JPH0762016A - Method for producing polyolefin - Google Patents

Abstract

(57) [Summary] (Modified) [Purpose] A polyolefin with a narrow molecular weight distribution that increases the polymer yield, eliminates the step of removing catalyst residues, increases the bulk density, and produces large good particles. A method of manufacturing. [Structure] Production of a polyolefin using a solid catalyst component obtained by reacting the solids [I], [II], [III] and [IV]. [I] (1) Silicon oxide and / or aluminum oxide, and (2) Titanium compound or reaction product of titanium compound and vanadium compound [II] (1) Magnesium halide, (2) General A compound represented by the formula Me (OR) _n X _z-n (Me is an element of I to IV groups of the periodic table, X is a halogen atom, R is a hydrocarbon residue having 1 to 20 carbon atoms), and ( 3) Titanium compound or a reaction product obtained by reacting a titanium compound with a vanadium compound [III] organoaluminum compound [IV] Si—O—C bond and / or Si—N—C
Silicon compound having a bond

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel method for producing a polyolefin. More specifically, the present invention significantly increases the polymer yield per solids and the polymer yield per transition metal, thereby eliminating the step of removing catalyst residues in the polymer, and the bulk of the resulting polymer. The present invention relates to a method for increasing the density and reducing the finely divided portion of the produced polymer to produce good particles having a large average particle size, and at the same time, for producing a polyolefin having a narrow molecular weight distribution.

[0002]

PRIOR ART AND PROBLEMS TO BE SOLVED BY THE INVENTION Conventionally, in this kind of technical field, magnesium halide,
Many catalysts are known in which an inorganic magnesium solid such as magnesium oxide or magnesium hydroxide is used as a carrier and a compound of a transition metal such as titanium or vanadium is supported on the carrier. However, in these known techniques, the bulk density of the obtained polyolefin is generally small, the average particle size is relatively small, and the particle size distribution is generally wide, so that there are many fine particle powder parts, and therefore, when molding and processing the polymer. Since problems such as generation of dust and a decrease in efficiency during molding occur, improvement in productivity and polymer handling has been strongly desired. Furthermore, improvement is still needed in order to omit the pelletization process, which has been increasing in demand in recent years, and to directly apply the powdery polymer to a processing machine.

The inventors of the present invention have previously found a new catalyst component that has improved the above-mentioned drawbacks, and have already filed various patent applications (Japanese Patent Publication No. 11651/1989, Japanese Patent Publication No. 12289/1988).
0-149605, JP 62-32105, JP 6
2-207306). When these catalyst components are used, a polymer having a high bulk density and a large average particle diameter can be obtained, but further improvement is required in order to omit the pelletizing step and directly apply the powdered polymer to a processing machine. Was done.

The present invention is intended to improve these drawbacks and to obtain a polymer having a high bulk density, a narrow particle size distribution, a remarkably small amount of fine particles of the polymer, and a good fluidity with extremely high activity. As a result of intensive research, the present invention has reached the present invention.

[0005]

That is, the present invention provides a method for polymerizing or copolymerizing an olefin by using a solid catalyst component and an organometallic compound as a catalyst, wherein the solid catalyst component has the following [I], [II], It relates to a method for producing a polyolefin, which is a reaction product obtained by reacting [III] and [IV] with each other.

[I] (1) Silicon oxide and / or aluminum oxide, and (2) Titanium compound or reaction product obtained by mutually reacting titanium compound and vanadium compound [II] (1) Halogenation magnesium, (2) the general formula _{Me (OR) n X z-} n ( wherein Me periodic table I~I
V group element, z is valence of element Me, n is 0 <n ≦ z,
X is a halogen atom, R is a hydrocarbon residue having 1 to 20 carbon atoms), and (3) a titanium compound or a reaction product obtained by mutually reacting a titanium compound and a vanadium compound. [III] Organoaluminum compound [IV] Silicon compound having at least one Si—O—C bond and / or at least one Si—N—C bond

By using the method of the present invention, a polyolefin having a relatively large average particle size, a narrow particle size distribution, and a small amount of fine particles can be obtained with extremely high activity, and the bulk specific gravity of the produced polyolefin is high and free flowing. It is also very advantageous in polymerization operation such as good property, and it can be used for molding not only when it is used as pellets but also in powder form, and there is no significant trouble during molding. can get.

The polymer obtained by using the catalyst of the present invention is also characterized in that the molecular weight distribution is extremely narrow, the hexane extraction amount is small, and the by-products of low-polymerization products are very small. Therefore, when the polyolefin having a narrow molecular weight distribution obtained by the method of the present invention is used for a film, it has many advantages such as high strength, excellent transparency, and excellent antiblocking property and heat sealing property. .

The present invention will be specifically described below.

The catalyst used in the method for producing a polyolefin of the present invention is [I] (1) silicon oxide and / or aluminum oxide ([I]-(1)) (2) titanium compound or titanium compound and vanadium compound. ([I]-(2)) to obtain a reaction product (component [I] component), and [II] (1) magnesium halide ([II]-
(1)) (2) General formula Me (OR) _n X _z-n (where Me is an element of Group I to IV of the periodic table, z is a valence of the element Me, and n is 0 <n ≦ z, X). Is a halogen atom, and R is a hydrocarbon residue having 1 to 20 carbon atoms) ([II]-
(2)) (3) Titanium compound or reaction product (component [II]) obtained by reacting titanium compound with vanadium compound ([II]-(3)), and [III] organoaluminum compound (Component [III]) and [IV] Silicon compounds having at least one Si—O—C bond and / or at least one Si—N—C bond (Component [IV]) are reacted with each other. It consists of a solid catalyst component consisting of the obtained substance and an organometallic compound.

<1> Solid catalyst component 1. Component [I] Silicon oxide used in the present invention ([I]-(1))
Is silica or a double oxide of silicon and at least one other metal of Group I to VII of the periodic table.

The aluminum oxide ([I]-(1)) used in the present invention is a composite oxide of alumina or aluminum and at least one other metal of Group I to VII of the periodic table.

Silicon or Aluminum and Periodic Table I
Al ₂ O ₃ .MgO and Al ₂ O ₃ .C are typical examples of complex oxides of at least one other metal of Group VII.
aO, Al ₂ O ₃ · SiO ₂ , Al ₂ O ₃ · MgO · C
aO, Al ₂ O ₃ · MgO · SiO ₂ , Al ₂ O ₃ · C
uO, Al ₂ O ₃ · Fe ₂ O ₃ , Al ₂ O ₃ · NiO,
Examples thereof include various natural or synthetic multiple oxides such as SiO ₂ .MgO. 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. As a matter of course, the silicon oxide and / or the aluminum oxide used in the present invention can be used without any problem even if it absorbs a small amount of water and contains a small amount of impurities.

The properties of these silicon oxides and / or aluminum oxides are not particularly limited as long as the object of the present invention is not impaired, but the particle size is preferably 1-2.
00 μm, pore volume 0.3 ml / g or more, surface area 5
Silica of 0 m ² / g or more is desirable. Before use, it is desirable to perform firing treatment at 200 to 800 ° C. in advance by a conventional method.

The titanium compound or the titanium compound and the vanadium compound ([I]-(2)) to be catalytically reacted with the silicon oxide and / or the aluminum oxide include titanium, titanium and vanadium halides, alkoxy halides and alkoxides. , Halogenated oxides. As the titanium compound, a tetravalent titanium compound and a trivalent titanium compound are preferable, and the tetravalent titanium compound is specifically represented by the general formula [T
i (OR) _{nX4 -n} ] (wherein R represents a hydrocarbon group such as an alkyl group having 1 to 20 carbon atoms, an aryl group or an aralkyl group, X represents a halogen atom, and n represents 0≤n≤.
It is 4. ) Are preferred, and titanium tetrachloride, titanium tetrahalide such as titanium tetrabromide and titanium tetraiodide, monomethoxytrichlorotitanium, dimethoxydichlorotitanium, trimethoxymonochlorotitanium, tetramethoxytitanium, monoethoxytrichlorotitanium. , Diethoxydichlorotitanium, triethoxymonochlorotitanium, tetraethoxytitanium, monoisopropoxytrichlorotitanium, diisopropoxydichlorotitanium, triisopropoxymonochlorotitanium, tetraisopropoxytitanium, monobutoxytrichlorotitanium, dibutoxydichlorotitanium, tributoxy. Monochlorotitanium, tetrabutoxytitanium, monopentoxytrichlorotitanium, monophenoxytrichlorotitanium, diphenoxydichlorotitanium, triphenoxymono Rorochitan, may be mentioned tetraphenoxysilane titanium. The trivalent titanium compound is obtained by reducing titanium tetrahalide such as titanium tetrachloride or titanium tetrabromide with hydrogen, aluminum, titanium or an organometallic compound of Group I to III metal of the periodic table. Examples include titanium. In addition, a general formula Ti (OR) _m X _4-m (where R is a carbon number of 1 to 20)
Represents a hydrocarbon group such as an alkyl group, an aryl group or an aralkyl group, and X represents a halogen atom. m is 0 <m ≦
It is 4. ) The tetravalent halogenated alkoxytitanium or tetraalkoxytitanium represented by
Examples thereof include trivalent titanium compounds obtained by reduction with an organometallic compound of Group I metal. Among these titanium compounds, halogen-containing titanium is preferable, and tetrahalogenated titanium is particularly preferable. Examples of the vanadium compound include tetravalent vanadium compounds such as vanadium tetrachloride, vanadium tetrabromide, vanadium tetraiodide and tetraethoxyvanadium, vanadium oxytrichloride, ethoxydichlorovanadyl, triethoxyvanadyl, tributoxyvanadyl and the like. Examples thereof include trivalent vanadium compounds, trivalent vanadium compounds such as vanadium trichloride and vanadium triethoxide.

