JP7767014B2 - Transition metal compound, catalyst for olefin polymerization, and method for producing olefin polymer - Google Patents

Description

The present invention relates to a novel transition metal compound, and more specifically to a novel transition metal compound that can be used as an olefin polymerization catalyst, an olefin polymerization catalyst containing the compound, and a method for producing an olefin polymer using the catalyst.

Catalysts consisting of a metallocene compound and a co-catalyst such as an organoaluminum oxy compound are known as catalysts for producing olefin polymers such as ethylene-α-olefin copolymers.

Transition metal compounds such as various types of metallocene compounds have been actively developed as such catalysts. For example, Patent Document 1 describes a transition metal compound (A) represented by the following general formula:

(In the formula, M represents a transition metal of Group 4 of the periodic table such as Ti, L represents a monovalent anionic ligand in which an element of Group 15 of the periodic table is a coordinating atom, X represents a halogen or the like, m represents an integer of 1 to 3, and R ¹ to R ⁵ represent hydrogen, a halogen, an alkyl group having 1 to 20 carbon atoms or the like.)

The publication also describes a process for producing a cyclic olefin copolymer by copolymerizing ethylene and/or an α-olefin having 3 to 20 carbon atoms with at least one cyclic olefin compound in the presence of a polymerization catalyst comprising one or more activators (B) selected from organoaluminum oxy compounds and organoboron compounds, and cites CpTi(t- _Bu2C =N) _Cl2 as a specific example of the transition metal compound (A), and Cp ^* Ti(2,6 ^-iPr2PhO ) _Cl2 as a comparative example. (Cp represents a cyclopentadienyl group, and Cp ^* represents ^an _η5 -pentamethylcyclopentadienyl group.)

On the other hand, Patent Document 2 discloses an example of the production of ultra-high molecular weight polyethylene using a complex having a Cp*[t-BuPN] _Cl2 skeleton.

JP 2007-63409 A Special Publication No. 2016-534165

However, when the transition metal compounds described in Patent Document 1 as metallocene compounds are used as catalysts for the polymerization of ethylene or α-olefins, it has been found that there is room for further improvement in terms of catalytic activity, copolymerizability, and the production of high-molecular-weight polymers.

Patent Document 2 does not disclose the polymerization reaction of ethylene using complexes other than those with the above structure. It also does not disclose the copolymerization of ethylene with other olefins. From this perspective, it is believed that there is room for further study of the polymerization activity and copolymerization performance.

In light of these conventional techniques, the present invention aims to provide novel transition metal compounds, particularly novel transition metal compounds that can be used as olefin polymerization catalysts suitable for various olefin polymerizations.

Another aspect of the present invention is to provide a highly active olefin polymerization catalyst capable of producing high-molecular-weight olefin polymers, as well as novel transition metal compounds that can be used in such olefin polymerization catalysts.

The present inventors have conducted research in light of the above-mentioned problems and objects, and have found that a compound having a specific half-metallocene structure exhibits favorable effects as an olefin polymerization catalyst, thereby completing the present invention. That is, the present invention has the following features.
[1] A transition metal compound represented by the following general formula [A-1]:

[In formula [A-1],
M is a titanium atom, a zirconium atom, or a hafnium atom;
n is an integer from 1 to 3,
X's each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a boron-containing group, an aluminum-containing group, or a diene-based divalent derivative group;
R ¹ to R ⁵ and R ⁶ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, or a phosphorus-containing group, and adjacent groups among R ¹ to R ⁵ may be bonded to each other to form a ring.
Furthermore, ^R7 and ^R8 are cyclic hydrocarbon groups.]

[2] The transition metal compound according to [1], represented by the following formula [A-2], in which R ⁷ and R ⁸ are 1-adamantyl groups.

[3] In the general formula [A-2],
The transition metal compound according to [2], wherein M is a titanium atom or a zirconium atom.
[4] In the general formula [A-2],
The transition metal compound according to [2], wherein M is a titanium atom.
[5] In the general formula [A-2], R ⁶ is an adamantyl group, [2] to [4].
1. The transition metal compound according to any one of claims 1 to 9.

[6] (A) a transition metal compound according to any one of [1] to [5];
(B) (B-1) organometallic compound,
(B-2) an organoaluminum oxy compound; and (B-3) at least one compound selected from the group consisting of compounds that react with the transition metal compound to form an ion pair.

[7] A method for producing an olefin polymer, comprising polymerizing an olefin in the presence of the olefin polymerization catalyst according to [6].
[8] The olefin is
(Z-1) The method for producing an olefin polymer according to [7], wherein the olefin is selected from olefins having 2 to 30 carbon atoms.

The transition metal compound of the present invention exhibits high activity when used as a catalyst in the polymerization or copolymerization of ethylene or olefins having 3 or more carbon atoms, and is characterized by producing high molecular weight polymers.

The transition metal compound according to the present invention is specified by the following structure. Furthermore, when the transition metal compound is used in an olefin polymerization reaction, it is preferable to use it in combination with an organometallic compound containing an element from Groups 1, 2, or 13 of the periodic table, such as an organoaluminum compound. Each component will be explained below.

[Transition metal compounds]
The transition metal compound of the present invention (hereinafter also referred to as transition metal compound (A)) is represented by the following general formula [A-1] and is specified by satisfying the following requirements.

In the formula [A-1], M is a titanium atom, a zirconium atom, or a hafnium atom.

The aforementioned M is a representative element of the so-called Group 4 elements of the periodic table, and is an element that is considered to have high anionic polymerizability. Among these, titanium and zirconium are preferred, and titanium is more preferred.

n is an integer of 1 to 3. When n is 2 or more, the groups represented by X may be the same or different and may be bonded to each other to form a ring.
X's each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a boron-containing group, an aluminum-containing group, or a diene-based divalent derivative group.

Preferably, each X is independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or an oxygen-containing group.
Specific examples of the halogen include fluorine, chlorine, bromine, and iodine, with chlorine or bromine being preferred.

R ¹ to R ⁵ and R ⁶ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, or a phosphorus-containing group, and adjacent groups among R ¹ to R ⁵ may be bonded to each other to form a ring.

Examples of hydrocarbon groups having 1 to 20 carbon atoms include alkyl groups having 1 to 20 carbon atoms, cyclic saturated hydrocarbon groups having 3 to 20 carbon atoms, linear unsaturated hydrocarbon groups having 2 to 20 carbon atoms, and cyclic unsaturated hydrocarbon groups having 3 to 20 carbon atoms.

Examples of alkyl groups having 1 to 20 carbon atoms include linear saturated hydrocarbon groups such as methyl, ethyl, n-propyl, allyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decanyl, and branched saturated hydrocarbon groups such as isopropyl, isobutyl, s-butyl, t-butyl, t-amyl, neopentyl, 3-methylpentyl, 1,1-diethylpropyl, 1,1-dimethylbutyl, 1-methyl-1-propylbutyl, 1,1-dipropylbutyl, 1,1-dimethyl-2-methylpropyl, 1-methyl-1-isopropyl-2-methylpropyl, and cyclopropylmethyl. The alkyl group preferably has 1 to 6 carbon atoms.

Examples of cyclic saturated hydrocarbon groups having 3 to 20 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornenyl, 1-adamantyl, and 2-adamantyl groups, as well as groups in which the hydrogen atoms of these cyclic saturated hydrocarbon groups are replaced with hydrocarbon groups having 1 to 17 carbon atoms, such as 3-methylcyclopentyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 4-cyclohexylcyclohexyl, and 4-phenylcyclohexyl. The number of carbon atoms in the cyclic saturated hydrocarbon group is preferably 5 to 11.

Examples of linear unsaturated hydrocarbon groups having 2 to 20 carbon atoms include alkenyl groups such as ethenyl (vinyl), 1-propenyl, 2-propenyl (allyl), and 1-methylethenyl (isopropenyl), and alkynyl groups such as ethynyl, 1-propynyl, and 2-propynyl (propargyl). The linear unsaturated hydrocarbon group preferably has 2 to 4 carbon atoms.

Examples of cyclic unsaturated hydrocarbon groups having 3 to 20 carbon atoms include cyclopentadienyl, norbornyl, phenyl, naphthyl, indenyl, azulenyl, phenanthryl, and anthracenyl groups; groups in which the hydrogen atoms of these cyclic unsaturated hydrocarbon groups are replaced with hydrocarbon groups having 1 to 15 carbon atoms, such as 3-methylphenyl (m-tolyl), 4-methylphenyl (p-tolyl), 4-ethylphenyl, 4-t-butylphenyl, 4-cyclohexylphenyl, biphenylyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, and 2,4,6-trimethylphenyl (mesityl); and groups in which the hydrogen atoms of linear or branched saturated hydrocarbon groups are replaced with cyclic saturated or unsaturated hydrocarbon groups having 3 to 19 carbon atoms, such as benzyl and cumyl. The cyclic unsaturated hydrocarbon group preferably has 6 to 10 carbon atoms.

Examples of alkylene groups having 1 to 20 carbon atoms include methylene, ethylene, dimethylmethylene (isopropylidene), ethylmethylene, 1-methylethylene, 2-methylethylene, 1,1-dimethylethylene, 1,2-dimethylethylene, and n-propylene. The alkylene group preferably has 1 to 6 carbon atoms.

Examples of arylene groups having 6 to 20 carbon atoms include o-phenylene groups, m-phenylene groups, p-phenylene groups, and 4,4'-biphenylylene groups. The number of carbon atoms in the arylene group is preferably 6 to 12.

Although aryl groups partially overlap with the examples of cyclic unsaturated hydrocarbon groups having 3 to 20 carbon atoms described above, examples include substituents derived from aromatic compounds, such as phenyl, 1-naphthyl, 2-naphthyl, anthracenyl, phenanthrenyl, tetracenyl, chrysenyl, pyrenyl, indenyl, azulenyl, pyrrolyl, pyridyl, furanyl, and thiophenyl. Phenyl and 2-naphthyl groups are preferred as aryl groups.

Examples of the aromatic compounds include aromatic hydrocarbons and heterocyclic aromatic compounds such as benzene, naphthalene, anthracene, phenanthrene, tetracene, chrysene, pyrene, indene, azulene, pyrrole, pyridine, furan, and thiophene.

Substituted aryl groups partially overlap with the examples of the cyclic unsaturated hydrocarbon groups having 3 to 20 carbon atoms described above, but include groups in which one or more hydrogen atoms of the aryl group have been substituted with a substituent selected from hydrocarbon groups having 1 to 20 carbon atoms, aryl groups, silicon-containing groups, nitrogen-containing groups, oxygen-containing groups, halogen atoms, and halogen-containing groups. Specific examples include 3-methylphenyl (m-tolyl), 4-methylphenyl (p-tolyl), 3-ethylphenyl, 4-ethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, biphenylyl, 4-(trimethylsilyl)phenyl, 4-aminophenyl, and the like. Examples of substituted aryl groups include 4-(dimethylamino)phenyl, 4-(diethylamino)phenyl, 4-morpholinylphenyl, 4-methoxyphenyl, 4-ethoxyphenyl, 4-phenoxyphenyl, 3,4-dimethoxyphenyl, 3,5-dimethoxyphenyl, 3-methyl-4-methoxyphenyl, 3,5-dimethyl-4-methoxyphenyl, 3-(trifluoromethyl)phenyl, 4-(trifluoromethyl)phenyl, 3-chlorophenyl, 4-chlorophenyl, 3-fluorophenyl, 4-fluorophenyl, 5-methylnaphthyl, and 2-(6-methyl)pyridyl. Substituted aryl groups also include the "electron-donating group-containing substituted aryl groups" described below.

