JPH07149814A - Production of polyolefin - Google Patents

Abstract

PURPOSE:To efficiently obtain polyolefin, particularly linear low-density polyethylene using a catalyst of high polymerization activity containing a specific metal compound, aluminoxane and organoaluminum compound as principal components. CONSTITUTION:Polyolefin is obtained by using a catalyst containing, as principal components, (A) a metal compound of the formula [M is Ti, Zr and Hf; Ar is aryl which may be substituted; (YRm-2)k is the bonding site between M and Ar and Y is an atom in group 2, groups 13, 14, 15, 16; R is H, halogen, 1-20 C alkyl; m is the valency of Y; k is integer of 2-20; n is integer of 1-4; X is H, halogen, 1-20 C alkyl, 1-20 C alkoxy], (B) a cyclic or straight-chain aluminoxane and (C) an organoaluminum compound, preferably (D) a pi electron- bearing compound.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an improvement in a method for producing a polyolefin, more specifically, a catalyst having a high polymerization activity is used without using an expensive metallocene compound as a polymerization catalyst, and a polyolefin, particularly a linear low density polymer, is used. The present invention relates to a method for efficiently producing polyethylene.

[0002]

2. Description of the Related Art In recent years, in the production of polyolefin,
As a new homogeneous catalyst, a catalyst composed of a metallocene compound of a transition metal and an aluminoxane has been proposed (JP-A-58-19309). This homogeneous catalyst has very high activity and excellent copolymerizability, but both the metallocene compound and the aluminoxane are expensive as compared with the conventional Ziegler-Natta catalyst, and there is a problem that the catalyst cost is high. there were. As a solution to these drawbacks, a method has been proposed in which a metallocene compound is not used, but a homogeneous catalyst composed of an oxygen-containing titanium compound and an aluminoxane is used (JP-A-63-3008). However, this method has a problem that the catalyst activity is low and the polyolefin cannot be efficiently produced. As a method to solve such problems,
The present inventors have previously proposed a method using a catalyst containing a specific transition metal compound, an aluminoxane, an organoaluminum compound and / or a compound having a π electron as a main component (Japanese Patent Application No. 4-234077). . However, in the production of polyolefin, although the above problems can be solved to some extent by applying these methods, the polymerization activity is still insufficient, and there is a problem that linear low density polyethylene has a large tendency. It was

[0003]

The present invention has been completed under such circumstances, and a catalyst having a high polymerization activity is used as a polymerization catalyst without using an expensive metallocene compound. It is an object of the present invention to provide a method for efficiently producing low density polyethylene.

[0004]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that a specific transition metal compound, an aluminoxane, an organoaluminum compound, and a compound having a π-electron used in some cases are selected. It has been found that the purpose can be achieved by using a solid catalyst containing. The present invention has been completed based on such findings. That is, the present invention provides: (a) (A) a metal compound represented by the following general formula (1):
(B) The method of producing polyolefin, which comprises using an aluminoxane and (C) a catalyst comprising an organoaluminum compound, as the main component, _{[Ar- (YR m-2) k} - ] _n MX _4-n ··· (1) (In the formula, M represents a transition metal selected from titanium, zirconium, and hafnium, Ar represents an aryl group or a substituted aryl group, and (YR _m-2 ) _k is a binding site of M and Ar. , Y is the periodic table 2, 13, 14, 15 or 1
Group 6 atoms, for example, carbon, silicon, germanium, aluminum, boron, nitrogen, etc., R is a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and 6 carbon atoms. ~ 20 aryl groups, 6 carbon atoms
20 aryloxy groups, silano groups or 1 to 20 carbon atoms
20 represents an alkylsilano group, m is the valence of Y, and k is
Represents an integer of 2 to 20, and n represents an integer of 1 to 4. X is a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or 6 to 6 carbon atoms.
It represents an aryl group having 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a silano group, or an alkylsilano group having 1 to 20 carbon atoms. However, when each of Y and R is 2 or more, each Y or R may be the same or different,
When two or more R are alkyl groups, they may be bonded to each other to form a ring. ) (B) (A) A metal compound represented by the above general formula (1),
A method for producing a polyolefin, which comprises using a catalyst containing (B) an aluminoxane and a compound having (D) π electrons as main components, or (c) the catalyst according to (a) above, further comprising (D) π A method for producing a polyolefin according to (a) above, which comprises a compound having an electron.
Hereinafter, the present invention will be described in more detail. In the following, the "present invention" refers to the above inventions (a), (b) and (c) unless otherwise specified. In the catalyst used in the present invention, the transition metal compound represented by the general formula (1) is used as the component (A).

