JP3268404B2 - Method for producing polyolefin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a novel polyolefin. More specifically, the present invention significantly increases the polymer yield per solid and the polymer yield per transition metal, thereby eliminating the need for steps to remove catalyst residues in the polymer and reducing the amount of polymer formed. The present invention relates to a process for producing fine particles having a high average density and a high average particle size by increasing the density of fine particles and reducing fine particles of the produced polymer, 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 specific gravity of the polyolefin obtained is generally small, the average particle size is relatively small, and the particle size distribution is generally broad, so that there are many fine-grained powder portions. 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 this catalyst component is 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 to apply the powder polymer to a processing machine as it is. Was.

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 is reacted with the reaction product of the following [I]. A method for producing a polyolefin, characterized by comprising reacting the reaction product of [II] first and reacting the reaction product with a compound of [III]; [I] (1) silicon oxide And / or an aluminum oxide and (2) a titanium compound or a reaction product obtained by reacting a titanium compound with a vanadium compound, and (3) a reaction product obtained by reacting an organoaluminum compound; [II] (1 ) Magnesium halide and (2) the general formula Me (OR) _n X _zn (where Me is Na, Mg, Ca, Zn, Cd, B, A
an element selected from l, Si and Sn , z is the valence of the element Me, n is 0 <n ≦ z, X is a halogen atom, and R is a hydrocarbon residue having 1 to 20 carbon atoms) A reaction product obtained by reacting the compound; and [III] a silicon compound having at least one Si—N—C bond.

Further, the present invention provides a method for polymerizing or copolymerizing an olefin using a solid catalyst component and an organometallic compound as a catalyst, wherein the solid catalyst component comprises a reaction product of the following [I] and a reaction product of [II]. A product obtained by reacting a compound of the formula [III] with the reaction product; [I] (1) a silicon oxide and / or an aluminum oxide And (2) a titanium compound or a reaction product obtained by reacting a titanium compound with a vanadium compound, and further (3) a reaction product obtained by reacting an organoaluminum compound; [II] (1) a magnesium halide (2) ) General formula Me (OR) _n X _zn (where Me is Na, Mg, Ca, Zn, Cd, B, A
an element selected from l, Si and Sn , z is the valence of the element Me, n is 0 <n ≦ z, X is a halogen atom, and R is 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 with a vanadium compound, and [III] a silicon compound having at least one Si-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 extremely 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 it can be used for molding even if it is in powder form as well as used as pellets, there are few troubles during molding, and polyolefin is produced very advantageously can do.

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 of the present invention comprises: [I] (1) a silicon oxide and / or an aluminum oxide, and (2) a titanium compound or a reaction product obtained by reacting a titanium compound with a vanadium compound. , (3) a reaction product further contacted with an organoaluminum compound (component (I)), (II) (1) magnesium halide, and (2) a general formula [Me (OR) _n X _z-n And (3) a reaction product obtained by reacting a titanium compound or a reaction product (component [II]) obtained by bringing a titanium compound and a vanadium compound into contact with each other, if desired. And [III] a solid catalyst component comprising a substance obtained by reacting a silicon compound having at least one Si-NC bond, and an organometallic compound. Consisting of compounds.

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

[0011] 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 multiple 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.

Examples of the titanium compound or the titanium compound and the vanadium compound to be brought into contact with the silicon oxide and / or the aluminum oxide include titanium, titanium and vanadium halides, alkoxy halides, alkoxides, and halogenated oxides. it can. As the titanium compound, a tetravalent titanium compound and a trivalent titanium compound are preferable, and as the tetravalent titanium compound, specifically, a general formula [Ti (OR) _n X _4-n ]
(Where R represents an alkyl group having 1 to 20 carbon atoms, an aryl group or an aralkyl group, and X represents a halogen atom.
n is 0 ≦ n ≦ 4. Are preferable, 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, triphenoxymonochrome Titanium,
Tetraphenoxytitanium and the like can be mentioned. Examples of the trivalent titanium compound include trihalide obtained by reducing titanium tetrahalide such as titanium tetrachloride and titanium tetrabromide with hydrogen, aluminum, titanium or an organic metal compound of a metal belonging to Group 1 to 3 of the periodic table. Titanium is mentioned. In addition, the general formula Ti (OR) _m X _4-m (where R is carbon number 1 to ₄ )
20 represents an alkyl group, an aryl group or an aralkyl group, and X represents a halogen atom. m is 0 ≦ m ≦ 4. )), A trivalent titanium compound obtained by reducing a tetravalent halogenated alkoxytitanium or tetraalkoxytitanium with an organometallic compound of a metal belonging to Group 1 to 3 of the periodic table. Among these titanium compounds, 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.

A silicon oxide and / or an aluminum oxide (hereinafter abbreviated as component [I]-(1)), a titanium compound or a titanium compound and a vanadium compound (hereinafter abbreviated as component [I]-(2)); The reaction ratio varies depending on whether or not the component [I]-(1) is calcined or the conditions of the component baking. However, the amount of the component [I]-(2) is 0.01 to 1 g per component [I]-(1). 10.0 mmol, preferably 0.1-5.0 mmol, more preferably 0.1 mmol.
It is desirable to use 2 to 2.0 mmol for 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), at a temperature of 20 to 300 ° C, preferably 50 to 150 ° C. For 5 minutes to 10 hours by heating, or component [I]-(1) and component [I]-
(2) is desirably brought into contact in the absence of an inert hydrocarbon to obtain a reaction product.