When the titanium compound and the vanadium compound are used in combination, the V / Ti molar ratio is preferably in the range of 2/1 to 0.01 / 1.

The reaction ratio between the silicon oxide and / or aluminum oxide ([I]-(1)) and the titanium compound or the titanium compound and the vanadium compound ([I]-(2)) is the component [I]-(. 1 g of component [I]-(1), depending on the presence or absence of the calcination treatment of 1) or the calcination treatment conditions.
Per component [I]-(2) 0.01-10.0 mm
It is desirable to use ol, preferably 0.1 to 5.0 mmol, and more preferably 0.2 to 2.0 mmol, to carry out the reaction.

Component [I]-(1) and component [I]-(2)
The reaction method is not particularly limited as long as the object of the present invention is not impaired, but in the presence of a sufficiently dehydrated inert hydrocarbon solvent (described later), the temperature is 20 to 300 ° C., preferably 50 to 150 ° C. For 5 minutes to 10 hours, and then the method of nitrogen blowing or vacuum removal of the inert hydrocarbon solvent at 50 to 150 ° C., or component [I]-(1) and component [I]-(2). A method of obtaining a reaction product by contacting as it is in the absence of an inert hydrocarbon solvent can be mentioned.
In the present invention, the method using an inert hydrocarbon solvent is preferable.

Component [I]-(1) and component [I]-
After the catalytic reaction with (2), the inert hydrocarbon may be removed after washing with the inert hydrocarbon several times.

2. Component [II] Magnesium halide used in the present invention ([II]
As-(1)), a substantially anhydrous one is used, and examples thereof include magnesium fluoride, magnesium chloride, magnesium bromide, and magnesium iodide, and magnesium chloride is particularly preferable.

In the present invention, these magnesium halides may be treated with an electron donor such as alcohol, ester, ketone, carboxylic acid, ether, amine and phosphine.

The general formula Me (OR) _n used in the present invention.
X _z-n (where Me is an element of Group I to IV of the periodic table, z
Is the valence of the element Me, n is 0 <n ≦ z, and X is a halogen atom. R has 1 to 20 carbon atoms, preferably 1 to
Examples of the compound ([II]-(2)) represented by hydrocarbon groups such as an alkyl group, an aryl group, an aralkyl group and the like, which may be the same or different,
For example, NaOR, Mg (OR) ₂ , Mg (OR) X,
Ca (OR) ₂ , Zn (OR) ₂ , Cd (OR) ₂ , B
(OR) ₃ , Al (OR) ₃ , Al (OR) ₂ X, Al
(OR) X ₂ , Si (OR) ₄ , Si (OR) ₃ X, S
i (OR) ₂ X ₂ , Si (OR) X ₃ , Sn (OR) ₄
Various compounds represented by Preferred examples of these include Mg (OC
₂ H ₅ ) ₂ , Mg (OC ₂ H ₅ ) Cl, Al (OC
_{H 3) 3, Al (OC} 2 H 5) 3, Al (On-C 3 H
_{7) 3, Al (Oi-} C 3 H 7) 3, Al (On-C 4
_{H 9) 3, Al (Osec} -C 4 H 9) 3, Al (Ot
_{-C 4 H 9) 3, Al} (OCH 3) 2 Cl, Al (OC
₂ H ₅ ) ₂ Cl, Al (OCH ₃ ) Cl ₂ , Al (Oi
_{-C 3 H 7) 2 Cl,} Al (Oi-C 3 H 7) Cl 2,
Si (OC ₂ H ₅ ) ₄ , Si (OC ₂ H ₅ ) ₃ Cl, S
i (OC ₂ H ₅ ) ₂ Cl ₂ , Si (OC ₂ H ₅ ) Cl ₃
Compounds such as

Magnesium halide ([II]-
(1)) and a compound represented by the general formula Me (OR) _n X _z-n ([II]-(2)), or a titanium compound or a titanium compound and a vanadium compound ([II]-( 3)) is specifically selected from various titanium compounds and vanadium compounds used as the component [I]-(2), and is the same as the component [I]-(2) or Although different compounds may be used, preferably they are represented by the general formula Ti (O
R) _n X _4-n (wherein R represents a hydrocarbon group such as an alkyl group, an aryl group or an aralkyl group having 1 to 20 carbon atoms, X represents a halogen atom, and n is 0 ≦ n ≦ 4). .) Alkoxy-containing titanium compounds represented by the formula (4) are preferable, and tetraalkoxy titanium is particularly preferable.

Component [II]-(1) and component [II]-
The reaction ratio with (2) is that Me / Mg (molar ratio) is 0.0
The range of 1 to 10, preferably 0.1 to 5 is desirable.

Further, the reaction ratio of the component [II]-(3) is 0.01 to 5, preferably 0. 5, in the component [II]-(3) / component [II]-(1) (molar ratio). The range of 05 to 1.0 is desirable.

Component [II]-(1), Component [II]-
The order of contact when the component (2) and the component [II]-(3) are reacted with each other is not particularly limited, and the component [II]-(1) and the component [II]-(2) are not particularly limited. And a method of simultaneously reacting components [II]-(3),
Although any method of contacting each component in any order may be used, preferably, a method of simultaneously contacting each component, or a component [II]-(1) and a component [II]-
After the catalytic reaction of (2) in advance, the component [II]-(3)
It is desirable that a method of further contacting

These catalytic reaction methods are not particularly limited, and in the presence or absence of an inert hydrocarbon solvent, at a temperature of 0 to 200 ° C. for 30 minutes to 50 hours, a ball mill, a vibration mill, a rod mill, A method of co-milling using an impact mill or the like may be used, and an organic solvent composed of an inert hydrocarbon, alcohols, phenols, ethers, ketones, esters, etc. or a mixture thereof (these are The organic solvent will be specifically described later) in 20 to 400 ° C., preferably 50 to 300 ° C.
A method may be used in which the mixture is heated at the temperature of 5 minutes to 10 hours for reaction by heating, and then the solvent is removed by evaporation. In the present invention, after the components [II]-(1) and the components [II]-(2) are co-ground, the co-ground product is reacted with the components [II]-(3) in an organic solvent. A method of removing the after-solvent by evaporation is preferably used. Thus, the [II] component is obtained.

3. Component [III] Component As the organoaluminum compound used as the component [III] in the present invention,

The general formula R _n AlX _3-n

(Where R is a hydrocarbon group having 1 to 24 carbon atoms, preferably 1 to 12 alkyl groups, aryl groups, aralkyl groups, etc., X is halogen, and n is 0 <n≤3). Compounds represented by are preferable, specifically, dimethyl aluminum chloride, diethyl aluminum chloride, diethyl aluminum bromide, diisopropyl aluminum chloride, methyl aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride, trimethyl aluminum, triethyl aluminum, Examples include triisopropylaluminum, triisobutylaluminum, trioctylaluminum, tridecylaluminum, ethylaluminum sesquichloride, and the like. Among these, diethylaluminium Chloride is especially preferred.

4. Component [IV] As the compound having at least one Si—O—C bond among the silicon compounds used in the present invention,

The general formula R ¹ _a R ² _b R ³ _c Si (OR
⁴ ) _d X _{4- (a + b + c + d)}

(Here, R ¹ , R ² and R ³ are hydrogen or a chain saturated hydrocarbon group such as an alkyl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, and an alicyclic carbon atom such as a cycloalkyl group. A hydrogen group, an aryl group, an aromatic hydrocarbon group such as an aralkyl group, and a hydrocarbon group such as a cross-linked hydrocarbon group, which may be the same or different, and R ⁴ has 1 to 2 carbon atoms.
0, preferably 1 to 12 chain saturated hydrocarbon groups such as alkyl groups, alicyclic hydrocarbon groups such as cycloalkyl groups, aromatic hydrocarbon groups such as aryl groups and aralkyl groups, crosslinked hydrocarbon groups, etc. It represents a hydrocarbon group, X represents a halogen atom such as chlorine, bromine and iodine, and a, b, c and d are 0 ≦ a <4, 0 ≦ b <4,0.
≦ c <4, 0 <d <4 and 0 <a + b + c <4, 1
<A + b + c + d ≦ 4). Examples of these compounds include R ¹ Si (OR ² ) _{3 and R} 1
_{Si (OR} 2 _{) 2} X, R ¹ Si (OR ² ) X ₂ , R ¹ R
² Si (OR ³ ) ₂ , R ¹ R ² Si (OR ³ ) X, R ¹
Examples thereof include various compounds represented by R ² R ³ Si (OR ⁴ ).

