JPH10330411A - Catalyst for olefin polymerization and polymerization of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a catalyst having excellent polymerization activity and useful for producing an olefin polymer having narrow molecular weight distribution and composition distribution by making the catalyst contain a specific translation metal amide compound and a baron-containing organic aluminumoxy compound, etc. SOLUTION: This catalyst contains (A) a transition metal amide compound of the formula: (R2 N)k MXj-k M is a group III to VI transition metal; (j) is a valence number of M; (k) is an integer of 1 to (j); R is a hydrocarbon, an organic silyl, etc.; X is a halogen, etc.} [e.g. a compound of formula I (Me is methyl), (B) an organic metal component selected from (B1) a boron-containing organic aluminumoxy compound of formula II (R<21> is a 1-10C hydrocarbon; R<22> is H, a halogen or a 1-10C hydrocarbon) and (B2) clay, a clay mineral or an ion-exchanging laminar compound, and (C) an organic metal compound, preferably in an amount of 10<-7> to 10<-3> mol of the component A per 1 L of the reaction volume and a molar ratio of (transition metal in the component A/aluminum in the component B1/the component C) of (1:20-2,000):0.05-2,000).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel catalyst for olefin polymerization and a method for polymerizing olefins using the catalyst for olefin polymerization.

[0002]

TECHNICAL BACKGROUND OF THE INVENTION Olefin polymerization catalysts include:
So-called Kaminsky catalysts are well known. This catalyst is characterized by a very high polymerization activity and a polymer having a narrow molecular weight distribution.

As a transition metal compound used for such a Kaminsky catalyst, for example, bis (cyclopentadienyl) zirconium dichloride (Japanese Patent Application Laid-Open No. 58-19 / 1983)
309) and ethylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride (Japanese Unexamined Patent Publication No.
No. 130314). It is also known that when the transition metal compound used for the polymerization is different, the olefin polymerization activity and the properties of the obtained polyolefin are greatly different.

Further, as a new catalyst for olefin polymerization, for example, Japanese Patent Application Laid-Open No. 8-245713 has proposed an olefin polymerization catalyst comprising a titanium amide compound having a titanium-nitrogen bond and aluminoxane.

Also, Organometallics 1996, 15,562-569
Describes an organometallic complex of Group 4 of the periodic table having a bis (borylamide) ligand represented by [Mes ₂ BNCH ₂ CH ₂ NBMes ₂ ] ^-2 , and this complex shows a slight ethylene polymerization activity. Is described.

[0006] Polyolefins are generally used in various fields such as for molded articles because of their excellent mechanical properties. However, in recent years, the demand for physical properties of polyolefins has been diversified, and polyolefins having various properties have been developed. Is desired. It is also desired to improve productivity.
Under such circumstances, the appearance of a method for producing a polyolefin having high polymerization activity and excellent properties using a catalyst containing a transition metal amide compound is desired.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide an olefin polymerization catalyst having excellent olefin polymerization activity and a method for polymerizing olefins using the catalyst.

[0008]

SUMMARY OF THE INVENTION The olefin polymerization catalyst according to the present invention comprises:
(A) a transition metal amide compound represented by the following general formula (I), and (R ₂ N) _k MX _jk (I) (wherein M represents a transition metal atom belonging to Groups 3 to 6 of the periodic table) And j is a valence of the transition metal atom M, k is an integer of 1 to j, R may be the same or different from each other,
A hydrogen atom, a hydrocarbon group, a halogenated hydrocarbon group, an organic silyl group or a substituent having at least one element selected from nitrogen, oxygen, phosphorus, sulfur and silicon;
A plurality of groups represented by R may be connected to each other to form a ring, and when k is 2 or more, two Rs bonded to different nitrogen atoms are connected to each other to form two nitrogen atoms. X may represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, sulfur, And when jk is 2 or more, they may be the same or different from each other. (B) (B-1) a boron-containing organoaluminum oxy compound represented by the following general formula (II),

[0009]

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(Wherein, R ²¹ is a hydrocarbon group having 1 to 10 carbon atoms, and R ^{22 s} may be the same or different from each other, and have a hydrogen atom, a halogen atom, or a 1-carbon atom.
And 10 to 10 hydrocarbon groups. ) Or (B-2) a clay, a clay mineral or an ion-exchange layered compound, and if necessary, (C) an organometallic compound.

The olefin polymerization method according to the present invention is characterized in that olefin is polymerized or copolymerized in the presence of the above-mentioned catalyst.

[0012]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the catalyst for olefin polymerization according to the present invention and a method for polymerizing olefins using the catalyst will be described in detail.

In the present specification, the term "polymerization" is sometimes used to mean not only homopolymerization but also copolymerization. The term "polymer" means not only homopolymer but also homopolymer. , May also be used in a meaning including a copolymer.

The olefin polymerization catalyst according to the present invention comprises:
(A) a transition metal amide compound represented by the following general formula (I), (B) (B-1) a boron-containing organoaluminum oxy compound, or (B-2) a clay, a clay mineral or an ion-exchangeable layered compound It is formed from (C) an organometallic compound as required.

First, each component forming the olefin polymerization catalyst of the present invention will be described. (A) Transition metal amide compound The transition metal amide compound (A) used in the present invention is a transition metal amide compound represented by the following general formula (I).

(R ₂ N) _k MX _jk (I) In the formula, M represents a transition metal atom belonging to Groups 3 to 6 of the periodic table;
It is preferably a transition metal atom of Group 4 of the periodic table, such as titanium, zirconium, or hafnium.

J represents the valence of the transition metal atom M. k is 1
To j. R may be the same or different from each other, and may be a hydrogen atom, a hydrocarbon group, a halogenated hydrocarbon group, an organic silyl group, or a substituent having at least one element selected from nitrogen, oxygen, phosphorus, sulfur and silicon. Represents a group.

