JPH0149165B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for highly active polymerization or copolymerization of α-olefins with good stereoregularity using a novel catalyst. Catalysts comprising titanium halides and organoaluminum compounds have been known as highly stereoregular polymerization catalysts for α-olefins. However, in polymerization using this catalyst system, although a highly stereoregular polymer can be obtained, the catalyst activity is low, so it is necessary to remove catalyst residues from the produced polymer. In recent years, many proposals have been made to improve the activity of catalysts. According to these proposals
It has been shown that a highly active catalyst can be obtained by using a catalyst component in which titanium tetrachloride is supported on an inorganic solid support such as MgCl ₂ . However, in the production of polyolefins, it is preferable that the catalyst activity be as high as possible, and catalysts with even higher activity have been desired. It is also important that the amount of atactic moieties formed in the polymer be as small as possible. In addition, in these known techniques, the average particle size of the resulting polymer is relatively small and the particle size distribution is generally wide, so there is a large proportion of fine powder particles, and improvements have been strongly desired from the viewpoint of productivity and slurry handling. . Furthermore, when molding these polymers, problems such as generation of dust and reduction in efficiency during molding occur, so the above-mentioned increase in bulk specific gravity,
It was strongly desired to reduce the particulate powder fraction.
Furthermore, improvements are still needed in order to omit the pelletizing step, which has been in increasing demand in recent years, and to directly apply the powdered polymer to a processing machine. The present inventors have proposed a technique for improving the particle properties of such polymers in Japanese Patent Application No. 56-42528, but when propylene is polymerized using this catalyst system, polymers with low stereoregularity Only coalescence was obtained, and further improvement was desired from the point of view of polymerization activity. As a result of intensive research on these points, the present inventors have discovered a novel catalyst here. That is, the present invention relates to a method for producing extremely highly active and highly stereoregular polyolefin using a novel catalyst. By using the catalyst of the present invention, the monomer partial pressure during polymerization is low and With short polymerization, the amount of catalyst residue in the produced polymer is extremely small, so the catalyst removal step can be omitted in the polyolefin manufacturing process, and the amount of attic moieties produced in the produced polymer is also extremely small. Effects can be obtained. Furthermore, the present inventors have conducted extensive research with the aim of obtaining a polymer that has a high bulk specific gravity, a large average particle size, a narrow particle size distribution, and a significantly reduced amount of fine particles. ,
This has led to the present invention. By using the method of the present invention, a polyolefin with a large average particle size, a narrow particle size distribution, and a good stereoregularity with a small particulate portion can be obtained with high activity, and the bulk specific gravity of the produced polyolefin is high. Furthermore, it can be used not only as pellets but also as a powder and can be subjected to molding, causing fewer troubles during molding, making it possible to produce polyolefins extremely advantageously. The present invention provides a novel catalyst system that has many of these features and improves on the drawbacks of the prior art described above, and it is surprising that these points can be easily achieved by using the catalyst of the present invention. I have to say it's the right thing to do. The present invention will be specifically explained below. That is,
The present invention [](1) silicon oxide and/or aluminum oxide, (2) magnesium dihalide (hereinafter abbreviated as magnesium halide) and the general formula Me
(OR) _o X _zo (Here, Me represents B, Mg or Al. R represents a hydrocarbon residue having 1 to 24 carbon atoms,
X represents a halogen atom. z represents the valence of Me, and n satisfies 0<n≦z. ) reaction product with a compound represented by (3) general formula

[Formula] (where R ¹ , R ² , and R ³ represent a hydrocarbon residue or an alkoxy group having 1 to 24 carbon atoms, and R ⁴ represents a carbon number of 1 to 24
The hydrocarbon residue of n is 1≦n≦30), and (4) a compound represented by the general formula Ti(OR) _n X _4-n (where R is 1 carbon number
-20 alkyl, aryl or aralkyl groups, and X represents a halogen atom. m
is 0≦m≦4. ) A solid catalyst component obtained by contacting titanium compounds (hereinafter abbreviated as titanium compounds) with each other and reacting, [] General formula