Specific examples of these include CH ₃ Si (O
_{CH 3) 3, CH 3 Si} (OC 2 H 5) 3, CH 3 Si
_{(Oi-C 3 H 7)} 3, C 2 H 5 Si (OCH 3) 3,
_{C 2 H 5 Si (OC 2} H 5) 3, C 2 H 5 Si (Oi-
_{C 3 H 7) 3, i} -C 3 H 7 Si (OCH 3) 3, i-
_{C 3 H 7 Si (OC 2} H 5) 3, i-C 3 H 7 Si (O
_{i-C 3 H 7) 3} , n-C 3 H 7 Si (OCH 3) 3,
_{n-C 3 H 7 Si (} OC 2 H 5) 3, n-C 3 H 7 Si
_{(Oi-C 3 H 7)} 3, n-C 4 H 9 Si (OCH 3)
_{3, n-C 4 H 9} Si (OC 2 H 5) 3, i-C 4 H 9
_{Si (OCH 3) 3, i} -C 4 H 9 Si (OC 2 H 5)
_{3, t-C 4 H 9} Si (OCH 3) 3, t-C 4 H 9 S
i (OC ₂ H ₅ ) ₃ , (PH) Si (OCH ₃ ) ₃ ,
(PH) Si (OC ₂ H ₅ ) ₃ , (CyH) Si (OC
H ₃ ) ₃ , (CyH) Si (OC ₂ H ₅ ) ₃ , (NO
R) Si (OCH ₃ ) ₃ , (NOR) Si (OC
₂ H ₅ ) ₃ , HSi (OCH ₃ ) ₃ , HSi (OC ₂ H
_{5) 3, HSi (Oi-} C 3 H 7) 3,

(CH ₃ ) HSi (OCH ₃ ) ₂ , (CH
_{3) HSi (OC 2 H 5} ) 2, (CH 3) HSi (Oi
_{-C 3 H 7) 2, (} C 2 H 5) HSi (OCH 3) 2,
_{(C 2 H 5) HSi (} OC 2 H 5) 2, (C 2 H 5) H
_{Si (Oi-C 3 H 7} ) 2, (i-C 3 H 7) HSi
_{(OCH 3) 2, (i} -C 3 H 7) HSi (OC
_{2 H 5) 2, (i} -C 3 H 7) HSi (Oi-C
_{3 H 7) 2, (n} -C 3 H 7) HSi (OCH 3) 2,
_{(N-C 3 H 7)} HSi (OC 2 H 5) 2, (n-C 3
_{H 7) HSi (Oi-C} 3 H 7) 2, (n-C 4 H 9)
_{HSi (OCH 3) 2, (} n-C 4 H 9) HSi (OC
_{2 H 5) 2, (i} -C 4 H 9) HSi (OCH 3) 2,
_{(I-C 4 H 9)} HSi (OC 2 H 5) 2, (t-C 4
_{H 9) HSi (OCH 3)} 2, (t-C 4 H 9) HSi
(OC ₂ H ₅ ) ₂ , (PH) HSi (OCH ₃ ) ₂ ,
_{(PH) HSi (OC 2 H} 5) 2, (CyH) HSi
(OCH ₃ ) ₂ , (CyH) HSi (OC ₂ H ₅ ) ₂ ,
_{(NOR) HSi (OCH 3)} 2, (NOR) HSi
(OC ₂ H ₅ ) ₂ ,

CH ₃ Si (OCH ₃ ) ₂ Cl, CH ₃ S
_{i (OC 2 H 5) 2} Cl, CH 3 Si (Oi-C
₃ H ₇ ) ₂ Cl, CH ₃ Si (OCH ₃ ) ₂ Br, CH
₃ Si (OC ₂ H ₅ ) ₂ Br, CH ₃ Si (Oi-C _{3
H 7) 2 Br, CH 3} Si (OCH 3) 2 I, CH 3 S
_{i (OC 2 H 5) 2} I, CH 3 Si (Oi-C 3 H 7)
₂ I, C ₂ H ₅ Si (OCH ₃ ) ₂ Cl, C ₂ H ₅ Si
_{(OC 2 H 5) 2 Cl} , C 2 H 5 Si (Oi-C
₃ H ₇ ) ₂ Cl, C ₂ H ₅ Si (OCH ₃ ) ₂ Br, C
₂ H ₅ Si (OC ₂ H ₅ ) ₂ Br, C ₂ H ₅ Si (Oi
_{-C 3 H 7) 2 Br,} C 2 H 5 Si (OCH 3) 2 I,
C ₂ H ₅ Si (OC ₂ H ₅ ) ₂ I, C ₂ H ₅ Si (Oi
_{-C 3 H 7) 2 I,} i-C 3 H 7 Si (OCH 3) 2 C
_{l, i-C 3 H 7} Si (OC 2 H 5) 2 Cl, i-C 3
_{H 7 Si (Oi-C 3} H 7) 2 Cl, n-C 3 H 7 Si
_{(OCH 3) 2 Cl, n} -C 3 H 7 Si (OC 2 H 5)
_{2 Cl, n-C 3 H} 7 Si (Oi-C 3 H 7) 2 Cl,
_{n-C 4 H 9 Si (} OCH 3) 2 Cl, n-C 4 H 9 S
_{i (OC 2 H 5) 2} Cl, n-C 4 H 9 Si (Oi-C
_{3 H 7) 2 Cl, i} -C 4 H 9 Si (OCH 3) 2 C
_{l, i-C 4 H 9} Si (OC 2 H 5) 2 Cl, i-C 4
_{H 9 Si (Oi-C 3} H 7) 2 Cl, t-C 4 H 9 Si
_{(OCH 3) 2 Cl, t} -C 4 H 9 Si (OC 2 H 5)
_{2 Cl, t-C 4 H} 9 Si (Oi-C 3 H 7) 2 Cl,
(PH) Si (OCH ₃ ) ₂ Cl, (PH) Si (OC
_{2 H 5) 2 Cl, (} PH) Si (Oi-C 3 H 7) 2 C
1, (CyH) Si (OCH ₃ ) ₂ Cl, (CyH) S
i (OC ₂ H ₅ ) ₂ Cl, (CyH) Si (Oi-C ₃
H _{7) 2} Cl,

CH ₃ Si (OCH ₃ ) Cl ₂ , CH ₃ S
_{i (OC 2 H 5) Cl} 2, CH 3 Si (Oi-C
₃ H ₇ ) Cl ₂ , C ₂ H ₅ Si (OCH ₃ ) Cl ₂ , C
₂ H ₅ Si (OC ₂ H ₅ ) Cl ₂ , C ₂ H ₅ Si (Oi
_{-C 3 H 7) Cl 2,} i-C 3 H 7 Si (OCH 3) C
_{l 2, i-C 3 H} 7 Si (OC 2 H 5) Cl 2, n-C
₃ H ₇ Si (OCH ₃ ) Cl ₂ , n-C ₃ H ₇ Si (O
_{C 2 H 5) Cl 2,} n-C 4 H 9 Si (OCH 3) Cl
_{2, n-C 4 H 9} Si (OC 2 H 5) Cl 2, i-C 4
_{H 9 Si (OCH 3) Cl} 2, i-C 4 H 9 Si (OC
_{2 H 5) Cl 2, t} -C 4 H 9 Si (OCH 3) C
_{l 2, t-C 4 H} 9 Si (OC 2 H 5) Cl 2, (P
H) Si (OCH ₃ ) Cl ₂ , (PH) Si (OC ₂ H
₅ ) Cl ₂ , (CyH) Si (OCH ₃ ) Cl ₂ , (C
yH) Si (OC ₂ H ₅ ) Cl ₂ ,

(CH ₃ ) ₂ Si (OCH ₃ ) ₂ , (CH
₃ ) ₂ Si (OC ₂ H ₅ ) ₂ , (C ₂ H ₅ ) ₂ Si (O
_{CH 3) 2, (C 2} H 5) 2 Si (OC 2 H 5) 2,
_{(I-C 3 H 7)} 2 Si (OCH 3) 2, (i-C 3 H
_{7) 2 Si (OC 2 H} 5) 2, (n-C 3 H 7) 2 Si
_{(OCH 3) 2, (n} -C 3 H 7) 2 Si (OC
_{2 H 5) 2, (n} -C 4 H 9) 2 Si (OCH 3) 2,
_{(N-C 4 H 9)} 2 Si (OC 2 H 5) 2, (i-C 4
_{H 9) 2 Si (OCH 3} ) 2, (i-C 4 H 9) 2 Si
_{(OC 2 H 5) 2,} (t-C 4 H 9) 2 Si (OC
_{H 3) 2, (t-} C 4 H 9) 2 Si (OC 2 H 5) 2,
(PH) ₂ Si (OCH ₃ ) ₂ , (PH) ₂ Si (OC
₂ H ₅ ) ₂ , (CyH) ₂ Si (OCH ₃ ) ₂ , (Cy
H) ₂ Si (OC ₂ H ₅ ) ₂ , (NOR) ₂ Si (OC
H ₃ ) ₂ , (NOR) ₂ Si (OC ₂ H ₅ ) ₂ ,

