JPH08253522A - Olefin polymerization catalyst and production of olefin polymer using the same - Google Patents

Abstract

PURPOSE: To obtain a catalyst which efficiently produces a polymer having a mol.wt. in a practically usable range even without using a chain transfer agent by incorporating a specific transition metal compd. and a compd. capable of reacting therewith to form an ionic complex into the catalyst. CONSTITUTION: This catalyst contains a transition metal compd. represented by formula I [wherein M is a group IV metal; Cp is substd. cyclopentadienyl group represented by formula II (wherein R is a 1-20C alkyl, a 6-20C aryl, a 7-20C aralkyl, or silyl provided adjacent R's may combine with each other to form a ring; and (n) is 1-4); and L<1> , L<2> , and L<3> are each a σ-bonding ligand] and a compd. capable of reacting with the foregoing compd. or its deriv. to form an ionic complex. The catalyst not only enables an efficient production of a polymer having a mol.wt. in a practically usable range without using a chain transfer agent, which reduces the catalyst activity, but also exhibits an excellent performance in copolymn. and can reduce the amt. of a comonomer used.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an olefin polymerization catalyst and a method for producing an olefin polymer using the same, and more specifically, to a catalyst for practical use without using a chain transfer agent which causes a decrease in catalytic activity. A catalyst for olefin polymerization capable of efficiently giving a polymer having a molecular weight, excellent in copolymerizability, and capable of reducing the amount of comonomer used, and an olefin polymer having a molecular weight in a practical range by using this catalyst, particularly The present invention relates to a method for efficiently producing linear low density polyethylene.

[0002]

2. Description of the Related Art In recent years, a catalyst composed of a metallocene compound of a transition metal and an aluminoxane (for example, JP-A-58-19309) has attracted attention as a new olefin polymerization catalyst. Although this catalyst exhibits extremely high polymerization activity and relatively good copolymerizability, it has a problem that it requires a large amount of aluminoxane and its copolymerizability is still insufficient. Therefore, the inventors of the present invention have previously proposed, as a catalyst exhibiting a high activity per aluminum and an extremely excellent copolymerizability, for olefin polymerization containing a specific transition metal compound and an aluminum oxy compound in a predetermined molar ratio. Proposed a catalyst (Japanese Patent Application No. 6-75691)
issue). This catalyst has excellent copolymerizability, high activity per aluminum and high activity per transition metal, and has an unprecedented excellent physical property, especially a linear polymer, having a narrow molecular weight distribution and a relatively wide composition distribution. Efficiently provides low density polyethylene. However, since the activity is high, the molecular weight is likely to increase, there is room for improvement in controlling the molecular weight, and it has been desired to further improve the copolymerizability. The use of a chain transfer agent is effective for controlling the molecular weight, but in general, the use of a chain transfer agent causes a problem that the catalytic activity is greatly reduced.

[0003]

Under the circumstances, the present invention can efficiently provide a polymer having a molecular weight in a practical range without using a chain transfer agent which causes a reduction in catalytic activity. , An olefin polymerization catalyst which is excellent in copolymerizability and can reduce the amount of comonomer used, and an olefin polymer having a molecular weight in a practical range, particularly a linear low-polymerization catalyst, without causing a large decrease in catalytic activity. It is an object of the present invention to provide a method for efficiently producing high density polyethylene.

[0004]

Means for Solving the Problems As a result of intensive studies for achieving the above-mentioned object, the present inventors have found that a specific cyclopentadienyl group having one substituted cyclopentadienyl group in which the kind and number of the substituents are defined. A transition metal compound, a compound capable of reacting with the transition metal compound or a derivative thereof to form an ionic complex,
More preferably, the catalyst in combination with a phenolic compound can efficiently give a polymer having a molecular weight in a practical range without using a chain transfer agent, has excellent copolymerizability, and reduces the amount of comonomer used. I found that Then, in the presence of this catalyst, without using a chain transfer agent, homopolymerization of olefins or copolymerization of olefins with other olefins and / or other polymerizable unsaturated compounds, the catalytic activity of It was found that an olefin polymer having a molecular weight in a practical range, particularly a linear low density polyethylene, can be efficiently obtained without causing a large reduction. The present invention has been completed based on such findings. That is, the present invention provides (A) general formula (I) CpML ¹ L ² L ³ ... (I) [wherein, M represents a metal element of Group 4 of the periodic table, and Cp represents
General formula (II)

[0005]

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(R represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms or a silyl group.
May be the same or different, and adjacent Rs may be bonded to each other to form a ring structure, and n is 1 to 4
Indicates an integer. ) Is a substituted cyclopentadienyl group. L ¹ , L ² and L ³ each represent a σ-bonding ligand, which may be the same or different. ] A transition metal compound represented by the formula (B), a compound capable of reacting with the transition metal compound of the component (A) or a derivative thereof to form an ionic complex, and optionally (C) a phenolic compound The present invention provides a catalyst for olefin polymerization.

The present invention is also characterized by homopolymerizing olefins or copolymerizing olefins with other olefins and / or other polymerizable unsaturated compounds in the presence of the above-mentioned olefin polymerization catalyst. It also provides a method for producing an olefin-based polymer. The catalyst for olefin polymerization of the present invention comprises (A) a transition metal compound, (B) a compound capable of reacting with the transition metal compound of the component (A) or a derivative thereof to form an ionic complex, and optionally, And (C) a phenolic compound. The transition metal compound of the component (A) is represented by the general formula (I) CpML ¹ L ² L ³ ... (I). In the general formula (I), M
Represents a metal element of Group 4 of the periodic table, and specific examples thereof include titanium, zirconium, hafnium, etc. Among them, titanium is particularly preferable in terms of activity, molecular weight control and copolymerizability. preferable. Cp is
General formula (II)

[0008]

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A substituted cyclopentadienyl group represented by Here, R represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a silyl group. The alkyl group having 1 to 20 carbon atoms may be linear, branched or cyclic,
Specific examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s
Examples thereof include ec-butyl group, t-butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, cyclopentyl group and cyclohexyl group. Carbon number 6 ~
The aryl group of 20 may have an appropriate substituent introduced into the aromatic ring, such as a lower alkyl group or a lower alkoxy group, and specific examples thereof include a phenyl group, a tolyl group, a xylyl group, a methoxyphenyl group, and an ethoxy group. Examples thereof include a phenyl group. The aralkyl group having 7 to 20 carbon atoms may have an appropriate substituent introduced into the aromatic ring, such as a lower alkyl group or a lower alkoxy group, and specific examples thereof include:
Examples thereof include a benzyl group, a phenethyl group and a methylbenzyl group. Examples of the silyl group include a trimethylsilyl group and a triphenylsilyl group. n
Is an integer of 1 to 4, when n is 0, the activity is low, and when n is 5, the molecular weight becomes too high and the effect of improving the copolymerizability is not sufficiently exhibited. From the viewpoint of activity, suppression of molecular weight and copolymerizability, the preferable range of n is 1 to
It is 3. When there are a plurality of Rs, the plurality of Rs may be the same or different, and adjacent groups may be bonded to each other to form a ring structure.

