JP2000239311A - Catalyst for polymerizing olefin and olefin polymerization using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To simply and easily prepare an inexpensive catalyst for polymerizing an olefin, easily to be handled and useful for polymerizing ethylene or the like by including a bis(cyclopentadienyl)titanium halide, a dialkylaluminum halide or the like. SOLUTION: This catalyst is prepared by including (A) a bis(cyclopentadienyl) titanium halide [preferably bis(cyclopentadienyl)titanium chloride], (B) a reaction product of a compound [preferably bis(cyclopentadienyl)zirconium dichloride] of the formula: Cp2Zr(X) (Y) (wherein, Cp is cyclopentadienyl; X and Y are each a halogen or the like) with an aluminum trichloride (preferably aluminum trichloride) and (C) a dialkylaluminum halide (preferably diethylaluminum chloride). The quantities of zirconium included in the ingredient B and the ingredient C are 0.5-1.5 g atom and 10-30 g mol respectively based on 1 g atom titanium in the ingredient A.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catalyst for the polymerization of olefins such as ethylene and propylene and a method for polymerizing olefins using the catalyst.

[0002]

2. Description of the Related Art Olefin polymerization catalysts comprising a metallocene compound as a catalyst component are known. Conventionally, metallocene,
Typically, zirconocene, which is the most practical,
(1) methylaluminoxane (hereinafter, referred to as MAO), (2) Ph ₂ MeHN · B (C ₆ F ₅ ) ₄ (where Ph represents a phenyl group and Me represents a methyl group),
(3) The catalyst component exhibits olefin polymerization ability for activation in combination with an organoaluminum compound and a heteropolyacid.

However, the MAO of the above (1) used for activating zirconocene must be used in a large amount, which increases the cost of the polymerization catalyst and increases the amount of catalyst residues in the obtained polymer. P in (2) above
Since h ₂ MeHN · B (C ₆ F ₅ ) ₄ is unstable, it is liable to be inactivated and inconvenient to handle, and the heteropolyacid type (3) has a low activity. is there.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide an olefin polymerization catalyst comprising a metallocene catalyst system which is simpler, cheaper and easier to handle, and a method for polymerizing olefins using the same.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a composition obtained by combining a reaction product of titanocene, zirconocene and aluminum trihalide, and a dialkylaluminum halide is obtained. It has been found that the object of the present invention can be achieved, and the present invention has been completed.

That is, the present invention relates to (1) bis (cyclopentadienyl) titanium halide, (2)
Bis (cyclopentadienyl) zirconium compound represented by Cp ₂ Zr (X) (Y) (where X is a halogen atom or an alkyl group having 1 to 8 carbon atoms, Y is a halogen atom or 1 to 8 carbon atoms) And X and Y may be the same.) And a reaction product of aluminum trihalide and (3) a dialkyl aluminum halide catalyst for olefin polymerization.

In the present invention, the bis (cyclopentadienyl) titanium halide is bis (cyclopentadienyl) titanium chloride, and the reaction product is bis (cyclopentadienyl) zirconium dichloride and aluminum trichloride. Wherein the dialkylaluminum halide is diethylaluminum chloride. Further, the present invention is characterized in that the reaction product is an equimolar reaction product of bis (cyclopentadienyl) zirconium dichloride and aluminum trichloride.

Further, the present invention provides a method for polymerizing an olefin, which comprises polymerizing the olefin in the presence of the catalyst for olefin polymerization.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The polymerization catalyst of the present invention comprises (1) bis (cyclopentadienyl) titanium halide
It is called component (1). ), (2) General formula Cp ₂ Zr
Bis (cyclopentadienyl) represented by (X) (Y)
A zirconium compound (provided that X represents a halogen atom or an alkyl group having 1 to 8 carbon atoms, Y represents a halogen atom or an alkyl group having 1 to 8 carbon atoms, and X and Y may be the same) and aluminum trihalide And (3) a dialkylaluminum halide (hereinafter, referred to as component (3)).

The component (1) includes bis (cyclopentadienyl) titanium chloride, bis (cyclopentadienyl) titanium bromide, bis (cyclopentadienyl) titanium iodide and the like. Dienyl) titanium chloride (Cp
₂ TiCl) is preferred. These components (1) are known compounds that can be easily produced, are inexpensive,
It is a stable compound.

