JP3268407B2 - Method for producing polyolefin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel process for producing polyolefins. More particularly, the present invention significantly increases the polymer yield per solid and the polymer yield per transition metal, thereby eliminating the step of removing catalyst residues in the polymer and reducing the bulk of the resulting polymer. The present invention relates to a process 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 producing a polyolefin having a narrow molecular weight distribution.

[0002]

BACKGROUND OF THE INVENTION Conventionally, in this type 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 solid. However, in these known techniques, the bulk density of the resulting polyolefin is generally low, the average particle size is relatively small, and the particle size distribution is generally broad, so that there are many fine powder portions, and it is difficult to process a polymer. Since problems such as generation of dust and reduction in efficiency at the time of molding are caused, improvement has been strongly demanded in view of productivity and polymer handling. Further, in order to omit the pelletizing step, which has been increasing in recent years, and to apply the powder polymer to a processing machine as it is, improvement is still required.

The present inventors have previously found a novel catalyst component which has improved the above-mentioned disadvantages, and have already filed various patent applications (Japanese Patent Publication No. 1-11651, Japanese Patent Publication No. 1-1289, Japanese Patent Application Laid-open No.
0-149605, JP-A-62-32105, JP-A-6-32105
2-207306 etc.). When these catalyst components are used, a polymer having a high bulk density and a large average particle size can be obtained, but further improvement is required in order to omit the pelletizing step and apply the powder polymer to a processing machine as it is. Was done.

The present invention solves these drawbacks, and further provides a highly active polymer having a high bulk density, a narrow particle size distribution, an extremely small number of polymer fine particles, and a good fluidity. As a result, the present inventors have reached the present invention as a result of intensive studies.

[0005]

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

[I] (1) a silicon oxide and / or an aluminum oxide, and (2) a titanium compound or a reaction product obtained by mutually reacting a titanium compound and a vanadium compound. [II] (1) halogenation Magnesium, (2) general formula Me (OR) _n X _zn (where Me is Na, Mg, Ca, Zn, Cd, B, A
l, elements selected from Si Contact and Sn, z is the valence of the element Me, n is 0 <n ≦ z, X is represented by a halogen atom, R represents a hydrocarbon residue having 1 to 20 carbon atoms) Compound
And (3) a titanium compound or a reaction product obtained by reacting a titanium compound and a vanadium compound with each other. [III] Organoaluminum compound [IV] At least one Si—O—C bond and / or at least one Si— Silicon compound having NC 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 number of fine particles can be obtained with very high activity, and the resulting polyolefin has a high bulk specific gravity and a free flowing property. It is very advantageous in polymerization operation, such as good properties, and can be used for molding even if it is in powder form as well as when used as pellets. can get.

The polymer obtained by using the catalyst of the present invention is characterized by having a very narrow molecular weight distribution, a small amount of hexane extracted, and a very small amount of low-polymer by-products. Therefore, when a 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, excellent antiblocking properties and excellent heat sealing properties. .

Hereinafter, the present invention will be described specifically.

The catalyst used in the method for producing a polyolefin according to the present invention comprises: [I] (1) a silicon oxide and / or an aluminum oxide ([I]-(1)) (2) a titanium compound or a titanium compound and a vanadium compound ([I]-(2)), a reaction product (component [I]), and [II] (1) magnesium halide ([II]-(1)) (2) Me (OR) _n X _zn (where Me is Na, Mg, Ca, Zn, Cd, B, A
l, elements selected from Si Contact and Sn, z is the valence of the element Me, n is 0 <n ≦ z, X is represented by a halogen atom, R represents a hydrocarbon residue having 1 to 20 carbon atoms) ([II]-(2)) (3) a titanium compound or a reaction product (component [II]) obtained by mutually reacting a titanium compound and a vanadium compound ([II]-(3)); And [III] an organoaluminum compound (component [III]), and [IV] a silicon compound having at least one Si-OC bond and / or at least one Si-NC bond (component [IV]) ) Are made to react with each other, and a solid catalyst component comprising a substance obtained by reacting with each other and an organometallic compound.

<1> Solid catalyst component Component [I] The silicon oxide ([I]-(1)) used in the present invention is silica or a double oxide of silicon and at least one other metal of Group 1 to 17 of the periodic table.

The aluminum oxide ([I]-(1)) used in the present invention is a double oxide of alumina or aluminum and at least one other metal of Groups 1 to 17 of the periodic table.