Examples of silicon-containing groups include alkylsilyl groups such as trimethylsilyl, triethylsilyl, t-butyldimethylsilyl, and triisopropylsilyl, which are hydrocarbon groups having 1 to 20 carbon atoms in which a carbon atom has been replaced with a silicon atom; arylsilyl groups such as dimethylphenylsilyl, methyldiphenylsilyl, and t-butyldiphenylsilyl; pentamethyldisilanyl; and trimethylsilylmethyl. The alkylsilyl group preferably has 1 to 10 carbon atoms, and the arylsilyl group preferably has 6 to 18 carbon atoms.

Examples of the nitrogen-containing group include an amino group, a nitro group, an N-morpholinyl group, and a dimethylamino group, diethylamino group, dimethylaminomethyl group, cyano group, pyrrolidinyl group, piperidinyl group, pyridinyl group, etc., which are groups in which the = _CH- structural unit in the above-mentioned hydrocarbon group having 1 to 20 carbon atoms or silicon-containing group is replaced with a nitrogen atom, a group in which the _-CH2- structural unit is replaced with a nitrogen atom to which a hydrocarbon group having 1 to 20 carbon atoms is bonded, or a group in which the -CH3 structural unit is replaced with a nitrogen atom to which a hydrocarbon group having 1 to 20 carbon atoms is bonded or a nitrile group. Preferred nitrogen-containing groups are dimethylamino group and N-morpholinyl group.

The oxygen-containing group may be a hydroxyl group, or a group in which the -CH ₂ - structural unit in the above-mentioned hydrocarbon group having 1 to 20 carbon atoms, silicon-containing group or nitrogen-containing group is replaced with an oxygen atom or a carbonyl group, or a -CH Examples of groups in which _three structural units are replaced by oxygen atoms bonded to hydrocarbon groups having 1 to 20 carbon atoms include methoxy, ethoxy, t-butoxy, phenoxy, trimethylsiloxy, methoxyethoxy, hydroxymethyl, methoxymethyl, ethoxymethyl, t-butoxymethyl, 1-hydroxyethyl, 1-methoxyethyl, 1-ethoxyethyl, 2-hydroxyethyl, 2-methoxyethyl, 2-ethoxyethyl, n-2-oxabutylene, n-2-oxapentylene, n-3-oxapentylene, aldehyde, acetyl, propionyl, benzoyl, trimethylsilylcarbonyl, carbamoyl, methylaminocarbonyl, carboxy, methoxycarbonyl, carboxymethyl, ethoxymethyl, carbamoylmethyl, furanyl, and pyranyl. As the oxygen-containing group, a methoxy group is preferred.

Examples of halogen atoms include group 17 elements such as fluorine, chlorine, bromine, and iodine.
Examples of the halogen-containing group include a trifluoromethyl group, a tribromomethyl group, a pentafluoroethyl group, and a pentafluorophenyl group, which are groups in which a hydrogen atom in the above-mentioned hydrocarbon group, silicon-containing group, nitrogen-containing group, or oxygen-containing group having 1 to 20 carbon atoms is substituted with a halogen atom.

^R6 is preferably a cyclic saturated hydrocarbon group, and particularly preferably an adamantyl group.
The above R ⁷ and R ⁸ are cyclic hydrocarbon groups, preferably saturated cyclic hydrocarbon groups. Specific examples of the structures thereof include the same groups as the cyclic hydrocarbon groups exemplified for R ¹ to R ⁶ .

Among the above transition metal compounds, a complex having a structure represented by the following formula [A-2] in which R ⁷ and R ⁸ are adamantyl groups is a preferred example.

The symbols in formula [A-2] are as defined in formula [A-1].
Specific examples of the structure of the phosphinimine moiety in the above formula [A-2] are shown below.

As described below, the transition metal compounds of the present invention tend to exhibit higher polymerization activity and copolymerizability than conventional half-metallocene transition metal compounds. This makes it possible to produce polymers with a wide range of melting points, flexibility, and impact resistance.

When polymerizing the olefin using the transition metal compound (A), at least one compound selected from the group consisting of (B-1) organometallic compounds, (B-2) organoaluminum oxy-compounds, and (B-3) compounds that react with the transition metal compound (A) to form an ion pair can be used in combination with the transition metal compound (A). Each of these components is described below.

((B-1) Organometallic compound)
Specific examples of the organometallic compound (B-1) used in the present invention include compounds containing at least one element of Groups 1, 2, 12, and 13 of the periodic table, represented by the following general formulas (B-1a) to (B-1c):
R ^ap _Al (OR ^b ) _q H _r Y _s ...(B-1a)
an organoaluminum compound represented by general formula (B-1a), wherein R ^a and R ^b may be the same or different and represent a hydrocarbon group having 1 to 15, preferably 1 to 4, carbon atoms, Y represents a halogen atom, p represents a number that satisfies 0<p≦3, q represents a number that satisfies 0≦q<3, r represents a number that satisfies 0≦r<3, s represents a number that satisfies 0≦s<3, and m+n+p+q=3;
M ³ AlR ^c ₄ ...(B-1b)
(in general formula (B-1b), ^M3 represents Li, Na, or K, and ^Rc represents a hydrocarbon group having 1 to 15, preferably 1 to 4, carbon atoms;
R ^d R ^e M ⁴ ...(B-1c)
(In general formula (B-1c), R ^d and R ^e may be the same or different and represent a hydrocarbon group having 1 to 15, preferably 1 to 4, carbon atoms, and M ⁴ represents Mg, Zn, or Cd.)

Examples of the organoaluminum compound of the general formula (B-1a) include the following compounds.
R ^ap _Al (OR ^b ) _3-p ...(B-1a-1)
(in formula (B-1a-1), R ^a and R ^b may be the same or different and represent a hydrocarbon group having 1 to 15, preferably 1 to 4, carbon atoms, and p is preferably a number satisfying 1.5≦p≦3),
R ^ap _{AlY 3-p} ...(B-1a-2)
(in formula (B-1a-2), R ^a represents a hydrocarbon group having 1 to 15, preferably 1 to 4, carbon atoms, Y represents a halogen atom, and p is preferably a number satisfying 0<p<3),
R ^ap AlH _3-p ... ₍ B-1a-3)
(in formula (B-1a-3), R ^a represents a hydrocarbon group having 1 to 15, preferably 1 to 4, carbon atoms, and p is preferably a number satisfying 2≦p<3),
R ^ap _Al (OR ^b ) _q Y _s ...(B-1a-4)
(In formula (B-1a-4), R ^a and R ^b may be the same or different and represent a hydrocarbon group having 1 to 15, preferably 1 to 4, carbon atoms; Y represents a halogen atom; p is a number that satisfies 0<p≦3, q is a number that satisfies 0≦q<3, s is a number that satisfies 0≦s<3, and p+q+s=3.)

More specific examples of the organoaluminum compound of general formula (B-1a) include tri-n-alkylaluminum compounds such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, and tridecylaluminum;
tri-branched alkylaluminums such as triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylbutylaluminum, tri-2-methylpentylaluminum, tri-3-methylpentylaluminum, tri-4-methylpentylaluminum, tri-2-methylhexylaluminum, tri-3-methylhexylaluminum, and tri-2-ethylhexylaluminum;
tricycloalkylaluminums such as tricyclohexylaluminum and tricyclooctylaluminum;
triarylaluminum such as triphenylaluminum and tritolylaluminum;
dialkylaluminum hydrides such as diisobutylaluminum hydride;
trialkenylaluminum such as triisoprenylaluminum represented by (iC ₄ H ₉ ) _x Al _y (C ₅ H ₁₀ ) _z (wherein x, y, and z are positive numbers, and z≧2x);
alkylaluminum alkoxides such as isobutylaluminum methoxide, isobutylaluminum ethoxide, and isobutylaluminum isopropoxide;
dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide, and dibutylaluminum butoxide;
alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide;
partially alkoxylated alkylaluminums having an average composition represented by R ^a _2.5 Al(OR ^b ) _0.5 (wherein R ^a and R ^b may be the same or different and represent a hydrocarbon group having 1 to 15, preferably 1 to 4, carbon atoms);
dialkylaluminum aryloxides such as diethylaluminum phenoxide, diethylaluminum (2,6-di-t-butyl-4-methylphenoxide), ethylaluminum bis(2,6-di-t-butyl-4-methylphenoxide), diisobutylaluminum (2,6-di-t-butyl-4-methylphenoxide), and isobutylaluminum bis(2,6-di-t-butyl-4-methylphenoxide);
dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, and diisobutylaluminum chloride;
alkylaluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, and ethylaluminum sesquibromide;
partially halogenated alkylaluminums such as alkylaluminum dihalides such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide, etc.;
Dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride;
Other partially hydrogenated alkylaluminums, such as alkylaluminum dihydrides, such as ethylaluminum dihydride and propylaluminum dihydride;
Examples include partially alkoxylated and halogenated alkylaluminums such as ethylaluminum ethoxychloride, butylaluminum butoxychloride, and ethylaluminum ethoxybromide.

Compounds similar to (B-1a) can also be used in the present invention, such as organoaluminum compounds in which two or more aluminum compounds are bonded via nitrogen atoms, such as ( _C2H5 ) _{2AlN ( C2H5 )} Al( _{C2H5 ) 2} .

Examples of the compound belonging to the general formula (B-1b) include LiAl(C ₂ H ₅ ) ₄ and LiAl(C ₇ H ₁₅ ) ₄ .

Examples of compounds belonging to the general formula (B-1c) include dimethyl magnesium, diethyl magnesium, dibutyl magnesium, butylethyl magnesium, dimethyl zinc, diethyl zinc, diphenyl zinc, di-n-propyl zinc, diisopropyl zinc, di-n-butyl zinc, diisobutyl zinc, bis(pentafluorophenyl)zinc, dimethyl cadmium, and diethyl cadmium.

Other examples of the organometallic compound (B-1) that can be used include methyllithium, ethyllithium, propyllithium, butyllithium, methylmagnesium bromide, methylmagnesium chloride, ethylmagnesium bromide, ethylmagnesium chloride, propylmagnesium bromide, propylmagnesium chloride, butylmagnesium bromide, and butylmagnesium chloride.

Also, compounds that form the above-mentioned organoaluminum compound in the polymerization system, such as a combination of aluminum halide and alkyllithium, or a combination of aluminum halide and alkylmagnesium, can be used as the organometallic compound (B-1).

Among the organometallic compounds (B-1), organoaluminum compounds are preferred from the viewpoint of catalytic activity.
The organometallic compounds (B-1) may be used singly or in combination of two or more.

((B-2) Organoaluminum oxy compound)
The organoaluminum oxy compound (B-2) used in the present invention may be a conventionally known aluminoxane, or may be a benzene-insoluble organoaluminum oxy compound such as those exemplified in JP-A-2-78687.

Conventionally known aluminoxanes can be produced, for example, by the following method, and are usually obtained as a solution in a hydrocarbon solvent.
(1) A method in which an organoaluminum compound such as trialkylaluminum is added to a hydrocarbon medium suspension of a compound containing adsorbed water or a salt containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, or cerous chloride hydrate, to react the adsorbed water or water of crystallization with the organoaluminum compound.

(2) A method in which water, ice, or water vapor is directly reacted with an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether, or tetrahydrofuran.

(3) A method in which an organoaluminum compound such as trialkylaluminum is reacted 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. After the solvent or unreacted organoaluminum compound is removed by distillation from the recovered aluminoxane solution, the resulting aluminoxane may be redissolved in a solvent or suspended in a poor solvent for the aluminoxane.