The component (2) has the general formula Cp ₂ Zr
Bis (cyclopentadienyl) represented by (X) (Y)
A zirconium compound (provided that X represents a halogen atom or an alkyl group having 1 to 8 carbon atoms, Y represents a halogen atom or an alkyl group having 1 to 8 carbon atoms, and X and Y may be the same) and aluminum trihalide And the reaction product of Examples of the halogen atom of X and Y in the above general formula of the bis (cyclopentadienyl) zirconium compound include chlorine, bromine, iodine and fluorine atoms, and a chlorine atom is particularly preferable. Also, the carbon number of J of X and Y is 1-8.
Alkyl groups include methyl, ethyl, propyl,
Examples include isopropyl, butyl, isobutyl, t-butyl, pentyl, isopentyl, hexyl, isohexyl, octyl, 2-ethylhexyl and the like, preferably methyl, ethyl and propyl, particularly preferably a methyl group. Bis (cyclopentadienyl) zirconium compounds are known compounds, many of which are commercially available,
As shown in the examples below, the production method is described in literatures or the like, or can be produced according to the method described in the literatures or the like. Bis (cyclopentadienyl)
Among zirconium compounds, bis (cyclopentadienyl) titanium chloride (Cp ₂ ZrCl ₂ ) is particularly preferred. Examples of the aluminum trihalide include aluminum trichloride (AlCl ₃ ), aluminum tribromide, and aluminum triiodide, and AlCl ₃ is particularly preferable.

The component (2) is preferably a reaction product of Cp ₂ ZrCl ₂ and AlCl ₃ , particularly an equimolar reaction product of both. The method of producing the component (2) by reacting the bis (cyclopentadienyl) zirconium compound with aluminum trihalide is performed in a medium inert to the reaction. Examples of the medium include saturated aliphatic hydrocarbons such as propane, butane, pentane, hexane and heptane; saturated alicyclic hydrocarbons such as cyclopropane and cyclohexane; and aromatic hydrocarbons such as benzene, toluene and xylene. However, aromatic hydrocarbons, especially toluene, are preferred. The reaction is carried out at 50 ° C. to the reflux temperature of the medium, 1 to 10
Complete in time. The reaction product obtained is preferably separated and purified. The component (2) is used in addition to the reaction product of the bis (cyclopentadienyl) zirconium compound and the aluminum trihalide in advance to form a reaction product thereof. May be supplied together with the component (1) or the component (3) so that they are brought into contact with each other in situ.

The polymerization catalyst of the present invention comprises the above-mentioned component (1), component (2) and component (3). The component (2) is the same as the component (2) per gram atom of titanium in the component (1). The zirconium in (2) is 0.1 to 10 g atoms, preferably 0.5 to 1.5 g atoms, and the component (3) is 0.1 g atom.
It is used in a proportion of 1 to 1,000 gmol, preferably 10 to 30 gmol.

When the olefin is polymerized, the polymerization catalyst composed of the above three components may be used as it is, or the three components may be mixed at the same time, but the components (1) and (2) may be used in advance. After mixing and contacting, it is preferable to use after mixing the component (3). Mixing and contacting of the component (1) and the component (2) are performed at -100 ° C to + 100 ° C, preferably
Performed at 30 ° C. for 0.5-60 minutes. This mixing and contacting can be performed in a suitable medium, for example, a hydrocarbon that may be used during the polymerization of olefin.

[0015] Further, the present invention provides
An olefin polymerization method comprising polymerizing an olefin. Olefin polymerization comprises homopolymerization or copolymerization of ethylene and / or olefins (excluding ethylene). Examples of olefins to be homopolymerized or copolymerized include α-olefins such as propylene, 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene. The present invention
It is suitable for homopolymerization of ethylene or propylene and for copolymerization of ethylene and propylene, and is particularly suitable for homopolymerization of ethylene.

The (co) polymerization reaction is usually carried out in a medium which is inert to the (co) polymerization reaction and which is liquid at the time of the (co) polymerization. As the medium, propane, butane, pentane, hexane, saturated aliphatic hydrocarbons such as heptane, cyclopropane, saturated alicyclic hydrocarbons such as cyclohexane,
Examples thereof include aromatic hydrocarbons such as benzene, toluene, and xylene. These media are not limited to one type, and two or more types can be used in combination. The above homopolymerization or copolymerization is usually performed at -100 ° C to + 100 ° C, preferably at 0 to 30 ° C for 0.5 to 100 hours.

