JPH07268014A - Catalyst component for olefin polymerization - Google Patents

Abstract

PURPOSE:To obtain the subject component free from release of a metallocene catalyst component from a solid carrier during polymerization by bringing a metallocene compound containing an electron-donating group into contact with a solid comprising an inorganic carrier and Lewis acid component supported thereon. CONSTITUTION:A synthetic metallocene compound containing an electron donating group is brought into contact with a solid comprising an inorganic carrier and a Lewis acid component supported thereon to produce the objective component having the metallocene catalyst component firmly supported on a solid particulate carrier. The release of the metallocene catalyst component from the solid during polymerization is controlled to thereby avoid fouling, etc., during polymerization, thus facililating the production of an olefin polymer. Since no activator such as alumoxane is contained in the catalyst, the deterioration of this component during long-term storage can be prevented.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel catalyst component for olefin polymerization, a method for producing the catalyst component, and polymerization of an olefin by a catalyst system containing the catalyst component.
Alternatively, it relates to a method for producing a copolymerized polyolefin.

[0002]

2. Description of the Related Art Conventionally, an olefin compound is polymerized or polymerized in the presence of a catalyst system which is composed of a transition metal compound and an organoaluminum compound and is insoluble in a hydrocarbon solvent, so-called Ziegler catalyst. By copolymerization, a linear and high molecular weight olefin polymer having high stereoregularity was obtained in high yield. In recent years, as one type of Ziegler catalyst, a metallocene compound in which a transition metal compound and a cyclopentadienyl compound are coordinate-bonded, for example, bis (cyclopentadienyl) titanium dialkyl, bis (cyclopentadienyl) zirconium dialkyl, etc. , It became clear that an active homogeneous catalyst composed of alumoxane obtained by the reaction of aluminum trialkyl and water is effective for the polymerization of olefin compounds, and is disclosed in various technical documents and patent documents. .

For example, the polymerization of ethylene with a catalyst system composed of bis (cyclopentadienyl) titanium dialkyl, trialkylaluminum and water is disclosed in German Patent 2,608,863. Further, an ethylene-based polymerization catalyst system comprising a zirconium metallocene compound represented by the general formula of (cyclopentadienyl) _n ZrY _4-n , an organoaluminum cocatalyst, and water is disclosed in German Patent No. 2,608,933. Further, other techniques relating to a homogeneous catalyst system comprising a metallocene compound and an alumoxane are disclosed in Kaminskii et al. European Patent Application No. 0069551. The advantage of the homogeneous catalyst system consisting of the metallocene compound and the alumoxane is that extremely high activity can be obtained in the olefin polymerization, but since this catalyst is soluble in a hydrocarbon solvent, if the olefin polymerization is carried out as it is. The obtained polymer has a wide particle size distribution and tends to be amorphous, which is industrially disadvantageous.

Therefore, a catalyst in which both metallocene and alumoxane are supported on SiO ₂ or the like having a good particle property has been developed and is disclosed in, for example, US Pat. No. 5,240,894. However, in the catalyst in which metallocene and alumoxane are co-precipitated on SiO ₂ , the catalyst component is only physically supported on SiO ₂ , and polymerization in a solution (solvent slurry method, bulk weight method) is performed. legal)
In, the active component is easily desorbed from SiO ₂ , the particles of the polymer become amorphous and powdery, are easily charged with static electricity, and are easily attached to the reaction tower (this phenomenon is referred to as “fouling”). In addition, the metallocene and the alumoxane are in contact with each other before the polymerization, and there is a drawback that the catalyst easily deteriorates during long-term storage.

[0005]

DISCLOSURE OF THE INVENTION In the present invention, a metallocene compound containing a novel electron-donating group is synthesized by a novel synthesis method, and the metallocene catalyst component is a solid having a Lewis acidic component supported on an inorganic carrier. The metal carrier is firmly supported on the particle carrier to prevent the metallocene catalyst component from desorbing from the solid carrier during the polymerization, thereby avoiding fouling and the like during the polymerization and easily producing the olefin polymer. A novel catalyst component for olefin polymerization, which provides a novel catalyst component for olefin polymerization and can prevent deterioration due to long-term storage because the supported catalyst does not contain an activator such as alumoxane. And a method for producing the catalyst component thereof, and a method for polymerizing an olefin using the catalyst component for polymerization.

[0006]

The present inventors have found that various electron donating compounds, for example, oxygen-containing compounds such as esters, ethers and alcohols, or nitrogen-containing compounds such as amines and amides are converted to MgCl ₂ . In view of binding to a representative Lewis acidic component, by producing a metallocene compound having an electron-donating group in the molecule, by reacting the compound with a solid particle carrier carrying a Lewis acidic component on an inorganic carrier, By firmly supporting the metallocene compound by utilizing the interaction between the electron-donating group and the carrier, the metallocene catalyst becomes insoluble in the hydrocarbon solvent and the particle size distribution is improved, so that the obtained polymer becomes granular. The inventors have found that fouling, etc. can be avoided, and have completed the present invention.