Specific examples of Cp include a methylcyclopentadienyl group; an ethylcyclopentadienyl group; n
-Propylcyclopentadienyl group; isopropylcyclopentadienyl group; n-butylcyclopentadienyl group; isobutylcyclopentadienyl group; sec-butylcyclopentadienyl group; t-butylcyclopentadienyl group; n -Hexylcyclopentadienyl group; cyclohexylcyclopentadienyl group; phenylcyclopentadienyl group; monosubstituted cyclopentadienyl group such as trimethylsilylcyclopentadienyl group, 1,3-di-methylcyclopentadienyl group 1,3-di-n-propylcyclopentadienyl group; 1,3-diisopropylcyclopentadienyl group; 1,3-di-n-butylcyclopentadienyl group; 1,3-di-t- Butylcyclopentadienyl group; 1,2-dimethylcyclopentadienyl group; 1,2- -n- propyl cyclopentadienyl group; 1,2--n- butyl cyclopentadienyl group; 1,3-diphenyl-cyclopentadienyl group; 1,
2-Substituted cyclopentadienyl group such as 3-bis (trimethylsilyl) cyclopentadienyl group, 1,3,4-trimethylcyclopentadienyl group; 1,3,4-tri-
n-propylcyclopentadienyl group; 1,3,4-tri-n-butylcyclopentadienyl group; 1,2,3-
Trimethylcyclopentadienyl group; 1,2,3-tri-n-propylcyclopentadienyl group; 1,2,3-
3-Substituted cyclopentadienyl group such as tri-n-butylcyclopentadienyl group, 1,2,3,4-tetramethylcyclopentadienyl group; 1-n-butyl-2,3,
4-substituted cyclopentadienyl groups such as 4-trimethylcyclopentadienyl are mentioned.

On the other hand, L ¹ , L ² and L ³ are σ
It is a σ ligand coordinated to the M by a bond. Examples of the σ-bonding ligand include R ′, OR ′, SR ′, S
Preferable examples include O ₃ R ′, NR′R ″, PR′R ″, hydrogen atom, halogen atom, 1-pyrrolyl group and 1-pyrrolidinyl group. Here, R ′ and R ″ are a hydrocarbon group having 1 to 20 carbon atoms or a silyl group containing a hydrocarbon group, and at least one of the σ ligands is O.
Preferably R ', NR'R "or PR'R", C
It is preferable that p and L ¹ , L ² and L ³ are bonded to each other so as not to form a cyclic structure.

[0012] In the above R'and R ", examples of the hydrocarbon group having 1 to 20 carbon atoms include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group and the like. For example, methyl group, ethyl group, n-propyl group, isopropyl group, n-
A butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, etc., and a cycloalkyl group such as a cyclopentyl group or a cyclohexyl group is an aryl group. Examples of the group include a phenyl group and a tolyl group, and examples of the aralkyl group include a benzyl group and a phenethyl group. As the silyl group containing a hydrocarbon group, for example, a trimethylsilyl group,
Examples thereof include a triphenylsilyl group. O
Specific examples of R'include methoxy group, ethoxy group, n-
Propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, t-butoxy group,
Examples thereof include an alkoxy group such as a pentoxy group, a hexoxy group, an octoxy group and a cyclohexoxy group, and an aryloxy group such as a phenoxy group. Also, SR '
Specific examples thereof include a methyl sulfide group, an ethyl sulfide group, a cyclohexyl sulfide group, and a phenyl sulfide group. And SO ₃ R '
Specific examples of alkylsulfonyl such as methanesulfonyl group, ethanesulfonyl group, n-propanesulfonyl group, isopropanesulfonyl group, n-butanesulfonyl group, sec-butanesulfonyl group, t-butanesulfonyl group, isobutanesulfonyl group. Group, an arylsulfonyl group such as a benzenesulfonyl group, and the like. Further, specific examples of NR'R "include dimethylamide group, diethylamide group, di (n-propyl) amide group, diisopropylamide group, di (n-butyl) amide group, diisobutylamide group, di (sec-butyl) group. )
Examples thereof include amide group, di (t-butyl) amide group, dipentylamide group, dihexylamide group, dioctylamide group, diphenylamide group, dibenzylamide group and methylethylamide group. In addition, specific examples of PR′R ″ include a dimethylphosphide group, a diethylphosphide group, a di (n-propyl) phosphide group, a diisopropylphosphide group, a di (n-butyl) phosphide group,
Diisobutylphosphide group, di (sec-butyl) phosphide group, di (t-butyl) phosphide group, dipentylphosphide group, dihexylphosphide group, dioctylphosphide group, diphenylphosphide group, dibenzylphosphide group, dibenzyl Examples thereof include naphthylphosphide group, methylethylphosphide group, (t-butyl) trimethylsilylphosphide group, and methyltrimethylsilylphosphide group. Further, as the halogen atom, chlorine,
Examples thereof include bromine and iodine.