(CH ₃ ) (C ₂ H ₅ ) Si (OCH ₃ ).
_{2, (CH 3) (C} 2 H 5) Si (OC 2 H 5) 2,
_{(CH 3) (i-C} 3 H 7) Si (OCH 3) 2, (C
_{H 3) (i-C 3} H 7) Si (OC 2 H 5) 2, (CH
_{3) (t-C 4 H} 9) Si (OCH 3) 2, (t-C 4
_{H 9) Si (OC 2 H} 5) 2, (C 2 H 5) (i-C 3
_{H 7) Si (OCH 3)} 2, (C 2 H 5) (i-C 3 H
_{7) Si (OC 2 H 5} ) 2, (C 2 H 5) (t-C 4 H
_{9) Si (OCH 3) 2} , (C 2 H 5) (t-C
₄ H ₉ ) Si (OC ₂ H ₅ ) ₂ , (C ₂ H ₅ ) (PH)
Si (OCH ₃ ) ₂ , (C ₂ H ₅ ) (PH) Si (OC
₂ H ₅ ) ₂ , (C ₂ H ₅ ) (CyH) Si (OCH ₃ ).
₂ , (C ₂ H ₅ ) (CyH) Si (OC ₂ H ₅ ) ₂ ,
_{(CH 3) 2 Si (Oi} -C 3 H 7) 2, (C 2 H 5)
_{2 Si (Oi-C 3 H} 7) 2, (i-C 3 H 7) 2 Si
_{(Oi-C 3 H 7)} 2, (t-C 4 H 9) 2 Si (Oi
_{-C 3 H 7) 2, (} PH) 2 Si (Oi-C
_{3 H 7) 2, (CyH} ) 2 Si (Oi-C 3 H 7) 2,

(CH ₃ ) ₂ Si (OCH ₃ ) Cl, (C
_{H 3) 2 Si (OC 2} H 5) Cl, (C 2 H 5) 2 Si
_{(OCH 3) Cl, (C} 2 H 5) 2 Si (OC 2 H 5)
_{Cl, (i-C 3 H} 7) 2 Si (OCH 3) Cl, (i
_{-C 3 H 7) 2 Si (} OC 2 H 5) Cl, (t-C 4 H
₉ ) ₂ Si (OCH ₃ ) Cl, (t-C ₄ H ₉ ) ₂ Si
(OC ₂ H ₅ ) Cl, (PH) ₂ Si (OCH ₃ ) C
1, (PH) ₂ Si (OC ₂ H ₅ ) Cl, (CyH) ₂
Si (OCH ₃ ) Cl, (CyH) ₂ Si (OC
₂ H ₅ ) Cl, (CH ₃ ) (t-C ₄ H ₉ ) Si (OC
_{H 3) Cl, (CH 3} ) (t-C 4 H 9) Si (OC 2
H ₅ ) Cl, (CH ₃ ) (PH) Si (OCH ₃ ) C
1, (CH ₃ ) (PH) Si (OC ₂ H ₅ ) Cl, (C
_{H 3) (CyH) Si (} OCH 3) Cl, (CH 3)
(CyH) Si (OC ₂ H ₅ ) Cl, (PH) ₂ Si
_{(Oi-C 3 H 7)} Cl, (CyH) 2 Si (Oi-C
₃ H ₇ ) Cl, (CH ₃ ) (t-C ₄ H ₉ ) Si (Oi
_{-C 3 H 7) Cl, (} CH 3) (PH) 2 Si (Oi-
_{C 3 H 7) Cl, (} CH 3) (CyH) 2 Si (Oi-
C ₃ H ₇ ) Cl,

(CH ₃ ) ₃ Si (OCH ₃ ), (C
_{H 3) 3 Si (OC 2} H 5), (C 2 H 5) 3 Si (O
_{CH 3), (C 2 H} 5) 3 Si (OC 2 H 5), (CH
_{3) 2 (t-C 4} H 9) Si (OCH 3), (CH 3)
_{2 (t-C 4 H 9} ) Si (OC 2 H 5), (CH 3) 2
_{(PH) Si (OCH 3)} , (CH 3) 2 (PH) Si
(OC ₂ H ₅ ), (CH ₃ ) ₂ (CyH) Si (OCH
_3), it may be mentioned _{(CH 3) 2 (CyH)} Si (OC 2 H 5), compounds such as. (PH = benzene ring, CyH = cyclohexyl ring, NOR = norbornene ring)

The silicon compound having at least one Si--N--C bond used in the present invention is

The general formula R ⁵ _a R ⁶ _b R ⁷ _c Si (NR
⁸ ₂ ) _d X _{4- (a + b + c + d)}

(Wherein R ⁵ , R ⁶ and R ⁷ represent hydrogen or a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 alkyl groups, aryl groups, aralkyl groups and the like, and R ⁸ represents carbon number. 1 to 20, preferably 1 to 12 alkyl, aryl and aralkyl hydrocarbon groups, R ⁵ and R ⁶
And R ⁷ may be the same as or different from each other, and when R ⁵ , R ⁶ and R ⁷ are hydrocarbon groups,
R ⁵ , R ⁶ , R ⁷ and R ⁸ may be the same or different from each other, X represents a halogen atom such as fluorine, chlorine, bromine and iodine, and a, b, c and d are 0 ≦ a <4. , 0
≦ b <4, 0 ≦ c <4, 0 <d ≦ 4, where 0 <a + b
+ C + d ≦ 4) can be mentioned.

Specific examples of these silicon compounds include:
_{Si {N (CH 3) 2} } 4, Si {N (C 2 H 5) 2}
₄ , HSi {N (CH ₃ ) ₂ } ₃ , HSi {N (C ₂ H
₅ ) ₂ } ₃ , CH ₃ Si {N (CH ₃ ) ₂ } ₃ , CH _{3
Si {N (C 2 H 5} ) 2} 3, C 2 H 5 Si {N (CH
₃ ) ₂ } ₃ , C ₂ H ₅ Si {N (C ₂ H ₅ ) ₂ } ₃ , C
₃ H ₇ Si {N (CH ₃ ) ₂ } ₃ , C ₃ H ₇ Si {N
_{(C 2 H 5) 2}} 3, C 4 H 9 Si {N (CH 3) 2}
₃ , C ₄ H ₉ Si {N (C ₂ H ₅ ) ₂ } ₃ , C ₆ H ₅ S
_{i {N (CH 3) 2} } 3, C 6 H 5 Si {N (C
_{2 H 5) 2} 3,} C 2 H 4 Si {N (CH 3) 2} 3,
_{C 2 H 4 Si {N (} C 2 H 5) 2} 3,

Si {NH (CH ₃ )} ₄ , Si {NH
(C ₂ H ₅ )} ₄ , HSi {NH (CH ₃ )} ₃ , HS
i {NH (C ₂ H ₅ )} ₃ , CH ₃ Si {NH (C
H ₃ )} ₃ , CH ₃ Si {NH (C ₂ H ₅ )} ₃ , C ₂
H ₅ Si {NH (CH ₃ )} ₃ , C ₂ H ₅ Si {NH
(C ₂ H ₅ )} ₃ , C ₃ H ₇ Si {NH (C
H ₃ )} ₃ , C ₃ H ₇ Si {NH (C ₂ H ₅ )} ₃ , C
₄ H ₉ Si {NH (CH ₃ )} ₃ , C ₄ H ₉ Si {NH
(C ₂ H ₅ )} ₃ , C ₆ H ₅ Si {NH (C
H ₃ )} ₃ , C ₆ H ₅ Si {NH (C ₂ H ₅ )} ₃ , C
₂ H ₄ Si {NH (CH ₃ )} ₃ , C ₂ H ₄ Si {NH
(C ₂ H ₅ )} ₃ ,

H ₂ Si {N (CH ₃ ) ₂ } ₂ , HCH _{3
Si {N (CH 3) 2} } 2, HC 2 H 5 Si {N (CH
₃ ) ₂ } ₂ , (CH ₃ ) ₂ Si {N (CH ₃ ) ₂ } ₂ ,
_{(CH 3) (C 2 H} 5) Si {N (CH 3) 2} 2,
_{(CH 3) (C 2 H} 4) Si {N (CH 3) 2} 2,
_{(CH 3) (C 6 H} 5) Si {N (CH 3) 2} 2,

