JP3142896B2 - Method for producing catalyst component for olefin polymerization and method for polymerizing olefin using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a catalyst component for olefin polymerization and a method for polymerizing olefins using the same.

[0002]

2. Description of the Related Art A method of polymerizing an olefin using a metallocene compound having a group having a conjugated π electron, particularly cyclopentadiene or a derivative thereof as a ligand, and a methylaluminoxane obtained by reacting trimethylaluminum with water is known. Have been. For example, JP-A-58-19309 discloses a method for polymerizing olefins using biscyclopentadienyl zirconium dichloride and methylaluminoxane as catalysts.

[0003]

SUMMARY OF THE INVENTION The above-mentioned Japanese Patent Application Laid-Open No. 58-19309 is disclosed.
The method by which the activity per transition metal is large and is an excellent method, but the bulk specific gravity of the resulting polymer after polymerization is small, handling is difficult, and when applied to a gas phase or liquid phase polymerization method, There are problems in using these as catalysts for polyolefin production on an industrial scale, such as adhesion of the polymer to the vessel wall, making it difficult to remove heat due to poor heat transfer, and the formation of polymer agglomerates. there were.

[0004]

Means for Solving the Problems The present inventors have solved the above-mentioned problems and have intensively studied a method for producing a polyolefin with high productivity with high productivity, and completed the present invention. That is, the present invention provides (a) a compound represented by the following general formula (3) or (4), wherein A and B are the same or different conjugated alkadienyl groups, and R is a hydrocarbon having 1 to 20 carbon atoms linking A and B. A residue or a compound containing silicon, germanium, tin,
X is a hydrocarbon residue or a halogen atom having 1 to 10 carbon atoms, M is a transition metal compound represented by the periodic table Group 4 metal atom),

[0005]

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[0006]

Embedded image (B) selected from aluminum, zinc and magnesium
And after treatment with an organometallic compound of a metal, or without treatment, selected from (c) aluminum, zinc and magnesium
A method for producing a catalyst component for olefin polymerization, which comprises contacting with an untreated smectite treated or untreated with an organometallic compound of a metal .

Further, the present invention is a method for polymerizing an olefin, which comprises polymerizing the olefin using the catalyst component.

In the present invention, the transition metal compound represented by the above general formula (3) or (4) includes A,
Compounds in which B, R, X and M are shown below are exemplified.

A and B are, for example, monocyclic or polycyclic alkadienyl groups having 5 to 30 carbon atoms. Specifically, cyclopentadienyl group or a part or all of the hydrogen is a compound having 1 to 3 carbon atoms. (Wherein the alkyl group may have a structure in which the terminal is again bonded to a cyclopentadiene ring), an indenyl group, a fluorenyl group or a part or all of hydrogen Those substituted with the alkyl groups of the formulas 1 to 10 can be exemplified.

As R, for example, R ' ₂ C, R' ₂ S
_{i, R '2 Ge, R} ' 2 Sn ( wherein R 'is also be the same or different alkyl radical of hydrogen or carbon number of 1 to 20) dialkyl methylene group represented by, dialkylsilylene group, a dialkylamino gel Millen group, and dialkyltin group can be preferably utilized, more - (CR _'2) n - polymethylene group represented by can be exemplified. (Wherein R ′ is the same as above).

X is a hydrocarbon residue having 1 to 10 carbon atoms or a halogen atom such as fluorine, chlorine, bromine or iodine.

Further, examples of M include transition metals of Group 4 of the periodic table, such as titanium, zirconium, and hafnium.

Specific examples include dicyclopentadienyl zirconium dichloride, isopropylcyclopentadienyl fluorenyl zirconium dichloride, dicyclopentadienyl hafnium dichloride, isopropylcyclopentadienyl fluorenyl hafnium dichloride.

In the present invention, the transition metal compound is
Used with or without treatment with an organometallic compound.

In the case of treatment, the organometallic compound includes
A metal compound selected from aluminum, zinc, and magnesium is used. These organometallic compounds have residues such as halogen, oxygen, hydrogen, alkyl, alkoxy, and aryl as ligands, and these ligands may be the same or different, but at least One has an alkyl group. For example, an alkyl metal compound having at least one alkyl residue having 1 to 12 carbon atoms bonded thereto, an alkyl metal halide, an alkyl metal alkoxide, or the like can be used.