The transition metal compound represented by the general formula (I) includes methylcyclopentadienyl titanium trichloride; isopropylcyclopentadienyl titanium trichloride; n-butylcyclopentadienyl titanium trichloride; t- Butylcyclopentadienyl titanium trichloride; 1,3-dimethylcyclopentadienyl titanium trichloride; 1,
2-dimethylcyclopentadienyl titanium trichloride; 1,3,4-trimethylcyclopentadienyl titanium trichloride; 1,2,3-trimethylcyclopentadienyl titanium trichloride; 1,
2,3,4-Tetramethylcyclopentadienyl titanium trichloride; methylcyclopentadienyl titanium trimethoxide; isopropylcyclopentadienyl titanium trimethoxide; n-butylcyclopentadienyl titanium trimethoxide; t- Butylcyclopentadienyl titanium trimethoxide; 1,3-
Dimethylcyclopentadienyl titanium trimethoxide; 1,2-Dimethylcyclopentadienyl titanium trimethoxide; 1,3,4-Trimethylcyclopentadienyl titanium trimethoxide; 1,2,3-Trimethylcyclopentadi 1,2,3,4-tetramethylcyclopentadienyltitanium trimethoxide; methylcyclopentadienyltitanium triisopropoxide; isopropylcyclopentadienyltitanium triisopropoxide;
n-Butylcyclopentadienyltitanium triisopropoxide; t-butylcyclopentadienyltitanium triisopropoxide; 1,3-dimethylcyclopentadienyltitanium triisopropoxide; 1,2-
Dimethylcyclopentadienyl titanium triisopropoxide; 1,3,4-Trimethylcyclopentadienyl titanium triisopropoxide; 1,2,3-Trimethylcyclopentadienyl titanium triisopropoxide; Methylcyclopentadienyl Titanium tree
sec-butoxide; isopropylcyclopentadienyltitanium tri-sec-butoxide; n-butylcyclopentadienyltitanium tri-sec-butoxide; t-butylcyclopentadienyltitanium tri-
sec-butoxide; 1,3-dimethylcyclopentadienyltitanium tri-sec-butoxide; 1,2-
Dimethylcyclopentadienyl titanium tri-sec
-Butoxide; 1,3,4-trimethylcyclopentadienyltitanium tri-sec-butoxide; 1,2,
3-trimethylcyclopentadienyl titanium tri-
sec-butoxide; 1,2,3,4-tetramethylcyclopentadienyltitanium tri-sec-butoxide; methylcyclopentadienyltitaniumdichloro-
sec-butoxide; isopropylcyclopentadienyltitaniumdichloro-sec-butoxide; n-butylcyclopentadienyltitaniumdichloro-sec-
Butoxide; t-butylcyclopentadienyltitaniumdichloro-sec-butoxide; 1,3-dimethylcyclopentadienyltitaniumdichloro-sec-butoxide; 1,2-dimethylcyclopentadienyltitaniumdichloro-sec-butoxide; 1, 3,4-trimethylcyclopentadienyl titanium dichloro-se
c-butoxide; 1,2,3-trimethylcyclopentadienyl titanium dichloro-sec-butoxide;
1,2,3,4-Tetramethylcyclopentadienyl titanium dichloro-sec-butoxide; methylcyclopentadienyl titanium chlorodimethoxide; isopropylcyclopentadienyl titanium chlorodimethoxide; n-butyl cyclopentadienyl titanium chloro Dimethoxide; t-butylcyclopentadienyl titanium chlorodimethoxide; 1,3-dimethylcyclopentadienyl titanium chlorodimethoxide; 1,2-
Dimethylcyclopentadienyl titanium chlorodimethoxide; 1,3,4-Trimethylcyclopentadienyl titanium chlorodimethoxide; 1,2,3-Trimethylcyclopentadienyl titanium chlorodimethoxide; 1,2,3,4- Tetramethylcyclopentadienyltitanium chlorodimethoxide; Methylcyclopentadienyltitaniumdichloro (diphenylamide); Isopropylcyclopentadienyltitaniumdichloro (diphenylamide); n-butylcyclopentadienyltitaniumdichloro (diphenylamide); t -Butylcyclopentadienyl titanium dichloro (diphenylamide); 1,3-dimethylcyclopentadienyl titanium dichloro (diphenylamide); 1,2-dimethylcyclopentadiene Le titanium dichloro (diphenylamide); 1,3,4-trimethyl cyclopentadienyl titanium dichloro (diphenylamide); 1,
2,3-trimethylcyclopentadienyltitanium dichloro (diphenylamide); methylcyclopentadienyltitanium chlorobis (diphenylamide); isopropylcyclopentadienyltitanium chlorobis (diphenylamide); n-butylcyclopentadienyltitanium Chlorobis (diphenylamide); t-butylcyclopentadienyltitanium chlorobis (diphenylamide); 1,3-dimethylcyclopentadienyltitanium chlorobis (diphenylamide); 1,2
-Dimethylcyclopentadienyltitanium chlorobis (diphenylamide); 1,3,4-trimethylcyclopentadienyltitanium chlorobis (diphenylamide); 1,2,3-trimethylcyclopentadienyltitanium chlorobis (diphenylamide) ); Methylcyclopentadienyl titanium dichloro (diphenylphosphide); Isopropyl cyclopentadienyl titanium dichloro (diphenylphosphide); n-Butyl cyclopentadienyl titanium dichloro (diphenylphosphide); t-butylcyclopentadienyl Titanium dichloro (diphenylphosphide); 1,3-dimethylcyclopentadienyl titanium dichloro (diphenylphosphide); 1,2-dimethylcyclopentadienyl titanium dichloride (Diphenylphosphine); 1,
3,4-trimethylcyclopentadienyl titanium dichloro (diphenylphosphide); 1,2,3-trimethylcyclopentadienyl titanium dichloro (diphenylphosphide); methylcyclopentadienyl titanium chlorobis (diphenylphosphide); Isopropyl cyclopentadienyl titanium chlorobis (diphenylphosphide); n-butylcyclopentadienyl titanium chlorobis (diphenylphosphide); t-butylcyclopentadienyl titanium chlorobis (diphenylphosphide); 1,3- Dimethylcyclopentadienyltitanium chlorobis (diphenylphosphide); 1,2-dimethylcyclopentadienyltitanium chlorobis (diphenylphosphide); 1,3,4-
Trimethylcyclopentadienyl titanium chlorobis (diphenylphosphide); 1,2,3-trimethylcyclopentadienyl titanium chlorobis (diphenylphosphide); Methylcyclopentadienyl titanium tris (dimethylamide); Isopropylcyclopentadi N-butylcyclopentadienyltitanium tris (dimethylamide); t-butylcyclopentadienyltitanium tris (dimethylamide); 1,3-dimethylcyclopentadienyltitanium tris (dimethylamide) );
1,2-dimethylcyclopentadienyltitanium tris (dimethylamide); 1,3,4-trimethylcyclopentadienyltitanium tris (dimethylamide);
1,2,3-Trimethylcyclopentadienyl titanium tris (dimethylamide); methylcyclopentadienyl titanium tris (diethylphosphide); isopropylcyclopentadienyl titanium tris (diethylphosphide); n-butylcyclopentadi Ethyl titanium tris (diethyl phosphide); t-butyl cyclopentadienyl titanium tris (diethyl phosphide); 1,3-dimethylcyclopentadienyl titanium tris (diethyl phosphide); 1,2-dimethyl cyclopentadienyl Titanium tris (diethylphosphide); 1,3,4-trimethylcyclopentadienyl titanium tris (diethylphosphide); 1,2,3
-Trimethylcyclopentadienyltitanium tris (diethylphosphide) and the like, and those in which titanium in these compounds is replaced with zirconium or hafnium. Of course, it is not limited to these.

In the polymerization catalyst of the present invention, the above (A)
The transition metal compound as a component may be used alone or in combination of two or more. In the polymerization catalyst of the present invention, as the component (B), a compound capable of reacting with the transition metal compound of the component (A) or a derivative thereof to form an ionic complex is used.

The component (B) includes (B-1)
Ionic complex that reacts with the transition metal compound of component (A)
Forming ionic compound, (B-2) aluminoxa
And (B-3) Lewis acid. (B-
As the component 1), the transition metal compound of the component (A) and
An ionic compound that reacts to form an ionic complex
Any of them can be used, but the following general formula
(III), (IV) ([L^Four-R¹]^{k +})_a([Z]^-)_b ... (III) ([L^Five]^{k +})_a([Z]^-)_b ... (IV) [However, L^FiveIs M², R²R³M³, R^Four ₃ C or R
^FiveM³Is. ] [(III), (IV) In formula, L^FourIs a Lewis base, [Z]
^-Is a non-coordinating anion [Z ¹]^-Or [Z²]^-, This
Here [Z¹]^-Is an anion in which multiple groups are bound to an element.
Nawachi [M¹G¹G²... G^f]^-(Where M¹Is
Periodic Table Group 5 to 15 elements, preferably Periodic Table 13
~ Group 15 elements are shown. G¹~ G^fAre hydrogen atoms,
Halogen atom, C1-20 alkyl group, C2
~ 40 dialkylamino group, C1-20 alco
Xy group, aryl group having 6 to 20 carbon atoms, 6 to 20 carbon atoms
Aryloxy group of 7 to 40 carbon atoms
Group, arylalkyl group having 7 to 40 carbon atoms, 1 carbon atom
~ 20 halogen-substituted hydrocarbon groups, C 1-20
Syloxy group, organic metalloid group, or 2 to 20 carbon atoms
The heteroatom-containing hydrocarbon group of is shown. G¹~ G^fOut of
Two or more may form a ring. f is [(central metal
M¹Valence of +1)]. ), [Z²]
^-Has a logarithm (pKa) of the reciprocal of the acid dissociation constant of -10 or less.
Bronsted acid alone or Bronsted acid and Rui
With a conjugate base of a combination of sulphonic acids, or, in general, superacids
The defined conjugate base is shown. Also, the Lewis base coordinates
May be. Also, R¹Is a hydrogen atom, having 1 to 20 carbon atoms
Alkyl group, aryl group having 6 to 20 carbon atoms, alkyl
An aryl group or an arylalkyl group, R²And R
³Are cyclopentadienyl group and substituted cyclopenes, respectively.
Tadienyl group, indenyl group or fluorenyl group, R^Four
Is an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkyl
An aryl group or an arylalkyl group is shown. R^FiveIs Tet
Macrocyclic compounds such as laphenylporphyrin and phthalocyanine
Show the order. k is [L^Four-R¹], [L^Five] Ion value of
Number is an integer of 1 to 3, a is an integer of 1 or more, b = (k × a)
Is. M²Is Periodic Table Nos. 1-3, 11-13, 17
It contains a group element, M³Is the 7th to 12th periodic table
Indicates a group element. ] Use preferably those represented by
Can be. Where L^FourAs a concrete example of
A, methylamine, aniline, dimethylamine, diet
Luamine, N-methylaniline, diphenylamine,
N, N-dimethylaniline, trimethylamine, trie
Cylamine, tri-n-butylamine, methyldipheni
Luamine, pyridine, p-bromo-N, N-dimethyl
Niline, p-nitro-N, N-dimethylaniline, etc.
Amines, triethylphosphine, triphenylphosphine
Phosphines such as tin and diphenylphosphine, tet
Thioethers such as lahydrothiophene, benzoic acid
Esters such as chill, acetonitrile, benzonitri
Examples thereof include nitriles such as nitrile.