[0013] Silicon or aluminum and Periodic Table 1
Representative examples of complex oxides of at least one other metal belonging to Group 17 include Al ₂ O ₃ .MgO and Al ₂ O ₃ .Ca
O, Al ₂ O ₃ .SiO ₂ , Al ₂ O ₃ .MgO.Ca
O, Al ₂ O ₃ .MgO.SiO ₂ , Al ₂ O ₃ .Cu
O, Al ₂ O ₃ .Fe ₂ O ₃ , Al ₂ O ₃ .NiO, S
Various natural or synthetic double oxides such as iO ₂ .MgO can be exemplified. Here, the above formula is not a molecular formula, but only a composition, and the structure and component ratio of the double oxide used in the present invention are not particularly limited. Needless to say, the silicon oxide and / or 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.
00 μm, pore volume 0.3 ml / g or more, surface area 5
A silica of 0 m ² / g or more is desirable. In use, it is desirable to perform a baking treatment in advance at 200 to 800 ° C. by an ordinary method.

The titanium compound or the titanium compound and the vanadium compound ([I]-(2)) to be brought into contact with the silicon oxide and / or the aluminum oxide include titanium, titanium and vanadium halides, alkoxy halides and alkoxides. And halogenated oxides. As the titanium compound, a tetravalent titanium compound and a trivalent titanium compound are preferable, and as the tetravalent titanium compound, specifically, the general formula [T
i (OR) _{nX4 -n} ] (where 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 represents 0 ≦ n ≦
4. Are preferred, and titanium tetrachloride, titanium tetrabromide such as titanium tetrabromide, titanium tetrabromide, monomethoxytrichlorotitanium, dimethoxydichlorotitanium, trimethoxymonochlorotitanium, tetramethoxytitanium, monoethoxytrichlorotitanium , Diethoxydichlorotitanium, triethoxymonochlorotitanium, tetraethoxytitanium, monoisopropoxytrichlorotitanium, diisopropoxydichlorotitanium, triisopropoxymonochlorotitanium, tetraisopropoxytitanium, monobutoxytrichlorotitanium, dibutoxydichlorotitanium, tribubutoxy Monochlorotitanium, Tetrabutoxytitanium, Monopentoxytrichlorotitanium, Monophenoxytrichlorotitanium, Diphenoxydichlorotitanium, Triphenoxymono Rorochitan, may be mentioned tetraphenoxysilane titanium. As the trivalent titanium compound, a trihalide obtained by reducing a titanium tetrahalide such as titanium tetrachloride or titanium tetrabromide with hydrogen, aluminum, titanium or an organometallic compound of a metal belonging to Group I to III of the periodic table. Titanium is mentioned. In addition, the 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 ≦
4. The tetravalent halogenated alkoxytitanium or tetraalkoxytitanium represented by the following formulas I to II
A trivalent titanium compound obtained by reduction with an organometallic compound of a Group I metal is exemplified. Of these titanium compounds, halogen-containing titanium is preferred, and titanium tetrahalide is particularly preferred. Examples of the vanadium compound include tetravalent vanadium compounds such as vanadium tetrachloride, vanadium tetrabromide, vanadium tetraiodide, and tetraethoxy vanadium; vanadium oxytrichloride; And trivalent vanadium compounds such as trivalent vanadium compounds, vanadium trichloride, and vanadium triethoxide.

When a titanium compound and a 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 the aluminum oxide ([I]-(1)) and the titanium compound or the titanium compound and the vanadium compound ([I]-(2)) is represented by the component [I]-( 1 g of the component [I]-(1) varies depending on the presence or absence of the baking treatment of 1) or the baking treatment conditions.
Per component [I]-(2) is 0.01 to 10.0 mm
and preferably 0.1 to 5.0 mmol, more preferably 0.2 to 2.0 mmol.

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), at a temperature of 20 to 300 ° C, preferably 50 to 150 ° C. For 5 minutes to 10 hours, followed by nitrogen blow or removal under reduced pressure of the inert hydrocarbon solvent at 50 to 150 ° C., or the component [I]-(1) and the component [I]-(2) A method of obtaining a reaction product by directly contacting in the absence of an inert hydrocarbon solvent.
In the present invention, a method using an inert hydrocarbon solvent is preferred.