Specific examples of the hydrocarbon group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl,
Octyl, decyl, octadecyl, etc. have 1 carbon atom
A linear or branched alkyl group having from 20 to 20; an aryl group having 6 to 20 carbon atoms such as phenyl and naphthyl; and a substituent such as the alkyl group having from 1 to 20 carbon atoms being 1 to these aryl groups. A substituted or substituted aryl group having from 5 to 5 cycloalkyl groups such as cyclopentyl, cyclohexyl, norbornyl and adamantyl; vinyl, propenyl,
Alkenyl groups such as cyclohexenyl; arylalkyl groups such as benzyl, phenylethyl and phenylpropyl;

Examples of the halogenated hydrocarbon group include groups in which the above hydrocarbon group is substituted with halogen. Specific examples of the organic silyl group include methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, triphenylsilyl and the like.

As the substituent having at least one element selected from nitrogen, oxygen, phosphorus, sulfur and silicon, the hydrocarbon group may be -COOCH ₃ , -N (C
_{H 3) C (O) CH} 3, -OC (O) CH 3, -CN,
_{-N (C 2 H 5) 2} , -N (CH 3) S (O 2) C
H ₃ and —P (C ₆ H ₅ ) ₂ are substituted.

The groups represented by R bonded to the same nitrogen atom may be linked to each other to form a ring such as an aliphatic ring. When k is 2 or more, R bonded to different nitrogen atoms
The groups represented by may be the same or different from each other,
Further, they may be connected to each other to form a bonding group for bonding two nitrogen atoms.

X represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group or a silicon-containing group; When jk is 2 or more, they may be the same or different from each other.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine. Examples of the hydrocarbon group having 1 to 20 carbon atoms include an alkyl group, a cycloalkyl group, an alkenyl group, an arylalkyl group, and an aryl group. More specifically, methyl, ethyl, propyl, butyl, and hexyl Alkyl groups such as octyl, nonyl, dodecyl and eicosyl; cycloalkyl groups such as cyclopentyl, cyclohexyl, norbornyl and adamantyl; alkenyl groups such as vinyl, propenyl and cyclohexenyl; arylalkyl groups such as benzyl, phenylethyl and phenylpropyl; Phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl,
And aryl groups such as propylphenyl, biphenyl, naphthyl, methylnaphthyl, anthryl, and phenanthryl.

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

Examples of the sulfur-containing group include a substituent in which the oxygen of the oxygen-containing group is substituted by sulfur, methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, p-toluene sulfonate. Sulfonate groups such as catenate, trimethylbenzenesulfonate, triisobutylbenzenesulfonate, p-chlorobenzenesulfonate and pentafluorobenzenesulfonate; methylsulfinate, phenylsulfinate, benzylsulfinate, p -Sulfinate groups such as toluenesulfinate, trimethylbenzenesulfinate and pentafluorobenzenesulfinate.

Examples of the silicon-containing group include silyls substituted with monohydrocarbons such as methylsilyl and phenylsilyl; silyls substituted with dihydrocarbons such as dimethylsilyl and diphenylsilyl; trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl and triphenylsilyl. Trialkyl-substituted silyls such as dimethylphenylsilyl, methyldiphenylsilyl, tritolylsilyl and trinaphthylsilyl; silyl ethers of hydrocarbon-substituted silyls such as trimethylsilyl ether; silicon-substituted alkyl groups such as trimethylsilylmethyl; silicon such as trimethylsilylphenyl And a substituted aryl group.

Of these, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a sulfonate group is preferred. Hereinafter, specific examples of the transition metal amide compound represented by the general formula (I) will be shown, but the invention is not limited thereto. Bis (dimethylamido) titanium dichloride, bis (diethylamido) titanium dichloride, bis (dipropylamido) titanium dichloride, diisopropylamidotitanium trichloride, bis (diisopropylamido) titanium dichloride, tris (diisopropylamido) titanium chloride, tetrakis (diisopropylamide) ) Titanium,
Dibutylamido titanium trichloride, bis (dibutylamido) titanium dichloride, tris (dibutylamido) titanium chloride, tetrakis (dibutylamido) titanium, bis (diisobutylamido) titanium dichloride, bis (dihexylamido) titanium dichloride, dioctylamido titanium trichloride ,
Bis (dioctylamide) titanium dichloride, tris (dioctylamide) titanium chloride, tetrakis (dioctylamide) titanium, bis (didecylamide) titanium dichloride, bis (dioctadecylamide) titanium dichloride, bis (diethylamide)
Bis [bis (trimethylsilyl) amido] titanium,
Bis [bis (trimethylsilyl) amide] titanium dichloride, tris [bis (trimethylsilyl) amide]
Titanium chloride, tetrakis [bis (trimethylsilyl) amide] titanium and the like.

In addition to the above, examples of the transition metal amide compound represented by the general formula (I) include compounds in which titanium in the above compound is replaced with zirconium or hafnium.

In the transition metal amide compound represented by the general formula (I), two Rs bonded to different nitrogen atoms are connected to each other to form a bonding group for bonding two nitrogen atoms. Examples of the compound include a compound represented by the following general formula (I-1).

[0030]

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In the formula, M is the same as M in the general formula (I).
The same as the above, it is preferably a transition metal atom of Group 4 of the periodic table such as titanium, zirconium, hafnium,
Particularly, titanium is preferable.

R ′ and R ″ may be the same or different and are selected from a hydrogen atom, a hydrocarbon group, a halogenated hydrocarbon group, an organic silyl group or nitrogen, oxygen, phosphorus, sulfur and silicon. It represents a substituent having at least one element, and is specifically the same as R in the general formula (I).

M is an integer of 0 to 2. n is 1 to 5
Is an integer. A represents an atom belonging to Groups 13 to 16 of the periodic table, and specifically includes a boron atom, a carbon atom, a nitrogen atom, an oxygen atom, a silicon atom, a phosphorus atom, a sulfur atom, a germanium atom, a selenium atom, a tin atom, and the like. And preferably a carbon atom or a silicon atom. When n is 2 or more, a plurality of A may be the same or different from each other.

E is a substituent having at least one element selected from carbon, hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, boron and silicon. When there are a plurality of groups represented by E, the plurality of groups represented by E may be the same or different from each other, and 2
Two or more groups may be connected to each other to form a ring.