[Formula] (where R ¹ , R ² , and R ³ represent a hydrocarbon residue having 1 to 24 carbon atoms or an alkoxy group, and R ⁴ represents a hydrocarbon residue having 1 to 24 carbon atoms. n is 1 ≦n≦30.)
The present invention relates to a method for producing a polyolefin, which comprises polymerizing or copolymerizing an α-olefin using a catalyst system comprising a combination of a compound represented by the formula and an organoaluminum compound (hereinafter abbreviated as an organometallic compound). The silicon oxide used in the present invention is silica or a double oxide of silicon and at least one other metal of groups 1 to 10 of the periodic table. The aluminum oxide used in the present invention is alumina or aluminum and the periodic table ~
It is a double oxide with at least one other metal of the group. Typical double oxides of silicon or aluminum and at least one other metal from Groups ~ of the periodic table include Al ₂ O ₃ · MgO, Al ₂ O ₃ · CaO,
Al ₂ O ₃・SiO ₂ , Al ₂ O ₃・MgO・CaO, Al ₂ O ₃・
MgO・SiO ₂ , Al ₂ O ₃・CuO, Al ₂ O ₃・Fe ₂ O ₃ ,
Various natural or synthetic complex oxides such as Al ₂ O ₃ ·NiO and SiO ₂ ·MgO can be exemplified. Here, the above formula is not a molecular formula but represents only the composition, and the structure and component ratio of the multiple oxide used in the present invention are not particularly limited. It goes without saying that the silicon oxide and/or aluminum oxide used in the present invention may adsorb a small amount of water without any problem, and can be used without any problem even if it contains a small amount of impurities. The magnesium halide used in the present invention is substantially anhydrous and includes magnesium fluoride, magnesium chloride, magnesium bromide, and magnesium iodide, with magnesium chloride being particularly preferred. In the present invention, these magnesium halides may be treated with an electron donor such as alcohol, ester, ketone, carboxylic acid, ether amine, or phosphine. General formula Me(OR) _o used in the present invention
X _zo (Here, Me represents B, Mg, or Al. R represents a hydrocarbon residue having 1 to 24 carbon atoms, and X represents a halogen atom. z represents the valence of Me, and n represents 0<
Examples of compounds represented by n≦z include Mg(OR) ₂ , Mg(OR)X, Al(OR) ₃ , Al
₍ OR _{) 2} X, B ₍ OR) ₃ , _B (OR) _{2 2} , Mg
(OC ₃ H ₇ ) ₂ , Al(OCH ₃ ) ₃ , Al(OC ₂ H ₅ ) ₃ , Al
( _OC2H5 ) _2Cl , Al _{( OC3H7} ) _{3 ,} Al( _OC4H9 ) ₃ , _Al
Examples include compounds such as (OC ₆ H ₅ ) ₃ , B(OC ₂ H ₅ ) ₃ and B(OC ₂ H ₅ ) ₂ Cl. In the present invention, in particular, the general formula Mg(OR) _o
Compounds represented by X _2-o , Al(OR) _o X _3-o and B(OR) _o X _3-o are preferred. Moreover, as R, an alkyl group having 1 to 4 carbon atoms and a phenyl group are particularly preferable. Magnesium halide and general formula Me(OR) _o
The method of reaction with the compound represented by X _zo is not particularly limited; ℃
The mixture and heating reaction may be carried out at a temperature of 5 minutes to 10 hours, or the reaction may be carried out by co-pulverization. In the present invention, a method using co-pulverization is particularly preferred. The equipment used for co-pulverization is not particularly limited, but ball mills, vibration mills, rod mills, impact mills, etc. are usually used, and those skilled in the art can easily determine conditions such as grinding temperature and grinding time depending on the grinding method. It is something that can be done. Generally, the grinding temperature is 0°C to 200°C, preferably 20°C to 100°C,
The grinding time is 0.5 to 50 hours, preferably 1 to 30 hours. Of course, these operations should be carried out in an inert gas atmosphere, and moisture should be avoided as much as possible. Magnesium halide and general formula Me(OR) _o
The reaction rate with the compound represented by X _zo is Mg:
Me (molar ratio) is 1:0.01 to 10, preferably 1:
A range of 0.01 to 5 is desirable. General formula used in the present invention