The component [I]-(1) and the component [I]-
After the contact reaction with (2), it may be washed several times with an inert hydrocarbon. Further, component [I]-(1) and component [I]
After the contact reaction with-(2), the inert hydrocarbon may be removed by evaporation, or the process may proceed to the next contact reaction with an organoaluminum compound without being removed by evaporation.

Next, the step of bringing the reaction product of the above-mentioned component [I]-(1) and component [I]-(2) into contact with an organoaluminum compound will be described.

The organoaluminum compound used in the present invention may be a compound represented by the general formula RnAlX3 _-n (where R is a hydrocarbon having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms, such as an alkyl group, an aryl group, and an aralkyl group). Residues, X represents a halogen, and n is 0 <n ≦ 3) are preferred, and specifically, dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum bromide, diisopropylaluminum chloride, methylaluminum Dichloride, ethylaluminum dichloride, isopropylaluminum chloride, trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, tridecylaluminum, ethylaluminum sesquichloride Rorido, it is possible and the like,
Diethyl aluminum chloride is particularly preferred.

Component [I]-(1) and Component [I]-(2)
The contact ratio between the contact product of (a) and the organoaluminum compound (hereinafter referred to as component [I]-(3) is
The molar ratio of component [I]-(2) is desirably 0.1 to 100, preferably 0.2 to 10, and more preferably 0.5 to 5.

Component [I]-(1) and Component [I]-(2)
The method of contacting the component [I]-(3) with the contact product of the above is not particularly limited, but specifically, the method of contacting the component [I]-
The contact product of (1) and component [I]-(2) and component [I]-(3) are reacted at a temperature of 2 in the presence of an inert hydrocarbon solvent.
0 to 300 ° C, preferably 50 to 150 ° C for 5 minutes to 10
Time, heating and mixing to bring them into contact with each other and react.After the completion of the reaction, the unreacted organoaluminum compound is removed by washing several times with an inert hydrocarbon, and then the inert hydrocarbon solvent is removed by evaporation. A method for obtaining the component [I] is exemplified as a preferable method.

2. Component [II] The magnesium halide used in the present invention is substantially anhydrous, and includes magnesium fluoride, magnesium chloride, magnesium bromide, and magnesium iodide, with magnesium chloride being particularly preferred. .

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

The general formula used in the present invention is Me (OR) _n X _zn (where Me is Na, Mg, C
selected from a, Zn, Cd, B, Al, Si and Sn
That elements, z is the valence of the element Me, n is 0 <n ≦ z, X is a halogen atom. R represents a hydrocarbon residue 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. , For example N
aOR, Mg (OR) ₂ , Mg (OR) X, Ca (O
R) 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 (O
Various compounds represented by R) ₂ X ₂ , Si (OR) X ₃ , Sn (OR) _{4 and the} like can be mentioned. Preferred examples of these include Mg (OC ₂ H ₅ ) ₂ , Mg
(OC 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 (Os
_{ec-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
_{(On-C 3 H 7)} 2 Cl, Al (Oi-C 3 H 7) 2
_{Cl, Al (On-C 4} H 9) 2 Cl, Al (Osec
—C ₄ H ₉ ) ₂ Cl, Al (Ot—C ₄ H ₉ ) ₂ Cl,
Al (OCH ₃ ) Cl ₂ , Al (OC ₂ H ₅ ) Cl ₂ ,
_{Al (On-C 3 H 7} ) Cl 2, Al (Oi-C 3 H
_{7) Cl 2, Al (On} -C 4 H 9) Cl 2, Al (O
_{sec-C 4 H 9) Cl} 2, Al (Ot-C 4 H 9) C
l ₂ , Si (OC ₂ H ₅ ) ₄ , Si (OC ₂ H ₅ ) ₃ C
1, Si (OC ₂ H ₅ ) ₂ Cl ₂ , Si (OC ₂ H ₅ )
And compounds such as Cl ₃ .

The magnesium halide and the general formula Me (O
The reaction ratio of the compound represented by _{R) n X z-n} is, Me
/ Mg (molar ratio) is 0.01 to 10, preferably 0.1
The range of ~ 5 is desirable.

Magnesium halide (the following component [I
I] - (1)) and the general formula _{Me (OR) n X z-} n compound represented by (hereinafter component [II] - (2)) the reaction method of the present invention is not particularly limited, an inert In the presence or absence of a hydrocarbon solvent 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, Both components [II]-(1) and [II] are used in an organic solvent composed of inert hydrocarbons, alcohols, phenols, ethers, ketones, esters, amines, nitriles, etc. or mixtures thereof. ]-(2) is 20
To 400 ° C., preferably 50 to 300 ° C. for 5 minutes to
A method of mixing and heating for 10 hours and then evaporating and removing the solvent may be used. In the present invention, a method in which both are pulverized is preferably used.