Specific examples of such a bonding group for bonding two nitrogen atoms represented by-((E _m ) A) _n -include the following groups. -CH ₂ -, - C (M
e) _2- , -C (Ph) _2- , -Si (Me) ₂ -,-
Si (Ph) _2- , -Si (Me) (Ph)-, -CH
_{2 CH 2 -, - CH 2} Si (Me) 2 -, - CH 2 CH
₂ CH ₂ —, —CH ₂ C (Me) ₂ CH ₂ —, —CH ₂
C (Et) ₂ CH ₂ —, —CH ₂ C (n Pr) ₂ CH _{2
-, - CH 2 C (i} Pr) 2 CH 2 -, - CH 2 C (n
Bu) ₂ CH ₂ —, —CH ₂ C (i Bu) ₂ CH ₂ —,
—CH ₂ C (s Bu) ₂ CH ₂ —, —CH ₂ C (c Pe
n) ₂ CH ₂ —, —CH ₂ C (c Hex) ₂ CH ₂ —,
_{-CH 2 C (Ph) 2 CH} 2 -, - CH 2 C (Me) (E
t) CH ₂ —, —CH ₂ C (Me) (i Pr) CH ₂ —,
_{-CH 2 C (Me) (i} Bu) CH 2 -, - CH 2 C (M
_{e) (t Bu) CH 2} -, - CH 2 C (Me) (i Pen)
CH ₂ —, —CH ₂ C (Me) (Ph) CH ₂ —, —CH
_{2 C (Et) (i Pr} ) CH 2 -, - CH 2 C (Et) (i
_{Bu) CH 2 -, - CH} 2 C (Et) (i Pen) CH
_{2 -, - CH 2 C (} iPr) (i Bu) CH 2 -, - CH 2 C
(I Pr) (i Pen) CH 2 -, - CH 2 Si (Me) 2
CH ₂ —, —CH ₂ Si (Et) ₂ CH ₂ —, —CH _{2
Si (n-Bu) 2 CH} 2 -, - CH 2 Si (Ph) 2 C
_{H 2 -, - CH (Me} ) CH 2 CH (Me) -, - CH
_{(Ph) CH 2 CH (Ph} ) -, - Si (Me) 2 OSi
(Me) _2- , -CH ₂ CH ₂ CH ₂ CH _2- , -Si
(Me) ₂ CH ₂ CH ₂ Si (Me) _2- ,

[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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In the above examples, Me represents a methyl group, Et represents an ethyl group, nPr represents an n-propyl group, iPr represents an isopropyl group, nBu represents an n-butyl group, and iBu represents an n-butyl group. Represents an isobutyl group, and sBu is sec-
Represents a butyl group, t-Bu represents a tert-butyl group, iP
en represents an isopentyl group, cPen represents a cyclopentyl group, cHex represents a cyclohexyl group, and Ph
Represents a phenyl group.

P is an integer from 0 to 4. X is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms,
It represents a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group or a silicon-containing group, and is specifically the same as X in the general formula (I). In addition,
When p is 2 or more, a plurality of groups represented by X may be the same or different from each other.

Of these, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a sulfonate group is preferred. The above general formula (I-
Specific examples of the transition metal amide compound represented by 1) are shown below, but the invention is not limited thereto.

[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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In the above examples, Me represents a methyl group, Et represents an ethyl group, iPr represents an isopropyl group, and tBu represents a tert-butyl group. In the present invention, a transition metal amide compound in which titanium is replaced with zirconium or hafnium in the above-described compounds can also be used.

In the present invention, among the transition metal amide compounds represented by the general formula (I-1), R ′ and R ″ represent a substituted aryl group in which 1 to 5 substituents such as an alkyl group are substituted. It is preferable to use a transition metal amide compound represented by the following general formula (I-2).

[0051]

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In the formula, M is the same as M in the general formula (I).
The same as the above, it is preferably a transition metal atom of Group 4 of the periodic table such as titanium, zirconium, hafnium,
Particularly, titanium is preferable.

R ^{1 to} R ¹⁰ may be the same or different, and each represents a hydrogen atom, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, an organic silyl group, an alkoxy group, an aryloxy group, —COOR ¹¹ , N (R ¹² ) C (O)
^{R 13, -OC (O) R} 14, -CN, -NR 15 2 , or -
N (R ¹⁶ ) S (O ₂ ) R ¹⁷ (where R ^{11 to} R ¹⁷ represent an alkyl group having 1 to 5 carbon atoms). However, at least one of R ^{1 to} R ⁵ is a group other than hydrogen, and at least one of R ^{6 to} R ¹⁰ is a group other than hydrogen.

As the halogen atom, the above-mentioned general formula (I)
And the hydrocarbon group, the halogenated hydrocarbon group and the organic silyl group are represented by the above general formula (I-
The same as R ′ and R ″ in 1).

Specific examples of the alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy and the like. Specifically as the aryloxy group, phenoxy, 2,
6-dimethylphenoxy, 2,4,6-trimethylphenoxy and the like.

-COOR ¹¹ , -N (R ¹² ) C (O)
^{R 13, -OC (O) R} 14, -CN, -NR 15 2 , or -
Examples of the group represented by N (R ¹⁶ ) S (O ₂ ) R ¹⁷ (where R ^{11 to} R ¹⁷ represent an alkyl group having 1 to 5 carbon atoms) include —COOCH ₃ and —N (CH ₃ ) C (O) CH
_{3, -OC (O) CH 3} , -CN, -N (C
_{2 H 5) 2, -N (} CH 3) S (O 2) such as CH ₃ and the like.

Further, two or more of the groups represented by R ^{1 to} R ⁵ , preferably, adjacent groups are connected to each other to form a ring such as an aromatic ring or an aliphatic ring together with a carbon atom to which each is bonded. Two or more of the groups represented by R ^{6 to} R ¹⁰ , preferably an aromatic ring, an aliphatic ring, etc. May form a ring.

M is an integer of 0 to 2. n is 1 to 5
Is an integer. A is the same as A in the general formula (I-1), and is preferably a carbon atom or a silicon atom. When n is 2 or more, a plurality of A may be the same or different from each other.

E is the same as E in formula (I-1), and is preferably a substituent containing at least one element selected from carbon, hydrogen, nitrogen and silicon. When there are a plurality of groups represented by E, the plurality of groups represented by E may be the same or different from each other, and two or more groups represented by E may be linked to each other to form a ring. You may.