Specific examples of organoaluminum compounds used in preparing aluminoxanes include the same organoaluminum compounds as those exemplified as organoaluminum compounds belonging to general formula (B-1a) above.

Of these, trialkylaluminum and tricycloalkylaluminum are preferred, and trimethylaluminum is particularly preferred.
The organoaluminum compounds as described above may be used singly or in combination of two or more.

Solvents that can be used in preparing aluminoxanes include aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and cymene; aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, and octadecane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane, and methylcyclopentane; petroleum fractions such as gasoline, kerosene, and diesel; and hydrocarbon solvents such as halides of the above aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons, especially chlorinated and brominated derivatives. Ethers such as ethyl ether and tetrahydrofuran can also be used. Of these solvents, aromatic hydrocarbons and aliphatic hydrocarbons are particularly preferred. These solvents can be used alone or in combination.

The organoaluminum oxy compound (B-2) according to the present invention may be selected from at least one of aluminoxanes having a structure represented by the following general formula (B-2a) or (B-2b), and aluminoxanes having a structure comprising a repeating unit represented by the following general formula (B-2c) and a repeating unit represented by the following general formula (B-2d).

(In the general formula, R ^c 's are each independently a hydrocarbon group having 1 to 10, preferably 1 to 4, carbon atoms. Specific examples include hydrocarbon groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an isopropenyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group, an eicosyl group, a cyclohexyl group, a cyclooctyl group, a phenyl group, a tolyl group, and an ethylphenyl group. Of these examples, a methyl group, an ethyl group, and an isobutyl group are preferred, and a methyl group is particularly preferred. In the general formulae (B-2a), (B-2b), and (B-2c), a part of R ^c's may be substituted with a halogen atom such as chlorine or bromine, and the halogen content may be 40% by weight or less.)

In the general formulae (B-2a) and (B-2b), r represents an integer of 2 to 500, preferably 6 to 300, and particularly preferably 10 to 100.
In the general formulae (B-2c) and (B-2d), s and t each represent an integer of 1 or more.

The aluminoxane having a repeating unit represented by the general formula (B-2c) and a repeating unit represented by the general formula (B-2d) preferably has a molecular weight in the range of 200 to 2,000 as measured by cryoscopic method in benzene.

The benzene-insoluble organoaluminum oxy-compounds used in this invention are preferably those in which the Al content in benzene at 60°C is typically 10% or less, preferably 5% or less, and particularly preferably 2% or less, calculated as Al atoms. In other words, they are preferably insoluble or poorly soluble in benzene.)

The organoaluminum oxy compound (B-2) used in the present invention may also include a boron-containing organoaluminum oxy compound represented by the following general formula (B-2e):

(In general formula (B-2e), R ¹⁵ represents a hydrocarbon group having 1 to 10 carbon atoms, and four R ¹⁶ may be the same or different and each independently represents a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 10 carbon atoms.)

The boron-containing organoaluminum oxy compound represented by the general formula (B-2e) can be produced by reacting an alkylboronic acid represented by the following general formula (B-2f) with an organoaluminum compound in an inert solvent under an inert gas atmosphere at a temperature between -80°C and room temperature for 1 minute to 24 hours.

R ¹⁵ -B (OH) ₂ ... (B-2f)
(In formula (B-2f), R ¹⁵ represents the same group as R ¹⁵ in formula (B-2e).)

Specific examples of alkylboronic acids represented by general formula (B-2f) 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, and 3,5-bis(trifluoromethyl)phenylboronic acid. Of these, methylboronic acid, n-butylboronic acid, isobutylboronic acid, 3,5-difluorophenylboronic acid, and pentafluorophenylboronic acid are preferred. These may be used alone or in combination of two or more.

Specific examples of organoaluminum compounds to be reacted with such alkylboronic acids include the same organoaluminum compounds as those exemplified as organoaluminum compounds belonging to general formula (B-1a) above.

The organoaluminum compound is preferably a trialkylaluminum or a tricycloalkylaluminum, with trimethylaluminum, triethylaluminum, or triisobutylaluminum being particularly preferred. These may be used alone or in combination of two or more.

When an organoaluminum oxy compound (B-2) such as methylaluminoxane is used as a co-catalyst component in addition to the transition metal compound (A), a very high polymerization activity for olefin compounds is exhibited.
The organoaluminum oxy compounds (B-2) may be used singly or in combination of two or more.

((B-3) Compound that reacts with transition metal compound (A) to form an ion pair)
Examples of the compound (B-3) (hereinafter referred to as "ionizing ionic compound") used in the present invention that reacts with the transition metal compound (A) to form an ion pair include Lewis acids, ionic compounds, borane compounds, and carborane compounds described in JP-A Nos. 1-501950 and 1-502036, JP-A Nos. 3-179005, 3-179006, 3-207703, and 3-207704, and U.S. Pat. No. 5,321,106. Further examples include heteropoly compounds and isopoly compounds.

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

Examples of the ionic compound include compounds represented by the following general formula (B-3a):

(In general formula (B-3a), R ¹⁷ represents H ⁺ , a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptyltrienyl cation, or a ferrocenium cation having a transition metal, and R ¹⁸ to R ²¹ may be the same or different and represent an organic group, preferably an aryl group or a substituted aryl group.)

Specific examples of the carbonium cation include tri-substituted carbonium cations such as triphenylcarbonium cation, tri(methylphenyl)carbonium cation, and tri(dimethylphenyl)carbonium cation.

Specific examples of the ammonium cation include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, tributylammonium cation, and tri(n-butyl)ammonium cation; N,N-dialkylanilinium cations such as N,N-dimethylanilinium cation, N,N-diethylanilinium cation, and N,N-2,4,6-pentamethylanilinium cation; and 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.

As R ¹⁷ , a carbonium cation or an ammonium cation is preferred, and a triphenylcarbonium cation, an N,N-dimethylanilinium cation, or an N,N-diethylanilinium cation is particularly preferred.

Other ionic compounds include trialkyl-substituted ammonium salts, N,N-dialkylanilinium salts, dialkylammonium salts, and triarylphosphonium salts.

Specific examples of the trialkyl-substituted ammonium salt include 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, and tri(n-butyl)ammonium tetra(o-tolyl)boron.

Specific examples of the N,N-dialkylanilinium salt include N,N-dimethylanilinium tetra(phenyl)boron, N,N-diethylanilinium tetra(phenyl)boron, and N,N,2,4,6-pentamethylanilinium tetra(phenyl)boron.

Specific examples of the dialkylammonium salt include di(1-propyl)ammonium tetra(pentafluorophenyl)boron and dicyclohexylammonium tetra(phenyl)boron.

Further examples of ionic compounds include triphenylcarbenium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, ferrocenium tetra(pentafluorophenyl)borate, triphenylcarbenium pentaphenylcyclopentadienyl complex, N,N-diethylanilinium pentaphenylcyclopentadienyl complex, and boron compounds represented by the following formula (B-3b) or (B-3c):

(In formula (B-3b), Et represents an ethyl group.)

(In formula (B-3c), Et represents an ethyl group.)

Specific examples of borane compounds, which are examples of ionizable ionic compounds (compound (B-3)), include decaborane;
Salts of anions such as bis[tri(n-butyl)ammonium]nonaborate, bis[tri(n-butyl)ammonium]decaborate, bis[tri(n-butyl)ammonium]undecaborate, bis[tri(n-butyl)ammonium]dodecaborate, bis[tri(n-butyl)ammonium]decachlorodecaborate, and bis[tri(n-butyl)ammonium]dodecachlorododecaborate;
Examples include salts of metal borane anions such as tri(n-butyl)ammonium bis(dodecahydride dodecaborate)cobaltate(III) and bis[tri(n-butyl)ammonium]bis(dodecahydride dodecaborate)nickelate(III).

Specific examples of carborane compounds, which are examples of ionizable ionic compounds, include 4-carbanonaborane, 1,3-dicarbanonaborane, 6,9-dicarbadecaborane, dodecahydride-1-phenyl-1,3-dicarbanonaborane, dodecahydride-1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarbaundecaborane, 2,7-dicarbaundecaborane, and undecahydride-7,8-dimethyl-1,3-dicarbanonaborane. methyl-7,8-dicarboxundecaborane, dodecahydride-11-methyl-2,7-dicarboxundecaborane, 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 tri(n-butyl)ammonium 6-carbadecaborate, tri(n-butyl)ammonium 6-carbadecaborate, tri(n-butyl)ammonium 7-carbaundecaborate, tri(n-butyl)ammonium 7,8-dicarboxaundecaborate, tri(n-butyl)ammonium 2,9-dicarboxaundecaborate, tri(n-butyl)ammonium dodecahydride-8-methyl-7,9-dicarboxaundecaborate, tri(n-butyl)ammonium undecahydride-8-ethyl-7,9-dicarboxaundecaborate Salts of anions such as undecahydride-8-butyl-7,9-dicarboxamdecaborate, tri(n-butyl)ammonium undecahydride-8-allyl-7,9-dicarboxamdecaborate, tri(n-butyl)ammonium undecahydride-9-trimethylsilyl-7,8-dicarboxamdecaborate, and tri(n-butyl)ammonium undecahydride-4,6-dibromo-7-carbaundecaborate;
Tri(n-butyl)ammonium bis(nonahydride-1,3-dicarbanonaborate)cobaltate(III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbandecaborate)ferrate(III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbandecaborate)cobaltate(III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbandecaborate)nickelate(III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbandecaborate)cuprate(III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbandecaborate)aurate(III), tri(n-butyl)ammonium bis(nonahydride-7,8-dimethyl-7,8-dicarbandecaborate)ferrate salt (III), tri(n-butyl)ammonium bis(nonahydride-7,8-dimethyl-7,8-dicarboxamdecaborate)chromate (III), tri(n-butyl)ammonium bis(tribromooctahydride-7,8-dicarboxamdecaborate)cobaltate (III), tris[tri(n-butyl)ammonium]bis(undecahydride-7-carboudecaborate)chromate (III), bis[tri(n-butyl)ammonium]bis(undecahydride-7-carboudecaborate)manganate (IV), bis[tri(n-butyl)ammonium]bis(undecahydride-7-carboudecaborate)cobaltate (III), and bis[tri(n-butyl)ammonium]bis(undecahydride-7-carboudecaborate)nickelate (IV).

Heteropoly compounds, which are examples of ionizable ionic compounds, are compounds containing atoms selected from silicon, phosphorus, titanium, germanium, arsenic, and tin, and one or more atoms selected from vanadium, niobium, molybdenum, and tungsten. Specific examples include, but are not limited to, phosphovanadic acid, germanovanadic acid, arsenic vanadic acid, phosphoniobic acid, germanoniobic acid, siliconomolybdic acid, phosphomolybdic acid, titanomolybdic acid, germanomolybdic acid, arsenic molybdic acid, tinmolybdic acid, phosphotungstic acid, germanotungstic acid, tintungstic acid, phosphomolybdovanadic acid, phosphotungstovanadic acid, germanotungstovanadic acid, phosphomolybdotungstovanadic acid, germanomolybdotungstovanadic acid, phosphomolybdotungstic acid, phosphomolybdoniobic acid, and salts of these acids. Examples of the salts include salts of the acids with, for example, alkali metals of Group 1 or alkaline earth metals of Group 2 of the periodic table, specifically, lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, etc., as well as organic salts such as triphenylethyl salts.