In order to make the present invention more effective, a magnesium compound and a compound represented by the general formula Me (OR) _{n Xz-n} are further used in combination with a titanium compound or a titanium compound and a vanadium compound. Can also. The titanium compound and the vanadium compound to be used in combination are, for example, arbitrarily selected from the various titanium compounds and vanadium compounds used as the component [I]-(2), and the components [I]-(2 ) May be the same or a different compound, but preferably is a compound of the general formula Ti (OR) _n X _4-n (where R is 1 carbon atom)
Represents an alkyl group, an aryl group or an aralkyl group, X represents a halogen atom, and n represents 0 ≦ n ≦ 4. ) Is desirable, and titanium tetrachloride is particularly desirable.

At this time, the amount of the titanium compound or the titanium compound and the vanadium compound (hereinafter abbreviated as [II]-(3)) is [II]-(3) / [II]-(1)
(Molar ratio) is desirably 0.01 to 5, preferably 0.05 to 1.

Component [II]-(1) and Component [II]
The contact method when the component [II]-(3) is further contacted with the component (II) is not particularly limited, and the component [II]-(1), the component [II]-(2), and the component The method of contacting [II]-(3) simultaneously or the method of contacting each component in an arbitrary order may be used, but preferably the components [II]-(1), component [II]-(2) and component [II]-(3) is contacted simultaneously, or after the component [II]-(1) is brought into contact with the component [II]-(2) as described above in advance, the component [II]-(3) is contacted. The method of contacting is desirable.

Component [II]-(1), Component [II]-
As a method for bringing (2) and component [II]-(3) into contact with each other, component [II]-(1) and component [II]
Similar to the contact method of-(2), a method of contacting in an organic solvent, a method of co-grinding, and the like are suitably mentioned, and preferably component [II]-(1) and component [II]-(2)
After co-milling, the co-milled product and the component [II]-(3)
Is desirably reacted in an organic solvent, and then the solvent is removed by evaporation, and a method of co-milling [II]-(1) to (3) is desirable.

Thus, component [II]-(1) and component [II]-(2) and, if desired, component [II]-
The component (II) is obtained by bringing (3) into contact with each other.

3. Examples of the silicon compound having at least one Si-N-C bond is used in the (III) components present invention, the general formula _{^{R 5 a R 6 b R 7}} c Si (NR 8 2) d X
Represented by _{4- (a + b + c +} d), R 5, R 6, R 7 is hydrogen or a C 1-20 In the formula, preferably hydrogen or 1 to 12 alkyl group, an aryl group, a hydrocarbon residue such as an aralkyl group And R ⁸ is a hydrocarbon residue of an alkyl group, an aryl group, or an aralkyl group having 1 to 20, preferably 1 to 12 carbon atoms, and R ⁵ , R ⁶ and R ⁷ may be the same or different from each other. When R ⁵ , R ⁶ and R ⁷ are hydrocarbon residues, R ⁵ , R ⁶ , R ⁷ and R ⁸ may be the same or different from each other, and X is fluorine, chlorine, bromine , Iodine or the like represents a halogen atom or a hydrogen atom, 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 4} , Si ｛N (C ₂ H ₅ )
₂ ｝ ₄ , HSi ｛N (CH ₃ ) ₂ ｝ ₃ , HSi ｛N
(C ₂ H ₅ ) _{2 ３ 3} , CH ₃ Si ｛N (C
H ₃ ) _{2 ３ 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 3} , C ₃ H ₇ Si ｛NC
H 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 3} , C ₄ H ₉ Si ｛N
(C ₂ H ₅ ) _{2 ３ 3} , C ₆ H ₅ Si ｛NCH ₃ ) _{2 ３ 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 3} ,

Si ｛NH (CH ₃ )｝ ₄ , Si ｛NH
(C ₂ H ₅ )｝ ₄ , HSi ｛NH (CH ₃ )｝ ₃ , H
Si ｛NH (C ₂ H ₅ )｝ ₃ , CH ₃ Si ｛NH (CH
_{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 (C ₃ ) ₂ ｝ ₂ , HC ₂ H ₅ Si ｛N (C
H ₃ ) ₂ ｝ ₂ , (CH ₃ ) ₂ Si ｛NCH 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 ２N (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 SiN
(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 S
iN (CH ₃ ) ₂ , (CH ₃ ) ₃ SiN (CH 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 SiN (C ₂ H ₅ ) ₂ , H
₂ C ₂ H ₅ SiN (C ₂ H ₅ ) 2, H (CH ₃ ) ₂ Si
N (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, (C
_{H 3) 2 (C 2 H} 5) SiN (C 2 H 5) 2, (C
H 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 SiNH (C ₂ H ₅ ), H ₂
C ₂ H ₅ SiNH (C ₂ H ₅ ), H (CH ₃ ) ₂ SiN
H (C ₂ H ₅ ), H (C ₂ H ₅ ) ₂ SiNH (C
_{2 H 5), (CH 3} ) 3 SiNH (C 2 H 5), (CH
₃ ) ₂ (C ₂ H ₅ ) SiNH (C ₂ H ₅ ), (CH ₃ )
(C ₂ H ₅ ) ₂ SiNH (C ₂ H ₅ ),