Specific examples of such a bonding group for bonding two nitrogen atoms represented by-((E _m ) A) _n- include the same groups as described above. p is an integer of 0 to 4.

X represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group or a silicon-containing group. And specifically the same as X in the general formula (I).

Of these, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a sulfonate group is preferred. When p is 2 or more, a plurality of groups represented by X may be the same or different from each other.

Specific examples of the transition metal amide compound represented by the above general formula (I-2) are shown below, but the invention is not limited thereto.

[0064]

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[0065]

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[0066]

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[0067]

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[0068]

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[0069]

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[0070]

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[0071]

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[0072]

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[0073]

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[0074]

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[0075]

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[0076]

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In the above examples, Me represents a methyl group, Et represents an ethyl group, iPr represents an iso-propyl group, nPr represents an n-propyl group, nBu represents an n-butyl group, and sBu represents an n-butyl group. sec-butyl group, t Bu is tert-butyl group,
nOct represents an n-octyl group.

In the present invention, a transition metal amide compound in which titanium is replaced with zirconium or hafnium in the above compounds may be used. In these transition metal amide compounds, M is titanium, A of the group connecting two nitrogen atoms is carbon or silicon,
Transition metal amide compounds wherein n is 2 or 3 are preferred.

These compounds may be used alone or
Two or more kinds may be used in combination. Further, the transition metal amide compound (A) as described above can be used together with a carrier compound by bringing it into contact with a particulate carrier compound (D), if necessary. As the particulate carrier compound,
An inorganic or organic compound having a particle size of 10 to 300
A granular or particulate solid of μm, preferably 20-200 μm, is used. Of these, a porous oxide is preferable as the inorganic compound, and specifically, SiO ₂ , Al ₂
O ₃ , MgO, ZrO, TiO ₂ , B ₂ O ₃ , CaO,
ZnO, BaO, ThO _{2 and the} like, or a mixture containing them, such as SiO ₂ —MgO, SiO ₂ —Al ₂ O ₃ ,
SiO ₂ —TiO ₂ , SiO ₂ —V ₂ O ₅ , SiO ₂ —Cr ₂ O
₃ , SiO ₂ —TiO ₂ —MgO and the like. Among them, those containing at least one component selected from the group consisting of SiO ₂ and Al ₂ O ₃ as a main component are preferable.

The above inorganic oxide contains a small amount of Na ₂ C
O ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO
₄ , Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (N
O ₃ ) ₂ , Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, Li ₂ O, and other carbonates, sulfates, nitrates, and oxide components may be contained.

Although the properties of such fine-particle carriers vary depending on the type and production method, the carriers preferably used in the present invention have a specific surface area of 50 to 1000 m ² / g, preferably 100 to 700 m ² / g. And the pore volume is desirably in the range of 0.3 to 2.5 cm ³ / g. The carrier is used by firing at 100 to 1000 ° C, preferably 150 to 700 ° C, if necessary.

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

(B-1) Boron-containing organic aluminum oxy
Compound (B-1) The boron-containing organoaluminum oxy compound used in the present invention is a compound represented by the following general formula (II).

[0084]

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In the formula, R ²¹ represents a hydrocarbon group having 1 to 10 carbon atoms. R ²² may be the same or different, and each has a hydrogen atom, a halogen atom or a carbon atom number of 1 to 1.
Shows 10 hydrocarbon groups.

The boron-containing organoaluminum oxy compound represented by the general formula (II) is composed of an alkylboronic acid represented by the following general formula (III) and R ²¹ -B- (OH) ₂ . Wherein R ²¹ represents the same group as described above.) It can be produced by reacting with an organoaluminum compound in an inert solvent under an inert gas atmosphere at a temperature of −80 ° C. to room temperature for 1 minute to 24 hours. .

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

Specific examples of such an organoaluminum compound to be reacted with an alkylboronic acid are described below (C
The same organoaluminum compounds as those exemplified as the organoaluminum compounds belonging to -1) can be mentioned.

Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum, triethylaluminum and triisobutylaluminum are particularly preferable. These are used alone or in combination of two or more.

The (B-1) boron-containing organoaluminum oxy compound as described above is used alone or in combination of two or more. Further, the above-mentioned boron-containing organoaluminum oxy compound (B-1) can be used together with the fine particle carrier by bringing it into contact with the fine particle carrier (D) as described above. When bringing into contact with the particulate carrier (D), the boron-containing organoaluminum oxy compound (B
-1) may be brought into contact with the particulate carrier, or both components of the boron-containing organoaluminum oxy compound (B-1) and the transition metal amide compound (A) may be brought into contact with the particulate carrier (D). Is also good.

(B-2) Clay, clay mineral or ion exchangeability
Clay used in the layered compound present invention is constructed normal clay mineral as a main component, ion-exchange layered compounds are those taken parallel to the stacked crystal structure from each other a weak bonding force plane formed by ion bonds And the contained ions are exchangeable. Most clay minerals are ion-exchangeable layered compounds. Examples of the clay, clay mineral or ion-exchange layered compound include ionic crystalline compounds having a layered crystal structure such as hexagonal dense packing type, antimony type, CdCl ₂ type and CdI ₂ type. As these clays, clay minerals, and ion-exchangeable layered compounds, not only natural products but also artificial synthetic products can be used.

Specific examples of such clays and clay minerals include kaolin, bentonite, Kibushi clay, gairome clay, allophane, hisingelite, pyrophyllite, plum group, montmorillonite group, vermiculite, ryokudeite group, palygorskite, Examples include kaolinite, nacrite, dickite, halloysite, and the like, and examples of the ion-exchange layered compound include α-Zr (HAsO ₄ )
₂ · H ₂ O, α-Zr (HPO ₄ ) ₂ , α-Zr (KPO ₄ ) ₂
3H ₂ O, α-Ti (HPO ₄ ) ₂ , α-Ti (HAsO
₄ ) ₂ · H ₂ O, α-Sn (HPO ₄ ) ₂ · H ₂ O, γ-Zr
(HPO ₄ ) ₂ , γ-Ti (HPO ₄ ) ₂ , γ-Ti (NH ₄
PO ₄ ) ₂ .H ₂ O and other crystalline acidic salts of polyvalent metals.