Isopoly compounds, an example of ionized ionic compounds, are compounds composed of metal ions of one type of atom selected from vanadium, niobium, molybdenum, and tungsten, and can be considered to be molecular ionic species of metal oxides. Specific examples include, but are not limited to, vanadic acid, niobic acid, molybdic acid, tungstic acid, and salts of these acids. Furthermore, examples of the salts include salts of the acids with metals from Group 1 or 2 of the periodic table, such as lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, and barium, as well as organic salts such as triphenylethyl salts.

The above-mentioned ionizing ionic compound (compound (B-3) which reacts with the transition metal compound (A) to form an ion pair) may be used singly or in combination of two or more kinds.
The olefin polymerization catalyst according to the present invention may contain the above-mentioned transition metal compound (A) (hereinafter may be abbreviated as "component (A)"), and at least one compound (B) (hereinafter may be abbreviated as "component (B)") selected from the group consisting of organometallic compounds (B-1), organoaluminum oxy compounds (B-2), and ionizing ionic compounds (B-3), and may also contain the following carrier (C), if necessary.

(C) Carrier
The carrier (C) used in the present invention is an inorganic or organic compound, and is a granular or fine particle solid. By supporting the transition metal compound (A) and the compound (B) on the carrier (C), a polymer with good morphology can be obtained.

The inorganic compound is preferably a porous oxide, a solid aluminoxane compound, an inorganic halide, clay, a clay mineral, or an ion-exchangeable layered compound.
Specific examples of the porous oxide that can _{be used include SiO2, Al2O3, MgO, ZrO, TiO2, B2O3 , CaO , ZnO ,} BaO, and _ThO2 , as well as composites or mixtures containing these, and further examples of natural or synthetic zeolites include SiO2 _{- MgO} , _SiO2 - _Al2O3 , SiO2 _{- TiO2} , _SiO2 - _V2O5 , _{SiO2 - Cr2O3} , and _SiO2 - _{TiO2 - MgO} . Of these, porous oxides containing _SiO2 and/or _Al2O3 as the main component are preferred.

The porous oxide may contain small amounts of _carbonates , sulfates, nitrates _, and oxides such as _Na2CO3 , _{K2CO3 , CaCO3} , _MgCO3 , _Na2SO4 , _Al2 ( _SO4 ) ₃ , _BaSO4 , _KNO3 , Mg( _NO3 ) ₂ , Al( _NO3 ) ₃ , _Na2O , _K2O , and _Li2O .

The properties of such porous oxides vary depending on the type and production method, but the porous oxides preferably used in the present invention have a particle size of 10 to 300 μm, preferably 20 to 200 μm, a specific surface area of 50 to 1000 ^m /g, preferably 100 to 700 ^m /g, and a pore volume of 0.3 to 3.0 ^cm /g. Such porous oxides are calcined, if necessary, at 100 to 1000°C, preferably 150 to 700°C before use.

The solid aluminoxane compound may be selected from at least one of the aluminoxanes shown in (B-2a) to (B-2d).
The solid aluminoxane used in the present invention differs from conventionally known olefin polymerization catalyst supports in that it does not contain inorganic solid components such as silica or alumina or organic polymer components such as polyethylene or polystyrene, but rather refers to a solidified product containing an alkylaluminum compound as the main component. The term "solid" as used in the present invention means that the aluminoxane component (B-2) remains substantially solid under the reaction environment in which it is used. More specifically, it refers to the fact that, for example, when component (A) and component (B) are contacted to prepare a solid catalyst component for olefin polymerization as described below, component (B) remains solid under specific temperature and pressure conditions in an inert hydrocarbon solvent such as hexane or toluene used in the reaction. Furthermore, when suspension polymerization is performed using a solid catalyst component for olefin polymerization prepared using component (B) as described below, it is also necessary that component (B) contained in the catalyst component remains solid under specific temperature and pressure conditions in a hydrocarbon solvent such as hexane, heptane, or toluene. The same applies to bulk polymerization in which polymerization is performed in a liquefied monomer instead of a solvent, or gas-phase polymerization in which polymerization is performed in a monomer gas.

While visual inspection is the most convenient method for determining whether component (B) is in a solid state under the above-described conditions, visual inspection is often difficult, for example during polymerization. In such cases, it is possible to determine this from the properties of the polymer powder obtained after polymerization and the state of adhesion to the reactor. Conversely, if the polymer powder has good properties and adhesion to the reactor is minimal, the spirit of this invention does not deviate from the scope of this invention even if some of component (B) leaches out under the polymerization environment. Indicators for determining the properties of the polymer powder include bulk density, particle shape, surface shape, and the presence of amorphous polymers, but polymer bulk density is preferred from the perspective of quantitative accuracy. In this invention, the bulk density is typically 0.01 to 0.9, preferably 0.05 to 0.6, and more preferably 0.1 to 0.5.

The solid aluminoxane used in the present invention has a solubility in n-hexane maintained at 25°C of typically 0 to 40 mol%, preferably 0 to 20 mol%, and particularly preferably 0 to 10 mol%.

The solubility of the solid aluminoxane used in this invention in n-hexane was determined by adding 2 g of the solid aluminoxane carrier to 50 ml of n-hexane maintained at 25°C, stirring for 2 hours, separating the solution using a G-4 glass filter, and measuring the aluminum concentration in the filtrate. Therefore, the solubility is determined as the ratio of aluminum atoms present in the filtrate to the amount of aluminum atoms equivalent to 2 g of aluminoxane used.

The solid aluminoxane of the present invention can be any known solid aluminoxane. Examples of known production methods include those described in JP-B No. 7-42301, JP-A No. 6-220126, JP-A No. 6-220128, JP-A No. 11-140113, JP-A No. 11-310607, JP-A No. 2000-38410, JP-A No. 2000-95810, and WO 2010/55652.

The average particle size of the solid aluminoxane according to the present invention is generally in the range of 0.01 to 50,000 μm, preferably 1 to 1,000 μm, and particularly preferably 1 to 200 μm.
The average particle size of solid aluminoxane is determined by observing the particles with a scanning electron microscope, measuring the particle sizes of 100 or more particles, and averaging the weights. The particle size of solid aluminoxane is determined by measuring the maximum length using the Pythagorean method from the particle image. That is, the length between two parallel lines in the horizontal and vertical directions of the particle image is measured, and the average particle size is calculated using the following formula:
Grain size = ((horizontal length) ² + (vertical length) ² ) ^0.5

The weight average particle size of the solid aluminoxane can be calculated using the particle size calculated above according to the following formula.
Average particle size=Σnd ⁴ /Σnd ³ (where n is the number of particles, and d is the particle size)

The solid aluminoxane preferably used in the present invention has a specific surface area of 50 to 1000 m ²
The surface area is preferably 100 to 800 m ² /g, and the pore volume is preferably 0.1 to 2.5 cm ³ /g.

Examples of inorganic halides that can be used include _MgCl2 , _MgBr2 , _MnCl2 , and _MnBr2 . The inorganic halides may be used as they are or may be pulverized using a ball mill or a vibration mill. Alternatively, the inorganic halides may be dissolved in a solvent such as alcohol and then precipitated into fine particles using a precipitating agent.

The clay is usually composed primarily of clay minerals. The ion-exchangeable layered compounds are compounds with a crystalline structure in which planes formed by ionic bonds or the like are stacked parallel to one another with weak bonding forces, and the ions they contain are exchangeable. Most clay minerals are ion-exchangeable layered compounds. These clays, clay minerals, and ion-exchangeable layered compounds are not limited to naturally occurring substances; synthetic compounds can also be used.

Examples of clay, clay minerals, or ion-exchangeable layered compounds include ionic crystalline compounds having layered crystal structures such as hexagonal close packing type, antimony type, CdCl ₂ type, and CdI ₂ type.

Furthermore, examples of clay and clay minerals include kaolin, bentonite, kibushi clay, gairome clay, allophane, hisingerite, pyrophyllite, ummo group, montmorillonite group, vermiculite, ryokudeite group, palygorskite, kaolinite, nacrite, dickite, halloysite, etc.
Examples of ion-exchange layered compounds include α-Zr(HAsO ₄ ) ₂ ·H ₂ O, α-Zr(HP
Examples _{of the crystalline acid salts include} crystalline acid salts _{of polyvalent} metals _{such as} α-Zr( _{KPO4 )2 ,} α-Zr( _KPO4 )2.3H2O, α-Ti(HPO4) ₂ , α- _Ti ( _HAsO4 )2.H2O, α-Sn(HPO4) _2.H2O , γ-Zr( _HPO4 ) ₂ , γ- _Ti (HPO4) ₂ , and _γ -Ti( _NH4PO4 ) _2.H2O .

Such clays, clay minerals, or ion-exchangeable layered compounds preferably have a pore volume of 0.1 cc/g or more, particularly preferably 0.3 to 5 cc/g, having a radius of 20 Å or more, as measured by mercury intrusion porosimetry. Here, the pore volume is measured by mercury intrusion porosimetry using a mercury porosimeter over a pore radius range of 20 to 30,000 Å.
When a carrier having a pore volume of less than 0.1 cc/g with a radius of 20 Å or more is used, it tends to be difficult to obtain high polymerization activity.

It is also preferable to chemically treat the clay and clay minerals used in the present invention. Chemical treatments include surface treatments that remove impurities from the surface and treatments that affect the crystalline structure of the clay. Specific examples of chemical treatments include acid treatment, alkali treatment, salt treatment, and organic treatment. Acid treatment not only removes surface impurities, but also increases the surface area by eluting cations such as Al, Fe, and Mg from the crystalline structure. Alkali treatment destroys the crystalline structure of the clay, resulting in structural changes. Salt treatment and organic treatment form ionic complexes, molecular complexes, and organic derivatives, which can change the surface area and interlayer distance.

The ion-exchangeable layered compound used in the present invention may be a layered compound in which the interlayer spacing is expanded by utilizing the ion exchange property and replacing the interlayer exchangeable ions with other large, bulky ions. Such bulky ions act as supports supporting the layered structure and are commonly called pillars. The introduction of another substance between the layers of a layered compound is called intercalation. Examples of intercalating guest compounds include cationic inorganic compounds such as _TiCl4 and _ZrCl4 , metal alkoxides such as Ti(OR) ₄ , Zr(OR) ₄ , PO(OR) ₃ , and B(OR) ₃ (where R is a hydrocarbon group, etc.), and metal hydroxide ions such as [ _Al13O4 ( _OH ) ₂₄ ] ⁷⁺ , [ _Zr4 (OH) ₁₄ ] ²⁺ , and [ _Fe3O ( _OCOCH3 ) ₆ ] ⁺ . These compounds can be used alone or in combination of two or more. Furthermore, when intercalating these compounds, polymers obtained by hydrolysis of metal alkoxides (where R represents a hydrocarbon group, etc.) such as Si(OR) ₄ , Al(OR) ₃ , and Ge(OR) _{4 ,} and colloidal inorganic compounds such as SiO ₂ can also be present. Examples of pillars include oxides produced by intercalating the above metal hydroxide ions between layers and then dehydrating them with heat.

The clays, clay minerals, and ion-exchange layered compounds used in the present invention may be used as is, or may be used after treatment such as ball milling or sieving. They may also be used after adding and adsorbing new water or after heat dehydration treatment. Furthermore, they may be used alone or in combination of two or more types.

Of these, clay or clay minerals are preferred, and montmorillonite, vermiculite, pectolite, taeniolite and synthetic mica are particularly preferred.
As described above, the carrier (C) is an inorganic or organic compound, and examples of the organic compound include granular or fine particle solids having a particle size in the range of 10 to 300 μm. Specific examples include (co)polymers produced mainly from an α-olefin having 2 to 14 carbon atoms, such as ethylene, propylene, 1-butene, and 4-methyl-1-pentene, or (co)polymers produced mainly from vinylcyclohexane or styrene, and modified products thereof.

