JP2002145925A - Polymerization catalyst for olefin and method for manufacturing olefinic polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new organic metal compound having sufficient catalytic activity and capable of polymerizing a linear olefin or cyclic olefin at a high conversion ratio and a method for preparing the same, an olefin polymerization catalyst containing the organic metal compound and a method for (co) polymerizing a linear or cyclic olefin using the catalyst. SOLUTION: The organic metal compound has a structure of the following general formula (I). In the formula, M is a transition metal atom of the group 6; R1, R2 and R3 are each H, a linear hydrocarbon group or a cyclic hydrocarbon group, and they may be identical to or different from each other; X is a halogen atom; m is an integer of 0<=m<=4; and n is an integer of 1<=n<=4. Further, method for preparing the organic metal compound, an olefin polymerization catalyst containing the organic metal compound, and a method for (co) polymerizing a linear or cyclic olefin using the catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organometallic compound containing a transition metal, a process for preparing the same, an olefin polymerization catalyst containing the organometallic compound, and a (co) olefin of a linear or cyclic olefin using the catalyst. It relates to a polymerization method.

[0002]

2. Description of the Related Art In recent years, various organometallic compounds represented by metallocene catalysts have been used as new catalysts for polymerizing olefins such as ethylene and propylene. The metallocene catalyst is a catalyst having characteristics such that a polymer having a property different from that of a conventional Ziegler catalyst or the like can be produced, and a large amount of polymer can be produced with a very small amount of catalyst. However, the metallocene catalyst has a disadvantage that a large amount of expensive methylaluminoxane (MAO) is required as a co-catalyst in order to obtain sufficient catalytic activity. On the other hand, as nonmetallocene-catalyzed organometallic compounds, J. Organomet.Chem., (1995), 503 edition, 30
On page 7, an amidinate-type Zr initiator is proposed. However, the polymerization activity of the Zr initiator is 1 g-P / mmol.atom.h
There was a drawback that the activity was very low as follows. Also,
The application of metallocene catalysts has also been proposed in the polymerization of cyclic olefins represented by norbornene. For example,
In JP-A-2-173112, isopropylidene (cyclopentadienyl) (fluorenyl) titanium dichloride is used.
A method for copolymerizing norbornene and ethylene using (tertiary butylamide) dimethyl (tetramethylcyclopentadienyl) silane titanium dichloride as a catalyst component is disclosed. Polymerization methods using these catalysts are excellent in that relatively high catalyst efficiency can be achieved.
However, there was a disadvantage that the conversion of the cyclic olefin was low.

[0003]

Accordingly, the present invention provides a novel organometallic compound having sufficient catalytic activity and capable of polymerizing a chain olefin or a cyclic olefin at a high conversion, and a process for preparing the same. It is an object of the present invention to provide an olefin polymerization catalyst containing the organometallic compound, and a (co) polymerization method of a linear or cyclic olefin using the catalyst.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned disadvantages of the prior art, and as a result, have found that a catalyst mainly composed of an organometallic compound having a specific compound as a ligand is used. By using the same, it was found that a chain olefin or a cyclic olefin can be (co) polymerized with a specifically high conversion, and the present invention has been completed. That is, the present invention relates to an organometallic compound having a structure represented by the following formula (I). (Wherein, M is a transition metal atom of Group 6; R ₁ , R ₂ and R ₃ are a hydrogen atom, a chain hydrocarbon group or a cyclic hydrocarbon group, which may be the same or different from each other; X is a halogen atom; m is an integer of 0 ≦ m ≦ 4;
Is an integer of 1 ≦ n ≦ 4. )

[0005] The present invention also relates to the following method for preparing an organometallic compound, characterized by reacting a component 1 with a component 2. Component 1) A transition metal compound having a structure represented by the following formula (II). MX _p (II) (wherein, M is a transition metal atom of Group 6; X is a halogen atom; p is an integer of 1 ≦ p ≦ 6). Component 2) The following formula (III) An alkali metal salt having a structure represented by the formula: (In the formula, R ₁ , R ₂ and R ₃ are a hydrogen atom, a chain hydrocarbon group or a cyclic hydrocarbon group, which may be the same or different.)

The present invention provides an olefin polymerization catalyst containing the above-mentioned organometallic compound, or the above-mentioned organometallic compound, further comprising an organoaluminum compound (B-1), an organoaluminum oxy compound (B-2) and an ionized ionic compound. Compound
The present invention relates to an olefin polymerization catalyst containing at least one compound (B) selected from (B-3). Also, the present invention
The present invention relates to an olefin polymerization method for polymerizing or copolymerizing a chain olefin or a cyclic olefin in the presence of the olefin polymerization catalyst.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The organometallic compound used in the method of the present invention is a compound having a structure represented by the following formula (I) (hereinafter, referred to as compound (A)). In the above formula (I), M is a transition metal atom of Group 6 of the periodic table. For example, there are chromium, molybdenum, and tungsten.