H ₂ Si {N (C ₂ H ₅ ) ₂ } ₂ , HCH
₃ Si {N (C ₂ H ₅ ) ₂ } ₂ , HC ₂ H ₅ Si {N
(C ₂ H ₅ ) ₂ } ₂ , (CH ₃ ) ₂ Si {N (C
₂ H ₅ ) ₂ } ₂ , (CH ₃ ) (C ₂ H ₅ ) Si {N (C
₂ H ₅ ) ₂ } ₂ , (CH ₃ ) (C ₂ H ₄ ) Si {N (C
₂ H ₅ ) ₂ } ₂ , (CH ₃ ) (C ₆ H ₅ ) Si {N (C
₂ H ₅ ) ₂ } ₂ ,

H ₂ Si {NH (CH ₃ )} ₂ , HCH ₃
Si {NH (CH ₃ )} ₂ , HC ₂ H ₅ Si {NH (C
_{H 3)} 2, (CH} 3) 2 Si {NH (CH 3)} 2,
(CH ₃ ) (C ₂ H ₅ ) Si {NH (CH ₃ )} ₂ ,
(CH ₃ ) (C ₂ H ₄ ) Si {NH (CH ₃ )} ₂ ,
(CH ₃ ) (C ₆ H ₅ ) Si {NH (CH ₃ )} ₂ ,

H ₂ Si {NH (C ₂ H ₅ )} ₂ , HCH
₃ Si {NH (C ₂ H ₅ )} ₂ , HC ₂ H ₅ Si {NH
(C ₂ H ₅ )} ₂ , (CH ₃ ) ₂ Si {NH (C
₂ H ₅ )} ₂ , (CH ₃ ) (C ₂ H ₅ ) Si {NH (C
₂ H ₅ )} ₂ , (CH ₃ ) (C ₂ H ₄ ) Si {NH (C
₂ H ₅ )} ₂ , (CH ₃ ) (C ₆ H ₅ ) Si {NH (C
₂ H ₅ )} ₂ ,

H ₃ SiN (CH ₃ ) ₂ , H ₂ CH ₃ Si
N (CH ₃ ) ₂ , H ₂ C ₂ H ₅ SiN (CH ₃ ) ₂ , H
_{(CH 3) 2 SiN (CH} 3) 2, H (C 2 H 5) 2
_{SiN (CH 3) 2, (} CH 3) 3 SiN (C
_{H 3) 2, (CH 3} ) 2 (C 2 H 5) SiN (CH 3)
_{2, (CH 3) (C} 2 H 5) 2 SiN (CH 3) 2,

H ₃ SiN (C ₂ H ₅ ) ₂ , H ₂ CH ₃ S
_{iN (C 2 H 5) 2} , H 2 C 2 H 5 SiN (C 2 H 5)
₂ , H (CH ₃ ) ₂ SiN (C ₂ H ₅ ) ₂ , H (C ₂ H
₅ ) ₂ SiN (C ₂ H ₅ ) ₂ , (CH ₃ ) ₃ SiN (C
₂ H ₅ ) ₂ , (CH ₃ ) ₂ (C ₂ H ₅ ) SiN (C ₂ H
₅ ) ₂ , (CH ₃ ) (C ₂ H ₅ ) ₂ SiN (C ₂ H ₅ ).
₂ ,

H ₃ SiNH (CH ₃ ), H ₂ CH ₃ Si
_{NH (CH 3), H 2} C 2 H 5 SiNH (CH 3), H
_{(CH 3) 2 SiNH (CH} 3), H (C 2 H 5) 2 S
iNH (CH ₃ ), (CH ₃ ) ₃ SiNH (CH ₃ ),
_{(CH 3) 2 (C 2} H 5) SiNH (CH 3), (CH
_{3) (C 2 H 5)} 2 SiNH (CH 3),

H ₃ SiNH (C ₂ H ₅ ), H ₂ CH ₃ S
iNH (C ₂ H ₅ ), H ₂ C ₂ H ₅ SiNH (C
₂ H ₅ ), H (CH ₃ ) ₂ SiNH (C ₂ H ₅ ), H
_{(C 2 H 5) 2 SiNH} (C 2 H 5), (CH 3) 3 S
_{iNH (C 2 H 5),} (CH 3) 2 (C 2 H 5) SiN
_{H (C 2 H 5),} (CH 3) (C 2 H 5) 2 SiNH
(C ₂ H ₅ ),

Si {N (CH ₃ ) ₂ } ₃ Cl, Si {N
_{(C 2 H 5) 2}} 3 Cl, HSi {N (CH 3) 2} 2
_{Cl, HSi {N (C 2} H 5) 2} 2 Cl, CH 3 Si
{N (CH ₃ ) ₂ } ₂ Cl, CH ₃ Si {N (C
_{2 H 5) 2} 2 Cl} , C 2 H 5 Si {N (CH 3) 2}
₂ Cl, C ₂ H ₅ Si {N (C ₂ H ₅ ) ₂ } ₂ Cl, C
₃ H ₇ Si {N (CH ₃ ) ₂ } ₂ Cl, C ₃ H ₇ Si
_{{N (C 2 H 5)} 2} 2 Cl, C 4 H 9 Si {N (CH
₃ ) ₂ } ₂ Cl, C ₄ H ₉ Si {N (C ₂ H ₅ ) ₂ } _{2
Cl, C 6 H 5 Si {} N (CH 3) 2} 2 Cl, C 6 H
₅ Si {N (C ₂ H ₅ ) ₂ } ₂ Cl, C ₂ H ₄ Si {N
_{(CH 3) 2} 2 Cl} , C 2 H 4 Si {N (C 2 H 5)
₂ } ₂ Cl,

Si {NH (CH ₃ )} ₃ Cl, Si {N
H (C ₂ H ₅ )} ₃ Cl, HSi {NH (CH ₃ )} ₂
Cl, HSi {NH (C ₂ H ₅ )} ₂ Cl, CH ₃ Si
{NH (CH ₃ )} ₂ Cl, CH ₃ Si {NH (C ₂ H
₅ )} ₂ Cl, C ₂ H ₅ Si {NH (CH ₃ )} ₂ C
1, C ₂ H ₅ Si {NH (C ₂ H ₅ )} ₂ Cl, C ₃ H
₇ Si {NH (CH ₃ )} ₂ Cl, C ₃ H ₇ Si {NH
(C ₂ H ₅ )} ₂ Cl, C ₄ H ₉ Si {NH (C
H ₃ )} ₂ Cl, C ₄ H ₉ Si {NH (C ₂ H ₅ )} ₂
Cl, C ₆ H ₅ Si {NH (CH ₃ )} ₂ Cl, C ₆ H
₅ Si {NH (C ₂ H ₅ )} ₂ Cl, C ₂ H ₄ Si {N
H (CH ₃ )} ₂ Cl, C ₂ H ₄ Si {NH (C
₂ H ₅ )} ₂ Cl, and the like. Also

[0057]

[Chemical 1]

[0058]

[Chemical 2]

Among these compounds, HSi (OCH ₃ )
_{3, (CH 3) HSi (} OCH 3) 2, (C 2 H 5) H
Si (OC ₂ H ₅ ) ₂ , (CH ₃ ) HSi (OC
_{2 H 5) 2, Si {} N (CH 3) 2} 4, CH 3 Si
_{{N (CH 3) 2}} 3, (CH 3) HSi {N (C
_{H 3) 2} 2, (} CH 3) HSi {N (C 2 H 5) 2}
₂ , (CH ₃ ) ₂ Si {N (CH ₃ ) ₂ } ₂ , (C
_{H 3) 2 Si {N (} C 2 H 5) 2} 2, etc. are particularly preferable.

Of course, two or more kinds of silicon compounds may be mixed and used.

5. Production of solid catalyst component In the present invention, the first component to the first component for obtaining the solid catalyst component
As the reaction sequence of the V component, (A) the [I] component and the [II] component are first reacted,
Next, the [III] component is reacted, and then the [I] component is reacted.
Method of reacting component V]; (B) first reacting component [I] and component [II],
Next, the [IV] component is reacted, and then the [II] component is reacted.
Method of reacting component I]; (C) first reacting component [I] with component [II],
Thereafter, a method of reacting a reaction product of the [III] component and the [IV] component may be used.

The reaction ratio between the component [I] and the component [II] is such that the component [II]-per 1 g of the component [I]-(1).
(1) is 0.01 to 20.0 mmol, preferably 0.1.
1 to 10 mmol, more preferably 0.2 to 4.0 m
It is desirable to set it to mol.

The reaction ratio of the component [III] is the same as the component [III] / (component [I] in any of the above reaction sequences.
-(2) + component [II]-(3)) (molar ratio) is 0.1
˜100, preferably 0.2 to 10, and more preferably 0.5 to 5.

The reaction ratio of the component [IV] is such that the component [IV] / (component [I]-
(2) + component [II]-(3)) (molar ratio) is 0.01
-10, preferably 0.03 to 5, and more preferably 0.05 to 1.