The olefin polymerization catalyst according to the present invention may contain, in addition to the above-mentioned transition metal compound (A), the above-mentioned compound (B), and, if necessary, the support (C), the following specific organic compound component (D) as required.

[(D) Organic compound component]
In the present invention, the organic compound component (D) is used, if necessary, for the purpose of improving the polymerization performance of the olefin polymerization catalyst of the present invention and the physical properties of the produced polymer (for example, the molecular weight of the produced polymer) (increasing the molecular weight, in the case of molecular weight). Examples of such organic compounds include, but are not limited to, alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, and sulfonates.

The alcohols and phenolic compounds are usually represented by R ²² -OH, where R ²² represents a hydrocarbon group having 1 to 50 carbon atoms (6 to 50 carbon atoms in the case of phenols) or a halogenated hydrocarbon group having 1 to 50 carbon atoms (6 to 50 carbon atoms in the case of phenols).

As the alcohols, those in which R ²² is a halogenated hydrocarbon group are preferred, and as the phenolic compounds, those in which the α,α'-positions of the hydroxyl group are substituted with hydrocarbons having 1 to 20 carbon atoms are preferred.

The carboxylic acid is usually represented by ^R23 -COOH, where ^R23 represents a hydrocarbon group having 1 to 50 carbon atoms or a halogenated hydrocarbon group having 1 to 50 carbon atoms, and a halogenated hydrocarbon group having 1 to 50 carbon atoms is particularly preferred.

As the phosphorus compound, phosphoric acids having a P—O—H bond, phosphates having a P—O bond, P—R, P═O bond, and phosphine oxide compounds are preferably used.
Examples of the sulfonate include those represented by the following general formula (Da).

(In general formula (D-a), ^M5 is an atom of Groups 1 to 14 of the periodic table; ^R24 is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms; Z is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms; t is an integer of 1 to 7; u is an integer of 1 to 7; and t-u≧1.)

<Method of producing olefin polymer>
The method for producing an olefin polymer according to the present invention includes a step of polymerizing or copolymerizing an olefin in the presence of the above-mentioned olefin polymerization catalyst to obtain an olefin polymer. As mentioned above, in this specification, the term "olefin" refers to any compound having a polymerizable double bond.

In the polymerization, the components constituting the catalyst of the present invention may be used in any manner and added to the polymerization vessel in any order, but the following methods are exemplified.
(1) A method in which the transition metal compound (A) is added alone to a polymerization reactor.
(2) A method in which the transition metal compound (A) and the compound (B) are added to a polymerization reactor in any order.
(3) A method in which a catalyst component in which a transition metal compound (A) is supported on a carrier (C) and the compound (B) are added to a polymerization reactor in any order.

(4) A method in which the catalyst component in which the compound (B) is supported on the carrier (C) and the transition metal compound (A) are added to a polymerization reactor in any order.
(5) A method in which a catalyst component in which the transition metal compound (A) and the compound (B) are supported on a carrier (C) is added to a polymerization reactor.

(6) A method in which a catalyst component in which transition metal compound (A) and compound (B) are supported on carrier (C), and compound (B) are added to a polymerization vessel in any order. In this case, compound (B) supported on carrier (C) and compound (B) added alone may be the same or different.

(7) A method in which a catalyst component in which the compound (B) is supported on the carrier (C) and the transition metal compound (A) are added to a polymerization vessel in any order.
(8) A method in which a catalyst component in which compound (B) is supported on a carrier (C), a transition metal compound (A), and compound (B) are added to a polymerization vessel in any order, in which case compound (B) supported on a carrier (C) and compound (B) added alone may be the same or different.

(9) A method in which a component in which the transition metal compound (A) is supported on the carrier (C) and a component in which the compound (B) is supported on the carrier (C) are added to a polymerization reactor in any order.
(10) A method in which a component in which a transition metal compound (A) is supported on a carrier (C), a component in which a compound (B) is supported on a carrier (C), and compound (B) are added to a polymerization reactor in any order. In this case, compound (B) supported on carrier (C) and compound (B) added alone may be the same or different.

(11) A method in which the transition metal compound (A), the compound (B), and the organic compound component (D) are added to a polymerization reactor in any order.
(12) A method in which the compound (B) and the organic compound component (D) are contacted in advance, and the transition metal compound (A) are added to a polymerization vessel in any order.

(13) A method in which the compound (B), the organic compound component (D) supported on the carrier (C), and the transition metal compound (A) are added to a polymerization reactor in any order.
(14) A method in which a catalyst component in which a transition metal compound (A) and a compound (B) have been previously contacted, and an organic compound component (D) are added to a polymerization vessel in any order.

(15) A method in which a catalyst component in which a transition metal compound (A) and a compound (B) have been previously contacted, compound (B), and an organic compound component (D) are added to a polymerization reactor in any order.
(16) A method in which a catalyst component in which a transition metal compound (A) and a compound (B) have been previously contacted, and a component in which a compound (B) and an organic compound component (D) have been previously contacted, are added to a polymerization vessel in any order. In this case, the compound (B) to be contacted with the transition metal compound (A) and the compound (B) to be contacted with the organic compound component (D) may be the same or different.

(17) A method in which a component in which a transition metal compound (A) is supported on a carrier (C), a compound (B), and an organic compound component (D) are added to a polymerization reactor in any order.
(18) A method in which a component in which a transition metal compound (A) is supported on a carrier (C) and a component in which a compound (B) and an organic compound component (D) are previously contacted are added to a polymerization reactor in any order.

(19) A method in which a catalyst component obtained by previously contacting a transition metal compound (A), a compound (B) and an organic compound component (D) in any order is added to a polymerization vessel.
(20) A method in which a catalyst component obtained by previously contacting a transition metal compound (A), a compound (B), and an organic compound component (D), and the compound (B) are added to a polymerization vessel in any order. In this case, the compound (B) that is brought into contact with the transition metal compound (A) and the organic compound component (D) and the compound (B) that is added alone may be the same or different.

(21) A method in which a catalyst in which a transition metal compound (A), a compound (B) and an organic compound component (D) are supported on a carrier (C) is added to a polymerization reactor.
(22) A method in which a catalyst component comprising a transition metal compound (A), a compound (B), and an organic compound component (D) supported on a carrier (C), and component (B) are added to a polymerization vessel in any order, in which the compound (B) supported on the carrier (C) and the compound (B) added alone may be the same or different.

The solid catalyst component in which the transition metal compound (A) is supported on the support (C) and the solid catalyst component in which the transition metal compound (A) and the compound (B) are supported on the support (C) may be prepolymerized with an olefin, or the prepolymerized solid catalyst component may have further catalyst components supported on it.

In the present invention, (co)polymerization can be carried out by either a liquid-phase polymerization method such as solution polymerization or suspension polymerization, or a gas-phase polymerization method. Specific examples of inert hydrocarbon media used in liquid-phase 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 mixtures thereof. The olefin to be (co)polymerized itself can also be used as the solvent.

When olefin polymerization is carried out using the above-mentioned olefin polymerization catalyst, the transition metal compound (A) is used in an amount of usually 10 ⁻¹² to 10 ⁻² mol, preferably 10 ⁻¹⁰ to 10 ⁻³ mol, per liter of reaction volume.

The organometallic compound (B-1) is used in an amount such that the molar ratio of the organometallic compound (B-1) to the total transition metal atoms (M) in the transition metal compound (A) [(B-1)/M] is typically 0.01 to 100,000, preferably 0.05 to 50,000. The organoaluminum oxy compound (B-2) is used in an amount such that the molar ratio of the aluminum atoms in the organoaluminum oxy compound (B-2) to the total transition metal atoms (M) in the transition metal compound (A) [(B-2)/M] is typically 10 to 500,000, preferably 20 to 100,000. The compound (ionizing ionic compound) (B-3) that reacts with the transition metal compound (A) to form an ion pair is used in an amount such that the molar ratio of the ionizing ionic compound (B-3) to the transition metal atoms (M) in the transition metal compound (A) [(B-3)/M] is typically 1 to 10, preferably 1 to 5.

The organic compound component (D) is used in an amount such that the molar ratio [(D)/(B-1)] to the organometallic compound (B-1) is typically 0.01 to 10, preferably 0.1 to 5. The organic compound component (D) is used in an amount such that the molar ratio [(D)/(B-2)] to the organoaluminum oxy compound (B-2) is typically 0.001 to 2, preferably 0.005 to 1. The organic compound component (D) is used in an amount such that the molar ratio [(D)/(B-3)] to the ionizing ionic compound (B-3) is typically 0.01 to 10, preferably 0.1 to 5.

The polymerization temperature for olefins using such an olefin polymerization catalyst is usually in the range of -50 to +200°C, preferably 0 to 170°C. The polymerization pressure is usually normal pressure to 100 kg/ ^cm2 -G, preferably normal pressure to 50 kg/ ^cm2 -G, and the polymerization reaction can be carried out in any of batch, semi-continuous, and continuous systems. Furthermore, the polymerization can be carried out in two or more stages with different reaction conditions.

The molecular weight of the resulting olefin polymer can be adjusted by adding hydrogen to the polymerization system or by changing the polymerization temperature. It can also be adjusted by the amount of compound (B) used.

The olefin that can be polymerized by the olefin polymerization catalyst of the present invention is not particularly limited as long as it has a polymerizable double bond, and examples thereof include linear or branched α-olefins having 2 to 30, preferably 2 to 20, and more preferably 2 to 10 carbon atoms, such as ethylene, propylene, 1-butene, 2-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene;
Examples of cyclic olefins include those having 3 to 30, preferably 3 to 20, and more preferably 3 to 10 carbon atoms, such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, and 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene.

The olefin polymerization catalyst of the present invention is more preferably used for the homopolymerization of ethylene or the copolymerization of ethylene with an olefin having 3 to 20 carbon atoms, preferably a linear or branched α-olefin having 3 to 10 carbon atoms. The α-olefin may be used alone or in combination of two or more types.

When copolymerizing ethylene with an α-olefin having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, the α-olefin (hereinafter also referred to as olefin A) is not particularly limited as long as the effects of the present invention are achieved. However, for example, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, and 1-decene are preferred. These α-olefins may be used alone or in combination of two or more. Of these, at least one selected from 1-butene, 1-hexene, 4-methyl-1-pentene, and 1-octene is more preferred.

When ethylene is used as the α-olefin and the above-mentioned olefin A is used, the molar ratio of ethylene to the above-mentioned olefin A is typically 1:10 to 5000:1, preferably 1:5 to 1000:1.

The olefin polymerization catalyst of the present invention may (co)polymerize known chain unsaturated hydrocarbons having polar groups (for example, carbonyl groups, hydroxyl groups, ether-bonded groups, etc.).
The olefin polymerization catalyst of the present invention may also be used to (co)polymerize vinylcyclohexane, dienes, polyenes, and the like.

Examples of the diene or polyene include cyclic or chain compounds having 4 to 30, preferably 4 to 20, carbon atoms and two or more double bonds. Specific examples include butadiene, isoprene, 4-methyl-1,3-pentadiene, 1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,3-hexadiene, 1,3-octadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, ethylidene norbornene, vinyl norbornene, and dicyclopentadiene;
7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene, 5,9-dimethyl-1,4,8-decatriene;
Further, aromatic vinyl compounds, for example, mono- or polyalkylstyrenes such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o,p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, and p-ethylstyrene;
functional group-containing styrene derivatives such as methoxystyrene, ethoxystyrene, vinylbenzoic acid, methyl vinylbenzoate, vinylbenzyl acetate, hydroxystyrene, o-chlorostyrene, p-chlorostyrene, and divinylbenzene;
and 3-phenylpropylene, 4-phenylpropylene, α-methylstyrene, and the like.