In the above formula (I), R ₁ , R ₂ and R ₃ are a hydrogen atom, a chain hydrocarbon group or a cyclic hydrocarbon group, which may be the same or different. Examples of the chain hydrocarbon group include those having 1 to 3 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and neopentyl, n-hexyl.
0, preferably 1 to 20 linear or branched alkyl groups; linear or branched alkenyl groups having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, such as vinyl, allyl and isopropenyl; Examples thereof include a linear or branched alkynyl group having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, such as ethynyl and propargyl. Examples of the cyclic hydrocarbon group include a cycloalkyl group and an aryl group. Examples of the cycloalkyl group include a saturated cycloalkyl group having 3 to 30, preferably 3 to 20 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and adamantyl, as well as cyclopentadienyl, indenyl and fluorenyl. And an unsaturated cycloalkyl group having 5 to 30 carbon atoms. As the aryl group, for example, phenyl, benzyl, naphthyl, biphenyl, terphenyl, phenanthryl, anthracenyl and the like have 6 to 30, preferably 6 carbon atoms.
In addition to the aryl groups of ２０20, alkyl-substituted aryl groups such as tolyl, iso-propylphenyl, t-butylphenyl, dimethylphenyl and di-t-butylphenyl are exemplified. R ₁ , R ₂ and R ₃ are preferably a methyl, isopropyl, n-butyl, t-butyl, cyclohexyl, phenyl and 2,6-diisopropylphenyl group.

Further, in the organometallic compound (A) represented by the formula (I) of the present invention, its catalytic activity is also affected by the steric influence of the types of R ₁ , R ₂ and R ₃ in the formula (I). It can vary, but can vary greatly depending on the electronic state of the central metal. That is, from the viewpoint of catalytic activity, the bonding mode between the metal and the ligand is important, and R ₁ , R ₂ and R ₃ in the formula (I) are not particularly limited to the above groups. Therefore, in the above formula (I), R ₁ , R ₂ and R ₃
Is a halogen atom, a hydroxy group, a carboxyl group, a cyano group, a nitro group, a sulfo group, a mercapto group, an alkoxy group, an alkylthio group, an aryloxy group, an arylthio group, an ester group, a thioester group, a heteroaryl group,
Even a silyl group, siloxy group or hydrocarbon group exerts a similar catalytic effect.

Here, as the halogen atom, for example,
Fluorine, chlorine, bromine and iodine. Examples of the alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy and t.
ert-butoxy and the like. Examples of the alkylthio group include methylthio and ethylthio. As the aryloxy group, for example, phenoxy, 2,
6-dimethylphenoxy and 2,4,6-trimethylphenoxy and the like. Examples of the arylthio group include phenylthio, methylphenylthio, and naphthylthio. Examples of the ester group include acetyloxy and benzoyloxy groups. Examples of the thioester group include acetylthio, benzoylthio, methylthiocarbonyl, phenylthiocarbonyl and the like. As the heteroaryl group, for example,
Nitrogen-containing heteroaryl groups such as pyrrolyl, pyridyl, pyrimidinyl, quinolyl and triazinyl; oxygen-containing heteroaryl groups such as furyl and pyranyl; sulfur-containing heteroaryl groups such as thienyl; and these heteroaryl groups have 1 to 1 carbon atoms. 30, further preferably a group further substituted with 1 to 20 substituents such as an alkyl group and an alkoxy group.

Examples of the silyl group include methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, diphenylmethylsilyl, triphenylsilyl, dimethylphenylsilyl, dimethyl-t-butylsilyl and dimethyl (pentafluorophenyl) silyl. And the like. Of these, methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, dimethylphenylsilyl and triphenylsilyl are preferred. Especially trimethylsilyl, triethylsilyl,
Triphenylsilyl and dimethylphenylsilyl are preferred. Examples of the siloxy group include trimethylsiloxy and the like.

Examples of the hydrocarbon group include a partially substituted hydrocarbon group in addition to the above-mentioned chain hydrocarbon group and cyclic hydrocarbon group. Examples of the partially substituted hydrocarbon group include halogen-substituted hydrocarbon groups having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms such as trifluoromethyl, pentafluorophenyl and chlorophenyl; and aryl-substituted alkyl groups such as benzyl and cumyl. A hydrocarbon group substituted hydrocarbon group such as a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group Substituted partially substituted hydrocarbon groups are exemplified.

In the formula (I) of the present invention, X represents a halogen atom. Here, examples of the halogen atom include fluorine, chlorine, bromine, and iodine. X is
It may be a hydrocarbon group. Examples of the hydrocarbon group include the same as the above-described hydrocarbon group, and preferably a methyl group, an ethyl group, and an allyl group. In the formula (I), m is an integer of 0 ≦ m ≦ 4, preferably 0 ≦ m ≦ 3
Is an integer. N is an integer of 1 ≦ n ≦ 4, preferably an integer of 1 ≦ n ≦ 3.

In the formula (I) of the present invention, any _two of R ₁ and R ₂ may be bonded to each other via an oxygen atom, a sulfur atom, an alkylsilylene group or a hydrocarbon group. Alternatively, they may be directly bonded. For example, two R ₁ together present in the compounds of the present invention (A) is, -R ₁ -O-R ₁ via an oxygen atom to one another - may also be combined with like, R ₁ each other It may be bonded directly like -R ₁ -R _1- . Here, examples of the alkylsilylene group include a methylsilylene group and a dimethylsilylene group. In addition, examples of the hydrocarbon group include an alkylene group and an ethylidene group.