The reaction method of the [I] component and the [II] component is not particularly limited, and the temperature is from 0 to 200 ° C.
At 30 minutes to 50 hours, a co-grinding treatment may be carried out, or an inert hydrocarbon, alcohols, phenols, ethers, ketones, esters, nitriles,
A method of mixing and heating at a temperature of 0 to 300 ° C. for 5 minutes to 48 hours in an organic solvent composed of amina or the like or a mixture thereof and then removing the solvent may be used, and preferably in an organic solvent. A method of removing the organic solvent after the treatment is desirable.

The method of reacting the reaction product of the [I] component and the [II] component with the [III] component first (addition order (A)) is not particularly limited, and inert carbon is used. The reaction can be carried out in the presence or absence of a hydrogen fluoride solvent, but it is particularly preferable to carry out the reaction in the presence of an inert hydrocarbon solvent. The reaction at this time is at a temperature of 0 to 3
5 minutes to 2 under heating at 00 ° C, preferably 20 to 150 ° C
It is desirable to do it for 0 hours. Furthermore, the method of reacting the [IV] component with the reaction product is not particularly limited, and the reaction can be performed in the presence or absence of an inert hydrocarbon solvent. Here, when the reaction product of the [I] component and the [II] component and the [III] component are reacted in the presence of an inert hydrocarbon solvent, the [IV] component is added as it is. Alternatively, the inert hydrocarbon solvent may be removed once by blowing nitrogen or under reduced pressure, and then the inert hydrocarbon solvent may be newly added to the reaction mixture [I
V] component may be added and reacted. Further, the component [IV] may be added and reacted without using an inert hydrocarbon solvent. When the reaction product of the component [I] and the component [II] and the component [III] are reacted in the absence of an inert hydrocarbon solvent, the component [IV] is added and reacted as it is. Alternatively, an inert hydrocarbon solvent may be newly added, and the component [IV] may be added and reacted. The reaction at this time is performed at a temperature of 0 to 300 ° C., preferably 2
It is desirable to perform the heating at 0 to 150 ° C. for 5 minutes to 20 hours.

The method of reacting the reaction product of the component [I] and the component [II] with the component [IV] (the order of addition (B)) is not particularly limited and may be inert carbon. The reaction can be carried out in the presence or absence of a hydrogen chloride solvent. The reaction at this time is desirably carried out under heating at a temperature of 0 to 300 ° C., preferably 20 to 150 ° C. for 5 minutes to 20 hours. Furthermore, in the above reaction product, the [II
The method of reacting the component I] is also not particularly limited, and the reaction can be carried out in the presence or absence of an inert hydrocarbon solvent as in the case of the addition order (A). The reaction at this time is performed at a temperature of 0 to 300 ° C., preferably 2
It is desirable to perform the heating at 0 to 150 ° C. for 5 minutes to 20 hours.

The reaction product of the component [I] and the component [II] is reacted with the reaction product of the component [III] and the component [IV] (addition order (C)): Although not particularly limited, the component [III] and the component [I
V] in the presence of an inert hydrocarbon solvent at 0 to 300 ° C,
Preferably, the reaction product reacted for 5 minutes to 20 hours under heating at 20 to 150 ° C. is added to the reaction product of the [I] component and the [II] component, and 0 to 300 ° C., preferably 20
A method of reacting for 5 minutes to 20 hours under heating at 150 ° C can be preferably used.

Of course, the component [I] and the component [II]
Preparation of Ingredients, Further Ingredients [III] and [IV]
The procedure for preparing the solid catalyst component by reacting the components is
It should be carried out in an inert gas atmosphere and moisture should be avoided as much as possible.

The component [I] and the component [I] of the present invention are
Preparation of component [I], and further component [III] and component [I]
The various organic solvents used when the component V] is reacted to prepare the solid catalyst component are as follows.

First, the inert hydrocarbon solvent used in the present invention is not particularly limited as long as it is a hydrocarbon solvent inert to a general Ziegler catalyst, and for example, pentane, hexane, cyclohexane, heptane, Octane, nonane, decane, benzene, toluene,
Examples thereof include xylene and the like, or a mixture thereof.

The alcohols and phenols used in the present invention are represented by the general formula ROH (where R is a hydrocarbon group having 1 to 20 carbon atoms such as an alkyl group, an alkenyl group, an aryl group and an aralkyl group, or oxygen, nitrogen). , Sulfur, an organic group containing chlorine and other elements), specifically, methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, 2-ethylhexanol, phenol, chlorophenol. , Benzyl alcohol, methyl cellosolve, ethyl cellosolve, etc., or a mixture thereof.

The ether used may be a hydrocarbon group having the general formula R-O-R '(wherein R and R'are alkyl groups having 1 to 20 carbon atoms, alkenyl groups, aryl groups, aralkyl groups, etc.). And may be the same or different. These may be organic groups containing oxygen, nitrogen, sulfur, chlorine and other elements, and R and R'may form a ring.) The compound represented by is preferably used, and specific examples thereof include dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, diamyl ether, tetrahydrofuran, dioxane, anisole and the like. Moreover, you may use these as a mixture.

The above-mentioned ketone to be used has a general formula

[0075]

[Chemical 3]

(Here, R and R'represent a hydrocarbon group having 1 to 20 carbon atoms such as an alkyl group, an alkenyl group, an aryl group and an aralkyl group, which may be the same or different.
These may be organic groups containing oxygen, nitrogen, sulfur, chlorine and other elements. Further, a compound represented by R and R ′ may form a ring) is preferably used, and specific examples thereof include acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl butyl ketone, dihexyl ketone, Acetophenone, diphenyl ketone, cyclohexanone and the like can be mentioned. Moreover, you may use these as a mixture.

The above-mentioned esters have 2 to 2 carbon atoms.
Examples of the organic acid ester of 30 include methyl formate, methyl acetate, ethyl acetate, propyl acetate, octyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl methacrylate, methyl benzoate, benzoic acid. Ethyl, propyl benzoate, octyl benzoate, phenyl benzoate, benzyl benzoate, ethyl o-methoxybenzoate, ethyl p-methoxybenzoate, butyl p-ethoxybenzoate, methyl p-toluate, ethyl p-toluate. , Ethyl p-ethylbenzoate, ethyl salicylate,
Examples include phenyl salicylate, methyl naphthoate, ethyl naphthoate, ethyl anisate, and the like, or mixtures thereof.

Examples of the nitriles include acetonitrile, propionitrile, butyl nitrile, pentylonitrile, benzonitrile, hexane nitrile,
And the like, and these may be used as a mixture,

As the amines, methylamine,
Ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine,
Examples include picoline and tetramethylenediamine, which may be used as a mixture.

Thus, a solid catalyst component is obtained by catalytically reacting the reaction product obtained by catalytically reacting the [I] component and the [II] component with the [III] component and the [IV] component.

<Examples> Examples are given below, but these are for the purpose of explaining the present invention, and the present invention is not limited thereto.

[Polymer physical property measuring method] n value: Shimadzu flow tester (CFT-500) was used, various loads were applied to the sample at 170 ° C., and the diameter was 2.0 ±.
It is extruded from a die having a length of 0.01 mm and a length of 40.0 ± 0.01 mm, and the shear rate gradient with respect to the shear stress is calculated by the following formula to obtain the n value.

[0083]

[Equation 1]

Hexane extraction: 180% copolymer powder
Roll kneading at 0 ° C, then press-molding into a sheet of 5 cm x 5 cm x 0.2 mm, which is placed in boiling hexane for 5 h.
The% of the weight loss at the time of r extraction was defined as the hexane extraction amount.

Melting point: 180 using a scanning calorimeter (DSC, manufactured by Seiko Denshi KK) with a sample weight of 5 mg.
Once melted at ℃, cooled to -40 ℃, then 10 ℃ / m
The temperature of the endothermic peak top when the temperature was raised at a rate of in was taken as the melting point.

Example 1 (a) Production of solid catalyst component A 500 ml three-necked flask equipped with a stirrer and a reflux condenser was replaced with nitrogen, and 50 g of silica (Fuji Davison, # 955) calcined at 600 ° C. was added thereto. Then, 160 ml of dehydrated hexane and 2.2 ml of titanium tetrachloride were added, and the mixture was reacted for 3 hours under hexane reflux. After cooling, the supernatant was removed by decantation and dried under reduced pressure at 120 ° C to remove hexane. (No. [I] component)

10 g of commercially available anhydrous magnesium chloride and 4.2 g of triethoxyaluminum were placed in a stainless steel pot having an internal volume of 400 ml containing 25 stainless steel balls each having a diameter of 1/2 inch and nitrogen atmosphere at room temperature. Ball milling was performed for 16 hours to obtain a reaction product.