[0039] _{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

[0041]

Embedded image

[0042]

Embedded image

A silicon compound having an isocyclic amino group can also be used. Among these compounds, Si ｛N (C
H ₃ ) _{2 ４ 4} , CH ₃ Si ｛N (CH ₃ ) ₂ ｝ ₃ , HC
H ₃ Si ｛N (CH ₃ ) ₂ ｝ ₂ , HCH ₃ Si ｛N (C
_{2 H 5) 2} 2,} (CH 3) 2 Si {N (CH 3) 2}
₂ , (CH ₃ ) ₂ Si ｛N (C ₂ H ₅ ) ₂ ｝ ₂ is particularly preferred.

4. Production of solid catalyst component The solid catalyst component in the present invention is obtained by first reacting the above-mentioned component [I] and component [II], and then reacting the component [II]
I] is obtained by contacting the components.

The reaction ratio of the component [I] to the component [II] is as follows: 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 between the reactant of the component [I] and the component [II] and the reaction of the component [III] is component [III] / (component [I]-(2) + component [II]-(3 )) (Molar ratio)
Is desirably 0.01 to 10, preferably 0.03 to 5, and more preferably 0.05 to 1.

The method of reacting the component [I] with the component [II] is not particularly limited, and the reaction is carried out at a temperature of 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,
In an organic solvent composed of amines or the like, or a mixture thereof, a method of mixing and heating at a temperature of 50 to 300 ° C. for 1 minute to 48 hours, and then removing the solvent may be used, preferably in an organic solvent. After the treatment, a method of removing the organic solvent is desirable.

The reaction method of the reaction product of the component [I] and the component [II] with the component [III] is not particularly limited, and the reaction may be carried out by a co-milling treatment. The reaction may be performed in the presence or absence of a hydrogen 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.

Of course, the operations for the preparation of the component (I), the component (II), the component (III) and the solid catalyst component should be carried out in an inert gas atmosphere. Should.

The components [I], [II], [III] and the various organic solvents used in the preparation of the solid catalyst component of the present invention 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 an alkyl group, alkenyl group, aryl group of hydrocarbon 1-20)
A hydrocarbon residue such as an aralkyl group or an organic residue containing oxygen, nitrogen, sulfur, chlorine or other elements), specifically, methanol, ethanol, propanol, butanol, pentanol Hexanol, octanol, 2-ethylhexanol, phenol, chlorophenol, benzyl alcohol, methyl cellosolve, ethyl cellosolve and the like, and mixtures thereof.

The ether to be used is a compound represented by the general formula R—O—R ′ (where R and R ′ are hydrocarbon residues such as alkyl, alkenyl, aryl and aralkyl groups having 1 to 20 carbon atoms). Which may be the same or different. These may be organic residues containing oxygen, nitrogen, sulfur, chlorine and other elements.R and R 'may form a ring. Is preferable. 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

[0055]

Embedded image

(Wherein R and R ′ are hydrocarbon residues such as alkyl, alkenyl, aryl and aralkyl having 1 to 20 carbon atoms, which may be the same or different. These may be oxygen, Organic compounds containing nitrogen, sulfur, chlorine and other elements may be used, and R and R 'may form a ring.) Specific examples include acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl butyl ketone, dihexyl ketone, acetophenone, diphenyl ketone, cyclohexanone and the like. These may be used as a mixture.

The esters may have 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 mixtures thereof.

The nitriles include, for example, acetonitrile, propionitrile, butyl nitrile, pentyronitrile, benzonitrile, hexanenitrile,
And these may be used as a mixture. Examples of the amines include methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline, tetramethylenediamine and the like. These may be used as a mixture.

Thus, the component [I] and the component [I]
The component I] is contact-reacted and then the component [III] is contact-reacted to obtain a solid catalyst component.

Such a solid powder can be used as it is as a solid catalyst component in the production of polyolefin and has a sufficient performance, but the solid component is converted to the component [I]-(3).
The effect of the present invention can be further enhanced by being used as a solid catalyst component after being subjected to a contact treatment with various organoaluminum compounds used as a catalyst. The organoaluminum compound used here may be the same compound as component [I]-(3) or a different compound.

The contacting method in this case is not particularly limited, but in the presence of an inert hydrocarbon solvent, at a temperature of 0 to 300 ° C., preferably 20 to 150 ° C., for 5 minutes to 5 hours.
After mixing and heating for 10 hours, a method of removing the solvent by evaporation is preferably used. Of course, these operations should be performed in an inert gas atmosphere, and moisture should be avoided as much as possible.

In this case, the contact reaction ratio of the organoaluminum compound is determined by the formula: organoaluminum compound / {component [I]-(2) + component [II]-(3) (optional component)}.
(Molar ratio) is 0.1 to 100, preferably 0.2 to 1
0, and more preferably 0.5 to 5.

