JPH0952911A - Catalyst for olefin (co)polymerization and production of olefin (co)polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject catalyst consisting essentially of a specific solid catalyst component and an organoaluminum compound, having high catalyst activity per solid catalyst and narrow composition distribution and capable of providing an olefin (co)polymer excellent in dynamic characteristics and weather resistance, etc. SOLUTION: This catalyst consists essentially of (A) a solid catalyst component obtained by reacting (i) a solid component obtained by reacting a halogenated silicon compound of the formula R<1> mSiX4-m [R<1> is a 1-20C alkyl, aryl or alkenyl; X is a halogen; 0<=(m)<4] and/or a halogenated aluminum compound of the formula R<2> nAlX3-n [R<2> is same as R<1> ; 0<=(n)<3] with an organomagnesium compound of the formula R<3> MgX and/or R<4> R<5> Mg (R<3> to R<5> are each same as R<1> ) in a solvent and then reacting the resultant halogen- containing solid magnesium component with a titanium compound with (iii) an organoaluminum compound in the presence of (ii) a titanium compound and (B) an organoaluminum compound.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an olefin (co).
Polymerization catalyst and olefin (co) using such catalyst
The present invention relates to a method for producing a polymer, particularly an ethylene / α-olefin copolymer. More specifically, a catalyst for producing an ethylene / α-olefin copolymer having a high activity per solid catalyst, a narrow composition distribution, and excellent mechanical properties, and ethylene / α
-It relates to a method for producing an olefin copolymer.
The ethylene / α-olefin copolymer obtained by the production method of the present invention is particularly useful as a film having excellent tackiness and transparency. In the present invention, olefin (co)
The polymer refers to a homopolymer of an olefin and / or a copolymer of an olefin and another olefin.

[0002]

2. Description of the Related Art Olefin (co) polymers are films,
It is used in numerous applications such as lamination, wire coating, injection molding, and special molded products. Further, in these applications, it is preferable that the molecular weight distribution and the composition distribution are narrow from the viewpoint of practical physical properties such as transparency, impact resistance, and blocking property. Particularly, in the ethylene / α-olefin copolymer, α-olefin is preferable. The influence of the molecular weight distribution and the composition distribution on the physical properties of the olefin copolymer increases as the content of C increases. Therefore, an olefin copolymer having a narrow molecular weight distribution and a narrow composition distribution is desired. Generally, a method for producing an ethylene / α-olefin copolymer includes,
It is well known to use a so-called Ziegler type catalyst consisting of a Group 6 transition metal compound and a Group 1 to 3 organometallic compound.

At present, the following two methods are carried out as methods for industrially producing olefin (co) polymers at high temperatures using these Ziegler type catalysts. The first method is generally called "high temperature solution polymerization method" and is a method of copolymerizing an olefin under a condition in which a (co) polymer is dissolved using a solvent such as cyclohexane. Is a method of polymerizing under conditions of 5 to 50 kg / cm ² . The second method is generally called a "high pressure ionic polymerization method", and is a method in which a olefin polymer produced is polymerized in a solvent-free state at high temperature and high pressure in a state of being dissolved in a supercritical olefin.

The high temperature solution polymerization method using a Ziegler type catalyst and the high pressure ionic polymerization method have advantages such as a compact reactor and a high degree of freedom in selecting comonomer.

On the other hand, various catalysts for high temperature polymerization have been improved in order to improve the quality of olefin (co) polymers obtained under such high temperature conditions (see, for example, JP-A-51-1443).
97, JP-A-54-52192, JP-A-5
6-18607, JP-A-56-99209, JP-A-57-87405, and JP-A-57-15.
No. 3007, JP-A-57-19009, and JP-A-58-208803), the composition distribution of the copolymer obtained using these methods is not sufficiently narrow, and the transparency and tackiness are It is hard to say that it is always satisfactory in terms of practical physical properties such as mechanical properties.

As means for solving such a problem, Japanese Patent Publication No. 64-12287 and Japanese Unexamined Patent Publication No. 5-202139.
Proposals have been made in Japanese publications. For example, Japanese Patent Publication No. 64-
According to 12287, (1) magnesium dihalide, (2) a compound represented by the general formula Si (OR) _m X _4-m , and (3) a titanium compound or a titanium compound and a vanadium compound are reacted. A method is disclosed in which a solid substance obtained by further reacting the reaction product obtained with (4) the compound represented by the general formula AlR _p X _3-p is used as one of the catalyst components. When used under high temperature conditions, there is a problem that the activity per transition metal decreases. The method disclosed in Japanese Patent Laid-Open No. 5-202139 also has similar problems.

Further, the aluminum halide compound represented by the general formula R ¹ _n AlX _3-n and / or the general formula R
A solid product obtained by reacting a silicon halide compound represented by ² _m SiX _4-m and an organomagnesium compound represented by the general formula R ³ MgX and / or R ⁴² Mg in a solvent is used as a carrier, A method for producing an ethylene polymer with high efficiency under high temperature conditions using a catalyst system comprising a solid catalyst component (A) supporting a titanium compound and / or a vanadium compound thereon and an organoaluminum compound (B) No. 3-41484), a copolymer having a narrow composition distribution cannot be obtained even by copolymerizing ethylene and an α-olefin using the production method.

[0008]

Under such circumstances, the problem to be solved by the present invention is that by using a novel catalyst, the activity per solid catalyst is high under high temperature conditions,
Olefin with a narrow composition distribution and excellent mechanical properties (co)
An object of the present invention is to provide a highly efficient method for producing a polymer, particularly an ethylene / α-olefin copolymer. That is, the object of the present invention is to provide a novel solid catalyst component for olefin (co) polymerization,
An olefin (co) polymerization catalyst containing the solid catalyst component and organoaluminum as main components and an olefin (co) polymer using the catalyst, and particularly a highly efficient method for producing an ethylene / α-olefin copolymer are provided. Especially.