Among them, alkyl aluminum compounds are preferably used. For example, trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, tributyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, diisopropyl aluminum chloride, diisopropyl aluminum isopropoxide, ethyl aluminum dichloride,
Ethyl aluminum diisopropoxide and the like. Of these, trialkylaluminums such as triethylaluminum and triisobutylaluminum are particularly preferably used.

As a method of treating with these organometallic compounds, the above transition metal compounds are treated with aromatic hydrocarbon compounds such as benzene, toluene and xylene or pentane, hexane, heptane, octane, nonane, decane, cyclopentane and cyclohexane. What is necessary is just to make it react with the said organometallic compound in a saturated hydrocarbon compound. The reaction temperature at this time is -100 to 100 ° C, preferably 0 to 30 ° C. The reaction time is in the range of 10 minutes to 10 hours, usually about 30 minutes. The usage ratio of the organometallic compound to the transition metal compound is from 1 to 100,000 mole times, usually from 1 to 5000 mole times.

In the present invention, the transition metal compound treated or untreated with the organometallic compound is then brought into contact with the smectite treated or untreated with the organometallic compound.

The smectite used in the present invention is called a layered clay mineral and is a kind of layered silicate.

When treating smectite with an organometallic compound, the organometallic compound to be used includes the above-mentioned compounds of metals selected from aluminum, zinc and magnesium. Further, as the organoaluminum compound, a compound represented by the following general formula 5 or 6 (where R ″ is a hydrocarbon residue having 1 to 3 carbon atoms, and n is an integer of 1 to 50), that is, aluminoxane can also be used.

[0021]

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[0022]

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As a treatment method with these organometallic compounds, smectite is converted into an aromatic hydrocarbon compound such as benzene, toluene, xylene or pentane, hexane, heptane, octane, nonane, decane, cyclopentane, or the like.
What is necessary is just to make it contact with the said organometallic compound in saturated hydrocarbon compounds, such as cyclohexane. The contact temperature at this time is -100 to 100 ° C, preferably 0 to 100 ° C. The contact time is in the range of 1 to 100 hours. The amount of the organometallic compound used is 0.1 to 100,000 mmol, usually 1 to 100 mmol per gram of smectite.

In the present invention, as a method for contacting the above-mentioned organometallic compound-treated or untreated transition metal compound with the organometallic compound-treated or untreated smectite, both of the above-mentioned hydrocarbons are used. The method of contacting in a solvent is preferred. As the contact temperature at this time,
It is -100 to 100 ° C, preferably 0 to 30 ° C. The contact time is in the range of 10 minutes to 10 hours, and usually 2 hours.
About an hour. The use ratio of the transition metal compound to smectite was 1 to 1 gram of smectite.
1100,000 mg, usually 10-1000 mg.

The product can be used as a slurry during the polymerization, but the solid may be taken out by filtration and used after drying.

The catalyst component prepared in this way has good properties as a catalyst component for use in gas-phase or liquid-phase polymerization of olefins. And, after contacting aluminoxane obtained by the reaction of alkyl aluminum and water, or after contacting the obtained catalyst component and trialkyl aluminum, an organoboron compound anion,
A compound containing an organoaluminum compound anion or the like is reacted and used.

Examples of the aluminoxane include the compounds represented by the above-mentioned general formula (Chemical Formula 5) or (Chemical Formula 6). The ratio of the aluminoxane to the above-mentioned catalyst component is determined by the molar ratio with the supported transition metal catalyst. Between 1 and 1000
00 times, usually 1 to 5000 times.

Compounds containing an organoboron compound anion, an organoaluminum compound anion and the like include (C ₆ H
₅ ) ₃ CB (C ₆ F ₅ ) ₄ , (C ₆ H ₅ ) ₃ CAl (C ₆ F ₅ ) _{4 and the} like. 0.1 to 10,000 in molar ratio with metal catalyst
Times, usually 0.5 to 5000 times.