The compound represented by the general formula (1) is preferably tetra (2-phenylethoxy) titanium, tetra (3-phenylpropoxy) titanium,
Tetra (4-phenylbutoxy) titanium, tri (3
-Phenylpropoxy) titanium monochloride, di (3-phenylpropoxy) titanium dichloride,
Mono (3-phenylpropoxy) titanium trichloride, tri (3-phenylpropoxy) titanium monoisopropoxide, di (3-phenylpropoxy) titanium diisopropoxide, mono (3-phenylpropoxy) titanium triisopropoxide, Tetra (dimethylphenylsiloxy) titanium, tetra [(dimethylphenylsilyl) methoxy] titanium,
An alkoxide compound having an aryl group such as tetra [2- (dimethylphenylsilyl) ethoxy] titanium, tetra [3- (dimethylphenylsilyl) propoxy] titanium, mono [(dimethylphenylsilyl) methoxy] titanium triisopropoxide, and the like; Tetra (benzyl-tert-butylamino) titanium, tetra (dimethylphenylsilyl-tert-butylamino) titanium, tri (dimethylphenylsilyl-te)
(rt-Butylamino) titanium monochloride, di (dimethylphenylsilyl-tert-butylamino)
Titanium dichloride, mono (dimethylphenylsilyl-tert-butylamino) titanium trichloride, mono (dimethylphenylsilyl-tert-butylamino) titanium triisopropoxide, tetra [(dimethylphenylsilyl) methyl-tert-butylamino] titanium , Titanium compounds such as amino compounds having an aryl group such as mono [(dimethylphenylsilyl) methyl-tert-butylamino] titanium trichloride, and zirconium compounds and hafnium compounds corresponding thereto.
The transition metal compound of the component (A) may be used alone or in combination of two or more. In the catalyst of the present invention, aluminoxane is used as the component (B). As the aluminoxane as the component (B), a conventionally known aluminoxane can be used, and particularly the general formula (2)

[0006]

[Chemical 1]

(Wherein R ⁵ represents a hydrocarbon group having 1 to 8 carbon atoms and r represents an integer of 2 to 100), or a general formula (3)

[0008]

[Chemical 2]

(In the formula, R ⁶ , R ⁷ and R ⁸ each represent a hydrocarbon group having 1 to 8 carbon atoms, which may be the same or different, and s represents an integer of 2 to 100. .) Is preferable.
Preferred examples of R ⁵ , R ⁶ , R ⁷ and R ⁸ include an alkyl group such as a methyl group, an ethyl group and an isobutyl group, and r and s are each preferably 7 to 40. These aluminoxanes can be prepared by a known method, for example, (1) a method in which a trialkylaluminum is directly reacted with water using an appropriate organic solvent such as toluene, benzene or ether, and (2) a salt water containing trialkylaluminum and crystal water. It can be produced by a hydrate, for example, a method of reacting with a hydrate of copper sulfate or aluminum sulfate, a method of reacting (3) trialkylaluminum with moisture impregnated in silica gel, and the like. In the aluminoxane thus obtained, trialkylaluminum which is the starting material for its synthesis may remain and may be contained as an impurity, but in the method of the present invention, it is not particularly required to be purified and it may be used as it is. It doesn't matter. The aluminoxane as the component (B) may be used alone or in combination of two or more kinds.

In the catalyst of the present invention, an organoaluminum compound is used as the component (C). Examples of the organoaluminum compound include general formula (4) R ⁹ _m AlX ¹ _3-m (4) [wherein R ⁹ is an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms]. , X ¹ is a halogen atom, carbon number 1
To an alkoxy group having 20 to 20 or an aryloxy group having 6 to 20 carbon atoms, and m is a real number greater than 0 and 3 or less. ] What is represented by these can be mentioned. Examples of such an organoaluminum compound include trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, triisopropylaluminum, diethylaluminum ethoxide. , Diisobutyl aluminum ethoxide, diethyl aluminum chloride, ethyl aluminum dichloride and the like. Among these, preferred are those represented by the general formula (5) AlR ¹⁰ R ¹¹ R ¹² (5) [wherein R ¹⁰ , R ¹¹ and R ¹² each have 1 to 20 carbon atoms].
Of alkyl groups, which may be the same or different from each other. ] It is a trialkyl aluminum represented by. The organoaluminum compound as the component (C) may be used alone or in combination of two or more.