[Formula] (where R ¹ , R ² and R ³ represent a hydrocarbon group having 1 to 24 carbon atoms, preferably 1 to 18 carbon atoms, an alkoxy group, hydrogen or a halogen, and R ⁴ has 1 to 24 carbon atoms, preferably represents a hydrocarbon residue of 1 to 18, n is 1≦n≦30. −
Butoxysilane, monomethyltriisopropoxysilane, monomethyltripentoxysilane, monomethyltrioctoxysilane, monomethyltristearoxysilane, monomethyltriphenoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiisopropoxysilane, dimethyldiphenoxysilane Sisilane, trimethylmonomethoxysilane, trimethylmonoethoxysilane, trimethylmonoisopropoxysilane, trimethylmonophenoxysilane, monoethyltrimethoxysilane, monoethyltriethoxysilane,
Monoethyltriisopropoxysilane, monoethyltriphenoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldiphenoxysilane, triethylmonomethoxysilane, triethylmonoethoxysilane, triethylmonophenoxysilane, monoisopropyltrimethoxysilane , mono n-butyltrimethoxysilane, mono n-butyltriethoxysilane, mono
The repeating unit obtained by condensing sec-butyltriethoxysilane, monophenyltriethoxysilane, diphenyldiethoxysilane, tetraethoxysilane, tetraisopropoxysilane and the above compounds is

Chain or cyclic polysiloxanes represented by the formula can be mentioned. It can also be used as a mixture of these. The titanium compound used in the present invention has the general formula _Ti (OR) _o
X represents a halogen atom. n is 0≦n≦4), titanium tetrachloride,
Titanium tetrabromide, titanium tetraiodide, monomethoxytrichlorotitanium, dimethoxydichlorotitanium, trimethoxymonochlorotitanium, tetramethoxytitanium, monoethoxytrichlorotitanium, diethoxydichlorotitanium, triethoxymonochlorotitanium, tetraethoxytitanium, monoisopropoxy Trichlorotitanium, diisopropoxydichlorotitanium, triisopropoxymonochlorotitanium, tetraisopropoxytitanium, monobutoxytrichlorotitanium, dibutoxydichlorotitanium, monopentoxytrichlorotitanium, monophenoxytrichlorotitanium, diphenoxydichlorotitanium, triphenoxytitanium Examples include cymonochlorotitanium and tetraphenoxytitanium. As the organometallic compound used in the present invention, an organoaluminum compound known as a component of Ziegler's catalyst is used. Specific examples include general formulas R ₃ Al, R ₂ AlX, RAlX ₂ , R ₂ AlOR, RAl
(OR) _{An organoaluminum compound represented by X and R 3 Al 2} are preferred, and triethylaluminum, triisopropylaluminium, triisobutylaluminum,
Examples include trisec-butylaluminum, tritert-butylaluminum, trihexylaluminum, trioctylaluminum, dodecylaluminum, diethylaluminum chloride, diisopropylaluminum chloride, diethylaluminum monoethoxide, ethylaluminum sesquichloride, and mixtures thereof. . In the present invention, the amount of the organometallic compound used is not particularly limited, but is usually
Can be used in 01 to 1000 mol times. Moreover, esters of organic carboxylic acids such as benzoic acid, o- or p-toluic acid, and p-anisic acid can also be used together with these organometallic compounds.
In the present invention, (1) silicon oxide and/or aluminum oxide (hereinafter abbreviated as component []-(1)), (2) magnesium halide and the general formula Me
(OR) Reaction product with the compound represented by _o X _zo (hereinafter abbreviated as component []-(2)), (3) General formula