[0009]

The present invention provides (A) a general formula R ¹ _m SiX _4-m (wherein R ¹ represents an alkyl group, an aryl group or an alkenyl group having 1 to 20 carbon atoms; Represents a halogen atom, and m is a number represented by 0 ≦ m <4) and a silicon halide compound represented by
Or the general formula R ² _n AlX _3-n (wherein R ² represents an alkyl group, an aryl group or an alkenyl group having 1 to 20 carbon atoms, X represents a halogen atom, and n represents 0 ≦ n <3. And an aluminum halide compound represented by the general formula R ³ MgX and / or R ⁴ R
⁵ Mg (wherein R ³ , R ⁴ and R ⁵ represent an alkyl group, an aryl group or an alkenyl group having 1 to 20 carbon atoms, and X represents a halogen atom) and a solvent. To the halogen-containing solid magnesium component (a-1) obtained by reacting in a titanium compound (a-
The solid component (A-
1) and a solid catalyst component obtained by reacting an organoaluminum compound (A-2) in the coexistence of a titanium compound (a-3), and (B) an olefin (co) polymerization containing an organoaluminum compound as a main component. The present invention relates to a catalyst for use and a method for producing an olefin (co) polymer using the catalyst.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in detail below.
You. The solid used as the catalyst component (A) in the present invention
The body catalyst component has the general formula R¹ _mSiX_4-m(Where R¹Is
C1-C20 alkyl groups, aryl groups, alkene
Represents a halogen atom and X represents a halogen atom. Also, m is 0 ≦
It is a number represented by m <4. ) Halogenated
Silicon compound (a- (1)) and / or general formula R²
_nAlX_3-n(Where R²Is an alky having 1 to 20 carbon atoms
Represents a group, an aryl group or an alkenyl group, and X is a halogen.
Represents an atom. In addition, n is a number represented by 0 ≦ n <3
You. ) An aluminum halide compound (a-
(2)) and the general formula R^ThreeMgX and / or R^FourR^Five
Mg (where R^Three, R^Four, R^FiveIs a carbon number of 1 to 20
Represents a alkyl group, an aryl group or an alkenyl group, and X is halo.
Represents a gen atom. ) An organomagnesium compound represented by
Halogen-containing solid polymer obtained by reacting and in a solvent
In addition to the gnesium component (a-1), the titanium compound (a-2)
Solid component (A-1) obtained by reacting
And an organoaluminium in the presence of a titanium compound (a-3)
In this case, the compound (A-2) is reacted.

(1) Synthesis of halogen-containing solid magnesium compound (a-1) The halogen-containing solid magnesium compound (a-1) used in the synthesis of the solid catalyst component (A) of the present invention has the general formula R
¹ _m SiX _4-m (wherein R ¹ represents an alkyl group, an aryl group or an alkenyl group having 1 to 20 carbon atoms, X represents a halogen atom, and m represents 0 ≦ m <4. A silicon halide compound (a-
(1)) and / or the general formula R ² _n AlX _3-n (wherein R ² is an alkyl group having 1 to 20 carbon atoms, an aryl group,
It represents an alkenyl group, and X represents a halogen atom. Also,
n is a number represented by 0 ≦ n <3. ) And an aluminum halide compound (a- (2)) represented by the general formula R ³ MgX and / or R ⁴ R ⁵ Mg (where R ³ ,
R ⁴ and R ⁵ represent an alkyl group, an aryl group or an alkenyl group having 1 to 20 carbon atoms, and R ⁴ and R ⁵ may be the same or different. X represents a halogen atom. ) It is obtained by reacting with an organomagnesium compound represented by.

(A) Organomagnesium compound The organomagnesium compound used for the synthesis of the catalyst is M
Any type of organomagnesium compound containing a g-C bond can be used. Particularly, a Grignard compound represented by the general formula R ³ MgX and a dialkyl magnesium compound represented by the general formula R ⁴ R ⁵ Mg are preferable.

The general formula R ³ MgX and the general formula R ⁴ R ⁵ M
Examples of the magnesium compound represented by g include R ³ ,
R ⁴ and R ⁵ represent an alkyl group, an aryl group or an alkenyl group having 1 to 20 carbon atoms, and specific examples thereof include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, amyl, isoamyl, hexyl, octyl, 2 Examples thereof include —ethylhexyl, phenyl and benzyl, and examples of the halogen atom represented by X include chlorine, bromine and iodine.

Further, preferred specific examples of the halogenated alkyl magnesium compound represented by the general formula R ³ MgX include methyl magnesium chloride, ethyl magnesium chloride, ethyl magnesium bromide, ethyl magnesium iodide, propyl magnesium chloride and propyl magnesium bromide. , Butylmagnesium chloride, butylmagnesium bromide,
Examples thereof include sec-butyl magnesium chloride, sec-butyl magnesium bromide, tert-butyl magnesium bromide, tert-butyl magnesium bromide, amyl magnesium chloride, isoamyl magnesium chloride, hexyl magnesium chloride, phenyl magnesium chloride and phenyl magnesium bromide.

Of these, the case where the halogen atom is chlorine is more preferable, and specifically, methylmagnesium chloride, ethylmagnesium chloride, propylmagnesium chloride, butylmagnesium chloride, sec-butylmagnesium chloride, tert.
-Butylmagnesium chloride, amylmagnesium chloride, isoamylmagnesium chloride, hexylmagnesium chloride, phenylmagnesium chloride.

Preferred specific examples of the compound represented by the general formula R ⁴ R ⁵ Mg include dimethyl magnesium, diethyl magnesium, dipropyl magnesium, diisopropyl magnesium, dibutyl magnesium and di-se.
Examples thereof include c-butyl magnesium, di-tert-butyl magnesium, butyl-sec-butyl magnesium, diamyl magnesium, dihexyl magnesium, diphenyl magnesium and butyl ethyl magnesium.

As the synthetic solvent for the above organomagnesium compound, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diisobutyl ether, diamyl ether, diisoamyl ether, dihexyl ether, dioctyl ether, diphenyl ether, dibenzyl ether, Ether solvents such as phenetole, anisole, tetrahydrofuran and tetrahydropyran can be used. Further, a hydrocarbon solvent such as hexane, heptane, octane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, or a mixed solvent of an ether solvent and a hydrocarbon solvent may be used.

The organic magnesium compound is preferably used in the form of an ether solution. In this case, the ether compound is an ether compound having 6 or more carbon atoms in the molecule or an ether compound having a cyclic structure. Used. It is particularly preferable to use the Grignard compound represented by the general formula R ³ MgX in the state of an ether solution from the viewpoint of catalytic performance.

It is also possible to use a hydrocarbon-soluble complex of the organomagnesium compound and the organometallic compound. Examples of such organometallic compounds include Li,
Organometallic compounds of Be, B, Al or Zn are mentioned.

(B) Silicon halide compound (a-
(1)) The halogenated silicon compound (a- (1)) used in the synthesis of the halogen-containing solid magnesium compound (a-1) is
General formula R ¹ _m SiX _4-m (where R ¹ has ¹ to 2 carbon atoms)
0 represents an alkyl group, an aryl group or an alkenyl group, and X
Represents a halogen atom. Further, m is a number represented by 0 ≦ m <4. )).