That is, the first invention of the present application is an olefin polymerization catalyst component comprising a metallocene compound containing an electron-donating group supported on a solid having a Lewis acidic component supported on an inorganic carrier. Aspect is the above-mentioned olefin polymerization catalyst component, wherein the electron-donating group is an oxygen-containing electron-donating group containing a hydroxyl group and the like, and the nitrogen-containing electron-donating group in which the electron-donating group contains an amino group and the like. It is the above-mentioned olefin polymerization catalyst component that is a group.

The second invention of the present case is to synthesize a metallocene compound containing an electron-donating group,
A method for producing a catalyst component for olefin polymerization, which comprises contacting a solid carrying a Lewis acidic component on an inorganic carrier, and as an embodiment, the synthesis of a metallocene compound containing an electron-donating group is an alkyl halide. N to amine
By reacting N'-bis (trialkylsilyl) urea,
Halogenated alkyl-di (trialkylsilyl) amine, which is reacted with magnesium to give a Grignard reagent, which is reacted with di (cycloalkadienyl) dihalosilane to give di [di (trialkylsilyl) amine
Aminoalkyl] di (cycloalkadienyl) silane, a lithium group is introduced into the cycloalkadienyl group of the silane, a tetrahalide of a transition metal is further reacted, and further reduced to an amino group with an alcohol. A method for producing the catalyst component for olefin polymerization, which comprises synthesizing an electron-donating group-containing metallocene compound having an amino group as an electron-donating group, and reacting a trialkylhalosilane with a halogenated alkyl alcohol. To give a halogenated alkyltrialkylsilanol, which is reacted with magnesium to give a Grignard reagent,
The reagent is reacted with di (cycloalkadienyl) dihalosilane to give di (trialkylsiloxyalkyl) di (cycloalkadienyl) silane, a lithium group is introduced into the cycloalkadienyl group of the silane, and further transition A method for producing a catalyst component for olefin polymerization, which comprises reacting a metal tetrahalide and further oxidizing the alcohol group with an acid to synthesize an electron-donating group-containing metallocene compound having an alcohol group as an electron-donating group, Is.

The third invention of the present case is a catalyst system comprising an alumoxane and a catalyst component for olefin polymerization in which a metallocene compound having an electron-donating group is supported on a solid in which a Lewis acidic component is supported on an inorganic carrier. A method for producing a polyolefin by (co) polymerizing an olefin using
As an embodiment thereof, a method for producing the above-mentioned polyolefin using a catalyst system further containing an organosilicon compound,
And a method for producing the above-mentioned polyolefin using a catalyst system preliminarily polymerized by contacting the catalyst system with an olefin.

The method for producing the olefin polymerization catalyst component of the present invention is shown, for example, by the following reaction formula. S
iO ₂ and dialkyl magnesium are reacted to carry the Mg component. A chlorinating agent (eg, SiCl
₄ ) is actuated to prepare SiO ₂ -supported magnesium chloride. Further, the solid particles are reacted with an electron-donating group-containing metallocene compound to obtain a catalyst component for olefin polymerization firmly supported. SiO ₂ + MgR ₁ R ₂ ─── → Mg component / Si
O ₂ Mg component _{/ SiO 2 + SiCl 4 ── →} MgCl 2
/ SiO ₂

[0011]

[Chemical 1]

R ₁ : C ₁ -C ₁₂ alkyl, alkenyl, cycloalkyl, aryl, aralkyl R ₂ : C ₁ -C ₁₂ alkyl, alkenyl, cycloalkyl, aryl, aralkyl Inorganic carrier used in the present invention The carrier is mainly a metal oxide, particularly an oxide of a metal selected from the group of elements of Group II to Group IV of the periodic table, and when they are exemplified,
B ₂ O ₃ , MgO, Al ₂ O ₃ , SiO ₂ , CaO, T
iO ₂ , ZnO, ZrO ₂ , SnO ₂ , BaO, ThO
₂ etc. Among these, B ₂ O ₃ , MgO, Al
₂ O ₃ , SiO ₂ , TiO ₂ , and ZrO ₂ are preferable, and SiO ₂ is particularly preferable. Furthermore, complex oxides containing these metal oxides such as SiO ₂ —MgO and SiO ₂ —A
l ₂ O ₃ , SiO ₂ —TiO ₂ , SiO ₂ —V ₂ O ₅ ,
_{SiO 2 -Cr 2 O 3, SiO} 2 -TiO 2 -MgO and the like may also be used.

The shape of these metal oxides is powder. Since the shape such as the size and shape of the powder often affects the shape of the obtained olefin polymer, it is desirable to appropriately adjust the shape. It is desirable that the metal oxide is burned at a temperature as high as possible and used so as not to come into direct contact with the atmosphere for the purpose of removing poisonous substances in use.

Lewis acidic component A component selected from the group of compounds represented by the following general formula (1). Specific examples thereof are MgCl ₂ and AlCl.
₃ , CaCl ₂ , CdCl ₂ , MnBr _{2 and the} like. MX _n (1) (In the formula, M is Mg, Al, Ca, Cd, Co, Mg, X is Cl, Br, I, and n is 2 or 3.) Metallocene compound The metallocene compound in the invention is a metallocene-based transition metal compound represented by the following general formula (2).