5 with separate stirrer and reflux condenser
The 00 ml three-necked flask was replaced with nitrogen, and 7.5 g of the reaction product and 5.0 g of tetrabutoxytitanium were added to 160 ml of dehydrated ethanol, and the mixture was reacted for 3 hours under the reflux of ethanol. (No. [II] component)

After cooling, 50 g of the component [I] was added, and the mixture was reacted for 3 hours under the reflux of ethanol. After cooling, the supernatant was removed by decantation, and vacuum drying was performed at 150 ° C for 6 hours.

Next, 150 ml of hexane and 80 mmol of diethylaluminum chloride were added, and the mixture was reacted under a hexane reflux for 1 hour. Then, after adding 24 mmol of methyldimethoxysilane and making it react at 40 degreeC for 1 hour, hexane was removed by nitrogen blowing at 70 degreeC, and the solid catalyst component was obtained.

(B) Gas phase polymerization A stainless steel autoclave equipped with a stirrer was used as a gas phase polymerization apparatus, and a loop was formed with a blower, a flow rate controller and a dry cyclone, and hot water was flown into the jacket of the autoclave. By adjusting the temperature. 80 ° C
The above solid catalyst component was added to the autoclave adjusted to 250
mg / hr and triethylaluminum 50 mmo
The gas was supplied at a rate of 1 / hr, the butene-1 / ethylene molar ratio in the autoclave gas phase was adjusted to 0.35, and hydrogen was supplied to the autoclave while adjusting the hydrogen content to 15% of the total pressure. While maintaining the total pressure at 8 kg / cm ² G, the gas in the system was circulated by a blower, and the produced polymer was intermittently withdrawn to carry out continuous polymerization for 10 hours. After the polymerization was completed, the inside of the autoclave was inspected, and it was found that no polymer was attached to the inner wall and the stirrer.

The catalyst efficiency is 220,000 g copolymer / g
It was extremely highly active with Ti. The produced ethylene copolymer has a melt flow rate (MFR) of 1.05 g / 1
0min, the density 0.9202g / cm ^3, a bulk density of 0.49 g / cm ^3, was a high granulate round bulk density average particle size 720μm shape. The melting point of this copolymer was 121.1 ° C, and the n value was 1.41, showing a very narrow molecular weight distribution.

Example 2 In Example 1, 24 mm of methyldimethoxysilane was added.
ol instead of using methyl dimethoxysilane 32
A solid catalyst component was prepared under the same conditions as in Example 1 except that mmol was used. Using the obtained solid catalyst component, vapor phase polymerization similar to that in Example 1 was performed. The results are shown in Table 1.
It was shown to.

Example 3 In Example 1, methyldimethoxysilane was added to 24 mm.
ol instead of using methyldiethoxysilane 24
A solid catalyst component was prepared under the same conditions as in Example 1 except that mmol was used. Using the obtained solid catalyst component, vapor phase polymerization similar to that in Example 1 was performed. The results are shown in Table 1.
It was shown to.

Example 4 In Example 1, methyldimethoxysilane was added to 24 mm.
The solid catalyst component was prepared under the same conditions as in Example 1, except that bisdimethylaminodimethylsilane was used in an amount of 8 mmol instead of ol. Using the obtained solid catalyst component, vapor phase polymerization similar to that in Example 1 was performed. The results are shown in Table 1.

Example 5 A 500 ml three-necked flask equipped with a stirrer and a reflux condenser was replaced with nitrogen, and 150 ml of hexane was reacted with the component [I] and the component [II] obtained in Example 1 to form a reaction product. 50 g of the product and 10 mmol of dimethyldimethoxysilane were added and reacted for 1 hour under hexane reflux, then 80 mmol of diethylaluminum chloride was added, and further reacted for 1 hour under hexane reflux. Then, hexane was removed by nitrogen blowing at 70 ° C. to obtain a solid catalyst component.

Using the solid catalyst component thus obtained, the same gas phase polymerization as in Example 1 was carried out. The results are shown in Table 1.

Example 6 A 500 ml three-necked flask equipped with a stirrer and a reflux condenser was replaced with nitrogen, and 150 ml of hexane was reacted to produce the reaction product of the [I] component and the [II] component obtained in Example 1. 50 g of the product was added. 100 mmol of diethylaluminum chloride and 30 mmol of methyldimethoxysilane.
The hexane mixed solution of was added and reacted under a hexane reflux for 1 hour. Then, hexane was removed by nitrogen blowing at 70 ° C. to obtain a solid catalyst component.

Using the obtained solid catalyst component, gas phase polymerization was carried out in the same manner as in Example 1. The results are shown in Table 1.

[0100]

[Table 1]

Example 7 (a) Production of solid catalyst component A 500 ml three-necked flask equipped with a stirrer and a reflux condenser was replaced with nitrogen, and 50 g of silica (Fuji Davison, # 955) calcined at 600 ° C. was added thereto. Then, 160 ml of dehydrated hexane and 6.8 ml of tetrabutoxytitanium were added, and the mixture was reacted for 3 hours under hexane reflux. After cooling, the supernatant was removed by decantation and dried under reduced pressure at 120 ° C to remove hexane. (No. [I] component)

10 g of commercially available anhydrous magnesium chloride and 4.2 g of triethoxyaluminum were placed in a stainless steel pot having an internal volume of 400 ml containing 25 stainless steel balls each having a diameter of 1/2 inch and at room temperature under a nitrogen atmosphere. Ball milling was performed for 16 hours to obtain a reaction product.

5 with separate stirrer and reflux condenser
The 00 ml three-necked flask was replaced with nitrogen, 160 ml of dehydrated ethanol and 10 ml of 2-ethylhexanol were added, 7.5 g of the reaction product and 5.0 g of tetrabutoxytitanium were added, and the mixture was reacted for 3 hours under the reflux of ethanol. (No. [II] component)

After cooling, 50 g of the component [I] was added, and the mixture was reacted under a reflux of ethanol for 3 hours. After cooling, the supernatant was removed by decantation, and vacuum drying was performed at 150 ° C for 6 hours.

Next, 150 ml of hexane and 100 mmol of diethylaluminum chloride were added, and the mixture was reacted under hexane reflux for 1 hour. Then, after adding 30 g of methyldimethoxysilane and reacting at 40 ° C. for 1 hour,
Hexane was removed by nitrogen blowing at 70 ° C. to obtain a solid catalyst component.

(B) Gas phase polymerization Gas phase polymerization was carried out in the same manner as in Example 1, and the catalyst efficiency was 180.
The activity was extremely high with 000 g copolymer / g Ti.
The produced ethylene copolymer has a melt flow rate (M
FR) 0.96 g / 10 min, density 0.9205 g /
cm ^3, and a bulk density of 0.50 g / cm ^3, was a high granulate round bulk density average particle size 680μm shape. The melting point of this copolymer was 120.4 ° C., and the n value was 1.41, showing a very narrow molecular weight distribution.

Example 8 (a) Preparation of solid catalyst component A 500 ml three-necked flask equipped with a stirrer and a reflux condenser was replaced with nitrogen, and silica (Fuji Devison, # 955) calcined at 600 ° C. was placed in the flask. ) 50 g was added, 160 ml of dehydrated hexane and 2.2 ml of titanium tetrachloride were added, and the mixture was reacted under a hexane reflux for 3 hours. After cooling, the supernatant was removed by decantation and dried under reduced pressure at 120 ° C to remove hexane. (No. [I] component)

10 g of commercially available anhydrous magnesium chloride and 4.2 g of triethoxyaluminum were placed in a stainless steel pot having an internal volume of 400 ml containing 25 stainless steel balls each having a diameter of 1/2 inch and nitrogen atmosphere at room temperature. Ball milling was performed for 16 hours to obtain a reaction product.

5 with separate stirrer and reflux condenser
A 00 ml three-necked flask was purged with nitrogen, 160 ml of dehydrated ethanol and 7.5 g of the reaction product were added, 2.8 g of titanium tetrachloride was added dropwise at 20 ° C. over 30 minutes, and then the mixture was reacted under a reflux of ethanol for 3 hours. It was (No. [I
I] component)

After cooling, 50 g of the component [I] was added, and the mixture was reacted for 3 hours under the reflux of ethanol. After cooling, the supernatant was removed by decantation, and vacuum drying was performed at 150 ° C for 6 hours.

Next, 150 ml of hexane and 80 mmol of diethylaluminum chloride were added, and the mixture was reacted for 1 hour under hexane reflux. Then, after adding 24 mmol of methyldimethoxysilane and making it react at 40 degreeC for 1 hour, hexane was removed by nitrogen blowing at 70 degreeC, and the solid catalyst component was obtained.

(B) Gas phase polymerization Gas phase polymerization was carried out in the same manner as in Example 1, and the catalyst efficiency was 230.
The activity was extremely high with 000 g copolymer / g Ti.
The produced ethylene copolymer has a melt flow rate (M
FR) 1.01 g / 10 min, density 0.9185 g /
It was cm ³ , and was a round granular material having a bulk density of 0.47 g / cm ³ and an average particle size of 700 μm. The melting point of this copolymer was 121.8 ° C. and the n value was 1.43, showing a very narrow molecular weight distribution.