Examples of the halogen atom represented by X include chlorine, bromine and iodine. Specific compounds include silicon tetrachloride, silicon tetrabromide, methylsilyl trichloride, dimethylsilyl dichloride, trimethylsilyl chloride, ethylsilyl trichloride, diethylsilyl dichloride, triethylsilyl chloride,
Examples thereof include butylsilyl trichloride, dibutylsilyl dichloride, tributylsilyl chloride, vinylsilyl trichloride and the like.

Of these, the general formula R ¹ _m S is preferred.
This is the case where the halogen atom represented by X in iX _4-m is chlorine.

Specific compounds include silicon tetrachloride,
Examples thereof include methylsilyl trichloride, dimethylsilyl dichloride, trimethylsilyl chloride, ethylsilyl trichloride, diethylsilyl dichloride, triethylsilyl chloride, butylsilyl trichloride, dibutylsilyl dichloride, tributylsilyl chloride, vinylsilyl trichloride and the like.

In the general formula R ¹ _m SiX _4-m , the smaller the value of _m , the better the result. Of these, silicon tetrachloride with m = 0 is most suitable.

(C) Aluminum halide compound (a
-(2)) An aluminum halide compound can also be used for the synthesis of the halogen-containing solid magnesium compound (a-1). The aluminum halide compound (a- (2)) is
General formula R ² _n AlX _3-n (where R ² has 1 to ² carbon atoms)
0 represents an alkyl group, an aryl group or an alkenyl group, and X
Represents a halogen atom. Further, n is a number represented by 0 ≦ n <3. ) Is an aluminum halide compound.

Other specific compounds include aluminum bromide, aluminum iodide, diethyl aluminum chloride, ethyl aluminum dichloride, ethyl aluminum sesquichloride, dibutyl aluminum chloride, butyl aluminum dichloride, hexyl aluminum dibromide and the like.

In the general formula R ² _n AlX _3-n , the smaller the value of _n , the better the result. Of these, anhydrous aluminum chloride is most suitable.

Halogen-containing solid magnesium compound (a-
1) used in the synthesis of a halogenated silicon compound (a-
(1)) and an aluminum halide compound (a-
Although each of (2)) can be used alone, these can also be used in combination. Of these,
From the viewpoint of catalyst performance, a halogenated silicon compound (a-
(1)) is more preferably used.

Halogen-containing solid magnesium component (a-
The synthesis of 1) is carried out in an atmosphere of an inert gas such as nitrogen or argon. The reaction of the organomagnesium compound with the silicon halide compound or the aluminum halide compound is preferably carried out in a solvent at 0 to 200 ° C, preferably 0 to 100 ° C.

As the solvent used, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diisobutyl ether, diamyl ether, diisoamyl ether, dihexyl ether, dioctyl ether, diphenyl ether, dibenzyl ether, phenetole, anisole, An ether solvent such as tetrahydrofuran or tetrahydropyran can be used. Further, a hydrocarbon solvent such as hexane, heptane, octane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, or a mixed solvent of an ether solvent and a hydrocarbon solvent may be used. Above all, it is preferable to carry out in a solvent containing an ether solvent from the viewpoint of polymerization activity.

The reaction ratio between the organomagnesium compound and the silicon halide compound and / or aluminum halide compound is 0.1 to 10.0, preferably 0.2 to 5.0, in terms of molar ratio.

The reaction product obtained by the above method is preferably filtered, washed with a sufficiently dried hydrocarbon solvent and dried to be used as a carrier. In particular, a carrier containing an electron-donating substance such as an ether solvent is preferable from the viewpoint of polymerization activity.

(2) Synthesis of Solid Component (A-1) The solid component (A-1) used in the synthesis of the solid catalyst component (A) of the present invention is the halogen-containing solid magnesium component (a-1), It is obtained by reacting the titanium compound (a-2).

(A) Titanium Compound The titanium compound (a-2) has the general formula TiM _a X _4-a (M
Is a group selected from _{^{OR 7, NR 8 2, SR}} 9, PR 10 2, R 7, R 8, R 9, R 10 represents a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen Represents an atom. Also, a
Is a number represented by 0 ≦ a <4. ) And a titanium compound represented by the formula (1). Among these,
An alkyl group having 1 to 18 carbon atoms and an aryl group having 6 to 18 carbon atoms are preferable. Particularly, a linear alkyl group having 1 to 18 carbon atoms is preferable. It is also possible to use a titanium compound having two or more different hydrocarbon groups.

Specific examples of R ⁷ , R ⁸ , R ⁹ and R ¹⁰ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, amyl, isoamyl and t.
Examples thereof include alkyl groups such as amyl, hexyl, heptyl, octyl, decyl and dodecyl, cycloaryl groups such as phenyl, cresyl, xylyl and naphthyl, allyl groups such as propenyl and aralkyl groups such as benzyl. Of the substituents represented by M, O is particularly preferable.
R ^7, is NR ⁸ _2.

Examples of the halogen atom represented by X include chlorine, bromine and iodine. Specifically, tetrahalogenated titanium compounds such as titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, methoxytitanium trichloride, ethoxytitanium trichloride, butoxytitanium trichloride, phenoxytitanium trichloride, ethoxytitanium tribromide. Trihalogenated alkoxytitanium compounds such as dimethoxytitanium dichloride, diethoxytitanium dichloride, dibutoxytitanium dichloride, diphenoxytitanium dichloride, dihalogenated dialkoxytitanium compounds such as diethoxytitanium dibromide,
Trimethoxytitanium chloride, triethoxytitanium chloride, tributoxytitanium chloride, triphenoxytitanium chloride, triethoxytitanium bromide and other monohalogenated trialkoxytitanium compounds, dimethylamidotitanium trichloride, diethylamidotitanium trichloride, dibutylamidotitanium trichloride. Trihalogenated amide titanium compounds such as diphenylamide titanium trichloride, dioctylamide titanium trichloride, diethylamide titanium tribromide, bisdimethylamide titanium dichloride, bisdiethylamide titanium dichloride, bisdibutylamide titanium dichloride, bisdiphenylamide titanium dichloride, bis Dioctylamide titanium dichloride, bisdiethylamidothio Dihalogenated bisamide titanium compounds such Nji bromide, tris dimethylamide titanium chloride, tris diethylamide titanium chloride,
Examples include monohalogenated trisamide titanium compounds such as trisdibutylamide titanium chloride, trisdiphenylamide titanium chloride, trisdioctylamide titanium chloride, and trisdiethylamide titanium bromide.