[0015]

[Chemical 2]

In the formula, L and L'represent a cycloalkadienyl group or a substituted cycloalkadienyl group,
It is essential that L and L ′ are bonded to an electron-donating group through another atom or atomic group, M _T is an element of Group 4B of the periodic table, and X is a halogen atom. . In addition, Y: Al, B, n = 1, m = 0 Y: Si, Ge, C, n = m = 1 _RA : electron donating group (carboxylic acids, alcohols described below, ethers, groups derived from amines) R _B: electron donating group, may be different from be the same as R _a.

The metallocene compound represented by the general formula (2) will be described in detail. M _T is a transition metal of Group 4B of the periodic table, preferably zirconium or hafnium,
X is a halogen atom, preferably chlorine or bromine, Y is an element of the 3A or 4A group, and silicon is preferable. R _A ,
R _B is an electron-donating group, and examples of the electron-donating group contained in the metallocene compound of the present invention include oxygen-containing groups derived from carboxylic acids, alcohols, ethers, ketones, esters and the like, amines. And nitrogen-containing groups derived from amides, amides, nitriles and the like. Of these, groups derived from alcohols and groups derived from amines are preferably used.

Specific examples of the carboxylic acid group include formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, pivalic acid, acrylic acid, methacrylic acid, crotonic acid and other aliphatic monocarboxylic acids, and malon. Acids, succinic acid, glutaric acid, adipic acid, sebacic acid, maleic acid, fumaric acid and other aliphatic dicarboxylic acids, tartaric acid and other aliphatic oxycarboxylic acids, cyclohexanemonocarboxylic acid, cyclohexenemonocarboxylic acid, cis-1,2 -Cyclohexanedicarboxylic acid, cis-4-methylcyclohexene-1,
Alicyclic carboxylic acids such as 2-dicarboxylic acid, benzoic acid, toluic acid, anisic acid, aromatic monocarboxylic acids such as p-tertiary butyl benzoic acid, naphthoic acid and cinnamic acid, phthalic acid, isophthalic acid, Terephthalic acid, naphthalic acid, trimellitic acid, hemimellitic acid, trimesic acid, pyromellitic acid,
Examples thereof include electron-donating groups derived from aromatic polycarboxylic acids such as mellitic acid.

The electron-donating group derived from alcohols is a group represented by the general formula --R ³ OH, where --R ³ --is an alkylene having 1 to 12 carbon atoms, alkenylene, cyclo. Alkylene, arylene and aralkylene. Specific examples thereof include methanol, ethanol, propanol, isopropanol, butanol,
Derived from isobutanol, pentanol, hexanol, octanol, 2-ethylhexanol, cyclohexanol, benzyl alcohol, allyl alcohol, phenol, cresol, xylenol, ethylphenol, isopropylphenol, p-tert-butylphenol, n-octylphenol, etc. An electron-donating group is mentioned.

The electron-donating group derived from ethers is represented by the general formula R ⁴ OR ⁵ . R in the general formula
⁴ , R ⁵ is an alkyl, alkenyl, cycloalkyl, aryl, aralkyl or a group thereof having 1 to 12 carbon atoms in which either one or both have a bonding group, and R ⁴ and R ⁵ are the same But it may be different. Specific examples thereof include diethyl ether, diisopropyl ether, dibutyl ether, diisobutyl ether, diisoamyl ether, di-2-ethylhexyl ether,
Examples thereof include electron-donating groups derived from diallyl ether, ethyl allyl ether, butyl allyl ether, diphenyl ether, anisole, ethyl phenyl ether and the like.

The electron-donating group derived from amines is a group represented by the general formula --R ⁶ NH ₂ , wherein --R ⁶ --is an alkylene having 1 to 12 carbon atoms, alkenylene, Cycloalkylene, arylene and aralkylene. Specific examples thereof include methylamine, ethylamine, propylamine, isopropylamine, butylamine, isobutylamine, pentylamine, hexylamine, octylamine, 2-ethylhexylamine, cyclohexylamine, benzylamine, allylamine, phenylamine, cresylamine, xyleramine. , An electron donating group derived from ethylphenylamine, isopropylphenylamine, p-tertiarybutylphenylamine, n-octylphenylamine and the like.

Specific examples of L and L'include cyclopentadienyl groups (hereinafter abbreviated as "Cp"), indenyl groups (hereinafter abbreviated as "Ind") as cycloalkadienyl groups.
Fluorenyl (hereinafter abbreviated as "Flu") can be used. Examples of the substituted cycloalkadienyl group include the following substituents. In case of Cp: methyl group, ethyl group, isopropyl group In case of Ind: 5-isopropyl group, 5-isopropyl-2-methyl group, 5,7-diisopropyl-2-methyl group In case of Flu: methyl group, ethyl group L The cycloalkadienyl groups of L'may be the same or different.