The compound represented by [Formula] (hereinafter abbreviated as component []-(3)) and (4) titanium compound (hereinafter abbreviated as component []-(4)) are brought into contact with each other and reacted. There are no particular restrictions on the order and contact method. The contact order is component []-(1) and component []
After contacting -(2), component []-(3) may be brought into contact and then component []-(4) may be brought into contact, or component []-(1) and component []-(3) may be brought into contact with component []-(4). ) may be contacted with component []-(2) and component []-(4). Further, the contact method is not particularly limited, and any known method can be employed. That is, a method of reacting in the presence or absence of an inert solvent at a temperature of 20 to 400°C, preferably 50 to 300°C for usually 5 minutes to 20 hours, a method of co-pulverization, or a method of using these methods as appropriate. The reaction may be carried out by combining them. The inert solvent is not particularly limited, and hydrocarbon compounds and/or derivatives thereof that do not normally inactivate the Ziegler type catalyst can be used. Specific examples of these include propane,
Various aliphatic saturated hydrocarbons such as butane, pentane, hexane, heptane, octane, benzene, toluene, xylene, cyclohexane, aromatic hydrocarbons, alicyclic hydrocarbons, and ethanol, diethyl ether, tetrahydrofuran, ethyl acetate,
Alcohols such as ethyl benzoate, ethers,
Examples include esters. When the reaction is carried out by co-pulverization, those skilled in the art can easily determine conditions such as pulverization temperature and pulverization time depending on the pulverization method used. Generally the grinding temperature is 0-200℃, preferably 20℃
-100°C, and the grinding time is 05-50 hours, preferably 1-30 hours. Of course, these operations should be carried out in an inert gas atmosphere, and moisture should be avoided as much as possible. Most preferred component []-(1) in the present invention,
The order and method of contacting []-(2), []-(3) and []-(4) are as follows. That is, first, a solvent in which the reaction product of component []-(2) magnesium halide and a compound represented by the general formula Me(OR) _o X _zo is dissolved is used, and component []-(1) is dissolved in the solvent. ) and component []-(2) at 0 to 300°C, preferably 10 to 200°C, most preferably 20 to 100°C, for 1 minute to 48 hours, preferably 2
Do this for minutes to 10 hours. The above solvent includes alcohol,
Tetrahydrofuran, ethyl acetate and the like are preferably used. In this case, component []-(1) and component []
The contact ratio of -(2) is 0.01 to 5 g, preferably 0.1 to 2 g of component []-(2) per 1 g of component []-(1). After the reaction, the solvent is removed to obtain a contact product of component []-(1) and component []-(2). Next, the general formula of component []-(3) is added to the contact product of component []-(1) and component []-(2) above.

The compound represented by [Formula] is added directly or in the presence of an inert solvent such as hexane, heptane, octane, benzene, toluene, etc. at a temperature of 20 to
It is desirable to conduct the reaction at 400°C, preferably 50 to 300°C, for 5 minutes to 20 hours. Furthermore, there is no problem in simultaneously mixing and reacting magnesium halide, a compound represented by the general formula Me(OR) _o X _zo , and component []-(3). The contact ratio between the contact product of component []-(1) and component []-(2) and the contact ratio of component []-(3) is the contact product of component []-(1) and component []-(2). Ingredients per 1g []-
(3) 0.01 to 5 g, preferably 0.1 to 2 g. Next, the titanium compound of component []-(4) is directly added to the contact product of component []-(1), component []-(2), and component []-(3), or hexane, heptane, etc. , in the presence of an inert solvent such as octane, benzene, toluene, etc., at a temperature of 20-300°C, preferably 50-300°C.
Heat and mix at 150℃ for 5 minutes to 10 hours to prepare component []-(1), component []-(2), and component []-(3).
A titanium compound is supported on the contact product. Preferably, the titanium compound and/or vanadium compound of component []-(4) is added to the contact product of component []-(1), component []-(2), and component []-(3) without a solvent. , at a temperature of 20-300℃, preferably 50-150℃.
Heat mixing is performed for 10 minutes to 10 hours, and the contact products of component []-(1), component []-(2), and component []-(3) are combined with the titanium compound of component []-(4) and/or Or support a vanadium compound. At this time, the amount of component []-(4) used is such that the amount of titanium compound contained in the produced solid component is 0.5 to 50% by weight, preferably 1 to 20% by weight. After completion of the reaction, unreacted titanium compounds and/or vanadium compounds are removed by washing the Ziegler catalyst several times with an inert solvent, and then the solvent is evaporated under reduced pressure to obtain a solid powder. In the present invention, the general formula used for the contact component []

If the amount of the compound represented by [Formula] is too large or too small, no effect can be expected, and it is usually 0.1 to 100 mol, preferably 0.1 to 100 mol, per 1 mol of the titanium compound in the catalyst component [].
It is within the range of 0.3 to 20 moles. In addition, in the present invention, the general formula of component []