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

2. Component [II] The magnesium halide used in the present invention ([II]
As-(1)), 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 _zn (where Me is Na, Mg, Ca, Zn, Cd,
An element selected from B, Al, Si and Sn , z is the valence of the element Me, n is 0 <n ≦ z, and X is a halogen atom. R represents a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms, such as an alkyl group, an aryl group, and an aralkyl group, which may be the same or different from each other ([II ]-(2)) is, for example, Na
OR, 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, Si (OR)
Various compounds represented by ₂ X ₂ , Si (OR) X ₃ , Sn (OR) _{4 and the} like can be mentioned. Preferred examples of these are Mg (OC ₂ H ₅ ) ₂ , Mg (O
C ₂ H ₅ ) Cl, Al (OCH 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 (O
CH ₃ ) ₂ Cl, Al (OC ₂ H ₅ ) ₂ Cl, Al (O
_{CH 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, S
i (OC ₂ H ₅ ) ₃ Cl, Si (OC ₂ H ₅ ) ₂ Cl
₂ , compounds such as Si (OC ₂ H ₅ ) Cl ₃ .

Magnesium halide ([II]-
(1)) and a titanium compound or a titanium compound and a vanadium compound ([II]-(), which are brought into contact with each other and reacted with a compound ([II]-(2)) represented by the general formula Me (OR) _n X _z-n. The component 3)) is arbitrarily selected from various titanium compounds and vanadium compounds used as the component [I]-(2), and may be the same as or a component [I]-(2). The different compounds may be either, but are preferably of the general formula Ti (O
R) _n X _4-n (where 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. ) Is desirable, and tetraalkoxytitanium is particularly preferable.

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

The reaction ratio of component [II]-(3) is 0.01 to 5, preferably 0.1 to 5, 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 brought into contact with each other is not particularly limited, and the component [II]-(1) and the component [II]-(2) And simultaneously reacting the components [II]-(3) with each other,
Any method of contacting the components in an arbitrary order may be used, but preferably a method of simultaneously contacting the components, or a component [II]-(1) and a component [II]-
After pre-contact reaction of (2), component [II]-(3)
Is desirable.

The method of the contact reaction is not particularly limited, and may be performed 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-grinding using an impact mill or the like may be used, or an organic solvent composed of inert hydrocarbons, alcohols, phenols, ethers, ketones, esters, etc., or a mixture thereof The organic solvent will be specifically described later).
The mixture may be reacted by heating at a temperature of 5 minutes to 10 hours, and then the solvent may be removed by evaporation. In the present invention, after the component [II]-(1) and the component [II]-(2) are co-ground, the co-ground product and the component [II]-(3) are reacted in an organic solvent. A method of removing the solvent by evaporation is preferably used. Thus, the component [II] is obtained.

3. Component [III] The organoaluminum compound used as the component [III] in the present invention includes:

General formula R _n AlX _3-n

(Where R is a hydrocarbon group having 1 to 24, preferably 1 to 12 carbon atoms, such as an alkyl group, an aryl group, an aralkyl group, X is a halogen, and n is 0 <n ≦ 3) Are preferred, specifically, dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum bromide, diisopropylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, isopropylaluminum dichloride, trimethylaluminum, triethylaluminum, Triisopropyl aluminum, triisobutyl aluminum, trioctyl aluminum, tridecyl aluminum, ethyl aluminum sesquichloride, and the like, among which diethyl aluminum Chloride is especially preferred.

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

Formula R ¹ _a R ² _b R ³ _c Si (OR
⁴ ) _{dX 4- (a + b + c + d)}

(Where R ¹ , R ² and R ³ are hydrogen or a chain saturated hydrocarbon group such as an alkyl group having 1 to 20, preferably 1 to 12 carbon atoms, or an alicyclic hydrocarbon such as a cycloalkyl group) A hydrogen group, an aryl group, an aromatic hydrocarbon group such as an aralkyl group, or 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 a chain saturated hydrocarbon group such as an alkyl group of 1 to 12, an alicyclic hydrocarbon group such as a cycloalkyl group, an aromatic hydrocarbon group such as an aryl group and an aralkyl group, a crosslinked hydrocarbon group and the like. X represents a hydrocarbon atom, X represents a halogen atom such as chlorine, bromine or iodine, and a, b, c and d represent 0 ≦ a <4, 0 ≦ b <4, 0
≦ c <4, 0 <d <4, and 0 <a + b + c <4, 1
<A + b + c + d ≦ 4). These compounds include, for example, R ¹ Si (OR ² ) _{3, 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
Various compounds represented by R ² R ³ Si (OR ⁴ ) and the like can be given.