In order to introduce the electron-donating group as described above into the metallocene compound, it has to be produced by a specific synthetic reaction. The method is as follows: the metallocene compound containing the electron-donating group is synthesized by an alkyl halide. A, N, N '
-Bis (trialkylsilyl) urea to give a halogenated alkyl-di (trialkylsilyl) amine, which is reacted with magnesium to give a Grignard reagent, which is converted to a di (cycloalkadienyl) dihalosilane The reaction is carried out to form di [di (trialkylsilyl) aminoalkyl] di (cycloalkadienyl) silane, a lithium group is introduced into the cycloalkadienyl group of the silane, and a tetrahalide of a transition metal is further reacted. And a method for producing the catalyst component for olefin polymerization, which further comprises reducing an amino group with an alcohol to synthesize an electron-donating group-containing metallocene compound having an amino group as an electron-donating group, and a halogen. Reaction of halogenated alkyl trialkylsilane with trialkylhalosilane And silanols, and Grignard reagent is reacted with magnesium in the silanol,
The reagent is reacted with di (cycloalkadienyl) dihalosilane to give di (trialkylsiloxyalkyl) di (cycloalkadienyl) silane, a lithium group is introduced into the cycloalkadienyl group of the silane, and further transition A method for producing a supported catalyst component for olefin polymerization, which comprises reacting a metal tetrahalide and further oxidizing it with an acid to an alcohol group to synthesize an electron-donating group-containing metallocene compound having an alcohol group as an electron-donating group. ,.

In order to introduce an electron-donating group as described above into a metallocene compound, it must be produced by a specific synthetic reaction. As a typical example of the method, an electron-donating group having a nitrogen-containing group is used. A method for producing cyclopentadienylzirconocene containing an electron-donating group derived from a halopropylamine will be described using a reaction formula.
The reaction formula is as shown in the scheme (I).

[0025]

[Chemical 3]

That is, N, N'- is added to bromopropylamine.
Bis (trimethylsilyl) urea was reacted to give bromopropyl-di (trimethylsilyl) amine, magnesium was reacted with the amine to give a Grignard reagent, and the reagent was reacted with di (cyclopentadienyl) dichlorosilane to give di (cyclopentadienyl) dichlorosilane. [Di (trimethylsilyl) aminopropyl] di (cyclopentadienyl) silane, which is reacted with methyllithium to introduce a lithium group into the cyclopentadienyl group, and further reacted with tetrachlorozirconium, and then with an alcohol In this method, an electron-donating group-containing metallocene compound having an amino group as an electron-donating group is synthesized by reducing an amino group and a chloro group. Also,
A method for producing cyclopentadienylzirconocene having an electron-donating group derived from a halopropyl alcohol as an electron-donating group having an oxygen-containing group will be described with reference to the reaction scheme. )
It is as in (II).

[0027]

[Chemical 4]

That is, bromopropyl alcohol is reacted with trimethylchlorosilane to form bromopropyloxytrimethylsilane, and the compound is reacted with magnesium to form a Grignard reagent, which is reacted with di (cyclopentadienyl) dichlorosilane. To produce di (trimethylsiloxypropyl) di (cyclopentadienyl) silane, which is reacted with methyllithium to introduce a lithium group into the cyclopentadienyl group, and further reacted with tetrachlorozirconium, followed by hydrochloric acid gas. And an electron donating group-containing metallocene compound having a hydroxyl group as an electron donating group is synthesized. The solid catalyst component carrying the electron-donating group-containing metallocene compound of the present invention uses a cocatalyst in combination, but uses a linear or cyclic alumoxane represented by the following general formulas (3) and (4).

[0029]

[Chemical 5] (In the formula, each R is, for example, 1 to 1 carbon atoms such as methyl and ethyl
6 alkyl groups, n is 2-40, preferably 10-2
Represents a number in the range 0. )

[0030]

[Chemical 6] (In the formula, R and n have the same definition as above.) The catalyst component of the present invention may be preliminarily polymerized before the main polymerization, and the metallocene compound-supported solid component (component A) is preliminarily polymerized by alumoxane. This is done by contacting with an olefin in the presence of (Component B).

As olefins for prepolymerization, in addition to ethylene, propylene, 1-butene, 1-hexene,
Alpha-olefins such as 4-methyl-1-pentene can be used. The prepolymerization is preferably carried out in the presence of an inert medium. The prepolymerization is usually performed at a temperature of 100 ° C or lower, preferably -30 ° C to + 30 ° C, more preferably -20 ° C to +1.
It is carried out at a temperature of 5 ° C. As a polymerization method, a batch method,
It may be continuous, or may be carried out in multiple stages of two or more stages. When carrying out in multiple stages, it goes without saying that the polymerization conditions can be changed.