As explained above, the transition metal compound (A) of the present invention has a novel structure in which specific substituents are introduced at specific positions on the metallocene skeleton. The olefin polymerization catalyst of the present invention, which contains compound (A), has superior α-olefin copolymerizability compared to conventional transition metal compounds having metallocene skeletons (which do not have specific substituents at specific positions), exhibits a good balance of olefin polymerization activity and copolymerizability, and is capable of producing ethylene copolymers with sufficient molecular weight and low density.

The reason for this is currently unknown, but the inventors believe it to be as follows: Specifically, this effect is thought to be due to the following: (i) the significant improvement in α-olefin copolymerization due to the introduction of a heteroatom-containing electron-donating substituent into a specific metallocene site in the transition metal compound (A) represented by the general formula [A-1] or [A-2]; and (ii) the effect of introducing a substituent into the vicinity to inhibit the activity reduction phenomenon caused by the introduction of a heteroatom.

Regarding the effect of the substituent, in more detail, it is believed that the bulkiness of the group bonded to the phosphine imide group, which is composed of multiple bulky cyclic hydrocarbon groups, is involved. In other words, the transition metal compound (A) exerts a moderate steric effect sufficient to maintain ion separation from the cocatalyst so that the polymerization reaction can continue, while positioning the bulky substituent at a position that presents a relatively low steric barrier to the olefin to be coordinated. Furthermore, this substituent restricts the direction of olefin coordination in some way with α-olefins having 3 or more carbon atoms, making chain transfer less likely to occur. Therefore, transition metal compound (A) may be able to polymerize olefins more efficiently, potentially contributing to copolymerization and the ease of obtaining high-molecular-weight polymers. Most preferably, it is speculated that there may be cases in which an excellent balance of the performances of activity, copolymerization, and the ease of obtaining high-molecular-weight polymers is achieved. To achieve this effect particularly effectively, an embodiment containing a cyclic hydrocarbon group as the substituent is considered preferable.

[Olefin polymer]
According to the present invention, an olefin polymer can be efficiently produced by polymerizing one or more olefins selected from α-olefins having 2 to 30 carbon atoms in the presence of an olefin polymerization catalyst containing the useful and novel transition metal compound (A) having the specific structure described above; preferably, by homopolymerizing ethylene or copolymerizing ethylene with at least one olefin A selected from olefins having 3 to 20 carbon atoms.

One embodiment of the olefin polymer is an ethylene-based polymer containing ethylene-derived structural units in a range of preferably 50 to 100 mol%, more preferably 70 to 100 mol%, and even more preferably 90 to 100 mol%. The ethylene-based polymer preferably contains olefin A-derived structural units in a total range of 0 to 50 mol%, more preferably 0 to 30 mol%, and even more preferably 0 to 10 mol%. The sum of the content of ethylene-derived structural units and the content of olefin A-derived structural units is 100 mol%. Ethylene-based polymers containing olefin A-derived structural units in the above range exhibit excellent moldability. They may also contain other structural units within the scope of the present invention. These contents can be measured by nuclear magnetic resonance spectroscopy or, if a reference substance is available, infrared spectroscopy.

Among these polymers, ethylene homopolymer, ethylene-propylene copolymer, ethylene-1-butene copolymer, ethylene-propylene-1-butene copolymer, ethylene-1-octene polymer, ethylene-1-hexene polymer, ethylene-4-methyl-1-pentene polymer, ethylene-propylene-1-octene polymer, ethylene-propylene-1-hexene polymer, and ethylene-propylene-4-methyl-1-pentene polymer are particularly preferred. The above copolymers are typically random copolymers, but they may also be so-called block copolymers (impact copolymers) obtained by mixing or continuously producing two or more selected from these polymers.

Among the polymers having the structural units described above, the ethylene-based polymer is preferably an α-olefin polymer consisting essentially of structural units derived from α-olefins having 2 to 20 carbon atoms. "Substantially" means that the proportion of structural units derived from α-olefins having 2 to 20 carbon atoms is 95% by weight or more of all structural units.

The weight-average molecular weight of the olefin polymer measured by gel permeation chromatography (GPC) is not particularly limited, but is preferably 10,000 to 5,000,000, more preferably 10,000 to 2,000,000, and particularly preferably 20,000 to 1,000,000. The molecular weight distribution (Mw/Mn), which is the ratio of the weight-average molecular weight (Mw) to the number-average molecular weight (Mn), is not particularly limited, but is preferably 1 to 10, more preferably 1 to 7, and particularly preferably 1 to 5.

The density of the olefin polymer is not particularly limited, but is preferably 875 kg/m ³ or more and 975 kg/m ³ or less.
The intrinsic viscosity [η] of the olefin polymer in decalin at 135° C. is not particularly limited, but is preferably 0.1 to 40 dl/g, more preferably 0.5 to 15 dl/g, and particularly preferably 1 to 10 dl/g.

The melt mass flow rate (MFR; unit: g/10 min) of the olefin polymer measured in accordance with ASTM D1238-89 at 190°C under a load of 2.16 kg is not particularly limited, but is preferably 0.001 g/10 min or more and 300 g/10 min or less, and more preferably 0.001 g/10 min or more and 200 g/10 min or less.

Furthermore, it is preferable that the value (I10/I2) obtained by dividing the MFR value measured under conditions of 190°C and a 10 kg load according to ASTM D1238-89 by the MFR value measured under the above conditions of 190°C and a 2.16 kg load is 5.0 or more and less than 300.
The detailed conditions for measuring the above physical properties are as described in the Examples.

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

[Measurement method]
[Structure of transition metal compounds]
The structure of the transition metal compound was determined using ¹ H-NMR spectrum (270 MHz, JEOL GSH-270) and FD-MS (JEOL JMS-T1000GC).

[Polymer weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn)]
The weight average molecular weight (Mw) and number average molecular weight (Mn) of the olefin polymer were determined by gel permeation chromatography (GPC), calculated from a molecular weight distribution curve obtained using a Waters "Alliance GPC 2000" gel permeation chromatograph (high-temperature size exclusion chromatograph), under the following operating conditions:

<Equipment and conditions used>
Measurement equipment: Gel permeation chromatograph Alliance GPC2000 (Waters)
Analysis software: Chromatography Data System Empower (trademark, Waters)
Column: TSKgel GMH6-HT x 2 + TSKgel GMH6-HT x 2
(Inner diameter 7.5 mm x length 30 cm, Tosoh Corporation)
Mobile phase: o-dichlorobenzene [ODCB] (Fujifilm Wako Pure Chemical Industries, Ltd., special grade reagent)
Detector: Differential refractometer (built into the device)
Column temperature: 140°C
Flow rate: 1.0mL/min
Injection volume: 400μL
Sampling time interval: 1 second Sample concentration: 0.15% (w/v)
Molecular weight calibration: Monodisperse polystyrene (Tosoh Corporation) / molecular weight 495 to 20.6 million

[Intrinsic viscosity ([η])]
Measurement was performed at 135 ° C. using decalin solvent. Approximately 20 mg of polymer was dissolved in 15 mL of decalin, and the specific viscosity η _sp was measured in an oil bath at 135 ° C. 5 mL of decalin solvent was added to this decalin solution to dilute it, and the specific viscosity η _sp was measured in the same manner. This dilution procedure was repeated two more times, and the value of η _sp /C when the concentration (C) was extrapolated to 0 was adopted as the limiting viscosity.
[η]=lim(η _sp /C) (C→0)

[Polymer Density]
A polymer melted at 190°C was melt-extruded through an orifice with an inner diameter of approximately 2.1 mm to prepare a strand, which was then heat-treated at 120°C for 30 minutes. The strand was left at room temperature for 1 hour and then cut to an appropriate length as needed to prepare a measurement sample. The density (kg/ ^m3 ) of this sample was measured by the density gradient tube method.

[Hexene content of polymer]
The hexene content in the ethylene-1-hexene copolymer was measured by FT-IR (JASCO FT-IR410 infrared spectrophotometer). For FT-IR, the polymer obtained in the examples was heated to 135°C, melt-stretched in a hot press, and then cooled under pressure at room temperature to obtain a film. FT-IR was measured at a light source wavenumber of 5000 cm ^-1 to 400 cm ^-1 . The hexene content was determined by using the C-CH ₂ CH ₂ CH ₂ CH ₃ skeletal vibration (1378 cm ^-1 ) of hexene as the key band and the ratio [D1378/D4321] of the absorbance of the key band (D1378) to the absorbance (D4321) of the internal standard band (4321 cm ^-1 : the combination sound of the C-H stretching vibration and the methylene and methyl deformation vibrations).

A calibration curve specifying the relationship between the hexene content and the ratio [D1378/D4321] was used to determine the hexene content. The calibration curve was prepared in advance from the [D1378/D4321] results obtained by subjecting ethylene copolymers of various compositions, the hexene contents of which had been specified by ^13C NMR, to FT-IR measurement using the method described above.

[Comonomer content of ethylene-propylene terpolymer]
The comonomer content of the ethylene-propylene terpolymer was measured by FT-IR (FT-IR410 infrared spectrophotometer manufactured by JASCO Corporation) or by ¹ H NMR measurement.

(FT-IR measurement method)
A film obtained in the same manner as in the ethylene-hexene copolymer was used as a measurement sample, and the propylene structural unit content and the ethylidenenorbornene structural unit content were measured using calibration curves.

The comonomer contents of the ethylene-propylene terpolymer samples used to prepare the calibration curve were determined by C NMR measurement under the following conditions: The calibration curve was obtained by using these samples to select peak intensity ratios of ^two specific absorption wavenumbers that showed a linear or nearly linear relationship with the propylene structural unit content and ethylidene norbornene structural unit content data, and then graphing this relationship.

( ^13C NMR measurement method)
13C NMR spectra were measured using o-dichlorobenzene/benzene- _d6 (4/1 {vol/vol%}) as the measurement solvent under the following conditions: measurement temperature 120°C, spectral width 250 ppm, pulse repetition time 5.5 seconds, pulse width ^4.7 μsec (45° pulse) (100 MHz, JEOL ECX400P); or measurement temperature 120°C, spectral width 250 ppm, pulse repetition time 5.5 seconds, pulse width 5.0 μsec (45° pulse) (125 MHz, Bruker Biospin AVANCEIII Cryo-500). Various signals were assigned in the usual way, and the comonomer content was quantified based on the integrated value of the signal intensity.

( ^1H NMR measurement)
H NMR measurements were performed using o-dichlorobenzene- _d4 as the measurement solvent, under the following conditions (500 MHz, Bruker Biospin AVANCE IIIcryo-500): measurement temperature ¹²⁰ °C, spectral width 250 ppm, pulse repetition time 7.0 seconds, pulse width 5.0 μsec (45° pulse). Various signals, such as methyl groups and ethylidene groups, were assigned according to standard methods, and the comonomer content was quantified based on the integrated signal intensities.

[Production of titanium compounds]
Example A1 Synthesis of Transition Metal Compound A Transition metal compound A represented by the following formula (A) was synthesized by the following method.