In the catalyst of the present invention, a compound having π electrons can be used as the component (D). The compound having a π electron of the component (D) is
Aromatic hydrocarbon compounds, aliphatic unsaturated hydrocarbon compounds,
Examples thereof include alicyclic unsaturated hydrocarbon compounds. As the aromatic hydrocarbon compound, for example, benzene,
Toluene, ethylbenzene, n-propylbenzene, n
-Alkylbenzenes such as octylbenzene, xylene, 1,3,5-trimethylbenzene, 1,2,3-trimethylbenzene, halogen-containing aromatic hydrocarbon compounds such as chlorobenzene and bromobenzene, nitrobenzene,
Nitrogen-containing aromatic hydrocarbon compounds such as aniline, benzyl methyl ether, 1,3-dimethoxybenzene, anisole, aromatic ether compounds such as o-methoxytoluene, m-methoxytoluene, methyl benzoate, ethyl benzoate, Examples thereof include aromatic ester compounds such as t-butyl benzoate, polynuclear aromatic compounds such as naphthalene, tetralin, anthracene and phenanthrene, and typical metal compounds containing aromatic hydrocarbons such as phenylsilane and phenyltrimethylsilane. Examples of the aliphatic unsaturated hydrocarbon compound include 2-butene and 2-
Hexene, 3-hexene, 2-methyl-2-heptene,
Internal olefins such as 2-methyl-3-heptene, 2-octene and 3-octene, 2,4-hexadiene, 2,
Internal dienes such as 6-octadiene and 3,5-octadiene, 2,4-hexazine, 2,6-octazine, 3,
Examples include internal dialkynes such as 5-octazine, and typical metal compounds containing aliphatic unsaturated hydrocarbons such as 2-octenyltrimethylsilane.

On the other hand, examples of the alicyclic unsaturated hydrocarbon compound include cyclopentene, cyclopentadiene, dicyclopentadiene, cyclohexene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, norbornene, norbornadiene, and further cyclopentadiene. Typical metal compounds containing alicyclic unsaturated hydrocarbons such as dienyltrimethylsilane, 2- (4-cyclohexenylethyl) methyldichlorosilane, 1-cyclohexenyloxytrimethylsilane and the like can be mentioned. Furthermore, as a particularly preferable compound having a π electron, general formula (6) Ar ^1- (Y′R ′ _p-2 ) _h —Ar ² (6) (wherein, Ar ¹ and Ar ² are each aryl) A group, which may be the same or different from each other, Y'represents an atom of Group 2, 13, 14, 15 or 16 of the periodic table, R'is a hydrogen atom, a halogen atom, An alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a silano group or an alkylsilano group having 1 to 20 carbon atoms; Where p is the valence of Y ', and h is 0 to
In the case where h is 2 or more, Y ′ may be the same or different, and when R ′ is plural, they may be the same or different, and two R ′ are alkyl groups. In this case, they may be combined to form a ring. The compound which has two or more aromatic rings in the molecule represented by () is used.

In the general formula (6), Ar ¹ and Ar ²
Specific examples of the aryl group represented by are phenyl group, tolyl group, xylyl group, octylphenyl group, fluorophenyl group, nitrophenyl group, biphenyl group, naphthyl group and the like. Then, in the general formula (6), connecting the two aryl groups represented by Ar ¹ and Ar ² _{'- (YR n-2) k} - "The bonding portion represented by, Y is the periodic table An atom of Group 2, 13, 14, 15 or 16 such as carbon, silicon, germanium, aluminum, boron, nitrogen, phosphorus, oxygen or sulfur. Specifically, methylene group, 1,1-ethylene group, 1,2-ethylene group, dimethylethylene group, 1,
A compound in which Y is a carbon atom, such as a 1-cyclohexylene group, a phenylmethylene group, and a diphenylmethylene group.
In addition, those in which Y is a silicon atom such as a silylene group, a methylsilylene group, a dimethylsilylene group, a diethylsilylene group, and a tetramethyldisilylene group, or those in which Y is a germanium atom such as a dimethylgermylene group,
A phenylaluminum group in which Y is an aluminum atom, a phenylboron group in which Y is a boron atom, a phenylamino group in which Y is a nitrogen atom, a phenylphosphine group in a Y Examples thereof include those that are phosphorus atoms and those where Y is an oxygen atom or a sulfur atom. Furthermore, the formula