The clay, clay mineral, and ion-exchange layered compound preferably have a pore volume of 0.1 cc / g or more at a radius of 20 ° or more measured by a mercury intrusion method.
Those having 3 to 5 cc / g are particularly preferred. Here, the pore volume is measured by a mercury intrusion method using a mercury porosimeter with a pore radius in the range of 20 to ³ × 10 ⁴ Å. The pore volume with a radius of 20 ° or more is 0.
When a compound smaller than 1 cc / g is used, high polymerization activity tends to be hardly obtained.

The clay and clay mineral used in the present invention can be subjected to a chemical treatment. As the chemical treatment, any of a surface treatment for removing impurities adhering to the surface and a treatment for affecting the crystal structure of the clay can be used. Specific examples include acid treatment, alkali treatment, salt treatment, and organic substance treatment. The acid treatment removes impurities on the surface and increases the surface area by eluting cations such as Al, Fe, and Mg in the crystal structure. Alkali treatment destroys the crystal structure of the clay, resulting in a change in the structure of the clay. In salt treatment and organic matter treatment,
Forming ionic complexes, molecular complexes, organic derivatives, etc.
The surface area and interlayer distance can be changed.

The ion-exchangeable layered compound used in the present invention utilizes an ion-exchange property to exchange the exchangeable ion between layers with another large bulky ion, thereby obtaining a layered compound in which the layers are expanded. You can also. Here, the bulky ions play a pillar-like role of supporting the layered structure, and are called pillars. Introducing another substance (guest compound) between layers of the layered substance is called intercalation.

The guest compounds to be intercalated include cationic inorganic compounds such as TiCl ₄ and ZrCl ₄ ; Ti (OR) ₄ , Zr (OR) ₄ , PO (OR) ₃ ,
B (OR) _3, (R is such as a hydrocarbon group) metal alcoholate such _{as; [Al 13 O 4 (OH} ) 2 4] 7+, [Zr 4 (O
H) ₁₄ ] ²⁺ , and metal hydroxide ions such as [Fe ₃ O (OCOCH ₃ ) ₆ ] ⁺ . These compounds are used alone or in combination of two or more. When intercalating these compounds,
A polymer obtained by hydrolyzing a metal alcoholate such as (OR) ₄ , Al (OR) ₃ , Ge (OR) ₄ (R is a hydrocarbon group), and a colloidal inorganic compound such as SiO ₂ coexist It can also be done. Other examples of pillars include oxides generated by intercalating the hydroxide ions between layers and then heating and dehydrating.

The clay, clay mineral, and ion-exchange layered compound used in the present invention may be used as they are, or may be used after being subjected to a treatment such as pulverization with a ball mill and sieving. Further, it may be used after newly adding and adsorbing water or performing a heat dehydration treatment. Further, they may be used alone or in combination of two or more. Among them, preferred are clay or clay mineral, and particularly preferred is montmorillonite.

In the present invention, (B-2)
When a clay, a clay mineral, or an ion-exchange layered compound is used, (C) an organometallic compound described later is used at the same time. In this case, as the (C) organometallic compound to be used, an organoaluminum compound belonging to (C-1) described below is preferably used, and particularly, a trialkylaluminum is preferably used.

(C) Organometallic Compound As the (C) organometallic compound used in the present invention, specifically, the following Periodic Table Groups 1, 2 and 12, 1
A group 3 organometallic compound is used.

[0100] In (C-1) the general formula _{^{R a m Al (OR b)}} n H p X q ( wherein, R ^a and R ^b may be the same or different from each other, the number of carbon atoms from 1 to 15 , Preferably 1 to 4 hydrocarbon groups, X represents a halogen atom, and m represents 0 <
m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is 0 ≦ q
<3 and m + n + p + q = 3. The organoaluminum compound represented by).

[0102] (C-2) In the general formula M ² AlR ^a ₄ (wherein, M ² represents a Li, Na or K, R ^a is the number of carbon atoms 1 to 15, preferably 1 to 4 hydrocarbon groups A complex alkylated product of a Group 1 metal and aluminum represented by the formula:

(C-3) Formula R ^a R ^b M ³ (wherein R ^a and R ^b may be the same or different and each have 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms) A dialkyl compound of a Group 2 or 12 metal represented by a hydrocarbon group, and M ³ represents Mg, Zn or Cd.

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

More specifically, the aluminum compounds belonging to (C-1) include trimethylaluminum, triethylaluminum, trin-butylaluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum and the like. Tri-n-alkylaluminum; triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, tri2-methylbutylaluminum,
3-methylbutylaluminum, tri-2-methylpentylaluminum, tri3-methylpentylaluminum, tri
Tri-branched alkyl aluminum such as 4-methylpentyl aluminum, tri 2-methylhexyl aluminum, tri 3-methylhexyl aluminum, tri 2-ethylhexyl aluminum; tricyclohexyl aluminum;
Tricycloalkyl aluminum such as tricyclooctyl aluminum; triaryl aluminum such as triphenyl aluminum and tolyl aluminum; dialkyl aluminum hydride such as diisobutyl aluminum hydride and diisobutyl aluminum hydride; (i-C ₄ H ₉ ) _x Al _y (C Alkenyl aluminum such as isoprenyl aluminum represented by ₅ H ₁₀ ) _z (where x, y, and z are positive numbers and z ≧ 2x); isobutylaluminum methoxide;
Alkylaluminum alkoxides such as isobutylaluminum ethoxide and isobutylaluminum isopropoxide; dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide and dibutylaluminum butoxide; alkylaluminum sesquitox such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide An alkoxide; a partially alkoxylated alkylaluminum having an average composition represented by ^Ra _2.5 Al (OR ^b ) _{0.5 and the} like; diethylaluminum phenoxide,
Diethyl aluminum (2,6-di-t-butyl-4-methylphenoxide), ethyl aluminum bis (2,6-di-t-butyl-4-methylphenoxide), diisobutyl aluminum (2,6-di-t- Alkyl aluminum aryloxides such as butyl-4-methylphenoxide) and isobutylaluminum bis (2,6-di-t-butyl-4-methylphenoxide); dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide Dialkylaluminum halides, such as diisobutylaluminum chloride; alkylaluminum sesquichlorides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide; ethylaluminum dichloride, propylaluminium Partially halogenated alkyl aluminum such as alkylaluminum dihalide such as mudichloride and butylaluminum dibromide; dialkylaluminum hydride such as diethylaluminum hydride and dibutylaluminum hydride; alkylaluminum such as ethylaluminum dihydride and propylaluminum dihydride Other partially hydrogenated alkyl aluminums such as dihydrides; partially alkoxylated and halogenated alkyl aluminums such as ethylaluminum ethoxycyclolide, butylaluminum butoxycyclolide, and ethylaluminum ethoxybromide.