(Synthesis of Ligand)
Under a nitrogen atmosphere, 1,000 mg (2.29 mmol) of Tris(1-adamantyl)phosphine (Strem), 30 mL of dehydrated toluene, and 396 mg of trimethylsilyl azide were added to a Schlenk flask and heated under reflux for 19 hours. The mixture was returned to room temperature, the solvent was distilled off under reduced pressure, and then washed with hexane. 1,094 mg of the target product (yield 90%) was obtained. The target product (hereinafter referred to as Ligand A1) was identified by ¹ H-NMR (CDCl ₃ ) measurement results.
^1H -NMR (270MHz, CDCl ₃ ) δ 0.05 (9H, s), 2.21-1.71 (45H, m) ppm

(Synthesis of transition metal compounds)
Under a nitrogen atmosphere, 100 mg (0.456 mmol) of cyclopentadienyltitanium trichloride, 250 mg (0.477 mmol) of Ligand A1 obtained in the previous reaction, and 50 mL of dehydrated toluene were added to a Schlenk flask and stirred at 100°C for 21.5 hours. After the solvent was removed by distillation under reduced pressure, the mixture was dissolved in dichloromethane and hexane was added. Half of the solvent was removed by distillation under reduced pressure, and the precipitated yellow powder was recovered by filtration, washed with hexane, and then dried under reduced pressure. 171 mg of a yellow solid (hereinafter referred to as transition metal compound A) was obtained in a yield of 59%. The target product was identified by measurement results of ¹ H-NMR (CDCl ₃ ) and FD-MS.
^1H -NMR (270MHz, CDCl ₃ ) δ 2.46-1.73 (45H, m),6
．． 51 (5H, s) ppm
FD-MS: m/z=633.3 (M ⁺ )

Example A2 Synthesis of Transition Metal Compound B Transition metal compound B represented by the following formula (B) was synthesized by the following method.

Under a nitrogen atmosphere, 100 mg (0.371 mmol) of indenyltitanium trichloride, 204 mg (0.389 mmol) of Ligand A1 obtained in Example A1, and 40 mL of dehydrated toluene were placed in a Schlenk flask and stirred at 100°C for 17 hours. The solvent was removed under reduced pressure to 10%, and hexane was then added. The precipitated yellow powder was collected by filtration. A small amount of dichloromethane was added to the resulting yellow solid, and the solution was added to hexane while removing insoluble matter using a membrane filter. The solvent was removed under reduced pressure to 25%, and the precipitated yellow powder was collected by filtration. After drying under reduced pressure, 201 mg of a yellow powder (hereinafter referred to as transition metal compound B) was obtained in a 79% yield. The target product was identified by ¹ H-NMR (CDCl ₃ ) and FD-MS.
^1H -NMR (270MHz, CDCl ₃ ) δ 2.48-1.73 (45H, m),6
．． 59 (2H, d, J = 3.3Hz), 7.10 (1H, t, J = 3.3Hz), 7.29
-7.24 (2H, m), 7.69-7.65 (2H, m) ppm
FD-MS: m/z=683.2 (M ⁺ )

Example A3 Synthesis of Transition Metal Compound C Transition metal compound C represented by the following formula (C) was synthesized by the following method.

Under a nitrogen atmosphere, 160 mg (0.401 mmol) of pentafluorophenylmethyl cyclopentadienyl titanium trichloride, 210 mg (0.401 mmol) of Ligand A1 obtained in Example A1, and 40 mL of dehydrated toluene were added to a Schlenk flask and stirred at 100°C for 18.5 hours. The solvent was removed by distillation under reduced pressure to 20%, and hexane was added. The precipitated yellow powder was collected by filtration. The resulting yellow solid was dissolved in a small amount of dichloromethane and added to hexane. The solvent was removed by distillation under reduced pressure to one-third of the original volume, and the precipitated yellow powder was collected by filtration. After drying under reduced pressure, 261 mg of a yellow powder (hereafter referred to as transition metal compound C) was obtained in an 80% yield. The target product was identified by ¹ H-NMR (CDCl ₃ ) and FD-MS.
¹ H-NMR (270 MHz, CDCl ₃ ) δ 2.47-1.73 (45 H, m), 4
．． 05 (2H, s) 6.28 (2H, t, J = 2.6Hz), 6.46 (2H, t, J = 2.6Hz) ppm
FD-MS: m/z=813.2 (M ⁺ )

Example A4 Synthesis of Transition Metal Compound D Transition metal compound D represented by the following formula (D) was synthesized by the following method.

Under a nitrogen atmosphere, 168 mg (0.475 mmol) of adamantyl-cyclopentadienyl titanium trichloride, 250 mg (0.477 mmol) of Ligand A1 obtained in Example A1, and 50 mL of dehydrated toluene were placed in a Schlenk flask and stirred at 100°C for 17 hours. The solvent was removed by distillation under reduced pressure to 10%, and hexane was added. The precipitated yellow powder was collected by filtration. The resulting yellow powder was dissolved in a small amount of dichloromethane and added to hexane. The solvent was removed by distillation under reduced pressure to two-thirds of its original volume, and the precipitated yellow powder was collected by filtration. After drying under reduced pressure, 206 mg of a yellow powder (hereinafter referred to as transition metal compound D) was obtained in a 56% yield. The target product was identified by ¹ H-NMR (CDCl ₃ ) and FD-MS.
¹ H-NMR (270MHz, CDCl ₃ ) δ 2.47-1.79 (60H, m), 6.48-6.41 (4H, m) ppm
FD-MS: m/z=767.4 (M ⁺ )

Example A5 Synthesis of Transition Metal Compound E Transition metal compound E represented by the following formula (E) was synthesized by the following method.

(Synthesis of Ligand E1)
Under a nitrogen atmosphere, 502 mg (1.39 mmol) of Di(1-adamantyl)-n-butylphosphine (cataCXium®, manufactured by Aldrich), 30 mL of dehydrated toluene, and 176 mg (1.53 mmol) of trimethylsilyl azide were added to a Schlenk flask and refluxed at 80°C for ⁵ hours. The temperature was returned to room temperature, the _solvent was distilled off under reduced pressure, and the mixture was washed with hexane. 536 mg of the target product (yield 86%) was obtained. The target product represented by the following formula (E1) (hereinafter referred to as ligand E1) was identified from the results of 1 H-NMR (CDCl 3 ).
¹ H-NMR (270 MHz, CDCl ₃ ) δ 0.00 (9H, s), 0.93 (3H, t), 1.32-1.96 (36H, m) ppm

(Synthesis of transition metal compounds)
Under a nitrogen atmosphere, 144 mg (0.657 mmol) of cyclopentadienyltitanium trichloride, 307 mg (0.689 mmol) of the ligand E1 obtained in the previous reaction, and 50 mL of dehydrated toluene were added to a Schlenk flask and stirred at 100°C for 16 hours. After the solvent was removed by distillation under reduced pressure, the mixture was dissolved in dichloromethane and hexane was added. Half of the solvent was removed by distillation under reduced pressure, and the precipitated yellow powder was recovered by filtration, washed with hexane, and then dried under reduced pressure. 294 mg of a yellow solid (hereinafter referred to as transition metal compound E) was obtained in an 82% yield. The target product was identified by ¹ H-NMR (CDCl ₃ ) and FD-MS.
¹ H-NMR (270 MHz, CDCl ₃ ) δ 1.02 (3H, t), 1.42-1.53 (2H, m), 1.68-2.35 (34H, m), 6.47 (5H, s) ppm
FD-MS: m/z=555.2 (M ⁺ )

Example A6 Synthesis of Transition Metal Compound F Transition metal compound F represented by the following formula (F) was synthesized by the following method.

Under a nitrogen atmosphere, 246 mg (0.616 mmol) of pentafluorophenylmethyl cyclopentadienyl titanium trichloride, 287 mg (0.664 mmol) of the ligand E1 obtained in the previous reaction, and 50 mL of dehydrated toluene were added to a Schlenk flask and stirred at 100°C for 16 hours. After the solvent was removed by distillation under reduced pressure, the mixture was dissolved in dichloromethane and hexane was added. Half of the solvent was removed by distillation under reduced pressure, and the precipitated yellow powder was recovered by filtration, washed with hexane, and then dried under reduced pressure. 287 mg of yellow powder (hereinafter referred to as transition metal compound (F)) was obtained in a 59% yield. The target product was identified by ¹ H-NMR (CDCl ₃ ) and FD-MS.
¹ H-NMR (270MHz, CDCl ₃ ) δ 0.95 (3H, t), 1.38-1.46 (2H, m), 1.68-2.09 (34H, m), 3.97 (2H, s), 6.20 (2H, d), 6.33 (2H, t) ppm
FD-MS: m/z=735.1 (M ⁺ )

Example A7 Synthesis of Transition Metal Compound G Transition metal compound G represented by the following formula (G) was synthesized by the following method.

Under a nitrogen atmosphere, 150 mg (0.559 mmol) of indenyltitanium trichloride, 261 mg (0.587 mmol) of the ligand E1 obtained in the previous reaction, and 50 mL of dehydrated toluene were added to a Schlenk flask and stirred at 100°C for 16 hours. After the solvent was distilled off under reduced pressure, the mixture was dissolved in dichloromethane and hexane was added. Half of the solvent was distilled off under reduced pressure, and the precipitated yellow powder was recovered by filtration, washed with hexane, and then dried under reduced pressure. 226 mg of yellow powder (hereinafter referred to as transition metal compound G) was obtained in a yield of 67%. The target product was identified by ¹ H-NMR (CDCl ₃ ) and FD-MS.
^1H -NMR (270MHz, CDCl ₃ )δ 0.96 (3H, t), 1.36-1.50 (2H, m) 1.36-2.83 (34H, m), 6.50 (2H, d), 6.91 (1H, t), 7.14-7.22 (2H, m), 7.57-7.62 (2H, m) ppm
FD-MS: m/z=605.2 (M ⁺ )

Comparative Synthesis Example a1: Synthesis of transition metal compound a Transition metal compound a represented by the following formula (a) was synthesized according to the method described in Organometallics 1999, 18, 1116-1118.
It was synthesized by the method described in

Comparative Synthesis Example a2: Synthesis of transition metal compound b A transition metal compound b represented by the following formula (b) was synthesized by the method described in J. Organomet. Chem. 2004, 689, 203.

Comparative Synthesis Example a3 Synthesis of Transition Metal Compound c Transition metal compound c represented by the following formula (c) was synthesized by the method described in JP-A-2006-169521.

Comparative Synthesis Example a4 Synthesis of Transition Metal Compound d Transition metal compound d represented by the following formula (d) was synthesized by the following method: In formula (d), "Adm" represents an adamantyl group.