[0014]

[Chemical 3]

Those represented by are listed. In addition,
In the general formula (6), R is a hydrogen atom, a halogen atom (chlorine, fluorine, bromine, iodine), a carbon number of 1 to 20.
Alkyl group (specifically, methyl group, ethyl group, propyl group, n-butyl group, isobutyl group, amyl group, isoamyl group, octyl group, 2-ethylhexyl group, etc.),
C1-C20 alkoxy group (specifically, methoxy group, ethoxy group, propoxy group, butoxy group, hexyloxy group, octyloxy group, 2-ethylhexyloxy group, etc.), C6-C20 aryl group (Specifically, phenyl group, tolyl group, xylyl group, naphthyl group, etc.), aryloxy group having 6 to 20 carbon atoms (specifically, phenoxy group, p-tolyloxy group, pt-butylphenoxy group) Etc.), a silano group or an alkylsilano group having 1 to 20 carbon atoms (specifically, a trimethylsilano group,
Triethylsilano group). And as a compound represented by general formula (6), specifically, diphenyldimethylsilane, diphenyldiethylsilane, triphenylmethylsilane; 1,2-diphenyltetramethyldisilane, dimethyldi-p-toluylsilane, diphenylmethane, Triphenylmethane, dibenzyl, biphenyl, 4-benzylbiphenyl, di (o-toluyl) methane; 2,2-diphenylpropane, triphenylaluminum, triphenylborane, tri (pentafluorophenyl) borane, N-methyldiphenylamine, tri Examples include phenylphosphine, diphenyl ether and diphenyl sulfide. The compound having π electrons as the component (D) may be used alone or in combination of two or more kinds.

In the method of the present invention, a polyolefin is produced by polymerizing an olefin in the presence of the solid catalyst prepared as described above. The type of this olefin is not particularly limited, and for example, α- having 2 to 10 carbon atoms can be used.
Any olefin such as olefin and cyclic olefin can be used as a monomer. Further, these olefins may contain, as comonomers, dienes such as butadiene, isoprene, chloroprene, and ethylidene norbornene. Further, the copolymerization can be carried out using an unsaturated monomer component other than the olefin which is copolymerizable with the olefin. The method of the present invention is
It is preferably applied to the production of ethylene polymers. In particular,
It is advantageous for application to the production of linear low density polyethylene. Further, the polymerization in the present invention may be homopolymerization of olefins or copolymerization of two or more kinds of olefins or olefins and dienes. Examples of cyclic olefins include cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene and the like.

In the present invention, in the production of the ethylene polymer, ethylene may be polymerized alone, or ethylene may be copolymerized with another α-olefin or diene compound. As the α-olefin, for example,
Examples thereof include linear or branched monoolefins having 3 to 18 carbon atoms, and α-olefins substituted with an aromatic nucleus. Specific examples of such α-olefins include propylene, butene-1, hexene-1, octene-1,
Nonene-1, decene-1, undecene-1, dodecene-
Linear monoolefins such as 1, 3-methylbutene-
1; 3-methylpentene-1; 4-methylpentene-
Examples thereof include branched-chain monoolefins such as 1; 2-ethylhexene-1; 2,2,4-trimethylpentene-1, and monoolefins substituted with an aromatic nucleus such as styrene.

Here, the diene compound is preferably a non-conjugated diolefin having a straight or branched chain having 6 to 20 carbon atoms. Specifically, 1,5-hexadiene; 1,6-heptadiene; 1,7-octadiene; 1,8-nonadiene; 1,9-decadiene; 2,5
-Dimethyl-1,5-hexadiene; 1,4-dimethyl-4-t-butyl-2,6-heptadiene, polyenes such as 1,5,9-decatriene, and endo such as 5-vinyl-2-norbornene. Methylene-based cyclic dienes and the like can be used.