Compounds similar to (C-1) can also be used, and examples thereof include organoaluminum compounds in which two or more aluminum compounds are bonded via a nitrogen atom. Specific examples of such a compound include (C ₂ H ₅ ) ₂ AlN (C ₂ H ₅ ) Al (C ₂ H ₅ ) ₂ .

Examples of the compound belonging to the above (C-2) include LiAl (C ₂ H ₅ ) ₄ LiAl (C ₇ H ₁₅ ) ₄ .

Further, as the organometallic compound (C), methyl lithium, ethyl lithium, propyl lithium, butyl lithium, methyl magnesium bromide, methyl magnesium chloride, ethyl magnesium bromide, ethyl magnesium chloride, propyl magnesium bromide, propyl Magnesium chloride, butylmagnesium bromide, butylmagnesium chloride, dimethylmagnesium, diethylmagnesium, dibutylmagnesium, butylethylmagnesium and the like can also be used.

Further, a compound which forms the above-mentioned organoaluminum compound in the polymerization system, for example, a combination of aluminum halide and alkyl lithium, or a combination of aluminum halide and alkyl magnesium can also be used.

Of these, organoaluminum compounds are preferred. The organometallic compound (C) as described above is used alone or in combination of two or more.

The olefin polymerization catalyst according to the present invention comprises the above transition metal amide compound (A), (B-1) a boron-containing organoaluminum oxy compound, or (B-2) a clay, a clay mineral or an ionic compound. It comprises at least one compound (B) selected from exchangeable layered compounds and, if necessary, (C) an organometallic compound.

In the polymerization, the use and order of addition of each component are arbitrarily selected, but (B-1) a boron-containing organoaluminumoxy compound is used as the component (B), and if necessary, (C) When an organometallic compound is used, the following method is exemplified. (1) A method in which the component (A) and the component (B-1) are added to the polymerization vessel in any order. (2) A method in which the catalyst in which the component (A) and the component (B-1) are brought into contact in advance is added to the polymerization reactor. (3) A method in which the catalyst component in which the component (A) is supported on the fine particle carrier (D) and the component (B-1) are added to the polymerization reactor in an arbitrary order. (4) A method in which the catalyst component in which the component (B-1) is supported on the particulate carrier (D) and the component (A) are added to the polymerization reactor in an arbitrary order. (5) A method in which the catalyst component in which the component (A) and the component (B-1) are supported on the fine particle carrier (D) is added to the polymerization reactor. (6) In each of the above methods (1) to (5), the component (C) is added in an arbitrary order.

In the solid catalyst component in which the component (A) and the component (B-1) are supported on the fine particle carrier (D), an olefin may be prepolymerized. When (B-2) clay, clay mineral or ion-exchangeable layered compound is used as component (B), component (A), component (B-2) and component (C-1) are usually contacted. After the preparation of the olefin polymerization catalyst (component), the olefin polymerization catalyst (component) is added to the polymerization reactor.

When the component (B-2) is a clay or a clay mineral, the molar ratio of the transition metal in the component (A) to the hydroxyl group in the clay or the clay mineral and the aluminum compound in the component (C-1) is changed. 1: 0.1 to 1 × 10 ⁵ : 0.1 to 1 × 10 ⁷ , preferably 1: 0.5 to 1 × 10 ⁴ : 0.5 to 1 × 10 ⁶
It is preferable to carry out the contact reaction so that

When the component (B-2) is an ion-exchange layered compound, the weight ratio of the transition metal in the component (A) to the aluminum in the component (C-1) is (B-2) ) Per gram of ingredients
It is preferable that the contact is made so as to be 1 × 10 ⁻⁵ to 1 (g): 1 × 10 ^{−3 to} 100 (g).

The contact may be carried out in an inert gas such as nitrogen, or in an inert hydrocarbon solvent such as pentane, hexane, heptane, toluene and xylene. The contact temperature is -2
It is carried out between 0 ° C. and the boiling point of the solvent, particularly preferably between room temperature and the boiling point of the solvent.

[0116] Examples of the contacting method include the following methods. (1) A method in which the component (A) is brought into contact with the component (B-2), and then the resulting contact product is brought into contact with the component (C-1). (2) A method in which the component (A) is brought into contact with the component (C-1), and then the resulting contact product is brought into contact with the component (B-2). (3) A method in which the component (B-2) is brought into contact with the component (C-1), and then the obtained contact product is brought into contact with the component (A). (4) A method of simultaneously contacting the component (A), the component (B-2) and the component (C-1).

Upon or after the contact of each component of the catalyst, the above-mentioned fine particle carrier (D) may be allowed to coexist or may be brought into contact. The olefin polymerization catalyst (component) thus obtained may be used alone for polymerization, or may be used for polymerization in combination with component (C). Component (C)
When used in combination with the above, the olefin polymerization catalyst (component) and the component (C) can be added to the polymerization reactor in any order. At this time, the component (C-1) used in preparing the olefin polymerization catalyst (component) and the component (C) added to the polymerization vessel may be the same or different.

The olefin polymerization catalyst (component) may be preliminarily polymerized with an olefin. The olefin polymerization catalyst (component) is preferably added as a slurry of an aliphatic hydrocarbon and an alicyclic hydrocarbon described below to a polymerization vessel.

In the olefin polymerization method according to the present invention,
An olefin polymer is obtained by polymerizing or copolymerizing an olefin in the presence of the olefin polymerization catalyst as described above.