As a specific example of these, 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 , (tC 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,
nC ₄ H ₉ Si (OCH ₃ ) ₂ Cl, nC 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, (tC 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 ), (CH ₃ ) ₂ (CyH) Si (OC ₂ H ₅ ), and the like. (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 includes:

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, preferably 1 to 12 carbon atoms, such as an alkyl group, an aryl group, an aralkyl group, and R ⁸ represents a carbon number. 1 to 20, preferably 1 to 12 alkyl, aryl, and aralkyl hydrocarbon groups; and R ⁵ and R ⁶
And R ⁷ may be the same or different from each other, and when R ⁵ , R ⁶ and R ⁷ are a hydrocarbon group,
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, iodine, etc., 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).

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 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 ),

[0055] _{Si {N (CH 3) 2} } 3 Cl, Si {N
(C ₂ H ₅ ) _{2 ３ 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]

Embedded image

[0058]

Embedded image

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 ２N (CH ₃ ) ₂ } ₂ , (C
H ₃ ) ₂ Si ｛N (C ₂ H ₅ ) ₂ ｝ ₂ , etc. are particularly preferred.

Of course, a mixture of two or more silicon compounds may be used.

5. Production of Solid Catalyst Component In the present invention, the components I to I in obtaining the solid catalyst component
The reaction order of the V component is as follows: (A) The component [I] and the component [II] are reacted first,
Next, the component [III] is reacted, and thereafter, the component [I]
(B) reacting the component [I] and the component [II] first,
Next, the component [IV] is reacted, and thereafter, the component [II]
(C) reacting the [I] component and the [II] component first;
Thereafter, a method of reacting the reactant of the component [III] with the component [IV] may be used.

The reaction ratio of the component [I] to the component [II] is determined by the ratio of the component [II]-to 1 g of the component [I]-(1).
(1) is 0.01 to 20.0 mmol, preferably 0.1 to 20.0 mmol.
1 to 10 mmol, more preferably 0.2 to 4.0 m
Desirably, it is mol.

The reaction ratio of the component [III] is such that the component [III] / (component [I]
− (2) + component [II] − (3)) (molar ratio) is 0.1
-100, preferably 0.2-10, more preferably 0.5-5.

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

The reaction method of the component [I] with the component [II] is not particularly limited, and the reaction temperature is 0 to 200 ° C.
For 30 minutes to 50 hours, a co-milling treatment may be performed, or an inert hydrocarbon, an alcohol, a phenol, an ether, a ketone, an ester, a nitrile,
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 amines or the like, or a mixture thereof, and then removing the solvent may be used. After the treatment, a method of removing the organic solvent is desirable.

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

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

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

Of course, the component [I] and the component [II]
Preparation of Ingredients, In addition, [III] and [IV]
The operation at the time of preparing the solid catalyst component by reacting the components,
It should be performed in an inert gas atmosphere and humidity should be avoided as much as possible.

The component [I] of the present invention and the component [I]
Preparation of the component [I], the component [III] and the component [I]
V] The various organic solvents used when the component 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. For example, pentane, hexane, cyclohexane, heptane, Octane, nonane, decane, benzene, toluene,
Xylene or the like, or a mixture thereof, or the like can be given.

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

The ether to be used is a compound represented by the general formula R—O—R ′ (where R and R ′ are hydrocarbon groups such as alkyl, alkenyl, aryl and aralkyl groups having 1 to 20 carbon atoms). And these may be the same or different, and may be an organic group containing oxygen, nitrogen, sulfur, chlorine, or another element, or may form a ring with R and R ′.) Are preferably used, and specific examples thereof include dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, diamyl ether, tetrahydrofuran, dioxane, and anisole. These may be used as a mixture.

The ketone used has a general formula

[0075]

Embedded image

(Where R and R ′ each 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. R and R ′ may form a ring) are preferably used, and specific examples thereof include acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl butyl ketone, dihexyl ketone, Examples include acetophenone, diphenyl ketone, and cyclohexanone. These may be used as a mixture.

The esters include those having 2 to 2 carbon atoms.
30 organic acid esters, specifically, 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 a mixture thereof.

Examples of the nitriles include acetonitrile, propionitrile, butylnitrile, pentyronitrile, benzonitrile, hexanenitrile,
And the like, and these may be used as a mixture,

The amines include methylamine,
Ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine,
Picoline, tetramethylenediamine, etc., and these may be used as a mixture.