[0017]

Next, the present invention will be described more specifically with reference to examples and comparative examples. (Example 1) [Synthesis of component 1] After thoroughly replacing a 100 ml three-necked flask with nitrogen, 0.88 g of titanium trichloride and 0.88 g of bis (cyclopentadienyl) magnesium were added, and 25 ml of tetrahydrofuran was added while cooling. Was added. After stirring at room temperature for 1 hour and refluxing at 80 ° C. for 2 hours, the solvent was distilled off to obtain a green-brown solid. This solid is placed under vacuum at 120 ° C.
To remove sublimation of bis (cyclopentadienyl) magnesium, and heated to 170 ° C. to synthesize bis (cyclopentadienyl) titanium chloride (Cp ₂ TiCl), which is purple-brown component 1.

[Synthesis of Component 2] A 100 ml three-necked flask was sufficiently purged with nitrogen and then sublimated and purified in advance.
g of aluminum trichloride, 50 ml of toluene solvent and 8.64 g of bis (cyclopentadienyl) zirconium dichloride (Cp ₂ ZrCl ₂ ) were charged in this order. Then, the mixture was reacted for 1 hour while stirring under reflux. After the completion of the reaction, the mixture was cooled to room temperature, and then only the liquid phase was collected by filtration, followed by degassing under vacuum to obtain a pale yellow solid. Further, this solid was washed five times with each 80 ml of purified hexane and dried under vacuum to synthesize a pale yellow component 2.

[Ethylene polymerization] Nitrogen-substituted 100 m
17 ml of toluene was placed in a 1 l flask, deaerated under reduced pressure while stirring well, and then ethylene was introduced. The amount of ethylene absorbed was measured with a mass flow meter. After the absorption of ethylene was not observed and the toluene was sufficiently saturated, 1 ml (27.3 μmol) of a 2.73 × 10 ⁻⁵ mol toluene slurry of the component 2 synthesized above was added. After confirming that the polymerization did not proceed with a mass flow meter, Cp ₂ TiCl of component 1 synthesized above was used.
Of toluene solution of 2.73 × 10 ^-5 mol was added. After stirring at room temperature for 5 minutes, polymerization was initiated by adding 1 ml of a 1.0 molar toluene solution of diethylaluminum chloride. One hour later, the polymerization was stopped by adding 5 ml of methanol to the polymerization solution. After precipitating in a large amount of methanol containing a small amount of 2N hydrochloric acid to recover the polymer, the polymer was filtered and reduced in pressure to obtain 1.67 g.
Of polyethylene was obtained.

(Example 2) [Synthesis of component 2] After sufficiently replacing a 100 ml three-necked flask with nitrogen, 6.03 g of Cp ₂ ZrCl ₂ and 50 ml of a purified diethyl ether solvent were charged. Then, 29.5 ml of a 14 mol / l methyllithium diethyl ether solution was added dropwise with stirring over 30 minutes. After stirring at room temperature for 15 hours, the solvent was removed by vacuum degassing. The remaining solid phase is purified hexane 400ml
And the soluble portion was recovered. In addition, about 100 ml
And concentrated by vacuum degassing until the volume reached. By cooling this concentrated solution to -78 ° C, bis (cyclopentadienyl) dimethylzirconium (Cp
₂ ZrMe ₂ ) was synthesized. In the synthesis of component 2 of Example 1, the Cp ₂ Z obtained above was replaced by Cp ₂ ZrCl ₂
Component ₂ was prepared in the same manner as in Example 1 except that rMe ₂ was used.
Was synthesized.

[Ethylene polymerization] Ethylene was polymerized in the same manner as in Example 1 except that Component 2 obtained above was used in place of Component 2 used in Example 1, and 0.013 g of ethylene was polymerized.
Of polyethylene was obtained.

(Example 3) [Synthesis of component 2] After sufficiently replacing a 100 ml three-necked flask with nitrogen, the Cp ₂ ZrMe ₂ 2.1 obtained in Example 2 was obtained.
1. 7 g, 50 ml of toluene solvent and Cp ₂ ZrCl ₂
51 g were placed in this order. Then, the reaction was carried out for 50 hours under reflux with stirring. After the reaction was completed, the solution was cooled to room temperature, and then degassed under vacuum to concentrate the solution to about half the volume. By cooling this concentrated solution to -78 ° C, bis (cyclopentadienyl) consisting of pale yellow crystals is obtained.
Zirconium methyl chloride (Cp ₂ ZrMeCl) was synthesized. In the synthesis of component 2 of Example 1, Cp ₂ Z
Component 2 was synthesized in the same manner as in Example 1 except that the Cp ₂ ZrMeCl obtained above was used instead of rCl ₂ .