<2> Organometallic Compound The catalyst used in the present invention comprises the solid catalyst component and an organometallic compound, and the organometallic compound is a group I to IV of the periodic table known as one component of a Ziegler catalyst. Can be used, and an organic aluminum compound and an organic zinc compound are particularly preferable. Specific examples include the general formulas R ₃ Al, R ₂ AlX, RAlX ₂ , and R ₂ Al
OR, RAl (OR) X and organoaluminum compounds of R ₃ Al ₂ X ₃ (where R represents an alkyl group or an aryl group having 1 to 20 carbon atoms, X represents a hydrocarbon group such as a halogen atom, and even if R is the same, Or an organic zinc compound of the general formula R ₂ Zn (where R is an alkyl group having 1 to 20 carbon atoms and the two may be the same or different); Triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, trit
Examples thereof include tert-butylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum chloride, diisopropylaluminum chloride, ethylaluminum sexchloride, diethylzinc and a mixture thereof. The amount of the organometallic compound used is not particularly limited, but it can be generally used in an amount of 0.1 to 1000 mol times the titanium compound and / or the vanadium compound.

In the present invention, the organometallic compound component can also be preferably used as a mixture or an addition compound of the organometallic compound and an organic acid ester.

In this case, when the organic metal compound and the organic acid ester are used as a mixture, the organic acid ester is usually used in an amount of 0.1 to 1 mol, preferably 0.2 to 0.5, per mol of the organic metal compound. Use moles. When used as an addition compound of an organic metal compound and an organic acid ester, the molar ratio of the organic metal compound: organic acid ester is 2: 1.
１ ： 1: 2 is preferred.

The organic acid ester used at this time is
An ester of a saturated or unsaturated monobasic or dibasic organic carboxylic oxygen having 1 to 24 carbon atoms and an alcohol having 1 to 30 carbon atoms. Specifically, methyl formate,
Ethyl acetate, amyl acetate, phenyl acetate, octyl acetate, methyl methacrylate, ethyl stearate, methyl benzoate, ethyl benzoate, n-propyl benzoate, i-propyl benzoate, butyl benzoate, hexyl benzoate, benzoic acid Cyclopentyl, cyclohexyl benzoate, phenyl benzoate, 4-tolyl benzoate, methyl salicylate, ethyl salicylate, methyl p-oxybenzoate, ethyl p-oxybenzoate, phenyl salicylate,
cyclohexyl p-oxybenzoate, salicylsan benzyl, ethyl α-resorcinate, methyl anisate, ethyl anisate, phenyl anisate, benzyl anisate, o
-Ethyl methoxybenzoate, methyl p-ethoxybenzoate, methyl p-toluate, ethyl p-toluate, p
-Phenyl toluate, ethyl o-toluate, ethyl m-toluate, methyl p-amine benzoate, ethyl p-amine benzoate, vinyl benzoate, allyl benzoate,
Benzyl benzoate, ethyl naphthoate and the like can be mentioned.

Of these, particularly preferred are alkyl esters of benzoic acid, o- or p-tolylic acid or p-anisic acid, and especially methyl esters of these.
Ethyl esters are preferred.

<3> Polymerization of Olefin Polymerization of olefin using the catalyst of the present invention can be carried out by slurry polymerization, solution polymerization or gas phase polymerization.
In particular, the catalyst of the present invention can be suitably used for gas-phase polymerization, and the polymerization reaction is carried out in the same manner as an ordinary olefin polymerization reaction using a Ziegler-type catalyst. That is, all reactions are carried out in the presence or absence of inert hydrocarbons with substantially no oxygen, water or the like. The polymerization conditions for the olefin are as follows: a temperature of 20 to 120 ° C., preferably 5 to 120 ° C.
0 to 100 ° C, and the pressure is from normal pressure to 70 kg /
cm ² , preferably 2 to 60 kg / cm ² .
The molecular weight can be controlled to some extent by changing the polymerization conditions such as the polymerization temperature and the molar ratio of the catalyst, but can be effectively controlled by adding hydrogen to the polymerization system. Of course, using the catalyst of the present invention, a multi-stage polymerization reaction of two or more stages with different polymerization conditions such as hydrogen concentration and polymerization temperature can be carried out without any problem.

The method of the present invention is applicable to the polymerization of all olefins that can be polymerized with a Ziegler catalyst, and particularly preferably α-olefins having 2 to 12 carbon atoms, for example, ethylene, propylene, 1-butene, hexene-1, Homopolymerization of α-olefins such as 4-methylpentene-1 and ethylene having 3 to 12 carbon atoms such as ethylene and propylene, ethylene and 1-butene, ethylene and hexene-1, and ethylene and 4-methylpentene-1 It is suitably used for copolymerization of olefins, copolymerization of propylene and 1-butene, and copolymerization of ethylene with two or more other α-olefins.

Copolymerization with a diene for the purpose of modifying a polyolefin is also preferably performed. Examples of the diene compound used at this time include butadiene and 1,4.
-Hexadiene, ethylidene norbornene, dicyclopentadiene and the like.