Example 9 In Example 1, 2.5 ml of a 1: 1 (molar ratio) mixture of titanium tetrachloride and vanadium tetrachloride was used in place of titanium tetrachloride in preparing the component [I]. A solid catalyst component was prepared in the same manner as in Example 1 except that.

Gas phase polymerization was carried out in the same manner as in Example 1, and the catalyst efficiency was 220,000 g copolymer / g Ti, which was a very high activity. The produced ethylene copolymer had a melt flow rate (MFR) of 1.40 g / 10 min and a density of 0.
9196 g / cm ³ and a bulk density of 0.45 g / cm
^{3. The} particles were round particles having an average particle size of 760 μm.
The melting point of this copolymer is 122.3 ° C, and the n value is 1.4.
5, the molecular weight distribution was extremely narrow.

Example 10 A solid catalyst component was prepared in the same manner as in Example 1 except that alumina was used in place of silica in preparing the component [I].

Gas phase polymerization was carried out in the same manner as in Example 1, and the catalyst efficiency was 140,000 g copolymer / gTi, which was a very high activity. The produced ethylene copolymer had a melt flow rate (MFR) of 1.30 g / 10 min and a density of 0.
9225 g / cm ³ and a bulk density of 0.46 g / cm
^{3. The} particles were round particles having an average particle size of 580 μm.
The melting point of this copolymer is 120.5 ° C, and the n value is 1.4.
2 and the molecular weight distribution was extremely narrow.

Example 11 A solid catalyst component was prepared in the same manner as in Example 1 except that silica-alumina was used in place of silica in preparing the component [I]. did.

Gas phase polymerization was carried out in the same manner as in Example 1, and the catalyst efficiency was 150,000 g copolymer / g Ti, which was extremely high activity. The produced ethylene copolymer had a melt flow rate (MFR) of 0.59 g / 10 min and a density of 0.
9227 g / cm ³ and a bulk density of 0.44 g / cm
^{3. The} particles were round particles having an average particle size of 610 μm.
The melting point of this copolymer is 121.2 ° C, and the n value is 1.4.
3, the molecular weight distribution was extremely narrow.

Example 12 The same procedure as in Example 1 was repeated except that 3.8 g of triethoxyboron was used instead of triethoxyaluminum in the preparation of the [II] component in Example 1. A solid catalyst component was prepared.

Gas phase polymerization was carried out in the same manner as in Example 1, and the catalytic efficiency was 190,000 g copolymer / g Ti, which was extremely high activity. The produced ethylene copolymer had a melt flow rate (MFR) of 0.73 g / 10 min and a density of 0.
9195 g / cm ³ and a bulk density of 0.47 g / cm
^{3. The} particles were round particles having an average particle size of 720 μm.
The melting point of this copolymer is 121.9 ° C, and the n value is 1.4.
5, the molecular weight distribution was extremely narrow.

Example 13 In the same manner as in Example 1, except that 3.0 g of diethoxymagnesium was used in place of triethoxyaluminum in the preparation of the [II] component in Example 1. A solid catalyst component was prepared.

Gas phase polymerization was carried out in the same manner as in Example 1, and the catalyst efficiency was 180,000 g copolymer / g Ti, which was extremely high activity. The produced ethylene copolymer had a melt flow rate (MFR) of 1.00 g / 10 min and a density of 0.
9196 g / cm ³ and a bulk density of 0.47 g / cm
^{3. The} particles were round particles having an average particle size of 670 μm.
The melting point of this copolymer is 120.8 ° C, and the n value is 1.4.
5, the molecular weight distribution was extremely narrow.

Comparative Example 1 (a) Production of solid catalyst component A 500 ml three-necked flask equipped with a stirrer and a reflux condenser was replaced with nitrogen, and 50 g of silica (Fuji Davison, # 955) calcined at 600 ° C. was added thereto. Then, 160 ml of dehydrated hexane and 2.2 ml of titanium tetrachloride were added, and the mixture was reacted under a hexane reflux for 3 hours. After cooling, the supernatant was removed by decantation and dried under reduced pressure at 120 ° C to remove hexane. (No. [I] component)

[0124] Commercially available anhydrous magnesium chloride (10 g) and triethoxyaluminum (4.2 g) were placed in a stainless steel pot having an internal volume of 400 ml containing 25 stainless steel balls each having a diameter of 1/2 inch and nitrogen atmosphere at room temperature. Ball milling was performed for 16 hours to obtain a reaction product.

5 with separate stirrer and reflux condenser
The 00 ml three-necked flask was replaced with nitrogen, and 7.5 g of the reaction product and 5.0 g of tetrabutoxytitanium were added to 160 ml of dehydrated ethanol, and the mixture was reacted for 3 hours under the reflux of ethanol. (No. [II] component)

After cooling, 50 g of the component [I] was added, and the mixture was reacted for 3 hours under the reflux of ethanol. After cooling, the supernatant was removed by decantation, and vacuum drying was performed at 150 ° C for 6 hours.

Next, 150 ml of hexane and 80 mmol of diethylaluminum chloride were added, and the mixture was reacted under hexane reflux for 1 hour. Then, hexane was removed by nitrogen blowing at 70 ° C. to obtain a solid catalyst component.

(B) Gas phase polymerization Gas phase polymerization was carried out in the same manner as in Example 1, and the catalyst efficiency was 250
It was 000 g copolymer / g Ti. The ethylene copolymer produced has a melt flow rate (MFR) of 0.95 g.
/ 10 min, the density was 0.9198 g / cm ³ , the bulk density was 0.45 g / cm ³ , and the average particle size was 650 μm. The melting point of this copolymer was 122.5 ° C, and the n value was 1.52.

Comparative Example 2 (a) Production of solid catalyst component A 500 ml three-necked flask equipped with a stirrer and a reflux condenser was replaced with nitrogen, and 50 g of silica (Fuji Davison, # 955) calcined at 600 ° C. was added thereto. Then, 160 ml of dehydrated hexane and 6.8 ml of tetrabutoxytitanium were added, and the mixture was reacted for 3 hours under hexane reflux. After cooling, the supernatant was removed by decantation and dried under reduced pressure at 120 ° C to remove hexane. (Component [1])

[0130] Commercially available anhydrous magnesium chloride (10 g) and triethoxyaluminum (4.2 g) were placed in a stainless steel pot having an internal volume of 400 ml containing 25 stainless steel balls each having a diameter of 1/2 inch and nitrogen atmosphere at room temperature. Ball milling was performed for 16 hours to obtain a reaction product.

5 with separate stirrer and reflux condenser
The 00 ml three-necked flask was replaced with nitrogen, 160 ml of dehydrated ethanol and 10 ml of 2-ethylhexanol were added, 7.5 g of the reaction product and 5.0 g of tetrabutoxytitanium were added, and the mixture was reacted for 3 hours under the reflux of ethanol. (No. [II] component)

After cooling, 50 g of the component [I] was added, and the mixture was reacted under a reflux of ethanol for 3 hours. After cooling, the supernatant was removed by decantation, and vacuum drying was performed at 150 ° C for 6 hours.

Next, 150 ml of hexane and 100 mmol of diethylaluminum chloride were added, and the mixture was reacted under a hexane reflux for 1 hour. Then, hexane was removed by nitrogen blowing at 70 ° C. to obtain a solid catalyst component.

(B) Gas phase polymerization Gas phase polymerization was carried out in the same manner as in Example 1, and the catalyst efficiency was 250.
It was 000 g copolymer / g Ti. The produced ethylene copolymer has a melt flow rate (MFR) of 0.86 g.
/ 10min, a density of 0.9190g / cm ^3, a bulk density of 0.44 g / cm ^3, an average particle size of 680 micrometer. The melting point of this copolymer was 122.0 ° C, and the n value was 1.48.

[Brief description of drawings]

FIG. 1 is a flow chart showing steps for producing a catalyst of the present invention.

Claims (1)

[Claims] 1. A method for polymerizing or copolymerizing an olefin using a solid catalyst component and an organometallic compound as a catalyst,
The method for producing a polyolefin, wherein the solid catalyst component is a reaction product obtained by mutually reacting the following [I], [II], [III] and [IV]. [I] (1) Silicon oxide and / or aluminum oxide, and (2) Reaction product obtained by mutually reacting titanium compound or titanium compound and vanadium compound [II] (1) Magnesium halide, ( 2) the general formula _{Me (OR) n X z-} n ( wherein Me periodic table I~I
V group element, z is valence of element Me, n is 0 <n ≦ z,
X is a halogen atom, R is a hydrocarbon residue having 1 to 20 carbon atoms), and (3) a titanium compound or a reaction product obtained by mutually reacting a titanium compound and a vanadium compound. [III] Organoaluminum compound [IV] Silicon compound having at least one Si—O—C bond and / or at least one Si—N—C bond