The compound represented by the formula may be used by reacting with the organometallic compound described above. The reaction rate at this time is the general formula

[Formula]: Organometallic compound (molar ratio) is in the range of 1:500 to 1:1, more preferably in the range of 1:100 to 1:2. general formula

The amount of the product obtained by reacting [formula] with the organometallic compound is Si:Ti (molar ratio) based on the titanium compound in the catalyst component [].
is preferably in the range of 0.1:1 to 100:1, and 0.3:1
A range of ˜20:1 is more preferred. Olefin polymerization using the catalyst of the present invention can be carried out by slurry polymerization, solution polymerization or gas phase polymerization. In particular, the catalyst of the present invention can be suitably used for gas phase polymerization, and the polymerization reaction is carried out in the same manner as an olefin polymerization reaction using a normal Ziegler type catalyst. That is, all reactions are carried out in the presence or absence of inert hydrocarbons, substantially deprived of oxygen, water, and the like. The polymerization conditions for olefin are as follows: temperature is 20 to 120℃, preferably
The temperature is 50 to 100℃, and the pressure is normal pressure to 70Kg/
cm ² , preferably 2 to 60 Kg/cm ² . Although the molecular weight can be adjusted to some extent by changing polymerization conditions such as polymerization temperature and catalyst molar ratio, it is effectively carried out by adding hydrogen to the polymerization system. Of course, using the catalyst of the present invention, a two-step or more multi-step polymerization reaction with different polymerization conditions such as monomer type, concentration, hydrogen concentration, polymerization temperature, etc. can be carried out without any problem. That is, it can be used very suitably in the production of so-called block copolymers, which is commonly carried out in polypropylene production processes. The method of the present invention is applicable to the polymerization of all α-olefins that can be polymerized using a Ziegler catalyst, and α-olefins having 3 to 12 carbon atoms are particularly preferred, such as propylene, 1-butene, 1-hexene,
Homopolymerization of α-olefins such as 4-methylpentene-1, and polymerization of α-olefins with each other or α-olefins.
- Suitable for use in copolymerization of olefins with other olefins, copolymerization of ethylene with two or more other α-olefins, etc. Copolymerization with dienes is also preferably carried out for the purpose of modifying polyolefins. Examples of diene compounds used at this time include butadiene, 1,4-hexadiene, ethylidenenorbornene, dicyclopentadiene, and the like. In the present invention, it can be particularly effectively used to polymerize or copolymerize α-olefins having 3 to 8 carbon atoms with good stereoregularity. Examples will be described below, but these are for illustrative purposes to carry out the present invention, and the present invention is not limited thereto. Example 1 (a) Preparation of solid catalyst component 10 g of commercially available anhydrous magnesium chloride and aluminum triethoxide were placed in a 400 ml stainless steel pot containing 25 1/2 inch diameter stainless steel balls.
4.2 g was added and ball milling was performed at room temperature under a nitrogen atmosphere for 16 hours to obtain a reaction product. A three-neck flask equipped with a stirrer and a reflux condenser was purged with nitrogen, and 5 g of the above reaction product and 5 g of silica (Fuji Davison, #952) calcined at 600°C were placed in the three-neck flask, and then tetrahydrofuran was added. After adding 100ml and reacting at 60℃ for 2 hours, drying under reduced pressure at 120℃,
Tetrahydrofuran was removed. Next, 50 ml of hexane was added and stirred, and then 1 ml of tetraethoxysilane was added and reacted for 2 hours under refluxing hexane to obtain a solid powder (A). The solid powder (A) obtained above was mixed with titanium tetrachloride 30
ml, reacted at 120°C for 2 hours, and washed with hexane until titanium tetrachloride was no longer detected in hexane to obtain a solid catalyst component.
The content of titanium in 1 g of the obtained solid catalyst component was 70 mg. (b) Gas-phase polymerization The gas-phase polymerization apparatus is a
A stainless steel autoclave was used. 100 mg of the above solid catalyst component and 2.5 m of triethylaluminum were placed in an autoclave adjusted to 60°C.
mol and phenyltriethoxysilane 0.5m
mol, and polymerization was carried out for 8 hours by continuously supplying propylene so that the total pressure was 8.5 Kg/cm ² ·G. 450 g of spherical polypropylene with a bulk density of 0.40 and an average particle size of 1000 μm was produced. Catalytic activity is
It was 64000g polypropylene/gTi. The residual percentage of this polypropylene extracted with boiling heptane was 87% by weight. Comparative Example 1 (a) Production of solid catalyst component A catalyst was produced in the same manner as in Example 1 except that tetraethoxysilane was not added. Obtained solid catalyst component 1
The titanium content in g was 35 mg. (b) Gas phase polymerization In Example 1, polymerization was carried out in the same manner as in Example 1 except that phenyltriethoxysilane was not added. 150 g of polypropylene with a bulk density of 0.35 and an average particle size of 700 μm was produced. The catalyst activity was 43000 g polypropylene/g Ti. The residual rate of extraction of this polypropylene with boiling heptane is 40% by weight.
It was hot. Example 2 (a) Production of solid catalyst component 10 g of commercially available anhydrous magnesium chloride and 4.2 g of aluminum triethoxide were placed in the ball mill pot described in Example 1, and ball milling was performed at room temperature under a nitrogen atmosphere for 16 hours to obtain a reaction product. I got it. 2.5 g of the above reaction product and 7.5 g of silica (Fuji Davison, #952) calcined at 600°C were placed in the 3-necked flask described in Example 1, and then 100 ml of tetrahydrofuran was added and reacted at 60°C for 2 hours. Afterwards, it was dried under reduced pressure at 120°C to remove tetrahydrofuran. next,