As trialkyl aluminum, triethyl aluminum, triisobutyl aluminum,
Tri-n-hexylaluminum, tri-n-octylaluminum and the like can be exemplified. The molar ratio of the trialkylaluminum to the above-mentioned catalyst component is from 1 to 10,000 times, usually from 1 to 10,000 times in molar ratio with the supported transition metal catalyst. 5000
It is twice.

Examples of the olefin used in the present invention include olefins having 2 to 25 carbon atoms, and specifically, ethylene, propylene, butene-1, pentene-1,
Hexene-1, heptene-1, octene-1, nonene-
1, decene-1, undecene-1, dodecene-1, tridecene-1, tetradecene-1, pentadecene-1, hexadecene-1, octadecene-1, etc., and 3-methylbutene-1 , 4-methylpentene-1, 4,4-dimethylpentene-1 and the like, and cyclic olefins such as cyclopentene and norbornene. These olefins are used not only for homopolymerization but also for mutual copolymerization.

The polymerization conditions for the olefin are not particularly limited, and include a solvent polymerization method using an inert medium,
A bulk polymerization method or a gas phase polymerization method in which substantially no inert medium is present can be used. The polymerization temperature is -100 to 200 ° C,
The polymerization pressure is from normal pressure to 100 kg / cm ² .

[0032]

The present invention will be further described with reference to the following examples.

(Synthesis of Transition Metal Catalyst Component) 3.0 g of smectite (SAN) (manufactured by Corp Chemical) dried at room temperature under reduced pressure was suspended in 30 ml of n-pentane, and a toluene solution containing 7.25 mmol of triethylaluminum was suspended. After adding 5 ml, the mixture was stirred at room temperature for 2 hours.

After the volatile components were distilled off, the residue was suspended again in 20 ml of n-pentane, and isopropylcyclopentadienyl-1-fluorene synthesized according to a conventional method was lithiated.
40 ml of an n-pentane suspension containing 200 mg of isopropyl (cyclopentadienyl-1-fluorenyl) zirconium dichloride obtained by reacting with zirconium tetrachloride was mixed and stirred at room temperature for 2 hours. Volatiles were distilled off from the obtained mixture under reduced pressure to obtain 2.44 g of a brown solid.

(Polymerization of propylene) 500 mg of the above catalyst component
And methylaluminoxane (Tosoh Akzo Co., Ltd.)
1.0 g was placed in an autoclave having an internal volume of 5 liters, and 1.5 kg of propylene was added, followed by polymerization at 60 ° C. for 2 hours. Unreacted propylene was purged to remove the polymer, which was dried to obtain 31.7 g of syndiotactic polypropylene. After the polymerization, no adhesion of the polymer to the polymerization vessel wall was observed.

The intrinsic viscosity of this polypropylene measured with a tetralin solution at 135 ° C. was 0.40 dl / g . Also, 1,
The ratio of the weight average molecular weight to the number average molecular weight measured with 2,4-trichlorobenzene was 1.6, and the syndiotacticity in ¹³ C-NMR was 0.775. Also,
The bulk specific gravity of the polymer was 0.35 g / ml.

[0037]

By using the catalyst obtained by the present invention, it is possible to produce a polyolefin with high productivity, and its industrial value is high.

[Brief description of the drawings]

FIG. 1 is a flowchart for helping an understanding of the present invention.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-5-301917 (JP, A) JP-A-5-105721 (JP, A) JP-A-4-100808 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) C08F 4/60-4/70

Claims (2)

(57) [Claims] (A) a conjugated alkadienyl group represented by the following chemical formula 1 or 2 wherein A and B are the same or different from each other, and R is a hydrocarbon having 1 to 20 carbon atoms linking A and B A transition metal compound represented by a residue or a compound containing silicon, germanium or tin, X is a hydrocarbon residue having 1 to 10 carbon atoms or a halogen atom, and M is a metal atom belonging to Group 4 of the periodic table. Embedded image Embedded image (B) selected from aluminum, zinc and magnesium
And after treatment with an organometallic compound of a metal, or without treatment, selected from (c) aluminum, zinc and magnesium
A method for producing a catalyst component for olefin polymerization, which comprises contacting with an untreated smectite treated or untreated with an organometallic compound of a metal . 2. A method for polymerizing an olefin, comprising polymerizing the olefin using the catalyst component according to claim 1.