[Ethylene polymerization] Ethylene was polymerized in the same manner as in Example 1 except that the component 2 obtained above was used instead of the component 2 used in Example 1, and 0.22 g of polyethylene was obtained. I got

(Example 4) [Polymerization of ethylene] 3.6 mg (27.3 micromol) of aluminum trichloride and 17 ml of toluene were placed in a 100-ml flask purged with nitrogen, and deaerated under reduced pressure with good stirring. Later, ethylene was introduced. The amount of ethylene absorbed was measured with a mass flow meter. After the absorption of ethylene is no longer observed and the toluene is sufficiently saturated, C
1 ml (27.3 micromoles) of a 2.73 × 10 ^-5 mol toluene solution of p ₂ ZrCl ₂ was added. After confirming that the polymerization does not progress with a mass flow meter,
1 ml of a 2.73 × 10 ⁻⁵ mol toluene solution of Cp ₂ TiCl was added. After stirring at room temperature for 5 minutes, a 1.0 M toluene solution of diethylaluminum chloride was added to 1 m
The polymerization was started by adding 1 l. One hour later, the polymerization was stopped by adding 5 ml of methanol to the polymerization solution. The polymer was recovered by precipitating it in a large amount of methanol containing a small amount of 2N hydrochloric acid, followed by filtration and reduced pressure to obtain 0.19 g of polyethylene.

Comparative Example 1 In Example 1, Cp ₂ T
Example 1 except that iCl (component (1)) was not used.
Polymerization of ethylene was carried out in the same manner as described above, but no polymer was obtained.

Comparative Example 2 Polymerization of ethylene was carried out in the same manner as in Example 1, except that diethyl aluminum chloride (component (3)) was not used, but no polymer was obtained. .

[0027]

The catalyst of the present invention is stable and easy to handle, can polymerize olefins at room temperature, and uses a large amount of an organoaluminum compound in combination with a metallocene compound as compared with that of a conventional aluminoxane. Therefore, the catalyst cost as well as the catalyst residue in the polymer can be reduced.

[Brief description of the drawings]

FIG. 1 is a flowchart showing a method for preparing a catalyst of the present invention.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Hiroyuki Ozaki 4-6-202 Onogawa Tsukuba, Ibaraki Prefecture (72) Inventor Hideaki Hagiwara 2-6-13-203, Akubo, Tsukuba City, Ibaraki Prefecture (72) Invention Person Michihiko Asai 3-711 Namiki, Tsukuba City, Ibaraki Prefecture (72) Inventor Yasumi Suzuki 2-805-808, Azuma, Tsukuba City, Ibaraki Prefecture (72) Inventor Tetsu Miyazawa 4-403-103, Matsushiro 4-chome 103-103 (72) Inventor Kenji Tsuchihara 2-806-703, Azuma, Tsukuba-shi, Ibaraki (72) Inventor Yoshifumi Fukui 4-63-507, Ninomiya 4-chome, Tsukuba-shi, Ibaraki 6-2-203 (72) Inventor Toshio Kase 5-2-2, Matsushiro, Tsukuba, Ibaraki Prefecture (72) Inventor Kazuo Soga 9-6-1, Midorigaoka, Tatsunokuchi-cho, Nomi-gun, Ishikawa Prefecture (72) InventorJin Jiju 2-7-2 Kotano, Kanazawa-shi, Ishikawa F term (reference)

Claims (4)

[Claims] (1) Bis (cyclopentadienyl) titanium halide, (2) General formula Cp ₂ Zr (X)
A bis (cyclopentadienyl) zirconium compound represented by (Y) (where X represents a halogen atom or an alkyl group having 1 to 8 carbon atoms, and Y represents a halogen atom or an alkyl group having 1 to 8 carbon atoms) X and Y may be the same.) An olefin polymerization catalyst comprising a reaction product of aluminum trihalide and (3) a dialkylaluminum halide. 2. The bis (cyclopentadienyl) titanium chloride is bis (cyclopentadienyl) titanium chloride, and the reaction product is a reaction product of bis (cyclopentadienyl) zirconium dichloride and aluminum trichloride. The catalyst for olefin polymerization according to claim 1, wherein the dialkylaluminum halide is diethylaluminum chloride. 3. The catalyst for olefin polymerization according to claim 2, wherein the reaction product is an equimolar reaction product of bis (cyclopentadienyl) zirconium dichloride and aluminum trichloride. 4. An olefin polymerization method comprising polymerizing an olefin in the presence of the olefin polymerization catalyst according to any one of claims 1 to 3.