Component B has a concentration of 10 to 5 in the prepolymerization system.
It is used in an amount of 00 mmol / liter, preferably 30 to 200 mmol / liter, and 1 to 50,000 mol per 1 gram atom of the transition metal in the component A.
It is preferably used in an amount of 2 to 1,000 mol. The olefin polymer is incorporated into the component A by the prepolymerization, but the amount of the polymer is 0.1 per 1 g of the component A.
It is desirable that the amount is ˜200 g, especially 0.5 to 50 g.
The catalyst component of the present invention prepared as described above can be diluted or washed with the above-mentioned inert medium,
From the viewpoint of preventing storage deterioration of the catalyst component, it is particularly desirable to wash. After washing, it may be dried if necessary. When the catalyst component is stored, it is desirable to store it at a temperature as low as possible.
A temperature range of ℃ to +5 ℃ is recommended.

The olefin which can be polymerized with the polymerization catalyst composed of such constituents is an olefin (unsaturated compound) having 2 to 20 carbon atoms, specifically, ethylene,
Propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl- 1-hexene, 4,4-dimethyl-
1-hexene, 4,4-dimethyl-1-pentene, 4-
Ethyl-1-hexene, 3-ethyl-1-hexene, 1
-Linear or branched olefins such as octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, styrene, dimethylstyrenes, allylbenzene, allyltoluenes, Aromatic unsaturated compounds such as vinylnaphthalenes and allylnaphthalenes, allyltrimethylsilane, allyltriethylsilane, 4-trimethylsilyl-1-butene, 6-trimethylsilyl-1-hexene, 8-trimethylsilyl-1-octene, 10-trimethylsilyl −
Examples thereof include unsaturated compounds such as 1-decene, and unsaturated alicyclic compounds such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, and tetracyclododecene. Preferably ethylene, propylene, 1-
Butene, 1-pentene, 1-hexene, 4-methyl-1
-Pentene, 3-methyl-1-pentene, 1-octene, 3-methyl-1-butene and the like may be mentioned, and they may be copolymerized alone or with at least one or more of the above monomers in an arbitrary ratio.

When the above-mentioned catalyst is used, the polymerization reaction may be carried out in a gas phase or a liquid phase. When the polymerization is carried out in a liquid phase, normal butane, isobutane, normal pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene, It can be carried out in an inert hydrocarbon such as toluene or xylene, or in a liquid monomer. The polymerization temperature is usually −80 ° C. to + 150 ° C., preferably 40 to 12
It is in the range of 0 ° C. The polymerization pressure may be, for example, 1 to 60 atmospheres. Control of the molecular weight of the resulting polymer is accomplished by the presence of hydrogen or other known molecular weight regulators. The polymerization reaction by the catalyst system according to the present invention is carried out as a continuous or batch reaction, and the conditions may be those usually used. The copolymerization reaction may be carried out in one step or in two or more steps.

[0035]

EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. (Example 1) Preparation of magnesium-containing solid (method for preparing Lewis acidic component-supporting solid on inorganic carrier) A 200 ml flask equipped with a dropping funnel and a stirrer was replaced with nitrogen gas. Into this flask, 10 g of silicon oxide (manufactured by Davison, trade name G-952) fired in a nitrogen stream at 200 ° C. for 2 hours and further at 700 ° C. for 5 hours and 80 ml of n-heptane were put. Furthermore, 40 ml of a 20% n-heptane solution of n-butylethylmagnesium (hereinafter referred to as "BEM") (Texas alkyls, trade name Magara BEM) was added, and the mixture was stirred at 90 ° C for 1 hour.

After the above suspension was cooled to 0 ° C., a solution of 22.4 g of tetraethoxysilane dissolved in 40 ml of n-heptane was added dropwise from the dropping funnel over 30 minutes. After the dropping is completed, the temperature is raised to 50 ° C over 2 hours, and the temperature is 50 ° C.
The stirring was continued for 1 hour. After the reaction was completed, the supernatant was removed by decantation, and the resulting solid was mixed with 100 ml of n
-Washing with heptane at room temperature and further decantation to remove the supernatant. This washing treatment with n-heptane was further performed 4 times.

To this, 100 ml of n-heptane was added,
Silicon tetrachloride (2 g) previously diluted with 30 ml of n-heptane was added dropwise at -20 ° C over 30 minutes. The temperature was raised to room temperature over 1 hour, and the mixture was stirred for 1 hour. Furthermore, 60 ℃
After treatment for 2 hours in the solid phase, 100 ml of n-
The solid was washed 4 times with heptane and then dried under reduced pressure to obtain 10.5 g of a white magnesium-containing solid.

Synthesis of metallocene compound represented by the following structural formula [Synthesis by reaction formula of scheme (I)]

[Chemical 7]

(I) Synthesis of a compound represented by the following structural formula

[Chemical 8]

A 1-liter, 3-necked flask equipped with a dropping funnel and a condenser was charged with 69 g of 3-bromopropylamine and 500 ml of methylene chloride. 122 g of N, N'-bis (trimethyl) over 2 hours with stirring
Urea was added dropwise. After the completion of dropping, the mixture was refluxed for 2 hours, the salt was filtered off, and 87 g of N, N-bis (trimethylsilyl) -3-bromopropylamine was obtained by distillation. Boiling point 70
° C / 1 mmHg, yield 62%.