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

<Examples> Examples will be described below, but these are only for the purpose of illustrating the present invention, and the present invention is not limited thereto.

[Method for Measuring Physical Properties of Polymer] n-value: Using a flow tester (CFT-500) manufactured by Shimadzu, various loads were applied to the sample at 170 ° C.
It is extruded from a die having a length of 0.01 mm and a length of 40.0 ± 0.01 mm.

[0083]

(Equation 1)

Hexane extraction: Copolymer powder was mixed with 180
And then press-molded into a sheet of 5 cm x 5 cm x 0.2 mm, which was placed in boiling hexane for 5 hours.
The percentage of the weight loss at the time of r extraction was defined as the amount of hexane extracted.

Melting point: 180 ° C. using a scanning calorimeter (DSC, manufactured by Seiko Denshi Co., Ltd.) at a sample weight of 5 mg.
Once melted at ℃, cooled to -40 ℃, then 10 ℃ / m
The temperature at the endothermic peak top when the temperature was raised at the rate of in was defined 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 purged with nitrogen, and 50 g of silica (Fuji Devison, # 955) calcined at 600 ° C. was placed therein. Was added, 160 ml of dehydrated hexane and 2.2 ml of titanium tetrachloride were added, and the mixture was reacted under hexane reflux for 3 hours. After cooling, the supernatant was removed by decantation, and hexane was removed by drying at 120 ° C. under reduced pressure. (Component [I])

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

[0088] 5 With another agitator and reflux condenser
The 00 ml three-necked flask was purged with nitrogen, 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 reflux of ethanol. (Component [II])

After cooling, 50 g of the component [I] was added, and the mixture was reacted for 3 hours under reflux of ethanol. After cooling, the supernatant was removed by decantation, followed by drying under reduced pressure 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. Thereafter, 24 mmol of methyldimethoxysilane was added and reacted at 40 ° C. for 1 hour, and hexane was removed at 70 ° C. by blowing nitrogen to obtain a solid catalyst component.

(B) Gas phase polymerization As a gas phase polymerization apparatus, a stainless steel autoclave equipped with a stirrer was used, and a loop was formed with a blower, a flow controller and a dry cyclone. The temperature was adjusted accordingly. 80 ℃
The above solid catalyst component was added to the autoclave adjusted to 250.
mg / hr and 50 mmol of triethyl aluminum
1 / hr, while supplying each gas while adjusting the butene-1 / ethylene molar ratio in the autoclave gas phase to 0.35, and further adjusting the hydrogen to 15% of the total pressure. The gas in the system was circulated by a blower while maintaining the total pressure at 8 kg / cm ² G, and continuous polymerization was carried out for 10 hours while intermittently extracting the produced polymer. After the polymerization was completed, the inside of the autoclave was inspected. As a result, no polymer was adhered to the inner wall and the agitator.

The catalyst efficiency was 220,000 g copolymer / g.
It was very highly active with Ti. The produced ethylene copolymer had 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. The molecular weight distribution was extremely narrow.

Example 2 In Example 1, methyldimethoxysilane was added at 24 mm.
instead of using methyldimethoxysilane
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, the same gas phase polymerization as in Example 1 was performed. Table 1 shows the results
It was shown to.

Example 3 In Example 1, methyldimethoxysilane was added at 24 mm.
instead of using methyldiethoxysilane for 24 hours.
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, the same gas phase polymerization as in Example 1 was performed. Table 1 shows the results
It was shown to.

Example 4 In Example 1, methyldimethoxysilane was added at 24 mm.
A solid catalyst component was prepared under the same conditions as in Example 1, except that 8 mmol of bisdimethylaminodimethylsilane was used instead of ol. Using the obtained solid catalyst component, the same gas phase polymerization as 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 purged with nitrogen, and 150 ml of hexane was reacted with the component [I] and the component [II] obtained in Example 1. Then, 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 the reaction was further performed for 1 hour under hexane reflux. Thereafter, hexane was removed by nitrogen blowing at 70 ° C. to obtain a solid catalyst component.

Using the obtained solid catalyst component, 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 purged with nitrogen, and 150 ml of hexane was reacted with the components [I] and [II] obtained in Example 1. 50 g of the product were added. There, 100 mmol of diethylaluminum chloride and 30 mmol of methyldimethoxysilane
Of hexane was added, and the mixture was reacted under hexane reflux for 1 hour. Thereafter, hexane was removed by nitrogen blowing at 70 ° C. to obtain a solid catalyst component.