From the viewpoint of polymerization activity, the general formula TiM is preferred.
The value of a of the titanium compound represented by _a X _4-a is a
= 0, and specific examples thereof are titanium tetrahalide compounds such as titanium tetrachloride, titanium tetrabromide and titanium tetraiodide.

The halogen atom represented by X is particularly preferably chlorine, and a specific example thereof is titanium tetrachloride.

As the reaction of the halogen-containing solid magnesium component (a-1) and the titanium compound (a-2) in the synthesis of the solid component (A-1), known methods such as an impregnation method, a kneading method and a coprecipitation method are known. Can be used.

Halogen-containing solid magnesium component (a-
The reaction between 1) and the titanium compound (a-2) is performed at room temperature to 150.
It is preferably carried out at a temperature of ° C. The reaction product is filtered, washed thoroughly with the produced hydrocarbon solvent, and used as it is or after drying.

(3) Synthesis of Solid Catalyst Component (A) In the present invention, the solid catalyst component (A) comprises a halogen-containing solid magnesium component (a-1) and a titanium compound (a-).
It is obtained by reacting the solid component (A-1) obtained by reacting 2) with the organoaluminum compound (A-2) in the coexistence of the titanium compound (a-3).

(A) Titanium compound (a-3) In the present invention, it is used for the reaction between the solid component (A-1) and the organoaluminum compound (A-2) in the coexistence of the titanium compound (a-3). Titanium compound (a-
As 3), the same compounds as the titanium compound (a-2) described above can be used. (A-2) and (a-3) may be the same or different. The catalytic performance is affected by the amount of titanium compound used. When the amount is small, the activity is low, and when the amount is large, the composition distribution is broad, which is not preferable.
Therefore, the amount of the titanium compound used is the solid component (A-1) 1
It is preferably 0.001-1 ml / g per g. Particularly preferably, it is 0.01 to 0.5 ml / g.

(B) Organoaluminum compound (A-2) Solid component (A-1) in the presence of titanium compound (a-3)
Used in the reaction of the organoaluminum compound (A-2) with
The organoaluminum compound having the general formula R ⁶ _pAl
Y_3-p(R⁶Is an alkyl group having 1 to 20 carbon atoms, aryl
Represents a group or an alkenyl group, and Y represents halogen, hydrogen or
Represents an alkoxy group. Also, p is represented by 0 <p ≦ 3
It is a number. ) Organoaluminum compounds represented by
You can

Among such compounds, the general formula R ⁶ _p AlY
Specific examples of the organoaluminum compound represented by _3-p include trimethylaluminum in which p = 3 in the general formula,
Examples of the trialkylaluminum such as triethylaluminum, triisobutylaluminum and trihexylaluminum, and the compound in which p is 0 <p <3 include dimethylaluminum hydride, diethylaluminum hydride, dialkylaluminum hydride such as diisobutylaluminum hydride, dimethylaluminum chloride, Examples thereof include dialkyl aluminum halides such as diethyl aluminum chloride and diisobutyl aluminum chloride, and alkyl aluminum dihalides such as methyl aluminum dichloride, ethyl aluminum dichloride and diisobutyl aluminum dichloride. It is also possible to use mixtures of trialkylaluminums and alkylaluminum halides, such as mixtures of triethylaluminium and diethylaluminium chloride.

More specifically, when p in the general formula is 0 <p <3 and Y is a halogen atom, examples of the organic aluminum include dimethyl aluminum chloride, methyl aluminum sesquichloride, methyl aluminum dichloride, dimethyl aluminum bromide and methyl aluminum. Sesquibromide, methyl aluminum dibromide, dimethyl aluminum iodide, methyl aluminum sesquiiodide, methyl aluminum diiodide, diethyl aluminum chloride, ethyl aluminum sesquichloride, ethyl aluminum dichloride, diethyl aluminum bromide,
Ethyl aluminum sesquibromide, ethyl aluminum dibromide, diethyl aluminum iodide, ethyl aluminum sesquiiodide, ethyl aluminum diiodide, dipropyl aluminum chloride, propyl aluminum sesquichloride,
Propyl aluminum dichloride, dipropyl aluminum bromide, propyl aluminum sesquibromide, propyl aluminum dibromide, dipropyl aluminum iodide, propyl aluminum sesquiiodide, propyl aluminum diiodide, diisopropyl aluminum chloride, isopropyl aluminum sesquichloride, isopropyl aluminum dichloride Ride, diisopropyl aluminum bromide, isopropyl aluminum sesquibromide, isopropyl aluminum dibromide, diisopropyl aluminum iodide, isopropyl aluminum sesquiiodide, isopropyl aluminum diiodide, dibutyl aluminum chloride, butyl al Pyridinium sesquichloride, butylaluminum dichroic chloride, dibutyl aluminum bromide, butyl aluminum sesqui bromide, butyl aluminum die bromide, dibutyl aluminum iodide, butyl aluminum sesqui iodide,
Butyl aluminum diiodide, diisobutyl aluminum chloride, isobutyl aluminum sesquichloride, isobutyl aluminum dichloride,
Diisobutyl aluminum bromide, isobutyl aluminum sesquibromide, isobutyl aluminum dibromide, diisobutyl aluminum iodide, isobutyl aluminum sesquiiodide, isobutyl aluminum diiodide, dihexyl aluminum chloride, hexyl aluminum sesquichloride, hexyl aluminum dichloride, dihexyl aluminum bromide, hexyl Aluminum sesquibromide, hexyl aluminum dibromide, dihexyl alum dichloride, dihexyl aluminum bromide, hexyl aluminum sesquibromide, hexyl aluminum dibromide, dihexyl aluminum iodide, hexyl aluminum sesquiiodide, Hexyl aluminum die iodide, dioctyl aluminum chloride, octyl aluminum sesquichloride, octyl aluminum dichroic chloride, dioctyl aluminum bromide,
Octyl aluminum sesquibromide, octyl aluminum dibromide, dioctyl aluminum iodide, octyl aluminum sesquiiodide,
Examples include alkyl aluminum halides such as octyl aluminum diiodide.