The compound (A) of the present invention represented by the formula (I)
May be an organometallic compound having a structure in which a solvent molecule is coordinated, as represented by the following formula (IV). Where D is a solvent molecule. The solvent molecule coordinated in this manner is not particularly limited, and examples thereof include tetrahydrofuran, ether, and pyridine. Also,
l is an integer of 1 ≦ l ≦ 4, preferably an integer of 1 ≦ l ≦ 3. Other R ₁ , R ₂ , R ₃ , M, X, n and m are the same as those listed in the formula (I).

The present invention also relates to a compound represented by the above formula (I), wherein component 1 and component 2 are reacted.
A method for preparing (A) is provided. Component 1 is a transition metal compound having a structure represented by the following formula (II). MX _p (II) In the formula, M is a transition metal atom belonging to Group 6 of the periodic table, and examples thereof include the same as those in the above formula (I). For example, chrome,
There are molybdenum and tungsten. X is a halogen atom, and examples thereof include the same ones as in the above formula (I). For example, there are fluorine, chlorine, bromine and iodine. X is
It may be a hydrocarbon group. Examples of the hydrocarbon group include the same as the above-mentioned hydrocarbon group, and preferably a methyl group, an ethyl group, and an allyl group. p is 1 ≦
It is an integer of p ≦ 6, preferably an integer of 1 ≦ p ≦ 4.

The component 1 may be a transition metal compound having a structure coordinated with a solvent molecule as represented by the following formula (V). MX _p (D) _q (V) In the formula, D is a solvent molecule. The solvent molecule coordinated in this manner is not particularly limited, and examples thereof include tetrahydrofuran, ether, and pyridine. Also,
p is an integer of 1 ≦ p ≦ 6, preferably an integer of 1 ≦ p ≦ 4. Further, q is an integer of 0 ≦ q ≦ 6, preferably an integer of 1 ≦ q ≦ 4. Other M and X are the same as those listed in the formula (II).

Component 2 is an alkali metal salt having a structure represented by the following formula (III). In the formula, R ₁ , R ₂ and R ₃ are a hydrogen atom, a chain hydrocarbon group or a cyclic hydrocarbon group, which may be the same or different. Examples of the chain hydrocarbon group and the cyclic hydrocarbon group include the same as those in the above formula (I). Preferably, methyl, isopropyl, n-butyl, t-butyl,
Cyclohexyl, phenyl and 2,6-diisopropylphenyl groups. Further, R ₁ , R ₂ and R ₃ are represented by the above formulas
A halogen atom, a hydroxy group, as listed in (I),
Carboxyl group, cyano group, nitro group, sulfo group, mercapto group, alkoxy group, alkylthio group, aryloxy group, arylthio group, ester group, thioester group,
A heteroaryl group, a silyl group, a siloxy group or a hydrocarbon group, which may be the same or different from each other. Also,
Any _{one of} R ₁ and R ₂ is an oxygen atom, a sulfur atom,
They may be bonded via an alkylsilylene group or a hydrocarbon group, or may be directly bonded without a group.

The alkali metal salt represented by the above formula (III) may be prepared from a carbodiimide compound represented by the following formula (VI) and an organic alkali metal compound. R ₁ —N ＝ C ＝ N—R ₂ (VI) In the formula, R ₁ and R ₂ are a hydrogen atom, a chain hydrocarbon group or a cyclic hydrocarbon group, which may be the same or different.
As the chain hydrocarbon group and the cyclic hydrocarbon group, for example,
The same as the above formula (I) can be mentioned. Preferably, it is a methyl, isopropyl, n-butyl, t-butyl, cyclohexyl, phenyl, 2,6-diisopropylphenyl group. Further, R ₁ and R ₂ are a halogen atom, a hydroxy group, a carboxyl group, a cyano group, a nitro group, a sulfo group, a mercapto group, an alkoxy group, an alkylthio group, an aryloxy group, as listed in the above formula (I). An arylthio group, an ester group, a thioester group, a heteroaryl group, a silyl group, a siloxy group or a hydrocarbon group,
They may be the same or different. Examples of the organic alkali metal compound include methyl lithium, n-butyl lithium, t-butyl lithium, phenyl lithium and the like. Preferably, they are methyllithium and phenyllithium. R ₃ in the formula (III) is introduced from the organic alkali metal compound used here.

Component 2 is prepared, for example, as follows. A carbodiimide compound represented by the formula (VI) as a solvent,
It is preferably dissolved in the solvent D, and the organic alkali metal compound is added at -90 to 50C, preferably -80 to 0C. At this time, the molar ratio of the carbodiimide compound to the organic alkali metal compound is, for example, 1: 1 to 1: 2, preferably 1: 1 to 1.5. This solution is added at
After stirring at 0 ° C. for 1 to 2 hours, the temperature is raised to 0 to 50 ° C., and the mixture is further stirred for 10 minutes to 2 hours to obtain an alkali metal salt of Component 2.