(Ii) Metallocene Synthesis SiCl ₄ (0.0117 ml) was dissolved in 200 ml of THF, and CpLi (0.0234 mol) was added thereto little by little. After stirring for 1.5 hours, the solvent was distilled off under reduced pressure, and then 200 ml of heptane was introduced. After filtration,
Cl ₂ SiCp ₂ (yield, 100%) was obtained by distilling off heptane. On the other hand, a Grignard reagent was prepared in THF from the compound prepared in (i) and Mg. Then, Cl ₂ SiCp ₂ was dissolved in 200 ml of THF, and the Grignard reagent was introduced so that the Grignard reagent and Cl ₂ SiCp ₂ were 2 to 1 (molar ratio).
After stirring overnight at room temperature, THF was distilled off under reduced pressure. Then, 200 ml of heptane was introduced and filtered, and then heptane was distilled off under reduced pressure to obtain a metallocene ligand with a yield of 93%.

The metallocene ligand was dissolved in 200 ml of diethyl ether, and n-BuLi (1.6M) was dissolved therein.
Hexane solution) was added dropwise so that the ratio of the ligand to n-BuLi was 2: 1 (molar ratio), and the mixture was stirred overnight at room temperature. After distilling off the diethyl ether under reduced pressure, the obtained solid was washed twice with 100 ml of heptane each time and then dried to obtain a diLi salt of the ligand in a yield of 98%. Zr
Cl ₄ (2.49 g) was suspended in 200 ml of methylene chloride and cooled to −78 ° C. The diLi salt of the ligand obtained above was added to this. (Ligand di-Li salt / Zr = 1 /
After reacting at -78 ° C for 5 hours, the temperature is raised to -3.
It was set to 0 ° C. After reacting at this temperature for another 10 hours,
The temperature was raised to room temperature. After filtration, methylene chloride in the solution part was distilled off under reduced pressure to obtain a crude metallocene product. After washing this with 50 ml of heptane, the solid portion was depressurized to obtain 2.1 g of metallocene (yield 50%).

(Iii) Desilylation [(Me ₃ Si) ₂ N (CH ₂ ) ₂ ] -Si-Cp ₂ Z
After adding 8 equivalents of methanol to the rCl ₂ solution and stirring at room temperature for 2 hours, the methanol and the solvent were removed under reduced pressure. Metallocene compound was obtained from the residue by extracting metallocene with an extraction solvent and drying. Preparation of metallocene-supported catalyst 10.5 g of the white magnesium-containing solid obtained in 10
It was suspended in 0 ml of toluene, and 100 ml of a toluene solution of 0.9 g of the metallocene compound obtained here was introduced. This solution was heat-treated at 80 ° C. for 2 hours, and then the solid portion was treated with 100 ml of toluene twice and then 100 times each.
It was washed 5 times with ml of hexane. Finally, it was dried under reduced pressure to obtain a solid component containing 1.9 wt% Zr. Polymerization of ethylene The polymerization of ethylene was carried out by the usual method. However, 19 mg of white granular polyethylene was obtained by using 10 mg of the supported catalyst, methylalumoxane as the cocatalyst (Al / Zr = 1000 mol ratio), and toluene as the solvent. The bulk density of the obtained polymer is 0.42 g / m.
It was l.

Example 2 Preparation of Magnesium-Containing Solid Example 1-was repeated.

Synthesis of metallocene compound represented by the following structural formula [Synthesis by reaction formula of scheme (II)]

[Chemical 9]

(I) Synthesized to a compound represented by the following structural formula

[Chemical 10]

In a 1-liter three-necked flask equipped with a dropping funnel and a condenser, 65 g of trichlorosilane, 47
g of pyridine and 500 ml of hexane were charged. With stirring, 70 g of 3-bromopropyl alcohol was added dropwise over 2 hours. After completion of the dropwise addition, the mixture was refluxed for 1 hour, then the salt was filtered off and distilled to obtain 77 g of 3-bromo-1-trimethylsiloxypropane. Boiling point 87 ° C / 5mmHg,
Yield 72%. (Ii) Synthesis of metallocene SiCl ₄ (0.0117 ml) was dissolved in 200 ml of THF, and CpLi (0.0234 mol) was added thereto little by little. After stirring for 1.5 hours, the solvent was distilled off under reduced pressure, and then 200 ml of heptane was introduced. After filtration,
Cl ₂ SiCp ₂ (yield 100%) was obtained by distilling off heptane. On the other hand, a Grignard reagent was prepared in THF from the compound prepared in (i) and Mg.

Next, Cl ₂ SiCp ₂ was added to THF200.
Dissolve in ml and mix with the Grignard reagent above Cl ₂ SrCp
_The Grignard reagent was introduced so that ₂ was 2 to 1 (molar ratio). After stirring overnight at room temperature, THF was distilled off under reduced pressure. Then, 200 ml of heptane was introduced and filtered, and then heptane was distilled off under reduced pressure to obtain a metallocene ligand with a yield of 93%. 2 metallocene ligands
Dissolve in 00 ml of diethyl ether and add n-Bu
Li (1.6 M hexane solution) was used as a ligand pair n-Bu.
Li was added dropwise at a ratio of 2: 1 (molar ratio), and 1 was added at room temperature.
Stir overnight. After distilling off the diethyl ether under reduced pressure,
The solid obtained is washed twice with 100 ml of heptane each time,
Then, by drying, the yield of diLi salt of the ligand is 9
Obtained at 8%.