Specific examples of R ¹ include hydrogen, methyl group,
Examples thereof include an ethyl group, a benzyl group and a trityl group. Specific examples of R ² and R ³ include a cyclopentadienyl group, a methylcyclopentadienyl group, an ethylcyclopentadienyl group and a pentamethylcyclopenta group. A dienyl group etc. can be mentioned. As a specific example of R ⁴ ,
Examples thereof include a phenyl group, p-tolyl group, p-methoxyphenyl group, and the like. Specific examples of R ⁵ include tetraphenylporphine, phthalocyanine, allyl, methallyl and the like. In addition, specific examples of M ² include Li, Na, K, Ag, Cu, Br, I, and I ₃ , and specific examples of M ³ include Mn,
Fe, Co, Ni, Zn etc. can be mentioned.

[Z ¹ ] ^- , that is, [M ¹ G ¹ G
² ... G ^f ], specific examples of M ¹ include B, A
1, Si, P, As, Sb, etc., preferably B and Al
Is mentioned. Specific examples of G ¹ and G ^{2 to} G ^f include a dimethylamino group and a diethylamino group as a dialkylamino group, a methoxy group, an ethoxy group, an n-butoxy group as an alkoxy group or an aryloxy group,
As a hydrocarbon group such as phenoxy group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group,
Fluorine, chlorine, bromine, etc. as halogen atoms such as isobutyl group, n-octyl group, n-eicosyl group, phenyl group, p-tolyl group, benzyl group, 4-t-butylphenyl group, 3,5-dimethylphenyl group. Iodine, p-fluorophenyl group as a hydrocarbon group containing a hetero atom, 3,5
-Difluorophenyl group, pentachlorophenyl group,
3,4,5-trifluorophenyl group, pentafluorophenyl group, 3,5-bis (trifluoromethyl) phenyl group, bis (trimethylsilyl) methyl group, etc. as organic metalloid group pentamethylantimony group, trimethylsilyl group, trimethyl Examples thereof include germyl group, diphenylarsine group, dicyclohexylantimony group and diphenylboron.

Further, a non-coordinating anion, that is, pKa
There -10 or less Bronsted acid alone or a combination of conjugate base of a Bronsted acid and Lewis acid [Z ^{2] -} trifluoromethanesulfonic acid anion Specific examples of (CF ₃ SO ₃₎ ^-, bis (trifluoromethanesulfonyl ) Methyl anion, bis (trifluoromethanesulfonyl) benzyl anion, bis (trifluoromethanesulfonyl) amide, perchlorate anion (Cl
O ₄ ) ^- , trifluoroacetic acid anion (CF ₃ CO ₂ )
^- , Hexafluoroantimony anion (Sb
F ₆ ) ^- , Fluorosulfonate anion (FS
O ₃ ) ^- , Chlorosulfonate anion (ClS
O ₃ ) ⁻ , fluorosulfonate anion / 5-antimony fluoride (FSO ₃ / SbF ₅ ) ⁻ , fluorosulfonate anion / 5-arsenic fluoride (FSO ₃ / As
F ₅ ) ^- , trifluoromethanesulfonic acid / 5-antimony fluoride (CF ₃ SO ₃ / SbF ₅ ) ^{-, and the} like.

Specific examples of the ionic compound which reacts with the transition metal compound of the component (A) to form an ionic complex, that is, the compound of the component (B-1) are as follows.
Triethylammonium tetraphenylborate, tri-n-butylammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, methyl (tri-n-butyl) ammonium tetraphenylborate, benzyl tetraphenylborate (tri-n- Butyl) ammonium, dimethyldiphenylammonium tetraphenylborate, triphenyl (methyl) ammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, benzylpyridinium tetraphenylborate, methyl tetraphenylborate (2-cyanopyridinium) , Tetrakis (pentafluorophenyl) borate triethylammonium, tetrakis (pentafluorophenyl) ) Tri-n-butylammonium borate, tetrakis (pentafluorophenyl) triphenylammonium borate, tetrakis (pentafluorophenyl) tetra-n-butylammonium borate, tetrakis (pentafluorophenyl) tetraethylammonium borate, tetrakis (pentafluorophenyl) Benzyl (tri-n-butyl) ammonium borate, Methyldiphenylammonium tetrakis (pentafluorophenyl) borate, Triphenyl (methyl) ammonium tetrakis (pentafluorophenyl) borate, Methylanilinium tetrakis (pentafluorophenyl) borate, Tetrakis (penta) Fluorophenyl) borate dimethylanilinium, tetrakis (pentafluorophenyl) borate trimethylanilinium, tetrakis Methylpyridinium pentafluorophenyl) borate, Benzylpyridinium tetrakis (pentafluorophenyl) borate, Methyl tetrakis (pentafluorophenyl) borate (2-cyanopyridinium), Benzyl tetrakis (pentafluorophenyl) borate (2-cyanopyridinium), Tetrakis ( Methyl (4-cyanopyridinium) pentafluorophenyl) borate, triphenylphosphonium tetrakis (pentafluorophenyl) borate, dimethylanilinium tetrakis [bis (3,5-ditrifluoromethyl) phenyl] borate, ferrocenium tetraphenylborate, tetraphenyl Silver borate, trityl tetraphenylborate, tetraphenylporphyrin manganese tetraphenylborate, tetrakis (pentafluorophenyl) borate fe Rothenium, tetrakis (pentafluorophenyl)
Boric acid (1,1′-dimethylferrocenium), tetrakis (pentafluorophenyl) decamethylferrocenium borate, tetrakis (pentafluorophenyl) silver borate, tetrakis (pentafluorophenyl) trityl borate, tetrakis (pentafluorophenyl) Lithium borate, sodium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate theoraphenylporphyrin manganese, silver tetrafluoroborate, silver hexafluorophosphate, silver hexafluoroarsenate,
Examples thereof include silver perchlorate, silver trifluoroacetate, and silver trifluoromethanesulfonate. This (B-
The ionic compound, which is the component (1) and which reacts with the transition metal compound of the component (A) to form an ionic complex, may be used alone or in combination of two or more. On the other hand, as the aluminoxane as the component (B-2),
General formula (V)

[0020]

[Chemical 4]

[Wherein R ⁶ is an alkyl group, an alkenyl group, an aryl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms,
It represents a hydrocarbon group such as an arylalkyl group or a halogen atom, w represents the degree of polymerization, and is generally an integer of 3 to 50, preferably 7 to 40. Each R ⁶ may be the same or different. ] A chain aluminoxane represented by
And general formula (VI)

[0022]

Embedded image

[In the formula, R ⁶ and w are the same as defined above. ] The cyclic aluminoxane shown by these can be mentioned. Examples of the method for producing the aluminoxane include a method in which an alkylaluminum and a condensing agent such as water are brought into contact with each other, but the means therefor is not particularly limited, and the reaction may be performed according to a known method. For example, a method in which an organoaluminum compound is dissolved in an organic solvent and then brought into contact with water, a method in which an organoaluminum compound is initially added at the time of polymerization and water is added later, water of crystallization contained in a metal salt, etc. , A method of reacting water adsorbed to an inorganic substance or an organic substance with an organoaluminum compound, a method of reacting a tetraalkyldialuminoxane with a trialkylaluminum, and further reacting with water. The aluminoxane may be insoluble in toluene. These aluminoxanes can be classified as shown below. (A) An alkylaluminoxane produced by using a single alkylaluminum (organoaluminum) compound,
For example, methylaluminoxane, ethylaluminoxane, n-propylaluminoxane, isopropylaluminoxane, n-butylaluminoxane, isobutylaluminoxane, sec-butylaluminoxane, t-butylaluminoxane and the like.