Of these alkylaluminum halide compounds, Y is preferably chlorine in view of polymerization activity. Specifically, dimethyl aluminum chloride,
Methyl aluminum sesquichloride, methyl aluminum dichloride, diethyl aluminum chloride, ethyl aluminum sesquichloride, ethyl aluminum dichloride, dipropyl aluminum chloride, propyl aluminum sesquichloride, propyl aluminum dichloride, diisopropyl aluminum chloride, isopropyl aluminum sesqui chloride, isopropyl aluminum Dichloride, dibutyl aluminum chloride, butyl aluminum sesquichloride, butyl aluminum dichloride, diisobutyl aluminum chloride, isobutyl aluminum sesquichloride, isobutyl aluminum dichloride, dihexyl aluminum chloride, hexyl aluminum Arm sesquichloride, hexyl aluminum dichroic chloride, dioctyl aluminum chloride, octyl aluminum sesquichloride,
Examples thereof include chlorine-containing organic aluminum compounds such as octylaluminum dichloride.

The reaction between the solid component (A-1) and the titanium compound (a-3) in the presence of the organoaluminum compound (A-2) is carried out by the reaction between the solid component (A-1) and the titanium compound (a-). Method 3) in which an organoaluminum compound (A-2) solution diluted with an appropriate diluent is added dropwise to a slurry prepared by diluting 3) with an inert hydrocarbon solvent, or an organoaluminum compound (A-) diluted with an inert hydrocarbon solvent (A- 2) Any of the methods of dropping a slurry diluted with an inert solvent into a solution can be carried out, but the former is preferable from the viewpoint of reaction control.

Examples of the inert hydrocarbon solvent used as a diluent in this reaction include aliphatic hydrocarbons such as pentane, hexane, heptane and octane, aromatic hydrocarbons such as benzene, toluene and xylene, cyclohexane and cyclopentane. Alicyclic hydrocarbons such as

The amount of the diluent used is not particularly limited, but when diluting the solid component, it is generally used within the range where the slurry concentration of the catalyst is 0.01 to 5.0 (g / l).

The dilution of the organoaluminum compound is not particularly limited as long as it is below the ignition limit concentration of the organoaluminum, but usually 5 to 10 wt% of the organoaluminum.
It is preferable to use it after diluting within the range.

The reaction temperature can be generally in the range of -40 ° C to 150 ° C, but it is preferable to carry out the reaction at a low temperature from the viewpoint of the copolymerization performance of the catalyst, particularly the composition distribution, specifically, -30. ~ 120 ° C temperature, more preferably 0 ° C
The range of -100 ° C is preferred.

The amount of the organoaluminum compound used is 0.05 to 50 with respect to the Ti atom in the solid component (A-1).
Although it can be selected from a wide range such as (mol / mol), it is preferably 0.1 to 30, and more preferably 1.0 to 2 from the viewpoint of the copolymerization performance of the catalyst, particularly the composition distribution.
0.

The rate of addition of the organoaluminum compound is not particularly limited as long as the temperature rise of the reaction solution due to heat generation of the reaction can be suppressed within the range of 10 ° C., but usually 5
~ 60 minutes. The reaction time is not particularly limited, but usually 30 minutes to 5 hours is suitable.

After completion of the reaction, the solid formed is washed with a suitable inert hydrocarbon solvent. The number of washings is usually 3 to 6 times,
As the solvent used for washing, pentane, hexane,
Aliphatic hydrocarbons such as heptane and octane, aromatic hydrocarbons such as benzene, toluene and xylene, and alicyclic hydrocarbons such as cyclohexane and cyclopentane can be used.

After the completion of washing, the produced solid is filtered to remove the solvent and then dried by vacuum drying or by passing dry nitrogen to obtain a solid catalyst component (A).

(B) Organoaluminum Compound The organoaluminum compound used as the catalyst component (B) in the present invention has the general formula R ¹¹ _z AlX.
_3-z (R ¹¹ represents a hydrocarbon group having 1 to 8 carbon atoms or a hydrogen atom, X represents a halogen atom or an alkoxy group, and z is a number represented by 0 <z ≦ 3. ) And the general formula R ¹⁴ R ¹⁵ (Al
OR ¹⁶ ) _b AlR ¹⁷ R ¹⁸ (R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R
Each ¹⁸ independently represents a hydrocarbon group having 1 to 8 carbon atoms. However, a ring structure in which any one of R ¹⁴ , R ¹⁵ and R ¹⁷ , R ¹⁸ is bonded to each other may be used. Moreover, b represents the number of 2-30. ) The aluminoxane compound represented by this is mentioned.

Of such compounds, the general formula R ¹¹ _Z AlX
Specific examples of the organoaluminum compound represented by _3-Z include triethylaluminum in which z = 3 in the general formula,
Trialkyl aluminum such as triisobutyl aluminum, trihexyl aluminum, diethyl aluminum hydride, dialkyl aluminum hydride such as diisobutyl aluminum hydride, dialkyl aluminum hydride such as diethyl aluminum hydride, trialkyl aluminum such as a mixture of triethyl aluminum and diethyl aluminum hydride A mixture of dialkylaluminum hydrides may be mentioned.

More specifically, examples of the organoaluminum in which p is 0 <z <3 and X is a halogen atom in the general formula are dimethyl aluminum chloride, methyl aluminum sesquichloride, methyl aluminum dichloride, dimethyl aluminum bromide, Methylaluminum sesquibromide, methylaluminum dibromide, dimethylaluminum iodide, methylaluminum sesquiiodide, methylaluminium diiodide, diethylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, diethylaluminum bromide, ethylaluminum sesquibromide, Ethyl aluminum dibromide, diethyl aluminum iodide, ethyl al Um sesquicarbonate iodide, ethyl aluminum die iodide, dipropyl aluminum chloride, propyl aluminum sesquichloride, propyl aluminum dichroic chloride, dipropyl aluminum bromide, propyl sesquichloride bromide, propyl aluminum die bromide,
Dipropyl aluminum iodide, propyl aluminum sesquiiodide, propyl aluminum diiodide, diisopropyl aluminum chloride, isopropyl aluminum sesquichloride, isopropyl aluminum dichloride, diisopropyl aluminum bromide, isopropyl aluminum sesquibromide, isopropyl aluminum dibromide, diisopropyl aluminum iodide , Isopropyl aluminum sesquiiodide, isopropyl aluminum diiodide, dibutyl aluminum chloride, butyl aluminum sesquichloride,
Butyl aluminum dichloride, dibutyl aluminum bromide, butyl aluminum sesquibromide, butyl aluminum dibromide, dibutyl aluminum iodide, butyl aluminum sesquiiodide, butyl aluminum diiodide, diisobutyl aluminum chloride, isobutyl aluminum sesquichloride, isobutyl aluminum dichloride, Diisobutyl aluminum bromide, isobutyl aluminum sesquibromide, isobutyl aluminum dibromide, diisobutyl aluminum iodide, isobutyl aluminum sesquiiodide, isobutyl aluminum diiodide, dihexyl aluminum chloride, hexyl aluminum sesquichloride, Cyl aluminum dichloride, dihexyl aluminum bromide, hexyl aluminum sesquibromide, hexyl aluminum dibromide, dihexyl alum dichloride, dihexyl aluminum bromide, hexyl aluminum sesquibromide, hexyl aluminum dibromide, dihexyl aluminum iodide, hexyl aluminum sesquiiodide, hexyl aluminum Aluminum diiodide, dioctyl aluminum chloride, octyl aluminum sesquichloride, octyl aluminum dichloride, dioctyl aluminum bromide, octyl aluminum sesquibromide,
Alkyl aluminum halides such as octyl aluminum dibromide, dioctyl aluminum iodide, octyl aluminum sesquiiodide, octyl aluminum diiodide and the like can be mentioned.