In the present invention, the polymerization can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization or a gas phase polymerization method. Specifically as the inert hydrocarbon medium used in the liquid phase polymerization method, propane, butane, pentane,
Aliphatic hydrocarbons such as hexane, heptane, octane, decane, dodecane, and kerosene; Alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; Aromatic hydrocarbons such as benzene, toluene, and xylene; ethylene chloride and chlorin Examples thereof include halogenated hydrocarbons such as benzene and dichloromethane, and mixtures thereof, and olefin itself can be used as a solvent. Among these inert hydrocarbon media, aliphatic hydrocarbons and alicyclic hydrocarbons are preferred. It is also preferable to use an α-olefin, an alicyclic vinyl compound, or a cyclic olefin itself used as a solvent in the polymerization.

In carrying out olefin polymerization using the above-mentioned olefin polymerization catalyst, the component (A) comprises:
The amount is usually 10 ^-8 to 10 ^-2 mol, preferably 10 ^-7 to 10 ^-3 mol, per 1 liter of the reaction volume.

The component (B-1) has a molar ratio [(B-1) / M] between the aluminum atom in the component (B-1) and the transition metal atom (M) in the component (A). Usually, it is used in an amount of 10 to 5000, preferably 20 to 2000.

The component (B-2) is used as a component in the olefin polymerization catalyst (component) described above, and the component (A) in the catalyst (component) is a reaction volume of 1 part. The amount is usually 10 ^-8 to 10 ^-2 mol, preferably 10 ^-7 to 10 ^-3 mol, per liter.

The component (C) is composed of the component (C) and the component (A)
The molar ratio with the transition metal atom (M) in [(C) / M] is
Usually 0.01 to 5000, preferably 0.05 to 200
It is used in such an amount that it becomes zero.

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

The molecular weight of the obtained olefin polymer can be adjusted by allowing hydrogen to be present in the polymerization system or by changing the polymerization temperature. Examples of olefins that can be polymerized by such an olefin polymerization catalyst include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, and 3-methyl-1-pentene. Ethyl-1-pentene, 4-methyl-1-pentene, 4-
Methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1
Α-olefins having 2 to 20 carbon atoms, such as -hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene;
Aromatic vinyl compounds such as styrene, dimethylstyrenes, allylbenzene, allyltoluenes, vinylnaphthalenes and allylnaphthalenes; vinylcyclohexane,
Alicyclic vinyl compounds such as vinylcyclopentane, vinylcycloheptane and allylnorbornane; cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl-1,4,5,8-
Cyclic olefins such as dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene; 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,5,9 A chain polyene having 4 to 20 carbon atoms such as -decatriene; and a cyclic polyene such as 5-ethylidene norbornene and dicyclopentadiene.

These olefins can be used alone or
It can be used in combination of more than one kind.

[0128]

The olefin polymerization catalyst according to the present invention has a high polymerization activity and an olefin having a narrow molecular weight distribution.
A polymer can be obtained, and an olefin copolymer having a narrow composition distribution when two or more olefins are copolymerized can be obtained.

According to the olefin polymerization method of the present invention, an olefin (co) polymer having a high polymerization activity and a narrow molecular weight distribution can be obtained, and the composition distribution is narrow when two or more olefins are copolymerized. An olefin copolymer can be obtained.

[0130]

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

In this example, the intrinsic viscosity ([η]) was measured at 135 ° C. in decalin.

[0132]

Example 1 Dissolution of a boron-containing organoaluminum oxy compound in toluene
Preparation of Liquid (B-1) 100 ml of toluene was charged into a 500 ml-volume glass reactor which had been sufficiently purged with nitrogen, and then 4.08 g (40 mmol) of n-butylboronic acid was charged. This is -6
After cooling to 0 ° C., 100 ml of a toluene solution of triisobutylaluminum (0.8 mol / l) was added dropwise over 30 minutes. After completion of the dropwise addition, the reaction temperature was raised from -60 ° C to 20 ° C over 1 hour, and further reacted at this temperature for 2 hours to obtain a toluene solution of the boron-containing organoaluminum oxy compound (B-1). ). This solution contained 0.4 mol / l of aluminum atoms.

Polymerization A 250 ml glass autoclave having an internal volume of 500 ml which had been sufficiently purged with nitrogen was charged with 250 ml of toluene, and ethylene was passed through the autoclave at a rate of 100 liter / hour, and the mixture was allowed to stand at 25 ° C. for 10 minutes. Then, diisobutyl aluminum (2,6-
0.1 mmol of di-t-butyl-4-methylphenoxide), 0.63 ml of the component (B-1) obtained above, and a titanium amide compound (A-1) represented by the following formula (a): Polymerization was started by adding 5 μmol in this order. Ethylene gas was continuously supplied at a rate of 100 liter / hour, polymerization was performed at 25 ° C. for 1 hour under normal pressure, and then a small amount of methanol was added to stop the polymerization. The polymerization reaction solution was added to a large excess of methanol-hydrochloric acid solution, and the obtained polymer was heated at 130 ° C.
For 12 hours under reduced pressure. As a result, 1.3 g of a polymer was obtained.

[0134]

Embedded image

[0135]

Example 2 250 ml of toluene was charged into a 500 ml-volume glass autoclave which had been sufficiently purged with nitrogen.
A mixed gas of ethylene and butene (70 liter / hour and 30 liter / hour, respectively) was passed through this,
For 10 minutes. Then, the components obtained in Example 1
3.2 ml of (B-1) and then 5 micromoles of the titanium amide compound (A-1) represented by the formula (a) were added to initiate polymerization. A mixed gas of ethylene and butene was continuously supplied, and polymerization was carried out at 25 ° C. for 1 hour under normal pressure. The polymerization reaction solution was added to a large excess of a methanol-hydrochloric acid solution, and the obtained polymer was dried under reduced pressure at 130 ° C. for 12 hours. As a result, 1.6 g of a polymer having an ethylene content of 86 mol% was obtained.