In the present invention, the polymerization method is not particularly limited, and any polymerization method such as slurry polymerization method, high temperature solution polymerization method, gas phase polymerization method, bulk polymerization method and the like can be adopted. The polymerization solvent has 5 to 18 carbon atoms.
Inert solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, such as n-pentane, isopentane, hexane, heptane, octane, nonane, decane,
Tetradecane, cyclohexane, benzene, toluene, etc. are used. These may be used alone or in combination of two or more.

Regarding the amount of each catalyst component used, the component (A) is 10 ^-8 to 10 ^-2 mol / liter, preferably 1
0 ^-7 to 10 ^-3 mol / liter, component (B) / component (A)
Value of 10 to 100,000, preferably 20 to 1000
0 (however, component (B) is equivalent to aluminum atom), value of component (C) / component (A) is 0.1 to 10000, preferably 1 to 5000, value of component (D) / component (A) is 1-1
It can be used so as to be 0000, preferably 1-1000. In the method of the present invention, as a polymerization catalyst, other than the above, a contact product obtained by previously contacting the components (A), (B) and (C), the component (A),
Contact product obtained by contacting components (B) and (D) in advance, or contact product obtained by contacting components (A), (B), (C) and (D) in advance. Can be used. The order of contacting each catalyst component is not particularly limited, but (1) the component (A) and the component (C) are contacted with each other, and then the component (B) is contacted with the component (2) or (B). It is preferable to contact the component (C) and the component (A) in this order. The component (D) may be added at any position. To catalytically treat each catalyst component, under an inert gas atmosphere in an inert solvent,
0.01 to 100 mmol / liter of the component (A),
The component (B) is contacted at a rate of 0.1 to 1000 mmol / liter (in terms of aluminum atom), the component (C) is contacted at a rate of 0.01 to 1000 mmol / liter, and the component (D) is contacted at a rate of 0.01 to 1000 mmol / liter. It is desirable to let

The temperature at the time of contact is not particularly limited,
The contact treatment may be performed at room temperature or may be performed under heating or cooling. The obtained solid catalyst may be used as it is, or may be used after being washed with an inert solvent. Examples of the inert solvent that can be used in the contact treatment include aliphatic hydrocarbons having 5 to 18 carbon atoms, alicyclic hydrocarbons, aromatic hydrocarbons, and the like. Specifically, n- or isopentane, Hexane, heptane, octane, nonane, decane, tetradecane, cyclohexane, benzene, toluene, xylene and the like can be mentioned.
These inert solvents may be used alone or in combination of two or more. The polymerization temperature is not particularly limited, but is usually selected in the range of 0 to 350 ° C, preferably 20 to 250 ° C. On the other hand, the polymerization pressure is not particularly limited, but usually 0 to 150 kg / cm ²
G, preferably in the range of 0 to 100 kg / cm ² G. Furthermore, the molecular weight and molecular weight distribution of the obtained polyolefin can be adjusted by a conventional method. That is, it can be easily carried out by raising the polymerization temperature or by adding hydrogen, alkylaluminum, alkylzinc or the like to the system during the polymerization.

[0022]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Example 1 (1) Synthesis of tetra (2-phenylethoxy) titanium A 50-mL two-necked flask was dried and purged with nitrogen, and then 8 mL of benzene was added with 1.42 g (5.0 mmol) of tetraisopropoxytitanium. Was dissolved. 2.44 g (20 mmol) of 2-phenylethanol was slowly added dropwise thereto, and the mixture was stirred at room temperature for 30 minutes. Next, the resulting 2-propanol was removed from the system while being heated to 80 ° C. and stirred for 24 hours. After the reaction, the residual 2-propanol was removed from the reaction mixture under reduced pressure to give tetra (2-phenylethoxy) titanium 2.6 g.
Was obtained as a pale yellow transparent oil. The structure of the product was confirmed by ¹ H-NMR and elemental analysis.