Further, the general formula R ¹⁴ R ¹⁵ (AlOR ¹⁶ ) _b A
Specific examples of the aluminoxane compound represented by 1R ¹⁷ R ¹⁸ include methylaluminoxane, ethylaluminoxane, propylaluminoxane, butylaluminoxane,
Isobutylaluminoxane, hexylaluminoxane,
Octylaluminoxane, decylaluminoxane, methylethylaluminoxane, methylpropylaluminoxane, methylbutylaluminoxane, methylisobutylaluminoxane, methylhexylaluminoxane, ethylbutylaluminoxane, ethylisobutylaluminoxane, ethylhexylaluminoxane and a mixture thereof, preferably methylaluminoxane, methylethyl. Examples thereof include methylaluminoxane derivatives such as aluminoxane, methylpropylaluminoxane, methylbutylaluminoxane, methylisobutylaluminoxane and methylhexylaluminoxane.

Of these, the general formula R ¹¹ _z Al is preferred.
A trialkylaluminum such as triethylaluminum, triisobutylaluminum, trihexylaluminum, etc., in which z = 3 in the general formula of the organoaluminum compound represented by X _3-z , a dialkylaluminum hydride such as diethylaluminum hydride, diisobutylaluminum hydride Examples thereof include mixtures thereof or dialkyl aluminum chlorides such as dimethyl aluminum chloride, diethyl aluminum chloride, dipropyl aluminum chloride, diisopropyl aluminum chloride, dibutyl aluminum chloride and diisobutyl aluminum chloride, wherein z = 2 and X is chlorine. .

The amount of the component (B) used is 0.1 to 1000 (mol / mol) with respect to the Ti atom in the catalyst component (A).
You can choose from a wide range, such as
The range of 100 is preferable from the viewpoint of catalyst activity and composition distribution of the copolymer.

The olefins applicable to the present invention are ethylene and α-olefins having 3 or more carbon atoms. Specific examples of the olefins that can be used include propylene, butene-1, pentene-1, hexene-1, and heptene-1. ,
Linear monoolefins such as octene-1, decene-1, 3-methylbutene-1,3-methylpentene-
Examples include branched monoolefins such as 1,4-methylpentene-1, vinylcyclohexane and the like.

The present invention also relates to ethylene containing at least 80 mol% or more of ethylene and other α-olefins, particularly propylene, butene-1,4-methylpentene-1, hexene-1, octene-1 and the like. It can be effectively applied to the production of a copolymer with an α-olefin.

The polymerization temperature in the present invention is 120 ° C. or higher,
Preferably 130 ° C to 350 ° C, more preferably 150 ° C
In the case of the solution method, the temperature and pressure are 5 to 10 ° C to 270 ° C.
0 kg / cm ² , preferably 10 to 50 kg / cm ² ,
350-3500 kg / c in case of high pressure ionic polymerization method
m ² , preferably 700 to 1800 kg / cm ² , and the polymerization system may be either batch system or continuous system.

The solvent used in the polymerization by the solution method using the catalyst system of the present invention is selected from hexane, cyclohexane, heptane, kerosene components, hydrocarbon solvents such as toluene and the like.

In the present invention, there are no particular restrictions on the method of supplying each catalyst component to the polymerization tank, except that the catalyst components are supplied under the condition of no water such as nitrogen and argon and oxygen.

[0067]

EXAMPLES The present invention will be described in detail below with reference to examples and comparative examples. The properties of polymers in Examples were determined by the following methods. (1) α-Olefin content: Determined from the intensity of characteristic absorption of ethylene and α-olefin by a calibration curve method using an infrared spectrophotometer (manufactured by JASCO Corporation) JASCO-302. (2) Index indicating composition distribution: HL110 using the ratio of the melting peak area of 110 ° C. or less to the total integrated area of the peak measured using a differential scanning calorimeter (manufactured by Seiko Denshi Kogyo) And This HL110 is the α-
Numerical value divided by olefin content (abbreviated as C.D.V.)
Is an index representing the composition distribution, and C.I. D. V. The larger the value, the narrower the composition distribution.

Example 1 (1) Synthesis of catalyst component A (1-a) Synthesis of solid component (A-1) (1-a-i) Synthesis of organomagnesium compound Stirrer, reflux condenser, dropping funnel, After replacing a 5-liter flask equipped with a thermometer with argon, 160.0 g of ground magnesium for Grignard was added. In a suitable funnel, 600 g of butyl chloride and 2 parts of dibutyl ether.
Charge 500 ml and add about 1 to magnesium in the flask.
50 ml was added dropwise to start the reaction. After the start of the reaction, the dropping was continued at 50 ° C for 4 hours, and after the dropping was completed, the addition was continued at 60 ° C for another
The reaction continued for an hour. Then, the reaction solution was cooled to room temperature,
The solid content was filtered off. Butyl magnesium chloride in the sampled reaction solution was hydrolyzed with 1N hydrochloric acid to give 1
When the concentration was determined by back titration with a normal sodium hydroxide aqueous solution (phenolphthalein was used as an indicator), the concentration was 2.1 mol / liter.