(B) A mixed alkylaluminoxane obtained by selecting two or more kinds from the alkylaluminoxanes produced in (a) above and mixing them in a predetermined ratio. (C) Copolymerization type alkylaluminoxane obtained by mixing two or more kinds of alkylaluminum (organoaluminum) compounds in a predetermined ratio during the production by the above methods (1), for example, methyl-ethylaluminoxane, methyl-n-propyl. Aluminoxane, methyl-isopropylaluminoxane, methyl-n-butylaluminoxane,
Methyl-isobutylaluminoxane, ethyl-n-propylaluminoxane, ethyl-isopropylaluminoxane, ethyl-n-butylaluminoxane, ethyl-isobutylaluminoxane and the like. These aluminoxanes may be used alone or in combination of two or more. Further, among the aluminoxanes, the alkylaluminoxane is particularly suitable. In the aluminoxane thus obtained, the alkylaluminum that is the starting material for its synthesis may remain and may be contained as an impurity.
It can be used as is.

The Lewis acid as the component (B-3) is not particularly limited and may be an organic compound or a solid inorganic compound. The organic compound is a boron compound or an aluminum compound, the inorganic compound is a magnesium compound,
Aluminum compounds and the like are preferably used. Examples of the aluminum compound include bis (2,6-di-t-
Butyl-4-methylphenoxy) aluminum methyl,
(1,1-Bi-2-naphthoxy) aluminum methyl and the like, magnesium compounds such as magnesium chloride and diethoxymagnesium, aluminum compounds such as aluminum oxide and aluminum chloride, and boron compounds such as triphenylboron. , Tris (pentafluorophenyl) boron, tris [3,5-
Bis (trifluoromethyl) phenyl] boron, tris [(4-fluoromethyl) phenyl] boron, trimethylboron, triethylboron, tri-n-butylboron, tris (fluoromethyl) boron, tris (pentafluoroethyl) boron, Tris (nonafluorobutyl) boron, tris (2,4,6-trifluorophenyl) boron, tris (3,5-difluoro) boron, tris [3,5-bis (trifluoromethyl) phenyl] boron, bis ( Pentafluorophenyl) fluoroboron, diphenylfluoroboron, bis (pentafluorophenyl) chloroboron, dimethylfluoroboron, diethylfluoroboron, di-n-
Examples thereof include butylfluoroboron, pentafluorophenyldifluoroboron, phenyldifluoroboron, pentafluorophenyldichloroboron, methyldifluoroboron, ethyldifluoroboron, n-butyldifluoroboron and the like. These Lewis acids may be used alone or in combination of two or more.

The ratio of the catalyst component (A) to the catalyst component (B) used in the polymerization catalyst of the present invention is such that when the compound (B-1) is used as the catalyst component (B), the catalyst activity, etc. From the aspect, it is preferable that the molar ratio is 10: 1 to 1: 100,
The range of 2: 1 to 1:10 is more preferable, and in the case of using the compound (B-2), the molar ratio is preferably 1: 1 to 1: 100,000 from the viewpoint of catalytic activity and the like.
The range of 0, more preferably 1:10 to 1: 10000 is desirable. The ratio of the (A) catalyst component to the (B-3) catalyst component used is preferably 1: 0.1 to 1: 2000, more preferably 1: 0.
2 to 1: 1000, more preferably 1: 0.5 to 1: 5
A range of 00 is desirable. In the polymerization catalyst of the present invention, as the component (B), the components (B-1) and (B-
2) and the component (B-3) may be used alone, or two or more kinds may be appropriately used in combination. In particular, the chain and / or cyclic aluminoxane of the component (B-2) is used as a catalyst. It is preferable in terms of activity and properties of the polymer obtained.

In the polymerization catalyst of the present invention, a phenolic compound or a Lewis base such as water can be used together with the above-mentioned components (A) and (B) for the purpose of further improving the activity, but in particular ( It is effective to use a phenolic compound as the component C). The phenolic compound has, for example, at least 1 hydrogen atom bonded to an aromatic ring such as a benzene ring or a naphthalene ring.
One hydroxyl group or at least one hydroxyl group and at least one
There may be mentioned compounds substituted with a substituent other than individual hydroxyl groups.

Examples of the substituent other than the hydroxyl group are shown below.
For example, R⁷, OR⁷, SR⁷, NR⁷R⁸， Halogen source
Child, nitro group, etc. R⁷, R⁸Has 1 carbon
~ 20 hydrocarbon groups, alkyl groups, cycloalkyl
Groups, aryl groups, aralkyl groups and the like. Alkyl group
Are, for example, methyl group, ethyl group, n-propyl
Group, isopropyl group, n-butyl group, isobutyl group, s
ec-butyl group, t-butyl group, pentyl group, hexyl
Group, octyl group, decyl group, dodecyl group, etc.
Examples of the alkyl group include a cyclopentyl group and a cyclo group.
An aryl group such as a lohexyl group is, for example,
Examples of aralkyl groups such as phenyl and tolyl are
Examples include benzyl and phenethyl groups.
Wear. OR⁷As specific examples of, methoxy group, ethoxy
Group, n-propoxy group, isopropoxy group, n-butoxy group
Si group, isobutoxy group, sec-butoxy group, t-but
Xy group, pentoxy group, hexoxy group, octoxy group,
Alkoxy group such as cyclohexoxy group, phenoxy group
And an aryloxy group. NR
⁷R⁸Specific examples of are dimethylamino group, diethyl
Amino group, di (n-propyl) amino group, diisopropyi
Ruamino group, di (n-butyl) amino group, diisobutyl
Amino group, di (sec-butyl) amino group, di (t-butyl)
Cyl) amino group, dipentylamino group, dihexylamido
Group, dioctylamino group, diphenylamino group, dibe
And the like. Also, halo
Examples of the gen atom include chlorine, bromine, iodine and fluorine.
Can be

As the phenolic compound used as the component (C), a phenolic compound substituted with a hydrocarbon group having 1 to 20 carbon atoms is preferable, and particularly, α of the hydroxyl group,
Phenolic compounds in which the α'-position is substituted with a hydrocarbon group having 1 to 20 carbon atoms are suitable.

