Table 1]

[Brief description of the drawings]

FIG. 1 is an explanatory view showing a process for preparing an olefin polymerization catalyst according to the present invention.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Toshiyuki Tsutsui 1-2-2 Waki, Waki-machi, Kuga-gun, Yamaguchi Prefecture Inside Mitsui Chemicals Co., Ltd. 6-1-2 Ki, F term in Mitsui Chemicals, Inc. (reference) 4J028 AA01A AB00A AB01A AC01A AC10A AC28A BA00A BA01B BB00A BB01B BC25B EA01 EB02 EB03 EB04 EB15 EB17 EB18 EB21 EC01 FA02 FA03 GA26 GB01

Claims (4)

[Claims] 1. A transition metal compound of Group 4 of the Periodic Table containing a ligand having a cyclopentadienyl skeleton, and (B)
The hydrocarbon group bonded to the aluminum atom includes a methyl group and at least one kind of long-chain alkyl group selected from alkyl groups having 4 to 20 carbon atoms in the main chain, wherein (methyl group + long-chain alkyl group + Other alkyl group) / aluminum atom (molar ratio) in the range of 1.5 to 2.5, and methyl group / (methyl group + long-chain alkyl group + other alkyl group) (molar ratio) is 0. An olefin polymerization catalyst comprising an organoaluminum oxy compound in the range of 70 to 0.95. 2. The transition metal compound of Group 4 of the periodic table containing a ligand having a cyclopentadienyl skeleton is a transition metal compound represented by the following general formula (Ic).
The catalyst for olefin polymerization described in 1 above; (Wherein, M ¹ is a transition metal atom selected from the periodic group 4, R ¹¹ may be the same or different carbon atoms represents from 1 to 6 hydrocarbon group, R ^12, R ¹⁴ , R ¹⁵
And R ¹⁶ may be the same or different from each other, and represent a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and R ¹³ may be the same or different and have 6 carbon atoms. And X ¹ and X ² may be the same or different from each other, and may represent a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, or an oxygen-containing group. , A sulfur-containing group, a silicon-containing group, a hydrogen atom or a halogen atom, and Y ¹ is
Divalent hydrocarbon group having 1 to 20 carbon atoms, divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, divalent silicon-containing group, divalent germanium-containing group, divalent tin Containing group, -O-, -CO-, -S-, -SO-, -SO
_{2 -, - Ge -, -} Sn -, - NR 9 -, - P (R 9)
-, - P (O) ( R 9) -, - BR 9 - or -AlR
⁹ - [however, R ⁹ may be the same or different and are each a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom or a halogen atom There is]. ) 3. A method for polymerizing olefins, comprising polymerizing or copolymerizing olefins in the presence of the catalyst for olefin polymerization according to claim 1. Description: 4. The olefin polymerization method according to claim 3, wherein the organoaluminum oxy compound (B) is added to the polymerization system as a solution of an aliphatic hydrocarbon or an alicyclic hydrocarbon.