(1-a-ii) Synthesis of halogen-containing solid magnesium component After replacing a 3-liter flask equipped with a stirrer and a dropping funnel with argon, the organomagnesium compound synthesized in (1-a-i) above While adding 1300 g of the solution and maintaining the temperature in the flask at 25 to 30 ° C, SiCl436
6 ml was gradually added dropwise from the dropping funnel over 4.5 hours. After the dropping was completed, the mixture was stirred at room temperature for 1 hour, and then 6 more.
After reacting at 0 ° C. for 1 hour, solid-liquid separation was performed at room temperature, and hexane 1.
Washing was performed 3 times with 5 liters. Then, the obtained solid was vacuum dried at 40 ° C. to obtain 421 g of halogen-containing solid magnesium component (a-1). When the composition of the produced solid was analyzed, the solid product contained 17.5 wt% of dibutyl ether.

(1-a-iii) Reaction of halogen-containing solid magnesium component (a-1) with titanium compound (a-2) After replacing a 50 ml flask equipped with a stirrer and a thermometer with argon, the above ( 5.0 g of the halogen-containing solid magnesium component (a-1) synthesized in 1-a-ii),
Subsequently, 12.5 ml of titanium tetrachloride was charged at room temperature. After that, the temperature of the flask was raised to 100 ° C., and the reaction was performed for 1 hour. After completion of the reaction, solid-liquid separation was performed at 40 ° C., and then hexane 30
It was washed 6 times with ml.

(1-b) Solid component (A-1) in the presence of titanium compound (a-3) and organoaluminum compound (A)
-2) Reaction with (1-a-iii) The solid product obtained in (1-a-iii) was added with 20 m of n-heptane.
1 was charged and the temperature was raised to 70 ° C. Next, 2.3 ml of titanium tetrachloride diluted 20-fold with n-heptane was added, and then 29.2 ml of a solution of diethylaluminum chloride in heptane (1 mmol / ml) was dropped into the flask and reacted for 1 hour. After completion of the reaction, solid-liquid separation was performed at 40 ° C., washing with 30 ml of hexane three times, and then vacuum drying to obtain 4.1 g of a solid catalyst component (A). As a result of composition analysis, the solid catalyst component contained 3.16% by weight of titanium atoms, 0.95% by weight of aluminum atoms and 0.91% by weight of dibutyl ether.

(2) Polymerization of ethylene and hexene-1 An autoclave equipped with a stirring blade and having an internal volume of 400 ml was vacuum-dried and replaced with argon, and then cyclohexane 1 was used as a solvent.
40 ml, 1-hexene 60 ml as α-olefin
Was charged and the reactor was heated to 210 ° C. After heating, feed ethylene while adjusting ethylene pressure to 25 kg / cm ² ,
After the system was stabilized, 1.0 mmol of triethylaluminum was charged as a catalyst component (B) from the catalyst feeder, and then 7.3 m of the solid catalyst component (A) synthesized in (1) above.
Then, the polymerization was started, and the polymerization was performed for 2 minutes while controlling the temperature at 210 ° C. to obtain 1.9 g of ethylene / hexene-1
A copolymer was obtained. Therefore, the activity per 1 g of catalyst is 26
It was 0 (g / g-catalyst), which was very high.
The hexene-1 content of the obtained copolymer determined by an infrared spectrophotometer was 6.54% by weight, and C.I. determined by a differential scanning calorimeter. D. V. Was 7.2, which was a copolymer having a very narrow composition distribution. The results are shown in Table 1.

Example 2 (1) Synthesis of catalyst component A (1-b) Reaction of solid component (A-1) with organoaluminum compound (A-2) in the presence of titanium compound (a-3) Synthesis was performed in the same manner as in (1-b) of Example 1 except that in the reaction of (1-b) of Example 1, the dilution ratio of titanium tetrachloride added was changed to 10 times to 4.7 ml. It was The Ti content of the obtained solid catalyst component was 6.92% by weight, the Al content was 1.16% by weight, and the butyl ether content was 0.51% by weight.

(2) Copolymerization of ethylene and hexene-1 In the same manner as (2) of Example 1 except that 7.6 mg of the solid catalyst component obtained in the above (1) was used as the solid catalyst component (A). Copolymerization was performed to obtain 3.1 g of ethylene / hexene-1 copolymer. Therefore, the activity was 420 (g / g-catalyst), and the activity per catalyst was very high. The hexene-1 content of the obtained copolymer was 11.2% by weight, and C.I. D. V. Was 6.6, which was a copolymer having a narrow composition distribution. The results are shown in Table 1.

Example 3 (2) Copolymerization of ethylene and hexene-1 In the copolymerization of ethylene and hexene-1 of Example 1 (2), except that triethylaluminum was changed to diethylaluminum chloride, the same as Example 1 was used. Polymerization was performed in the same manner. The results are shown in Table 1. The activity per catalyst was very high, and the copolymer obtained had a narrow composition distribution.

Comparative Example 1 (2) Copolymerization of ethylene and hexene-1 An autoclave with an internal volume of 400 ml equipped with a stirring blade was vacuum dried and replaced with argon, and then 90 m of toluene was used as a solvent.
1, 110 ml of 1-hexene was charged as the α-olefin, and the reactor was heated to 210 ° C. After the temperature was raised, ethylene was fed while adjusting the ethylene pressure to 25 kg / cm ² , and after the system became stable, 1.0 mmol of triethylaluminum was added as a catalyst component (B) from the catalyst feeder, and subsequently, Example 1 (1 -Solid component (A-1) 2 synthesized in a)
Polymerization was started by charging 2.0 mg, and polymerization was carried out for 2 minutes while controlling the temperature at 210 ° C. to obtain 2.1 g of ethylene / hexene-1 copolymer. Therefore, the activity is 100 (g /
g-catalyst). The hexene-1 content is 12.7% by weight, and C.I. determined by a differential scanning calorimeter. D. V. Is 3.9
As compared with the results using the solid catalyst component obtained in the present invention, the copolymer had a low catalytic activity and a wide composition distribution.

Comparative Example 2 (1) Synthesis of catalyst component A (1-b) Reaction of solid component (A-1) with organoaluminum compound (A-2) in the presence of titanium compound (a-3). Synthesis was performed in the same manner as in (1-b) of Example 1 except that titanium tetrachloride was not added in the reaction of (1-b) in Example 1. The Ti content of the obtained solid catalyst component was 1.6.
The content was 0% by weight, the Al content was 0.95% by weight, and the butyl ether content was 0.91% by weight.