After adding 50 ml of hexane and stirring, 1 ml of diethyldiethoxysilane was added and reacted for 2 hours under refluxing hexane to obtain a solid powder (B). The solid powder (B) obtained above was mixed with titanium tetrachloride 30
ml, reacted at 120°C for 2 hours, and washed with hexane until titanium tetrachloride was no longer detected in hexane to obtain a solid catalyst component.
The content of titanium in 1 g of the obtained solid catalyst component was 60 mg. (b) Gas phase polymerization The following gas phase polymerization was carried out using the apparatus described in Example 1. In an autoclave adjusted to 60℃, add 100 mg of the above solid catalyst component and 2.5 mg of triethylaluminum.
mmol, and phenyltriethoxysilane
0.5 mmol was added, and propylene was continuously supplied so that the total pressure was 8.5 Kg/cm ² ·G, and polymerization was carried out for 8 hours. 430 g of spherical polypropylene with a bulk density of 0.45 and an average particle size of 900 μm was produced. Also, the catalyst activity is 72000g polypropylene/g
It was Ti. The residual percentage of this polypropylene extracted with boiling heptane was 89% by weight. Example 3 (a) Production of solid catalyst component 10 g of commercially available anhydrous magnesium chloride and 1.3 g of magnesium diethoxide were placed in the ball mill pot described in Example 1, and ball milling was performed at room temperature under a nitrogen atmosphere for 16 hours to obtain a reaction product. I got it. 5 g of the above reaction product and 5 g of alumina calcined at 600°C were placed in the three-necked flask described in Example 1, and then 100 g of tetrahydrofuran was added.
ml and reacted at 60℃ for 2 hours,
Drying was performed under reduced pressure at 120°C to remove tetrahydrofuran. Next, 50 ml of hexane was added and stirred, and then 2 ml of tetraethoxysilane was added and reacted for 2 hours under refluxing hexane to form a solid powder.
I got (C). The solid powder (C) obtained above was mixed with titanium tetrachloride 30
ml, reacted at 120°C for 2 hours, and washed with hexane until titanium tetrachloride was no longer detected in hexane to obtain a solid catalyst component. The content of titanium in 1 g of the obtained solid catalyst component was 100 mg. (b) Gas phase polymerization The following gas phase polymerization was carried out using the apparatus described in Example 1. In an autoclave adjusted to 60℃, add 100 mg of the above solid catalyst component and 2.5 mg of triethylaluminum.
mmol, and 0.7 m of tetraethoxysilane
mol, and propylene was continuously supplied so that the total pressure was 8.5 Kg/cm ² ·G, and polymerization was carried out for 8 hours. 500 g of spherical polypropylene with a bulk density of 0.41 and an average particle size of 950 μm was produced. Catalytic activity is 50000
g polypropylene/g Ti, and the residual ratio after extraction with boiling heptane was 92% by weight. Example 4 (a) Production of solid catalyst component 10 g of commercially available anhydrous magnesium chloride and 4.2 g of aluminum triethoxide were placed in the ball mill pot described in Example 1, and ball milling was performed at room temperature under a nitrogen atmosphere for 16 hours to obtain a reaction product. I got it. 5 g of the above reaction product and 5 g of alumina calcined at 600°C were placed in the three-necked flask described in Example 1, and then tetrahydrofuran was added.
After adding 100ml and reacting at 60℃ for 2 hours,
Drying was performed under reduced pressure at 120°C to remove tetrahydrofuran. Next, 50 ml of hexane was added and stirred, and then 2 ml of diethyldiethoxysilane was added and reacted for 2 hours under refluxing hexane to obtain a solid powder (D). The solid powder (D) obtained above was mixed with titanium tetrachloride 30
ml, reacted at 120°C for 2 hours, and washed with hexane until titanium tetrachloride was no longer detected in hexane to obtain a solid catalyst component. The content of titanium in 1 g of the obtained solid catalyst component was 75 mg. (b) Gas phase polymerization The following gas phase polymerization was carried out using the apparatus described in Example 1. In an autoclave adjusted to 60℃, add 100 mg of the above solid catalyst component and 2.5 mg of triethylaluminum.
mmol, and diethyldiethoxysilane
0.5 mmol was added, and propylene was continuously supplied so that the total pressure was 8.5 Kg/cm ² ·G, and polymerization was carried out for 8 hours. 450 g of spherical polypropylene with a bulk density of 0.40 and an average particle size of 980 μm was produced. Catalytic activity is 60000g polypropylene/gTi, and extraction residue with boiling heptane is 90% by weight.
It was hot. Example 5 A stainless steel autoclave equipped with an induction stirrer was replaced with nitrogen, and 1000 ml of hexane was added.
2.5 mmol of triethylaluminum and 50 mg of the solid catalyst component obtained in Example 1 were added, and further 0.25 mmol of phenyltriethoxysilane was added, and the temperature was raised to 50° C. with stirring. Next, propylene was charged to 85Kg/cm ²・G to start polymerization.
Polymerization was carried out for 8 hours while maintaining the autoclave pressure at 8.5 kg/cm ² ·G. After the polymerization was completed, the polymer slurry was transferred to a beaker, and hexane was removed under reduced pressure to obtain 34.4 g of polypropylene. This polypropylene has a bulk density of 0.41 and an average particle size
They were spherical particles of 1300 μm. Catalyst activity is 98000
g polypropylene/g Ti. The residual rate after extraction with boiling heptane was 75% by weight.