The organometallic compound (A) represented by the formula (I) is
It is prepared by reacting the above components 1 and 2 as follows, for example. First, component 1 and a solvent, preferably solvent D, are added to 1 g of component 1, for example, and 1 to 1000 ml, preferably 5 to 100 ml, of solvent D are added and mixed to prepare a solvent solution of component 1. In a solvent solution of this component 1, -90 to 50 ° C, preferably -80 to 0 ° C
At the temperature of the above, the alkali metal salt of the above component 2 was added,
After stirring for 2 hours, the temperature is raised to 0 to 50 ° C., and the mixture is further stirred overnight. Thereafter, the solvent was distilled off under vacuum, and 1 to 1000 ml, preferably 5 to 500 m
Add l toluene. The resulting solution is -30 to 50
Stir further at 0 ° C, preferably 0-40 ° C, overnight. The precipitated salt is filtered and the toluene is distilled off under vacuum. A minimum amount of THF to dissolve the obtained solid was added, and further added T
Hexane is added at 0.1 to 10 times the amount of HF. By recrystallizing from these mixed solvents, the organometallic compound (A) of the present invention is obtained.

The organometallic compound represented by the above formula (I)
(A) can be used as the olefin polymerization catalyst of the present invention, by using the compound (A) alone or by combining the compound (B) as a promoter. The term "promoter" as used in the present invention means that it interacts with the organometallic compound of the present invention,
It refers to a compound that generates a polymerization active species for a chain olefin and a cyclic olefin. As the compound (B) used as the cocatalyst, for example, an organic aluminum compound (B-1), an organic aluminum oxy compound (B-
2) and one or more compounds selected from ionized ionic compounds (B-3).

As the organic aluminum compound (B-1), known organic aluminum compounds can be used.
Preferably, it is an organoaluminum compound having a structure represented by the formula E1 _a AlZ _(3-a) (provided that E1 is a hydrocarbon group having 1 to 8 carbon atoms, and even if all E1 are the same) Z represents hydrogen or halogen, and all Z may be the same or different.
Represents an integer of 1 to 3. ).

Examples of the organoaluminum compound (B-1) represented by the formula E1 _a AlZ _(3-a) include, for example, trialkyl aluminum such as trimethyl aluminum, triethyl aluminum, tripropyl aluminum, triisobutyl aluminum, and trihexyl aluminum. aluminum;
Dialkylaluminum chlorides such as dimethylaluminum chloride, diethylaluminum chloride, dipropylaluminum chloride, diisobutylaluminum chloride and dihexylaluminum chloride; alkylaluminums such as methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride and hexylaluminum dichloride Dichloride; dialkylaluminum hydride such as dimethylaluminum hydride, diethylaluminum hydride, dipropylaluminum hydride, diisobutylaluminum hydride and dihexylaluminum hydride; Among them, preferred are trialkylaluminums, and more preferred are triethylaluminum and triisobutylaluminum.

The organic aluminum oxy compound (B-
As 2), a known organic aluminum compound can be used. Preferably, the formula {-Al (E2) -O-} cyclic aluminoxane having a structure represented by _{b (B-2-1)} or Formula E3 {-Al (E3) -O-} c AlE3 2 structure (Where E2 and E3 are a hydrocarbon group having 1 to 8 carbon atoms, preferably methyl, ethyl, normal propyl, isopropyl, normal butyl, isobutyl, normal butyl). An alkyl group such as pentyl and neopentyl, more preferably a methyl group or an isobutyl group, all E2 and all E3 may be the same or different, b is 1 or more, preferably 2 to 2; An integer of 40, and c is 1 or more, preferably an integer of 1 to 40.)

The above-mentioned aluminoxane (B-2) is produced without any particular limitation by various known methods. For example, there is a method in which a solution prepared by dissolving a trialkylaluminum (for example, trimethylaluminum or the like) in a suitable organic solvent (for example, benzene or an aliphatic hydrocarbon) is brought into contact with water. Further, there is a method in which a trialkylaluminum (for example, trimethylaluminum or the like) is brought into contact with a metal salt (for example, copper sulfate hydrate or the like) containing water of crystallization.

The ionized ionic compound (B-3) refers to a compound which reacts with the organometallic compound (A) to form an ion pair. Examples of the ionized ionic compound (B-3) include a boron compound (B-3-1) represented by the formula BQ1Q2Q3 and a boron compound (B-3-2) represented by the formula J ⁺ (BQ1Q2Q3Q4) ^-. , Formula (LH) ⁺ (BQ1Q2Q3
Q4) ^- boron compound represented by (B-3-3) can be mentioned. Boron compound represented by the formula BQ1Q2Q3 (B-3
In -1), B is a boron atom in a trivalent valence state, and Q1 to Q3 are a halogen atom, a hydrocarbon group containing 1 to 20 carbon atoms, and containing 1 to 20 carbon atoms. A halogenated hydrocarbon group, a hydrocarbon-substituted silyl group containing 1 to 20 carbon atoms, an alkoxy group containing 1 to 20 carbon atoms or a disubstituted amino group containing 2 to 20 carbon atoms, May be the same or different.
Preferred Q1 to Q3 are a halogen atom, a hydrocarbon group containing 1 to 20 carbon atoms, and a halogenated hydrocarbon group containing 1 to 20 carbon atoms. As the boron compound (B-3-1) represented by the formula BQ1Q2Q3, for example, tris (pentafluorophenyl) borane, tris (2,3)
5,6-tetrafluorophenyl) borane, tris (2,3,4,5-tetrafluorophenyl) borane,
Tris (3,4,5-trifluorophenyl) borane,
Tris (2,3,4-trifluorophenyl) borane and phenylbis (pentafluorophenyl) borane are exemplified. Most preferably, it is tris (pentafluorophenyl) borane.