Specific examples of the phenolic compound include:
Phenol; 2-methylphenol; 2-ethylphenol; 2-n-propylphenol; 2-isopropylphenol; 2-n-butylphenol; 2-sec-
Butylphenol; 2-tert-butylphenol;
3-tert-butylphenol; 4-tert-butylphenol; 4-tert-octylphenol; 2
-N-dodecylphenol; 2-phenylphenol;
4-phenylphenol; 2,6-dimethylphenol; 2,6-diethylphenol; 2,6-di-ter
t-Butylphenol; 2,4-di-tert-butylphenol; 2-tert-butyl-4-methylphenol; 2-tert-butyl-5-methylphenol;
2-tert-butyl-6-methylphenol; 2-n
-Dodecyl-4-methylphenol; 4-n-dodecyl-2-methylphenol; 2,6-diphenylphenol; 2,6-di-tert-butyl-4-methylphenol; 2,6-di-tert-butyl -4-ethylphenol; 2,4,6-tri-tert-butylphenol; 2,2'-methylenebis (4-methyl-6-ter)
t-butylphenol); 2,2'-methylenebis (4
-Ethyl-6-tert-butylphenol); 4,
4'-methylenebis (2,6-di-tert-butylphenol); 4,4'-butylidenebis (6-tert
-Butyl-m-cresol); 4,4'-thiobis (6
-Tert-butyl-m-cresol); α-naphthol; β-naphthol; 2-fluorophenol; 3-fluorophenol; 4-fluorophenol; 2,4-
2,5-difluorophenol; 2,6-difluorophenol; 2-methoxyphenol; 3-methoxyphenol; 4-methoxyphenol; 2,6-di-tert-butyl-4-methoxyphenol; N, N -Dimethyl-3-aminophenol;
N, N-diethyl-3-aminophenol; N, N-di-n-butyl-3-aminophenol; 2,6-di-t
ert-butyl-4-dimethylaminophenol; 2-
3-Nitrophenol; 3-Nitrophenol; 4-Nitrophenol; 2-Nitro-4-methylphenol; 3-
4-nitro-3-methylphenol; 5-nitro-2-methylphenol; 5-nitro-2-methylphenol; catechol; resorcinol; hydroquinone; 3-methylcatechol; 4-methylcatechol; 4-tert-butylcatechol; 2- 5-methylresorcinol; 5-methylresorcinol; methylhydroquinone; tert-butylhydroquinone; 2,5-di-tert-butylhydroquinone; 1,2-dihydroxynaphthalene; 1,4-
Dihydroxynaphthalene; 1,5-dihydroxynaphthalene; 1,6-dihydroxynaphthalene; 1,7-dihydroxynaphthalene; 2,3-dihydroxynaphthalene; 2,7-dihydroxynaphthalene; pyrogallol;
Phloroglucinol; 1,2,4-trihydroxybenzene; hexahydroxybenzene and the like. These phenolic compounds may be used alone or in combination of two or more.

The phenolic compound as the component (C) is
When used in combination with the aluminoxane as the component (B-2), the activity improving effect is particularly remarkable. In this case, the molar ratio of the hydroxyl group of the phenolic compound / the arunoxane (in terms of aluminum) of the component (B-2) is It is preferable to use it in the range of 0.001 to 0.8. This molar ratio is 0.
If it is less than 001, the activity improving effect is insufficient, and if it is less than 0.
On the contrary, when it exceeds 8, the activity tends to decrease. From the viewpoint of improving the activity, a more preferable molar ratio is in the range of 0.01 to 0.6, particularly preferably in the range of 0.05 to 0.5.

In the polymerization catalyst of the present invention, an organoaluminum compound may be used as the component (D), if necessary, for the purpose of improving the activity. Examples of the organoaluminum compound as the component (D) include general formula (VII) R ⁹ _V AlJ _3-V (VII) [wherein, R ⁹ is an alkyl group having 1 to 10 carbon atoms, and J is a hydrogen atom. , An alkoxy group having 1 to 20 carbon atoms, and 6 to 20 carbon atoms
Represents an aryl group or a halogen atom, and v is an integer of 1 to 3. ] The compound shown by these is used. Specific examples of the compound represented by the general formula (VII) include trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, methyl aluminum dichloride, ethyl aluminum dichloride, dimethyl aluminum fluoride. ，
Examples include diisobutylaluminum hydride, diethylaluminum hydride, ethylaluminum sesquichloride. These organoaluminum compounds may be used alone or in combination of two or more. From the standpoint of catalytic activity, etc., the use ratio of the (A) catalyst component and the (D) catalyst component is preferably 1: 1 to 1: 1 in terms of molar ratio.
The range of 0000, more preferably 1: 5 to 1: 2,000, and even more preferably 1:10 to 1: 1,000 is desirable. By using the catalyst component (D), the polymerization activity per transition metal can be improved, but if it is too much, the organoaluminum compound is wasted and a large amount remains in the polymer, which is not preferable.

In the present invention, at least one of the catalyst components can be used by supporting it on a suitable carrier. There is no particular limitation on the type of the carrier, an inorganic oxide carrier,
Although any other inorganic carrier or organic carrier can be used, an inorganic oxide carrier or another inorganic carrier is particularly preferable. Specific examples of the inorganic oxide carrier include SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ and TiO ₂ .
₂ , Fe ₂ O ₃ , B ₂ O ₃ , CaO, ZnO, BaO,
Examples include ThO ₂ and mixtures thereof, such as silica alumina, zeolite, ferrite, and glass fiber. Of these, SiO ₂ and Al ₂ O ₃ are particularly preferable. The inorganic oxide carrier is a small amount of carbonate,
It may contain nitrates, sulfates and the like.

On the other hand, as a carrier other than the above, MgC
Examples thereof include magnesium compounds represented by the general formula MgR ¹⁰ _x X ¹ _y represented by magnesium compounds such as l ₂ and Mg (OC ₂ H ₅ ) ₂ and complex salts thereof.
Here, R ¹⁰ is an alkyl group having 1 to 20 carbon atoms, and 1 carbon atom
To an alkoxy group having 20 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, X ¹ represents a halogen atom or an alkyl group having 1 to 20 carbon atoms, x is 0 to 2, y is 0 to 2, and x + y =
It is 2. Each R ¹⁰ and each X ¹ may be the same,
It may also be different.

As the organic carrier, polystyrene,
Styrene-divinylbenzene copolymer, polyethylene,
Examples thereof include polymers such as polypropylene, substituted polystyrene and polyarylate, starch, carbon and the like. As the carrier used in the present invention, MgC
l ₂ , MgCl (OC ₂ H ₅ ), Mg (OC ₂ H ₅ ) ₂ ,
SiO ₂ , Al ₂ O _{3 and the} like are preferable. The properties of the carrier vary depending on the type and production method, but the average particle size is usually 1 to 300 μm, preferably 10 to 200 μm, and more preferably 20 to 100 μm. When the particle size is small, fine powder in the polymer increases, and when the particle size is large, coarse particles in the polymer increase, which causes a decrease in bulk density and clogging of the hopper. The specific surface area of the carrier is usually 1 to 1000 m ² /
g, preferably 50 to 500 m ² / g, the pore volume is usually
It is 0.1 to ⁵ cm ³ / g, preferably 0.3 to ³ cm ³ / g. If either the specific surface area or the pore volume deviates from the above range, the catalytic activity may decrease. The specific surface area and the pore volume can be obtained from the volume of nitrogen gas adsorbed according to, for example, the BET method (Journal of the American Chemical Society, Volume 60, page 309 (1983)). reference). Furthermore, it is desirable that the above-mentioned carrier is usually calcined at 150 to 1000 ° C., preferably 200 to 800 ° C. before use.