Using the obtained solid catalyst component, the same gas phase polymerization as in Example 1 was performed. 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 purged with nitrogen, and 50 g of silica (Fuji Devison, # 955) calcined at 600 ° C. was placed therein. Was added, 160 ml of dehydrated hexane and 6.8 ml of tetrabutoxytitanium were added, and the mixture was reacted under hexane reflux for 3 hours. After cooling, the supernatant was removed by decantation, and hexane was removed by drying at 120 ° C. under reduced pressure. (Component [I])

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

5 with another agitator and reflux condenser
The 00 ml three-necked flask was purged 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 under reflux of ethanol for 3 hours. (Component [II])

After cooling, 50 g of the component [I] was added, and the mixture was reacted for 3 hours under reflux of ethanol. After cooling, the supernatant was removed by decantation, followed by drying under reduced pressure 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. Thereafter, after adding 30 g of methyldimethoxysilane and reacting at 40 ° C. for 1 hour,
Hexane was removed at 70 ° C. by nitrogen blowing 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,
000 g copolymer / gTi, which was extremely high.
The produced ethylene copolymer is melt flow rate (M
FR) 0.96 g / 10 min, density 0.9205 g /
cm ³ , and had a bulk density of 0.50 g / cm ³ and an average particle size of 680 μm. The melting point of this copolymer was 120.4 ° C., and the n value was 1.41. The molecular weight distribution was extremely narrow.

Example 8 (a) Production of solid catalyst component A 500-ml three-necked flask equipped with a stirrer and a reflux condenser was purged with nitrogen, and silica calcined at 600 ° C. (Fuji Devison, # 955) ) 50 g was added, 160 ml of dehydrated hexane and 2.2 ml of titanium tetrachloride were added, and the mixture was reacted under hexane reflux for 3 hours. After cooling, the supernatant was removed by decantation, and hexane was removed by drying at 120 ° C. under reduced pressure. (Component [I])

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

5 with separate agitator 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, and 2.8 g of titanium tetrachloride was added dropwise at 20 ° C. over 30 minutes, and then reacted under reflux of ethanol for 3 hours. Was. (No. [I
I] component)

After cooling, 50 g of the component [I] was added, and the mixture was reacted for 3 hours under reflux of ethanol. After cooling, the supernatant was removed by decantation, followed by drying under reduced pressure 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. Thereafter, 24 mmol of methyldimethoxysilane was added and reacted at 40 ° C. for 1 hour, and then hexane was removed at 70 ° C. by blowing nitrogen to obtain a solid catalyst component.

(B) Gas phase polymerization The gas phase polymerization was carried out in the same manner as in Example 1, and the catalyst efficiency was 230,
000 g copolymer / gTi, which was extremely high.
The produced ethylene copolymer is melt flow rate (M
FR) 1.01 g / 10 min, density 0.9185 g /
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. Further, the melting point of this copolymer was 121.8 ° C., and the n value was 1.43, and the molecular weight distribution was extremely narrow.

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]. Except for the above, a solid catalyst component was prepared in the same manner as in Example 1.

The gas phase polymerization was carried out in the same manner as in Example 1, and the catalytic efficiency was 220,000 g copolymer / gTi, which was extremely high. The resulting ethylene copolymer had a melt flow rate (MFR) of 1.40 g / 10 min and a density of 0.1.
9196 g / cm ³ and a bulk density of 0.45 g / cm ^3
3. Round particles having an average particle diameter of 760 μm.
The melting point of this copolymer is 122.3 ° C., and the n value is 1.4.
5 and the molecular weight distribution was very narrow.

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

The gas phase polymerization was carried out in the same manner as in Example 1, and the catalyst efficiency was as high as 140,000 g copolymer / gTi. The produced ethylene copolymer had a melt flow rate (MFR) of 1.30 g / 10 min and a density of 0.1.
9225 g / cm ³ and a bulk density of 0.46 g / cm ^3
3. Round particles having an average particle diameter 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 very narrow.