In the boron compound (B-3-2) represented by the formula J ⁺ (BQ1Q2Q3Q4) ^- , B is a boron atom in a trivalent valence state, and Q1 to Q4 are the boron compound (B It is the same as Q1 to Q3 in -3-1). Also,
J ⁺ is an inorganic or organic cation. Examples of the J ⁺ include a ferrocenium cation, an alkyl-substituted ferrocenium cation, and a silver cation as inorganic cations, and a triphenylmethyl cation as an organic cation. Wherein (BQ1Q2Q3Q4) ^- include, for example, tetrakis (pentafluorophenyl)
Borate, tetrakis (2,3,5,6-tetrafluorophenyl) borate, tetrakis (2,3,4,5-
Tetrafluorophenyl) borate, tetrakis (3
4,5-trifluorophenyl) borate, tetrakis (2,2,4-trifluorophenyl) borate, phenylbis (pentafluorophenyl) borate and tetrakis (3,5-bistrifluoromethylphenyl) borate Can be Therefore, the formula J ⁺ (BQ1Q2Q3Q
As the boron compound represented by ^{(B-3-2), - 4} )
For example, ferrocenium tetrakis (pentafluorophenyl) borate, 1,1′-dimethylferrocenium tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate, triphenylmethyltetrakis (pentafluorophenyl) borate and And triphenylmethyltetrakis (3,5-bistrifluoromethylphenyl) borate. More preferred is triphenylmethyltetrakis (pentafluorophenyl) borate.

In the boron compound (B-3-3) represented by the formula (LH) ⁺ (BQ1Q2Q3Q4) ^- , B is a trivalent boron atom, and Q1 to Q4 are as defined above. It is the same as Q1 to Q3 in the boron compound (B-3-1).
L is a neutral Lewis base, and (LH) ⁺ is a Bronsted acid. Examples of (LH) ⁺ include trialkyl-substituted ammonium, N, N-dialkylanilinium, dialkylammonium, and triarylphosphonium. The above (BQ1Q2Q3Q
4) ^- as, for example, the boron compound (B-3-2)
And the same as those described in (1).

[0030] Therefore, the formula ^{(L-H) + (BQ1Q2Q3Q4} ) - as a boron compound represented by (B-3-3), for example, triethylammonium tetrakis (pentafluorophenyl) borate, tripropyl ammonium tetrakis (penta Fluorophenyl) borate, tri (n)
-Butyl) ammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (3,5-bistrifluoromethylphenyl)
Borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (pentafluorophenyl)
Borate, N, N-2,4,6-pentamethylanilinium tetrakis (pentafluorophenyl) borate,
N, N-dimethylanilinium tetrakis (3,5-bistrifluoromethylphenyl) borate, di-iso
-Propylammonium tetrakis (pentafluorophenyl) borate, dicyclohexylammonium tetrakis (pentafluorophenyl) borate, triphenylphosphonium tetrakis (pentafluorophenyl) borate, tri (methylphenyl) phosphonium tetrakis (pentafluorophenyl) borate and tri (dimethylphenyl) ) Phosphonium tetrakis (pentafluorophenyl) borate and the like. More preferred is tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate or N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate.

In the olefin polymerization method of the present invention, a chain olefin or a cyclic olefin can be polymerized or copolymerized in the presence of the olefin polymerization catalyst. Here, as described above, the olefin polymerization catalyst contains the organometallic compound (A) represented by the formula (I), and further comprises the organoaluminum compound (B-1) and the organoaluminum oxy compound (B-2). ) And an ionized ionic compound (B-3). Examples of the chain olefin that can be polymerized by the olefin polymerization catalyst of the present invention include, for example, ethylene, propylene, 1-butene, 2-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, and 4-methyl. -1-
Pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-
2 to 2 carbon atoms such as octadecene and 1-eicosene
30, preferably 2 to 20 linear or branched α-
Olefins and the like. Among them, ethylene, propylene and 1-hexene are preferred. Examples of the cyclic olefin that can be polymerized by the olefin polymerization catalyst of the present invention include, for example, cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene and 2-methyl 1,4,5,8- Dimethano-1,2,3,
Examples thereof include cyclic olefins having 3 to 30, preferably 3 to 20 carbon atoms, such as 4,4a, 5,8,8a-octahydronaphthalene. Among them, cyclopentene, cyclohexene and norbornene are preferred.

Other monomers that can be polymerized by the olefin polymerization catalyst of the present invention include, for example, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride and bicyclo (2,2,1) -5-heptene. Α, β-unsaturated carboxylic acids such as -2,3-dicarboxylic anhydride and metal salts thereof such as sodium salt, potassium salt, lithium salt, zinc salt, magnesium salt and calcium salt; methyl acrylate,
Ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, Α, β-unsaturated carboxylic esters such as isopropyl methacrylate, n-butyl methacrylate and isobutyl methacrylate; vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate and trifluoroester Vinyl esters such as vinyl acetate; and unsaturated glycidyls such as glycidyl acrylate, glycidyl methacrylate and monoglycidyl itaconate.