The comonomer content in the copolymerization can be arbitrarily selected. For example, in the case of copolymerization of ethylene with an α-olefin having 3 to 12 carbon atoms, ethylene / α-olefin copolymer may be used. The content of the α-olefin in the polymer is desirably 0 to 40 mol%, preferably 0 to 30 mol%.

[0072]

The olefin homopolymer or copolymer obtained by using the solid catalyst component and the organometallic compound of the present invention as catalysts has a remarkably high bulk specific gravity, a relatively large average particle size, a narrow particle size distribution and fine particles. The small amount of powdery particles reduces the amount of polymer adhering to the reactor wall during polymerization, enabling stable operation, preventing dust during molding and increasing efficiency during molding. Alternatively, the pelletizing step may be omitted.

Further, since the molecular weight distribution of the polymer is narrow, especially when it is applied to a film, it has high strength and excellent transparency,
And many effects such as excellent anti-blocking property and heat sealing property can be exhibited.

[0074]

(Polymer property measurement method)

Melting point: When using a scanning calorimeter (DSC, manufactured by Seiko Denshi Co., Ltd.) with a sample weight of 5 mg, melt once at 180 ° C., cool to −40 ° C., and then raise the temperature at a rate of 10 ° C./min. Was determined as the melting point. Hexane extraction: The copolymer powder is roll-kneaded at 180 ° C., then press-molded into a sheet of 5 cm × 5 cm × 0.2 mm, and extracted with hexane to extract the percentage of weight loss when extracted in boiling hexane for 5 hours. Amount. N value: Using a Shimadzu flow tester (CFT-500), apply various loads to the material at 170 ° C.
It is extruded from a die of ± 0.01 mm and length of 40.0 ± 0.01 mm, and the shear rate gradient with respect to the shear stress is calculated by the following equation to obtain an N value.

[0075]

(Equation 1)

Example 1 (a) Production of solid catalyst component SiO ₂ (Fuji Devison, Japan) fired at 600 ° C. in a 500 ml three-necked flask equipped with a stirrer and a reflux condenser.
# 955) 50 g was added thereto, and 160 ml of dehydrated hexane and 3.3 ml of titanium tetrachloride were added thereto and reacted under hexane reflux for 3 hours. After cooling, 45 ml of a 1 mmol / cc hexane solution of diethylaluminum chloride was added, and the mixture was reacted again with hexane reflux for 2 hours.
Drying under reduced pressure at 20 ° C. removed hexane. 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 aluminum triethoxide were placed at room temperature under a nitrogen atmosphere at room temperature. Ball milling was performed for an hour to obtain a reaction product.
5.4 g of the reaction product was dissolved in 160 ml of dehydrated ethanol, and the whole solution was added to a three-necked mouth containing the component [I], reacted under ethanol reflux for 3 hours, and dried under reduced pressure at 150 ° C. for 6 hours. Was done. Next, 1.0 ml of bis (dimethylamino) dimethylsilane was added and 90
The reaction was carried out at a temperature of 3 ° C. for 3 hours to obtain a solid catalyst component.

(B) Gas phase polymerization As a gas phase polymerization apparatus, a stainless steel autoclave equipped with a stirrer is used, and a loop is 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 triethyl aluminum 50 mm
ol / hr, while supplying each gas while adjusting the butene-1 / ethylene molar ratio to 0.30 and the hydrogen / ethylene molar ratio to 0.1 in the autoclave gas phase, 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 performed for 10 hours while intermittently blowing out the produced polymer. The produced ethylene copolymer is melt flow rate (MF
R) 1.01 g / 10 min, (ASTM-D1238)
-65T compliant, condition 190 ° C, load 2.16 kg), density 0.9201 g / cm ³ , bulk density 0.47 g
/ Cm ³ and an average particle size of 740 μm. The catalyst efficiency was as high as 200,000 g copolymer / gTi. After the continuous polymerization for 10 hours, the inside of the autoclave was inspected. As a result, no polymer was adhered to the inner wall and the stirrer.
The N value of this copolymer is 1.42, the molecular weight distribution is extremely narrow, the melting point is 121.3 ° C., and the hexane extraction amount is 2.0 wt.
%Met.

Example 2 Example 1 was the same as Example 1 except that 1.4 ml of tetrakis (dimethylamino) silane was used instead of 1.0 ml of bis (dimethylamino) dimethylsilane as the component [III]. A solid catalyst component was synthesized by the method. When polymerization was carried out in the same manner as in Example 1 using the solid catalyst component, the catalyst efficiency was as high as 200,000 g copolymer / gTi, and the MFR was 0.92 g / 10 mi.
n, density 0.9208 g / cm ³ , bulk specific gravity 0.44 g
/ Cm ³ , and a round granular material having an average particle size of 760 μm was obtained. The N value was 1.42, and the molecular weight distribution was narrow, the melting point was 121.6 ° C, and the hexane extraction amount was 2.1 wt%.