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

The gas phase polymerization was carried out in the same manner as in Example 1, and the catalyst efficiency was 150,000 g copolymer / gTi, which was extremely high. The produced ethylene copolymer had a melt flow rate (MFR) of 0.59 g / 10 min and a density of 0.1.
9227 g / cm ³ and a bulk density of 0.44 g / cm 3
^3. Round particles having an average particle diameter of 610 μm.
The melting point of this copolymer is 121.2 ° C., and the n value is 1.4.
3 and a very narrow molecular weight distribution.

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

The gas phase polymerization was carried out in the same manner as in Example 1, and the catalyst efficiency was extremely high at 190,000 g copolymer / gTi. The produced ethylene copolymer had a melt flow rate (MFR) of 0.73 g / 10 min and a density of 0.1.
9195 g / cm ³ and a bulk density of 0.47 g / cm 3
^3. Round particles having an average particle diameter of 720 μm.
The melting point of this copolymer is 121.9 ° C., and the n value is 1.4.
5 and the molecular weight distribution was very narrow.

Example 13 The procedure of Example 1 was repeated, except that 3.0 g of diethoxymagnesium was used instead of triethoxyaluminum in the preparation of the component [II]. A solid catalyst component was prepared.

The gas phase polymerization was carried out in the same manner as in Example 1, and the catalyst efficiency was as high as 180,000 g copolymer / gTi. The produced ethylene copolymer had a melt flow rate (MFR) of 1.00 g / 10 min and a density of 0.1.
9196 g / cm ³ and a bulk density of 0.47 g / cm 3
^3. Round particles having an average particle diameter of 670 μm.
The melting point of this copolymer is 120.8 ° C., and the n value is 1.4.
5 and the molecular weight distribution was very 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 purged with nitrogen, and 50 g of silica (Fuji Devison, # 955) calcined at 600 ° C. was placed therein. Was added, 160 ml of dehydrated hexane and 2.2 ml of titanium tetrachloride were added, and the mixture was reacted under hexane reflux for 3 hours. After cooling, the supernatant was removed by decantation, and hexane was removed by drying at 120 ° C. under reduced pressure. (Component [I])

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

5 with separate agitator and reflux condenser
The 00 ml three-necked flask was purged with nitrogen, 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 reflux of ethanol. (Component [II])

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

Next, 150 ml of hexane and 80 mmol of diethylaluminum chloride were added and reacted for 1 hour under hexane reflux. Thereafter, 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,
000 g copolymer / gTi. The produced ethylene copolymer 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 purged with nitrogen, and 50 g of silica (Fuji Devison, # 955) calcined at 600 ° C. was placed therein. Was added, 160 ml of dehydrated hexane and 6.8 ml of tetrabutoxytitanium were added, and the mixture was reacted under hexane reflux for 3 hours. After cooling, the supernatant was removed by decantation, and hexane was removed by drying at 120 ° C. under reduced pressure. (1st component)

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

5 with another agitator and reflux condenser
The 00 ml three-necked flask was purged 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 under reflux of ethanol for 3 hours. (Component [II])

After cooling, 50 g of the component [I] was added, and the mixture was reacted for 3 hours under reflux of ethanol. After cooling, the supernatant was removed by decantation, followed by drying under reduced pressure 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. Thereafter, hexane was removed by nitrogen blowing at 70 ° C. to obtain a solid catalyst component.

(B) Gas phase polymerization The gas phase polymerization was carried out in the same manner as in Example 1, and the catalyst efficiency was 250,
000 g copolymer / gTi. 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 the drawings]

FIG. 1 is a flowchart showing a production process of a catalyst of the present invention.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-7-10929 (JP, A) JP-A-7-10928 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 4/65-4/658

Claims (1)

(57) [Claims] 1. A method for polymerizing or copolymerizing an olefin using a solid catalyst component and an organometallic compound as catalysts,
A 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) a silicon oxide and / or an aluminum oxide, and (2) a titanium compound or a reaction product obtained by mutually reacting a titanium compound and a vanadium compound. [II] (1) a magnesium halide; 2) General formula Me (OR) _n X _zn (where Me is Na, Mg, Ca, Zn, Cd, B, A
l, elements selected from Si Contact and Sn, z is the valence of the element Me, n is 0 <n ≦ z, X is represented by a halogen atom, R represents a hydrocarbon residue having 1 to 20 carbon atoms) Compound
And (3) a titanium compound or a reaction product obtained by reacting a titanium compound and a vanadium compound with each other. [III] Organoaluminum compound [IV] At least one Si—O—C bond and / or at least one Si— Silicon compound having NC bond