Further, vinylcyclohexane, diene, polyene and the like can be polymerized with the catalyst for olefin polymerization of the present invention. Here, as the diene or polyene, for example,
A cyclic or chain compound having 4 to 30, preferably 4 to 20 carbon atoms and having two or more double bonds is exemplified. Specifically, 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 ,Five-
Octadiene, 1,6-octadiene, 1,7-octadiene,
Ethylidene norbornene, vinyl norbornene, dicyclopentadiene; 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene and 5,9-dimethyl-1,
4,8-decatriene; mono- or polyalkyl such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene and p-ethylstyrene Aromatic vinyl compounds such as styrene; functional group-containing styrene derivatives such as methoxystyrene, ethoxystyrene, vinylbenzoic acid, methyl vinylbenzoate, vinylbenzyl acetate, hydroxystyrene, o-chlorostyrene, p-chlorostyrene and divinylbenzene 3-phenylpropylene, 4-phenylpropylene and α-methylstyrene.

The chain olefin and the cyclic olefin,
Alternatively, other monomers can be polymerized or copolymerized alone or in combination of a plurality of olefins and / or monomers. In the olefin polymerization method of the present invention, the copolymer of cyclic olefin and ethylene exhibits the most significant effect of the olefin polymerization catalyst of the present invention.

The polymerization method that can be employed in the olefin polymerization method of the present invention is not particularly limited, and a known polymerization method can be employed. Examples of the olefin polymerization method of the present invention include a batch or continuous gas phase polymerization method, a bulk polymerization method, a solution polymerization method using an appropriate solvent, and a slurry polymerization method. When a solvent is used, various solvents can be used as long as the catalyst is not deactivated. Solvents that can be used in the present invention include, for example, benzene,
Hydrocarbons such as toluene, pentane, hexane, heptane and cyclohexane; and halogenated hydrocarbons such as dichloromethane and ethylene dichloride. In the polymerization of the olefin, the compound (A) and the compound (B) may be added in an arbitrary order, or a compound obtained by arbitrarily combining
A mixture obtained by previously contacting (A) and / or compound (B) may be added.

The amount of compound (A) used is, for example, based on the total amount of all olefins and / or monomers used,
0.000001 to 1 mol%, preferably 0.0000
1 to 0.1 mol%. The amount of compound (B) used is such that the molar ratio of compound (B) / compound (A) is, for example, 0.1.
The range is from 01 to 10,000, preferably from 0.5 to 5,000. When each compound is used in a solution state, the compound
The concentration of (A) is 0.0001 to 5 mmol / liter,
Preferably, it is in the range of 0.001 to 3 mmol / liter. The concentration of the compound (B) is 0.001 to 50.
00 mmol / liter, preferably 0.001 to 3
000 mmol / l. There is no particular limitation on the polymerization temperature, and the polymerization is carried out, for example, at a temperature of -100 to 250C, preferably -50 to 200C. There is no particular limitation on the pressure, for example, 9.8 MPa
Hereinafter, it is preferably carried out at 0.1 MPa to 4.9 MPa. In addition, a chain transfer agent such as hydrogen may be added to adjust the molecular weight of the polymer. Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

[0037]

EXAMPLES The structure of the compound obtained in the example was FT-I
R (manufactured by Nicole, MAGN-IR860), 1H NMR (manufactured by JEOL Ltd., JNM-EX270), high-temperature GPC (manufactured by Waters, ALC / GPC150-)
C), DSC device (manufactured by Seiko, DSC220C), metal content analysis,
It was determined using carbon, hydrogen, nitrogen content analysis and the like. (Example 1) (1) Synthesis of transition metal complex [N, N'-bis (cyclohexyl) methylamidinato] ₂ CrCl
Synthesis of ([N, N'-Bis (cyclohexyl) methylamidinat] ₂ CrCl) complex In a 100 ml Schlenk atmosphere under an argon atmosphere, N, N'-
Bis (cyclohexyl) carbodiimide (N, N'-Bis (cyclo
412 mg (2 mmol) of hexcyl) carbodiimide) in THF
Dissolve in 10 ml and at -78 ° C 1.14 M methyllithium (M
eLi) / diethyl ether solution (1.75 ml, 2 mmol) was added. After stirring this solution at -78 ° C for 2 hours, it was heated to room temperature and further stirred for 30 minutes to obtain a white suspension. This suspension was added to a separately prepared C at a temperature of -78 ° C.
rCl ₃ (thf) ₃ 374 mg (1 mmol) in THF 10 ml
Added to the solution. The solution was stirred at -78 ° C for 1 hour and then at room temperature overnight. Thereafter, THF is distilled off under vacuum,
40 ml of toluene was added, and the mixture was further stirred at room temperature overnight.
The precipitated salt was filtered and toluene was distilled off under vacuum. The minimum amount of THF for dissolving the obtained solid was added and completely dissolved, and then the same amount of hexane as THF was added. This mixed solution was concentrated to about 1/3 and left at −20 ° C. for 2 weeks. By washing the precipitated crystals with cold hexane,
[N, N'-bis (cyclohexyl) methylamidinate] ₂ CrCl
([N, N'-Bis (cyclohexyl) methylamidinate] ₂ CrCl) complex was obtained (yield 21%).