(2) Copolymerization of ethylene and hexene-1 In the same manner as in (2) of Example 1 except that 30.2 mg of the solid catalyst component obtained in (1) above was used as the solid catalyst component (A). Copolymerization was performed. The results are shown in Table 1. The catalytic activity was very low as compared with the results using the solid catalyst component obtained in the present invention.

Comparative Example 3 (1) Synthesis of catalyst component A In the synthesis of the catalyst component, only titanium tetrachloride and diethyl aluminum chloride were reacted at 70 ° C. for 1 hour.
(Al / Ti molar ratio = 7)

(2) Copolymerization of ethylene and hexene-1 Copolymerization was carried out in the same manner as in (2) of Example 1 except that the catalyst component obtained in the above (1) was used as the solid catalyst component (A). It was Table 1 shows the results. As compared with the results using the solid catalyst component obtained in the present invention, the copolymer had a low catalytic activity and a wide composition distribution.

Example 4 (2) Copolymerization of ethylene and hexene-1 Using the solid catalyst component (A) synthesized in the same manner as in Example 1, ethylene / hexene-1 copolymerization was carried out under the following polymerization conditions. I went. Polymerization temperature: 230 ° C. Polymerization pressure: 800 Kg / cm ² Residence time: 55 seconds Hexene-1 concentration: 45.5 mol% Organic Al: triethylaluminum (Al / Ti molar ratio = 3.7) The results are shown in Table 1. The activity per catalyst was very high, and the copolymer obtained had a narrow composition distribution.

Example 5 (2) Copolymerization of ethylene and hexene-1 In the copolymerization of ethylene and hexene-1 of (2) of Example 4, except that triethylaluminum was changed to diethylaluminum chloride, Polymerization was performed in the same manner. The results are shown in Table 1. The activity per catalyst was very high, and the copolymer obtained had a narrow composition distribution.

[0083]

[Table 1]

[0084]

As described above, by using the catalyst of the present invention, it is possible to produce an ethylene / α-olefin copolymer having a high catalytic activity per solid catalyst, a narrow composition distribution, and excellent mechanical properties. It will be possible. Further, since the catalytic activity is high, it becomes possible to produce an ethylene / α-olefin copolymer excellent in weather resistance, low coloring property and low corrosion property.

[Brief description of drawings]

FIG. 1 is a flowchart for helping the understanding of the present invention. The flowchart is a representative example of the embodiment of the present invention, and the present invention is not limited to this.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Akio Imai 5-1 Anesaki Kaigan, Ichihara City, Chiba Sumitomo Chemical Co., Ltd.

Claims (7)

[Claims] 1. A general formula R ¹ _m SiX _4-m (where R
¹ represents an alkyl group having 1 to 20 carbon atoms, an aryl group or an alkenyl group, and X represents a halogen atom. Further, m is a number represented by 0 ≦ m <4. ) And / or the general formula R ² _n AlX
_3-n (wherein R ² represents an alkyl group, an aryl group or an alkenyl group having 1 to 20 carbon atoms, X represents a halogen atom, and n is a number represented by 0 ≦ n <3) ) And an aluminum halide compound represented by the general formula R ³
MgX and / or R ⁴ R ⁵ Mg (where R ³ ,
R ⁴ and R ⁵ represent an alkyl group, an aryl group or an alkenyl group having 1 to 20 carbon atoms, and X represents a halogen atom. )
A halogen-containing solid magnesium component (a obtained by reacting an organomagnesium compound represented by
-1), the titanium compound (a-2) and the solid component (A-1) obtained by reacting the titanium compound (a-2).
-3) in the coexistence of the organoaluminum compound (A-2) with a solid catalyst component (wherein the titanium compound (a
-2) and (a-3) may be the same or different. ), And (B) an organoaluminum compound as a main component, an olefin (co) polymerization catalyst. Wherein the titanium compound (a-2), (a -3) is the general formula TiM _a X _4-a (M _{^{is, OR 7, NR 8 2,}} SR 9,
A group selected from _{^{PR 10 2, R 7, R}} 8, R 9, R
¹⁰ represents a hydrocarbon group having 1 to 20 carbon atoms, X
Represents a halogen atom. Further, a is a number represented by 0 ≦ a <4. 3. The catalyst for olefin (co) polymerization according to claim 1, which is a titanium compound represented by the formula (1). 3. A titanium compound (a-2) or (a-3)
The catalyst for olefin (co) polymerization according to claim 1, which is a titanium compound represented by the general formula TiX ₄ . 4. The organoaluminum compound (A-2) has the general formula R ⁶ _p AlY _3-p (R ⁶ is an alkyl group, an aryl group or an alkenyl group having 1 to 20 carbon atoms, and Y is a halogen atom or hydrogen. Represents an atom or an alkoxy group, and p is 0 <p
It is a number represented by ≦ 3. 3. An olefin (co) polymerization catalyst according to claim 1, which is an organoaluminum compound represented by the formula (1). 5. (A) The general formula R ¹ _m SiX _4-m (where R
¹ represents an alkyl group having 1 to 20 carbon atoms, an aryl group or an alkenyl group, and X represents a halogen atom. Further, m is a number represented by 0 ≦ m <4. ) And / or the general formula R ² _n AlX
_3-n (wherein R ² represents an alkyl group, aryl group, or alkenyl group having 1 to 20 carbon atoms, X represents a halogen atom, and n is a number represented by 0 ≦ n <3) ) And an aluminum halide compound represented by the general formula R ³
MgX and / or R ⁴ R ⁵ Mg (where R ³ ,
R ⁴ and R ⁵ represent an alkyl group, an aryl group or an alkenyl group having 1 to 20 carbon atoms, and X represents a halogen atom. )
A halogen-containing solid magnesium component (a obtained by reacting an organomagnesium compound represented by
-1), a titanium compound (a-2), and a solid component (A-1) obtained by reacting the titanium compound (a-2) with the titanium compound (a).
-3) is allowed to react with the organoaluminum compound (A-2) in the presence of the solid catalyst component (wherein the titanium compounds (a-2) and (a-3) are the same or different) ), And (B) an olefin (co) polymer using a catalyst containing an organoaluminum compound as a main component. 6. The method for producing an olefin (co) polymer according to claim 5, wherein the olefin is (co) polymerized under the condition that the polymerization temperature is higher than 120 ° C. 7. A polymerization temperature of 140 ° C. to 350 ° C. and a pressure of 3
The method for producing an olefin (co) polymer according to claim 5, wherein the olefin is (co) polymerized by a high pressure ionic polymerization method under the condition of 0 to 3500 Kg / cm ² .