In a nitrogen atmosphere, 354 mg (1 mL) of adamantyl-cyclopentadienyl titanium trichloride was placed in a Schlenk flask.
．． 00 mmol), 1,1,1-tri-tert-butyl-N-(trimethylsilyl)-phosphanimine 326
mg (1.12 mmol) and 50 mL of dehydrated toluene were added, and the mixture was stirred at 100°C for 19 hours. After the solvent was distilled off under reduced pressure, a small amount of dichloromethane was dissolved and the solution was added to hexane. The precipitated yellow powder was collected by filtration. The obtained yellow powder was dissolved in a small amount of dichloromethane, and hexane was added to the solution, followed by recrystallization at -10°C. The precipitated crystals were collected by filtration, washed with hexane, and dried under reduced pressure to obtain 326 mg of a yellow solid in a yield of 61%. ¹ H-NMR (CD
The target substance was identified by the results of measurement using HCl ₃ ) and FD-MS.
¹ H-NMR (270 MHz, CDCl ₃ ) δ 2.03-1.52 (42 H, m), 6.45-6.39 (4 H, m) ppm
FD-MS: m/z=533.2 (M ⁺ )

[Production of ethylene polymer and ethylene-1-hexene copolymer]
[Example p1]
Under a nitrogen atmosphere, using a reactor equipped with a stirrer and having an internal volume of 270 L, 10 kg of silica gel (manufactured by Fuji Silysia Chemical Ltd., cumulative 50% particle size of volume distribution by laser light diffraction scattering method: 70 μm, specific surface area: 340 m ² /g, pore volume: 1.3 cm ³ /g, dried at 250 ° C. for 10 hours) was suspended in 77 L of toluene and then cooled to 0-5 ° C. 19.4 L of a toluene solution of methylaluminoxane (3.5 mol/L in terms of Al atoms) was added dropwise to this suspension over 30 minutes. At this time, the temperature in the system was maintained at 0-5 ° C. Next, these were contacted at 0-5 ° C. for 30 minutes, and then the temperature in the system was raised to 95 ° C. over 1.5 hours, and then contacted at 95 ° C. for 4 hours. Thereafter, the temperature was lowered to room temperature, the supernatant liquid was removed by decantation, and the mixture was further washed twice with toluene to prepare a total of 115 L of carrier slurry. A portion of the resulting carrier slurry was sampled and analyzed, revealing that the solid concentration was 122.6 g/L and the Al concentration was 0.612 mol/L.

Under a nitrogen atmosphere, 30 mL of toluene and 1.63 mL of the support slurry (solids weight 0.2 g) were added to a 200 mL reactor equipped with a stirrer. Next, a 5.0 μmol toluene solution of transition metal compound A obtained in Synthesis Example A1 was added, and the mixture was allowed to come into contact with each other for 1 hour at a system temperature of 20-25°C. After that, the supernatant was removed by decantation, and the mixture was washed twice with hexane. This resulted in the preparation of a total catalyst slurry of 40 mL.

500 mL of heptane was added to a 1 L stainless steel autoclave that had been thoroughly purged with nitrogen. Ethylene was then passed through to saturate the reactor with ethylene. Next, 1-hexene was added in the amount shown in Table 1, followed by 0.375 mmol of triisobutylaluminum and 2.5 mg of Adeka Pluronic L-71 (manufactured by ADEKA Corporation) as a decane solution. The catalyst slurry was then added in an amount equivalent to 20.0 mg of solids. The temperature and pressure were then increased to 80°C and 0.8 MPaG with ethylene, and the polymerization reaction was carried out for 90 minutes. The resulting polymer was filtered and dried under reduced pressure at 80°C for 10 hours to yield 41.5 g of ethylene polymer. The polymer production per gram of catalyst slurry solids (activity in Table 1) was calculated to be 2,070 g/g-cat. The analytical values of the resulting polymer are shown in Table 1.

[Examples p2 to p8]
Preparation of a catalyst slurry and production of an ethylene polymer and an ethylene-1-hexene copolymer were carried out in the same manner as in Example p1, except that the amounts of the transition metal compound and 1-hexene added in Example p1 were changed to those shown in Table 1. The activity (g/g-cat) calculated from the amount of the obtained polymer and the analytical values of the polymer are shown in Table 1.

[Comparative examples p1 to p8]
Preparation of a catalyst slurry and production of an ethylene polymer and an ethylene-1-hexene copolymer were carried out in the same manner as in Example p1, except that the amounts of the transition metal compound and 1-hexene added in Example p1 were changed to those shown in Table 1. The activity (g/g-cat) calculated from the amount of the obtained polymer and the analytical values of the polymer are shown in Table 1.

The following can be seen from the values in Table 1 above.
In ethylene homopolymerization, embodiments of the present invention tend to have high activity.
- Tends to have a high content of olefins with 3 or more carbon atoms.
Generally, as the content of olefins having 3 or more carbon atoms increases, the polymerization activity tends to decrease. However, in the embodiment of the present invention, even if the olefin content is high, the polymerization activity is at approximately the same level as or higher than that of the comparative example.
Generally, as the olefin content increases, the molecular weight tends to decrease, but in the embodiment of the present invention, even if the olefin content is high, the molecular weight is at the same level or higher.

[Example p9]
A solid aluminoxane was synthesized according to the method described in International Publication WO 2010/055652 (Preliminary Experiment 1 and Example 5) and used as a support. However, in consideration of safety concerns such as the risk of fire from trimethylaluminum, the experiment was carried out at a concentration approximately 1/6 of the conditions disclosed in the document.

Specifically, 100 mL of a toluene solution of trimethylaluminum adjusted to 0.5 mol/L was placed in a glass reactor equipped with a stirrer. This solution was cooled to 15°C, and 2.18 g of benzoic acid was slowly added thereto at a rate that maintained the solution temperature below 25°C. The mixture was then heated and aged at 50°C for 1 hour. At this time, the molar ratio of trimethylaluminum to oxygen atoms in benzoic acid was 1.40. The reaction solution was heated at 70°C for 4 hours, then at 60°C for 6 hours, and then cooled to room temperature. It was then heated at 100°C for 8 hours to precipitate a solid component. After cooling the solution to below 30°C, 100 mL of hexane was added with stirring for washing. After standing for 30 minutes, 150 mL of the supernatant was removed, and another 150 mL of hexane was added with stirring. After standing for 15 minutes, 150 mL of the supernatant was removed, and another 150 mL of hexane was added with stirring. Finally, after allowing to stand for 15 minutes, 180 mL of the supernatant was removed, and hexane was added to a total volume of 14.6 mL to obtain a carrier slurry. A portion of the obtained carrier slurry was sampled and analyzed, and the solid concentration was found to be 41.0 g/L and the Al concentration was 0.583 mol/L. Furthermore, particle observation of the obtained carrier with a scanning electron microscope revealed that the average particle size was 6.8 μm and the specific surface area was 18.1 ^m2 /mmol-Al.

Under a nitrogen atmosphere, 30 mL of toluene and 2.44 mL of the support slurry (solids weight 0.1 g) were added to a 200 mL reactor equipped with a stirrer. Next, a 5.0 μmol toluene solution of transition metal compound A was added, and the mixture was allowed to come into contact for 1 hour at a system temperature of 20-25°C. The supernatant was then removed by decantation, and the mixture was washed twice with hexane. This resulted in the preparation of a total catalyst slurry of 40 mL.

500 mL of heptane was added to a 1 L stainless steel autoclave that had been thoroughly purged with nitrogen. Ethylene was then passed through to saturate the reactor with ethylene. Next, 1-hexene was added in the amount shown in Table 1, followed by 0.25 mmol of triisobutylaluminum and 2.5 mg of Adeka Pluronic L-71 (manufactured by ADEKA Corporation) as a decane solution. The catalyst slurry was then added in an amount equivalent to 5.0 mg of solids. The temperature and pressure were raised to 75°C and 0.65 MPaG using an ethylene/hydrogen mixed gas with a hydrogen concentration of 0.10 vol%, and the polymerization reaction was carried out for 90 minutes. The resulting polymer was filtered and dried under reduced pressure at 80°C for 10 hours to yield 48.6 g of ethylene polymer. The polymer production per gram of catalyst slurry solids (activity in Table 2) was calculated to be 9710 g/g-cat. The analytical values of the resulting polymer are shown in Table 2.

[Examples pp. 10-16]
Preparation of catalyst slurry and production of ethylene polymer and ethylene-1-hexene copolymer were carried out in the same manner as in Example p9, except that the amounts of transition metal compound and 1-hexene added in Example p9 were changed to those shown in Table 2. The activity (g/g-cat) calculated from the amount of the obtained polymer and the analytical values of the polymer are shown in Table 2.

[Comparative Examples pp. 9 to 16]
Preparation of catalyst slurry and production of ethylene polymer and ethylene-1-hexene copolymer were carried out in the same manner as in Example p9, except that the amounts of transition metal compound and 1-hexene added in Example p9 were changed to those shown in Table 2. The activity (g/g-cat) calculated from the amount of the obtained polymer and the analytical values of the polymer are shown in Table 2.

The results in the table above also show that the present invention has higher polymerization activity than the comparative example, and the molecular weight is roughly the same.

[Examples pp. 17-20]
Preparation of catalyst slurry and production of ethylene polymer and ethylene-1-hexene copolymer were carried out in the same manner as in Example p9, except that the amounts of transition metal compound and 1-hexene used in Example p9 were changed to the conditions shown in Table 3. The results of Examples pp. 17 to 20 are shown in Table 3, along with the results of Comparative Examples 9 and 11 to 13.

The results in Table 3 show that in embodiments using transition metal compounds E to G, polymers with higher molecular weights than conventional methods tend to be obtained more easily.

[Example p21]
<Production of ethylene-propylene-ENB copolymer>
A 2-L stainless steel autoclave, thoroughly purged with nitrogen, was charged with 1030 mL of hexane and ethylidene norbornene (ENB). The system temperature was raised to 95°C, and then propylene was added at a predetermined partial pressure. Ethylene was then supplied to adjust the total pressure to 1.6 MPa-G. Next, 0.3 mmol of triisobutylaluminum, 0.05 micromoles of the transition metal compound E obtained above as the main catalyst, and triphenylcarbenium tetrakis(pentafluorophenyl)borate as a cocatalyst in an amount 4 times the molar amount of the transition metal compound were introduced under nitrogen pressure. Polymerization was initiated by adjusting the stirring speed to 250 rpm. Ethylene alone was then continuously supplied to maintain the total pressure at 1.6 MPa-G, and polymerization was carried out for 15 minutes at 95°C. The polymerization was terminated by adding a small amount of ethanol to the system, after which unreacted ethylene was purged. The resulting polymer solution was poured into a large excess of a methanol/acetone mixed solution to precipitate the polymer. The polymer was recovered by filtration and dried overnight under reduced pressure at 120° C. to produce an ethylene-propylene-ENB copolymer.
The analytical results of the obtained polymer are shown in Table 4.

[Examples pp. 22-24, Comparative Examples pp. 17-20]
An ethylene-propylene-ENB copolymer was produced in the same manner as in Example p21, except that the amounts of transition metal compound and ENB used in Example p21 were changed to the conditions shown in Table 4. The results are shown in Table 4.

The results in Table 4 show that in embodiments using transition metal compounds E to G, polymers with a higher content of structural units derived from α-olefins such as propylene and ethylidene norbornene or diene compounds tend to be obtained more easily than in conventional embodiments.

Claims (7)

A transition metal compound represented by the following general formula [A-2]:
[In formula [A-2],
M is a titanium atom, a zirconium atom, or a hafnium atom;
n is an integer from 1 to 3,
X's each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a boron-containing group, an aluminum-containing group, or a diene-based divalent derivative group;
R ¹ to R ⁵ and R ⁶ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, or a phosphorus-containing group, and adjacent groups among R ¹ to R ⁵ may be bonded to each other to form a ring . ] In the general formula [A-2],
2. The transition metal compound according to claim 1, wherein M is a titanium atom or a zirconium atom. In the general formula [A-2],
2. The transition metal compound of claim 1, wherein M is a titanium atom. 4. The transition metal compound according to claim 1, wherein in the general formula [A-2], R ⁶ is an adamantyl group. (A) the transition metal compound according to any one of claims 1 to 4;
(B) (B-1) organometallic compound,
(B-2) an organoaluminum oxy compound; and (B-3) at least one compound selected from the group consisting of compounds that react with the transition metal compound to form an ion pair. A method for producing an olefin polymer by polymerizing an olefin in the presence of the olefin polymerization catalyst described in claim 5. The olefin is
7. The method for producing an olefin polymer according to claim 6, wherein (Z-1) is an olefin selected from olefins having 2 to 30 carbon atoms.