Example 3 The same as Example 1 except that 3.5 ml of bis (dimethylamino) methylsilane was used in place of 1.0 ml of bis (dimethylamino) dimethylsilane as component [III]. A solid catalyst component was synthesized by the method. When polymerization was carried out in the same manner as in Example 1 using the solid catalyst component, the catalyst efficiency was as high as 230,000 g copolymer / gTi, and the MFR was 1.05 g / 10 mi.
n, density 0.9198 g / cm ³ , bulk specific gravity 0.44 g
/ Cm ³ , and a round granular material having an average particle size of 830 μm was obtained. Further, the N value was 1.43, the molecular weight distribution was narrow, the melting point was 121.8 ° C, and the hexane extraction amount was 2.2 wt%.

Example 4 In Example 1, instead of 3.3 ml of titanium tetrachloride as the component [I]-(2), tetrakisbutoxycitane 10 was used.
A solid catalyst component was synthesized in the same manner as in Example 1 except that ml was used, to obtain a solid catalyst component containing 20 mg of titanium per gram. Polymerization was carried out in the same manner as in Example 1 except that the butene-1 / ethylene (molar ratio) in the gas phase of the autoclave was changed to 0.35.
The catalyst efficiency is as high as 260,000 g copolymer / gTi, the MFR is 0.86 g / 10 min, and the density is 0.9201.
g / cm ^3, bulk density 0.46 g / cm ^3, average particle size 8
Round granules having a shape of 60 μm were obtained. Further, the N value was 1.42, and the molecular weight distribution was narrow, the melting point was 120.5 ° C, and the hexane extraction amount was 2.0 wt%.

Example 5 A solid catalyst was prepared in the same manner as in Example 1 except that 3.6 g of boron triethoxide was used instead of aluminum triethoxide as the component [II]-(2). The components were synthesized. When polymerization was carried out in the same manner as in Example 1 using the above solid catalyst component, the catalyst efficiency was as high as 200,000 g copolymer / gTi, and MFR was high.
0.83 g / 10 min, density 0.9205 g / c
m ³ , bulk specific gravity 0.45 g / cm ³ , average particle size 720 μm
Round granules of m shape were obtained. The N value is 1.4.
4, the molecular weight distribution was narrow, the melting point was 121.7 ° C., and the amount of hexane extracted was 2.3 wt%.

Example 6 A solid catalyst component was prepared in the same manner as in Example 1 except that 2.9 g of magnesium ethoxide was used instead of aluminum triethoxide as component [II]-(2). Was synthesized. When the polymerization was carried out in the same manner as in Example 1 using the above solid catalyst component, the catalyst efficiency was as high as 190,000 g copolymer / gTi, and MFR was high.
1.10 g / 10 min, density 0.9206 g / c
m ³ , bulk specific gravity 0.45 g / cm ³ , average particle size 680 μm
Round granules of m shape were obtained. The N value is 1.4.
4, the molecular weight distribution was narrow, the melting point was 120.6 ° C., and the hexane extraction amount was 2.2 wt%.

Example 7 A solid catalyst component was synthesized in the same manner as in Example 1 except that Al ₂ O ₃ was used instead of SiO ₂ as the component [I]-(1). When polymerization was carried out in the same manner as in Example 1 using the solid catalyst component,
The catalyst efficiency is as high as 150,000 g copolymer / gTi, the MFR is 1.40 g / 10 min, and the density is 0.9235.
g / cm ³ , bulk specific gravity 0.44 g / cm ³ , average particle size 5
Round granules having a shape of 90 μm were obtained. The N value was 1.41 and the molecular weight distribution was narrow, the melting point was 120.3 ° C., and the hexane extraction amount was 2.1 wt%.

[0084] Component Example 8 Example 1 [I] - (1) as a solid catalyst component in the same manner as in Example 1 except for the use of _SiO 2 _-Al 2 _{O 3} instead of SiO ₂ Synthesized. The catalyst efficiency is as high as 160,000 g copolymer / g Ti,
MFR 0.69 g / 10 min, density 0.9237 g /
cm ³ , bulk specific gravity 0.42 g / cm ³ , average particle size 610
Round granules of μm shape were obtained. The N value is 1.
The molecular weight distribution was as narrow as 42, the melting point was 120.9 ° C., and the amount of hexane extracted was 2.2 wt%.

Example 9 Example 9 was repeated except that 3.3 ml of titanium tetrachloride was used instead of 3.3 ml of titanium tetrachloride and 0.5 ml of triethoxyvanadyl as the component [I]-(2). A solid catalyst component was synthesized in the same manner as in Example 1 to obtain a solid catalyst component containing 20 mg of titanium and 6 mg of vanadium per gram. When polymerization was carried out in the same manner as in Example 1 using the above solid catalyst component, the catalyst efficiency was 2
High activity of 20,000g copolymer / gTi, MFR
1.51 g / 10 min, density 0.9206 g / c
m ³ , bulk specific gravity 0.43 g / cm ³ , average particle size 760 μm
Round granules of m shape were obtained. The N value is 1.4.
The molecular weight distribution was 5 and the melting point was 122.1 ° C., and the hexane extraction amount was 2.4 wt%.