(2) Copolymerization of ethylene and 1-octene In 200 ml of Schlenk bottle, hexane 13
7 ml, hexane solution of triisobutylaluminum as component (C) (1.0 mol / liter) 3.0 ml, hexane solution of tetra (2-phenylethoxy) titanium as component (A) (0.1 mol / liter) ) 3.0 ml was added and stirred for 10 minutes. Further, 7.5 ml of a hexane dispersion liquid of methylaluminoxane (2.0 mol / liter) was added as the component (B), and the mixture was stirred for 60 minutes for contact treatment. The obtained contact-treated product was aged at room temperature for 24 hours. After replacing the inside of the dried 1 liter polymerization reactor with a stirrer with dry nitrogen,
360 ml of dried n-hexane and 40 ml of 1-octene were charged. Furthermore, triisobutylaluminum (6.0 mmol), catalytic reaction product of the above three components (0.1 mmol).
5 ml (1.0 micromol-Ti) was added to the polymerization reactor and the temperature was immediately raised to 80 ° C. Then, ethylene gas was introduced, and polymerization was carried out at 80 ° C. for 60 minutes while maintaining the total pressure at 8 kg / cm ² G. Immediately after the completion of the polymerization, the pressure was released, and methanol was added to the polymerization reactor.
The polymerization was stopped. The contents of the polymerization reactor were put into a large amount of ethanol-hydrochloric acid mixed solution to decalcify. The polymer was filtered and fractionated, dried under reduced pressure at 80 ° C. for 4 hours, and then ethylene-1-
4.9 g of an octene copolymer was obtained. Activity 103kg / g
-Ti / Hr, [η] was 4.0, and the melting point was 116 ° C.

Comparative Example 1 In the same manner as in Example 1 except that 3.0 ml of a hexane solution of tetrabutoxytitanium (0.1 mol / liter) was used instead of tetra (2-phenylethoxy) titanium. Carried out. The results are shown in Table 1. Example 2 200 ml of Schlenk bottle was mixed with 13 parts of hexane.
4 ml, 3.0 ml of a hexane solution of triisobutylaluminum as the component (C) (1.0 mol / liter), 3.0 ml of a hexane solution of dimethyldiphenylsilane as the component (D) (1.0 mol / liter) , A hexane solution of tetra (2-phenylethoxy) titanium as component (A) (0.1 mol / l)
3.0 ml was added and stirred for 10 minutes. Further, 7.5 ml of a hexane dispersion liquid of methylaluminoxane (2.0 mol / liter) was added as the component (B),
The contact treatment was carried out by stirring for a minute. The obtained contact-treated product was aged at room temperature for 24 hours. Thereafter, the reaction was carried out in the same manner as in Example 1. The results are shown in Table 1. Comparative Example 2 The same procedure as in Example 2 was performed except that 3.0 ml of a hexane solution of tetrabutoxytitanium (0.1 mol / liter) was used instead of tetra (2-phenylethoxy) titanium. The results are shown in Table 1.

Examples 3 and 4 In Examples 1 and 2, instead of tetra (2-phenylethoxy) titanium, a solution of tetra (3-phenylpropoxy) titanium synthesized in the following manner in hexane (0.1 mol / mol) was used. Example 3 and Example 4 respectively except that 3.0 ml was used.
Was carried out. The results are shown in Table 1. (1) Synthesis of tetra (3-phenylpropoxy) titanium A 50 ml two-necked flask was dried, and after nitrogen substitution, 1.42 g (5.0 mmol) of tetraisopropoxytitanium was dissolved in 8 ml of benzene. It was In this, 4-phenylpropanol 4.10 g (30
(Mmol) was slowly added dropwise, and the mixture was stirred at room temperature for 30 minutes.
Next, the resulting 2-propanol was removed from the system while being heated to 80 ° C. and stirred for 24 hours. After the reaction
The residual 2-propanol and excess 3-phenylpropanol were removed from the reaction mixture under reduced pressure to give tetra (3-
2.9 g of phenylpropoxy) titanium was obtained as a colorless transparent oily substance. The structure of the product was confirmed by ¹ H-NMR.

Example 5 The inside of a dried 1 liter polymerization reactor equipped with a stirrer was replaced with dry nitrogen, and then 360 ml of dried n-hexane and 40 ml of 1-octene were charged. Further, 0.1 mmol of dimethyldiphenylsilane, 5.0 mmol of methylaluminoxane, and 0.01 mmol of tetra (3-phenylpropoxy) titanium were added to the polymerization reactor, and the temperature was immediately raised to 80 ° C. Next, while introducing ethylene gas and keeping the total pressure at 8 kg / cm ² G, 80
Polymerization was performed at 60 ° C. for 60 minutes. Thereafter, the reaction was carried out in the same manner as in Example 1. The results are shown in Table 1. Comparative Example 3 In Example 5, tetra (3-phenylpropoxy)
Instead of titanium, tetrabutoxytitanium 0.
The same procedure was carried out except that 01 mmol was used.
The results are shown in Table 1.