When at least one catalyst component is supported on the carrier, at least one of (A) catalyst component and (B) catalyst component, preferably (A) catalyst component and (B).
It is desirable to support both catalyst components. In the carrier,
The method of supporting at least one of the component (A) and the component (B) is not particularly limited. For example, a method of mixing at least one of the component (A) and the component (B) with a carrier, an organoaluminum compound as a carrier. Alternatively, a method of treating with a halogen-containing silicon compound and then mixing with at least one of the components (A) and (B) in an inert solvent, a carrier, a component (A) and / or a component (B) and an organoaluminum compound, or Method of reacting with halogen-containing silicon compound, method of loading component (A) or component (B) on carrier and then mixing with component (B) or component (A), component (A) and component (B) It is possible to use a method of mixing a reaction product of contact with the carrier with a carrier, a method of allowing a carrier to coexist in the contact reaction between the component (A) and the component (B), and the like. In the above reaction and
It is also possible to add a phenolic compound as the component (C) and / or an organoaluminum compound as the component (D).

The catalyst thus obtained may be used for the polymerization after the solvent is once distilled off and taken out as a solid, or may be used for the polymerization as it is. Further, in the present invention, the catalyst can be produced by carrying out the loading operation of at least one of the component (A) and the component (B) on the carrier in the polymerization system. For example, at least one of the components (A) and (B), a carrier, and optionally a phenolic compound of the component (C) and an organoaluminum compound of the component (D) are added, and an olefin such as ethylene is added at atmospheric pressure to 20 kg / cm ² G plus -20 to 200
It is possible to use a method in which catalyst particles are produced by carrying out prepolymerization at a temperature of 1 minute to 2 hours.

In the present invention, the above compound (B-1)
The ratio of the component to the carrier used is preferably 1: 5 by weight.
˜1: 10000, more preferably 1:10 to 1:50
0 is desirable, and the ratio of the component (B-2) to the carrier is preferably 1: 0.5 to 1: 1000 by weight.
More preferably, the ratio is 1: 1 to 1:50,
The weight ratio of the component (B-3) to the carrier is preferably 1: 5 to 1: 10000, more preferably 1:10.
It is desirable to be set to about 1: 500. When two or more kinds of catalyst components (B) are mixed and used, it is desirable that the weight ratio of each component (B) to the carrier be within the above range. The ratio of component (A) to the carrier is preferably 1: 5 to 1: 10000 by weight, more preferably 1:10 to 1: 500 by weight.

Component (B) [Component (B-1), (B-
If the ratio of the component (2) or the component (B-3)] to the carrier or the ratio of the component (A) to the carrier deviates from the above range, the activity may decrease. The average particle size of the polymerization catalyst of the present invention thus prepared is usually 2 to 200.
μm, preferably 10 to 150 μm, particularly preferably 2
0 to 100 μm, and the specific surface area is usually 20 to 100
0 m ² / g, preferably from 50 to 500 m ² / g.
If the average particle diameter is less than 2 μm, fine powder in the polymer may increase, and if it exceeds 200 μm, coarse particles in the polymer may increase. If the specific surface area is less than 20 m ² / g, the activity may decrease, and 1000 m ² / g
If it exceeds, the bulk density of the polymer may decrease. Moreover, in the catalyst of the present invention, the amount of transition metal in 100 g of the carrier is usually 0.05 to 10 g, and particularly preferably 0.1 to 2 g. If the amount of transition metal is out of the above range, the activity may decrease. By thus supporting on a carrier, a polymer having a high bulk density industrially advantageous and an excellent particle size distribution can be obtained.

In the method for producing an olefin polymer of the present invention, in the presence of the polymerization catalyst prepared as described above, homopolymerization of olefins or olefins with other olefins and / or other polymerizable non-polymerizable Copolymerization with a saturated compound is carried out. The olefins are not particularly limited and include, for example, ethylene; propylene; butene-1; pentene-1; hexene-1; heptene-1; octene-
1; nonene-1; decene-1; 4-phenylbutene-
1; 6-phenylhexene-1; 3-methylbutene-
1; 4-methylpentene-1; 3-methylpentene-
1; 3-methylhexene-1; 4-methylhexene-
1; 5-methylhexene-1; 3,3-dimethylpentene-1; 3,4-dimethylpentene-1; 4,4-dimethylpentene-1; 3,5,5-trimethylhexene-
1; α-olefins such as vinylcyclohexane, hexafluoropropene; tetrafluoroethylene; 2-fluoropropene; fluoroethylene; 1,1-difluoroethylene; 3-fluoropropene; trifluoroethylene; 3,4-dichlorobutene-1. And halogen-substituted α-olefins such as Further, the other olefins described above may be appropriately selected from the above olefins. In the present invention, the olefins may be used alone or in combination of two or more.

In the present invention, other polymerizable unsaturated compounds copolymerized with the above olefins include, for example, cyclic olefins, cyclic diolefins, chain conjugated diolefins, chain non-conjugated diolefins. , Aromatic vinyl compounds, unsaturated esters, lactones, lactams, epoxides and the like can be used. Examples of the cyclic olefins include cyclopentene; cyclohexene; norbornene; 5-methylnorbornene; 5
-Ethyl norbornene; 5-propyl norbornene;
5,6-dimethylnorbornene; 1-methylnorbornene; 7-methylnorbornene; 5,5,6-trimethylnorbornene; 5-phenylnorbornene; 5-benzylnorbornene and the like, and examples of cyclic diolefins include 5- Examples include ethylidene norbornene; 5-vinyl norbornene; dicyclopentadiene; norbornadiene.

Further, as the chain conjugated diolefins,
For example, 1,3-butadiene; isoprene and the like, and as the chain non-conjugated diolefins, for example, 1,
4-hexadiene; 4-methyl-1,4-hexadiene; 5-methyl-1,4-hexadiene; 5-methyl-
1,4-dienes such as 1,4-heptadiene, 1,5
-Hexadiene; 3-methyl-1,5-hexadiene;
3-Ethyl-1,5-hexadiene; 3,4-Dimethyl-1,5-hexadiene; 1,5-heptadiene; 5-
Methyl-1,5-heptadiene; 6-methyl-1,5-
Heptadiene; 1,5-octadiene; 5-methyl-
1,5-octadiene; 1,5-dienes such as 6-methyl-1,5-octadiene, 1,6-octadiene;
6-methyl-1,6-octadiene; 7-methyl-1,
6-octadiene; 7-ethyl-1,6-octadiene; 1,6-nonadiene; 7-methyl-1,6-nonadiene; 4-methyl-1,6-nonadiene and the like 1,6-
Dienes, 1,7-octadiene; 3-methyl-1,7
-Octadiene; 3-ethyl-1,7-octadiene;
3,4-Dimethyl-1,7-octadiene; 3,5-Dimethyl-1,7-octadiene; 1,7-Nonadiene;
Examples thereof include 1,7-dienes such as 8-methyl-1,7-nonadiene, 1,11-dodecadiene and 1,13-tetradecadiene.