Example 10 SiO ₂ (Fuji Devison, Japan) fired at 600 ° C. in a 500 ml three-necked flask equipped with a stirrer and a reflux condenser.
# 955) 50 g was added thereto, and 160 ml of dehydrated hexane and 3.3 ml of titanium tetrachloride were added thereto and reacted under hexane reflux for 3 hours. After cooling, 45 ml of a 1 mmol / cc hexane solution of diethylaluminum chloride was added and reacted again with hexane reflux for 2 hours.
Drying under reduced pressure at 120 ° C. removed hexane. 1/2
25 stainless steel balls with inch diameter
10 g of commercially available anhydrous magnesium chloride, 4.2 g of aluminum triethoxide, and 2.7 g of titanium tetrachloride were placed in a stainless steel pot having an inner volume of 400 ml, and ball milling was performed at room temperature under a nitrogen atmosphere for 16 hours to carry out a reaction. The product was obtained. (Component [II]) 5.4 g of the reaction product was dissolved in 160 ml of dehydrated ethanol, and the solution was added to a three-necked flask containing the whole amount of the component [I], and reacted for 3 hours under ethanol reflux. Vacuum drying was performed at 6 ° C. for 6 hours. Next, 1.2 ml of bis (dimethylamino) dimethylsilane was added and reacted at 90 ° C. for 3 hours to obtain a solid catalyst component. The content of titanium in 1 g of the obtained solid catalyst component was 25 mg. When polymerization was carried out in the same manner as in Example 1 using the solid catalyst component, the catalyst efficiency was as high as 260,000 g copolymer / gTi, and the MFR was 0.85 g / 10 m
in, density 0.9201 g / cm ³ , bulk specific gravity 0.46
A round granular material having a shape of g / cm ³ and an average particle size of 840 μm was obtained. Further, the N value is 1.42 and the molecular weight distribution is narrow,
The melting point was 122.1 ° C., and the amount of hexane extracted was 2.4 wt%.

Comparative Example 1 SiO ₂ (Fuji Devison, Japan) fired at 600 ° C. in a 500 ml three-necked flask equipped with a stirrer and a reflux condenser.
# 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, 30 ml of a 1 mmol / cc hexane solution of diethylaluminum chloride was added, and the mixture was reacted again with hexane reflux for 2 hours.
Drying under reduced pressure at 20 ° C. removed hexane. (Component [I]) 10 g of commercially available anhydrous magnesium chloride and 4.2 g of aluminum triethoxide 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 nitrogen. Under an atmosphere, ball milling was performed at room temperature for 16 hours to obtain a reaction product. (Component [II]) 5.4 g of the reaction product was dissolved in 160 ml of dehydrated ethanol, and the whole solution was added to a three-necked flask containing the component [I], and reacted for 3 hours under ethanol reflux. Drying under reduced pressure at 150 ° C. for 6 hours gave a solid catalyst component. When polymerization was carried out in the same manner as in Example 1 using the above solid catalyst component, the catalyst efficiency was 200,00.
0g copolymer / gTi and high activity, MFR 1.00g /
A granular material having a shape of 10 min, a density of 0.9208 g / cm ³ , a bulk specific gravity of 0.45 g / cm ³ , and an average particle diameter of 600 μm was obtained. Further, the N value was 1.48, which was broader in molecular weight distribution as compared with the examples, the melting point was 122.9 ° C., and the hexane extraction amount was as large as 3.6 wt%.

[Brief description of the drawings]

FIG. 1 is a flowchart showing an example of manufacturing a catalyst used in the present invention.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-6-80722 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 4/65-4/658

Claims (2)

(57) [Claims] 1. A method for polymerizing or copolymerizing an olefin using a solid catalyst component and an organometallic compound as catalysts,
The solid catalyst component comprises a reaction product of the following [I] and [II]
First, the reaction product of
(I) a method for producing a polyolefin, comprising a substance obtained by reacting the compound (I); (I) (1) a silicon oxide and / or an aluminum oxide and (2) a titanium compound or a titanium compound and a vanadium compound And (3) a reaction product obtained by reacting an organoaluminum compound; (II) (1) a magnesium halide; and (2) a general formula Me (OR) _n X _zn ( Here, Me is Na, Mg, Ca, Zn, Cd, B, A
an element selected from l, Si and Sn , z is the valence of the element Me, n is 0 <n ≦ z, X is a halogen atom, and R is a hydrocarbon residue having 1 to 20 carbon atoms) A reaction product obtained by reacting the compound; and [III] a silicon compound having at least one Si-NC bond. 2. A method for polymerizing or copolymerizing an olefin using a solid catalyst component and an organometallic compound as catalysts,
The solid catalyst component comprises a reaction product of the following [I] and [II]
First, the reaction product of
(I) a method for producing a polyolefin, comprising a substance obtained by reacting the compound (I); (I) (1) a silicon oxide and / or an aluminum oxide and (2) a titanium compound or a titanium compound and a vanadium compound And (3) a reaction product obtained by reacting an organoaluminum compound; (II) (1) a magnesium halide; (2) a general formula Me (OR) _n X _zn (here And Me is Na, Mg, Ca, Zn, Cd, B, A
an element selected from l, Si and Sn , z is the valence of the element Me, n is 0 <n ≦ z, X is a halogen atom, and R is 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 with a vanadium compound; and [III] a silicon compound having at least one Si-NC bond.