ZrCl ₄ (2.46 g) was suspended in 200 ml of methylene chloride and cooled to -78 ° C. The diLi salt of the above-obtained ligand was added thereto. (Ligand di Li
After reacting for 5 hours at −78 ° C., the temperature was raised to −30 ° C. After reacting for 10 hours at this temperature, the temperature was raised to room temperature. After filtration, methylene chloride in the solution part was distilled off under reduced pressure to obtain a crude metallocene product. This was washed with 50 ml of heptane, and then 2.1 g of metallocene (yield 50%) whose solid part was depressurized was obtained. (Iii) desilylated, dechlorination [Me ₃ SiO (CH _{2) 3] 2} -Si-Cp ₂ ZrC
After blowing 2 equivalents of hydrogen chloride gas into the ₁₂ solution over 3 hours, the solvent was removed under reduced pressure. The metallocene compound was obtained by extracting metallocene from the residue with an extraction solvent and drying it.

Preparation of metallocene-supported catalyst Example 1 except that 0.9 g of the metallocene obtained above was used.
By repeating-, a metallocene-supported catalyst was prepared. Ethylene Polymerization Example 1-Except that 10 mg of the catalyst component obtained above was used
Polymerization of ethylene was carried out in the same manner as in. 14 g of polyethylene was obtained. The bulk density of the obtained polymer is 0.41.
It was g / ml.

(Examples 3 to 5) In Example 1-
Various substituted cycloalkadienyl Ls whose CpLi are shown in Table 1
A metallocene-supported catalyst was prepared in the same manner as in Example 1 except that various metallocenes were prepared in place of i and used.
Using polypropylene as a monomer, polypropylene was obtained by the following polymerization method. In a nitrogen autoclave equipped with a stirrer and having an internal volume of 1.5 liters, 10 mg of a catalyst component and a methylalumoxane toluene solution (Al / Zr = 1000 mol / mol) were placed under a nitrogen gas atmosphere. Then, 1 liter of liquefied propylene was injected under pressure. Reaction system 7
After heating to 0 ° C., polymerization was carried out at 40 ° C. for 1 hour. The results obtained are shown in Table 1.

Comparative Example 1 Racemic-Me ₂ Si (In
d) ₂ ZrCl ₂ 0.9 g and a magnesium-containing solid 9.6 g synthesized in the same manner as in Example 1-Example 1
It was treated under the same conditions as for − to obtain a catalyst solid component. When 10 mg of this solid was used to polymerize propylene in the same manner as in Example 3, 48 g of polypropylene (Tm =
However, it contained 27% by weight of fine powder components (100 μm or less) and had a low bulk density of 0.27 g / ml. The results obtained are shown in Table 1.

[0053]

[Table 1]

[0054]

EFFECTS OF THE INVENTION A novel catalyst which can easily produce a polyolefin while providing the characteristics of a metallocene catalyst is provided, and a novel polyolefin which cannot be produced by a conventional Ziegler catalyst can be synthesized.

[Brief description of drawings]

FIG. 1 is a flow chart of an olefin polymerization catalyst.

[Procedure amendment]

[Submission date] June 27, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0023

[Correction method] Change

[Correction content]

In order to introduce the electron-donating group as described above into the metallocene compound, it has to be produced by a specific synthetic reaction. The method is as follows: the metallocene compound containing the electron-donating group is synthesized by an alkyl halide. A, N, N '
-Bis (trialkylsilyl) urea to give a halogenated alkyl-di (trialkylsilyl) amine, which is reacted with magnesium to give a Grignard reagent, which is converted to a di (cycloalkadienyl) dihalosilane The reaction is carried out to form di [di (trialkylsilyl) aminoalkyl] di (cycloalkadienyl) silane, a lithium group is introduced into the cycloalkadienyl group of the silane, and a tetrahalide of a transition metal is further reacted. And a method for producing the catalyst component for olefin polymerization, which further comprises reducing an amino group with an alcohol to synthesize an electron-donating group-containing metallocene compound having an amino group as an electron-donating group, and a halogen. Reaction of halogenated alkyl trialkylsilane with trialkylhalosilane And silanols, and Grignard reagent is reacted with magnesium in the silanol,
The reagent is reacted with di (cycloalkadienyl) dihalosilane to give di (trialkylsiloxyalkyl) di (cycloalkadienyl) silane, a lithium group is introduced into the cycloalkadienyl group of the silane, and further transition reacting a tetrahalide of a metal, a manufacturing method of the olefin polymerization catalysts components in which further synthesis is oxidized to alcohol groups electron donating group-containing metallocene compounds having an alcohol group as the electron-donating group with an acid ,.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0025

[Correction method] Change

[Correction content]

[0025]