(2) Norbornene polymerization In a 100 ml Schlenk purged with argon, [N, N'-
Bis (cyclohexyl) methylamidinato] ₂ CrCl ([N, N'-
Bis (cyclohexyl) methylamidinate] ₂ CrCl) complex 2.3μ
mol was dissolved in 1 ml of dehydrated toluene.
Modified methylaluminoxane (trimethylaluminum / triisobutylaluminum = 7/3) toluene solution [Tosoh Akzo Co., Ltd., MMAO-3A, 5.8% by mass Al]
3 ml (6.4 mmol as Al) was added, and the mixture was stirred at room temperature for 30 minutes. To this solution, 1 g of a 75% by mass norbornene toluene solution was added to initiate polymerization. The mixture was stirred at room temperature for 12 hours under a nitrogen atmosphere. Thereafter, the reaction solution was diluted with hydrochloric acid 1
It was poured into a mixture of 0 ml and 100 ml of methanol, and the precipitate was filtered to obtain a white solid. The white solid was washed with methanol and dried under reduced pressure to obtain a purified polymer (360 mg, yield: 48%). The resulting polymer was analyzed by the FT-IR, C-H stretching vibration of methylene chains 2800 to 3000 cm ^-1 are scissor vibration of methylene group was observed in 1450~1470cm ^-1. Alkene stretching vibration of 1640 to 1660 cm ^-1 observed in the case of the ring-opened polymer was not observed. Therefore, it was confirmed that the polymer had a structure in which norbornene was addition-polymerized while maintaining a ring structure.

Example 2 100 m purged with argon
l During Schlenk, [N, N'-bis (cyclohexyl) methyl
Rumidinato]_TwoCrCl ([N, N'-Bis (cyclohexyl) methylami
dinate]_Two2.3 μmol of CrCl) complex in 1 m of dehydrated toluene
1) Add the solution dissolved in
Minoxane (trimethylaluminum / triisobutyl
Aluminum, molar ratio = 7/3) toluene solution [Toso
-Akzo Corporation, MMAO-3A, 5.8 mass% Al] 3
ml (6.4 mmol as Al) and add at room temperature for 30 minutes
Stirred. After freezing and degassing, ethylene is introduced at 1 atm and polymerized
Started. After stirring at room temperature for 2 hours, the reaction solution was diluted with hydrochloric acid (1).
Into a mixture of 0 ml and 100 ml of methanol.
The residue was filtered to obtain a white solid. The white solid is methanol
And dried under reduced pressure to obtain 65 mg of a purified polymer.
Was. The obtained polymer was analyzed by FT-IR described above.
2,800-3000cm^-1To CH extension of methylene chain
Shrinking vibration is 1450-1470cm^-1Of the methylene group
Scissors vibrations were observed. Also, 720cm ^-1In phase with
The methylene roll vibration of was observed. Therefore, the polymer
Was confirmed to be polyethylene. Polymerization activity
Was 4 g-P / mmol.atom.h. Polymer fusion
The point (Tm) was 137 ° C.

Example 3 (1) Synthesis of Transition Metal Complex [N, N'-bis (2,6-diisopropylphenyl) methylamidinato] ₂ CrCl ([N, N'-Bis (2,6-diisopropylphenyl) methyl
amidinate] ₂ CrCl) under argon atmosphere complex, in 100ml Schlenk, N, N'
Bis (2,6-diisopropylphenyl) carbodiimide (N,
N'-Bis (2,6-diisopropylphenyl) carbodiimide) 748
mg (2 mmol) in 10 ml of THF,
A 1.14M methyllithium (MeLi) / diethyl ether solution (1.75 ml, 2 mmol) was added. This solution was added to -78
After stirring at 2 ° C. for 2 hours, the mixture was heated to room temperature and further stirred for 30 minutes. The obtained solution was mixed with 374 mg (1 mmol) of CrCl ₃ (thf) ₃ separately prepared at −78 ° C. in THF.
Added to 10 ml solution. The solution was stirred at -78 ° C for 1 hour and then at room temperature overnight. Thereafter, THF was distilled off under vacuum, 40 ml of toluene was added, and the mixture was further stirred at room temperature overnight. The precipitated salt was filtered and toluene was distilled off under vacuum. The minimum amount of THF for dissolving the obtained solid was added and completely dissolved, and then the same amount of hexane as THF was added. This mixed solution is concentrated to about 1/3, and
Left for a week. The precipitated crystals are washed with cold hexane to give [N, N'-bis (2,6-diisopropylphenyl) methylamidinato] ₂ CrCl ([N, N'-Bis (2,6-diisopropylph
enyl) methylamidinate] ₂ CrCl) complex was obtained (yield 15
%).