[0136]

EXAMPLE 3 60 ml of heptane and then 40 ml of 1-octene were charged into a 200 ml-volume glass autoclave which had been sufficiently purged with nitrogen, and ethylene was passed at a rate of 20 l / h, and the mixture was kept at 50 ° C. for 20 minutes. I left it. 0.1 mmol of diisobutylaluminum (2,6-di-t-butyl-4-methylphenoxide), 0.63 ml of the component (B-1) obtained in Example 1, and the following formula (b) The titanium amide compound (A-2) represented by the formula (2) was added in an amount of 2 μmol in this order to initiate polymerization. Ethylene gas is continuously supplied at a rate of 20 liters / hour, under normal pressure,
After polymerization at 50 ° C. for 5 minutes, a small amount of methanol was added to terminate the polymerization. The polymerization reaction solution was added to a large excess of a methanol-hydrochloric acid solution, and the obtained polymer was dried under reduced pressure at 130 ° C. for 12 hours. As a result, [η] becomes 0.
2.5 g of a polymer with 78 dl / g and an ethylene content of 19 mol% were obtained.

[0137]

Embedded image

[0138]

Example 4 The procedure of Example 3 was repeated except that the titanium amide compound (A-3) represented by the following formula (c) was used in an amount of 2 μmol in place of the titanium amide compound (A-2). In the same manner as in Example 3, copolymerization of ethylene and 1-octene was performed. As a result, 2.3 g of a polymer having [η] of 0.73 dl / g and an ethylene content of 18 mol% was obtained.

[0139]

Embedded image

[0140]

Example 5 5 ml of toluene was charged into a 20 ml glass container which had been sufficiently purged with nitrogen, and 1.25 ml of the component (B-1) obtained in Example 1 was added thereto, followed by bis [bis (trimethylsilyl). ) Amide] zirconium dichloride ([(Me ₃ Si) ₂ N] ₂ ZrCl ₂ ) (1 μmol) was added and stirred for 5 minutes to prepare a pre-contact catalyst (a-1).

Separately from the above, toluene 3 was placed in a 1-liter stainless steel autoclave sufficiently purged with nitrogen.
00 ml and then 100 ml of 1-hexene were charged. In addition, diisobutylaluminum (2,6-di-t-butyl-4-
Methylphenoxide) was charged in an amount of 0.2 mmol, and the inside of the system was heated to 40 ° C. Next, the pre-contact catalyst (a-
1) The polymerization was started by injecting the whole amount with ethylene. Total pressure 8kg / cm while continuously supplying ethylene
After polymerization at ^2- G at 70 ° C. for 30 minutes, a small amount of methanol was added by injection to terminate the polymerization. The polymerization reaction solution was added to a large excess of a methanol-hydrochloric acid solution, and the obtained polymer was dried under reduced pressure at 130 ° C. for 12 hours. As a result, 2.4 g of an ethylene / 1-hexene copolymer having [η] of 3.2 dl / g was obtained.

[0142]

Example 6 Preparation of Catalyst A glass reactor having an internal volume of 200 ml was charged with 5 g of montmorillonite (Montmorillonite K10, manufactured by Aldrich). After sufficiently replacing the inside of the reactor with nitrogen, toluene 50m
was charged to obtain a slurry. To this, at room temperature, a toluene solution of trimethylaluminum (1 mol / L)
25 ml was added dropwise over 30 minutes. After the completion of the dropwise addition, the reaction was further performed at room temperature for 2 hours. Filtering the resulting slurry,
After washing twice with 50 ml of hexane, the slurry was resuspended in 100 ml of heptane to obtain a slurry (d).

Separately from the above, 5 ml of heptane was charged into a 20 ml-volume glass container which had been sufficiently purged with nitrogen. 0.5 ml of a heptane solution of triisobutylaluminum (0.1 mol / l) was added thereto, and the above formula (a)
Was added in this order and contacted for 5 minutes. Furthermore, a catalyst slurry (e) was obtained by adding and contacting 5 ml of the slurry (d) obtained above.

Polymerization Separately from the above, 250 ml of heptane was charged into a 500 ml-volume glass autoclave sufficiently purged with nitrogen, and ethylene was passed through the autoclave at 100 liter / hour, and the mixture was allowed to stand at 50 ° C. for 10 minutes. Thereafter, 0.1 mmol of diisobutylaluminum (2,6-di-t-butyl-4-methylphenoxide) was added to the slurry (e) obtained above.
Were added in this order to initiate polymerization. Ethylene gas was continuously supplied at a rate of 100 liter / hour, polymerization was carried out at 50 ° C. for 1 hour under normal pressure, and then a small amount of methanol was added to terminate the polymerization. The polymerization reaction solution was added to a large excess of methanol-hydrochloric acid solution, and the obtained polymer was heated at 130 ° C.
For 12 hours under reduced pressure. As a result, 1.2 g of a polymer was obtained.

[Brief description of the drawings]

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

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Terunori Fujita 1-2-1, Waki, Waki-machi, Kuga-gun, Yamaguchi Prefecture Inside Mitsui Petrochemical Industry Co., Ltd.

Claims (2)

[Claims] (A) a transition metal amide compound represented by the following general formula (I): (R ₂ N) _k MX _jk (I) wherein M is a group 3 to 6 of the periodic table Wherein j is a valence of the transition metal atom M, k is an integer of 1 to j, and Rs may be the same or different from each other;
A hydrogen atom, a hydrocarbon group, a halogenated hydrocarbon group, an organic silyl group or a substituent having at least one element selected from nitrogen, oxygen, phosphorus, sulfur and silicon;
A plurality of groups represented by R may be connected to each other to form a ring, and when k is 2 or more, two Rs bonded to different nitrogen atoms are connected to each other to form two nitrogen atoms. X may represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, sulfur, And when jk is 2 or more, they may be the same or different from each other. (B) (B-1) a boron-containing organoaluminum oxy compound represented by the following general formula (II): (Wherein, R ²¹ is a hydrocarbon group having 1 to 10 carbon atoms, and R ²² may be the same or different, and may be a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 10 carbon atoms. Or (B-2) a clay, a clay mineral or an ion-exchangeable layered compound, and if necessary, (C) an organometallic compound. 2. A method for polymerizing an olefin, comprising polymerizing or copolymerizing an olefin in the presence of the catalyst for olefin polymerization according to claim 1.