[Chemical 3]

[Procedure 3]

[Document name to be amended] Statement

[Name of item to be corrected] 0027

[Correction method] Change

[Correction content]

[0027]

[Chemical 4]

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0038

[Correction method] Change

[Correction content]

Synthesis of metallocene compound represented by the following structural formula [Synthesis by reaction formula of scheme (I)]

[Chemical 7]

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0041

[Correction method] Change

[Correction content]

(Ii) Metallocene synthesis SiCl ₄ (0.0117 mol ) was added to THF 200 m.
It is dissolved in 1, and here, CpLi (0.0234 mol)
Was added little by little. After stirring for 1.5 hours, the solvent was distilled off under reduced pressure, and then 200 ml of heptane was introduced. After filtration, the heptane was distilled off to remove Cl ₂ SiCp.
₂ (yield, 100%) was obtained. On the other hand, a Grignard reagent was prepared in THF from the compound prepared in (i) and Mg. Then, Cl ₂ SiCp ₂ is added to THF 20.
Dissolve in 0 ml and mix above Grignard reagent with Cl ₂ Si
The Grignard reagent was introduced so that Cp ₂ became 2: 1 (molar ratio). After stirring overnight at room temperature, THF was distilled off under reduced pressure. Then, 200 ml of heptane was introduced and filtered, and then heptane was distilled off under reduced pressure to obtain a metallocene ligand with a yield of 93%.

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0043

[Correction method] Change

[Correction content]

The (iii) The desilylation _{[(Me 3 Si) 2 N (} CH 2) 3 ] ₂ -Si
-Cp ₂ ZrCl ₂ solution 8 equivalents of methanol was added and after stirring for 2 hours at room temperature, the methanol was removed and the solvent under reduced pressure. Extract metallocene from the residue with an extraction solvent,
The title metallocene compound was obtained by drying. Preparation of metallocene-supported catalyst 10.5 g of the white magnesium-containing solid obtained in 10
It was suspended in 0 ml of toluene, and 100 ml of a toluene solution of 0.9 g of the metallocene compound obtained here was introduced. This solution was heat-treated at 80 ° C. for 2 hours, and then the solid portion was treated with 100 ml of toluene twice and then 100 times each.
It was washed 5 times with ml of hexane. Finally, it was dried under reduced pressure to obtain a solid component containing 1.9 wt% Zr. Polymerization of ethylene The polymerization of ethylene was carried out by the usual method. However, 19 mg of white granular polyethylene was obtained by using 10 mg of the supported catalyst, methylalumoxane as the cocatalyst (Al / Zr = 1000 mol ratio), and toluene as the solvent. The bulk density of the obtained polymer is 0.42 g / m.
It was l.

[Procedure Amendment 7]

[Document name to be amended] Statement

[Name of item to be corrected] 0045

[Correction method] Change

[Correction content]

Synthesis of metallocene compound represented by the following structural formula [Synthesis by reaction formula of scheme (II)]

[Chemical 9]

[Procedure Amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0047

[Correction method] Change

[Correction content]

In a 1-liter three-necked flask equipped with a dropping funnel and a condenser, 65 g of trichlorosilane, 47
g of pyridine and 500 ml of hexane were charged. With stirring, 70 g of 3-bromopropyl alcohol was added dropwise over 2 hours. After completion of the dropwise addition, the mixture was refluxed for 1 hour, then the salt was filtered off and distilled to obtain 77 g of 3-bromo-1-trimethylsiloxypropane. Boiling point 87 ° C / 5mmHg,
Yield 72%. (Ii) Metallocene synthesis SiCl ₄ (0.0117 mol ) in THF 200 m
It is dissolved in 1, and here, CpLi (0.0234 mol)
Was added little by little. After stirring for 1.5 hours, the solvent was distilled off under reduced pressure, and then 200 ml of heptane was introduced. After filtration, the heptane was distilled off to remove Cl ₂ SiCp.
₂ (yield 100%) was obtained. On the other hand, a Grignard reagent was prepared in THF from the compound prepared in (i) and Mg.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Masahide Murata 1-3-1 Nishitsurugaoka, Oi-cho, Iruma-gun, Saitama Prefecture Tonen Corporation Research Institute (72) Inventor Satoshi Ueki Nishitsurugaoka, Oi-cho, Iruma-gun, Saitama Prefecture 1- 3-1 Inside Tonen Research Institute

Claims (3)

[Claims] 1. A catalyst component for olefin polymerization, comprising a metallocene compound having an electron-donating group supported on a solid in which a Lewis acidic component is supported on an inorganic carrier. 2. A method for producing a catalyst component for olefin polymerization, which comprises synthesizing a metallocene compound having an electron-donating group and bringing the metallocene compound into contact with a solid having a Lewis acidic component supported on an inorganic carrier. 3. An olefin is produced by using a catalyst system comprising an alumoxane and an olefin polymerization catalyst component in which a metallocene compound containing an electron donating group is supported on a solid in which a Lewis acidic component is supported on an inorganic carrier. A method for producing a (co) polymerized polyolefin.