(2) Norbornene polymerization In a 100 ml Schlenk purged with argon, [N, N '
-Bis (2,6-diisopropylphenyl) methylamidinato]
₂ CrCl ([N, N'-Bis (2,6-diisopropylphenyl) methylami
dinate] ₂ CrCl) complex 2.3 μmol in dehydrated toluene 1 m
and a solution of modified methylaluminoxane (trimethylaluminum / triisobutylaluminum, molar ratio = 7/3) in toluene [manufactured by Tosoh Akzo Co., Ltd., MMAO-3A, 5.8% by mass Al] 3
ml (6.4 mmol as Al) was added and stirred at room temperature for 30 minutes. To this solution, 1 g of a 75% by mass norbornene toluene solution was added to initiate polymerization. The mixture was stirred at room temperature for 12 hours under a nitrogen atmosphere. Thereafter, the reaction solution was diluted with hydrochloric acid 1
It was poured into a mixture of 0 ml and 100 ml of methanol, and the precipitate was filtered to obtain a white solid. The white solid was washed with methanol and dried under reduced pressure to obtain 590 mg of a purified polymer (78% yield). The resulting polymer was analyzed by the FT-IR, C-H stretching vibration of methylene chains 2800 to 3000 cm ^-1 are scissor vibration of methylene group was observed in 1450~1470cm ^-1. Alkene stretching vibration of 1640 to 1660 cm ^-1 observed in the case of the ring-opened polymer was not observed. Therefore, it was confirmed that the polymer had a structure in which norbornene was addition-polymerized while maintaining a ring structure. The weight average molecular weight of the polymer is 700
It was 0.

Example 4 In a 100 ml Schlenk purged with argon, [N, N'-
Bis (2,6-diisopropylphenyl) methylamidinate] ₂
CrCl ([N, N'-Bis (2,6-diisopropylphenyl) methylamid
inate] ₂ CrCl) complex, 2.3 μmol, dehydrated toluene 3 m
Then, a solution of 625 μmol of ethyl aluminum dichloride (EtAlCl ₂ ) in hexane was added, and the mixture was stirred at room temperature for 30 minutes. After freezing and degassing, polymerization was started by introducing ethylene at 1 atm. After stirring at 0 ° C. for 2 hours, the reaction solution was diluted with 10 ml of hydrochloric acid and 100 ml of methanol.
And the precipitate was filtered to give a white solid. The white solid was washed with methanol and dried under reduced pressure to obtain 65 mg of a purified polymer. The obtained polymer was subjected to F
When analyzed by T-IR, it was 2800 to 3000 cm ^-1.
The CH stretching vibration of the methylene chain is 1450-1470
A scissor vibration of a methylene group was observed at cm ^-1 . Also,
A methylene roll vibration at the same phase at 720 cm ^-1 was observed. Therefore, it was confirmed that the polymer was polyethylene. The polymerization activity is 120 g-P / mmol-atom-h
Met. The polymer had a Tm of 135 ° C. and a weight average molecular weight of 470,000.

[0043]

According to the present invention, an olefin polymerization catalyst having high polymerization activity for a chain olefin or a cyclic olefin is provided. Further, according to the olefin polymerization method of the present invention, an olefin (co) polymer can be produced with high polymerization activity.

Continued on the front page (72) Inventor Toru Tokimitsu 20-1 Miyuki-cho, Otake City, Hiroshima Prefecture F-term in Central Research Laboratory, Mitsubishi Rayon Co., Ltd. EB02 EB03 EB04 EB05 EB06 EB07 EB08 EB09 EB10 EB17 EB18 FA01 FA02 FA04 4J128 AA01 AB00 AC41 AC42 BA00A BA01B BB00A BB01B BC14B BC18B BC24B BC25B BC42B EB01 EB02 EB03 FA04 EB04 EB04 EB04 EB04 EB04 EB05 EB05

Claims (6)

[Claims] An organometallic compound having a structure represented by the following formula (I): (Wherein, M is a transition metal atom of Group 6; R ₁ , R ₂ and R ₃ are a hydrogen atom, a chain hydrocarbon group or a cyclic hydrocarbon group, which may be the same or different from each other; X is a halogen atom; m is an integer of 0 ≦ m ≦ 4;
Is an integer of 1 ≦ n ≦ 4. ) 2. In the formula (I), M is chromium; R ₁ and R ₂ are cycloalkyl groups or aryl groups, which may be the same or different from each other; and R ₃ is an alkyl group. Item 7. The organometallic compound according to Item 1. 3. The method for preparing an organometallic compound according to claim 1, wherein the component 1 and the component 2 are reacted as described below. Component 1) A transition metal compound having a structure represented by the following formula (II). MX _p (II) (wherein, M is a transition metal atom of Group 6; X is a halogen atom; p is an integer of 1 ≦ p ≦ 6). Component 2) The following formula (III) An alkali metal salt having a structure represented by the formula: (In the formula, R ₁ , R ₂ and R ₃ are a hydrogen atom, a chain hydrocarbon group or a cyclic hydrocarbon group, which may be the same or different.) 4. A catalyst for olefin polymerization, comprising the organometallic compound according to claim 1 or 2. 5. An organic aluminum compound (B-
The catalyst for olefin polymerization according to claim 4, comprising 1 or more compounds (B) selected from 1), an organoaluminum oxy compound (B-2) and an ionized ionic compound (B-3). 6. A method for polymerizing an olefin, comprising polymerizing or copolymerizing a chain olefin or a cyclic olefin in the presence of the olefin polymerization catalyst according to claim 4 or 5.