[Brief explanation of drawings]

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

Claims (1)

[Claims] 1 [](1) Silicon oxide and/or aluminum oxide, (2) Magnesium dihalide and general formula Me
(OR) _o X _zo (Here, Me represents B, Mg or Al. R represents a hydrocarbon residue having 1 to 24 carbon atoms,
X represents a halogen atom. z represents the valence of Me, and n satisfies 0<n≦z. ) reaction product with a compound represented by (3) general formula (Here, R ¹ , R ² , R ³ represent a hydrocarbon residue having 1 to 24 carbon atoms or an alkoxy group, and R ⁴ represents a hydrocarbon residue having 1 to 24 carbon atoms. n is 1
≦n≦30), and (4) a compound represented by the general formula Ti(OR) _o X _4-o (where R is a carbon number of 1
-20 alkyl, aryl or aralkyl groups, and X represents a halogen atom. n
is 0≦n≦4)) A solid catalyst component obtained by contacting and reacting titanium compounds represented by [] General formula (Here, R ¹ , R ² , R ³ represent a hydrocarbon residue having 1 to 24 carbon atoms or an alkoxy group, and R ⁴ represents a hydrocarbon residue having 1 to 24 carbon atoms. n is 1≦n≦
A method for producing a polyolefin, which comprises polymerizing or copolymerizing an α-olefin using a catalyst system comprising a combination of a compound represented by 30) and an organoaluminum compound.