Example 6 (1) Synthesis of mono (dimethylphenylsilyl-tert-butylamino) titanium triisopropoxide 2.5 mmol of dimethylphenylsilyl-tert-butylaminolithium and monochlorotitanium in 100 ml of hexane. 2.5 mmol of triisopropoxide was added, and the mixture was stirred at room temperature for 1 hour and reacted. The product was used as such without purification. (2) Copolymerization of ethylene and 1-octene After replacing the inside of a dry 1 liter polymerization reactor equipped with a stirrer with dry nitrogen, 360 ml of dried n-hexane and 40 ml of 1-octene were charged. Furthermore, triisobutylaluminum 1.5 mmol, methylaluminoxane 3.5 mmol, and mono (dimethylphenylsilyl-tert-butylamino) titanium triisopropoxide 0.01 mmol-Ti synthesized above were added to the polymerization reactor, Immediately, the temperature was raised to 80 ° C. Then, ethylene gas was introduced, polymerization was carried out at 80 ° C. for 30 minutes while maintaining the total pressure at 8 kg / cm ² G, and ethylene-
30.8 g of 1-octene copolymer was obtained. Activity is 129k
It was g / g-Ti / Hr. Comparative Example 4 In Example 6, mono (dimethylphenylsilyl-t
The same procedure was used except that 0.01 mmol of tetrabutoxytitanium was used in place of (ert-butylamino) titanium triisopropoxide. The results are shown in Table 1.

[0028]

[Table 1]

[0029]

[Table 2]

[0030]

According to the method of the present invention, a polyolefin, particularly a linear low density polyethylene, can be efficiently produced by using a catalyst having high polymerization activity without using an expensive metallocene compound as a polymerization catalyst. You can

[Brief description of drawings]

FIG. 1 is a flowchart showing an example of an embodiment of the present invention.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Mizuchi Takeuchi 1 Iezaki Kaigan, Ichihara City, Chiba Prefecture Idemitsu Petrochemical Co., Ltd.

Claims (3)

[Claims] 1. A method for producing a polyolefin, which comprises using a catalyst containing (A) a metal compound represented by the following general formula (1), (B) an aluminoxane and (C) an organoaluminum compound as main components. . _{[Ar- (YR m-2) k} - ] _{n MX 4-n ··· (1} ) ( wherein, M represents a transition metal selected from titanium, zirconium and hafnium, Ar is an aryl group or a substituted aryl group (YR _m-2 ) _k is a binding site between M and Ar, and Y is 2, 13, 14, 15 or 1 of the periodic table.
Group 6 atom, R is hydrogen atom, halogen atom, carbon number 1
~ 20 alkyl groups, C1-20 alkoxy groups,
It represents an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a silano group or an alkylsilano group having 1 to 20 carbon atoms, m is a valence of Y, and k is an integer of 2 to 20. , And n represents an integer of 1 to 4. X is a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a silano group or It represents an alkylsilano group having 1 to 20 carbon atoms. However, Y
And each R is 2 or more, each Y or R may be the same or different, and when two or more R are alkyl groups, each may be bonded to form a ring. Good. ) 2. A polyolefin comprising a catalyst containing (A) a metal compound represented by the following general formula (1), (B) an aluminoxane and (D) a compound having a π electron as main components. Production method. _{[Ar- (YR m-2) k} - ] _{n MX 4-n ··· (1} ) ( wherein, M represents a transition metal selected from titanium, zirconium and hafnium, Ar is an aryl group or a substituted aryl group (YR _m-2 ) _k is a binding site between M and Ar, and Y is 2, 13, 14, 15 or 1 of the periodic table.
Group 6 atom, R is hydrogen atom, halogen atom, carbon number 1
~ 20 alkyl groups, C1-20 alkoxy groups,
It represents an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a silano group or an alkylsilano group having 1 to 20 carbon atoms, m is a valence of Y, and k is an integer of 2 to 20. , And n represents an integer of 1 to 4. X is a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a silano group or It represents an alkylsilano group having 1 to 20 carbon atoms. However, Y
And each R is 2 or more, each Y or R may be the same or different, and when two or more R are alkyl groups, each may be bonded to form a ring. Good. ) 3. The method for producing a polyolefin according to claim 1, wherein the catalyst according to claim 1 further comprises (D) a compound having π electrons.