Further, examples of the aromatic vinyl compound include styrene and α-methylstyrene, p-methylstyrene; m-methylstyrene; o-methylstyrene; pt-butylstyrene; p-phenylstyrene. Alkyl or aryl styrenes, p-methoxystyrene; m-methoxystyrene; p-ethoxystyrene; pn-propoxystyrene; alkoxystyrenes such as pn-butoxystyrene, p-chlorostyrene; p-bromostyrene. Halogenated styrenes such as p-iodostyrene, p-trimethylsilylstyrene;
m-trimethylsilylstyrene; o-trimethylsilylstyrene; p-dimethylphenylsilylstyrene; p-
Methyldiphenylsilylstyrene; alkyl- or aryl-group-containing silylstyrenes such as p-triphenylsilylstyrene, p-dimethylchlorosilylstyrene; p
-Methyldichlorosilylstyrene; halogen-containing silylstyrenes such as p-trichlorosilylstyrene, p-
(2-propenyl) styrene; m- (2-propenyl)
Styrene; p- (3-butenyl) styrene; m- (3-
Butenyl) styrene; o- (3-butenyl) styrene;
Alkenyl styrenes such as p- (3-butenyl) -α-methylstyrene, and further 4-vinylbiphenyl; 3
-Vinyl biphenyl; vinyl biphenyls such as 2-vinyl biphenyl, 1- (4-vinylphenyl) naphthalene; vinylphenyl naphthalene such as 2- (3-vinylphenyl) naphthalene; 1- (4-vinylphenyl)
Anthracene; vinylphenylanthracenes such as 2- (4-vinylphenyl) anthracene; 1- (4-vinylphenyl) phenanthrene; vinylphenylphenanthrenes such as 2- (4-vinylphenyl) phenanthrene; 1- (4-vinyl Phenyl) pyrene; 2- (4
Examples thereof include vinylphenylpyrenes such as -vinylphenyl) pyrene. Next, as unsaturated esters, for example, ethyl acrylate, methyl methacrylate, etc., as lactones, for example, β-propiolactone, β-butyrolactone, γ-butyrolactone, etc., and as lactams, For example, ε-caprolactam, δ-valerolactam, and the like, and examples of the epoxides include epoxypropane; 1,2-epoxybutane and the like. In the present invention, the polymerizable unsaturated compound to be copolymerized with the olefin may be used alone, or may be used in combination of two or more kinds, and may be used in combination with the above-mentioned other α-olefins. .

The polymerization method in the present invention is not particularly limited, and any polymerization method such as slurry polymerization method, high temperature solution polymerization method, gas phase polymerization method, bulk polymerization method, suspension polymerization method and the like can be adopted. You can When a polymerization solvent is used, the solvent is, for example, an inert solvent such as an aliphatic hydrocarbon having 5 to 18 carbon atoms, an alicyclic hydrocarbon, or an aromatic hydrocarbon having 6 to 20 carbon atoms, specifically n. -Pentane, isopentane, hexane, heptane, octane, nonane,
Decane, tetradecane, cyclohexane, benzene, toluene, xylene, ethylbenzene and the like can be mentioned.
These may be used alone or in combination of two or more. Further, the polymerization temperature is not particularly limited, but it is usually selected in the range of 0 to 350 ° C, preferably 20 to 250 ° C. On the other hand, the polymerization pressure is not particularly limited, but is usually 0 to 150 kg / cm ² G, preferably 0 to 10
It is selected in the range of 0 kg / cm ² G. Examples of the method for adjusting the molecular weight of the polymer include the type and amount of each catalyst component, the selection of the polymerization temperature, and the like. Thus, the molecular weight in the practical range, that is, the number average molecular weight of about 2 × 10 ⁴ to 2 × 10 ⁵ , the intrinsic viscosity [η] (measured in decalin at 135 ° C.) 1
An olefin polymer having a narrow molecular weight distribution of about 5 deciliters / g and a relatively wide composition distribution and having unprecedented excellent physical properties can be obtained. The process of the invention is particularly suitable for producing linear low density polyethylene.

[0045]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Example 1 A heat-dried 1 liter autoclave was purged with nitrogen at room temperature, and then 390 ml of toluene, 10 ml of 1-octene, 1 mmol of methylaluminoxane as a catalyst component (B) (90 ° C. manufactured by Tosoh Akzo Co., Ltd.)
Then, 1 micromol of 1,2-dimethylcyclopentadienyltitanium trimethoxide as a catalyst component (A) was used in this order, and the mixture was stirred for several minutes, and then the solution was adjusted to 80 The temperature was raised to 0 ° C., ethylene was continuously introduced so that the total pressure was 8 kg / cm ² G, and polymerization was carried out for 30 minutes. Then, the pressure was released, and methanol was added to stop the polymerization. The reaction product was poured into a methanol / hydrochloric acid solution, the obtained polymer was collected by filtration, washed with methanol several times, and then dried under reduced pressure. The yield was 1.2 g, and the catalytic activity was 25 kg / g-Ti. The intrinsic viscosity [η] of the polymer (135 ° C., measured in decalin) was 3.1 deciliter / g, and the melting point was 97 ° C.

Examples 2 and 3 and Comparative Example 1 Polymerization was carried out in the same manner as in Example 1 except that the catalyst component (A) shown in Table 1 was used. The results are shown in Table 1.

[0047]

[Table 1]

As can be seen from Table 1, when the number of substituents on the cyclopentadienyl ring decreases, the molecular weight of the copolymer decreases and the intrinsic viscosity [η] decreases. Further, the copolymerizability is improved and the melting point of the copolymer is lowered. If there is no substituent on the cyclopentadienyl ring, the catalytic activity will be about 2 kg.
/ G-Ti, which is low.

Examples 4 to 6 and Reference Example 1 A 1 liter autoclave that had been dried by heating was replaced with nitrogen at room temperature, and then 390 ml of toluene, 10 ml of 1-octene, and methylaluminoxane (a product of Albemarle as it is) as a catalyst component (B). 1 mmol, 2,6-di-t-butylphenol 0.2 mmol as catalyst component (C) and second as catalyst component (A)
After adding 1 micromol shown in the table in this order and stirring for several minutes, the temperature of the solution was raised to 80 ° C.
Polymerization was carried out in the same manner as in. The results are shown in Table 2.

[0050]

[Table 2]

As can be seen from Table 2, the intrinsic viscosity and melting point of the copolymer show almost the same tendency as in Table 1.

[0052]

The olefin polymerization catalyst of the present invention can efficiently give a polymer having a molecular weight in a practical range without using a chain transfer agent which causes a decrease in catalytic activity, and has excellent copolymerizability. The amount of comonomer used can be reduced. By using this polymerization catalyst,
An olefin-based polymer having a molecular weight in a practical range and having a narrow molecular weight distribution and a relatively wide composition distribution and having unprecedented excellent physical properties without lowering the catalytic activity,
Particularly, linear low density polyethylene can be efficiently obtained.

Claims (5)

[Claims] 1. (A) General formula (I) CpML ¹ L ² L ³ ... (I) [wherein, M represents a metal element of Group 4 of the periodic table, and Cp represents
General formula (II): (R represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms or a silyl group, and when there are plural Rs, the plural Rs may be the same or different. Or adjacent Rs may be bonded to each other to form a ring structure, and n represents an integer of 1 to 4), and represents a substituted cyclopentadienyl group.
L ¹ , L ² and L ³ each represent a σ-bonding ligand, which may be the same or different. ]
An olefin polymerization catalyst comprising a transition metal compound represented by: and (B) a compound capable of reacting with the transition metal compound of the component (A) or a derivative thereof to form an ionic complex. 2. A compound capable of forming an ionic complex by reacting with (A) a transition metal compound represented by the general formula (I), (B) a transition metal compound of the component (A) or a derivative thereof. And (C) a catalyst for olefin polymerization comprising a phenolic compound. 3. The catalyst for olefin polymerization according to claim 1, wherein the component (B) is a chain and / or cyclic aluminoxane. 4. The phenolic compound as the component (C) has a hydroxyl group in the aromatic ring and a hydrocarbon group having 1 to 20 carbon atoms in the α-position and / or α'-position thereof. The catalyst for olefin polymerization described. 5. In the presence of the catalyst for olefin polymerization according to claim 1, olefins are homopolymerized or olefins are copolymerized with other olefins and / or other polymerizable unsaturated compounds. A method for producing an olefin-based polymer, comprising: